Polyurethanes

TdB_Umschlag_Meier Westhues_mit Logo_englisch.qxd 23.10.
2007 15:26 Seite 2
Dr. Ulrich Meier-Westhues, born 1955, studied Chemistry European Coatings Tech Files
at the RWTH Aachen, Germany. After four years with
Herberts, Wuppertal, he joined Bayer BU Coatings and
Colorants in 1989. Today he is responsible for Business
Development Polyisocyanates in the Coatings, Adhesives Ulrich Meier-Westhues
and Sealants BU of Bayer MaterialScience, Leverkusen.
Polyurethanes
Coatings, Adhesives and Sealants
Ulrich Meier-Westhues • Polyurethanes

The Mission: Acknowledged experts provide clear,
detailed discussions of the principles behind polyurethanes
and their applications in coatings, adhesives and sealants.
This compendium, aimed at the market, contains everything
that raw materials manufacturers and paint producers need
to know about this leading class of binder.
The Audience: Newcomers to the coatings, adhesives and

sealants industries, technology students, development and
application engineers, and all readers, who have an interest
in and enjoy reading about technological advances.
The Value: Readers will increase their knowledge of current

polyurethane technologies while learning from examples
how to adjust their research and development effectively
and efficiently. This will result in coatings, adhesives and
sealants that satisfy modern applications profiles.
ISBN 3-87870-334-1
ISBN 978-3-87870-334-1
Ulrich Meier-Westhues
Polyurethanes
Coatings, Adhesives
and Sealants
VIN Meier_eng.indb 1 24.10.2007 17:28:59 Uhr

European Coatings Tech Files
Polyurethanes
Coatings, Adhesives
and Sealants

Cover picture: Bayer MaterialScience AG
Bibliographic Information from the German Library

The German Library lists this publication in the German National Library;
detailed biographic data can be accessed at: http://dnb.ddb.de
Polyurethanes – Coatings, Adhesives and Sealants
Hannover: Vincentz Network, 2007
(European Coatings Tech Files)
ISBN 3-87870-334-1
ISBN 978-3-87870-334-1
© 2007 Vincentz Network GmbH & Co. KG, Hannover

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Foreword
Foreword
Developing products that meet market needs, devising efficient and environmen-
tally friendly manufacturing processes, and asserting a position in the global com-
petitive environment – these are the drivers for innovation and technological ad-
vancement. Coating, adhesive and sealant technologies are playing an increas-
ingly significant role in this regard.
Polyurethane chemistry has had a considerable impact in these industrial appli-
cations, and in many cases has been the key to technology implementation. The
enormous diversity and possible combinations of polyurethane raw materials
result in the impressive variability of their properties. Their extraordinary adapt-
ability to meet the most diverse requirements enables the development of specific,
customized solutions.
Polyurethane chemistry has become established throughout the world in many
coating, adhesive and sealant applications, and its potential for further development
is by no means exhausted. New applications are continually being discovered, and
the polyurethane raw material product offerings are being systematically optimized
to meet growing demands.
While solventborne formulations have occupied center stage for many years, the
significance of solvent-free, waterborne or UV-cured systems is steadily increasing.
In this respect, polyurethane chemistry demonstrates that environmental improve-
ments, better quality and economy need not be mutually exclusive, but can ideally
be synergistic.
Polyurethane raw materials were first used in coating and adhesive applications 50
years ago. Since that time, the market has developed dramatically. Steady, above-
average growth is also expected over the coming decades. The reason for this is
both the extraordinary potential for innovation offered by this chemistry, as well
as the increasing globalization of the industry. The result is an expansion of produc-
tion capacities worldwide.
In this context, the chemical industry’s voluntary commitment to “Responsible
Care” made at the 2002 World Summit for Sustainable Development in Johannes-
burg takes on additional significance. Lawmakers and industry are both faced with
meeting and solving today’s global ecological challenges.
The fiftieth anniversary of polyurethanes has provided the impetus for writing this
book, which gives a comprehensive overview of the potential offered by polyure-
thane chemistry, and builds on the book “Polyurethanes for Coatings” published in
2001 by Manfred Bock and his team of authors. The content has been updated and
expanded to include adhesives and new areas of application. The book opens with

Foreword
an introduction to polyurethane chemistry, followed by a discussion of the many

different applications, their current significance and their future prospects.
The information in this book will give newcomers to the field an understanding of
the principles of polyurethane chemistry and an impression of the areas of applica-
tion in the coating, adhesive and sealant segments.
Experienced specialists can update their knowledge about current developments
and perspectives. They may also find it useful as a compendium of information
about important innovations in the field of polyurethanes for coatings, adhesives
and sealants, which may be outside their areas of specialization.
However, this book also particularly addresses the reader who has an interest in
and enjoys reading about technological advances, and views innovation as the key
to commercial success. This book seeks to provide such readers with stimulation
for their own creativity.
The chapters have all been written by experts in their fields. This book would not
have been possible without their commitment and I would like to thank them for
their contributions and many discussions.
Th. Bäker, Dr. B. Baumbach, Dr. H. Blankenheim, Dr. M. Brahm, Dr. J. Brück,
M. Casimir, Dr. H. Casselmann, R. Clemens, Dr. S. Dörr, Dr. Th. Fäcke, Th. Feller,
Dr. W. Fischer, Dr. U. Freudenberg, Dr. O. Ganster, S. Grace, M. Grahl, Dr. D.
Greszta-Franz, Dr. Ch. Gürtler, Dr. E. Haensel, Dr. R. Halpaap, B. Hausstätter,
Dr. W. Henning, R. Hertrampf, Dr. S. Hofacker, Dr. M. Homann, Dr. W. Hovestadt,
Dr. Ch. Irle, J. Jakubowski, O. Kirihara, Dr. H.-J. Laas, Dr. H.-W. Lucas, Dr. M.
Mager, Dr. M. Matner, Dr. E. Mayer, Dr. M. Mechtel, Dr. M. Melchiors, Dr. H.
Mertes, H. Müller, V. Nebe, Dr. A. Nennemann, Dr. K.-L. Noble, Dr. S. Nowak,
J. Perry, Dr. R. Pires, Dr. T. Pohl, Dr. J. Rosthauser, Dr. J. Schmitz, Dr. J. Schrot,
Dr. Ed Squiller, Dr. H. Stepanski, Dr. Th. Stingl, Dr. N. Stöckel, Dr. J. Tillack,
Dr. R. Trinks, Dr. M. Vollmer, Dr. J. Weikard, A. a. d. Wieschen, Dr. M. Wintermantel,
K.-H. Wührer, A. Wylie, P. Yu, D. Zielinski
Thanks go to Ms. M. E. Beenen-Fuchs and Ms. S. Köster for their tireless work in
producing and correcting the manuscript.The English translation was coordinated by
Ms. E. Britton of the Language Service, Bayer Industry Services GmbH& Co. OHG.
I would also like to thank Mr. B. Steinhilber, Bayer MaterialScience AG, for his
support of this project.
Leverkusen , Germany, October 2007
Dr. Ulrich Meier-Westhues

Foreword
In line with the publisher’s guidelines, the authors have identified trade-
marked product names by enclosing them within quotation marks “ ”. While
every effort has been made to identify all products in this way, there can be
no guarantee of completeness. If a product is not identified thus, it should
not be construed to imply that the name can be used freely. It is also possible
in individual cases that unprotected product names may inadvertently have
been designated as registered trademarks. If the reader intends to use these
terms, he must himself investigate the associated proprietary rights. No li-
ability can be assumed for such usage. The same applies to the attribution
of product names to certain manufacturers. This does not necessarily imply
that the trademarks are the property of the respective manufacturers.
It should also be noted that the authors have expressed their personal views,
based upon their own knowledge. This does not absolve the reader of the
responsibility to perform their own tests with respect to the uses and ap-
plications of the various processes or products described herein, and/or to
obtain additional advice regarding the same. Any liability of the authors or
of Bayer MaterialScience AG is excluded, inasmuch as and to the extent
permitted by law, subject to all legal interpretations.

Contents
Contents
1 Introduction....................................................................... 14
1.1 Historical aspects................................................................. 14
1.2 Definition of scope.............................................................. 16
2 Economic aspects and market analysis............................ 17
2.1 Coatings............................................................................... 17
2.2 Adhesives and sealants........................................................ 20
3 Chemical principles........................................................... 25
3.1 Di- and triisocyanates.......................................................... 25
3.2 Isocyanate reactions............................................................. 28
3.3 Polyisocyanates................................................................... 30
3.4 Prepolymers......................................................................... 35
3.5 Blocked polyisocyanates..................................................... 35
3.6 Hydrophilically modified polyisocyanates.......................... 43
3.7 Coreactants.......................................................................... 45
3.7.1 Polyacrylate polyols............................................................ 46
3.7.2 Polyester polyols................................................................. 47
3.7.3 Polyether polyols................................................................. 49
3.7.4 Polycarbonate polyols......................................................... 49
3.7.5 Polycaprolactone polyols..................................................... 49
3.7.6 Polyurethane polyols........................................................... 50
3.7.7 Polyamines.......................................................................... 50
3.8 Aqueous dispersions............................................................ 52
3.8.1 Polyurethane dispersions..................................................... 52
3.8.2 Polyacrylate dispersions...................................................... 55
3.9 Urethane acrylates............................................................... 57
4 Coating technology principles.......................................... 62
4.1 Aspects of one- and two-component coating technology.... 62
4.2 Solventborne and solvent-free systems............................... 65
4.3 Waterborne systems............................................................. 67
4.4 Process technology.............................................................. 71
4.4.1 Processing of one-component polyurethane coatings......... 71
4.4.2 Processing of two-component polyurethane coatings......... 71
4.5 Polyurethane powder coatings............................................. 76
4.6 Radiation curing.................................................................. 78
4.6.1 Technology and coating formulation................................... 78

10 Contents
4.6.2 Binders for radiation curing................................................. 79

4.6.3 Urethane acrylates for UV (mono-cure) and electron
beam curing applications . .................................................. 80
4.6.4 Waterborne UV-curing polyurethane coatings.................... 82
4.6.5 Urethane acrylates for UV powder applications.................. 83
4.6.6 Isocyanato urethane acrylates for dual-cure technology .... 83
4.7 Nanotechnology in polyurethane coatings.......................... 85
5 Applications for polyurethane coatings........................... 90
5.1 Wood coating....................................................................... 90
5.1.1 Requirements of wood and furniture coatings..................... 91
5.1.2 Polyisocyanates for wood and furniture coatings................ 92
5.1.3 Solventborne two-component polyurethane coatings......... 93
5.1.4 Moisture-curing coatings..................................................... 96
5.1.5 Urethane-modified oil and alkyd resin coatings.................. 96
5.1.6 Radiation-curing urethane acrylate coatings....................... 97
5.1.7 Waterborne polyurethane coatings...................................... 98
5.1.8 Waterborne UV-curing one-component
polyurethane coatings.......................................................... 100
5.1.9 Outlook................................................................................ 101
5.2 Metal coating....................................................................... 102
5.2.1 General industrial coating.................................................... 102
5.2.1.1 Technical aspects of polyurethane coatings......................... 103
5.2.1.2 Waterborne polyurethane coatings...................................... 105
5.2.2 Coil coating......................................................................... 108
5.2.3 Can coating.......................................................................... 115
5.2.4 Powder coating.................................................................... 118
5.2.4.1 Powder coating technology................................................. 118
5.2.4.2 Polyurethane powder coatings............................................. 119
5.2.5 Corrosion protection............................................................ 125
5.2.5.1 Technical aspects of polyurethane anti-corrosion coatings 126
5.2.5.2 Primers................................................................................. 128
5.2.5.3 Intermediate coats................................................................ 128
5.2.5.4 Topcoats............................................................................... 129
5.2.5.5 Polyurethane/hydrocarbon resin combinations................... 129
5.2.5.6 Polyaspartic coatings........................................................... 130
5.2.5.7 Pipe coating......................................................................... 131
5.2.6 Wire coating........................................................................ 134
5.3 Automotive OEM finishing................................................. 136
5.3.1 Cathodic electrodeposition primers..................................... 138
5.3.2 Seam sealing, underbody coating and sound insulation...... 139
5.3.3 Primer surfacers................................................................... 141

Contents 11
5.3.4 Basecoats and clearcoats..................................................... 143

5.3.5 Outlook................................................................................ 149
5.4 Automotive refinish and transportation coating.................. 151
5.4.1 Property profile.................................................................... 153
5.4.2 Steps in automotive refinishing and transportation coating 154
5.4.3 Application and characteristic data of two-component
polyurethane coatings.......................................................... 156
5.4.4 Raw material selection........................................................ 157
5.4.5 Low emission polyurethane coatings.................................. 160
5.4.5.1 Two-component polyurethane high solid coatings.............. 162
5.4.5.2 Two-component very high solid polyurethane coatings...... 162
5.4.5.3 Waterborne polyurethane coatings...................................... 165
5.4.6 Radiation-curing coatings.................................................... 173
5.4.7 Interior coating of large vehicles......................................... 174
5.4.8 Light-stable, thick film coatings.......................................... 174
5.5 Plastic coating...................................................................... 181
5.5.1 Market evaluation................................................................ 182
5.5.2 Coating process................................................................... 182
5.5.3 Raw material selection........................................................ 185
5.5.4 Coating concepts for automotive add-on components........ 188
5.5.5 Soft-feel coatings................................................................. 190
5.5.6 Industrial plastic coating...................................................... 192
5.5.7 UV technology in plastic coating........................................ 193
5.5.8 In-mold coating................................................................... 193
5.5.9 Polyurethane gelcoats.......................................................... 196
5.6 Application on glass............................................................ 200
5.6.1 Coatings for glass containers............................................... 200
5.6.2 Glass fiber sizing................................................................. 202
5.7 Use on textiles and leather................................................... 203
5.7.1 Textile coating..................................................................... 203
5.7.2 Polyurethane synthetic leather and microporous coatings.. 208
5.7.3 Leather coating.................................................................... 210
5.8 Coating and finishing of paper and films............................. 212
5.8.1 Paper manufacturing............................................................ 212
5.8.2 Paper coating....................................................................... 212
5.8.3 The production of decorative coating materials for
furniture and interior design................................................ 214
5.8.4 Finishing of technical papers and films............................... 214
5.9 Construction applications.................................................... 215
5.9.1 Floor coatings...................................................................... 215
5.9.1.1 Technology of polyurethane floor coatings......................... 217

12 Contents
5.9.1.2 Examples of applications..................................................... 220

5.9.2 Wall coatings....................................................................... 223
5.9.2.1 Coating systems................................................................... 224
5.9.2.2 Polyurethane wall coatings.................................................. 225
5.9.3 Surface sealing..................................................................... 228
5.9.3.1 Sealing flat roofs with liquid polyurethane membranes...... 228
5.9.3.2 Sealing balconies with polyurethane membranes................ 231
6 Polyurethane adhesives..................................................... 243
6.1 Introduction......................................................................... 243
6.2 Classification....................................................................... 244
6.3 Polyurethane reactive adhesives.......................................... 245
6.3.1 Raw materials...................................................................... 246
6.3.2 Two-component polyurethane reactive adhesives............... 248
6.3.3 Moisture-curing one-component reactive adhesives........... 251
6.3.3.1 One-component polyurethane systems................................ 251
6.3.3.2 One-component silane-terminated polyurethanes............... 254
6.3.4 Polyurethane laminating adhesives..................................... 254
6.4 Solventborne adhesives based on hydroxyl polyurethanes 259
6.4.1 Hydroxyl polyurethanes...................................................... 259
6.4.2 Isocyanate crosslinkers for solventborne adhesives............ 262
6.5 Polyurethane dispersion adhesives...................................... 262
6.5.1 Products............................................................................... 262
6.5.2 Formulation......................................................................... 263
6.5.3 Isocyanate crosslinkers for dispersion adhesives................ 264
6.5.4 Drying.................................................................................. 266
6.5.5 The principle of heat-activated adhesive bonding............... 266
6.5.6 Applications and application technology............................ 268
6.5.7 Latently reactive polyurethane dispersion adhesives.......... 269
6.6 Hot-melt adhesives.............................................................. 271
6.6.1 Non-reactive hydroxyl polyurethane hot-melt adhesives.... 271
6.6.2 Reactive polyurethane hot-melt adhesives.......................... 274
7 Polyurethane sealants........................................................ 283
7.1 Terms and definitions.......................................................... 283
7.2 Chemical structure............................................................... 283
7.2.1 Isocyanate crosslinking systems.......................................... 283
7.2.2 Silane-modified polymers.................................................... 284
7.3 Formulation......................................................................... 286
7.3.1 NCO-reactive one-component polyurethane sealants......... 286
7.3.2 Silane-terminated polyurethanes......................................... 287
7.4 Processing............................................................................ 288

Contents 13
8 New areas of application for polyurethanes.................... 290

9 Combinatorial material development
and high-throughput testing............................................. 293
9.1 Combinatorial material development.................................. 293
9.2 Statistical experimental design and high-throughput
analysis in the laboratory..................................................... 294
9.3 Blocked isocyanates with a lower baking temperature –
an example of combinatorial development.......................... 295
10 Occupational hygiene in the manufacture and
processing of polyurethane coatings and adhesives........ 300
10.1 Occupational health and safety............................................ 300
10.1.1 Monomeric and polymeric isocyanates............................... 300
10.1.1.1 Labeling............................................................................... 302
10.1.1.2 Exposure limits.................................................................... 304
10.1.1.3 Isocyanate analysis.............................................................. 306
10.1.2 Coreactants for polyisocyanates.......................................... 307
10.1.3 Processing of polyurethane coatings................................... 307
10.1.3.1 General protective measures................................................ 307
10.1.3.2 Spray application................................................................. 309
10.1.3.3 Waterborne one-component and two-component
reactive systems................................................................... 310
10.1.3.4 Baking urethane resins........................................................ 311
10.1.3.5 Special aspects of processing MDI-based products............ 311
10.1.4 Disposal of polyisocyanate residues and cleaning of
soiled containers.................................................................. 313
10.2 Consumer protection aspects............................................... 314
10.2.1 Polyurethane coatings and indoor air quality...................... 314
10.2.2 Do-it-yourself and polyurethanes........................................ 315
10.2.3 Relevant legal provisions covering raw materials for
coatings and adhesives in contact with foodstuffs............... 316
10.2.4 Polyurethane coatings and drinking water.......................... 318
10.2.5 Behavior of polyurethane coatings in the event of fire........ 319
11 Ecology................................................................................ 323
11.1 Solvent emissions................................................................ 323
11.2 Waste products..................................................................... 329
11.3 Wastewater........................................................................... 330
12 Sustainable Development.................................................. 332
13 General references............................................................. 334
Index................................................................................... 337

14 Introduction
1 Introduction
1.1 Historical aspects

Coating, bonding and sealing are techniques that humankind has used for many
thousands of years. For a long time, only natural resins, oils and fats were used for
these purposes.
Shellac, a natural resin secreted by the scaly lac insect, has been used in India for
centuries as a weather-resistant coating for surfaces. The word lacquer in English
is derived from the Sanskrit word laksha, which means one hundred thousand and
describes the unimaginably large number of insects required to produce shellac
lacquers. Later it was learned that lacquer resins could also be obtained from other
sources, e.g. by boiling down wood oil.
Animal products, especially bones and hide, were the basis for glues and adhesives
for many centuries. The makers of high-quality glues were called Kellepsos in
ancient Greece. During the Middle Ages, development was largely static. The
invention of the printing press by Johannes Gutenberg then led to a new and rapidly
growing need for adhesives in the emerging bookbinding industry.
The development of synthetic resins began in the early 20th century and made
possible the production of coatings and adhesives of vastly improved quality. Poly-
urethanes were discovered in 1937 when Heinrich Rinke produced 1,6-hexameth-
ylene diisocyanate (HDI) and Otto Bayer developed the diisocyanate polyaddition
process [1–3]. Initial research in this new field of poly-
mer chemistry in the 1940s focused on polyurethane
fibers, while the first polyurethane foams were pro-
duced a little later.
Fifty years ago, the first polyurethane coatings were
developed. Otto Bayer and his team discovered that the
technical properties of alkyd resins could be improved
through modification with diisocyanates. However, the
real conquest of the coatings sector by polyurethanes
only began with the development and industrial use of
low-monomer polyisocyanates. The first products were
based on toluene diisocyanate. Because of the aromatic
Figure 1.1: Otto Bayer –
nature of the base isocyanate, these tend to yellow on
Inventor of polyurethane exposure to light and can therefore only be used for
chemistry [6] interior applications or in primers.

Historical aspects 15
The range of applications was broadened later with the introduction of products
based on aliphatic diisocyanates, initially hexamethylene diisocyanate. “Desmodur
N” was the first product of this type, and was launched in the early 1960s. Gradually,
the two-component (DD) coatings made by combining polyisocyanates (“Desmo-
dur”) with polyols (“Desmophen”) replaced the traditional alkyd coatings, first in
the field of large vehicle production. The driving force was the quality of the coat-
ings which, even when dried under mild conditions, matched the performance of
coatings which had been baked. This is important when coating large vehicles (air-
planes, rail wagons and buses) as their size makes baking impossible.
In the 1970s, it was found that the quality of automotive refinish coatings could be
substantially improved with the help of polyurethane chemistry. By adding poly-
isocyanates based on isophorone diisocyanate (IPDI) to the medium-oil alkyd
resins mainly used at that time, the hardness, overcoatability and gasoline resis-
tance of the resulting coatings could be improved significantly. Today, two-com-
ponent polyurethane coatings have almost completely replaced alkyd resin chem-
istry in this segment.
The broad range of applications for polyurethanes in coatings was quickly recog-
nized. Other examples of applications include wood finishing, corrosion protection
and construction, as well as textile coating. Another advance has been the develop-
ment of two-component metering technology. The breakthrough in automotive
OEM finishing occurred in the mid-1980s, and since this time, plastic coatings have
become a further domain for polyurethanes.
Polyurethane adhesives came onto the market in the 1950s with the development
of the hydroxyl polyurethanes and the first trifunctional isocyanate crosslinker,
“Desmodur R”. The early 1960s also saw the development of plasticizer-resistant
hydroxyl polyurethanes, which laid the foundation for the success of these products
in shoe manufacture.
Solvent-free polyurethane reactive adhesives have been used since the 1970s, first
in automotive production, and then in the manufacture of laminated films and
sandwich elements. They were later joined by reactive sealants. Since the 1990s,
polyurethane-based reactive and aqueous dispersion adhesives have gained market
share in furniture manufacture, bookbinding and shoe sole production.
The process of substituting traditional technologies in coatings, adhesives and
sealants with polyurethane is still incomplete, and can be observed occurring
around the world [4, 5]. Against a background of increasingly demanding quality
requirements, ever more stringent environmental legislation, and cost optimization
of the end-product manufacturing processes, there has been growth in the use of
low-solvent, solvent-free, waterborne and radiation-curing formulations of one-
and two-component polyurethane systems. Bearing in mind current concomitant

16 Introduction
developments, e.g. nanotechnology, polyurethanes will continue to gain further

importance. Their spectrum of use will thus expand beyond the established appli-
cations into other new areas.
1.2 Definition of scope

This book describes the use of polyurethane raw materials for coatings, adhesives
and sealants in selected application areas. Topics covered include applications in
the wood and furniture industry, the automotive sector, construction, the broad area
of metal coatings including corrosion protection, the shoe industry, and plastic
coating and bonding. Also discussed are the manufacture of laminated films and
the coating of textiles, leather, glass and paper. In addition to describing the chem-
ical and technical principles involved, the issues of occupational hygiene and ecol-
ogy associated with the handling of polyurethane coatings, adhesives and sealants
are covered. The broad spectrum of applications is evidence of one key property
of polyurethanes: the variability resulting from their chemistry which is also
exploited in segments other than coatings, adhesives and sealants.
For example, polyurethane raw materials are used in the manufacture of foams:
rigid foams for insulation (construction industry, refrigerators) or energy-absorbing
components in automobile interiors (instrument panels); integral skin foams, e.g.
for furniture and medical applications; flexible foams for upholstery, mattresses
and packaging materials. Other applications for polyurethanes are found in the
manufacture of versatile elastomers for the footwear and electrical industries, ther-
moplastic urethanes, e.g. for sports and leisure equipment, and polyurethane elas-
tic fibers for stretch fabrics.
This book does not intend to address all these applications. Detailed information
can be found in other sources such as the Plastics Handbook by Guenter Oertel [7].
References
[1] DRP 728 981 (1937) I. G. Farben
[2] O. Bayer, Angew. Chem. 59 (1947) 257
[3] D. Dieterich, Chemie in unserer Zeit, 24 (1990) 135
[4] M. Bock, et al., Globalisierung der Fahrzeugindustrie - eine Herausforderung bei der
Lackrohstoffentwicklung, Farbe und Lack 102 (9) (1996) 132
[5] M. Bock, H. Meiss, H.-U. Meier-Westhues, Globalisierung aus Sicht eines Lackroh
stoffproduzenten, 6. DFO-Automobiltagung, September 1998, Weimar, Berichtsband
Nr. 38, 1 ff.
[6] Bayer Archiv
[7] G. Oertel in: Kunststoff-Handbuch, G. W. Becker, D. Braun (Hrsg.), 3. Auflage, Band 7:
Polyurethane. Carl Hanser Verlag, München, Wien 1993

Coatings 17
2 Economic aspects and

market analysis
2.1 Coatings
World production of coatings for industrial applications, i.e. the total production
of coating systems – excluding dispersions for architectural coatings, totaled 13.0
million tons in 2005 [1]. This represented global consumption of 8.2 million tons
of coating raw materials or binders in supply form, corresponding to a value of
EUR 14.4 billion.
Material and regional distribution
The distribution of world coating raw material consumption is fairly balanced, with
one third going to Europe, the Middle East and Africa (EMEA), just under a third
going to the Americas (NAFTA and LATAM), and slightly more than a third going
to Asia-Pacific (APAC). It should be emphasized here that APAC’s share of global
coating raw materials consumption has grown in the last ten years from 27 % to
approximately 37 % [1] (Figure 2.1).
The distribution by raw material type and volume shows that the traditional sys-
tems, such as alkyd resins, wax-free polyesters, amino and phenolic resins and
nitrocellulose, are still of great importance. In 2005, these product groups accounted
for just over 40 % of world consumption. However, there is a clear trend toward
higher-quality modern raw materials. For example, in the past ten years, the propor-
tion of polyurethane coating raw materials in global consumption has risen from
about 9 to 13 %, equivalent to 1.05 million tons.
Figure 2.1: World consumption in 2005 of coating raw materials by region,

total: 8.2 million tons

18 Economic aspects and market analysis
The volume of waterborne coating resins, including those for cathodic electrode-
position (CED), from all chemical raw material classes totaled 8 %, as did the
volume of all types of powder coating resins. UV-curing resins now make up 3 %
of the world’s coating raw material consumption (Figure 2.2).
The distribution by value across all coating raw material classes shows that the
traditional systems now account for just 30 %. Polyurethane coating raw materials
hold a share of 18 %, worth EUR 2.6 billion, which shows that these raw materials
are used primarily in those market segments with more exacting quality require-
ments. In terms of value, waterborne coating resins have a share of approximately
12 %, with powder coating resins accounting for 9 %. UV-curing resins comprise
approx. 7 % of global consumption (Figure 2.3).
Figure 2.2: World consumption in 2005 of coating raw materials by product type
(volume), total: 8.2 million tons
Figure 2.3: World consumption in 2005 of coating raw materials by product type (value),
total: Euro 14.4 billions

Coatings 19
Components
The main components of polyurethane coating raw materials are polyisocyanates
and polyols such as polyacrylates, polyesters and polyethers. The 1.05 million tons
of polyurethane coating raw materials used worldwide are distributed as follows:
• Polyisocyanates: 300,000 tons
• Polyacrylates: 370,000 tons
• Polyesters: 330,000 tons
• Polyethers and others: 50,000 tons
The key polyisocyanates used in coating raw materials are the aliphatic polyiso-
cyanates and prepolymers based on hexamethylene diisocyanate (HDI), isophorone
diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (H12MDI), the aromatic
isocyanates toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI)
and the derivatives of these diisocyanates.
Fields of application
The main field of application for coating raw materials (excluding dispersions for
architectural coatings) in Europe, the Middle East and Africa (EMEA) is the construc-
tion industry with 28 %. This is followed by general industrial coatings with 24 %.
After wood and furniture coating with 14 %, automotive finishing and corrosion
protection each hold a roughly equal share of around 10 % (Figure 2.4).
The weighting is different if one considers only polyurethane coating raw materials,
total consumption of which in EMEA in 2005 amounted to 490,000 tons. The most
important fields of application in EMEA are wood and furniture coating and automo-
tive finishing with 30 % and 25 % respectively. They are followed by general indus-
trial coatings with 15 %. This shows clearly that high-quality polyurethane raw
Figure 2.4: Consumption of coating raw materials EMEA in 2005 by area of application,
total: 2.7 million tons

materials are preferred for applications with more exacting requirements in terms
of quality and durability – and these are correspondingly in a higher price segment
(Figure 2.5).
Market forecasts
For the coming years, annual market growth of some 5 % is forecast for polyure-
thane coating raw materials. It is expected that growth in the Asia-Pacific region
(APAC) will be above average at up to 10 %, whereas the European and North
American markets will grow at an average of 3 to 4 %. The market for polyurethane
coating raw materials is expected to reach a volume of over 1.3 million tons world-
wide by the year 2010.
It is expected that, especially in Europe, the Middle East, Africa and the Americas,
most of this growth will be accounted for by waterborne polyurethane coating raw
materials. By contrast, in Asia-Pacific, solventborne polyurethane coating raw
materials will continue to post strong growth.
2.2 Adhesives and sealants

In 2003, the world adhesive and sealant industry had a volume of approx. 9.2 mil-
lion tons and was worth some EUR 23 billion [2]. Between 1998 and 2005, volume
and value growth in this industry sector averaged around 3 %. World production of
formulated adhesives and sealants reached approx. 10 million tons in 2006, which
according to the latest estimates represent a value of approx. EUR 27 billion [3]
(Figure 2.6). The total volume of formulated adhesives and sealants corresponds
to global consumption of approx. 5.2 million tons (dry) of the corresponding indus-
trial raw materials in 2006 [4].
Figure 2.5: Consumption of polyurethane coating raw materials in EMEA in 2005 by area
of application, total: 490,000 tons

Coatings 21
Material and regional distribution

The regional distribution of global adhesive and sealant consumption is fairly
balanced between Europe, the Middle East and Africa (EMEA), Latin America
(LATAM) and North America (NAFTA), and the Asia-Pacific region (APAC),
each accounting for approximately one third of the total. Asia in particular has
seen above-average growth in recent years, and this is expected to hold steady for
the coming years.
If the total consumption of adhesives and sealants is broken down by the underly-
ing raw material classes, the diversification of the chemistry used in the adhesive
and sealant industry becomes apparent. In addition to the polyurethane-based raw
materials, natural products and a multitude of polymer materials can be used to
formulate adhesive and sealant systems. Polyurethanes account for around 9 % of
the total adhesives raw material market [4, 5] (Figure 2.7, page 24).
In recent years, however, the more complex application profiles in adhesive pro-
cesses have led to growing demand for high-quality adhesive and sealant systems.
Alongside other adhesive raw materials in particular, the polyurethanes and systems
based on that chemistry are benefiting due to their outstanding property profile
compared with other adhesive raw materials (Figure 2.8 and Figure 2.9, page 24).
Although solventborne adhesives and sealants are still traditionally used in some
applications, industry’s departure from these systems to ensure compliance with
VOC guidelines has been facilitated by the development of waterborne polyure-
thane raw materials and raw materials that are entirely solvent-free. Additionally,
new raw materials, such as silane-terminated polymers, satisfy the market demand
for tailor-made solutions, both for adhesives and sealants.
Figure 2.6: World consumption in 2005 of adhesives and sealants by region (volume),
total: approx. 10 million tons [2]

Figure 2.7: World consumption in 2005 of raw materials for adhesives and sealants by
chemical class (volume), total: approx. 5 million tons (dry) [4, 5]
Figure 2.8: Consumption of raw materials for adhesives and sealants in EMEA in 2005 by
application (volume), total: approx. 3.3 million tons (supply form) [6]
Figure 2.9: Consumption in 2005 of polyurethane raw materials for adhesives and sealants
in EMEA in 2005 by application (volume), total: approx. 0.2 million tons (supply form) [6]
*Sealants excl. transportation

Coatings 23
Components
The main components of polyurethanes for adhesives and sealants are isocyanates,
polyisocyanates and prepolymers, and polyols such as polyesters or polyethers. The
most important isocyanates, polyisocyanates and prepolymers for adhesive and
sealant raw materials are based on the aromatic diphenylmethane diisocyanate
(MDI) and toluene diisocyanate (TDI), as well as on the aliphatic hexamethylene
diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diiso-
cyanate (H12MDI), and the corresponding derivatives of these diisocyanates.
Polyesters may have an aliphatic, aromatic or araliphatic structure, vary in chain
length, and exhibit amorphous or crystalline properties. Polyethers can be varied
to yield the desired property profile through the choice of starter or chain-building
monomers.
The total world market of all polyurethane raw materials for adhesives and sealants
(including polymer reaction products) amounts to approx. 450,000 tons (dry) [4, 5].
Fields of application
The main field of application for adhesive and sealant raw materials in Europe, the
Middle East and Africa (EMEA) is the packaging segment (approx. 34 %; 3.3 million
tons), followed by pressure-sensitive adhesives (PSA, 16 %), the construction indus-
try (16 %), transportation (12 %), sealants (7 %), furniture manufacture (6 %), assem-
bly (4 %), bookbinding (<3 %) and disposable products (<2 %). Household/do-it-
yourself (DIY) applications and shoe manufacture each have a share of less than 1%.
Consideration of just the polyurethane-based adhesive and sealant raw materials
provides a completely different picture. Of the total market of approximately
190,000 tons, around 30 % is attributable to transportation, 18 % to sealants, 17 %
to packaging, 16 % to furniture and 12 % to construction. The remaining 7 % is
distributed between assembly, shoes, pressure-sensitive adhesives (PSA), house-
hold/DIY applications, disposable products and bookbinding. This shows clearly
that high-quality polyurethane adhesive and sealant raw materials are preferred for
applications with more exacting requirements in terms of quality and durability –
and these are correspondingly in a higher price segment (Figure 2.9).
Market forecasts
Adhesive and sealant applications in important industry segments such as transpor-
tation, construction, assembly (electronics) and furniture will see global growth at a
rate of between 2 and 5 % in the coming years. Regional differences are evident.
Depending on the industry segment, above-average growth of 4 to 8 % is anticipated
for the APAC region, while rather more moderate growth is expected in the remain-
ing regions (EMEA: approx. 3 %; NAFTA: approx. 1.5 %) [7].

The same magnitude of growth is expected in the markets for adhesive and sealant
raw materials. At least in Western Europe, a shift is anticipated in the adhesive
technologies used. Due to statutory regulations (VOC), the share of raw materials
for use in solventborne adhesives will drop significantly, with a proportional rise
in the share of materials for aqueous adhesives or entirely solvent-free systems. For
the time being, the less developed regions such as Eastern Europe, the Middle East
and Africa (MEA), LATAM and APAC do not anticipate substitution of the sol-
ventborne adhesive systems.
The relocation of entire production segments and manufacturing units from the
developed countries to emerging economies such as the Czech Republic, Slovakia,
Poland, Russia and China will lead in the coming years to increased demand there
for highly developed adhesive systems. Adhesive raw materials based on polyure-
thane chemistry will participate strongly here.
References
[1] Bayer MaterialScience AG, Market Intelligence, non-published market studies 2006
[2] ChemResearch, The global adhesive and sealant industry 2003–2006, at 2004
[3] ICIS news, October 2, 2006
[4] ChemResearch, The global adhesive and sealant industry 2003–2006 (dry resin demand),
at 2004
[5] CAS-EMEA-ADH, Internal knowledge, 2006
[6] CAS market database, EMEA-ADH, 2006, non-published
[7] Global Polymers Outlook, 2006

Di- and triisocyanates 25
3 Chemical principles
3.1 Di- and triisocyanates

As a rule, isocyanates are obtained by the phosgenation of the corresponding pri-
mary amines [1, 2] (Figure 3.1).
Alternatively, phosgene-free manufacturing processes have been developed. One
such process involves reacting an amine with urea and alcohol to form a urethane
that can then be split thermally to yield an isocyanate. This process is also used in
the industrial production of some diisocyanates [3]. Figure 3.2 shows the principle
of this synthetic route.
The standard commercial polyisocyanates used in coatings and adhesives are all
derived from just a few diisocyanates with aliphatic, cycloaliphatic or aromatic
isocyanate groups [4]. The most important diisocyanates that are available on an
industrial scale are summarized in Table 3.1 (page 28).
Figure 3.1: Manufacture of isocyanates by phosgenation of primary amines
Figure 3.2: Manufacture of isocyanates via the urea route

In addition to these, a number of other diisocyanates for the manufacture of coating

raw materials have already been described. However, these have yet to achieve any
industrial significance. The synthesis of monomeric triisocyanates such as triiso-
cyanatononane (TIN) was likewise developed. Table 3.2 shows some examples.
Table 3.1: Industrial diisocyanates
Manufacturers /
Trade names
Hexamethylene diisocyanate (HDI) Bayer MaterialScience:
NCO “Desmodur H”
OCN BASF: “Basonat H”
Rhodia: “Tolonate HDI”
Isophorone diisocyanate (IPDI) Bayer MaterialScience:
(3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate) “Desmodur I”
Degussa: “Vestanat IPDI”
H3C CH3
CH3
OCN
NCO
Bis-(4-isocyanatocyclohexyl)methane (H12MDI) Bayer MaterialScience:

“Desmodur W”
Degussa:
OCN CH2 NC O
“Vestanat H12MDI”
2,4- and 2,6-Toluene diisocyanate (TDI) Bayer MaterialScience:

“Desmodur T”
CH3 CH3
BASF: “Lupranat T”
NCO OCN NCO
Rhodia: “Scuranate T”
Lyondell: “Scuranate T”
DOW: “Voranate T”
NCO
Diphenylmethane-4,4’- and/or -2,4’-diisocyanate (MDI) Bayer MaterialScience:

“Desmodur 44 M”
OCN CH2 NCO CH2 NCO
BASF: “Lupranat M”
NCO
ICI: “Suprasec”
DOW: “Isonate”

Di- and triisocyanates 27
Table 3.2: Di- and triisocyanate specialties (selection)

Manufacturers /
Trade name
Xylylene diisocyanate (XDI) Takeda:
1,3-Bis(isocyanatomethyl)benzene “Takenate 500”
NCO
NCO
Hydrogenated xylylene diisocyanate (H6-XDI) Takeda:

1,3-Bis(isocyanatomethyl)cyclohexane “Takenate 600”
NCO
NCO
2,2,4- and 2,4,4-Trimethyl-1,6-diisocyanatohexane Degussa:
NCO
“Vestanat TMDI”
NCO
OCN OCN
H3C CH3 CH3 H3C H3C CH3
Tetramethylxylene diisocyanate (TMXDI) [5] Cytec: TMXDI

1,3-Bis(1-isocyanato-1-methylethyl)benzene
NCO
H3C CH3
CH3
NCO
H3C
Triisocyanatononane (TIN) [6] Bayer MaterialScience

4-Isocyanatomethyl-1,8-octane diisocyanate
NC O
NC O
OCN

Manufacturers /
Trade name
Triphenylmethane-4,4’,4’’-triisocyanate Bayer MaterialScience:
OCN NCO “Desmodur RE”
H
C
NCO
Tris(p-isocyanatophenyl)thiophosphate Bayer MaterialScience:
OCN “Desmodur RFE”
NC O
O
S
P
O O
NCO
With the exception of MDI, which is accorded special status on account of its low
vapor pressure, the German Ordinance on Hazardous Substances classifies mono-
meric diisocyanates as toxic substances. TDI has recently been classified as a highly
toxic substance and must be labeled T+. For occupational health reasons, mono-
meric diisocyanates are generally not used as coating raw materials. They must first
be converted into higher molecular weight, physiologically benign polyisocyanates
using suitable modification reactions.
3.2 Isocyanate reactions

The most frequent reactions of isocyanates are additions of coreactants containing
active hydrogen. Reactions with hydroxyl, amino or carboxylic acid groups are
particularly easy to carry out. Table 3.3 provides an overview of basic reactions of
the isocyanate group.
Isocyanate groups can also react with each other. The reaction products shown in
Table 3.4 are formed with varying selectivity. The reactions shown here by way of
example are used in the manufacture of oligomeric polyisocyanates for coating and

Isocyanate reactions 29
adhesive raw materials. Together with the isocyanate-functional prepolymers, biurets

and cyclopolymers (see Table 3.4, page 33) are of particular significance. Isocyanate-
functional prepolymers are generally produced via urethanization from diisocyanates
in excess with hydroxyfunctional compounds. The properties of the prepolymers can
vary widely as a function of the type, molecular weight and functionality.
Table 3.3: Reaction principles of isocyanates (schematic)

Reaction Reaction equation
with:
Alcohol to O
urethane: NCO + HO R NH C O R
Urethane to O O
allophanate: NCO + NH C O R N C O R
C O
NH
Amine to O
urea: NCO + H2N R NH C NH R
Water to O
urea: 2 NCO + H2O NH C NH + CO2
Urea to O O
biuret : [7] NCO + NH C NH N C NH
C O
NH
Carboxylic O
acid to NCO + HOOC R NH C R + CO2
amide:
Amide to O O
acyl urea: NCO + NH C R N C R
C O
NH
Anhydride to O O
imide:
NCO + O N + CO2
O O

Reaction Reaction equation

with:
Epoxide to O
oxazolidone: R' N O
NCO +
O
R'
Oxime to O
oxime NCO + HO N NH C O N
R R
carbamate:
R R
Carbon O
dioxide to
N N
oxadiazine 2 NCO + CO2
trione [8]: O O O
The aforementioned reactions also allow the crosslinking of oligomeric isocyanates

with suitable coreactants. For example, polyisocyanate and polyol react to form
polyurethane, or polyisocyanate and polyamine or water react to form polyurea
with the formation of a coating or adhesive on the substrate.
The rates of these reactions vary widely and depend on the type of isocyanate used
and, if applicable, on the structure of the coreactant. Aryl isocyanates, for example,
are far more reactive with alcohols than alkyl isocyanates. In the latter, a decline in
reactivity from primary through secondary to tertiary NCO groups can also be
observed [9] unless steric or catalytic influences result in a reversal of reactivity [10].
The reaction of isocyanates with primary or secondary amines is extremely fast and
urea forms spontaneously at room temperature. At higher temperatures, optionally
in the presence of suitable catalysts, ureas and urethanes react with excess isocya-
nate to form biuret and allophanates respectively. Special catalysts are required for
the cyclooligomerization of aromatic and aliphatic isocyanates, and a number of
suitable products are available for industrial use.
3.3 Polyisocyanates
A further argument in favor of converting diisocyanates into polyisocyanates –
apart from the occupational health aspect already mentioned – is the increase in
functionality achieved. The reactions described above make it possible to produce

Polyisocyanates 31
Table 3.4: Cyclopolymerization and polymerization of isocyanates (schematic)

Formation of: Reaction equation
Uretdione [11] O
2 NCO N N
Isocyanurate [12] O
N N
3 NCO
O N O
Iminooxadia- O
zine dione [13]

N N
3 NCO
O O N
Linear polymer O O O O
n NCO N C N C N C N C
(α-Nylon)
Carbodiimide [14] 2 NCO N C N + CO2
Uretonimine [14]
N
3 NCO N N + CO2
polyisocyanates with a functionality greater than two which is necessary for spa-
tial crosslinking. Only then is the crosslinking density in the paint film adequate
to ensure high resistance properties. Otherwise, the characteristic properties of the
base isocyanate are retained in the derivative, e.g. the lightfastness of the aliphat-
ics compared with the tendency to yellow of the aromatics. Polyisocyanates based
on cycloaliphatic diisocyanates yield hard and, in certain circumstances, brittle
coatings which can be flexibilized via the choice of polyol, if necessary. In contrast,
polyisocyanates based on linear diisocyanates such as HDI result in flexible films
which can be adjusted with a wide range of polyols to meet various requirements
in terms of flexibility and hardness. As far as the reactivity is concerned, the same
applies to polyisocyanates as to diisocyanates. It is influenced by steric effects and
by the type of NCO bond – primary, secondary or tertiary.

Derivatization
The reaction principles shown in Figure 3.3 have gained industrial significance in
the derivatization of diisocyanates.
The following product classes are of special interest for coating applications:
• Isocyanate-functional urethanes and prepolymers obtained by reaction with
polyols (e.g. “Desmodur L”, “Desmodur E”)
Figure 3.3: Manufacture of polyisocyanates from monomeric diisocyanates (schematic)

Polyisocyanates 33
• Biurets obtained, for example, by reaction of three diisocyanate molecules with

one water molecule [7, 11] (e.g. “Desmodur N 100”)
• Isocyanurates (e.g. “Desmodur N 3300”), iminooxadiazine diones (e.g. “Desmo
dur XP 2410”) or uretdiones (e.g. “Desmodur N 3400”) obtained by catalytic
trimerization or dimerization of diisocyanates [11, 15]
• Allophanates obtained by reaction with alcohols in the presence of suitable
catalysts [16]
The manufacturing process does not yield these polyisocyanates in the form of
defined compounds – such as pure isocyanurate triisocyanates – but as oligomer
mixtures exhibiting a molecular weight distribution.
This is explained by the fact that not only the monomeric base diisocyanates but
also the polyisocyanates which are forming continue to react, yielding higher
molecular weight structures. In order to prevent the formation of highly crosslinked,
highly polymeric products, only some of the isocyanate groups are reacted and the
unreacted excess of diisocyanate is subsequently removed from the reaction mix-
ture by distillation.
The mean molecular weight and the molecular weight distribution of the oligomeric
polyisocyanate mixtures obtained in this way are directly related to the degree of
conversion of the base monomers. This makes it possible to customize product
properties such as equivalent weight, mean isocyanate functionality and viscosity
within certain ranges.
Whereas a higher degree of conversion, corresponding to an increase in the mean
molecular weight, increases the product viscosity and the isocyanate functionality,
a lower degree of conversion increases the proportion of lower molecular weight
oligomers and thus yields polyisocyanates of particularly low viscosity and reduced
functionality. The reactions used in the manufacture of polyisocyanates can be
steered to produce specific coating properties. In this way, for example, via a high
degree of conversion, corresponding to an increased content of higher molecular
weight polymers, the degree of physical drying (initial drying) of the paint film can
be increased. By contrast, steering the reaction to produce lower molecular weight
polyisocyanates provides the route to environmentally friendly low-solvent and
solvent-free coatings.
Monomer separation
Strict requirements are set for polyisocyanates for coatings in terms of their color-
lessness. To remove the diisocyanate excess which has not reacted, only extremely
mild processes can be used which have no detrimental effect on the color quality
of the product. This is usually done by distillation in thin-film evaporators, a process
which exposes the product to high temperatures for only a brief time.

Table 3.5: Aliphatic coating polyisocyanates (selection)

Type Manufacturers Trade name
HDI biuret Bayer MaterialScience “Desmodur N 100”
Rhodia “Tolonate HDB”
BASF “Basonat HB 100”
HDI trimer Bayer MaterialScience “Desmodur N 3300”
Bayer MaterialScience “Desmodur N 3600”
Rhodia “Tolonate HDT”
BASF “Basonat HI 100”
HDI dimer Bayer MaterialScience “Desmodur N 3400”
IPDI trimer Bayer MaterialScience “Desmodur Z 4470”
Degussa “Vestanat T 1890”
Rhodia “Tolonate IDT 70 B”
BASF “Basonat IT 170 B”
Table 3.6: Aromatic coating polyisocyanates (selection)

Type Manufacturer Trade name
TDI adduct Bayer MaterialScience “Desmodur L”
Sapici “Polurene AD”
Benasedo “Hartben 75”
Synthesia “Synthane P-80”
TDI trimer Bayer MaterialScience “Desmodur IL”
Sapici “Polurene 2391”
Benasedo “Hartben SV 100”
Synthesia “Synthane R-51”
TDI/HDI trimer Bayer MaterialScience “Desmodur HL”
Sapici “Polurene 1K D”
Benasedo “Hartben AM 30”
TDI prepolymer Bayer MaterialScience “Desmodur E 1361”
Sapici “Ucopol M 33”
Benasedo “Hartben MC 35”
MDI prepolymer Bayer MaterialScience “Desmodur E 21”
Baxenden “Trixene SC 782”
Dow “Isonate M 636”

Prepolymers 35
To ensure that handling is not hazardous, the content of volatile monomeric diiso-
cyanates in the polyisocyanates used in coating applications must be reduced to a
residual amount of less than 0.5 % by weight. Even after prolonged storage, this
threshold may not be exceeded. The polyisocyanates and any secondary products
which occur during their manufacture must therefore be stable to splitting back into
the free diisocyanates.
Tables 3.5 and 3.6 list some of the standard commercial polyisocyanates available
for the formulation of coatings.
3.4 Prepolymers
Prepolymers based on aliphatic and aromatic diisocyanates are also of special
significance (Table 3.6). These products are manufactured by reacting diisocya-
nates with long-chain polyols, especially polyether polyols (see Figure 3.4), but
also polyester and polycarbonate diols, with the excess monomeric diisocyanate
removed if necessary.
Prepolymers are primarily used for one-component moisture-curing coatings, as
well as for adhesives. Moreover, they find application in blocked form and also as
silane-terminated prepolymers (STP).
3.5 Blocked polyisocyanates

Blocking
Polyisocyanates can be reacted via their NCO groups with what are referred to as
blocking agents (Figure 3.6, page 38) to yield stable adducts, which when combined
with polyols produce mixtures that are stable at room temperature. The blocking
agent is cleaved at elevated temperatures, thus liberating the NCO group for cross-
linking with the polyol component (Figure 3.5, page 38).
Figure 3.4: Manufacture of polyether-based prepolymers

Figure 3.5: Principle of one-component polyurethane baking coating (schematic)
Figure 3.6: Selection of blocking agents used (HBI)
Blocked polyisocyanates are used as the hardeners in one-component polyure-

thane baking coatings. A selection of standard commercial products is shown in
Table 3.7.
The advantages of blocked polyisocyanates are their ease of handling and the lack
of sensitivity to atmospheric humidity of, for example, the coatings they are used
to formulate. Therefore, aqueous one-component polyurethane coatings with
adequate storage stability can be formulated without difficulty. However, the
advantage of easy handling is procured with the limitation that blocked polyiso-
cyanates can only be used in baking systems.
The type of blocking agent used is of significance in a number of respects. Reactiv-
ity, thermal yellowing and other specific coating properties are significantly affected
by the blocking agent. It is also of relevance in terms of occupational hygiene and
economic aspects.
Blocking with malonic ester or cyclopentanone-2-carboxymethyl ester (CPME)
represents a special case. The use of crosslinkers blocked with malonic ester results
in transesterification (see Figure 3.7, page 38). When working with CPME-blocked
polyisocyanates, the blocking agent is not cleaved but instead incorporated into the
paint film during the crosslinking reaction. Thus, the result is not a polyurethane
structure, but rather an ester amide structure. Crosslinking with amines yields a
polyamide structure [17].

Blocked polyisocyanates 37
Table 3.7: Blocked solventborne polyisocyanates (selection)
Blocking agent Base diisocya- Manufacturer Trade name

nate
Butanone oxime HDI Bayer MaterialScience “Desmodur BL 3175”
Bayer MaterialScience “Desmodur VP LS 2257”
Rhodia “Tolonate D2”
Takeda “Takenate 160 N”
IPDI Bayer MaterialScience “Desmodur BL 4265”
Degussa “Vestanat B 1370”
Takeda “Takenate 140 N”
“Desmodur W” Bayer MaterialScience “Desmodur VP LS 2117”
Dimethylpyrazole HDI Bayer MaterialScience “Desmodur VP LS 2253”
(DMP) Bayer MaterialScience “Desmodur VP LS 2376”
Bayer MaterialScience “Desmodur PL 350”
Baxenden “Trixene BI 7982”
IPDI Bayer MaterialScience “Desmodur PL 340”
Malonic ester HDI / IPDI Bayer MaterialScience “Desmodur BL 3475”
MDI Bayer MaterialScience “Desmotherm 2170”
Diisopropylamine HDI / IPDI Bayer MaterialScience “Desmodur VP LS 2352”
Diisopropylamine/ HDI Bayer MaterialScience “Desmodur BL 3370”
malonic ester
Dimethylpyrazole/ HDI Baxenden “Trixene BI 7992”
malonic ester IPDI Baxenden “Trixene BI 7990”
Diisopropylamine/ IPDI Bayer MaterialScience “Desmodur VP LS 2114”
triazole
ε-Caprolactam HDI Bayer MaterialScience “Desmodur BL 3272”
TDI Bayer MaterialScience “Desmodur BL 1100”
IPDI Bayer MaterialScience “Desmodur VP LS 2078”
Cyclopentanone- HDI Bayer MaterialScience “Desmodur XP 2626”
2-carboxymethyl
ester (CPME)
Isononylphenol TDI Bayer MaterialScience “Desmocap 11”
“Desmocap 12”

Figure 3.7: Blocking and crosslinking reaction with malonic esters and CPME-blocked
polyisocyanates
Cleavage reactions
One-component polyurethane coatings react at different temperatures, depending
on the blocking agent and the polyisocyanate on which they are based. The reactiv-
ity of blocked polyisocyanates with polyols has been studied by dynamic mechan-
ical analysis (DMA) on model systems formulated with various blocking agents
that are readily available on an industrial scale [18] (Table 3.8).
The results obtained confirm the experience that polyisocyanates blocked with ε-
caprolactam are very difficult to crosslink thermally, while by contrast, those
blocked with malonic ester can be crosslinked readily. What is interesting in this
respect is the catalytic effect of DBTL (dibutyl tin dilaurate), which substantially
reduces the initial crosslinking temperature. DBTL has been shown to be a less
suitable catalyst only in the case of malonic ester, which has been attributed to the
different crosslinking mechanism (see Figure 3.7). In this special case, the use of
a titanium compound has proven beneficial [19]. In the case of the CPME-blocked
system, a drop in the crosslinking temperature can be achieved through the use of
a zinc catalyst (e.g. zinc neodecanoate).

Using thermogravimetric analysis (TGA) on model systems, the effect of the polyol
on the deblocking temperature has been found to be quite significant (Table 3.9).
Whereas DMA measures the curing (crosslinking) of the one-component polyure-
thane system, TGA records the release of the blocking agent by weighing. The
deblocking process can be tracked and the deblocking temperature determined. The
underlying chemical procedure is identical in both cases, but different parameters
are measured.
Comparison of Tables 3.8 and 3.9 shows that the crosslinking temperatures measured
by DMA for the non-catalyzed system are of the same magnitude as the deblocking
temperatures measured by TGA (Table 3.9, left-hand column) for the analogous
one-component polyurethane system. In contrast, the deblocking temperatures of
Table 3.8: Effect of DBTL catalyst on the initial crosslinking temperature when using
various blocking agents (DMA method)
Blocking agent Initial crosslinking temperatures [°C]
with 1% DBTL, based without DBTL
on the solid resin catalysis
ε-Caprolactam 163 175
Diethylamine 144 173
Cyclopentanone-2-carboxymethyl 140* 160
ester (CPME)
Butanone oxime 137 156
3,5-Dimethylpyrazole 112 158
Diisopropylamine 115 136
BEBA 100 –
Imidazole 98 123
Diethyl malonate – 104
* Zinc neodecanoate catalyst, 0.5 % by wt. based on the solid resin
Table 3.9: “Polyol effect” on the initial deblocking temperature when using various block-
ing agents (TGA method)
Blocking agent Initial deblocking temperatures [°C]
with polyol without polyol
ε-Caprolactam 177 234
Butanone oxime 157 220
3,5-Dimethylpyrazole 167 220
Diisopropylamine 140 220

the pure blocked polyisocyanates, i.e. in the absence of polyol coreactants, are
unexpectedly high. They are in the range of the cleavage temperature of aliphatic
urethanes, which is approximately 240 °C.
Blocked polyisocyanates per se are relatively heat-stable compounds. Only in the
presence of a coreactant are feasible crosslinking temperatures achieved, which can
be lowered further by catalysis.
Reactivity
The reactivity sequence for the blocking agents revealed by DMA and TGA mea-
surements has been confirmed in systems other than the model system used. The
only difference is smaller fluctuations in the crosslinking temperatures when using
other aliphatic polyisocyanates or polyols. Corresponding data for blocked aromatic
polyisocyanates are not yet available. However, in the light of past experience, it
is expected that their initial crosslinking temperatures will be around 10 °C lower.
A better understanding of the curing process in one-component polyurethane coat-
ings can be obtained by measuring the curing state as a function of baking time and
temperature. The relevant parameters for assessing the paint films are the glass
transition temperature (Tg) and the residual blocking agent content.
Table 3.10 shows the analysis of three one-component clearcoat systems in which dif-
ferent blocking agents were used and a two-component polyurethane reference system.
Of the many measured values [18], only two curing states are shown since these are
sufficiently representative. In terms of the blocking agent, 3,5-dimethylpyrazole is
the most reactive. At baking conditions of 30 minutes at 140 °C, a higher Tg is attained
and the content of still unreacted blocked NCO groups, i.e. the residual 3,5-dimeth-
ylpyrazole content, is correspondingly lower. At the same time, however, the cross-
linking process is not yet complete under these baking conditions and a relatively
large amount of blocking agent remains in the paint film in bound form.
Table 3.10: Curing states of one-component polyurethane coatings as a function of the baking
time, characterized by Tg of the paint film and residual blocking agent in the paint film
Baking temperature 140 °C
Baking time 30 min Baking time 60 min
Blocking agent Tg [°C] Residual blocking Tg [°C] Residual blocking
agent content [%] agent content [%]
3,5-Dimethylpyrazole 73 14 80 5
Butanone oxime 68 27 77 12
For comparison: 80 – 80 –
Corresponding two-
component polyure-
thane coating

Yellowing
When used in one-component coatings, blocked polyisocyanates can result in sig-
nificant thermal yellowing, especially under overbaking conditions (see Table 3.11).
The blocking agent is mainly responsible for this. Thermal yellowing is determined
colorimetrically using the CieLab method. The one-component polyurethane
clearcoats with various blocking agents are applied on top of a white basecoat. After
baking for 30 minutes at 140 °C, the colorimeter displays the yellowing on the
individual test panels as the b value. The higher this value is, the yellower the coat-
ing appears. The baked paint films are then overbaked for 30 minutes at 160 °C and
measured again.
In Table 3.11, the difference between the two yellowing values, i.e. the overbake
yellowing Δb, is assessed. Values less than 1 are acceptable whereas those greater
than 1 are generally not. In systems blocked with malonic ester, for example, Δb
values up to 20 are observed.
Of the blocking agents shown in the table, only 3,5-dimethylpyrazole and BEBA
are so resistant to thermal yellowing (Table 3.11) that they pass the overbaking test
required by the automotive industry.
Generally speaking, the thermal yellowing of blocked polyisocyanates can be
mitigated and reduced to an acceptable level by the addition of stabilizers such as
hydrazide or HALS compounds (hindered amine light stabilizers; manufactured by
Ciba Specialty Chemicals) [20].
Suitability characteristics
Normally, different blocking agents should not affect the film properties yielded
by a one-component polyurethane coating, provided that the blocking agent is
completely cleaved and evaporates. In practice, however, the properties are not only
determined by the polyisocyanate and polyol, but also by the blocking agent.
Table 3.11: Thermal yellowing as a function of the blocking agent used
Blocking agent b
Butanone oxime 1 to 3
BEBA 0.8 to 1
Imidazole 2 to 5
Diethyl malonate 10 to 20
3,5-Dimethylpyrazole 0.6 to 1
Cyclopentanone-2-carboxymethyl ester 0.8 to 1.2
Diisopropylamine approx. 21*
*A diisopropylamine-blocked isocyanate undergoes substantially less yellowing under coil coating baking condi-
tions, with a ∆b of approx. 0.5. In this case, it would seem that the proportion of blocking agent remaining in the
film is lower as a result of the higher baking temperature

The residual blocking agent that remains in the paint film at a certain baking tem-
perature (Table 3.10) has a detrimental effect on the film quality. A comparative test
of one- and two-component polyurethane OEM clearcoats shows that one-compo-
nent polyurethane baking coatings have lower etch resistance, for example.
Malonic ester blocking agents are again the exception [21, 22]. Here, crosslinking is
not initiated by cleavage of the blocking agent but by transesterification with the
polyol with cleavage of the alcohol (see Figure 3.7). This reaction yields ester
groups instead of urethane groups. The cured paint film is therefore softer and less
resistant to solvents. These disadvantages can be overcome by selecting suitable
polyols and polyisocyanates.
Occupational hygiene
Within the context of the German Ordinance on Hazardous Substances, all of the
above-named blocking agents have some degree of hazard potential. Diethyl mal-
onate is the least hazardous and is approved for food-contact applications, for
example, in seals for crown corks.
Butanone oxime, 1,2,4-triazole, 3,5-dimethylpyrazole and diisopropylamine require
labeling as sensitizing, irritating or corrosive. For this reason, blocked polyisocya-
nates should be manufactured in such a way as to minimize the content of free,
excess blocking agent. It is not difficult to control the manufacturing processes to
ensure that the content of free blocking agent is less than 1 %.
Systems blocked with cyclopentanone-2-carboxymethyl ester have the great advan-
tage that the blocking agent is incorporated into the coating. For this reason, the
blocking agent does not feature in the product label.
During the baking process, the blocking agents split off and enter the waste air.
They should be treated in the same way as solvent vapors (VOC) to render them
harmless, for example, by incineration.
Cost-effectiveness
ε-Caprolactam, butanone oxime and diisopropylamine are products manufactured
on bulk scale, and are thus inexpensive. In contrast, diethyl malonate, 1,2,4-triazole,
3,5-dimethylpyrazole [23] and BEBA are relatively expensive, although they are
easily accessible on a large scale. The cost-effectiveness of diethyl malonate is not
only reduced by the relatively high purchase price but also by the large amounts
required because of its molecular mass.
Bearing in mind these factors, one-component polyurethane baking coatings can
be customized to meet a wide range of end-user requirements. Compared with
two-component polyurethane technology, the main advantage of one-component
systems is their ease of handling. However, this is frequently offset by reduced film

Hydrophilically modified polyisocyanates 43
quality. In other words, although blocking makes handling easier, it in no way

enhances the quality of the paint film. It should therefore be decided on a case-by-
case basis whether two-component polyurethane systems would be better for rea-
sons of quality or whether one-component polyurethane coatings should be pre-
ferred because of technical considerations (application equipment).
3.6 Hydrophilically modified polyisocyanates

Aqueous two-component polyurethane systems already represent a low-VOC alter-
native to conventional solventborne coatings in a large number of application areas.
In these two-phase systems, the use of a suitable aqueous polyol dispersion and, in
particular, the choice of polyisocyanate crosslinker are critically important to the
quality of the resulting paint film.
Basically, there are two options for crosslinking aqueous polymer dispersions [24]:
• The use of hydrophobic, preferably low-viscosity polyisocyanates, such as those
also used in conventional two-component polyurethane coatings
• The use of hydrophilically modified, self-emulsifying polyisocyanates specially
developed for this purpose
Whereas low-viscosity hydrophobic polyisocyanates can only be incorporated into
aqueous dispersions with the concomitant use of suitable organic cosolvents and
high shear (e.g. using stirring or dispersion apparatus), the use of hydrophilically
modified polyisocyanates enables the production of a homogeneous and cosolvent-
free mixture of binder and crosslinker by simple manual stirring.
Various approaches have been used in the manufacture of hydrophilic polyisocya-
nates. In addition to the use of external emulsifiers [25, 26], which exhibit various
disadvantages, the partial reaction of hydrophobic polyisocyanates with hydrophilic
coreactants has proven especially effective. Highly active emulsifier molecules are
produced in situ in the polyisocyanate mixture. In this way, coatings can be manu-
factured that meet the highest quality requirements.
The simple reaction of aliphatic or cycloaliphatic polyisocyanates, such as HDI or
IPDI trimers, with a shortfall of monofunctional polyethylene oxide polyether alco-
hols [27, 28] leads to, for example, polyisocyanate mixtures containing nonionic emul-
sifiers of the polyether urethane type (see Figure 3.9, structure [a]). In this way,
hydrophilically modified polyisocyanates can be easily emulsified in water by hand,
without the application of high shear forces. Water-emulsifiable polyisocyanates
of this type (e.g. “Bayhydur 3100”, “Bayhydur 401-70”) are today established as
the standard crosslinkers for most aqueous coating and adhesive applications.

The chemical hydrophilic modification of polyisocyanates via urethanization with

polyether alcohols always leads, however, to a reduction in the average isocyanate
functionality and thus yields paint films with lower crosslinking density, which
usually becomes apparent through lower chemical resistance [24].
This effect spurred the development of improved polyether-modified polyisocya-
nates in which the hydrophilic polyether chains are each linked with two polyiso-
cyanate molecules (see Figure 3.9, emulsifier structure [b]) by means of allophana-
tization [29]. In the case of these second-generation, nonionic, hydrophilically mod-
ified polyisocyanates, the polyether modification increases rather than reduces the
isocyanate functionality. As a smaller amount of polyether alcohol also suffices to
achieve a defined dispersibility of these products, hydrophilic polyisocyanates con-
taining a polyether allophanate emulsifier (e.g. “Bayhydur 304”, “Bayhydur 305”)
yield paint films with much better water and chemical resistance than those pro-
duced with the standard crosslinkers described above.
Despite their broad market acceptance for many applications, all polyether-modi-
fied polyisocyanates have a fundamental disadvantage. Especially when used as
the crosslinkers in aqueous two-component polyurethane coatings, a high polyether
content is required to ensure satisfactory dispersibility, which results in a relatively
long drying time and gives the coatings permanent hydrophilicity. The latter is the
reason why polyether-modified polyisocyanates have not been accepted for appli-
cations requiring the highest levels of resistance, for example in automotive base
coats or for anti-graffiti coatings. These disadvantages were finally overcome with
the development of special, ionically modified polyisocyanates.
Aliphatic polyisocyanates react with 3-(cyclohexylamino)-1-propanesulfonic acid
(CAPS) (Figure 3.8), a zwitterionic aminosulfonic acid, in the presence of tertiary
neutralizing amines under mild conditions [30]. The sulfonate urea derivatives that
are produced are excellent emulsifiers (see Figure 3.9, structure [c]).
Irrespective of the salt groups, CAPS-modified polyisocyanates have good storage
stability, are free from turbidity and yield a highly dispersed emulsion in water,
even with a relatively low sulfonate group content. A range of ionically modified
polyisocyanates is now available (e.g. “Bayhydur XP 2487/1,” “Bayhydur XP 2547,”
“Bayhydur XP 2570”, “Bayhydur XP 2655”) and can be used in the formulation of
environmentally friendly, aqueous two-component polyurethane coatings of high
quality for a broad spectrum of applications. These coatings are every bit as good
as conventional, solventborne systems in terms of
drying, curing and chemical resistance [31–33]. Due
to new legislation mandating further reductions in
VOCs (volatile organic compounds), these cross-
linkers will see increased usage in the future, since
Figure 3.8: 3-(Cyclohexyl- they result in no reduction in quality compared to the
amino)-1-propanesulfonic acid solventborne systems.

Coreactants 45
Figure 3.9: Hydrophilically modified HDI polyisocyanurates – emulsifier structures

(idealized)
3.7 Coreactants
The properties of polyurethane coatings are not only affected by the polyisocyanate,
but also in large measure by the hydroxyfunctional coreactant, the polyol. Selecting
suitable polyols and polyisocyanates makes it possible to control key characteristics
of the coating and the resulting paint film. Solids content, drying, gloss, elasticity
and hardness, resistance to chemicals and hydrolysis, and cost-effectiveness are
just some examples in this respect. Research in the past has therefore concentrated
greatly on the development of new and improved resins.

The most important coreactants for polyisocyanates currently are hydroxyl-bearing

polymers such as polyacrylate, polyester and polyether polyols. Of lesser impor-
tance are polycarbonate, polycaprolactone and polyurethane polyols. Products
containing amino groups have much higher reactivity with isocyanates, and thus
are used only in special applications or when blocked. The following paragraphs
describe the principal routes for synthesizing important coreactants for polyiso-
cyanates. Their special significance in individual applications will be addressed
in later chapters.
3.7.1 Polyacrylate polyols

The term polyacrylate polyols covers copolymers of acrylic and/or methacrylic acid
esters – ethyl acrylate, butyl acrylate and methyl methacrylate – which also bear
hydroxyl groups. In practice, other comonomers are frequently used together with
these, e.g. styrene, vinyl ester or maleates. The hydroxyl groups needed for reaction
with isocyanate groups are usually introduced directly via functionalized esters of
acrylic and methacrylic acid, e.g. hydroxyethyl acrylate, hydroxyethyl methacrylate
or hydroxypropyl methacrylate (Figure 3.10). Another way of generating hydroxyl
groups is by polymer-analog reactions on finished polyacrylates [34].
Manufacture
The industrial manufacture of polyacrylate polyols is performed by thermally ini-
tiated radical polymerization of the monomers in organic solvents or in substance
[35–37]
. There are two ways of manufacturing aqueous products. They can be pro-
duced as primary dispersions by emulsion or suspension polymerization directly
in water [38-42]. Alternatively, they are first produced in organic solution and then
dispersed in water to yield secondary dispersions [43-45].
The initiators used in radical polymerization in solution or substance and in suspen-
sion polymerization are azo compounds such as azobisisobutyronitrile or peroxides
such as t-butyl peroxy-2-ethyl hexanoate. In the case of emulsion polymerization,
water-soluble initiators such as ammonium peroxodisulfate are used.
Properties
The properties of polyacrylate polyols
and the polyurethane coatings in which
they are used are largely governed by the
choice of monomer, the hydroxyl content,
the molecular weight and the glass transi-
tion temperature (Tg) [46]. The molecular
Figure 3.10: Structure of a polyacrylate weight of the polyacrylate can be influ-
polyol enced significantly by the polymerization

Coreactants 47
temperature, the type and amount of initiator used and the addition of molecular
weight controllers such as mercaptans [47]. The Tg can be set via the selection of
hardening and softening monomers [46] and the hydroxyl content by the amount of
hydroxy monomer used.
Applications
Polyacrylate polyols occupy a significant position in polyurethane coatings technol-
ogy. As a result of the ongoing development of these products, the market now
offers a broad range of resins for use in a wide variety of applications, as shown by
the following examples:
• Wood/furniture coating with the need for fast drying
• Automotive refinishing with its special requirements in terms of quality and
cost-effectiveness
• Automotive OEM finishing with the requirement for long-term resistance prop-
erties such as gloss retention
• Plastic coatings requiring high flexibility and good chemical resistance
• Corrosion protection expecting good long-term resistance properties in the
topcoats
3.7.2 Polyester polyols

Polyester polyols are produced by the polycondensation of di- and polycarboxylic
acids with an excess of polyfunctional alcohols (polyols) (see Figure 3.11). The
most important polycarboxylic acids and their anhydrides which are available on
an industrial scale for the manufacture of polyester polyols include the aromatic
acids phthalic acid and isophthalic acid, the aliphatic acids adipic acid and maleic
acid, and the cycloaliphatic acids such as tetrahydrophthalic acid and hexahydro
phthalic acid.
The polyols used are aliphatic alcohols such as ethane diol, 1,2-propanediol, 1,6-
hexanediol, neopentyl glycol, glycerol and trimethylolpropane, and cycloaliphatic
alcohols such as 1,4-cyclohexanedimethanol. In addition, monofunctional alcohols
or carboxylic acids such as 2-ethyl hexanol or 2-ethyl hexanoic acid can be used
as chain terminators.
Figure 3.11: Structure of a linear polyester polyol based on 1,6-hexanediol/adipic acid

Reaction process
As already mentioned, polyester polyols are produced by a condensation reaction
of polycarboxylic acids with polyols, splitting off water. There are two processes
which are used in particular. The first is the melt condensation process in which the
coreactants are reacted in the melt at temperatures of approximately 160 to 260 °C.
The reaction is performed either in a vacuum or in a stream of inert gas to remove
the water. The second process is azeotropic esterification performed in an organic
solvent which acts as the carrier to remove the reaction water.
The condensation reaction can be accelerated by increasing the reaction tempera-
ture and the amount of inert gas used, by reducing the pressure and/or by the addi-
tion of catalysts, which is particularly advantageous towards the end of the esteri-
fication process. Suitable catalysts include bases such as lithium hydroxide or tin
compounds such as di-n-butyl tin oxide. As a binder for coatings, the polyester
polyol is used either solvent-free as a viscous resin or it is dissolved in a solvent.
It may also be used in solid form or as a dispersion in water [48].
Formulation
Aqueous supply forms require the availability of sufficiently hydrophilic centers
in the polymer. These may be neutralized acid groups which are introduced prefer-
ably after the condensation reaction by reacting the polyester polyol with dicarbox-
ylic acid anhydrides, e.g. tetrahydrophthalic acid anhydride, and opening the anhy-
dride ring. However, this often yields a polyester that is susceptible to saponification
[49]
. To produce resins that are resistant to saponification, the carboxyl group is
introduced via dimethylol propionic acid with the aid of diisocyanates such as
isophorone diisocyanate [50].
Properties and applications
The properties of polyester polyols and of the polyurethane coatings in which they
are used are determined by the choice of raw materials, the molecular weight, the
Tg and the functionality [51]. Generally speaking, saturated polyester polyols have
good pigmentability and yield coatings with good weather stability and high gloss.
This makes them suitable for a broad range of applications from vehicle finishing
(including aircraft) to general industrial coatings (machinery). However, only the
non-aromatic products yield good UV stability, since aromatic polyesters tend to
Figure 3.12: Manufacture of a polyether polyol based on 1,2-propanediol

Coreactants 49
yellow on exposure to light. Unsaturated aliphatic/cycloaliphatic polyesters based

on maleic acid anhydride represent a special case. Despite the double bond, they
have particularly high UV stability [52].
3.7.3 Polyether polyols
Polyether polyols are formed by the addition of ethylene oxide and/or propylene
oxide to polyfunctional starter molecules (Figure 3.12). As a rule, polyvalent alco-
hols such as ethylene glycol, 1,2-propanediol, glycerol and trimethylolpropane, or
amines such as ethylenediamine (which yields tetrafunctional polyether alcohols)
are used as the starter molecules. The addition of the alkene oxide is usually per-
formed in an alkaline medium with sodium hydroxide as the base. Key properties
of the polyether such as the melting point, viscosity, hydrophilicity and compatibil-
ity can be controlled via the ratio of the ethylene oxide to propylene oxide.
Due to their low viscosity, polyether polyols are used mainly in solvent-free coat-
ing systems. However, because of the poor weather stability of polyethers – a
consequence of oxidative polyether chain degradation – their use is restricted to
interior applications or to the formulation of primers. On the other hand, these
systems are characterized by particularly good resistance to hydrolysis and mechan-
ical stability. For these reasons, they are often used in the construction sector for
coatings on mineral substrates such as concrete.
3.7.4 Polycarbonate polyols
Strictly speaking, polycarbonate polyols are esterification products formed by the
reaction of carbonic acid with polyols. In practice, the carbonate structure is intro-
duced using phosgene or carbonic acid diesters [53]. Because of their poor solubility,
aromatic polycarbonates based on bisphenol A are not used in coating applications.
In contrast, linear aliphatic polycarbonates [54] are used both as binders in high-qual-
ity polyurethane coatings and in the production of polyurethane binders, especially
polyurethane dispersions [55]. Aliphatic polycarbonate polyols are characterized by
their low viscosity, and the resulting coatings by good weather stability and very
good resistance to hydrolysis.
3.7.5 Polycaprolactone polyols
Polycaprolactone polyols are produced by the ring-opening polymerization of
ε-caprolactone. Suitable starter molecules are polyfunctional alcohols such as ethyl-
ene glycol,1,2-propanediol, glycerol and trimethylolpropane [56–58]. The ring-opening
polymerization takes place at temperatures of approximately 120 to 200 °C and can
be accelerated by the addition of catalysts such as organometallic compounds. The
process yields low viscosity products with defined functionality. These are used
either as sole binders or as reactive thinners in solvent-free or high solid two-com-
ponent polyurethane coatings.

Polycaprolactone polyols are also used as polyol building blocks in the manufacture
of high molecular weight polyurethanes. A further use of the ring-opening polymeriza-
tion of ε-caprolactone is in the modification of higher molecular weight polyols, e.g.
polyacrylate polyols [59]. The technical advantages of polycaprolactone polyols include
their flexibility and weather stability, in addition to their low viscosity. The main
applications for these materials are in two-component polyurethane coatings for plas-
tics (automotive sector) and in solvent-free coatings for construction applications.
3.7.6 Polyurethane polyols
Polyurethane polyols are produced using the diisocyanate polyaddition process [60–62]
in which diisocyanates are reacted with an excess of diols and/or polyols. On account
of their high viscosity, these products are as yet of little importance in the field of
solventborne coating systems. By contrast, hydroxyfunctional aqueous polyurethane
dispersions are used successfully in one-component and two-component systems for
wood and plastic coatings, e.g. for producing soft-feel effects, and for glass coatings.
3.7.7 Polyamines
Unblocked amino groups have very high reactivity with isocyanate groups. Polyurea
coatings can therefore only be applied using two-component application equipment
developed for this purpose. At the present time, polyether amines are normally used
in combination with aromatic isocyanate prepolymers. Aliphatic prepolymers have
only played a subordinate role up to now. The main applications are coatings for
concrete or systems for heavy-duty corrosion protection [63, 64].
The reactivity can be lowered by significantly reducing the reactivity of one of the
coreactants, e.g. by blocking. One example of this is the reaction of TDI prepoly-
mers (e.g. “Desmocap”) with aromatic amines. Such combinations are frequently
used to flexibilize epoxy/amine systems [65, 66].
Blocking reactions
Low molecular weight blocked diamines have become particularly significant as
reactive thinners for high solid polyurethane coatings, e.g. for automotive refinish-
ing. The most important blocking reactions for amines are those with aldehydes to
form aldimines [67, 68] and with ketones to form ketimines [67, 69–71] (see Figure 3.13).
On contact with water, e.g. atmospheric humidity, the blocking reaction is reversed
to produce the starting amines, which are then available to react with isocyanate
groups [71, 72]. Even in the absence of water, crosslinking can be achieved – espe-
cially under the influence of heat. In this case, cyclic ureas are formed by dispro-
portionation [74].
Reacting amino alcohols with aldehydes or ketones (Figure 3.14) splits off water
and yields 1,3-oxazolanes (oxazolidines), another class of blocked amines [73, 76].
These can reacted with diisocyanates via available hydroxyl groups to form bifunc-
tional blocked amines (bisoxazolidines).

Coreactants 51
Polyaspartics
Polyaspartic esters are special polyamines with secondary amino groups. These can
be produced either by the addition of primary aliphatic diamines to maleic or
fumaric acid di(cyclo)alkyl esters [77, 78] (Figure 3.15), or by the addition of primary
aliphatic amines to unsaturated oligoesters or polyesters [78, 79].
Polyaspartic esters based on diethyl maleate and cycloaliphatic diamines are sol-
vent-free, low viscosity substances with secondary amino groups, whose reactivity
is reduced by electronic and steric effects to such an extent that they can be used
to formulate highly reactive two-component polyurethane coatings with an ade-
quate pot life.
This specifically adjustable reactivity enables the formulations of fast-drying coat-
ings for highly productive, modern coating concepts. These systems are of par-
ticular interest for use in automotive refinish, large vehicle and industrial coatings,
corrosion protection and construction. The polyaspartics are used as the main binder
or as reactive thinners [81– 83].
R = (cyclo)alkylene, R‘ = (cyclo)alkyl, R” = (cyclo)alkyl, H

Figure 3.13: Aldimine and ketimine formation as blocking reactions for amines
R = (cyclo)alkyl
Figure 3.14: Formation of 1,3-oxazolanes
R = (cyclo)alkyl, R’ = (cyclo)alkylene
Figure 3.15: Manufacture of diaspartic acid esters

3.8 Aqueous dispersions
3.8.1 Polyurethane dispersions

The application viscosity of solutions of polyurethanes or polyurethane ureas in
organic solvents required for technical reasons imposes a restriction in terms of the
molecular weight. By contrast, polyurethane/urea dispersions can be produced in
the heterogeneous phase with almost any desired molecular weight without sig-
nificantly affecting the viscosity of the dispersion. The degree of crosslinking can
also be increased appreciably in the heterogeneous phase [84].
Composition
The two-phase systems with the greatest industrial significance are aqueous disper-
sions in which water forms the continuous phase. In this dispersion state, the
thermodynamics of which are inherently unfavorable, special auxiliaries and addi-
tives (emulsifiers) can be used to stabilize the hydrophobic macromolecules. In
this respect, a distinction is made between external and internal emulsifiers that
can be further categorized as anionic, cationic or nonionic emulsifiers, depending
on their charge.
Among the external emulsifiers used in polyurethane chemistry are high molecular
weight polyvinylpyrrolidones or alkylphenol-initiated ethylene oxide polyethers.
These are added in concentrations varying from 0.5 to 5 % [85]. However, internal
emulsifiers provide far more application variability and enhanced product proper-
ties. They are incorporated into the polymer backbone and anchored there via
covalent bonds. Polyethers with a high ethylene oxide content are used as nonionic
hydrophilic building blocks which are incorporated into the polymer backbone
[84, 86]
. Hydroxyfunctional polyvinylpyrrolidones are also available as nonionic
hydrophilic building blocks [87].
In polyurethane dispersions with anionic modification, the polymer can be

hydrophilically modified by incorporating carboxylate or sulfonate groups.
These functional groups are introduced into the polymer backbone via building
blocks with OH or NH functionality which contain the necessary acid groups.
The products are then neutralized with alkalis such as trialkyl amines or alkali
hydroxides. An ionic group content of less than 1 % is sufficient for the production
of stable aqueous dispersions [88]. The incorporation of tertiary amino groups,
for example from aminoalcohols, yields polyurethane dispersions with internal
cationic hydrophilic modification after protonation with acid or quaternization
with an alkylating agent [89, 90]. The building blocks of polyurethane dispersions
can be selected such that the films obtained are biodegradable under composting
conditions [91].

Aqueous dispersions 53
Stabilization
The stability of polyurethane dispersions is affected by a large number of factors,
both internal and external [86, 92–94]. The attracting van der Waals forces between the
particles in the dispersion are counteracted by various repelling interactions. One
of these is the electrostatic repulsion of the charged particles which is the dominant
effect in ionically stabilized polyurethane dispersions. By contrast, the stability of
nonionically stabilized polyurethane dispersions can be explained by an entropy
effect. The conformation freedom of the polyether chains that penetrate the aqueous
phase is limited by the approach of particles, which constitutes inadequate stability.
This is thermodynamically unfavorable and leads to the particles being repelled.
Moreover, the polyether chains themselves interact as they approach each other.
These interactions are less favorable than the interactions with the dispersion
medium (water) and thus the approach of the particles is prevented.
Ionically stabilized polyurethane dispersions are more vulnerable to the addition
of salts or to changes in the pH value and easily lose their stability when they freeze
or are exposed to high shear forces. By contrast, nonionically stabilized aqueous
dispersions are more sensitive to high temperatures. The best stabilization is
achieved by a combination of both mechanisms – ionic and nonionic – in the same
polymer chain [86, 94].
Manufacturing process
There are many processes which can be used to manufacture high molecular weight
polyurethane dispersions, with hydroxyfunctionality if required. The basic general
principle for achieving high molecular weights is the chain extension of NCO-
functional prepolymers with (blocked) polyamines, water or aminoalcohols. Since
the high molecular weights are only achieved after dispersion, prepolymers with
relatively low molecular weights can be produced – this confers significant advan-
tages for their manufacture.
In the emulsifier/shear force process, external emulsifiers and high shear forces are
used to produce emulsions or dispersions of low molecular weight NCO-functional
prepolymers [95, 96]. Chain extension with the dispersion medium (water) combined
with condensation or the addition of diamines allows the production of higher
molecular weight polyurethane ureas with good stability.
In the melt dispersion process (Figure 3.16, page 54), sufficiently low viscosity,
ionic and/or nonionic hydrophilically modified NCO prepolymers are placed in an
aqueous dispersion. The amine component used as the chain extender can either be
added to the dispersion water or to the prepolymer dispersion following the disper-
sion stage. By contrast, in the ketimine/ketazine process, the blocked diamine

Figure 3.16: Manufacture of a polyurethane dispersion by the melt dispersion process
(ketimine) or hydrazine (ketazine) is mixed homogeneously with the NCO prepoly-

mer. After conversion to the aqueous phase, the diamine or hydrazine is released
by hydrolysis and reacts spontaneously with the NCO prepolymer to produce chain
extension. Like the prepolymer/ionomer process, this process theoretically also
allows the manufacture of crosslinked dispersions.
The acetone process is a universal technology for the production of polyurethane
dispersions [97]. In this process, ionically modified prepolymers in acetone solution
are reacted with diamines or polyamines to produce high molecular weight polyure-
thane urea ionomers that are then converted to the aqueous phase. In an alternative
process, the ionic modification of the NCO-functional prepolymers takes place during
chain extension. After removing the acetone by distillation, a fine dispersion contain-
ing no cosolvent is obtained. In addition, there are mixed versions of the processes
described in which the respective advantages can be used in combination.
Current developments make possible the production of high solid dispersions, in
which, for example, the solids content can be increased from 40 to 60 % while
retaining comparable properties. In addition to advantages in logistics and storage,
higher machine utilization and lower energy costs can be achieved by using disper-
sions of this type [98, 99].

Aqueous dispersions 55
Properties and structure

The typical mean particle size of an aqueous polyurethane dispersion is between
10 and 500 nm. Compared with other dispersions, the particle size distribution is
relatively broad. With increasing hydrophilicity, the particle size decreases, the
viscosity increases and the dispersion becomes more stable. The mean particle size
also depends on the molecular weight of the polyurethane. Chain extension after
dispersion makes it possible to manufacture polyurethane dispersions with a higher
solids content and a molecular weight that is sufficient for forming films by phys-
ical drying alone, with an excellent property profile for many applications.
Polyurethane dispersions are being used increasingly in aqueous coating and adhe-
sive systems. Among the characteristic properties of these dispersions is the vari-
ability of the properties yielded by coatings, e.g. high film elasticity and hardness
achieved at low curing temperatures. These features can be achieved because it is
possible to produce defined hard and soft segments in the polymer. As a result of this
specifically induced incompatibility of the segments, hard and soft domains are pro-
duced during film formation. The hydrophilic chain segments result in swelling and
plasticization of the particles by water. This lowers the film-forming temperature [94].
Combination of polyurethane dispersions with other types of dispersions provides
further options for customizing the property profile [100 –103]. Such mixed dispersions
include simple blends, but also dispersions with covalently bonded polyacrylate-
polyurethane molecules. These result, for example, by incorporating unsaturated
polyurethanes – referred to as macromonomers – into the polyacrylate backbone.
3.8.2 Polyacrylate dispersions
Hydroxyfunctional polyacrylate dispersions represent an important class of com-
pounds in the formulation of aqueous polyurethane coatings. Polyacrylate disper-
sions are differentiated into primary and secondary dispersions. Primary dispersions
[104, 105]
are produced directly in water via emulsion polymerization of acrylate mono-
mers with the use of emulsifiers. They are characterized by high molecular weights
and are usually solvent-free.
Secondary dispersions [106 –108] on the other hand are prepared via polymerization
of the corresponding monomers in a suitable solvent. Following this step, a neu-
tralizing amine and water are added to this organic solution, whereby a phase
reversal takes place with the formation of a dispersion (Figure 3.17, page 58).
Secondary dispersions are characterized by moderate molecular weights and can
contain up to 10 % cosolvent.
Polyacrylate secondary dispersions can be used to formulate aqueous two-com-
ponent polyurethane coating systems [109, 110] that yield high-quality paint films. In
particular, properties such as gloss, chemical resistance and mechanical strength
are at levels comparable to films yielded by solventborne two-component poly-
urethane coatings.

Figure 3.17: Results for synthesizing polyacrylate dispersions
Figure 3.18: Basic structures of urethane acrylates
Figure 3.19: Structure-property relationships in urethane acrylates [112, 113]

Urethane acrylates 57
3.9 Urethane acrylates

Introduction
Urethane acrylates are used in radiation-curing coatings for industrial applications.
The development goal in the area of urethane acrylates is to combine the high
performance and many possible applications of polyurethane coating systems with
the curing rate and efficiency of photopolymerization. Urethane acrylates are
available as solutions in reactive thinners (low viscosity (meth)acrylate esters), as
low viscosity oligomers, as solids for powder coating technologies or as urethane
acrylate dispersions. Isocyanato-urethane acrylates are a special group used in dual
cure technology.
Chemistry of urethane acrylates
Urethane acrylates are manufactured by the addition of hydroxyalkyl acrylates,
diisocyanates and polyols, or by the direct addition of hydroxyalkyl acrylates to
polyisocyanates [111]. A new alternative that yields especially low viscosity products
consists of the polyaddition of low molecular weight polyester acrylates produced
via azeotropic transesterification with diisocyanates. The idealized basic structures
are shown in Figure 3.18.
The factors that can be varied to adjust the coating raw material properties, the UV
reactivity of the resulting coating and the properties of the cured paint film are:
• The chemical nature of the di- and polyisocyanates
• The chemical nature of the residual polyol
• Double bond functionality
• Double bond density
• Molecular weight
The basic structure-property relationships are summarized in Figure 3.19.
While these parameters cannot be varied wholly independently of each other, the
structure of the resin can be optimized over a broad range to yield the desired end
properties of the coatings. This makes urethane acrylates one of the most versatile
and useful binder classes in the area of radiation curing, and is resulting in signifi-
cant growth.
References
[1] C. Six, F. Richter, Ullmann’s Encyclopedia of Industrial Chemistry, Chapter 4, DOI:
10.1002/14356007.a14_611 by Wiley-VCH, Organic Isocyanates, 2002
[2] EP 289 840 (1987) Bayer AG
[3] DE 4 231 417 (1992) Hüls AG, DE 4 413 580 (1994) Bayer AG, WO 97/17 323 (1995)
BASF AG

[4] W. Wieczorrek in: Lackharze, D. Stoye, W. Freitag (Hrsg.), Carl Hanser Verlag,
München, Wien 1996, 183 ff.
[5] R. Saxon, R. W. Dexter, G. C. Hewitt, Cellular Polymers 4 (1985) 117
[6] EP 749 958 (1995) Bayer AG
[7] DE 1 101 394 (1958) Bayer AG
[8] EP 379 914 (1989) Bayer AG
[9] H. J. Laas, R. Halpaap, J. Pedain, Farbe und Lack, 100 (1994) 330
[10] R. Lomölder, F. Plogmann, P. Speier, Journal of Coatings Technology, 69 (1997) 51–57
[11] H. J. Laas, R. Halpaap, J. Pedain, J. prakt. Chem. 336 (1994) 185
[12] EP 10589 (1978) Bayer AG
[13] DE 196 11 849 (1996) Bayer AG
[14] K. Wagner, K. Findeisen, W. Schäfer, W. Dietrich, Angew. Chem. 93 (1981) 855
[15] H. Mundstock, R. Pires, F. Richter, J. Schmitz, Macromol. Symp., 187 (2002) 281–292
[16] EP 666 276 (1994) Bayer AG; EP 682 012 (1994) Bayer AG
[17] Ch. Gürtler et al., Farbe und Lack 11-2005, 111, 22–23
[18] Th. Engbert, E. König, E. Jürgens, Einsatz einkomponentiger Einbrennurethan
beschichtungen, Farbe und Lack 102 (1996) 51–58
[19] 1K Polyurethaneinbrennlacke und deren Verwendung: DE 10 109 228 (2002) Bayer AG
[20] Stabilisation against thermal yellowing: EP 615 992 (1993) Miles Inc.; US 5 216 078
(1992) BASF; EP 654 490 (1993) Bayer AG
[21] U. Röckrath et al., Investigations of crosslinking mechanism of etch resistant clearcoats,
22. Int. Conference in Org. Coatings Science and Technology, Athens, June 1996
[22] V. Mirgel, K. Nachtkamp, Farbe und Lack 89 (1983) 928–934
[23] Procedure to synthesize DMP blocked polyisocyanates: EP 713 871 (1994) Bayer AG
[24] R. Pires, H. J. Laas, Easy emulsification plus improved chemical resistance: Hydro-
philic polyisocyanates with high functionality improve waterborne 2K-PUR coatings,
European Coatings Journal 11 (2001) 16 –22
[25] WO 97/31960 (1996) Rhodia Chimie
[26] EP 486 881 (1990) BASF AG
[27] EP 206 059 (1985) Bayer AG
[28] EP 540 985 (1991) Bayer AG
[29] EP 959 087 (1998) Bayer AG
[30] WO 01/88006 (2000) Bayer AG
[31] M. Melchiors, H. J. Laas, M. Mechtel, Sulfonathydrophilierte Polyisocyanate: die nächste
Härtergeneration für wässrige Zweikomponenten-Polyurethanlacke; 69. Vortragstagung
der GDCh-Fachgruppe „Anstrichstoffe und Pigmente“, 22.–24. September 2004, Ulm/
Neu-Ulm
[32] M. Mechtel, Ch. Irle, H. J. Laas, M. Melchiors, New Hydrophilic Polyisocyanates for
Waterborne 2K-PU-Coatings; The European Coatings Conference: Polyurethanes for
High Performance Coatings III, March 18–19, 2004, Berlin/Germany
[33] M. Melchiors, H. J. Laas, T. Münzmay, R. Gertzmann, Graffiti resistant waterborne 2K
Polyurethane Coatings, XXVIIIth FATIPEC Congress, June 12–14, 2006, Budapest,
Hungary
[34] Applications of Cardura E 10, Technical Manual CA 1.2 by Shell (1990)
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[36] W. H. Brown, T. J. Miranda, J. Paint Technol. 36 (2) (1964) 92

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[38] Emulsion Polymerization of Acrylic Monomers, Publication CM 104 v. Rohm & Haas
[39] Emulsionspolymerisation von Acrylmonomeren, Publication by Ugilor, Paris 1971
[40] H. Fikentscher, H. Gerrens, H. Schuller, Angew. Chem. 72 (1960) 856
[41] H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen. Springer Verlag,
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[42] G. Markert in: Houben-Weyl, Methods of Organic Chemistry, 4th ed., Vol. E20/2,
H. Bartl, J. Falbe (Hrsg.). Georg Thieme Verlag, Stuttgart 1987, 1150
[43] E. Knappe in: Glasurit-Handbuch: Lacke und Farben, BASF Farben und Fasern AG
(Hrsg.). Vincentz Verlag, Hannover 1984, 66–69
[44] EP 358 979 (1988) Bayer AG
[45] DE 4 322 242 (1993) BASF AG
[46] P. Denkinger in: Lackharze, D. Stoye, W. Freitag (Hrsg.). Carl Hanser Verlag, München,
Wien 1996, p. 317
[47] G. Henrici-Olive, S. Olive, Adv. Pol. Sci. 2 (1961) 496–577
[48] A. Sickert, D. Stoye in: Lackharze, D. Stoye, W. Freitag (Hrsg.). Carl Hanser Verlag,
München, Wien 1996, 51–54
[49] E. T. Turpin, J. Paint Technol. 47 (602) (1975) 40–46
[50] H. Blum, P. Höhlein, J. Meixner, Farbe und Lack 94 (5) (1988) 342–344
[51] A. Sickert, D. Stoye in: Lackharze, D. Stoye, W. Freitag (Hrsg.), Carl Hanser Verlag,
München, Wien 1996, 49–51
[52] EP318 800 (1987) Bayer AG
[53] W. Freitag in: Lackharze, D. Stoye, W. Freitag (Hrsg.), Carl Hanser Verlag, München,
Wien 1996, 103–104
[54] US 2 999 844 (1956) Bayer AG
[55] DE 1 770 245 (1968) Bayer AG
[56] US 2 933 477 (1956) Union Carbide Corp.
[57] EP 117 538 (1983) Union Carbide Corp.
[58] A. Balas, G. Palka, J. Foks, H. Janik, J. Appl. Polym. Sci. 29 (1984) 2261
[59] EP 279 311 (1987) Bayer AG
[60] DRP 728 981 (1937) I.G. Farben
[61] O. Bayer, Angew. Chem. 59 (1947) 257
[62] G. Oertel in: Kunststoff-Handbuch, G. W. Becker, D. Braun (Hrsg.), 3. Auflage, Band 7:
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[67] DE 2 546 536 (1975) Bayer AG
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[70] US 4 046 744 (1976) Rohm & Haas
[71] DE 1 694 237 (1968) Bayer AG
[72] DE 1 719 121 (1967) Bayer AG

[73] DE 2 446 438 (1974) Bayer AG

[74] DE 2 632 513 (1976) Bayer AG
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[77] EP 403 921 (1989) Bayer AG
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[79] GB-A 1 017 001 (1963) Bayer AG
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[87] EP 754 713 (1995) BASF AG
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of Coatings Technology 66 (830) (1994) 47
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References 61
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[111] For example: PKT Oldring (Ed.) Chemistry Technology of UV-, EB Formulations for
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[113] W. Fischer, Pitture e Vernici-European Coatings 6/2000, 16–22

62 Coating technology principles
4.1 Aspects of one- and two-component

coating technology
With the exception of film lamination, the formation of an organic coating usually
involves a liquid phase. This is also true for powder coatings, since these are con-
verted from the solid phase to a liquid phase through melting after application. The
liquid coating material then solidifies on the substrate. Generally speaking, two
drying mechanisms are involved in the formation of a solid paint film: physical
drying with evaporation of the medium in which the coating is dissolved or dis-
persed, and chemical curing, i.e. film formation by means of a chemical reaction.
Both mechanisms may overlap during the drying process.
Physical drying
Resins which form a film solely by physical drying mechanisms are used in a
number of applications. Such resins include polymers such as polyurethanes and
polyurethane ureas dissolved in organic solvents. These are valued in, for example,
coatings for plastics and textiles.
Above all, physically drying binders in the form of aqueous dispersions have come
to dominate in formulations for do-it-yourself construction applications. These
one-component systems are easy to handle and, as a rule, fulfill the purpose for
which they are intended unless extreme demands are made on their resistance
properties. It should be pointed out here that physically drying systems are not
crosslinked – the film hardness results from associative interactions between the
molecular chains. As a result, they can be resolubilized (dissolved/swollen) by
solvents and cleaning agents.
To improve the resistance properties in such systems, high mean molecular weights
of up to 150,000 g/mol are the goal [1]. However, an infinite increase in the molecu-
lar mass is not feasible due to the associated increase in viscosity of the coating
and the resulting application problems. The situation is different in the case of
aqueous and non-aqueous dispersed two-phase systems. There, the limitations
imposed by high molecular weights are applicable only to a limited extent.
Chemical drying
In the case of reactive coatings, a distinction must be made between systems with
one or two and more components.

Aspects of one- and two-component coating technology 63
One-component polyurethane systems can be divided into those that crosslink by

baking and those that crosslink at room temperature. The latter exploit the reactiv-
ity of isocyanates with water in the form of atmospheric moisture, and are known
as moisture-curing polyurethane coatings. The drying rate of the paint film depends
on the atmospheric humidity and on:
• temperature
• reactivity of the isocyanate groups
• film thickness
• hydrophilicity of the coating material
• degree of branching (functionality) of the polymer
• molecular weight of the polymer
• type and amount of any catalysts used
Suitable external catalysts include compounds that contain tertiary amino groups,
e.g. DABCO (1,4-diazabicyclo[2,2,2]octane), and the salts of metals such as tin,
zinc and bismuth [2]. If the catalysts are incorporated as building blocks in the poly-
mer matrix so that they are unable to migrate from the coating, they are termed
internal catalysts. These coating materials are produced by, for example, the incor-
poration of hydroxyamines or polyethers containing tertiary amino groups.
Typical systems
In addition to one-component binders based on moisture-curing isocyanate pre-
polymers, stable one-component systems can be formulated by combining poly-
isocyanates with polyols or polyamines. However, this requires the modification
of the reactive groups of the individual components or of the overall system. The
following coating systems of this basic type are currently in use:
• blocked polyisocyanates/polyols
– in dissolved form for baking coatings
– in solid form as powder coatings
• polyisocyanates/blocked amines that react with atmospheric moisture to yield
free amines or react with isocyanates at elevated temperatures
• microencapsulated systems in which the coreactants are separated by a diffusion
barrier and the crosslinking reaction is initiated thermally [3]
Air-drying coatings
One-component polyurethane coatings which cure at room temperature include
those systems with polyunsaturated hydrocarbon chains which crosslink with
oxygen. These are produced, for example, by the incorporation of suitable fatty
acids or fatty alcohols into the polyurethane polymer. The addition of driers (cat-
alysts) based on salts of cobalt, lead and manganese (primary driers) and of mag-
nesium, zinc, calcium and strontium (auxiliary driers) allows these products to

crosslink in air. Depending on the resin structure and the ambient conditions, dif-
ferent reactions will occur [4]. The crosslinking reaction is usually based on a rad-
ical mechanism with secondary reactions yielding ketones, aldehydes and other
oxidation products.
In contrast to the fatty acid-modified polyurethanes described above, coatings that
contain double bonds activated by carbonyl groups in the alpha position or allyl
ether groups can be cured in seconds by exposure to high-energy radiation such as
UV light (radiation curing) [5]. The precondition for this type of curing process is
an adequately high density of double bonds in the one-component system and the
addition of photoinitiators.
Dual-cure technology
Of particular interest are dual-cure systems that combine polyurethane and UV
crosslinking mechanisms. The advantages are, on the one hand, the cost-effective
process control and, on the other hand, the fact that the coating cures chemically
in those areas that are hidden from the radiation source. The quality of the resulting
paint films is high, and investigations are currently underway to determine the suit-
ability of these systems in coating both metal and plastics.
Silyl-modified polyurethanes
Polyurethanes modified with trialkoxysilyl groups are a new class of products that
can also be processed as one-component systems [6]. These products are obtained
by reacting NCO-functional prepolymers with special aminoalkoxysilanes. Catal-
ysis with metal salts hydrolyzes the alkoxysilyl groups to form silanols. Crosslink-
ing results from the subsequent silane polycondensation.
Application
The advantages of one-component applica-
tion of moisture-curing coating systems are
offset by several disadvantages including
the complex formulation procedure and the
need for careful pre-drying of the pigments
if they are moist. The conditions are differ-
ent in the case of systems containing two
or more components where particular
attention must be given to the exact meter-
ing of the polyol and the hardener.
In contrast, pigmented two-component coat-

Figure 4.1: Two-component metering ings can be formulated without pre-drying
unit [7] of the pigments, provided the pigments are

Solventborne and solvent-free systems 65
added to the polyol component. A further advantage of two-component technology

lies in the blister-free curing of the paint film at high film thickness. The pot life
can be varied widely by the use of different catalysts.
Two-component polyurethane coatings are applied by a number of different meth-
ods and the pot life plays an important role. In the case of binder combinations
based on aromatic polyisocyanates, rather than aliphatic polyisocyanates, the pot
life is so short that, as a rule, they require two-component units specially designed
for processing two-component materials (see Figure 4.1, page 64).
The reactivity of polyisocyanates with aliphatic amines is so high that even two-
component units* are not suitable for their application. Due to the fast crosslinking
reaction, various components of the equipment (hoses, spray guns, etc.) become
blocked as a result of polyurea formation. To facilitate a controlled crosslinking
reaction, these amines must be suitably modified, e.g. blocked or sterically hindered.
4.2 Solventborne and solvent-free systems

Solventborne one- and two-component polyurethane coatings account for the largest
volumes applied. They are used in a broad spectrum of industrial applications: in
vehicle coating (automotive OEM and refinishing, coatings for aircraft and railcars),
in plastic coatings, in anti-corrosion coatings, and in wood/furniture finishing.
Solventborne one-component polyurethane coatings (air-drying, moisture-curing or
baking) also have a broad spectrum of applications spanning parquet finishes, coil
coatings, primer surfacers for automotive OEM finishing and plastic coatings.
Classification
Depending on the solids content (low, medium or high), a distinction is made
between low, medium and high solids coatings (LS, MS and HS coatings), although
there is no universal definition of the boundaries between these three types. As a
rule, the point of reference is the solids content at spray viscosity. In order to reduce
the organic solvent content and thus satisfy increasingly stringent environmental
protection requirements, there is a clear trend towards high solid coatings with a
solids content of more than 60 %. These coatings require low viscosity (low molec-
ular weight) coreactants – polyisocyanates and polyols – if necessary, blended with
reactive thinners.
Applications
Liquid solvent-free polyurethane coatings are used in the construction and corro-
sion protection sectors, and also as underbody coating systems for vehicles. A
particular requirement is blister-free coatings, even at high film thicknesses. This
requirement can only be met by using solvent-free one- and two-component for-
mulations, which greatly restricts the choice of suitable polymers.
*The designation “two-component” or “2K” has been adopted for practical reasons. When referring to two-component spray units
or 2K spray guns, for example, two-component of course always relates to the coating processed using the equipment.

Low viscosity polyethers are of special significance in two-component applications,

as are polycarbonates to a certain extent, and MDI polymers such as “Desmodur
VL” are important as the hardener component. The pot life of coatings formulated
in this way is so short that two-component units must be used.
Solvent-free one-component polyurethane systems are also used in construction
and anti-corrosion applications. They are based on moisture-curing aromatic or
aliphatic prepolymers containing NCO groups, e.g. “Desmodur E” products. How-
ever, only relatively thin films can be produced as these systems tend to foam due
to CO2 generation. Other solvent-free one-component polyurethane formulations
are based on blocked NCO prepolymers and may contain plasticizers. They are
used as baking systems, for example, seam sealers for automotive applications.
The various systems cure at a wide range of temperatures. Moisture-curing poly-
urethane coatings harden at room temperature, whereas blocked polyisocyanates
may require baking at up to 500 °C, e.g. in the case of wire enameling.
Two-component polyurethane systems dry relatively quickly without exposure to
heat due to their reactive NCO groups. However, these systems are often force-dried
at up to 80 °C or baked at temperatures above 120 °C. Higher temperatures yield
shorter curing times, resulting in faster production cycles and increased efficiency
(equipment utilization). However, there are limits to these possibilities since, as a
rule, temperatures of more than 200 °C and baking times of more than 30 minutes
trigger thermal degradation reactions in polymers.
Quality characteristics
Whether using solventborne or solvent-free two-component polyurethane coatings,
the film quality obtained is largely independent of the drying temperature. Even at
the lowest temperatures, an adequately long curing time results in a degree of
crosslinking equivalent to that achieved under baking conditions. This fact was
instrumental in the switch to this technology for coating aircraft and for refinishing
in automotive body shops, both segments where baking is not an option. Two-
component polyurethane coatings have also made an important contribution towards
the use of plastics in automotive engineering. For reasons including design (color
matching with the body), they are used increasingly to finish add-on components
such as fenders. They also provide long-term protection and prevent the plastic
from becoming brittle on exposure to weathering.
The curing conditions for two-component polyurethane coatings can be influenced
with catalysts as required. Particularly suitable for this purpose are metal salts, e.g.
tin or zinc salts, and tertiary amines (chemical drying). There is a wealth of litera-
ture that discusses the use of catalysts in polyurethane crosslinking [8 –11].

Waterborne systems 67
4.3 Waterborne systems

The significance and market share of waterborne products in the coating raw mate-
rials market as a whole has been growing steadily for several decades. This devel-
opment is not driven by ecological motives or legislation (VOC Guidelines) alone
– there are also tangible economic reasons. Particularly in times of increasing crude
oil prices, the loss of significant amounts of valuable raw materials to the atmo-
sphere in the form of organic solvents must be avoided, as must the need to recover
them by expensive processes or even burn them off. In addition, the health risks
associated with organic solvents, as well as the danger of fire and explosion, require
considerable expenditures in the area of safety technology. Modern environmen-
tally friendly coatings therefore have a greatly reduced content of organic solvents
(high solid coatings, solvent-free or waterborne systems). In many cases, water-
borne coating systems are comparable to their solventborne counterparts with
regard to technical properties; often they even exceed them.
Waterborne coating systems based on polyurethane are extensively used due to
their high quality, and they continue to rapidly gain importance. Typical uses are
automotive OEM and large vehicle finishes, wood, metal and plastic coatings,
construction applications, as well as the coating of textiles, glass and paper. In
addition, waterborne systems have great potential in non-conventional coatings
applications such as cosmetics and medical technology. A great deal of innovation
can be expected in these fields.
Waterborne polyurethane systems are usually based on polyurethane dispersions
that may, if desired, be formulated with further polyacrylate, polyester, or polycar-
bonate-based dispersions, with or without crosslinking agents. With regard to pro-
cessing methods, they are essentially no different than their solventborne counter-
parts. Waterborne coatings are applied by conventional methods such as painting,
spreading, curtain coating, dipping or spraying.
After the application of dispersion-based coating systems, the water and other
volatile components evaporate from the paint film. A number of different models
have been proposed for the actual mechanism of film formation [12]. What is undis-
puted, however, is that good film formation only occurs if there is a polymer chain
exchange between adjacent particles as soon as these come into contact with each
other (see Figure 4.2, page 68). Film formation is therefore largely governed by the
polymer structure, the glass transition temperature of the soft segment phase, the
type and amount of any coalescing agent or solvent used, the application conditions,
and lastly the film thickness [13].
Despite their favorable properties, the use of high molecular weight, physically
drying polyurethane dispersions as binders often does not suffice to yield coatings
that satisfy all requirements in terms of resistance and mechanical properties. This

Figure 4.2: Film formation of a polyurethane dispersion
can only be achieved by post-crosslinking the dispersion on the substrate. In prin-

ciple, such reactive coatings can be divided into one- and two-component systems.
Waterborne one-component polyurethane systems
Depending on the area of application, waterborne one-component polyurethane coat-
ings can be customized in terms of crosslinking, curing and film properties. The most
important polyurethane dispersions for waterborne one-component coatings include:
• Polyurethane dispersions for crosslinking with blocked isocyanates for baking
coatings
These are OH- or NH-functional dispersions combined with raw materials that
contain isocyanates with thermally reversible blocking. The blocked polyiso-
cyanates suitable here can be used in their unmodified, i.e. hydrophobic, form.
In this case, the resin dispersion (OH- or NH-terminated) must have a co-dis-
persing function. In contrast, hydrophilically modified blocked polyisocyanates
themselves form stable dispersions and are mixed into the resin dispersion [14, 15].
The blocked isocyanate group can also be bound directly to the OH- or NH-
terminated polymer backbone. Such systems are designated self-crosslinking
dispersions [16].
• Polyurethane dispersions for melamine or epoxide crosslinking
COOH- or OH-functional polyurethane dispersions combined with polyepoxides
or alkoxymethyl melamines (melamine crosslinking) [17–19].
• Radiation-curing polyurethane dispersions
Modification with hydroxyalkyl acrylates or allyl alcohols yields polyurethane
dispersions for coatings that cure within seconds with on exposure to high-
energy radiation [20].
• Polyurethane dispersions that dry by oxidation
Polyurethane dispersions modified with unsaturated polyester units can be dried
by reaction with atmospheric oxygen. These are generally fatty acid-modified
polyurethane dispersions, the crosslinking of which is often accelerated by the
addition of driers such as cobalt salts [21].

Waterborne systems 69
Crosslinking via aziridines [22] and polycarbodiimides [23] are described as additional
curing methods. Polyurethane dispersions that contain ketoester groups can be
crosslinked with polyamines or polyhydrazides [24] and polyurethane dispersions
that contain trialkoxysilyl groups crosslink by condensation [25]. Occasionally, mixed
crosslinking mechanisms are used, for example in the manufacture of baking sys-
tems. These combine an OH-functional dispersion with a blocked polyisocyanate
crosslinker and a melamine crosslinker.
Waterborne two-component polyurethane systems
High-grade waterborne two-component polyurethane coatings were first described
in 1988 [26–29]. Free polyisocyanates are emulsified in an aqueous hydroxyfunctional
polymer dispersion or solution. Dispersions of hydroxyfunctional polyurethane,
polyacrylate, polyester or urethane-modified polyester are normally used.
Key coating properties such as gloss and resistance depend directly on the forma-
tion of a homogeneous and dense polymer network. The main prerequisite for
achieving this is to ensure that the hydroxyfunctional polymer dispersion and the
polyisocyanate are mixed as homogeneously as possible. The dispersion of the
polyisocyanate in the aqueous phase is supported by three factors: reducing the
interfacial tension, applying high shear forces during emulsification and ensuring
the low viscosity of the dispersed phase (the polyisocyanate component) [30].
The interfacial surface tension can be reduced by using a polyisocyanate with
internal hydrophilic modification, e.g. “Bayhydur 3100”. External emulsifiers such
as a suitable polyol can also produce this effect [31–33]. However, excessive hydro-
philic modification will have a negative impact on the coating properties. Lower
hydrophilicity requires the use of a dispersion technique in which high shear forces
are applied. Jet dispersion has proven very effective, and this technique, together
with the selection of suitable polyols, enables the use of purely hydrophobic poly-
isocyanates (Figure 4.3, page 70).
Modern internally modified polyisocyanates thus combine high functionality
(highly branched coating systems) with low viscosity (good mixing). Anionically
modified polyisocyanates exhibit the best property profile in this regard. After
mixing the polyisocyanate with the aqueous polyol, a number of reactions take
place in parallel during the pot life and curing (Figure 4.4, page 70).
In addition to the desired crosslinking reaction between the isocyanate and hydroxy
groups to form urethane, the isocyanate groups also react with water to form urea
and carbon dioxide. However, this reaction is relatively slow, and also increases
the crosslinking density. The carboxylate groups of anionically stabilized polyol
dispersions likewise react with isocyanates. However, this can only occur to any
significant extent once the neutralizing agent has evaporated from the paint film.
The consequence of the slow reaction between the isocyanate groups and water is

that the application properties of the coating remain fairly constant throughout the
pot life. With a judicious choice of components, pot lives of up to 8 hours can be
achieved. When a suitable binder is used, the carbon dioxide that is formed as the
film cures does not lead to blistering, since it can diffuse out of the film at the time
it is generated (in statu nascedi) [34, 35].
Figure 4.3: Emulsifying hydrophobic polyisocyanates
Figure 4.4: Reaction in waterborne two-component polyurethane systems

Process technology 71
4.4 Process technology

Most polyurethane coating raw materials are used in reactive systems. Depending
on whether they are one- or two-component systems, the various coatings require
the use of specific application technologies. This does not apply to one-component
polyurethane coatings based on blocked polyisocyanates that are non-reactive at
room temperature. Since these only crosslink above the cleavage temperature of
the blocking agent, they can be applied by conventional techniques such as spray-
ing, roller coating, curtain coating and dipping.
4.4.1 Processing of one-component polyurethane coatings
One-component polyurethane coatings that are reactive at room temperature cross-
link through reaction with ambient atmospheric humidity. To prevent uncontrolled
crosslinking, a viscosity increase or thickening, e.g. during storage of the coating,
the containers must be kept tightly sealed prior to application. Only solvents with
a defined low water content of no more than 0.05 % by weight, referred to as poly-
urethane-grade solvents, can be used. To improve the storage stability of pigmented
coatings, water-scavenging chemicals are added to bind the residual moisture from
the pigments. Suitable substances are Additive TI and Additive OF (e.g. Borchers)
and “Desmodur MT” (Bayer MaterialScience).
4.4.2 Processing of two-component polyurethane coatings
The main feature of all two-component polyurethane coatings is their restricted pot
life because the crosslinking reaction starts as soon as the components are mixed.
This results in an increase in viscosity to a threshold viscosity at which point the
coating begins to gel (gel time).
The pot life is the period of time in which the coating can be applied without any
detrimental effects on the quality. In practice, it ranges from a matter of minutes to
several hours, depending on the formulation. The shorter the pot life, the more
difficult manual application will be, i.e. mixing of the components by hand and
subsequent application. Generally speaking, two-component units and spray guns
are used to apply highly reactive two-component coatings with a pot life of less
than 30 minutes and for industrial finishing [36].
Two-component spray application
There are two options for the industrial application of two-component coatings. In
the first case, the material is homogenized either by hand or in a mixer unit, and is
then fed via a hose to the spray gun. The disadvantage is that there may be long
hoses that require rinsing, resulting in a loss of coating material and solvents. It is
very important to clean out the coating reservoir and the feed unit within the reac-
tion time (pot life) of the components that have been mixed. The alternative is to
use two-component spray guns with integrated or attached static (Kenics) mixers.

Of the variety of mixer units available, static mixers are the ones most frequently
used in two-component application [36]. The mixing efficiency is essentially deter-
mined by the viscosities and the product affinities of the coating components. High
viscosities or wide differences in viscosity require a correspondingly large number
of screw elements in the mixer. To improve the feed properties, mixing and appli-
cation, it is common to process high viscosity materials in the “hot” state, e.g. at
40–60 °C. The supply tanks and feed hoses are therefore designed to be heatable.
The noticeable limitation of this mode of operation is that the pot life for the two-
component system is significantly reduced.
Under certain circumstances, static or dynamic (Ultraturrax) mixers may not be able
to achieve adequate homogenization of two-component coatings with critical mis-
cibility. This is true in the case of waterborne two-component polyurethane coatings,
for example, in which non-hydrophilically modified polyisocyanates are used as the
hardener component. Such systems are best mixed by jet dispersion (see Figure 4.5),
which yields a high degree of homogenization even with components which are
extremely difficult to mix. This allows good film quality to be achieved [37].
When working with jet dispersion, the polyisocyanate and polyol components are
first pre-emulsified via a flat spray nozzle. The jet disperser – a nozzle bored with
facing pairs of holes – releases the pressure of the formulation (∆p >20 bar) and
yields a microdispersion with a maximum particle size of approx. 1 µm.
Depending on the viscosity of the two-component system used, a spray coater will
use a spray gun with air atomization (high- and low-pressure processes) or, in the
case of high viscosity, an airless spray gun, i.e. techniques that are also commonly
used for one-component coatings. In addition, an air-assisted airless atomizer can
also be used, in which a fast-flowing stream of coating is homogenized by air jets [38].
Figure 4.5: Schematic design of a jet dispersion unit

Electrostatic application is primarily used in industrial coating environments [39]. An

electric field is created between the high voltage-conducting spray gun and the
grounded workpiece. The coating material is charged in the spray gun. Due to the
electric field and the attractive forces exerted by the workpiece, the coating droplets
are drawn toward and deposited on the workpiece with minimal overspray. The most
favorable conductivity range for coating materials is between 10 –10 and 10 –8 S/cm.
Polyurethane coatings also fall within this range. The electrostatic coating processes
can be divided into three categories, depending on the atomization and electrostatic
charging mechanisms: the electrostatic compressed air and the airless process, the
electrostatic atomizing process, and the high-speed rotation process [39].
Electrostatic spray guns (see Figure 4.6) atomize the coating material by the same
mechanism as conventional spray guns, but the coating droplets receive an elec-
trostatic charge as well. Nearly all coatings can be sprayed in this manner.
In the electrostatic atomization process, the coating is fed into a high voltage-con-
ducting rotating bell (up to 3,000 rpm) or disk, and is atomized by strong electrical
forces. Highly conductive coating systems such as waterborne coatings cannot be
applied by this process. By contrast, in the high-speed rotation process, atomization
takes place through purely mechanical forces, and is largely independent of the
electrical properties of the coating. For example, electrostatic high-speed rotating
bells with speeds between 15,000 and 70,000 rpm are used. The coating is expelled
tangentially from the bell, which is under high voltage (90 kV) (see Figure 4.7).
Such processes are used primarily in automatic coating units, particularly in the
field of automotive finishing and increasingly in general industrial coating applica-
tions. The application of a waterborne two-component polyurethane coating is
described in 5.3 [41].
Figure 4.6: Electrostatic Figure 4.7: Electrostatic high-speed rotating

spray gun [40] atomizer (bell) in automotive coating [42]

Two-component metering units

Two-component metering units meter the hardener and mill base components in
the desired volume mixing ratio. Depending on the type of unit, the material may
be mixed and conveyed as well as metered (see Figure 4.8).
The materials – mill base and hardener – are fed into the two-component metering
unit from pressure pots or via ring lines, for example. Two types of pumps can be
used to meter the components: piston pumps or gear pumps. Piston pumps are
robust and are also suitable for operation at high pressure to meter viscous materi-
als. They have a dual effect in that they convey the material on both the upward
and the downward strokes. Due to the intermittent acceleration of the piston (minima
at the turning points), pulsation may occur in the spray stream which, in the case
of longer hoses, can be attenuated by bleeding the hose.
Because piston pumps operate by forced feed, the metering accuracy is ensured by
the constant volume of the cylinder and the defined stroke length. However, because
of the time and effort involved in cleaning, it is not possible to achieve a quick
changeover to a different color. If several colors are to be used, parallel piston units
are normally used. Suitable units are available for a variety of applications.
Gear pumps ensure pulsation-free application. So as not to restrict the metering
accuracy (slippage), they are normally used in the low to medium pressure ranges
Figure 4.8: Schematic illustration of a two-component metering unit [43]

(up to 50 bar). Variable air-driven and electric motors are used to drive the pumps.
The feed volume is governed by the chamber size and speed of the gear pump.
Because of the small volumes involved (from 2 ml), flushing can be achieved
quickly and efficiently, especially if the unit is equipped with flank flushing with
alternating air and solvent intervals (less than 30 s). This allows rapid changeover
to a different color. When using flushable gear pumps, only one metering unit is
required for the mill base.
In continuous coating operations, e.g. production line coating, electronically con-
trolled and monitored two-component units are used.
A microprocessor control and regulation device compares the actual values against
the specified metering ratios, and if necessary, automatically adjusts the amounts
within a tolerance threshold of ±5 %. Color changeover with automatic intermedi-
ate flushing takes place in the color changeover block.
General conditions for applying two-component polyurethane coatings
A number of important prerequisites must be met when applying two-component
polyurethane coatings so as to ensure optimal coating quality. These include care-
ful observation of the pot life (see above), good mixing of the mill base and hard-
ener, and observance of the tolerance threshold of ±5 % for metering accuracy, in
particular at the given mixing ratio of the two components. If operating within these
thresholds, there is no reason to expect any deterioration in the film quality. In order
to test the function of the unit, it is recommended that the mixing ratio of the two
components, mill base and hardener, is checked regularly by measuring the volume
flows of the materials.
One key requirement for the successful application of two-component polyurethane
coatings is careful handling. This includes flushing the spray guns and other com-
ponents of the application unit (hoses) during the pot life. A 1:1 mixture of butyl
acetate/xylene is suitable as the flushing solvent when applying solventborne sys-
tems. When flushing the spray gun, the operator must avoid inhaling the solvent
vapors that are emitted. When applying aqueous two-component polyurethane coat-
ing systems, a mixture of water, butylene glycol and dimethylethanolamine in a
ratio of 89:10:1 is used as the flushing solvent on the mill base side (component A).
On the hardener side (component B), butyl acetate is used to flush the unit.
If the unit contains hardener, exposure to water or moisture, e.g. via the flushing
solvent or leaks in the unit, must be prevented. For this reason, the hardener tanks
are overlaid with nitrogen or dry air. When the filling level falls as the hardener is
used, more air must be fed in through a drying cartridge. Brief contact with atmo-
spheric moisture, e.g. when transferring the product from one container to another,
has no detrimental effect.

Moving parts such as piston rods in the metering pump are protected from their
surroundings by a fluid seal. Plasticizers such as “Mesamoll” are especially suit-
able as lubricants and sealants, since they prevent the formation of polyurea on
the piston rods.
Safety precautions
Stainless steel is normally used to manufacture two-component units, pipes and
transport containers. Zinc-galvanized surfaces are entirely unsuitable owing to the
catalytic effect of the zinc. Plastics are generally unsuitable as container materials
because of their permeability to water vapor. Multilayer plastic composites, which
are considered impermeable in this respect, have not yet found use in this field. The
hoses used to convey the hardener, e.g. made from nylon, must be emptied and
flushed before long interruptions in operation, for example on weekends, to prevent
gelling as the result of moisture diffusion. This does not apply to Teflon hoses, but
their limited flexibility restricts the handling of the spray gun.
Compared with one-component coatings, the processing of two-component coat-
ings is inherently more complex, and more expensive if two-component units are
used. However, there are numerous case studies showing that, if the units are oper-
ated properly and maintained regularly, they can function for many years without
breakdown.
Two-component technology is particularly strongly represented in automotive
OEM finishing. Two-component polyurethane coatings are being utilized increas-
ingly in the automotive industry, and can be applied reliably when suitably main-
tained two-component units are used. The manual spray application of two-com-
ponent polyurethane coatings has also proven successful and is employed world-
wide, for example, in car repair shops.
4.5 Polyurethane powder coatings

Powder coatings constitute an important class of products that can be used in a wide
variety of general industrial coating applications. This segment is characterized by
dynamic growth. Polyurethane powder coatings represent a specialty for high-per-
formance coatings that are used in many industrial applications.
ε-Caprolactam-blocked polyurethane powder coatings
Most of the polyurethane powder coatings on the market today consist of a com-
bination of solid hydroxyfunctional polymers (polyesters or polyacrylates) and
solid blocked polyisocyanate crosslinkers. The standard commercial polyurethane
powder coating crosslinkers are based on cycloaliphatic diisocyanates such as IPDI
or H12MDI and contain ε-caprolactam as the blocking agent. This is cleaved at
baking temperatures above 170 °C and the liberated isocyanate groups then cross-

Polyurethane powder coatings 77
link with the hydroxyl groups of the binder to form urethane [44]. However, the
blocking agent content is being viewed increasingly critically, since these cleaved
substances are released during the crosslinking reaction and may enter the environ-
ment at least to some extent.
Blocking agent free polyurethane powder coatings
Powder coating crosslinkers containing uretdione groups represent an alternative
to blocked polyisocyanates [45]. As has already been described, isocyanate groups
may dimerize to form uretdiones. This reaction is reversible (Figure 4.9). Uretdio-
nes are therefore also characterized as internally blocked isocyanates.
Reacting uretdione diisocyanates with suitable diols yields linear polyuretdione
polyurethanes, which can be used as crosslinkers in the manufacture of blocking
agent free polyurethane powder coatings (see Fig. 4.10).
At sufficiently high temperatures, the uretdione rings open to form free isocyanate
groups which then take part in a crosslinking reaction. However, a baking
temperature of at least 180 °C is required for uretdione crosslinking, higher than is
needed for hardeners blocked with ε-caprolactam. Catalysis with suitable amidine
bases reduces the baking temperature to approx. 150 °C [46].
Only in very recent times has it been possible to develop a catalyst system that
enables the curing of uretdione powder coatings at a temperatures of 130 °C, which
is extremely low for powder coating systems [47]. This catalyst system, which con-
tains zinc acetylacetonate as the main component, is now commercially available
Figure 4.9: Dimerization of isocyanates
Figure 4.10: Structure of an IPDI uretdione powder coating crosslinker

Figure 4.11: Low temperature crosslinking of a uretdione with the formation of allophanate
as a masterbatch in a saturated OH polyester (“Crekat XP 2571”). In contrast to the

non-catalyzed uretdione powder coatings or existing catalyzed systems, crosslink-
ing in the presence of the new zinc catalyst does not form urethane but allophanate
structures (see Figure 4.11).
This low temperature technology opens up new areas of application for polyure-
thane powder coatings, such as automotive, plastic and wood finishing.
4.6 Radiation curing

4.6.1 Technology and coating formulation
In coating technology, the term radiation curing in the strictest sense is the curing
of coatings or printing inks with
• accelerated electrons (electron beam curing, EBC), in the energy range 90 to
250 keV (higher if necessary)
• ultraviolet light (UV curing), useful wavelengths 420 nm to approx. 240 nm
(Figure 4.12)
Radiation-curing coating systems have shown above-average growth for many
years, because they have replaced processes that are less productive or less envi-
ronmentally friendly [48].
The vast majority of radiation-curing coatings are based on acrylate chemistry and
crosslink via radical polymerization. For special applications, cycloaliphatic epoxy
resins are used. These are cured via a cationic mechanism. The most important of
the radical curing systems are the formulations with nearly 100 % solids, possibly
containing just a small amount of solvent. Water-reducible systems still have a
relatively small market share, though this is growing rapidly. Radiation-curing
powders are at present still limited to special applications.
The following raw materials are used for radical curing systems (basic formulation):
• Binder/oligomer: Responsible for the desired film properties such as resistance
to scratching, abrasion and weathering, etc.
• Reactive thinner or water: Reactive thinners are low viscosity acrylates used
primarily to lower the viscosity. The functionality and double bond density of
the reactive thinners also influence the properties of the cured paint film

Radiation curing 79
• Photoinitiator: Absorbs UV radiation, decomposes into radicals and initiates

the radical chain polymerization. Photoinitiation is unnecessary in EBC
• Additives/fillers: E.g. for good flow, degassing, gloss and weather resistance, etc.
4.6.2 Binders for radiation curing
Figure 4.13 shows the consumption of unsaturated acrylate binders in radiation-

curing applications. Urethane acrylates hold a share of approx. 20 %, and are the
most versatile class of binders in use.
Their outstanding properties in comparison to epoxy, ester or ether acrylates are:
• mechanical resistance properties (resistance to abrasion, scratching, impact, etc.)
• flexibility (viscoelasticity)
• weather stability
• adhesion
Urethane acrylates are used as binders in the mono-cure and dual-cure systems, as
well as in UV-curing dispersions and powders.
Figure 4.12: Radiation sources for curing coatings and printing inks
Figure 4.13: World consumption in 2005 of unsaturated acrylate binders, total: 215,000 tons

4.6.3 Urethane acrylates for UV (mono-cure) and electron beam

curing applications
Interior applications
The addition of hydroxyalkyl acrylates to diisocyanates and monomeric polyols
yields oligomers with higher viscosity due to urethane hydrogen bridge bonding.
This is especially true when cycloaliphatic diisocyanates such as IPDI and H12MDI
are used. Products of this type are most often commercially available as solutions
in reactive thinners. However, thinning with a high proportion of reactive thinner
inevitably leads to a deterioration in the desired coating properties. Figure 4.14
demonstrates this by the example of abrasion resistance.
For novel urethane acrylates, low molecular weight polyester acrylates produced
by azeotropic esterification are reacted with diisocyanates via polyaddition. Using
these combined processes, resins with a viscosity lower than 10,000 mPa·s (23 °C)
can be manufactured (e.g. “Desmolux U 100”, “U 200”). These require only small
amounts of reactive thinner, and for the most part their property profiles can be
transferred to application-ready formulations. Applications include floor, furniture
and plastic coatings (Figure 4.15).
Exterior applications
Weather-stable coatings must not only be resistant to yellowing and hydrolysis,
but also to thermal and photochemical processes. In the radiation curing segment,
Figure 4.14: Property development in UV coatings with increasing amounts of reactive

thinners [49]

Radiation curing 81
these requirements are fulfilled by

aliphatic urethane acrylates, and in
particular, the reaction products of
hydroxyethyl(propyl) acrylate and
HDI-based polyisocyanates. This
type of product has been exten-
sively described in the literature [51].
However, the higher molecular
weight fraction of the HDI oligo-
mers leads to a high viscosity in the
corresponding urethane acrylates. Figure 4.15: UV curing of parquet flooring
Low viscosity, highly functional panels coated with urethane acrylate
urethane acrylates with allophanate
structures are under development, and will be available commercially without
any thinners [50, 52, 53] (see Figure 4.16).
Due to its weather stability, high density of allophanate and urethane structures,
well-balanced functionality and double-bond density, this new product type has the
potential for use in a wide range of plastic coating applications (see Figure 4.17,
page 84). Metal coatings are also being developed.
Figure 4.16: Structure of a novel allophanate urethane acrylate

4.6.4 Waterborne UV-curing polyurethane coatings

Waterborne UV-curing coatings allow the use of radiation curing in new areas of
application. In comparison to conventional UV-curing coatings with 100 % solids,
waterborne UV-curing coatings are characterized by:
• decoupling of molecular weight and viscosity
• simple application even by spraying
• easier mattability
• better adhesion
Urethane chemistry also offers the option of manufacturing products with specific
properties. Since they have double bonds, polyester and epoxy acrylates with inher-
ent hydroxyfunctionality can be used. By variation of the saturated and unsaturated
components, choice of diisocyanate,
and variation of the diols and hydro-
philic modification, many different
property profiles can be created, for
example:
• physical drying, (dispersions yielding
tack-free films after evaporation of
the water)
• UV reactivity
• hardness/elasticity
• weather stability, etc.
High molecular weight urethane acrylate
dispersions are manufactured by the ace-
Figure 4.17: Weather- and scratch-
tone process [54]. Subsequent dispersion
resistant urethane acrylate coating for in water ensures monomer- and solvent-
automotive headlamp lenses free supply forms (see Figure 4.18).
Figure 4.18: Structure of UV-curing urethane acrylate dispersions

Radiation curing 83
UV-curing polyurethane dispersions are thus primarily used for spray coatings, e.g.
for wood, furniture and plastics. They are also applied by printing and roller coat-
ing on PVC flooring, and are used as printing inks.
4.6.5 Urethane acrylates for UV powder applications

Reduced thermal stress on the products being coated, shorter processing times and
the decoupling of flow and crosslinking of the applied powder coatings are impor-
tant development goals in the area of powder coating technology. With the introduc-
tion of the radiation curing method for the crosslinking and curing of powder
coatings, these goals can largely be realized. UV-curing powder binders must thus
meet the contradictory requirements of perfect grindability and storage stability on
the one hand, and lower processing temperature on the other. In this regard, poly-
urethane chemistry offers optimal possibilities balancing crystallinity, glass transi-
tion temperature (Tg ), surface tension and melt viscosity [55]. These goals can be
achieved using amorphous linear urethane acrylates.
They are easily grindable and yield UV-curing powders with good storage stability
and excellent film properties. Up to the present, the still young UV powder coating
technology has been used primarily in finishing MDF furniture components.
4.6.6 Isocyanato urethane acrylates for dual-cure technology

Dual-cure generally refers to a combination of two chemically different crosslink-
ing mechanisms. Isocyanato urethane acrylates are used in coating systems that are
crosslinked by photochemically or thermally initiated radical polymerization and
by isocyanate reactions [56]. Dual-cure systems are commonly crosslinked first by
UV radiation and then via an isocyanate reaction (see Figure 4.19, page 84).
In comparison to coatings that are cured only by exposure to radiation (mono-cure),
dual-cure technology offers the following advantages:
• improvement in the adhesion due to the reaction of the isocyanate group with
the substrate
• fewer geometrical limitations because the NCO/OH reaction takes place even
in those areas hidden from the radiation source
• better through-curing of pigmented UV coatings, via an NCO/OH reaction in
deep layers that radiation can reach only with difficulty
The reversal of the dual-cure process with upstream thermal drying, as shown in
Figure 4.20, opens up completely new possibilities in coating technology. Formable
foils are foils that are pre-coated but thermoplastic, enabling them to conform to
the geometry of the respective workpiece. The end properties desired can be
obtained via UV post-curing (see Figure 4.21).

Figure 4.19: Dual-cure mechanism; initial UV curing
Figure 4.20: Dual-cure mechanism; UV post-curing
Thermoforming and UV curing
Figure 4.21: Manufacturing concept for coated post-formable films

Nanotechnology in polyurethane coatings 85
4.7 Nanotechnology in polyurethane coatings

In recent years, nanotechnology has experienced rapid growth, and has been des-
ignated as one of the key technologies of the 21st century. According to a study
conducted by the German Federal Ministry of Education and Research, the global
market for nanotechnology products and processes is currently worth EUR 100 bil-
lion and is expected to climb to EUR 1 trillion by 2010 [57]. The reduction of dimen-
sions down to the nanoscale domain as well as the combination of inorganic
nanoparticles with organic building blocks yields materials with complementary
properties and novel functions. They are of special significance for coating applica-
tions where commercial success was achieved at an earlier stage. Key products
were launched in the fields of photocatalytic coatings, self-cleaning or easy-to-clean
coatings, OEM clearcoat applications and corrosion protection [58, 75].
Inorganic nanoparticles can be incorporated in various ways into coating raw mate-
rials or formulations. Current processes include the dispersion of nanoparticles in the
polymer matrix, or their creation in situ. The latter can take place, for example, via
sol-gel processes or microemulsion precipitation in monomers [58–61]. In most cases
it is necessary to modify the particle surface to achieve the necessary compatibility
and thus a homogeneous distribution[62]. Also useful are special dispersion techniques
such as wet grinding or jet dispersion [63] for the breakdown of agglomerates.
A number of functional nanoparticles are available commercially, which differ in
their morphology and chemistry. These can yield a variety of functions in the result-
ing nanocomposite coatings, preserving the transparency that can be achieved
below a critical particle size depending on the specific refractive index. Principally,
nanoparticles may be spherical, rod-shaped and lamellar. The morphology can be
of fundamental importance in determining the properties. For example, lamellar
silicates can be used as barrier materials in coatings to reduce the migration of gases
or liquids [67–69] (see Figure 4.22).
If rod-shaped carbon nanotubes are
successfully uncoiled, they exhibit
high conductivity and mechanical
strength, even when used in small
amounts [70,71]. Spherical nanoparticles
are characterized by an especially
large spectrum of chemical and phys-
ical properties. These nanoparticles
influence catalysis (Au, Pt, double
hydroxides, etc.), biocidal activity Figure 4.22: Schematic illustration of the
(Ag, Cu), scratch resistance (SiO2, barrier model for lamellar silicate nanocom-
Al2O3, ZrO2, POSS), UV protection posites [67]

(CeO2, ZnO), IR reflection (ZrO2, TiO2), photocatalysis (TiO2) and much more [59–
61, 65]
. In addition to the introduction of nanoparticles, attention is also now focusing
on hybrid technologies used to combine organic polymers with sol-gel processes.
In this way, interpenetrating networks or in situ precipitated nanoparticles, or com-
bined systems can be formed [59,60,64]. With the aid of such hybrid technologies,
further improvements can be made to easy-to-clean and self-cleaning properties,
water resistance, adhesion and corrosion protection [75].
From a market perspective (raw material manufacturers and end users), the greatest
potential lies in automotive OEM and refinishing, marine applications, corrosion
protection, metal and wood finishes, general industrial coatings and architectural/
decorative uses. The biggest technological leaps expected by raw material manu-
facturers and end users center on scratch resistance, self-cleaning/easy-to-clean
properties, improved durability, antimicrobial properties, UV protection, water
resistance, adhesion and photocatalysis.[58, 66]
Polyurethane coatings are already used in such applications on account of their
property profiles, but their range of performance can continue to grow with the
utilization of nanotechnology. For example, in two-component polyurethane top-
coats, the use of silica nanoparticles and chemical customization of the polymer
matrix significantly improve scratch resistance[73, 74]. The literature describes a
hybrid topcoat based on polyurethane in which silica gel produced by a sol-gel
process is combined with ceroxide nanoparticles. Both the scratch resistance and
the weather stability are improved [64].
In addition to the expectations and the positive effects of the nanotechnology-modi-
fied coatings already discovered, challenges such as processability, cost, environ-
mental issues and hygiene must be considered. Thus the manufacture, formulation
and applications technology of such coating raw materials in conventional processes
can lead to complications so technological pathways must be attempted and the cor-
responding formulation and application technical know-how must be learned [58, 72].
The higher costs for incorporating nanoparticles must be justified either on the basis
of the corresponding improvements in the properties, or by keeping the amounts
used to a minimum. The effect of nanomaterials on the environment and health
is currently under intense investigation, and these factors have been accepted by
industry from the very beginning. Consortia that include industry and independent
research institutions have dedicated themselves to a series of international projects
on this subject, in order to be able to assess any potential risks early on [58].
Nanotechnology has shown itself to be an emerging field with great potential for
coating and adhesive applications. Despite initial successes, there is still enormous
need for further development so that technological advances can be converted into
innovative products. In many applications, polyurethane-based coatings have dem-
onstrated strengths due to their property profiles. Nanotechnology can serve to raise
the level of quality even higher. This should yield options for accessing new appli-
cations for polyurethanes.

Nanotechnology in polyurethane coatings 87
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90 Applications for polyurethane coatings
5 Applications for polyurethane

coatings
5.1 Wood coating

Because of their extremely broad chemical variability, polyurethane raw materials
have become very important binders for the formulation of wood and furniture coat-
ings. The applications range from the coating of wood for outdoor use, e.g. windows
and doors, through the coating of wood and wood materials for furniture, to the
finishing of parquet flooring, musical instruments or wooden trim parts in cars. The
variability in the resin structure and the associated wide range of properties with
high quality levels predestine polyurethane systems for use in a broad variety of
applications and for meeting substrate-specific requirements in the wood segment.
Polyurethane coatings have therefore become one of the most important coating
systems for wood and furniture. Figures 5.1 and 5.2 show the distribution of wood
and furniture coating production (industrial application and trade parquet coating)
worldwide with altogether 2,290,000 tons (2005), classified according to tech-
nologies and regions [1]. Solventborne coatings (84 %, Figure 5.1) are by far the
dominant system. The largest part of production comes from Asia (Figure 5.2). The
People’s Republic of China is the largest producer of wood coatings worldwide.
The largest part, about 40 % of all wood and furniture coatings, is accounted for by
polyurethane technology with the important class of two-component polyurethane
systems, that is those formulated with aromatic and aliphatic polyisocyanate hardeners.
Polyurethane systems dominate particularly in Italy and Spain (market share around
60 %) and Germany (about 30 %). Solventborne polyurethane coatings are also
Polyurethanes 42 %
Figure 5.1: Industrial wood and furniture coatings, world production by system, 2005;
total: approx. 2.3 million tons [1]

Wood coating 91
represented strongly in Japan. The market share of two-component polyurethane

coatings in China is probably larger than 70 %, although there are no reliable data
to support this assumption.
5.1.1 Requirements of wood and furniture coatings
Productivity
The manufacture of individual components in modern furniture production and the
large volumes involved, e.g. in the coating of window frames, chairs and tables,
require high levels of productivity, that is, fast drying and sandability. This is all
the more important since wood and furniture finishes are always multi-coat systems,
which consist of at least a primer and a topcoat. Achieving the earliest possible
sandability of the primer and/or primer surfacer is equally important for achieving
rapid stackability of the top-coated parts.
Substrate-specific requirements
Woods differ in their color, grain, pore structure, density and the type and content
of specific constituents. The various wood-based materials such as chipboard, hard-
board, medium-density fiberboard (MDF) and plywood, which are also available
with veneer or laminated film finishes, differ widely in their surface structures.
Exact knowledge of a substrate allows selection of a polyurethane system which
ensures optimum coating results. In order to achieve special surface effects and
qualities, various coatings can be combined in the overall coating system. In con-
trast to nitrocellulose coatings, unsaturated polyesters or UV-curing systems, poly-
urethane coatings usually present no problems in terms of compatibility, overcoat-
ability and intercoat adhesion.
Application-specific requirements and standards
Depending on their subsequent use, coated wood and furniture components have
to comply with a variety of requirements. For example, the coating on a dining
Figure 5.2: Industrial wood and furniture coatings, world production by region, 2005;

table is expected to have much better

resistance properties than the coating
used on a bedroom wardrobe. Coat-
ings for window frames must satisfy
different requirements compared to
parquet sealers. Generally recognized
and widely used property profiles for
furniture coatings are contained in these
standards:
Figure 5.3: Testing the mechanical resistance • EN 12 720 (European standard)
of parquet coatings under actual conditions • A 1605 (Austria)
• Möbelfakta (Scandinavia)
Among the requirements specified by these standards is resistance to household
cleaning agents, scratching and abrasion. European standard EN 927 (parts 1–6)
specifically describes the requirements made of wood coatings for outdoor applica-
tions. Sealers for high-durability parquet flooring and wood floors are covered by
German standards DIN 18 356 and 18 032. In addition to these, large manufacturers
have often defined their own in-house standards. In particular, the standards set by
Swedish furniture group Ikea have gained considerable importance.
Technological and environmental requirements
Depending on the shape of the components to be coated, the specific benefits of
various application processes can be exploited. Conventional spraying techniques
(compressed air, airless, airmix) are widely used, as are the corresponding electro-
static variants. Curtain coating has proved ideal for large flat components. Flow and
roller coating are also used. The coatings are dried at room temperature or, to accel-
erate drying, are force-dried at temperatures up to 70 °C in flat, vertical or rack dryers.
These techniques can be used for both solventborne and environmentally friendly
waterborne one- and two-component polyurethane systems. The significance of
waterborne systems is growing as they satisfy the European Union’s VOC Directive
and existing national environmental legislation.
5.1.2 Polyisocyanates for wood and furniture coatings

The principal requirements which must be satisfied by polyisocyanates for wood
and furniture coatings are:
• very low monomeric diisocyanante content, preferably below 0.5 %
• excellent compatibility
• stability also at low concentrations
A wide range of polyisocyanates with different structures and qualities enables
selection of the right substance or combination to satisfy the requirements made of
wood and furniture coatings. Yellowing resistance is the main requirement. For

Wood coating 93
non-yellowing coatings, HDI-based polyisocyanates are required, usually isocyan-

urates or biurets. The coating properties yielded by the various polyisocyanates are
shown in Table 5.1 (page 94).
5.1.3 Solventborne two-component polyurethane coatings

Alkyd resin combinations
Of all the polyurethane systems, combinations of hydroxyfunctional alkyd resins
(alkyd polyols) with aromatic polyisocyanates have come to dominate in wood and
furniture coating. The fundamental technical developments date back to the 1960s
and 1970s, with the successful introduction of these products in Italy.
Short-oil, highly condensed alkyd resins with an oil content of less than 45 % are
the basis for manufacturing these systems. They are normally modified with soya,
peanut, olive or coconut oil fatty acids. Mixtures of these fatty acids with castor oil
or its fatty acid are often used to improve pot life and resistance properties.
The solids content of the resins in their supply form vary between 50 and 75 %.
Due to the relatively high molar masses, a solids content of 50 to 55 % is preferred.
The hydroxyl content is between 2.5 and 4.0 %, calculated on the solid resin. In
order to shorten the drying time and increase the solids content, small amounts of
high viscosity cellulose nitrate are often added. This also improves the pore-filling
properties of the coating.
Crosslinking reaction
These resins are crosslinked with TDI isocyanurates such as “Desmodur IL 1451”
mixed with a TDI adduct such as “Desmodur L” to improve elasticity and increase
the pot life. The mixing ratios of these two polyisocyanates in the hardener solution
vary between 75:25 for primers to 40:60 for topcoats. To make these two-compo-
nent coatings easy to apply, whole-number mixing ratios between the A component
and the polyisocyanate hardeners are the target. For this, the hardener is thinned to
a solids content of between 30 and 50 %. The mixing ratio of A to B component
varies between 1:1 and 4:1, depending on the hydroxyl content and the required
crosslinking degree. The application viscosity is set using suitable thinners, mainly
mixtures of esters and ketones. Particularly in Asia, xylene and toluene are also
used. The resultant coatings have a solids content of 25 to 38 %.
The use of TDI polyisocyanate hardeners and the addition of cellulose nitrate mean
that the coatings yellow on exposure to light. However, this behavior is tolerated as
the woods are often dark or dark-stained. In addition, furniture is usually not exposed
to direct sunlight, but only to sunlight filtered through windows. Yellowing of the
coating is accepted far more readily than fading of the wood. If the yellowing is
unattractive, e.g. on pale woods, the pure TDI hardener combination can be replaced
with hardeners based on HDI/TDI isocyanurate such as “Desmodur HL”.

94
VIN Meier_eng.indb 94
Table 5.1: Properties of polyisocyanates
HDI HDI TDI HDI/TDI TDI TDI Trend
isocyanurate biuret adduct isocyanurate isocyanurate isocyanurate
low viscosity high viscosity
Viscosity increasing
Reactivity increasing
Sandability increasing
Pot life longer
Flexibility increasing
Compatibility
with
NC increasing
CAB increasing
High viscosity
Applications for polyurethane coatings
alkyd resin increasing
Yellowing
HDI HDI TDI HDI/TDI TDI TDI Trend
isocyanurate biuret adduct isocyanurate isocyanurate isocyanurate
low viscosity high viscosity
Yellowing decreasing
24.10.2007 17:30:41 Uhr

Wood coating 95
The advantageous properties of these coatings are:

• high reactivity
• early sandability
• resistance to household cleaning agents
• good pore-filling properties
• outstanding grain wetting
• high mechanical strength
Above all, these coatings are inexpensive which is why they are widely used to
coat chairs, tables, furniture for living rooms, bedrooms and dining rooms, frames
and battens.
Acrylic resin combinations
In Central Europe, polyurethane systems based on hydroxyfunctional polyacrylates
crosslinked with HDI biurets such as “Desmodur N 75” are widely used for furni-
ture coating. Most of the binders are pure acrylates. Less expensive variants contain
styrene. However, these products have poorer compatibility with cellulose aceto-
butyrate (CAB) or cellulose acetopropionate (CAP). The hydroxyl content of the
polyacrylic resins varies between 1 to 2 %, calculated on the solid resin.
Formulation variants
Drying, hardening, solids content and pore-filling properties can be customized via
the combination of the polyacrylate with CAB in mixing ratios of 85:15 to 40:60,
calculated on solids. This made it possible to formulate adequately fast-drying
furniture coatings using “Desmodur N”. Coatings on this basis satisfy the high
requirements usually specified by manufacturers of high-quality kitchens, office
furniture and home furniture. Two-component polyurethane coatings based on such
polyacrylate/aliphatic polyisocyanates make it possible to provide long post-sale
warranties, since a color match is also ensured if a range of furniture is extended
at a later date. Coatings based on these binders comply with the requirements of
EN 12 720, whether in the form of pigmented, clear or special effect coatings.
In the case of dark or dark-stained woods and when using dark-colored coatings,
the expensive cellulose acetobutyrate is often replaced by small amounts of the less
expensive higher molecular cellulose nitrate. A long pot life of 1 to 2 days, ease of
application, combined with a short dust-dry time, good through-curing and outstand-
ing end properties have made such two-component polyurethane coatings the uni-
versal coating for high-quality furniture finishes. However, the high solvent content
of up to 75 % restricts the future importance of these systems in the face of more
environmentally friendly alternatives such as waterborne and UV-curing coatings.
A less expensive variant, obtained by replacing pure aliphatic polyisocyanates such
as “Desmodur N” with partially aromatic types such as “Desmodur HL”, has
achieved considerable market significance. Although this combination does not

yield the same usually high yellowing resistance, the quality is sufficient for a large
number of applications, e.g. in the field of home furnishings.
Polyester/polyether combinations
Highly crosslinked wood coatings with outstanding resistance to abrasion and chem-
icals can be formulated using highly branched hydroxyl-bearing polyesters and poly-
ethers. The normally high hydroxyl content of these resins, which can be between 5
and 12 % (calculated on the solid resin) requires crosslinking with reactive polyiso-
cyanates like the “Desmodur L” products. Such combinations yield parquet and stair
coatings with outstanding wear resistance. These systems have also proved ideal as
a barrier coating for tropical woods with a high content of phenolic substances, e.g.
rosewood, which are to be coated with radically curing binders. Without the barrier
coating, the radical crosslinking reaction would be disrupted by chain termination.
High solids
In the field of industrial wood coatings, in contrast to the coating of metals, high
solids systems have not been widely used for satisfying emission requirements. The
main reason is the slower curing speed of high solids systems which can be com-
pensated only to a small extent by a higher curing temperature. Faster curing sys-
tems based on low viscosity polyaspartics, aldimines and/or ketimines also enable
reduction of the solvent content of ready-to-use two-component polyurethane coat-
ings for industrial wood finishing. This principle can be used to formulate high
solids wood coatings with a solids content of up to 70 %.
5.1.4 Moisture-curing coatings

In the wood coating industry, one-component polyurethane systems are used as mois-
ture-curing formulations. For reactivity reasons, only TDI prepolymers such as “Des-
modur E 1361” are suitable to ensure fast drying. These systems are used as sealers
for wood and parquet floors. Only PU grade solvents with a water content of less than
0.05 % can be used to formulate the coating. It must also be ensured that no com-
pounds which can react with isocyanates are incorporated into the coating via other
constituents such as additives (matting agents, etc.). Coatings formulated in accor-
dance with the principles described above are easy to apply. The cured paint films
are characterized by outstanding properties, especially high abrasion resistance.
5.1.5 Urethane-modified oil and alkyd resin coatings

Remarkable property variations can be achieved by using urethane to modify oils or
long-oil alkyds which dry by oxidation. The positive properties of oils and long-oil
alkyds:
• solubility in mineral spirit
• storage stability
• pigment wetting

Wood coating 97
are enhanced by:

• faster drying
• greater hardness
• better elasticity and
• lower abrasion
The resistance to water and chemicals,
especially alkalis, is also improved.
Urethane-modified oils and urethane
alkyd resins are used to formulate var- Figure 5.4: UV-curing urethane acrylate
nishes and clearcoats for wood in coatings ensure long-term resistance, also
under tough conditions
indoor and outdoor applications, e.g.
wall and ceiling paneling, window frames and doors. These products are also used
for parquet coatings, clearcoats for the carpentry business and coatings for the
do-it-yourself sector.
Urethane-modified oils and resins are also suitable for the formulation of pigmented
coatings. These may be high gloss or matte and have outstanding mechanical
strength and high resistance to cleaning agents. This chemistry can also be used to
formulate primers or fillers with early sandability, referred to as fast-sanding prim-
ers, which are normally applied by brushing or rolling.
5.1.6 Radiation-curing urethane acrylate coatings

In the last 20 years, the highest growth rates have been achieved with radiation-
curing unsaturated acrylates, alongside waterborne coatings. The main applications
for such resins are furniture and paper coatings, and UV-curing printing inks. In
2005, production of wood and furniture coatings based on unsaturated acrylates
was 30,000 tons in Western Europe and about 80,000 tons worldwide. For particu-
larly high-quality applications such as the coating of highly abrasion-resistant
ready-to-lay parquet flooring, coatings based on urethane acrylates are used. These
coatings are characterized by their outstanding resistance to abrasion, toughness
combined with elasticity and, as a rule, resistance to yellowing (see Figure 5.4).
Generally, two radiation curing methods are used for these products. Of these, UV
curing has prevailed [2] over electron beam curing for wood and furniture coating
on account of the much lower capital investment required. The supply viscosity of
urethane acrylates is set using reactive thinners such as di- or tripropylene glycol
diacrylate. Modern products are free of reactive thinners. The application viscosity
is also set using reactive thinners. The photoinitiators needed to trigger the curing
reaction and all other additives required must be tailored to the formulation and
application conditions [3].

Thanks to their lower price, unsaturated urethane acrylates based on TDI are ideal
for use in UV-curing coatings for cork tiles. These are used as an alternative to
parquet and as wall and ceiling paneling.
5.1.7 Waterborne polyurethane coatings
Waterborne polyurethane systems also offer many options for favorably influencing
the technical properties of wood coatings. It was only as recently as 1975 that
urethane-modified, medium-oil, water-reducible alkyd resins were first used in any
significant quantity to formulate wood varnishes.
Since the mid-1970s, polyurethane dispersions have been used increasingly in the
formulation of wood and furniture coatings. The reasons for this are not only
environmental as the result of the reduced solvent requirement but also economic
since there is no need for thermal waste gas incineration. These waterborne systems
are used mainly as trade and do-it-yourself coatings for parquet. In Germany,
waterborne coatings now account for more than 70 % of the systems used in this
area of application.
Waterborne one-component polyurethane coatings
One-component polyurethane dispersions have now achieved considerable market
importance. These dispersions, usually based on the aliphatic diisocyanates IPDI
and H12MDI, are characterized by their high level of toughness with elasticity,
resistance to chemicals and weather stability. They are therefore suitable as, for
example, modifying resins for polyacrylate dispersions, above all to improve the
mechanical properties. Such combinations comply with the requirements of EN927.
These products are used in the industrial coating of wooden window frames, in
parquet coatings, and in furniture coatings. Polyurethane/polyacrylate dispersions
based on aliphatic or aromatic isocyanates are being used increasingly for parquet
coating. In addition, pure aliphatic polyurethane dispersions are often used, in
particular for sealing light woods such as maple or beech. Properties such as abra-
sion and scratch resistance can be improved further by the addition of nanoscale
fillers, usually based on inorganic materials.
The N-methylpyrrolidone (NMP) still found in many polyurethane dispersions is
now viewed as a critical issue. In the mid term, this will lead to replacement of the
dispersions presently available on the market with new NMP-free dispersions, par-
ticularly in Europe. Coatings with a low or no co-solvent content can be formulated
using polyurethane or polyurethane/polyacrylate dispersions produced by the acetone
process. Of particular benefit is the low solvent content of the ready-to-use coatings.
Waterborne two-component polyurethane coatings
Waterborne two-component polyurethane coatings were first used in the wood and
furniture industry as pigmented systems for coating kitchen and office furniture.

Wood coating 99
Hydroxyl-bearing acrylates and hydroxyl-terminated polyurethane dispersions (or

combinations thereof) are crosslinked with hydrophilically modified aliphatic poly-
isocyanates. The use of flexibilizing HDI-based hardeners makes it possible to use
polyols with very high glass transition temperatures to achieve the necessary short
drying times.
The raw materials now available, both water-dispersible polyisocyantates and water-
borne polyols, are at a far more advanced stage of development than the first-gen-
eration products. Recently, for example, new polyisocyanates with improved mixing
and/or greatly enhanced resistance properties have been introduced. The recently
introduced polyols allow the formulation of waterborne wood and furniture coatings
that have the typical look and feel of solventborne polyurethane coatings [5]. A sample
formulation is shown in Table 5.2.
Table 5.2: Formulation and technical data of a semi-matte waterborne two-component
furniture coating
Raw materials Percent
Component A:
Water 24.5
(1) “Bayhydrol XP 2651” 57.8
(2) “Byk 028” 0.5
(3) “Tego Airex 902W” 0.4
(4) “Acematt TS 100” 1.7
(5) “Hydropalat 140” 0.3
(5) “DSX 1514” *0.3
Component B:
“Bayhydur XP 2655”, 80 % in MPA
14.5
100.0
Technical data:
Viscosity: *Set flow time of Component A to
17 s / DIN 4 by adding thickener.
Component A + B approx.
38 s / DIN 4
Solids content 37 %
Pot life approx. 3 h
(1) Bayer MaterialScience, Leverkusen

(2) Byk Chemie, Wesel
(3) Degussa, Essen
(4) Degussa, Frankfurt
(5) Cognis, Düsseldorf

Waterborne two-component polyure-

thane systems are now also used for
trade-applied parquet sealers. A water-
borne two-component polyurethane
formulation ideally fulfils the require-
ment for a highly durable and odor-free
system. Compared to coatings based on
non-chemically crosslinked one-com-
ponent systems, the waterborne formu-
lations display greatly improved resis-
Figure 5.5: Waterborne two-component poly-
urethane coatings are highly resistant to food- tance to chemicals and mechanical
stuffs, beverages and household chemicals strength [4].
Pine, primarily Nordic pine, is the wood most commonly used in the manufacture of
window frames. Particularly at the knotholes left by a tree’s many branches, discol-
oration may occur as the result of phenolic constituents leaching from the wood and
adhesion may be poor. Highly crosslinked waterborne two-component polyurethane
systems based on acrylic resins have proved ideal as barrier coatings.
5.1.8 Waterborne UV-curing one-component polyurethane coatings
Since the mid-1990s, the industrial wood and furniture coating market has been
showing considerable interest in UV-curing dispersions. Particularly in the current
phase of the introduction of European emission control standards, growth of this
Figure 5.6: Crosslinking routes for polyurethane coatings: comparison of a two-component

polyurethane coating and a waterborne UV-curing one-component polyurethane coating

Wood coating 101
technology has been dramatic. For one thing, waterborne UV-curing coatings can
be applied using all conventional methods (curtain coating, spraying, rolling) and
they allow cost-effective manufacturing due to the fast crosslinking reaction. A
further benefit is found in the outstanding property profile of the coatings. They are
resistant to abrasion, scratching and chemicals and comply with EN 12720. In short,
application and properties are virtually identical to those of solventborne two-com-
ponent polyurethane coatings, but are coupled with extremely low emissions.
Important in this context is that many of UV-curing dispersions are polyurethane
dispersions. The cured paint films are thus similar to conventional two-component
polyurethane coatings in chemical terms as well. Similar raw materials are used to
achieve much the same end result as that yielded by solventborne two-component
polyurethane coatings. However, very different routes are followed (Figure 5.6).
In a UV-curing coating, in contrast to a two-component coating, the time-determin-
ing polyol/isocyanate reaction already takes place during manufacture of the poly-
urethane dispersion. All that is needed for the coating to crosslink on the substrate
is a few seconds of exposure to UV light. It is obvious that these systems allow a
considerably faster process speed.
A further advantage is the recyclability of the coatings by, for example, ultrafiltra-
tion or application in a wet-on-wet spray booth. This makes spray application an
economically viable option even for shaped components. For this reason, one
important field of application for these coatings is on chairs and other furniture and
stairs. The drying times can be shortened further by using special dryers to acceler-
ate flash-off of the water before UV-curing. Newly developed dryers have been
designed particularly for drying waterborne coatings. The various systems use
infrared or microwave radiation or apply a pre-dried air current to the substrate. An
interesting new use of waterborne UV-curing coatings, on account of their high
weather stability, is in the industrial coating of wooden window frames.
5.1.9 Outlook
The increased market share of waterborne polyurethane coatings – in Europe driven
mainly by strict solvent emission legislation – has resulted in an enormous variety
of raw materials. This in turn has driven the development of waterborne polyure-
thane systems, resulting in a large number of solutions that are of interest not only
in ecological terms. UV-curing waterborne coatings especially are seeing strong
growth worldwide, as application is much faster and overspray losses lower than
is the case with conventional solventborne systems.
The success of modern waterborne polyurethane coatings is foreseeable. In Europe,
this development will be at the cost of solventborne products, including equivalent
polyurethane systems. In parallel, the global market for solventborne two-component
polyurethane coatings continues to grow, a situation which is not expected to change
in the foreseeable future. The reason for this is the rapid growth in strong polyure-

thane coating markets such as the People’s Republic of China. The competition with
other solventborne systems will most likely result in polyurethane coatings continu-
ing to gain greater global importance in the field of wood and furniture coating.
5.2 Metal coating

The trend towards enhanced surface protection and an attractive appearance has
resulted in the widespread use of polyurethane coating raw materials in industrial
applications. This is valid for solventborne, waterborne and powder coating sys-
tems. Polyurethane coatings have become particularly well established in general
industrial coating and in coil and can coating.
5.2.1 General industrial coating
The term general industrial coating is used to describe the industrial OEM applica-
tion of coatings on various metal substrates, e.g. construction, agricultural and tool
machines, vehicle chassis and accessories, and other industrial consumer goods.
Typical substrates are chromated aluminum, untreated and zinc-galvanized or phos-
phated steel plate.
Economy, quality and environmental compatibility govern the requirements made
of these coatings. An industrial coating is considered economical if it can be applied
easily and efficiently, dries rapidly, and thus quickly achieves the strength necessary
for assembly and packaging. Other criteria are the early achievement of water
resistance, good anti-corrosion properties, high abrasion resistance and good opti-
cal properties.
Depending on the application, one- and two-component polyurethane coatings are
available for air-drying and for baking. Reactive two-component polyurethane coat-
ings are used mainly for high-quality industrial goods whose size and structure
make the use of one-component baking coatings impossible.
Figure 5.7: Coating systems used in general industrial coating in Europe, 2004,
total: 2.9 million tons [6]

Metal coating 103
Industrially coated goods are now found in virtually all segments of the consumer
and capital goods industries. Among the largest users of industrial coatings are the
transportation, machine engineering, construction, and household appliances seg-
ments. With European legislators seeking to reduce solvent emissions from coating
processes by means of laws such as the Solvent Emissions Directive (SED), and the
Decopaint Directive (DPD), there is a significant trend toward the use of more
environmentally friendly coating systems, particularly in the field of general indus-
trial coating. High solids coatings, waterborne coatings, powder coatings, and radi-
ation-curing systems are becoming increasingly important (Figure 5.7). Since qual-
ity requirements are also developing steadily, above-average growth of polyurethane
coatings, especially waterborne polyurethane coatings, can be anticipated.
5.2.1.1 Technical aspects of polyurethane coatings
At present, alkyd coatings are still the standard systems in many general industrial
coating applications. A first step in the introduction of polyurethanes in this field
was the modification of alkyd resins with polyisocyanates. On account of their good
property profile and their application efficiency, two-component polyurethane coat-
ings have now become firm favorites for protecting high-quality industrial goods.
Variants
Owing to the wide variability of their components (polyisocyanates and polyol
polymers), polyurethanes coatings can be used in many applications. Combinations
of aromatic polyisocyanates such as TDI adducts and trimers with polyols are
particularly suitable for use as primers and one-coat finishes. These coatings dry
quickly and the resulting paint films have good resistance to chemicals. However,
the coatings crosslinked with aromatic isocyanates show a distinct tendency to
yellowing, which thus limits their use in pale-colored topcoats. Aliphatic polyiso-
cyanates are more versatile and can be used to formulate primers, one-coat finishes
and topcoats. These coatings have good resistance to weathering, chemicals and
yellowing. HDI-based polyisocyanates flexibilize the paint films, whereas IPDI
polyisocyanates exhibit rapid physical drying. The properties of the paint films are
governed largely by the polyol component. The resin type and hydroxyl content
influence the gloss, adhesion and resistance properties of such coatings.
Primers are usually epoxy resin systems or two-component polyurethane formu-
lations (mainly polyester-based). These provide good corrosion protection com-
bined with good adhesion – especially at low hydroxyl contents. When using
polyacrylates in the formulation of primers, these often have a hydroxyl content
of 1.3 to 3 %. If better weather stability is required, products with a hydroxyl
content of about 4 % must be used, thereby yielding a higher crosslinking density.
A hydroxyl content of more than 5 % produces good chemical resistance up to
easy-clean properties.

Solventborne two-component polyurethane coatings normally have a solids content

of 55 to 60 % by weight on application. It is possible to formulate coatings with a
solids content of 70 to 75 % (high solids) using low viscosity aliphatic polyisocya-
nates combined with suitable polyols. An even higher solids content can be achieved
if all or part of the binder in the formulation is a low viscosity, aminofunctional
product. Aspartates, aldimines and ketimines are particularly suitable. The high
reactivity and very low product viscosities of aminofunctional binders ideally
complement each other.
Table 5.3: Formulation of a solventborne two-component white polyurethane coating for
industrial applications
Constituents Products
Component 1 Polyol “Desmophen A 170”
Mill base Anti-settling agent “Bentone 38”
Pigment “Tronox R-KB-4”
Solvent Methoxypropyl acetate (MPA)/
butyl acetate (BA)
Let-down Polyol “Desmophen A 170”
Flow promoter “Baysilone Paint Additive OL 31”
Catalyst Dibutyltin dilaurate
Solvent Methoxypropyl acetate/butyl acetate
Component 2 Polyisocyanate “Desmodur N 75”
Table 5.4: Comparison of a solventborne two-component polyurethane industrial coating

and an alkyd resin industrial coating
Two-component One-component
polyurethane coating alkyd coating
Solids content at spray viscosity 63 –65 44 – 46
(25 s /DIN cup 4 mm) [%]
Pot life 8h 3 – 6 months
Drying [h]
– dust-dry approx. 1 approx. 1.5
– tack-free approx. 5–6 approx. 4.5 –5
Gloss 20° 85–90 80 – 85
Pendulum hardness after 7 days 110 –120 25– 30
at RT [s]
Elasticity, Erichsen indentation [mm] 6–7 6–7
Solvent resistance after 7 days at RT* 1 5
Weather stability* 1 4
* 1 = very good, 4 = satisfactory, 5 = poor

Metal coating 105
Properties
The requirements made of coatings
used for general industrial applications
vary as widely as the range of possible
applications. In the case of two-compo-
nent polyurethane coatings, it has been
found that systems which are suitable
for automotive refinishing can also be
used in many general industrial applica-
tions. They meet many of the require-
ments specified. Table 5.3 shows the Figure 5.8: Polyurethane coating for
formulation of a typical white coating extreme conditions
for industrial applications.
The main prerequisites for a uniform appearance and property profile of the paint
films are homogeneous mixing of the components and a suitable application pro-
cess. Depending on the specification, coatings of this type can be dried under
conditions ranging from room temperature to baking. Table 5.4 compares two
industrial coatings, one based on polyurethane and the other on an alkyd resin. It
clearly shows the characteristic advantages of polyurethane coatings in terms of
hardness, resistance to solvents and weather stability.
Applications
Large objects such as construction and agricultural machinery are normally coated
with air-drying systems. Smaller objects such as wheels and window frame profiles
can be baked on-line, e.g. for 15 to 20 minutes at 130 °C.
Air-drying, solventborne one-component polyurethane coatings, usually applied in
thick coats, provide resistance to abrasion and absorb noise and heat. They are
formulated on the basis of moisture-curing, aromatic or aliphatic polyisocyanates.
Solventborne one-component polyurethane baking coatings also have specific
advantages. These combinations of blocked polyisocyanates with polyester and
polyacrylate polyols are preferred to polyester/melamine coatings, above all because
of their superior mechanical and chemical resistance properties. This has led to the
addition of blocked polyisocyanates to polyester/melamine coatings to improve
their resistance properties or film strength. Such coatings are applied by spraying
and crosslinked at the temperature needed to split off the blocking agent. Examples
of applications for one-component polyurethane baking coatings are household
appliances and components for bicycles and cars.
5.2.1.2 Waterborne polyurethane coatings
In order to effectively reduce solvent emissions during coating, low-solvent and
solvent-free binders have been developed since the beginning of the 1990s for

industrial coating applications. The driving force here is the constant tightening of
environmental legislation in Europe and North America. Following initial success
with water-reducible alkyd and polyester coatings, which have the disadvantage of
a relatively high co-solvent content, waterborne polyurethane systems, both air-
drying and baking, now hold a significant market share.
Waterborne one-component polyurethane coatings
Compared with other air-drying coatings, air-drying one-component coatings based
on polyurethane dispersions are characterized by their high mechanical resistance
properties such as abrasion resistance. The reason lies in their chemical structure
comprising urethane and urea groups. This is why they are also used as modifiers
in other waterborne coating systems, e.g. acrylate dispersions.
The film properties can be improved further by intramolecular or intermolecular
crosslinking. This is achieved in, for example, polyester/alkyd polyurethane disper-
sions by oxidative drying under the catalytic influence of metal salts. These disper-
sions yield coatings with particularly good resistance to hydrolysis, good pigment
wetting properties and high gloss (Table 5.5). Key applications for such coatings
are in the production of automotive accessories and components for agricultural
and construction machinery.
Waterborne one-component polyurethane baking systems are already widely used
in industrial coating. Hydrophilic or hydrophobic, blocked polyisocyanates (“Bay-
hydur BL” or “Desmodur BL”) are used as the crosslinkers. Polyesters, acrylates
or epoxy resins are used as the hydroxyfunctional polyols. The emulsifying effect
of the polyol dispersions makes it possible to use hydrophobic polyisocyanates, for
example, in electrodeposition coating processes.
Table 5.5: Properties of an air-drying waterborne one-component polyurethane coating in
comparison with a solventborne one-component alkyd resin coating
PES/polyurethane Solventborne
dispersion one-component
(dried in air or by alkyd resin coating
oxidation)
Solids content at spray viscosity 50–55 44–46
(25 s /DIN cup 4 mm) [%]
Drying at RT [h] 4–6 4–6
Gloss 20° / 60° approx. 85/90 approx. 80/85
Pendulum hardness after 7 days 90 –110 30–40
at RT [s]
Water resistance* 1 2
Weather stability* 2 4
* 1 = very good, 2 = good, 4 = satisfactory

Metal coating 107
Waterborne one-component polyurethane systems can be applied continuously or

discontinuously by spraying, dipping (including electrodeposition), flow coating
or roller coating. The necessary application rate and the substrate dimensions are
the main factors in selecting the application technique. The paint films yielded by
air-drying, waterborne one-component polyurethane systems can already be han-
dled a few hours after application. However, they do not achieve their end proper-
ties until about two weeks later. Force-drying at 60 to 80 °C accelerates this reaction.
In the case of polyurethane baking systems, the crosslinking temperature and time
are dependent on the blocking agent. Baking usually takes 30 minutes or less at a
temperature of 150 to 180 °C.
Waterborne two-component polyurethane coatings
The goal of development in the field of waterborne coatings was to reproduce the
good properties of solventborne two-component polyurethane systems in water-
borne systems. As already described, the mixing and dispersion stability of the
hydrophilically modified polyisocyanates is of particular importance in waterborne
formulations. To further improve the general resistance properties, low viscosity
hydrophobic polyisocyanates can be used instead or in part (Table 5.6). By combin-
ing hydrophobic and hydrophilic polyisocyanates, the results can be optimized with
respect to the mixing of the hardener and the resultant film quality. To compensate
for the side reaction between the polyisocyanate and water, it is usual to work with
a surplus of polyisocyanate crosslinker, equivalent to a molar ratio (NCO/OH) of
up to 1.5:1. The pot life of waterborne two-component polyurethane coating formu-
lations is limited. Depending on the resin type, it varies between three and five
hours. Individual factors which govern the pot life are the functional group content,
the stoichiometry and the pH of the ready-to-use coating.
After thorough mixing of the components, waterborne two-component polyurethane
coatings are applied using standard spraying techniques. Waterborne two-component
Table 5.6: Composition of a waterborne two-component polyurethane topcoat (white)
Constituents Products
Component 1 Polyol dispersion “Bayhydrol”
Mill base Dispersion aid “Surfynol 104 BC”
Pigment “Tronox R-KB-4”
Water
Let-down Polyol dispersion “Bayhydrol”
Thickener “Borchigel PW 25”
Flow promoter “Baysilone Paint Additive 3468”
Component 2 Polyisocyanate “Bayhydur 3100”
and/or “Desmodur N 3600”
Organic solvent E.g. methoxypropylacetate

polyurethane topcoats yield a high standard of quality, which corresponds to or even

exceeds that of solventborne polyurethane coatings. Of particular note is the out-
standing weather stability achieved using polyacrylate polyols (Florida weathering:
around 90 % gloss retention after two years), as well as good optical properties,
chemical resistance and hardness. It is also possible to produce relatively thick dry
films. In recent years, binders have been developed which are characterized by, for
example, particularly fast drying and a comparatively long pot life. Others make it
possible to produce certain effects (e.g. textured coatings).
Thanks to these advantages, waterborne two-component polyurethane topcoats
have a broad spectrum of use in industrial coating. Examples of their application
include construction and agricultural machinery, vehicle chassis and components,
wall elements, doors and window frames, industrial machinery, containers, shelf
units and steel furniture.v
5.2.2 Coil coating
Coil coating is a continuous process used to apply an organic coating on steel or
aluminum coils [7]. This process includes the cleaning and chemical pretreatment of
the metal surface followed by the single or multiple roller application of liquid
coatings on either one side or both sides of the substrate. Heat is used for film
formation. The process can also be used to apply powder coatings or to laminate
the coils with plastic film (Figure 5.9).
Substrate: Steel, zinc-galvanized steel, aluminum

Coil width: Max. 1,900 mm (steel), 2,700 mm (aluminum)
Coil thickness: Approx. 0.2–3.0 mm
Coil speed: Approx. 10–200 m/min
Film thickness: Approx. 2–200 µm
Drying: <1 min at approx. 200 – 260 °C object temperature
Figure 5.9: Flow chart and characteristics of the coil coating process [7]

Metal coating 109
Because a coil coating unit is a closed system that is equipped with thermal waste
gas incineration, it is both economical and environmentally friendly. Working by
the motto finish first, fabricate later, coil coating yields a material with a precoated
surface (Figure 5.10), which can be supplied to the metal-processing industry for
cutting, shaping and processing as required.
Market evaluation
The introduction of this precoated material in manufacturing represented an impor-
tant change. Subsequent processing was simplified because post-manufacture coat-
ing was no longer necessary. The outsourcing of production processes in many
industrial sectors has given a significant boost to coil coating in recent years.
In 2005, approximately 18 million tons of steel and aluminum were coil coated
worldwide, with Europe, the Americas (NAFTA + South America) and ROW (Asia,
Africa, Australia) each accounting for approximately one third. In Europe, this
volume corresponds to nearly 1.4 billion square meters of coil coated metal (Figure
5.11, page 110). Considerable growth of the market for coil coated material is also
expected in the coming years.
The most important areas of application for coil coated materials (Figure 5.12, page
110) are construction (cladding and roofing), transportation (automotive and large
vehicle engineering, mobile homes), household appliances (white goods) and gen-
eral engineering.
Coating systems
Worldwide, approximately 550,000 tons of coating materials are applied by the
coil coating process. In 2005, about 170,000 tons of coatings were used in Europe
alone (Figure 5.13, page 110). Most of this volume is accounted for by solventborne
coating systems. The use of waterborne systems is difficult on account of waste
gas incineration and the problems associated with applying powder coatings to a
Figure 5.10: Schematic representation of coil-coated metal [7]

Figure 5.11: Deliveries of coil coated steel and aluminum in Europe, 2005 [8]
Figure 5.12: Uses of coil coated metal in Europe, 2005, total: 1,370 million m2 [8]
Figure 5.13: Coil coating consumption in Europe, 2005, total: approx. 170,000 tons [8]

Metal coating 111
fast-moving metal coil have not yet been solved. The use of radiation-curing coat-
ings has been under investigation for some time, but no industrial application has
been found as yet.
Due to the growing demands made of the coating material in terms of flexibility
and resistance properties, polyurethane systems have posted above-average growth
rates in recent years and already rank third (with 11%) after polyester/melamine
systems and PVC plastisols in the field of topcoats. In the area of primers, their
share is estimated to be significantly higher. Table 5.7 shows typical properties of
the coating systems used for coil coating.
Polyester/melamine systems, which account for the largest share of the coating
materials in terms of volume, are characterized by their good resistance and shap-
ing properties. They are used for primers, topcoats and backing coatings.
Polyurethane systems are characterized by an excellent balance between hardness
and flexibility, outstanding resistance to chemicals and good weather stability. They
are preferred for applications requiring extremely good shaping properties (suit-
ability for deep drawing) and resistance properties. They are used for primers,
topcoats and backing coats.
PVC plastisols are used exclusively in the formulation of topcoats. They can be
applied in very high film thicknesses, yielding good corrosion resistance in aggres-
sive atmospheres and very good shaping properties. However, these materials are
sensitive to strong UV radiation and a high thermal load.
PVDF systems are also used exclusively for topcoats. They display high UV resis-
tance and very low chalking. They are characterized by the longest durability in
outdoor applications.
On account of their inadequate weather stability, epoxy resin systems can only be used
for backing coats and primers. They are characterized by good adhesion on metal and
good corrosion resistance, but show certain disadvantages in terms of flexibility.
Table 5.7: Comparison of coil coating systems [9]

Coating type Thickness Balance of Chemical Weather
range (µm) hardness resistince stability
and flexibility
Polyester / melamine 15 –30 + + +
Polyurethane 15 –50 ++ ++ +
PVC plastisol 100 –200 + ++ +
PVDF 20 –25 + ++ ++
Epoxy resin 5–15 – ++ –
++ excellent, + good, – poor

Polyurethane systems
The standard polyurethane systems used in coil coating are combinations of
blocked polyisocyanates and hydroxyfunctional polymers, usually saturated poly-
esters. The ratio of binder to hardener is usually chosen to yield an equivalent ratio
of hydroxyl-bearing and blocked polyisocyanate groups. Depending on the appli-
cation, the coatings also contain fillers, pigments and additives. Polyurethane sys-
tems formulated in this way are stable at room temperature and only cure after
application on the substrate and on exposure to the necessary baking temperature
(PMT = peak metal temperature). After the blocking agent has split off, the poly-
isocyanate groups react with the hydroxyl groups to form a high molecular poly-
urethane network.
It is a special characteristic of the polyurethane systems that raw material and coat-
ing manufacturers can custom-formulate coating systems by specific choice of the
components. This modular principle permits coating materials with a wide property
spectrum that is unsurpassed.
The choice of blocked polyisocyanate affects the reactivity of the coating system
and the properties of the resulting polyurethane paint film, such as a balance between
hardness and flexibility and resistance properties. The reactivity of the blocked
polyisocyanates depends mainly on the blocking agent, but can be increased by the
use of a suitable catalyst, such as DBTL, which lowers the baking temperature.
While aromatic blocked polyisocyanates are mainly used for the production of
backing coats and primers on account of their low resistance to light, the lightfast
aliphatic polyisocyanates can also be used for topcoats. Polyisocyanates based
on linear aliphatic diisocyanates such as HDI, e.g. “Desmodur BL 3175” are
Figure 5.14: Shaping properties of polyurethane coil coatings [9]

Metal coating 113
characterized mainly by their low viscosity and yield paint films with high resis-
tance properties and very high elasticity. Products based on cycloaliphatic diiso-
cyanates such as IPDI, e.g. “Desmodur BL 4265“ or H12MDI, range from highly
viscous to solid and yield tough but flexible coatings with particularly good resis-
tance to chemicals and abrasion. A wide range of hydroxyfunctional polyesters are
available, e.g. the “Desmophen T” product line. The typical hydroxyl contents are
reflected in OH numbers between 5 and 100. The molar masses are between 3,000
and 30,000 g/mol. The ratio of aliphatic and aromatic components can also be
varied within wide boundaries. The excellent balance of hardness and flexibility in
polyurethane coatings is also demonstrated in Figure 5.14.
The superior flexibility of polyurethane coatings compared to polyester/melamine
systems can be attributed to the chemical structure of the hardener used. Blocked
polyisocyanates have a relatively uniform functionality of about three and yield a
largely homogeneous network structure while forming hard and soft segments. In
the case of melamine hardeners, a self-crosslinking reaction takes place in addition
to the desired reaction with the hydroxyfunctional polyester, as a result of which
clusters develop which have an adverse effect on the flexibility (Figure 5.15).
Figure 5.15: Idealized network structure of polyurethane coil coatings [9]

Table 5.8 shows typical properties of polyurethane coatings and the resulting fields
of application. Polyester/melamine or epoxy resin systems are normally used for
backing coats. Polyurethane systems are preferred for the production of sandwich
Table 5.8: Properties of polyurethane coil coatings [9]
Properties Especially important for:
Corrosion resistance All applications (primers)
Overcoatability All applications (universal primers)
Balance between hardness and flexibility, low All applications (primers,
thermal cracking topcoats)
High-build coatings Construction and automotive
(primers, topcoats)
Chemical resistance (hydrolysis, chemicals, spot- Appliances and general engineer-
ting) ing (topcoats)
Weather stability Construction (topcoats)
Abrasion resistance Construction (topcoats)
Printability Automotive (topcoats)
Foam adhesion, gluability All applications (backing coats)
Figure 5.16 a to d: Typical applications of polyurethane-coated coils [9]

Metal coating 115
panels for the construction and household appliance industries, because they form
an outstanding bond with rigid polyurethane foams.
Polyurethane primers are used where high requirements are made in terms of flex-
ibility, adhesion and corrosion protection and they are suitable as so-called univer-
sal primers. These coating materials can be applied to nearly all substrates (cold-
rolled steel, electrolytically and hot-dip galvanized steel, galfan, galvalume, alu-
minum) and can be overcoated with a variety of topcoats based on different chem-
istries (polyurethane, polyester/melamine, PVDF systems). They are widely used
in construction, transportation and the household appliances industry.
Special combinations of blocked polyisocyanates and hydroxyfunctional epoxy
resins are used in automotive engineering for the formulation of weldable anti-cor-
rosion primers [10]. The outstanding corrosion protection properties eliminate the
need for the labor-intensive application of cavity sealing systems.
At present, the main fields of application for polyurethane topcoats are in construc-
tion (cladding and roofing), but also in the production of sun protection systems,
window frame profiles, garage doors (Figure 5.16), the automotive industry, e.g.
trucks, mobile homes, traffic signs, and the household appliance industry, e.g. white
goods, lamps and electronic equipment.
Important criteria for the use of these coatings are their excellent flexibility, out-
standing weather stability and resistance to chemicals, as well as special properties
such as overcoatability and printability. High-build polyurethane coatings are being
used increasingly as substitutes for PVC plastisols in the production of cladding
and roofing. Combination of a polyurethane-based primer and topcoat can yield a
total dry film thickness of about 80 to 100 µm. The coatings can also be modified
with polyamide powder to optimize the abrasion resistance.
Polyurethane systems have gained increasing importance as primers, topcoats and
backing coats in the coil coating industry. Their decorative, protective and other
functional properties enable their use in demanding applications in the metal-pro-
cessing industry. Above-average growth is expected to continue.
5.2.3 Can coating

Can coating is the term used for the coating of metal packagings, cans and tubes or
the sheet metal panels and coils used for their manufacture. The substrates used are
cold-rolled packaging sheet metals such as electroplated steel (white plate), chro-
mium plated steel (ECCS) and aluminum ranging in thickness from 0.2 to 0.5 mm.
One-component baking systems are the preferred coatings and are applied by roll-
er. Interior coatings for two-piece beverage cans are applied by spraying[11]. These
systems are baked for ten to twelve minutes at temperatures ranging from 180 to
200 °C. Continuous high-performance plants are used for the process. Interior can

coatings (golden varnishes) differ from the basecoats (stamping paints) and
clearcoats (silver varnishes) for exterior can coatings (Figure 5.17). The dry film
thicknesses are generally 13 g/m² or 12 µm at the most.
Sheet metal packagings are used in various forms for receiving, transporting and
storing various fillings, primarily foodstuffs (food, luxury food, animal food), but
also chemical products. Much of this packaging is produced from pre-coated sheets
using cutting, soldering, welding, stamping and other shaping processes, such as
deep and stretch drawing. Coil coated metal is processed to a lesser extent. Packag-
ing produced by this resource-kind process can be recycled after use.
Metal packaging has been divided into the following categories corresponding to
its use [12, 13]:
• Beer and beverage
• Food cans
• Aerosol cans
• General line
• Crowns, caps and closures
• Can ends
• Collapsible tubes
Market evaluation
An estimated 520,000 tons
of coatings material are used
worldwide for can coating ap-
plications. In 2004, 155,000 tons
of coatings were used in Europe
alone (Figure 5.18).
Corresponding to the variety
of applications, a wide range
of coating materials is found,
Figure 5.17: Schematic representation of the
the main functions of which are
coating sequence on a three-piece can protective and decorative.
Figure 5.18: Can coating consumption in Europe, 2004, total: approx. 155,000 tons [13]

Metal coating 117
Coating systems
Interior can coatings (golden varnishes) have the function of creating an impene-
trable barrier between the metal substrate and the product contained by the can. As
well as general coating properties such as adhesion, elasticity, hardness and resis-
tance of the paint film to metal shaping processes, typical preservation properties
are also required. These are resistance to acidic foodstuffs and food additives, even
when subjected to heat sterilization, pasteurization or hot filling, as well as non-
toxicity and tastelessness. Non-toxicity in respect of foodstuffs is governed by EU
legislation (EC Directive 2002/72/EC) and the regulations of the U.S. Food and
Drug Administration (FDA §175300). In the case of chemical products, a large
number of special resistance properties are required. These include resistance to
emulsion paints or to the propellants used in aerosol cans. Most interior can coat-
ings are based on combinations of epoxy and phenol resins.
Basecoats (stamping paints) are used as exterior can coatings. These are pigmented
systems which, in addition to the general coating properties already mentioned, must
display good hiding power, optimal levelling, good gloss, stackability, resistance to
yellowing and perfect printability, even with UV-curing printing inks. Initially, mod-
ified alkyd resins and epoxy resins were used to formulate stamping paints. These
were then replaced by polyester and polyacrylate resins, which are now being sub-
stituted by polyurethane systems to satisfy growing coating quality requirements.
Polyurethane systems have the deep drawing properties required in particular for
processing two-piece food cans and satisfy sterilization resistance requirements.
Clearcoats, which give a metallic silver effect on white plate and are therefore also
called silver varnishes, provide the optical finish to an exterior coating. They are
expected to protect complex printed designs from scratching and other damage and
to yield a brilliant appearance with a strong promotional effect.
Epoxy resins and combinations of polyester and amino resins were initially used
for clearcoats as well, but are now being substituted increasingly by polyurethane
systems. Figure 5.19 shows ex-
amples of the application of poly-
urethane coatings as basecoats
and clearcoats.
Polyurethane systems
Solventborne polyurethane sys-
tems for can coating applications
consist of blocked polyisocya-
nates (“Desmodur BL”) and hy-
droxyfunctional polymers (“Des- Figure 5.19: Applications for polyurethane
mophen”). systems in the can coating segment

HDI-based products are preferred for applications which require particularly high
elasticity and deep drawing properties, while products based on IPDI or H12MDI are
used for applications which require special resistance to chemicals and abrasion.
Waterborne polyurethane systems for can coating applications consist of hydro-
philically modified polyisocyanates (“Bayhydur BL”) and water-reducible, hy-
droxyfunctional polymers (“Bayhydrol”). These waterborne systems produce low
emissions and yield coatings which are resistant to sterilization and equal to sol-
ventborne coatings in terms of their other properties. Due to VOC legislation,
waterborne systems will win market share from solventborne systems.
5.2.4 Powder coating

The economic and ecological benefits of powder coatings have ensured the contin-
ued dynamic growth of this technology. Whereas worldwide consumption in 1995
was only around 450,000 tons, demand in 2005 had already reached 1,030,000
tons [14]. This trend is expected to continue, although growth will slow.
Powder coating is a cost-effective process which yields a quality suitable for a wide
range of applications. One of the main reasons for the dynamic growth of this
technology is the fact that the coatings can be applied without any solvent emis-
sions, making them environmentally friendly. Powder coating is thereby of great
importance with respect to the tightened environmental legislation in the coating
industry (Solvent Emissions Directive, Decopaint Directive). Moreover, powder
coatings can be recycled directly, with the overspray in the paint booth being re-
turned to the coating operation.
5.2.4.1 Powder coating technology
A powder coating is a finely ground solid coating material with latently reactive
components. It is applied by spraying and then melted, before undergoing thermal
curing to yield a thermoset film. Powder coatings are usually manufactured in the
following steps [15]: weighing, pre-mixing, extrusion, grinding, sieving, packaging.
Extrusion is performed in single-screw, twin-screw or planetary screw extruders.
Grinding may be done using an air separation mill with the maximum particle size
distribution between 35 and 45 µm.
Application methods
Powder coatings are normally applied by electrostatic spraying, using either the
corona or tribo process [15]. In the corona process 1), a voltage of between 50 and
70 kV is applied between the spray gun and the object to be coated. The powder
coating is forced pneumatically from the spray gun. The particles take up charges
from the corona zone around the spray gun nozzle, follow the field lines to the object
1) The corona is a poorly defined zone – usually just a few millimeters thick – of air ions (including some free electrons) which
forms close to a high-voltage electrode as the result of the high field strengths that exist there.

Metal coating 119
and adhere to the surface due to their

electrostatic charge. In the alterna-
tive tribo application process 2), the
electrostatic charge of the powder
particles is produced by friction in
the tribo gun. There is no need to
apply a high voltage.
Application efficiency
The major advantage of the spray
application of powder coatings com-
pared to liquid coatings is that the Figure 5.20: Powder coating application using
powder which is not deposited on the corona process
the object – the overspray – can be
collected and mixed with fresh powder without any great need for cleaning. This
results in a high material yield of nearly 100 % which, together with the absence of
solvent emissions and off-gas purification, minimal disposal costs and low operat-
ing costs, makes powder coating an interesting alternative compared to the applica-
tion of liquid coatings, both from ecological and economic aspects.
Uses
The downside is that the use of powder coatings is still limited by a number of
framework conditions.
• Relatively high baking temperatures are required (120 to 220 °C).
• Film thicknesses of about 60 to 70 µm are usually achieved, which is relatively
high compared to liquid coatings (30 to 40 µm).
• In many cases, poorer leveling and resistance properties must be accepted.
In recent years, considerable effort has therefore been invested in overcoming these
disadvantages and expanding the range of applications for powder coatings, for
example, to automotive finishing [16]. Although the films yielded by the coatings are
already of a high quality, there is still the need to further reduce the film thickness
for cost reasons. The success of these efforts is shown by the fact that powder coat-
ings, including polyurethane-based systems, are now used as both primer surfacers
and clearcoats by individual automotive producers in Europe and NAFTA.
5.2.4.2 Polyurethane powder coatings

As already described, polyurethane powder coatings usually consist of hydroxyl-
bearing polyesters cured with blocked cycloaliphatic polyisocyanates.
2) Tribo is short for triboelectric, meaning electric by contact or friction.

Powder crosslinkers
Blocking is necessary because the powder coatings are manufactured by extrusion
at temperatures up to 140 °C. Moreover, powder coatings are expected to have good
storage stability. As a rule, the reactivity of unprotected compounds with NCO
end groups is too high and they would cure prematurely with the coreactant, e.g.
during extrusion.
The reactivity can be controlled by the type of blocking agent used. Today, IPDI
products blocked with ε-caprolactam [17] are widely used. As the powder melts dur-
ing the baking process, such hardeners help produce favorable rheological proper-
ties which has a positive effect on leveling. This is because some of the ε-capro-
lactam remains in the paint film and promotes the flow behavior of the melt [18].
Some of the caprolactam is emitted in the off gas, which explains the low VOC
content of such powder coating systems.
Increasingly, internally blocked polyuretdione hardeners containing no blocking
agent are used, which represents an important step toward the emission-free ap-
plication of polyurethane powder coatings. Typical baking conditions for these
second-generation polyurethane powder coatings are ten minutes at 180 °C object
temperature. Development work to further decrease this temperature by catalysis
has yielded the first successes in recent years. Polyuretdione hardeners can now be
crosslinked fully by baking for ten minutes at 140 °C [19].
There is no doubt that this development will yield new application possibilities for
powder coating systems. Uretdione powder hardeners are characterized by their
very good pigmentability [20]. The outstanding optical properties such as gloss and
leveling are also worth particular mention. These result above all from the low melt
viscosity yielded by polyuretdiones [21].
Powder resins
Hydroxyfunctional terephthalic acid polyesters with different OH numbers and
functionalities have proven ideal as the coreactants for the polyurethane powder
hardeners described above. Due to the variety of binders available on the market,
it is now possible to produce high gloss to dull matte films with good leveling [22],
depending on the formulation.
In a typical industrial coating formulation, polyesters with a hydroxyl number of
30 to 50 are used. Given stoichiometric crosslinking, this yields coatings with good
mechanical resistance (reverse impact) and weather stability (Florida, 5° south: at
least 50 % gloss retention after one year). Stoichiometric crosslinking of polyesters
with a higher hydroxyl number yields coatings with excellent chemical resistance.
Polyesters with a hydroxyl number of 100 or more are suitable for use in the easy-
to-clean coatings that are now increasingly in demand. As well as terephthalic acid

Metal coating 121
polyesters, isophthalic acid esters have been available for some years. These yield
coatings with particularly good weather stability, referred to as super durable (Flor-
ida, 5° south: at least 50 % gloss retention after two years) [23]. Hydroxyl-bearing
polyacrylates are also used to a small extent.
Properties
A powder coating is not only required to remain chemically stable during prolonged
storage, even at temperatures of 40 to 50 °C, but it must also be free-flowing and
retain its application properties. This must be borne in mind when selecting the
binder. As a rule, a polyurethane powder coating is formulated to have a glass
transition temperature (Tg) of above 50 °C. Due to their pronounced polar proper-
ties, polyurethane powder coatings are characterized by their particularly good
tribo application properties (see above). Depending on the formulation and applica-
tion, the coatings are cured for 10 to 25 minutes at temperatures between 150 and
210 °C. Table 5.9 describes a typical guide formulation for a blocking agent free
polyurethane powder coating.
The main uses for polyurethane powder systems are as coatings for household ap-
pliances, bicycle frames, metal furniture, add-on automotive components, toys and
sports equipment as well as window frames (see Figure 5.21, page 122).
A primary development goal still lies in increasing the reactivity of polyurethane
powder coatings. Reducing the minimum baking temperature to below 140 °C should
open up a range of other applications such as plastics finishing and wood coating.
Table 5.9: Guide formulation for a polyurethane powder coating

Component Content [%]
Hydroxyl polyester 1) 52.8
Polyuretdione hardener 2)
9.2
Flow promoter 3)
1.5
Catalyst 4) 1.0
Antifoamer 5)
0.5
Titanium dioxide 6)
27.0
Barytes 7) 8.0
100.0
1) E.g. “Uralac P 1480” (DSM), “Crylcoat 2840-2” (Cytec), “Albester 3870” (Hexion),
“Rucote 102” (Bayer MaterialScience)
2) E.g. “Crelan EF 403” (Bayer MaterialScience), “Vestagon BF 1540” (Degussa)
3) E.g. “Modaflow P III” (Monsanto), “Resiflow PV 88” (Worlee Chemie)
4) E.g. “Addocat 9594” (Rhein-Chemie)
5) E.g. benzoin
6) E.g. “Kronos 2160” (Kronos), “Tronox R-KB-5” (Kerr McGee)
7) E.g. Sachtleben micro (Sachtleben)

Polyurethane powder coatings in

industrial finishing
Depending on individual requirements,
various powder coating systems are
now used in industrial finishing. Epoxy
and epoxy/polyester systems are nor-
mally used in applications which do
not require a high level of weather sta-
bility. These coatings have good anti-
corrosion properties. Weather-stable
coatings are yielded by polyurethane
Figure 5.21: A window frame finished with a powder coatings and the following (in
one-shot matte polyurethane powder coating [32] addition to polyurethane coatings):
• in the USA, polyester/triglycidyl isocyanurate (TGIC, “Araldit PT 810”, Hunts-
man)
• in Europe, polyester/di- or triglycidylesters (“Araldit PT 910”, PT 912, Hunts-
man) or polyester/hydroxyalkyl amide (“Primid XL 552”, Ems-Chemie)
or to a lesser extent
• acrylate copolymers in combination with carboxylic acids (Mitsui Chemicals,
Cytec)
Market situation
It is noticeable that polyurethane powder coatings have gained widespread accep-
tance in North America and Japan, but little in Europe [24-26]. This development has
been influenced by regional differences in the availability of raw materials and also
by the very high quality requirements specified for gloss and leveling in the United
States and Japan. These requirements are best satisfied using polyurethanes blocked
with ε-caprolactam [15]. In Europe, the use of these products is restricted to niche
applications due to the emission of ε-caprolactam. In the United States and Japan,
systems blocked with ε-caprolactam are widely used. However, interest in blocking
agent free polyurethane systems based on polyuretdione hardeners also increased.
Figure 5.22 shows a general market overview.
In Europe, polyester/hydroxyalkyl amide powder coatings have displaced TGIC,
which dominated the market for weather-stable coatings for many years. This is
because TGIC (and thus also powder coatings containing TGIC) now have to be
labelled toxic (T) in the EU. The more stringent labelling requirements have led to
a search for alternative technologies in the coating and coating raw material indus-
try. As a consequence, the following alternatives were introduced into the market:
• carboxyl polyester/hydroxyalkyl amide (e.g. “Primid XL 552”, “Primid QM
1260”, Ems-Chemie) [28]
• carboxyl polyester/glycidyl hardener (“Araldit PT 910”, PT 912, Huntsman) [29]

Metal coating 123
Table 5.10: Comparison of the properties of selected powder coatings for outdoor applications
COOH- COOH- COOH- OH-
polyester/ polyester/ polyester/ polyester/
TGIC “Primid “Araldit “Crelan
XL 552” PT 910” EF 403”
Appearance, flow ++ + ++ ++
Mechanical properties ++ ++ ++ ++
Weather stability ++ ++ ++ ++
Powder stability + + o +
Overbaking resistance ++ o + +
Gas oven resistance ++ – + +
Cleavage products none water none none
Blister-free in thick coats ++ – ++ +
++ = very good, + = good, 0 = moderate, – = poor
Figure 5.22: World powder coating consumption by chemical system, 2005, approx:
1 million tons [27]
• hydroxy polyester/blocking agent free polyisocyanate hardener (uretdione hard-

ener “Crelan EF 403”, Bayer MaterialScience)
Table 5.10 compares the properties of these alternative technologies [30].
Considerable experience has already been gained using powder coatings contain-
ing “Primid”. These yield good resistance and mechanical properties. They are also

r elatively cost-effective. The yellowing tendency during baking, particularly in di-

rectly heated gas ovens, as well as the blistering that occurs when the coatings are
applied in thick coats do not predestine this chemistry as a fully equivalent alternative
to TGIC.
Carboxyl polyesters cured with glycidyl, such as powder coatings based on “Araldit
PT 910” or “PT 912”, do not have these disadvantages. However, the stability of
certain powder coating formulations is limited. Moreover, powder coatings based
on “PT 910” are also classified as irritant (Xi). Powder coatings based on the poly-
uretdione hardener “Crelan EF 403” yield a balanced profile of performance and
application properties compared to the alternatives described here [31].
From today’s perspective it can be assumed that all these systems will be found in
the market in the future, although they will vary in importance depending on their
application and specific property profile. This provides the user with the option of
using the system with the predominant characteristic to suit his specific purpose.
Figure 5.23: World market for anti-corrosion and marine coatings, 2005,
Figure 5.24: Use of anti-corrosion and marine coatings in Europe 2005, total: 380,000 tons [35]

Metal coating 125
5.2.5 Corrosion protection

The corrosion of steel causes considerable economic damage. It is estimated that
more than one percent of the world’s gross domestic product is lost as the result of
corrosion each year [33]. Corrosion can be restricted by means of active corrosion
protection, i.e. applying an impressed current as cathodic protection or using base
metals as sacrificial anodes, or by passive corrosion protection with the aid of coat-
ings. According to prevailing opinion in Europe, the field of anti-corrosion coatings
in steel construction includes all applications in factory coating operations and those
in the context of civil and hydraulic engineering works as defined by ISO12 944 [34].
Protective coatings as globally understood are also used on stationary objects of
industrial and public infrastructure, with concrete usually included as a substrate
as well as steel. The anti-corrosion coating market also covers the marine and
offshore sectors.
The world market for anti-corrosion coatings is estimated at 1.6 million tons with
a material value of about EUR 4.5 billion. Some 750,000 tons of this total are
protective coatings and 850,000 tons are coatings for marine and offshore applica-
tions (see Figure 5.23).
In Europe, 380,000 tons of anti-corrosion coatings based on various technologies
are used, as shown in Figure 5.24. Within the market of the extended European
Union, at least 200,000 tons of anti-corrosion coatings with a value of EUR 640
million are used in civil engineering applications [36] (see Table 5.11). About 50 % of
this volume was for new construction projects (approx. 8 million tons of steel with
a coating area of about 160 million square meters), of which half (about 50,000 tons)
was shop-applied. The other half was applied on-site. The application of rehabilita-
tion coatings (approx.100,000 tons) takes place almost exclusively on-site.
Table 5.11: EU market for anti-corrosion coatings by system, 2004 [36]

Factory coatings and temporary corrosion protection 16,000 t 8%
Inorganic and organic zinc silicate/phosphate primers 10,000 t 5%
Two-component primers and intermediate coats 34,000 t 17 %
One-component primers and intermediate coats 21,000 t 10.5 %
Two-component topcoats 34,000 t 17 %
One-component topcoats 38,000 t 19 %
Surface-tolerant coatings 28,000 t 14 %
Tank coatings 10,000 t 5%
Highly heat-resistant and flame-retardant coatings 9,000 t 4.5 %
200,000 t 100 %

The raw material and coating manufac-

turers collaborate on concepts for inno-
vative coatings in corrosion protection.
The activities aim to develop more ef-
ficient solutions in response to the con-
stantly changing quality and environ-
mental requirements in corrosion pro-
tection. Coatings based on epoxy and
polyurethane raw materials play the
central role in corrosion protection us-
Figure 5.25: Sehto Ohasi Bridge in
Japan [37] ing organic coating materials, with ep-
oxy systems holding the lead in terms
of volume, but both types of system
generating approximately the same
value. The following key applications
are mentioned by way of example:
Civil engineering:
• Industrial plant
• Conveyor systems
Figure 5.26: Polyurethane coating in a
marine application • Bridges, cranes, high-voltage pylons
• Load-bearing structures, e.g. for fac-
tories, pipe bridges
Hydraulic engineering:
• Harbor installations, sheet pilings;
• Locks, docks
Offshore and marine engineering:
• Offshore drilling platforms
• Ships
Pipeline engineering:
• External pipe coatings
• Internal pipe coatings (oil, gas, water,
chemicals)
Figure 5.27: Pipeline rehabilitation with a • Internal coatings for pressurized
polyurethane coating [42] pipes
5.2.5.1 Technical aspects of polyurethane anti-corrosion coatings
Polyurethane anti-corrosion coatings can be formulated as one- or two-component
systems. In the case of two-component systems, the coreactants for both aliphatic and
aromatic polyisocyanate components are H-acid compounds such as polyalcohols or
polyamines. The one-component systems are moisture-curing.

Metal coating 127
Quality parameters for anti-corrosion coatings are properties such as hardness,

long-term flexibility, abrasion resistance, and high resistance to weathering, water,
chemicals and solvents. The systems must also offer application reliability under
different climatic conditions. All of these properties are provided by polyurethane
systems.
Polyurethane coatings are often used for the corrosion protection of steel because
they are particularly economical to apply. They dry quickly and can therefore be
overcoated at short intervals. They can also be applied largely independently of the
weather conditions and are resistant to impact. The latter property favors their use
as factory coatings (primer or primer and intermediate coating) for steel components
which have to be transported over long distances to the construction site. Transpor-
tation damage remains minimal, and the repair effort is correspondingly low.
As far as their basic composition and application properties are concerned, poly-
urethane coatings do not differ greatly from other commonly used anti-corrosion
systems. They consist of binders, pigments, extenders, co-resins, additives and
solvents – unless they are solvent-free formulations. They are applied by conven-
tional techniques such as brushing, rolling and spraying (one- or two-component
spraying units). Both one- and two-component polyurethane systems can be used
as primers and intermediate coatings on steel in civil and hydraulic engineering
applications. The topcoats used in civil engineering are mainly lightfast aliphatic
two-component polyurethane systems. In hydraulic engineering, aromatic one-
component or solvent-free two-component polyurethane systems are used. Due to
their extremely high reactivity, solvent-free aromatic two-component polyurethane
systems, which are used, for example, as external coatings for pipelines, must be
applied by two-component spraying.
The anti-corrosion effect of organic coatings is founded on a number of factors:
Adhesion on the metal substrate, active corrosion protection and the barrier effect of
pigments and fillers, chemical and thermal resistance, and resistance to ageing thanks
to their weather stability [38]. However, the requirement profile is so varied that a
single coat cannot usually yield all the properties required. For this reason, corrosion
protection concepts normally consist of several coats, each of which has a specific
role. Three-coat concepts with a total film thickness of 0.2 to 0.3 mm represent the
standard for steel in civil engineering (e.g. as per ISO 12944). They consist of a
primer and an intermediate coat, protected by a lightfast topcoat. Economic consid-
erations are driving development toward two-coat concepts that provide the same
level of corrosion protection. These consist of a primer and a lightfast topcoat with
a total film thickness at least equal to that yielded by the three-coat concept.
Corresponding attempts to reduce the number of coats are also being made in ap-
plications for which two-coat concepts are the standard at present. The primer and
the topcoat are replaced by a topcoat which is applied directly to the metal.

In addition to the established polyurethane systems, high solid polyurethane sys-

tems are becoming increasingly important in meeting the stricter requirements for
reducing solvent emissions.
5.2.5.2 Primers
The main function of primers is corrosion protection. In addition, they ensure the
bond between the metal substrate and the subsequent coats. Epoxy systems are often
preferred because of their higher resistance to moisture. However, polyurethane
systems cure faster and more reliably, especially at low temperatures. Most poly-
urethane primers are moisture-curing one component systems based on aromatic
TDI and MDI prepolymers, for example from the “Desmodur E” product line. They
can be applied on shotblasted surfaces and on surfaces which have had minimal
preparation, e.g. surfaces which have been derusted by hand or using power tools.
The fast drying of these systems yields logistical benefits, especially when applied
on new structures. In rehabilitation projects, a key advantage is their application at
low temperatures and high humidity [39].
One-component polyurethane/zinc dust primers have been found in practice to be
extremely resistant to mud cracking. The universal overcoatability of one-compo-
nent primers also allows their use as temporary corrosion protection and as welding
primers. Depending on the corrosive conditions, primers can be formulated with
or without active pigments (zinc dust or zinc phosphate) and/or barrier-forming
lamellar pigments (aluminum flakes or micaceous iron oxide). The barrier greatly
slows the migration of corrosion stimulators through the coating and thus also
delays the corrosion process. In two-component polyurethane coatings, zinc phos-
phate has proved to be better than zinc dust or zinc oxide because these have an
excessive catalytic effect on the polyaddition reaction. However, because of its high
water content, zinc phosphate cannot be used in one-component polyurethane coat-
ings, in which zinc dust is preferred.
To ensure adequate storage stability of one-component polyurethane coatings, the
moisture adsorbed by the pigment must be removed during production by the ad-
dition of a dryer such as tosyl isocyanate. It is generally recommended that the
pigments and extenders used have a water content of less than 0.2 %.
5.2.5.3 Intermediate coats
The intermediate coat has the function of protecting the primer, increasing the film
thickness to enhance corrosion protection and ensuring optimal adhesion between
the primer and the topcoat. Formulations based on epoxy resin and one- or two-
component polyurethane raw materials are used as intermediate coats, as well as
for the primer. It is not unusual for structural steel elements used in the construction
industry to be stored outdoors for long periods before they are needed. There is a
risk of film degradation if the shop coating used is not lightfast. This entails laborious

Metal coating 129
cleaning before application of a two-component polyurethane topcoat to prevent

impaired adhesion. Lightfast two-component polyurethane coatings are an eco-
nomical alternative to epoxy coatings as the intermediate shop coating and are
therefore attracting growing interest. The extenders normally used in intermediate
coats, such as talc or barytes, serve to increase the individual coating thickness and
thus enhance the protective effect. If necessary, these coatings can be applied in a
dry film thickness of 0.2 mm. The film is pore-free, blister-free and crack-free. In
practice, a film thickness of 0.1 mm is usually sufficient.
5.2.5.4 Topcoats
Proven in this application over more than 35 years are two-component polyurethane
coatings based on “Desmodur N” in combination with polyols, preferably hydrox-
yl acrylate resins. Their particular advantages are application reliability, fast drying,
ease of repair and high resistance to weathering, water and chemicals. This type of
system is used on steel in civil and marine engineering. A two-component polyure-
thane topcoat ensures weather stability and preserves the decorative appearance of
the structure in the long term.
5.2.5.5 Polyurethane/hydrocarbon resin combinations
Thanks to their outstanding corrosion protection properties, polyurethane/hydro-
carbon resin combinations have been used for more than 20 years on steel in hy-
draulic engineering applications, especially drilling platforms, sheet pilings and
locks, and also on tanks installed underground. These systems are characterized by
their water resistance, good wet adhesion, abrasion resistance, impact resistance
and flexibility. The film properties of these systems are adjusted to suit both the
object being coated and the requirements. This is possible due to the wide variety
of available polyisocyanate and polyol components. Polymeric MDI products or
NCO prepolymers with different NCO content can be reacted with, for example,
short-chain diols, polyethers,
and/or polyester polyols with
varying hydroxyl content and
branching factor.
Owing to their inherent color,
these coatings can only be func-
tional. One-component polyure-
thane/hydrocarbon resin com-
binations are used primarily in
multicoat concepts (three to five
coats) with a total dry film thick-
Figure 5.28: Olympic Stadium in Berlin, corrosion
ness between 0.4 and 0.6 mm. protection with a two-component polyurethane
Solvent-free two-component topcoat [40]

polyurethane/hydrocarbon resin combinations are primarily suitable as one-coat

high-build systems with a dry film thickness between 0.5 and 2 mm. The anit-
corrosion properties of multicoat one-component polyurethane/hydrocarbon resin
systems can be improved by combination with a one-component polyurethane/zinc
dust primer. The use of a one-component polyurethane primer (possibly as a zinc
dust formulation) with a two-component polyure-
thane/hydrocarbon resin topcoat also improves
corrosion protection.
5.2.5.6 Polyaspartic coatings
Polyaspartic acid esters – also called polyaspar-
tics – represent a relatively new class of binder
(“Desmophen NH” product line) for anti-corrosion
topcoats. They are sterically hindered aliphatic
amines which exhibit moderate reactivity with
polyisocyanates.
Compared to solventborne two-component poly-
urethane systems, polyaspartic coatings are char-
acterized by the following advantages:
• High solids content with VOC contents lower
than 100g/l
Figure 5.29: Robust corrosion • Fast drying (T1 approx. 1.5 hours, T6 approx.
protection with a single-coat
polyaspartic formulation [41] 4 hours)
• High blister-free film thickness in a single
pass
These advantages mean that the use of polyaspartic
topcoats increases application productivity. Along-
side the faster drying, the application of a high film
thickness is of key importance here. This property
makes it possible to reduce the number of coats
applied (e.g. the intermediate coat), with a corre-
sponding reduction in application costs.
In addition to the advantages of increased produc-
tivity and low solvent content, polyaspartic coat-
ings offer a high level of application reliability
and can be applied by the methods normally used
in corrosion protection such as spraying, brush-
Figure 5.30: Wind turbine: tow-
ing or rolling. Polyaspartic topcoats are mainly
er coated with two-component
polyurethane, blade coated with used in the factory coating of steel components,
polyaspartic gelcoat as productivity is of particular importance here.

Metal coating 131
For example, the further processing and transport of the coated steel components
are possible much earlier. Figure 5.29 shows a typical application of a single-coat
polyaspartic finish on shotblasted steel.
Wind energy plants
Wind energy is a fast-growing market. Globally installed capacities are expected
to reach 132,000 MW in 2010, an increase from 59,000 MW in 2005 [42]. The de-
mands on coatings in this market are very high since a service life of 30 to 40 years
is expected and typically maintenance is difficult to carry out. Due to the fact that
high performance is inherent to the nature of polyurethanes, they are widely used
in the wind energy market. The main parts of a wind turbine on which polyurethanes
are commonly used are the tower and the blades (see Figure 5.30). The towers are
often made out of steel and therefore have to be protected against corrosion. The
standard in protective coatings is a three-coat system comprising a primer, inter-
mediate coat and topcoat. Two-component polyurethane systems based on acrylic
polyols and aliphatic polyisocyanates are the standard binders for these topcoats.
As a new approach, polyaspartic coatings are used as topcoats for the steel segments
because they yield increased productivity by allowing higher film thicknesses.
The blades are made of composite materials which combine light weight with high
strength. Composites consist of a fibrous reinforcing network embedded in a polymer
matrix. A gelcoat can be used to reduce the fiber patterns on the surface of the parts.
Aliphatic two-component polyurethanes are suitable for these gelcoats due to their
long-term durability, high abrasion resistance and outstanding weather stability. A
two-component polyurethane may consist of a branched short-chain polyester and
an aliphatic HDI polyisocyanate. Recent gelcoat developments focus on polyaspar-
tics which offer the benefits of a shorter curing time and customizable pot life.
5.2.5.7 Pipe coating
A specialty in the segment of heavy corrosion protection is the exterior coating of
pipelines installed in the ground or under water. Deviating from the typical three-
coat structure used in civil engineering applications, an exterior pipe coating is
usually a one-coat system. This is applied directly to the metal substrate without a
primer and has the necessary resistance properties thanks to the high film thick-
nesses of 800 μm to 1,500 μm that are required. This ensures long-term corrosion
protection of the pipelines after installation. The coating systems used for pipes can
be roughly classifed according to the application, depending on whether single pipe
sections are coated in the factory or complete pipelines (or only weld joints) are
coated on-site. In the case of factory coatings (OEM), three-coat systems compris-
ing an epoxy powder primer, epoxy adhesive and polyolefin finish are often used
in addition to pure epoxy powder systems. Also, two-component polyurethane
coating systems are being used increasingly because of the advantages they offer.

Using reactive, solvent-free two-component polyurethane coatings eliminates the

need for costly heating of the pipe sections to about 220 °C, which is necessary for
baking the epoxy powder systems, and subsequent cooling to about 80 °C, so that
the pipes can be stacked quickly (see Figure 5.31).
Liquid, solvent-free two-component polyurethane and epoxy coatings have proved
ideal for on-site application. Two-component polyurethane systems offer the ad-
vantages of good mechanical properties coupled with rapid application due to their
high reactivity, even at low temperatures (see Figure 5.32). This translates into
significant cost benefits. Even on vertical surfaces, sag-free application in a single
pass can be achieved with two-component polyurethane coating systems. The good
sag resistance is yielded either by conventional rheological additives or by
Table 5.12: Minimum requirements for polyurethane coatings as per DIN EN 10290
Property Minimum specification (summary)
Film thickness Class A: 800 µm, Class B: 1,500 µm
Shore D hardness According to project specification
Pore test 12 kV for 1,500 µm film thickness, max. 20 kV
Impact resistance ≥5 J x mm dft x k (at 23 ºC), ≥ 3 J x mm dft x k (at – 5 ºC)
Adhesion Knife test, rate ≤3 (23 ºC), rate ≤4 (80 ºC)
Flexibility Bending test at 23 ºC and 0 ºC
Elongation ≥10%
Indentation resistance ≤0.2 mm (23 ºC, 1,500 µm), ≤0.45 mm (80 ºC, 1,500 µm)
Thermal aging 100 d value for 60 ºC, 80 ºC and 100 ºC
Cathodic disbonding Disbonding: ≤ 8 mm (23 ºC, 28 d), ≤ 8 mm (60 ºC, 2 d)
Spec. electrical resistance 107 Ωm² (23 ºC, 100 d), 104 Ωm² (at max. operating
temperature, 30d)
Figure 5.31: Applying an OEM polyure- Figure 5.32: Rehabilitating a gas pipeline
thane coating on a pipeline [43] in the Ukraine [44]

Metal coating 133
chemical thickening during application. Table 5.12 gives an overview of the most
important requirements for underground pipelines as per DIN EN 10290.
In the case of underground pipelines, the mechanical properties of the exterior
coating system are of the greatest importance. For example, the high impact resis-
tance of the coating prevents damage during transportation or subsequent installa-
tion. A flexible coating system makes it possible to cold bend pipe sections in the
field without cracks forming. Good long-term flexibility, even at low temperatures,
and good adhesion on the metal surface are essential for lasting protection of un-
derground pipelines. These properties can be provided by appropriately formulated
aromatic two-component polyurethane systems. As the protective current for pipe-
lines serves as active corrosion protection, the pipe coatings have to pass the ca-
thodic disbondment test as per ASTM G8 or ASTM G42 [45] (Figure 5.33).
Given the many raw materials available for formulating solvent-free two-compo-
nent polyurethane systems, the mechanical properties, viscosity and reaction time
can be optimized specifically to satisfy individual requirement profiles. Standard
products for the development of reactive two-component polyurethane systems are
polyols based on polyethers, polyether/polyester combinations, polyether/polyac-
rylate combinations, polymeric MDI isocyanates, amines and catalysts [46].
Special one-component polyurethane coatings or high viscosity two-component
polyurethane systems are used as repair systems (for spot repair). It should be men-
tioned that the adhesion properties of polyurethane pipe coating systems, especially
if cathodic protection is applied, depends greatly on the pretreatment of the sub-
strate. In both OEM and repair coating work, the substrate has to be shotblasted (SA
3.0 for OEM and SA 2.5 for spot repair, as per ISO 8501-1). The depth of roughness
Rz is between 50 μm to 90 μm as per the given specifications (ISO 4287-1). After
Figure 5.33: Schematic representation of the cathodic protection test system based on
ASTM G42

shotblasting, the surface is checked. The mill parings, mill scale, weld beads and
other surface defects exposed by blasting have to be removed. Particularly in the
case of on-site coating, it is advisable to monitor ambient conditions. The coating
process must be interrupted if the temperature on the steel surface falls 3 °C below
the dew point of the ambient air or is lower than 5 °C, or the relative humidity is
more than 90 %.
Interior pipe coatings
As a rule, only one coat is applied as the interior coating for steel pipes. However, the
film thicknesses are very different to those of the exterior coating and may vary great-
ly depending on specification and application. For the interior coating of gas pipelines,
for example, film thicknesses between 50 μm and 100 μm are required for both OEM
and repair applications. Solvent-free two-component polyurethane systems are also
used for this, as are to solventborne epoxy coatings.
The depth of roughness Rz is in the re-
gion of 50 μm to 70 μm as per the given
specifications (ISO 4287-1). In the case
of drinking water pipelines, the film
thicknesses of the OEM interior coat-
ing range between 300 μm and 500 μm,
while repair coatings are in the region
of 1,000 μm to 3,000 μm. In this appli-
cation, solvent-free, reactive, aliphatic
polyurea systems based on aliphatic
Figure 5.34: Applying an aliphatic poly- polyisocyanates combined with special
urea coating to the interior of a drinking amines have proved ideal due to their
water pipe [44]
outstanding mechanical properties.
These systems are already approved for
drinking water applications in a number
of EU countries (see Figure 5.34).
5.2.6 Wire coating
The winding wires used for electric coils
that produce magnetic fields, in contrast
to electric cables, have only thin insula-
tion layers in the range between 5 and
100 µm. The wires are wound tightly to
yield effective current densities and coil
performance in electrical components
Figure 5.35: Armature winding of coated (see Figure 5.35). The insulation layer
copper wire to produce an AC electric motor of these winding wires is produced by

Metal coating 135
coating in film thicknesses of 5 to 100 μm. The coating is applied by wetting the
wires in an enamel bath and then stripping them through a die or, in the case of fine
wires, through felt. Several coats of the same coating, usually five to ten, are applied
in succession. The wire is dried in an oven after application of each coat. The oven
temperature is 500 °C or above. The contact times are in the region of seconds on
account of the production speed and vary greatly with the diameter of the wire.
The wire is nearly always made from copper or, more rarely, aluminum. Diameters
typically vary from 0.1 mm to 1 mm in circular wires. However, there are also very
fine wires with diameters starting at approximately 0.018 mm and heavy rectangu-
lar wires with edge lengths in the centimeter range.
The coated wires have to meet many requirements:
• Flexibility
• Coating adhesion
• Abrasion resistance
• Thermal resistance (softening range)
• Temperature index
• Resistance to chemicals (sealants)
• Resistance to oxidation
• Dielectric strength
• Threshold temperature of the operating range (tan delta)
• Direct solderability
Coils which are used in generators, electric motors and transformers – all apparatus
which operate at high energy densities or high ambient temperatures – are subjected
to correspondingly high continuous temperature loads. Polymers with high thermal
resistance are used as the insulation material because they can meet the requirement
profile. Polyesters are most widely used, followed by polyester imides and amide
imides. Imides and polyhydantoins are used for special applications. For their appli-
cation as coatings, however, it is essential that these polymers are completely
soluble in organic solvents. N-methylpyrrolidone (NMP), cresols and phenols are
often the only solvents suitable. The solvents which evaporate during drying of the
coatings are catalytically burned in the wire coating machine, thus contributing a
considerable amount of energy for operating the drying oven.
If wires are to be joined by soldering or in some other way, the insulating coating
must first be burned off or removed mechanically. This usually involves increased
effort. It is generally perceived as a disadvantage that polyurethanes have lower
heat resistance than polyester imides, but this has proved to be a significant advan-
tage in wire coating. At the temperatures used in direct soldering (starting at around
320 °C), the urethane groups are split off so quickly that the entire coating film
vaporizes in just a few seconds, depending on the wire diameter. Polyurethane-
coated wires can therefore be directly soldered without pretreatment, an undeniable

advantage in the automated manufacture of electrical components. For this reason,

these wires are used primarily in electronics applications in which very high com-
ponent temperatures are not expected during operation. Standard polyurethane-
coated wires are used in applications with continuous temperature loads of 130 °C
(heat class B) and 155 °C (heat class F).
The polyurethane coatings are processed as one-component systems and usually
consist of a branched blocked isocyanate and a branched hydroxyl-bearing poly-
ester. The isocyanate is normally an adduct of trimethylolpropane and toluene
diisocyanate (TDI). Phenol or cresol is used as the blocking agent. Whereas the
blocked isocyanate used to be supplied as a solid (e.g. “Desmodur AP stable”)
which then had to be dissolved, it is now usually synthesized directly in solution
by wire coating manufacturers. If higher thermal resistance is required, blocked
TDI trimers are also used [47].
As well as TDI-based products, blocked MDI isocyanate crosslinkers are used to
formulate wire coatings. These display better resistance to moisture, an important
requirement in Asia especially, and tend to result in better thermal resistance. The
downside, however, is reduced solderability. World binder consumption for the
insulation of winding wires totals about 50,000 tons, with polyurethanes estimated
to account for about 20 %.
5.3 Automotive OEM finishing

The economic significance of raw materials for automotive coatings equates with
the high economic standing of the automotive industry. In 2004, about 860,000 tons
of coatings, excluding wax conservation, flange adhesives, seam sealing and under-
Figure 5.36: Coating process in automotive production

Automotive OEM finishing 137
body protection, were used in automotive OEM finishing. This is equivalent to

about 400,000 tons [48] of coating raw materials in their supply form.
Originating with the coach enamels used at the end of the 19th century, automotive
OEM finishing has now developed into one of the most technically sophisticated
of all coating applications. With few exceptions, all the major coating systems
available today are used in this segment in various forms: solventborne high solid,
waterborne dispersions, solvent-free liquids or solids (powders). Automotive OEM
finishing is governed by the fixed speeds of mass production. Unlike the air-drying
coach enamels of former times that took several days to cure, modern automotive
coatings are baking systems that cure by chemical crosslinking within 20 to 30
minutes at temperatures ranging from 120 to 180 °C. This is the only way to achieve
the high quality required.
The automotive OEM finishing process
The modern automotive OEM finishing process is relatively uniform and can be
divided into four phases:
• Cleaning and pretreatment of the uncoated car bodies
• Application of a cathodic electrodeposition (CED) primer
• Application of a primer sur-
facer
• Application of a topcoat
The application of each coating
(CED primer, primer surfacer and
topcoat) is followed by a baking
cycle. Cavity and exterior sealing
is performed separately, usually
after final assembly of the vehicle
(Figure 5.36).
Traditionally, the coating process
also includes the application of an
underbody coating system, seam
sealing compounds and, if neces-
sary, a separate stone chip-resistant
coating. However, the latter is used
only on certain areas of the car body
that are particularly vulnerable to
stone chipping. Depending on the
design of the coating line, under-
body sealing and seam sealing
systems are applied either before Figure 5.37: Diagram of an automotive OEM
or after baking of the CED primer. finish (door section)

If an additional stone chip-resistant coating is required, this is applied before baking

the primer surfacer (wet-on-wet application). The coats applied in each phase of the
process fulfill specific functions in the overall finish (Figure 5.37). The passivating
pretreatment (phosphating) of the steel and the CED primer are largely responsible
for protecting the car body against corrosion. The primer surfacer fills any remain-
ing unevenness in the substrate and is often sanded after baking to improve surface
smoothness. Today, this coat increasingly has the additional role of providing stone
chip protection. Polyurethane-based stone chip primer surfacers represent a quantum
leap in the quality of automotive finishing. The primer surfacer also protects the usu-
ally non-lightfast CED primer against UV transmission, which could cause delamina-
tion of the coatings over it if the primer surfacer did not have sufficient opacity.
The topcoat, which nowadays is usually a two-coat system consisting of a basecoat
and a clearcoat, has other requirements to fulfill: gloss, brilliance, color and often,
special effects – all properties related to the appearance of the finish. It is also
important that the topcoat is resistant to light and weathering, to various household,
industrial and natural chemicals and, not least, to mechanical damage (scratching,
stone chipping, car washes). All this means that only high-quality, lightfast and
weather-stable binders can be considered for formulating topcoats.
5.3.1 Cathodic electrodeposition primers
The first true coating applied after cleaning and passivating (zinc phosphating) of
the car body is the waterborne dip primer applied electrophoretically. Today, this
is almost always a cathodic electrodeposition (CED) system, which is applied by
using the metal car body as the cathode. The anode is either the bath containing a
coating of defined conductivity or an electrode that is suitably positioned in the
bath (Figure 5.38).
Figure 5.38: Cathodic electrodeposition (CED) coating

As a result, the binder particles carry a positive charge which, given simultaneous
charge equilibrium, enables them to coagulate as a deposit on the car body that
serves as the cathode. Polyurethane/epoxy resin combinations dominate as binders
in this application. As a rule, these are amine-extended, aromatic epoxy resins based
on bisphenol A and incorporating blocked di- or polyisocyanates. Quaternization
of the tertiary amine function with organic acids yields the necessary positive
charge on the particles.
The reversibly blocked isocyanate groups incorporated in the resin molecule allow
subsequent crosslinking in the baking oven at temperatures of 150 to 180 °C.
The di- or polyisocyanates used to synthesize the polyurethane/epoxy system are
based on toluene diisocyanate (TDI) and increasingly also diphenylmethane diiso-
cyanate (MDI). Monomeric MDI can be used, but the oligomeric prepolymerized
form is preferred. CED primers formulated with these materials are characterized by
improved bath stability and the increased stone chip resistance of the baked film.
CED systems formulated with aliphatic isocyanates based on HDI or IPDI or their
derivatives are a specialty (Japan). The advantages of these systems are their low
baking temperatures of 150 to 160 °C and their lightfastness. However, the corro-
sion protection properties of these products are inferior to MDI systems.
Among the blocking agents used are ε-caprolactam, methyl ethyl ketoxime or ether
alcohols such as diethylene glycol monomethyl ether. When selecting the blocking
agent, it is important that the resulting products have adequate stability, e.g. to
hydrolytic degradation (bath stability), and that the unblocking temperature is not
too high. Development work by automotive coating manufacturers is aimed at
achieving lead-free systems and lower baking temperatures to satisfy ecological
requirements, and improved stone chip resistance and corrosion protection in
response to technical demands.
5.3.2 Seam sealing, underbody coating and sound insulation

Seam sealing and underbody coating systems are usually applied successively after
baking the CED primer. Owing to their very balanced application-specific property
profile and their good cost/benefit relationship, PVC plastisols dominate both appli-
cations worldwide. Depending on the material-specific properties, each plastisol
system is pre-gelled at about 120 °C. The primer surfacer is then applied and all
three coats are baked together at temperatures between 140 and 160 °C.
Underbody coating systems are applied in relatively thick layers on the underside of
the vehicle. In seam and overlap zones, a thickness of more than 2 mm may be
achieved. This protects the CED primer from stone chipping. The underbody coating
system must have good adhesion on the CED primer and be highly resistant to abra-
sion. The PVC plastisols used in formulating underbody coating systems often con-
tain blocked aliphatic or aromatic polyisocyanates to act as adhesion promoters.

Seam sealers are used to seal the weld seams in a car body. The welding process
removes anti-corrosion layers such as the zinc galvanization or organic precoats
on the steel, exposing it to the risk of corrosion at the weld seams. To provide
adequate protection, a seam sealer must be sufficiently flexible and suitable for
application in a thickness of several millimeters. Polyurethane systems meet both
requirements and thus have specific advantages over the established PVC systems.
In contrast to PVC materials, solvent-free polyurethane systems can be applied in
coats thinner than 100 μm which yield a compact film with outstanding adhesion
on the CED primer. Despite the thinner film thickness, their abrasion resistance is
as good as that of PVC systems (Figure 5.39). For this reason, polyurethane under-
body coating systems can be applied in thin layers in areas of the car body which
are less exposed to stone chipping. This contributes to an overall reduction in the
weight of the vehicle.
Depending on the polyol/polyisocyanate combination, one- and two-component
polyurethane systems can be formulated to yield the desired flexibility. One par-
ticular advantage is that the flexibility at low temperatures is not reduced signifi-
cantly, so the stone-chip resistance of the systems remains effective. As well as
seam sealing and underbody coating systems, materials are applied to provide
sound insulation. These are usually mats based on bituminous substances that are
fitted by hand. The mats melt during pre-gelling of the underbody coating system
and adhere to the substrate.
Figure 5.39: Abrasion resistance of PVC and polyurethane underbody coating systems
(Sablux test)

Suitable solvent-free polyurethane systems can also be formulated for this applica-
tion. These coatings can be applied on the automated line. They have excellent
long-term adhesion to the substrate and satisfy the sound insulation requirements
of the automotive industry. Also available are solvent-free, one-component poly-
urethane underbody coating and seam sealing systems containing microencapsu-
lated hardeners, e.g. TDI-based. Depending on the type of microencapsulation,
these systems can be baked at temperatures of 100 °C. The microcapsules are
destroyed by the heat, releasing the hardener for the crosslinking reaction. However,
because of its relatively high price, this technology is used only in niche applica-
tions[49]. One alternative technology to the use of coatings for underbody protection,
as described above, is to fit plastic panels on the undersides of cars. These provide
stone-chip protection and sound insulation.
5.3.3 Primer surfacers
Originally conceived as an intermediate coat with filling properties, the primer
surfacer has undergone considerable transformation in recent decades, with more
change still to come. For example, it has increasingly assumed a color-imparting
function in support of the topcoat. In order to satisfy demands for solvent reduction,
waterborne binders have been developed which have a property profile fully equiv-
alent to solventborne primer surfacer resins.
Solventborne primer surfacers
The stone-chip protection properties required of a primer surfacer can be optimized
using polyurethane resins, which has allowed their breakthrough in this field of
application. Polyurethanes yield primer surfacers that combine toughness with flex-
ibility yet retain good sanding properties. Moreover, the stone-chip resistance of
primer surfacers formulated with alkyd and polyester resins crosslinked with
melamine and/or urea resins can be improved considerably by adding blocked
polyisocyanates. This improves the stone-chip behavior of the overall finish.
The greatest effect is achieved using blocked polyisocyanates based on hexameth-
ylene diisocyanate (HDI) or diphenylmethane diisocyanate (MDI). Considering the
baking temperatures of 130 to 150 °C that are typical for primer surfacers, estab-
lished blocking agents such as methyl ethyl ketoxime and malonic acid ester are
suitable, but not, for example, ε-caprolactam [50].
A typical primer surfacer formulation (solventborne) is shown in the left column of
Table 5.13 (page 142). In 2003, around 40 % of the solventborne primer surfacers
used in Europe contained blocked polyisocyanates, either combined with melamine
or used as the sole hardener. In this way, a very broad spectrum of requirements
with respect to application reliability, leveling and stone-chip resistance can be
satisfied. The solvent can be chosen to match the flash-off behavior of the primer
surfacer to the conditions on individual coating lines.

Waterborne primer surfacers

The good performance of polyurethane binders is even more evident in the recent
dramatic growth of the waterborne primer surfacer segment. These systems are based
on polyester or polyurethane dispersions, used either separately or as combinations.
In analogy to the solventborne systems, suitable hardeners include melamine resins
and blocked polyisocyanates, as well as combinations of the two. These polyisocya-
nates are hydrophilically modified and are easy to incorporate into water [51]. The
binders described allow the two-fold exploitation of the benefits of polyurethane
chemistry. On the one hand, there is blocked polyisocyanate in the hardener, and on
Table 5.13: Comparison of two typical formulations for solventborne and waterborne
primer surfacers
Solventborne primer Waterborne primer
surfacer [% by wt.] surfacer [% by wt.]
Polyester “Desmophen T 1665”*/** “Bayhydrol PT 241” **
“Desmophen 670” (calculated on solids) 19%
(calculated on solids) 21%
Polyisocyanate “Desmodur BL 3175” ** “Bayhydur BL 5140” **
(blocked) (calculated on solids) 7 % (calculated on solids) 7 %
Melamine 9% 3%
Pigments/fillers 30 % 21 %
Org. solvent 33 % 5%
Water – 45 %
Sum 100 % 100 %
* “Desmophen T” designates wax-free polyesters.
** Supplied by Bayer MaterialScience
Figure 5.40: The primer surfacer market in Europe, 2003 [52]

the other hand a waterborne polyurethane dispersion is used in the polyol component.
Good conditions therefore exist to produce primer surfacers with properties typical
of polyurethane systems, such as flexibility and stone-chip resistance.
A waterborne primer surfacer formulation is shown in Table 5.13 (right column).
In 2003, the automotive industry in Europe used waterborne primer surfacers on
some 9 million cars, which is equivalent to about 46 % of the total market. The
upward trend in the use of waterborne primer surfacers remains strong (Figure
5.40). Since 2000, Japanese and Chinese automakers have also been increasingly
using waterborne primer surfacers.
To ensure reliable application of waterborne primer surfacers, the spray booths and
flash-off zones must be air-conditioned to maintain the correct humidity and tem-
perature. The addition of 5 to 10 % by weight of co-solvent improves the flash-off
behavior, making the resulting paint film less vulnerable to fluctuating conditions
on the coating line. Despite the low solids content of around 50 % by weight, com-
pared to 70 % by weight in the case of high solid systems, solvent emissions from
waterborne primer surfacers are halved.
Alternative concepts
Other new concepts have been developed in parallel with waterborne primer surfacer
systems. One example is a process in which, instead of applying and baking a primer
surfacer in a separate operation, a functional coat of reduced film thickness is applied.
This may or may not be force-dried before wet-on-wet application of the topcoat.
Both coats, or in the case of metallic coatings, all three coats, are then baked together.
For both economic and environmental reasons, these 3 Coat-1 Bake systems have
attracted great interest in Europe and Asia and are already in use there [53].
A further alternative to the classic primer surfacer is represented by powder coating
systems. So far, this technology has only been used in niche applications in Europe.
In the United States, on the other hand, powder primer surfacers has been used on
nearly 2.5 million cars and light commercial vehicles since 1997 – almost 15% of
total production. Most of these powder systems are based on polyester/epoxy chem-
istry. If high stone-chip protection is required, U.S. automakers may also consider
polyurethane powder systems and these are already in use there.
5.3.4 Basecoats and clearcoats
Around 80 % of the topcoats used in the automotive industry are two-coat systems
consisting of a color-imparting basecoat and a clearcoat applied wet-on-wet (see
Figure 5.41, page 144). The remaining 20 % are one-coat systems, i.e. pigmented
topcoats, which – as the term implies – are applied and baked on in a single layer.
As the optical and long-term resistance properties of these coatings are inferior to
two-coat systems, their use is declining. This technology will therefore not be
discussed further here.

Basecoats
The main function of the basecoat is to impart color and special effects. Modern
basecoats cannot only be formulated in virtually any color but also to yield metal-
lic or pearlescent effects. A key function of the basecoat binder is to maximize
these effects.
Both solventborne and waterborne basecoat systems are found on the market.
There is a particularly pronounced trend toward the use of waterborne systems as
these allow a large reduction in solvent emissions of up to 85 % compared to sol-
ventborne formulations. Moreover, waterborne systems have advantages with
regards to special effects and stone-chip resistance. In 2004, waterborne basecoats
were applied on around 60 % of all the vehicles produced in Europe and the trend
remains on the increase.
Most basecoat formulations contain combinations of polyacrylate and polyurethane
binders. Polyurethane resins, e.g. “Bayhydrol”, greatly enhance important quality
characteristics such as brilliance, adhesion, leveling, flexibility, and, as a result,
stone-chip resistance.
Clearcoats
The binders used in clearcoats are expected to satisfy particularly high requirements
in terms of lightfastness, weather stability, resistance to etching and scratching, and
retention of optical properties (gloss, brilliance), even after many years of use. Most
of the binders used today in the formulation of automotive clearcoats are acrylic
resins crosslinked with various hardener systems.
Figure 5.41: Coating line for waterborne basecoats and two-component polyurethane
clearcoats in the automotive industry [62]

Two-component polyurethane clearcoats

Since they were first used in automotive OEM finishing by Mercedes-Benz in the
mid-1980s, polyurethane clearcoats have achieved a significant and steadily increas-
ing market share. Of the 60 million vehicles produced worldwide in 2005, approx-
imately 25 % were finished with a clearcoat containing polyurethane structures. A
solventborne two-component polyurethane clearcoat was used on around 7.5 mil-
lion vehicles. The key factors in the market success of these systems are the supe-
rior properties of polyurethane systems compared to conventional acrylate/melamine
systems (thermosetting acrylics = TSA). This applies to optical properties such as
gloss and leveling, as well as to mechanical and chemical resistance properties.
Moreover, the high compatibility of two-component polyurethane clearcoats with
waterborne basecoats has further boosted market growth in recent years. Today,
almost all automakers in Europe, NAFTA and Asia are investigating the use of
polyurethane clearcoats.
Two-component polyurethane systems are based on hydroxyfunctional acrylates,
and in some cases polyester resins, which are crosslinked with aliphatic polyisocya-
nates[53], such as the HDI-based
“Desmodur N” and the IPDI-
based “Desmodur Z”. Due to
their higher reactivity, they are
baked for around 20 to 30 min-
utes at between 130 and 140 °C.
Two-component polyurethane
systems differ from conventional
technologies in the following
aspects (Figure 5.43):
• Improved chemical and, in
particular, etch resistance Figure 5.42: Coating robot used in automotive
• Good mechanical properties OEM finishing [73]
(resistance to scratching and
stone-chipping)
• Outstanding optical proper-
ties (long-term gloss reten-
tion, brilliance)
• High solids content
• Reactivity
In addition to the technical
advantages over TSA coatings,
the higher material costs of two-
component polyurethane coat-
ings must be taken into account. Figure 5.43: Property profile of automotive clearcoats

However, these represent a relatively insignificant 20 % of total costs compared to

the process costs, which are estimated at 80 %. Higher capital expenditures must also
be considered because two-component equipment, hardener storage tanks and addi-
tional ring pipelines are required. In automotive OEM finishing, the application of
two-component polyurethane clearcoats is largely automated. Static Kenics mixers
have proved ideal for mixing the two components. As a rule, spraying is performed
electrostatically. Automatic flushing programs ensure that the formulation, once
mixed, does not remain in the mixer or spray gun longer than the pot life.
Two-component application equipment is more expensive to maintain than one-
component equipment. By modifying TSA coatings with blocked polyisocyanates,
it is possible to formulate one-component polyurethane clearcoats that represent a
compromise between two-component polyurethane and TSA coatings in terms of
their technical properties and can be applied using one-component equipment.
Intensive development work has been in progress for many years in an effort to
improve resistance to scratching, etching and chemicals. For this purpose, a number
of test methods have been developed which have a significant effect on the results.
In Europe in particular, the Amtec Kistler laboratory car wash simulator (Figure
5.44) is widely used for testing scratch resistance, while the gradient oven method
is used to determine chemical resistance (Figure 5.45).
Two-component polyurethane clearcoats based on linear or only slightly branched
polyacrylic or polyester resins and an HDI-based hardener such as “Desmodur N”
yield films with a relatively low glass transition temperature, high flexibility and
excellent scratch resistance.
Figure 5.44: Scratch resistance testing in Figure 5.45: Determining chemical

the laboratory car wash simulator [56] resistance by the gradient oven method [56]

The addition of an IPDI-based hardener such as “Desmodur Z” or the use of poly-

acrylates with a higher hydroxyl number increases the glass transition temperature
and hardness of the clearcoat films. However, their scratch resistance is noticeably
lower than that of the flexible formulations, although their resistance to etching and
chemicals is much higher [55, 56].
This inverse relationship between scratch and chemical resistance is derived from
basic laws of polymer physics and is also observed in other crosslinking technologies.
However, in the case of polyurethane crosslinking, both requirements can be satisfied
in high measure, thanks to the high chemical stability of the urethane bonds.
To further optimize scratch resistance while retaining high chemical resistance, two
approaches are being pursued in the latest generation of two-component polyure-
thane clearcoats. One approach uses inorganic nanoparticles [57–59] and has resulted
in a marked improvement in resistance to dry scratching. The second approach
involves clearcoats with a high crosslinking density and flexible network arcs.
When there is a balanced relationship between these two parameters, such two-
component polyurethane clearcoats are characterized by high reflow behavior. This
property is promoted by the formation of hydrogen bridge bonds between the ure-
thane groups, which contributes to the stability of the network [60, 61].
If heat is applied to a slightly scratched two-component polyurethane coating, the
scratches are observed to partially fill (Figure 5.46). This reflow effect can be
tracked in practice by gloss measurements and visually.
Waterborne two-component polyurethane clearcoats
The recently developed waterborne two-component polyurethane systems can be
considered as modern ecological variants of solventborne two-component polyure-
thane clearcoats [63-66]. The base resins used in these formulations are aqueous disper-
sions of hydroxyfunctional polyacrylates, polyesters or polyurethanes. The harden-
ers are hydrophobic, low viscosity isocyanurates like those used for high solid two-
component polyurethane coatings. If a low dispersion pressure is applied or if the
Figure 5.46: Self-healing two-component polyurethane clearcoat with high reflow capacity

co-solvent content of the waterborne two-component polyurethane clearcoat is very

low, hydrophilically modified isocyanurates can be added to the hardener to ensure
the adequate mixing quality of the clearcoat. In automotive OEM finishing applica-
tions, polyisocyanates containing sulfonate groups should be used [67]. The co-solvent
content of these clearcoats is about 5 to 10 %, depending on composition and disper-
sion pressure, but it will be possible to reduce this still further in the future.
Jet dispersion has been found to be better than conventional mixing technologies
for ensuring the optimal mixing of the aqueous polyol component with the non-
aqueous polyisocyanate. Two concepts have been applied in optimizing jet disper-
sion for two-component application in automotive OEM finishing [68, 69].
The physical relationships between the binder structure and film properties that
apply in two-component solventborne systems are also found to a large extent in
the equivalent waterborne systems. This means that the waterborne systems almost
fully match the solventborne systems in terms of high resistance properties and
good optical properties, brilliance, and leveling (Table 5.14).
One-component polyurethane clearcoats
Since the early 1990s, process technology and economic considerations have
resulted in an increasing use of solventborne one-component polyurethane systems,
sometimes containing melamine resins in the hardener, alongside two-component
polyurethane clearcoats.
Table 5.14: Quality profile of selected OEM clearcoats

Technology Chemical Weather Mechanical Optical
resistance stability properties properties
TSA – – – +
One-component + + ++ +
polyurethane/TSA
Two-component ++ ++ ++ ++
polyurethane, hs
One-component + + + -
polyurethane,
waterborne
Two-component + ++ ++ ++
polyurethane,
waterborne
Powder + + + +
++ = very good, + = good, - = moderate

The addition of blocked IPDI-based polyisocyanates can greatly increase the acid
resistance of solventborne melamine-crosslinked clearcoat systems. Here too,
blocked HDI-based polyisocyanates primarily increase the scratch resistance. On
account of their tendency to yellow on exposure to heat, blocked polyisocyanates
were long considered unsuitable for use in automotive OEM topcoats. Today, hard-
eners blocked with 3,5-dimethylpyrazole are used almost exclusively since they
are virtually non-yellowing [70]. However, the other film properties are not of the
same high level as those yielded by two-component polyurethane coatings. Block-
ing polyisocyanates therefore does not serve primarily to improve the film proper-
ties but to allow a simplification of the application process compared with two-
component technology.
Waterborne one-component polyurethane clearcoats
Alternative systems based on aqueous products have also been developed for one-
component automotive clearcoats. In the same way as for solventborne clearcoats,
the addition of blocked polyisocyanates in waterborne one-component systems
greatly improves the resistance properties. A slurry clearcoat based on blocked
polyisocyanates has been in use in automotive OEM finishing for many years as a
solvent-free alternative to powder clearcoats. The leveling and brilliance of the
waterborne one-component clearcoats are highly dependent on the rate of evapora-
tion of the water and thus on ambient conditions, making process control more
complex than when using solventborne systems. Waterborne two-component
clearcoat systems perform far better in this respect as they are less sensitive to
fluctuations in humidity and temperature.
5.3.5 Outlook
Since their first use in 1985, polyurethane clearcoats have experienced dramatic
growth rates in automotive OEM finishing. In 2005 around 15 million cars world-
wide were finished with two-component polyurethane clearcoats, polyurethane-
modified one-component clearcoats, or clearcoats containing polyurethane struc-
tures (carbamate systems). This upward trend is continuing, especially in the case
of two-component polyurethane clearcoats. Strong growth rates are expected in the
coming years, particularly in Asia, often in combination with the introduction of
waterborne basecoats. The waterborne two-component polyurethane clearcoats
described above represent ecologically interesting alternatives which permit a fur-
ther reduction in solvent emissions from the coating process.
UV-curing polyurethane clearcoats also represent an innovative development. They
can be crosslinked just photochemically (mono-cure) or by a combination of pho-
tochemical and thermal curing (dual-cure) [71]. This technology would appear to
offer further scope for optimizing the scratch and chemical resistance properties
(see Figure 5.47, page 150).

In the automotive OEM segment, environmental requirements have become as

important as the demands for increased quality and lower costs. All these consid-
erations are contributing significantly to technological change. In the light of this,
UV, powder, and waterborne coating technologies are certain to see further market
growth and it will be possible to reduce solvent emissions still further.
New routes must also be followed in the effort to reduce costs since the savings
potential with regards material prices has been exhausted. Current development
work is focused on optimizing process technologies. Important here are the inte-
grated processes in which the primer surfacer is omitted and the basecoat assumes
its role, or the primer surfacer also fulfils the function of the basecoat. UV-curing,
which accelerates production cycles, could play an important role in clearcoat
development.
One important aspect at present is the globalization of the automotive industry with
the construction of new production facilities all over the world. This has resulted
in globalization of the supplier industries as well and has far-reaching consequences:
the construction of overseas production facilities, cooperation with local suppliers,
the standardization of products and technologies, and the observance of other
national regulations and legislation, etc. [72].
The strategic positioning of the supplier industries, including the supplies of coat-
ings and coating raw materials industries, in the international market will make
globalization a vital instrument in improving competitiveness.
Figure 5.47: Optimization potential of scratch and etch resistance of OEM clearcoats

Automotive refinish and transportation coating 151
5.4 Automotive refinish and transportation coating

Automotive refinish coatings differ from OEM coatings in that the former can
be cured at maximum temperatures of 60 °C, while OEM coatings can be cured
at much higher temperatures (typically 130 to 180 °C). In automotive refinishing,
coatings are applied to complete vehicles, including temperature-sensitive plastic
components, filled gas tanks, and car tires, which is why curing at high tempera-
tures is impossible. The situation is similar in the transportation sector (buses,
trucks, airplanes, and rail vehicles). Due to the size of these vehicles, it is not eco-
nomical to cure the coatings in drying booths at temperatures significantly above
room temperature. As the property profiles and application conditions are similar,
slightly modified or even original automotive refinish coatings are often used for
transportation coating.
The history of automotive refinish coatings dates back to the early 20th century as
the popularity of motoring grew. The coach enamels used at that time, based on
natural resins, were succeeded by nitrocellulose lacquers around 1925. A few years
later, medium-oil alkyd coatings were developed. Starting in 1940, spray applica-
tion, the technical innovation of the day, replaced conventional brush application.
Polyurethane chemistry came into refinishing in the form of reactive thinners for
medium-oil alkyd resins. These thinners were dilute solutions of IPDI adducts,
later IPDI trimers, which were added to the coatings before their application. They
greatly improved the overcoatability, through-drying and solvent resistance of the
alkyd coatings.
The solventborne two-component polyurethane coating systems which came onto
the market around 1970 became the dominant resin systems for automotive refin-
ish coating within just 20 years (Figure 5.50, page 154). More recent development
work, especially in Europe, has been directed by the trend towards reducing the sol-
vent content of coatings. This resulted in the introduction of waterborne basecoats
and high solid clearcoats.
Figure 5.48 and 5.49: Examples of the application of two-component polyurethane coatings

This development was preceded in 1965 by the first use of lightfast two-component
polyurethane coatings on the exterior of airplanes and rail vehicles. Polyurethane
coatings now dominate the transportation sector (including trucks and buses)
worldwide [74]. The reason for this success is the high resistance properties of
polyurethane systems compared to the previously used coatings based on nitrocel-
lulose and alkyd resins.
The use of polyurethane systems on rail vehicles meant that the intervals between
necessary repair finishing and complete recoating could be prolonged. Compared
to coatings based on nitrocellulose or alkyd resins, polyurethane systems display
much higher resistance to both alkaline and acid cleaning agents, which are used
Figure 5.50: Technology developments in the West European automotive refinishing
Figure 5.51: Comparison of the weather stability of various clearcoats for automotive
refinishing (here: UV-A weathering)

to remove brake dust and insect remains, as well as better weather stability (UV
radiation, Figure 5.51). German railway operator Deutsche Bahn, for example,
chose polyurethane systems for its vehicles not only because of the extended main-
tenance intervals, but also because the rail vehicles retain their new appearance
much longer, which has a positive impact on the company’s image.
In addition to the typical two-component polyurethane systems which dominate as
primer surfacers, topcoats and clearcoats in automotive refinishing, there are coat-
ings based on other types of resins for use in special applications. These include,
for example, solventborne one-component basecoats formulated with cellulose
acetobutyrate (CAB) and co-resins. Another example is found in the high-grade
corrosion protection primers (wash primers) based on polyvinyl butyral (PVB)
combined with phosphoric acid. Lastly, alkyd and nitrocellulose resins are used to
formulate one-component primer surfacers and topcoats of medium quality.
5.4.1 Property profile

The success of polyurethane coatings in automotive refinish applications is basi-
cally easy to explain. No other coating system crosslinks at room temperature yet
yields properties so close to those of OEM finishes. Despite the different conditions
in which automotive refinish and OEM systems (Table 5.15) are applied, the coated
surfaces are expected to differ little in terms of general quality and, above all,
appearance [74]. The two-component polyurethane coatings currently in use for auto-
motive refinishing fully satisfy these requirements as well as customers’ demand
that there be no deterioration compared with the original finish. This demand for
Table 5.15: Comparison of requirements in automotive OEM finishing and refinishing

Automotive and truck Transportation coating Automotive and trans-
OEM finishing portation refinishing
Industrial scale Industrial scale Bodyshops
Identical units Identical units Very different units
High volume Medium volume Very low volume
Automated application Partly automated, partly Manual application
manual application
Precise control of film Partial control of film thick- Variable film thickness
thickness ness
Special, manufacturer- Special, manufacturer- Universal formulations
specific formulations specific formulations needed
Drying at high temperatures Drying at low temperatures Drying at low temperatures
(130 to 180 °C) (RT to 80 °C) (RT to 80 °C)

high quality also applies to transportation coating. In this sector, too, polyurethane
systems have set benchmarks and in many cases already yield the same high qual-
ity as automotive OEM coatings.
However, a refinish coating must not only provide optimum surface protection, it
must also be economical, i.e. fast-drying, so that bodyshop capacity can be used
efficiently. Guide values for drying times are maximum 30 minutes at 60 °C or 4
hours at room temperature.
5.4.2 Steps in automotive refinishing and transportation coating
Figure 5.52 shows the typical sequence of automotive refinishing. The damaged car
body component is hammered out and sanded to improve the adhesion of the sub-
sequent functional coats. Dents deeper than 1 mm can be covered with a polyester
knifing filler, which is then sanded to give a smooth surface. A one-component anti-
rust primer, known as a wash primer, is then applied in a thickness of about 10 µm
Figure 5.52: Process steps in automotive spot refinish
Figure 5.53: Cross-section of an automotive refinish coating

to prevent the corrosion of any areas of metal that may have been laid bare by sand-
ing. This primer is based on polyvinyl butyral and contains phosphoric acid.
A two-component polyurethane primer surfacer is applied in a thickness of 60 μm

to further smooth the surface and protect the knifing filler and wash primer. After
intermediate sanding, a high-quality two-component polyurethane topcoat or a
basecoat/clearcoat combination is applied. The resulting refinish system has an
average total film thickness of 150 μm (excluding the knifing filler) – about twice
the film thickness of an OEM coating (Figure 5.53). In contrast, a transportation
coating system is usually much simpler, but also more customized, depending on
vehicle type. In the case of maintenance operations, the old coating is removed
either by sandblasting (rail vehicles, airplanes) or by aggressive solvent mixtures
(airplanes). The bare metal is coated with a direct-to-metal primer in a thickness of
about 100 μm, which protects against corrosion and ensures surface smoothness.
Prior to this, any dents deeper than 1 millimeter can be filled with a polyester knif-
ing filler, which is sanded smooth.
In OEM transportation coating, a two-component polyurethane primer surfacer is

often applied in a thickness of about 100 μm to further smooth the surface and
protect the knifing filler and primer. After intermediate sanding of the primer (refin-
ish) or primer surfacer (OEM), a high-quality pigmented two-component polyure-
thane topcoat is applied. Increasingly, the transportation sector is using a two-coat
finish of a basecoat (20 μm) and a two-component polyurethane clearcoat (60 μm),
e.g. on buses, passenger trains and truck cabins.
The resulting system has an average total film thickness of about 200 μm (exclud-
ing knifing filler) in the case of refinishing and about 300 μm in the case of OEM
coating, making it much thicker that an automotive refinish coating. The main
reason for this is that the system does not include a CED primer so corrosion
protection has to be ensured mainly by application of a higher film thickness
(Figure 5.54).
Figure 5.54: Cross-section of a transportation coating

5.4.3 Application and characteristic data of two-component

polyurethane coatings
The two-component polyurethane coatings used in automotive refinishing are mixed
shortly before application. The mill base (polyol) and hardener (polyisocyanate) are
metered in parts by volume using a graduated metering stick, which is then used to
mix the coating. The coatings are adjusted to spray viscosity before application, that
is, they are thinned with suitable solvents or water to the extent required for spray
application. The technical information sheet indicates the amounts needed. The
typical viscosity of an automotive refinish coating is 20 s flow time at 23 °C in a
DIN 4 cup. In Western Europe, the coatings are normally applied using HVLP (high
volume, low pressure) spray guns, which reduce spray mist formation. The two-
component polyurethane primer or the primer surfacer is sanded after drying for
about three hours at ambient temperature, and then overcoated with a two-compo-
nent polyurethane topcoat. In the case of automotive refinish coating, the topcoat is
dried in a drying booth for 20 to 30 minutes at 60 °C or at room temperature. When
refinishing smaller areas, an IR lamp can be used to accelerate drying.
Table 5.16: Characteristic data of a solventborne two-component polyurethane clearcoat

for automotive refinishing and transportation coating
Coating/film parameter Characteristic data
Solids content [%] 45
Mixing ratio of mill base to hardener
[parts by volume] 2:1
Pot life [h] 4
Drying at 23 °C T1 (sand-dry) [h] <1
T3 (touch-dry) [h] 1-2
Drying after 30 min at 60 °C T1 (sand-dry) [h] immediate
T3 (touch-dry) [h] immediate
Blister-free dry film thickness [µm] > 100
Pendulum hardness
after 30 min at 60 °C + 1 day [s] 100
7 days [s] 180
Condensation resistance (240 h/40 °C) OK
Chemical resistance OK
Outdoor weathering, 24 months in Florida 88/84
Gloss 20°, before/after
Accelerated weathering, 1,000 h QUV (313 nm)
Gloss 20°, before/after 88/84

On account of the larger coating volumes that are processed in transportation coating,
stirring units (rail vehicles, buses) or even two-component mixing equipment (OEM
truck coating) are often used. The application is usually performed using the airless
or airmix method. The ideal mixing ratio for topcoats is 2 : 1 (mill base : hardener),
but for primer surfacers it is usually 4 : 1 due to the lower hardener requirement.
In the transportation sector, drying is often done at room temperature. When coat-
ing rail vehicles, the maximum oven temperature is 60 °C. Only truck cabins are
finished with baking coatings that are dried at temperatures similar to those used
in automotive OEM finishing (130 to 160 °C). However, the trend here is also
towards lower drying temperatures. Table 5.16 summarizes the typical character-
istic data of a refinish coating dried at low temperature. The key features are out-
standing optical properties (gloss, leveling), the retention of these optical properties
over long periods, mechanical resistance (resistance to scratching and stone chip-
ping), gasoline resistance and resistance to chemicals and etching (acid rain, caus-
tic cleaning agents). The coatings are formulated to yield blister-free films at the
high film thicknesses (more than 100 μm) which may occur in refinishing.
5.4.4 Raw material selection

Various polyol components are available on the market for the formulation of two-
component polyurethane primer surfacers and topcoats. As a rule, these are hydroxy-
functional polyacrylates or polyesters with various characteristics (hardness, flex-
ibility, hydroxyl content), which are combined with suitable polyisocyanate harden-
ers. Table 5.17 (page 160) shows key raw materials for solventborne (medium
solids) formulations for automotive refinish and transportation coating.
Mill base
The resins used have a hydroxyl content between 2 and 8 % by weight (calculated
on the solid resin) and an average molecular weight between 5,000 and 20,000 g/
mol. The relationship between the molecular weight and specific coating properties
is of particular significance when drying at room temperature. Although resins with
a high molecular weight produce the fast drying required, a correspondingly large
amount of solvent is needed to adjust the coating to spray viscosity (flow time).
This is not compatible with the demand for environmentally friendly coatings (see
VOC problems). In principle, the solvent content of a ready-to-spray coating can
be more easily reduced when using polyester resins than when using polyacrylates.
However, polyacrylates generally exhibit much faster drying and better weather
stability than polyesters, which has made polyacrylates the dominant binder type
in automotive refinish clearcoats. The conflict between achieving fast drying and
a high solid content remains the focus of intense research activity, which has led
to the development of high solid systems and reactive thinners such as aldimines,
ketimines and aspartic esters.

Table 5.17: Aliphatic polyisocyanates and polyols for automotive refinishing systems
Type Typical NCO con- Glass Properties and
solids tent [%] 1) transition applications
content [%] tempera-
and solvent ture Tg [°C]
HDI biuret 3) 75 MPA/X 16.5 approx. – 60 Standard grade for
primers, primer surfac-
ers and topcoats
HDI isocyan 90 BA/SN 19.6 approx. – 60 Standard grade for

urate 4) primers, primer surfac-
ers and topcoats
IPDI trimer 5)
70 MPA/X 11.9 approx. +60 Combination hardener
for blends
Type Typical OH content Glass Properties and
solids [%] 2) transition applications
content [%] tempera-
solvent ture Tg [°C]
Polyacry- 50 BA/X approx. 2 approx. +70 Standard grade, fast-
late 6)
drying, combination resin
Polyacrylate 60 X approx. 2.7 approx. +20 Standard grade for
primers and primer
surfacers (low hardener
requirement)
Polyacrylate 70 BA approx. 4.2 approx. +20 Topcoats and clearcoats
Polyester 7) 80 BA approx. 4.3 approx. -25 Flexibilizing combination
resin
Polyester 70 BA approx. 3.0 approx. +10 Especially for topcoats/
transportation coating
(very good pigment wet-
ting properties)
Polyester 65 MPA approx. 8.2 approx. –5 For high-resistance
clearcoats and top-
coats, especially for
transportation coating
1) Calculated on supply form; 2) Calculated on solid resin; 3) e.g. “Desmodur N75 MPA/X”; 4) “Desmodur
N 3390 BA/SN”; 5) “Desmodur Z 4470”; 6) “Desmophen A 450 BA/X”; 7) “Desmophen 650 BA”

By mixing suitable polyols, formulations can be customized for various coating

requirements. Adding polyacrylates with a high glass transition temperature and
high molecular weight to two-component polyurethane coating systems yields
faster drying and increased hardness, consistently good optical properties, but
relatively low elasticity. These formulations are therefore ideal for use as primer
surfacers with early sandability or as fast-drying clearcoats and topcoats.
The addition of polyesters with a low molecular weight flexibilizes two-component
polyurethane systems. The use of suitable catalysts (typically dibutyl tin dilaurate
= DBTL) yields coatings with an adequate pot life that dry under normal application
conditions. This type of combination is preferred for the refinishing of plastic com-
ponents. Polyesters are also uses to formulate topcoats for transportation coating.
Their outstanding pigment wetting properties result in high-gloss films.
At the same time, their slower drying results in better spray mist absorption. In
transportation coating, this means that a second coat can still be easily absorbed by
the first in overlapping coating zones, without causing any irregularities in the paint
film. Such systems are used, for example, as topcoats for bus and rail vehicles.
Hardener
As automotive refinish systems are required to have good weather stability, only
aliphatic polyisocyanates can be used as the hardener component. The most
important products by far are biurets and isocyanurates (trimers) of hexameth-
ylene diisocyanate. In automotive refinish coating, trimers are increasingly
favored over biurets because they allow the formulation of high solid coatings
and improve the long-term resistance properties of the paint films. IPDI-based
polyisocyanates are also added to improve physical drying. Catalysts and special
high and low boiling solvents allow the formulations to be customized to meet
application requirements:
• Mixing with IPDI-based polyisocyanates – fast drying (spot refinishing, winter
application)
• Addition of catalysts (e.g. DBTL)
– Improved chemical through-curing (spot refinishing, winter application, air
drying)
• Use of solvents with graduated evaporation rates
– Addition of high boiling solvents (full refinishing, summer application)
– Addition of low boiling solvents (spot refinishing, winter application)
Although aromatic, i.e. non-lightfast, polyisocyanates were once used for primers,
nowadays lightfast hardeners are used almost exclusively. The main reasons for
this are the simplification of inventories, the elimination of mix-ups when various
hardeners are available, and the improved stone-chip resistance.

5.4.5 Low emission polyurethane coatings

Whereas in the past the emphasis was primarily on improving the quality of auto-
motive refinish coatings, the focus today is on environmental protection and the
preservation of resources. Legislative initiatives in Europe and the United States
(e.g. California) aim to reduce the use of organic solvents and thus cut emissions
in automotive refinishing. In some Asian countries, for example in Japan and Korea,
there is some evidence of similar approaches.
In 1999 and 2004, the European Union passed directives which define limits for the
maximum content of volatile organic components (VOC) in coatings. These direc-
tives must be adopted as national law (largely finalized) by all EU member states
and enter into force in 2007. Maximum permissible emissions are set depending on
the application and the type of coating (Solvent Emissions Directive 1999/13/EC
and Decopaint Directive 2004/42/EC). From January 1, 2007, the following thresh-
olds must be observed in automotive refinishing (Table 5.18).
There are two routes for reducing emissions from automotive refinish and trans-
portation coatings:
1. The formulation of solventborne coatings with a high solid content: high solid
coatings, HS (VOC ≤ 420 g/l for topcoats; VOC ≤540 g/l for primers and primer
surfacers)
2. The formulation of waterborne coatings
Waterborne and solventborne coating systems are in competition with each other.
In Western Europe, solventborne coatings with a high solid content (high solid
Table 5.18: VOC values of low emission automotive refinish coatings

Automotive refinish VOC1) value [g/l] Technology
system according to DPD
Knifing filler 250 UPE
Primer 540 Two-component polyurethane MS/HS
Primer surfacer Waterborne two-component
polyurethane
Basecoat 420 Waterborne one-component
Clearcoat 420 Two-component polyurethane HS
Waterborne two-component
polyurethane
Solid-color topcoat 420 Two-component polyurethane HS

Waterborne two-component polyurethane
1) VOC = Volatile organic compounds in grams per liter of coating

coatings) are preferred for automotive refinish coating because they are easier to
handle and because statutory VOC threshold values are higher. In many ways, high
solid coatings perform similarly to their conventional counterparts, e.g. in terms of
process reliability for the applicator. Only in the case of basecoats are there no
alternatives to waterborne systems due to their solids content of about 20 to 30 %.
High solid, solventborne basecoats make little technical sense, since the aluminum
particles (flakes) contained in metallic systems require a large liquid content (water
in the case of waterborne basecoats) to ensure their uniform alignment as the coat-
ing dries. Waterborne basecoats already have a market share of about 50 % in
Europe (2006). Waterborne primer surfacers and clearcoats are also already on the
market, but as yet with limited success.
The situation in the case of transportation coating is totally different (Solvent
Emissions Directive 1999 /13/EC). The legislator has set much lower thresholds
than those for automotive refinishing, depending on the metal surfaces being coated.
Moreover, transportation coating is often a (semi-) industrial process, which per-
mits better control during the preparation and application of the coatings. In the
past, certain companies (e.g. Deutsche Bahn) switched to the use of waterborne
coating systems to better protect their employees from solvent emissions and to
promote their (green) image. In their function as opinion leaders, these compa-
nies significantly furthered the market penetration of waterborne formulations in
transportation coating. Germany, the largest Western European market, often uses
waterborne two-component polyurethane primers and almost always waterborne
two-component polyurethane topcoats in refurbishing passenger rail vehicles and
locomotives. These systems are being tested in France, Austria and the United
Kingdom, and are already used to a certain extent. Waterborne two-component
polyurethane topcoats have been used with great success in the OEM coating of
truck chassis for some years.
Figure 5.55 shows a comparison

of a solventborne automotive
refinish coating and a modern
concept with 60 % lower solvent
emissions [75]. At the present
stage of development, it would
seem that the implementation
and practical use of such a tech-
nology is entirely feasible. In the
transportation sector, the situa-
tion is more complex due to leg-
Figure 5.55: Comparison of solvent emissions in
islative requirements. In addi- kg per car body from different coating concepts
tion to high solid topcoats, which used in automotive refinishing

are used for buses and airplanes, waterborne topcoats and, more recently, water-
borne basecoat/clearcoat systems have been used increasingly, especially for rail
vehicles and trucks. Waterborne primers (direct-to-metal) and primer surfacers are
already available and in use.
5.4.5.1 Two-component polyurethane high solid coatings
Two-component high solid polyurethane coatings are based on the same chemistry
as the established solventborne two-component polyurethane coatings. However,
the coreactants used are lower molecular weight products with a narrow molecular
weight distribution that ensure that less solvent is required to adjust the coatings to
application viscosity. A large range of polyisocyanates and polyols is available to
achieve that goal (Table 5.19). The end properties of the paint films are of the high
quality required.
In the case of high solid acrylates, the average molecular weight is only half that
of conventional acrylates. Various polyols are available depending on the required
property profile of the film. As automotive refinish coatings are also expected to
yield scratch-resistant paint films, suitable polyols have been developed. One
approach is to formulate self-healing clearcoats via an increased crosslinking den-
sity and a low glass transition temperature (Tg) [60, 61].
Compared to the conventional system, the molecular weight of low viscosity HDI
isocyanurate is also about 20 % lower (Table 5.19). The viscosity of the supply form
is thereby reduced from 3,000 to 1,200 mPa·s. Using a special catalyst technology,
the trimerization of hexamethylene diisocyanate can be made to produce predom-
inantly asymmetric trimers (iminooxodiazine dione). This molecular structure
greatly reduces the viscosity of the HDI isocyanurate to 700 mPa·s, while the
functionality of less than 3 is retained [76]. Coatings based on the high solid products
described above yield VOC values of less than 420 g/l. They thus meet the require-
ments of the Decopaint Directive 2004/42/EC.
5.4.5.2 Two-component very high solid polyurethane coatings
Low emission two-component polyurethane coatings with a VOC value of less than
250 g/l require the use of additive resins, such as reactive thinners, which have a
strong viscosity-reducing effect. These substances are mixed with the polyols or
can be used without polyols. Special, extremely low viscosity polyisocyanates are
used as hardeners. Suitable reactive thinners such as aldimines, ketimines and
aspartates are shown in Table 5.20 [77] (page 164). These amine reactive thinners
crosslink via secondary amino groups. They are sterically hindered to reduce their
reactivity, making them easy to handle.
The low viscosity symmetric and asymmetric HDI trimers described above are used
as the polyisocyanates in very high solid (VHS) coatings. Also suitable are HDI
allophanates and uretdiones adjusted to extremely low viscosities (Table 5.19).

Table 5.19: Coating raw materials for low emission two-component polyurethane
high solid topcoats
Type Typical NCO Vis- Glass Properties and
solids content cosity transition applications
content and func [mPa·s] tempera-
[%] and tionality 23 °C ture Tg [°C]
solvent [%] 1)
HDI isocyan- 100 23.0 / 3.1 1,200 approx. -60 Standard for all
urate 3) applications
HDI iminooxa- 100 23.5 / 3.1 700 approx. -60 HDI trimers
diazine dione 4) with the lowest
viscosity at a
functionality > 3
HDI allophan- 100 19.8 / 2.5 350 approx. -60 Low viscosity
ate
HDI uretdione 5) 100 21.8 / 2.5 150 approx. -60 Low viscosity
HDI uretdione 100 22.5 / 2.3 80 approx. -60 Polyisocyanate
with the lowest
viscosity
IPDI allophan- 80 BA 15.0 / 2.5 2,800 approx. +60 Low viscos-

ate 6) ity IPDI-based
polyisocyanate
Type Typical OH Vis- Glass Properties and
solids content cosity transition applications
content [%] 2) [mPa ·s], tempera-
[%] and 23 °C ture Tg [°C]
solvent
Polyacrylate 70 BA 4.0 1,200 approx. +30 Standard type
Polyacrylate 7) 75 BA 4.8 5,000 approx. +25 Standard type

with improved
gasoline resis-
tance
Polyacrylate 75 BA 7.2 3,500 approx. +15 Improvedscratch
resistance
Polyester 75 BA 6.0 4,000 approx. +10 Topcoats and
clearcoats
1) Calculated on supply form; 2) Calculated on solid resin; 3) e.g. “Desmodur N 3600”; 4) “Desmodur
XP 2410”; 5) “Desmodur N 3400”; 6) “Desmodur XP 2565”; 7) “Desmophen A XP 2594”

By combining these low viscosity

polyisocyanates with high solid
acrylates and reactive thinners, it is
possible to achieve VOC values of
250 g/l. The products are compatible
with one another and, despite the
presence of amino functions, the pot
life is adequate for normal applica-
tion conditions. The films through-
dry quickly at room temperature and
when force-dried at 30 minutes at
Figure 5.56: Freight cars with a very high 60 °C. The reduction in viscosity
solids coating based on “Desmophen NH”: also results in a reduction in func-
half the coating time, low emissions and high
coating quality
tionality of the polyisocyanates dis-
cussed here – to the detriment of the
crosslinking density (Table 5.19). For this reason, attention must be paid to the
solvent and chemical resistance of these formulations to ensure compliance with
the required specification [78, 79].
In the United States, these products are being used to formulate two-component
polyurethane primer surfacers, clearcoats and topcoats for automotive refinish coat-
ing. In Western Europe, they are being tested for primer surfacers in particular.
There is also growing interest in these systems as alternatives to waterborne for-
mulations for transportation coating. Figure 5.56 shows a freight car finished with
a one-coat system based on aspartate/polyisocyanate. The coating time was halved
compared to the use of a conventional two-coat system (epoxy primer and poly-
urethane topcoat), without incurring any reduction in coating quality.
Table 5.20: Reactive thinners for high solid coatings

Type Amine
SC Viscosity CV
equivalent
[%] [mPa ·s]
weight
Aldimine 100 25 20 139
Ketimine 100 100 < 100 167
Aspartic ester 90 130 50 326
100 1,400 < 100 290
100 1,500 < 100 276
100 < 100 < 100 234
SC = Solids content
CV = Color value (APHA [American Public Health Association]/DIN EN 1557)

5.4.5.3 Waterborne polyurethane coatings

Waterborne coating systems perform very differently to solventborne systems in
terms of their application and drying properties. This is due largely to the special
physics of water, which results in the different evaporation behavior and usually
higher susceptibility to blistering of waterborne systems compared to solventborne
coatings. Moreover, ambient conditions such as temperature and humidity play a
larger role in the application of waterborne coatings. Furthermore, waterborne two-
component polyurethane coatings [80, 81] are a two-phase system, consisting of an
aliphatic polyisocyanate dissolved in an organic solvent and a waterborne polyol
dispersion, which are mixed shortly before application. A number of peculiarities
of waterborne two-component polyurethane coatings compared with solventborne
formulations must be considered in manual application. In automotive refinishing,
and to some extent in the transportation sector, it is usual to mix the polyisocyanate
hardener and the mill base by hand using a measuring stick. Only polyisocyanates
with good emulsification properties in water yield the desired fine droplet size of
less than 200 nm. This is essential to achieve transparent films after spray applica-
tion and drying.
Waterborne two-component polyurethane coatings are also expected to have a pot
life of at least three hours. It must be possible to apply the premixed two-component
coating within this time without any turbidity occurring. This is only possible if the
polyol dispersion stabilizes the fine polyisocyanate droplets and prevents their
agglomeration. The increase in viscosity which is frequently observed after mixing
the polyol dispersion and polyisocyanate hardener is typical for two-component
waterborne coatings, but it is less critical because it remains far below double the
value. However, it is dependent on the formulation.
When using waterborne two-component polyurethane formulations in automotive
refinish coating, particular attention must be given to the mixing quality (fluctuation
is hard to avoid in bodyshop application), as well as to the effect of temperature and
humidity on the paint film. The maximum blister-free dry film thickness is particu-
larly important as it is far more dependent on application conditions when applying
waterborne coatings than when working with solventborne coating. In contrast,
modern waterborne two-component polyurethane coatings have drying speeds and
resistance properties which are equal to those of solventborne formulations.
The situation in some areas of transportation coating is different. In the coating of
rail vehicles, where comparatively few vehicles can be coated in one unit of time,
and the coating is in some cases dried overnight, the cost effectiveness of the drying
process does not play the central role. Mechanical stirring units are often used to mix
the hardener and polyol components. After all, the requirements made of the coating’s
optical properties are lower than compared to automotive refinish coating.

Figure 5.57: Deutsche Bahn uses waterborne two-component polyurethane coatings in

rail vehicle refinishing
Truck coating is an industrial process similar to automotive OEM finishing, which

often allows good control over temperature and humidity during coating and drying.
Drying temperatures above 60 °C and fully automated two- or three component
(polyol plus hardener plus water) mixing equipment are frequently used. Water-
borne systems have successfully prevailed in recent years in both truck and rail
vehicle coating. Figure 5.57 shows the refinish process in a Deutsche Bahn repair
shop. A waterborne two-component polyurethane primer and a waterborne two-
component polyurethane topcoat are used. This concept has since been proven in
many years of practical use [82].
Waterborne basecoats
In Germany, waterborne basecoats hold a market share of about 50 % in the auto-
motive refinishing segment and this continues to grow. Like solventborne basecoats,
one-component technology has also become established in this segment. Crosslink-
ing with (often hydrophilically modified) polyisocyanates is used as well. In trans-
portation coating too, the share of basecoat/clearcoat systems is currently increas-
ing compared to pigmented topcoats. Waterborne basecoats are thus gaining impor-
tance in this segment.
The resins used for waterborne basecoats are acrylic dispersions, urethanized poly-
esters, polyurethane dispersions and combinations of these. Polyurethane dispersions
are preferred as co-resins to improve coating quality and have the following advan-
tages over acrylic dispersions:

• Greater hardness and toughness (Tg: 10 to 30 °C) with a low minimum film-
forming temperature (< 0 °C)
• Improved pigment wetting
• Improved substrate adhesion
• Improved elasticity and thus increased stone-chip resistance
The particular advantage of waterborne basecoats lies in the reduced organic sol-
vent emissions. If the application process is included in the emission calculation,
a reduction of up to 60 % can be achieved. In addition, the better hiding power of
these materials means that two spray passes instead of the usual three are sufficient
to ensure good coverage.
Experience has shown that the quality (storage stability, effects, shade matching)
and cost-effectiveness (spray passes, coating times, drying cycles) of waterborne
basecoats are equivalent to those of solventborne basecoats. In the case of special
colors or when working with solvent-sensitive substrates, their performance is in
fact superior to solventborne systems.
Waterborne two-component polyurethane systems for automotive refinish

and transportation coating
Automotive refinish coating, with a requirement profile similar to that of OEM
finishing but drying at a maximum of 60 °C, and transportation coating, character-
ized by the large surfaces to be coated, present significant challenges for waterborne
coatings. On the polyol side (Table 5.21, page 169), emulsion polymers (primary
dispersions) and acrylate-based secondary dispersions are available for the formu-
lation of waterborne two-component polyurethane systems for these applications.
They yield paint films with the necessary hardness. Secondary dispersions are
characterized by medium molecular weights and a co-solvent content as high as
10 %. After curing with suitable polyisocyanate hardeners, they yield paint films
with excellent optical and resistance properties. The spectrum of secondary disper-
sions ranges from grades that produce good industrial coating quality (a lower
hydroxyl group content) to high-quality products for finish that satisfies automotive
standards. Fast-drying grades satisfy the requirement for high coating process effi-
ciency coupled with retention of the good film property profile. Polyester polyac-
rylate hybrid dispersions are also used. Their strengths lie in the formulation of
pigmented systems and higher application reliability.
Primary dispersions have much higher molecular weights than secondary disper-
sions and can be produced without co-solvents. They can be used to formulate
primer surfacers or sanding fillers, for example, which require very fast drying or
sandability. However, they are not suitable for high-grade topcoat applications
(Table 5.21, page 169).

Especially suitable on the polyisocyanate side are low viscosity hardeners, which
may be matched to the viscosity of the waterborne polyol component by dilution
with organic solvents, making them easier to incorporate. These hardeners are based
on low viscosity isocyanurates and iminooxadiazine diones of hexamethylene
diisocyanate (HDI), HDI and IPDI allophanates, and HDI uretdiones (Table 5.19).
Iminooxadiazine diones (asymmetric HDI trimers) in particular are excellent hard-
eners for waterborne two-component polyurethane coatings due to their high iso-
cyanate functionality (>3) and their good dispersibility in waterborne systems (as
a result of their very low viscosity). On the other hand, polyisocyanates modified
with emulsifiers (hydrophilically modified polyisocyanates) are also used in the
formulation of waterborne two-component polyurethane coatings for automotive
refinish and transportation coating due to their easy incorporation in waterborne
systems (Table 5.22, page 170).
The products yielded by reacting hydroxyfunctional polyethers with an excess of
HDI or IPDI trimer are characterized by good miscibility with polyol dispersions
on application of low shear (manual processing). In the polyether allophanate-
modified polyisocyanates, the hydrophilic polyether segments are connected to
the base polyisocyanate via allophanate structures, resulting in a higher isocya-
nate functionality and a reduced emulsifier content with reduced hydrophilicity of
the hardener. Such hardeners are particularly suitable for transportation coating,
where good hardness and high resistance properties are required. The polyiso-
cyanate hardeners of the third generation, which are hydrophilically modified
with ionic amino sulfonate units, are characterized by a significantly reduced
content of hydrophilic groups – with a comparably good dispersibility. The
chemical resistance, the drying and hardness development of films cured with
this new type of hardener offer scope for further significant improvement. On
account of the fast drying and excellent optical film properties, these hardeners
are particularly suitable for formulating clearcoats and topcoats for automotive
refinish and transportation coating, which make very high demands in terms of
film resistance properties.
When selecting a polyisocyanate hardener, it is important to find the best com-
promise between easy and reliable incorporation in the polyol dispersion on the
one hand (possibly considering manual mixing) and achieving the necessary
coating properties (especially hardness, gloss/haze, water resistance) on the other
hand. Good compromises can be achieved by mixing low viscosity with hydro-
philically modified hardeners, typically in a ratio of 1 : 1. Also, as is common in
the formulation of solventborne coatings for automotive refinish and transporta-
tion coating, mixtures of an HDI trimer with an IPDI allophanate or trimer can
be used to accelerate drying. One of these two components is hydrophilically
modified.

Table 5.21: Polyol dispersions for waterborne two-component polyurethane coatings
Polyol type Form OH Viscosity Org. co-sol pH Tg [°C] Characteristics

supplied content [mPa·s] vent 1) Type/ value
[%] [%] conc. [%]
Polyester polyacrylate
For large objects 2) 47 3.8 1,850 BDG 2.5 7.5 +6 – Good blister-free film thickness
Hard and flexible 3) 45 3.8 1,500 BG 8 7 + 45 – For fast-drying primer surfacers
and topcoats
Polyacrylate
Industrial coating quality 45 2.5 1,500 PnB 8 8.4 + 30 – Inexpensive (resin + coating
4)
45 3.3 950 BG/SN 8 8 + 28 system)
5)
Standard – Wide range of uses, good perfor-
45 3.9 2,000 PnB/SN 8 7.8 + 50 mance level
6)
High quality – Very good resistance and optical
film properties
Polyacrylate
fastdrying
Automotive refinish and transportation coating
Industrial coating quality 48.5 3.0 1,600 PnB/SN 4 8.5 + 35 – Fast drying. low VOC
7)
45 3.9 2,000 PnB/SN 8 7.8 + 50 – Fast drying. very good perfor-
8)
High quality mance level achieved rapidly
41 4.8 < 200 – – 7.5 – Two-component primer surface
Early sandability 9) with early sandability
1) BG = butylene glycol; BDG = butylene diglycol; PnB = propylene glycol n-butyl ether; SN = solvent naptha 100; 2) “Bayhydrol LS 2139/2”; 3) “Bayhydrol
LS 2290”; 4) “Bayhydrol XP 2469”; 5) “Bayhydrol A 145”; 6) “Bayhydrol XP 2470”; 7) “Bayhydrol XP 2620”; 8) “Bayhydrol 2601”; 9) “Bayhydrol XP 2546”
169
24.10.2007 17:33:21 Uhr

170

Table 5.22: Hydrophilically modified polyisocyanate curing agents for waterborne two-component polyurethane coatings
Polyisocyanate type Form sup- Viscosity NCO con- NCO Characteristics
plied [%] [mPa·s] tent [%] functional-
ity
HDI / standard 1) 100 3,300 17.4 3.2 – Hydrophilically modified standard
hardener
– Universal application, good perfor-
mance level
HDI / allophanate – High functionality
Low hydrophilicity 2) 100 4,000 18.2 3.8 – Better dispersibility / resistance ratio
3)
High hydrophilicity 100 6,800 16.2 3.8 compared to standard
HDI / sulfonate – Ionic hydrophilic modification
Low viscosity 4) 100 600 23.0 3.0 – Fast drying, hardness, stability com-
Low hydrophilicity 5) 100 5,400 20.5 3.4 pared to standard, lower hydrophilicity
6)
Medium hydrophilicity 100 3,500 21.2 with comparable dispersibily
IPDI / standard 7) 70 (BA) 600 13.4 3.0 – High glass transition temperature for
fast drying and high hardness
– Excellent weather stability
1) “Bayhydur 3100”; 2) “Bayhydur 304”; 3) “Bayhydur 305”; 4) “Bayhydur XP 2547”; 5) “Bayhydur XP 2487/1”; 6) “Bayhydur XP 2655”;
7) “Bayhydur 401-70”
24.10.2007 17:33:21 Uhr

The current trends in waterborne two-component polyurethane systems for automo-

tive refinish and transportation coating can be summarized as follows:
• Improvement of cost-effectiveness (faster drying, fewer coats)

• Improvement of robustness (blister-free film thickness)
• Further reduction of the co-solvent content
• Further improvement of technical properties such as adhesion on metal, intercoat
adhesion and chemical resistance
The first two targets will only be achieved through intensive cooperation between
the manufacturers of raw materials, equipment and coatings. New mixing, drying
and application concepts could be the key to boosting market penetration of water-
borne two-component polyurethane systems in the automotive refinish and trans-
portation coating segments. It is anticipated that greater efforts will made in these
directions with the entry into force of European VOC legislation in 2007. Raw
material manufacturers are already currently working intensively on further reduc-
ing the co-solvent content in dispersions.
Two-component polyurethane primer surfacers

Waterborne primers and primer surfacers based on acrylates, epoxy resins or poly-
urethanes are undergoing market testing in automotive refinish coating. They are
already used in transportation coating applications. Preference is given to crosslink-
able (two-component) systems with greatly reduced thermoplasticity, which are
less likely to clog the abrasive paper used in machine sanding.
On account of their good drying properties and pronounced hardness (resulting in

good sandability), emulsion polymers are often used in the formulation of these
systems. Mixtures of hydrophobic and hydrophilic polyisocyanates or purely
hydrophobic, low viscosity polyisocyanates are used as the hardeners. The resulting
systems satisfy requirements with respect to other key properties, such as a pot life
longer than 3 hours, blister-free films thicker than 100 μm, sandability after just 3
hours at 23 °C, and overcoatability with either solventborne or waterborne two-
component topcoats. On the downside, the adhesion of the overall coating system
(primer surfacer, basecoat and clearcoat) on a component sanded down to the bare
metal is inadequate on exposure to moisture (salt spray and condensation). Work
is focused on improving these characteristics.
Waterborne two-component polyurethane primers are replacing the solventborne

epoxy systems traditionally used to coat rail vehicles. This is due in particular to the
better sandability and homogeneous closed film yielded by the polyurethane primer
and to the possibility of applying a two-component polyurethane topcoat wet-on-
wet. Entirely waterborne systems are also being used in rail vehicle coating.

Two-component polyurethane topcoats

As in automotive OEM finishing, two-coat topcoats consisting of a basecoat and
clearcoat are being used increasingly in automotive refinishing. For this reason,
priority is being given to the development of waterborne clearcoats that satisfy
automotive refinishing requirements.
Table 5.23: Comparison of solventborne and waterborne two-component polyurethane
clearcoats
Parameter Two-component Two-component
polyurethane, polyurethane,
solventborne waterborne
Solids content [%] 45 45
Co-solvent content [%] 55 ≤10
VOC [g /l] >500 ≤ 200
Pot life [h] 6 3
Gloss 20° 90 87
Drying T1 (sand-dry) [h] ≤1 1
T3 (touch-dry) [h] ≤7 <7
Force-drying 1)
(30 min/60 °C) 0 0
Blister-free film
thickness [µm] ≥100 80
Solvent resistance 1)
7 d at RT 1 1
7 d at RT + 16 h at 50 °C 0 0
Water resistance1)
7 d at RT 0 0 –1
7 d at RT + 16 h at 50 °C 0 0
Pendulum hardness
7 d at RT [s] 100 160
7 d at RT + 16 h at 50 °C [s] 180 160
Outdoor weathering,
24 months in Florida 88 / 86 87 / 85
Gloss 20° before/after
1,000 h QUV (313 nm)
Gloss 20° before/after 88 / 86 87 / 85
1) Rating: 0 = good, 5 = unsatisfactory

In analogy to solventborne coatings,

polyacrylate dispersions are the domi-
nant type of binder used (Table 5.21).
They are crosslinked with third-genera-
tion hydrophilically modified harden-
ers. Table 5.23 compares the coating
and film properties of these waterborne
formulations to those of a solventborne
two-component coating.
Of particular note is the considerable
reduction in solvent emissions (≤200 g/l Figure 5.58: Waterborne two-component
compared to >500 g/l) from the ready- polyurethane topcoats improve the graffiti
to-spray coating. Other key parameters resistance of coating systems
such as the pot life, drying, optical prop-
erties, chemical resistance and weather stability have been improved to a level
that has greatly increased market acceptance, especially in transportation coating.
Waterborne two-component polyurethane clearcoats and basecoats based on bind-
ers and polyisocyanate hardeners from the latest product generation are already
superior to the solventborne systems in some respects. For example, they are more
resistant to the penetration of dyes (graffiti resistance, Figure 5.58) and in some cases
display better reactivity and faster drying. Although waterborne two-component
polyurethane clearcoats for automotive refinishing are now available commercially,
market penetration remains low. Further reductions in VOC thresholds should make
waterborne two-component polyurethane clearcoats the system of choice.
5.4.6 Radiation-curing coatings

As high drying speed and efficiency are two of the most important criteria for auto-
motive refinish systems, recent years have seen a growth in work to develop radia-
tion-curing automotive refinish coatings. Urethane acrylates are among the preferred
binders due to their good weather stability and film properties. These systems are
characterized by extremely fast drying and through-curing (the reaction is completed
within minutes). Furthermore, they are one-component systems, i.e. no metering or
mixing of the components is necessary, and the systems have no pot life.
Low-energy UV-A hand lamps (Figure 5.59, page 174) are used for curing, not least
for reasons of occupational safety. However, the coatings often fail to react com-
pletely. It is particularly difficult to prevent inhibition of the polymerization reaction
by atmospheric oxygen at the coating surface (surface inhibition). Moreover, the
shrinkage which occurs during polymerization can cause adhesion problems. These
can be overcome by choosing a suitable binder and adjusting the coating formu-
lation accordingly. UV-curing coatings are currently being developed and tested
for automotive refinish and transportation coating. The first systems have already

been introduced to the market. As well

as the pure radiation-curing coatings,
dual-cure systems are also available,
which combine radiation curing with
a second crosslinking mechanism (e.g.
NCO/OH).
5.4.7 Interior coating of
large vehicles
The production of rail, utility and other
large vehicles is very time-consuming
Figure 5.59: UV-curing polyurethane
coatings for fast refinish operations
and thus cost-intensive. Various areas
of the interior are usually finished with
PVC and/or textile floor coverings. For
both economic and technical reasons,
the market is showing growing interest
in spray systems as an alternative to the
floor coverings used (see Figure 5.60).
Two-component polyurethane systems
can also contribute here, particularly as
the production process requires low-
temperature curing. Spray-applied two-
component polyurethane floor coat-
ings yield seamless and wear-resistant
Figure 5.60: Decorative polyurethane floor surfaces on nearly all objects. These
coating for large vehicles
greatly improve cleaning properties
and enhance sound insulation. Two-component polyurethane floor coatings also
provide wide design scope such as individual choice of color. Solvent-free aliphatic
polyurethane systems, which due to their elasticity are highly resistant to abrasion
and other influences, are particularly suitable for this application.
5.4.8 Light-stable, thick film coatings
Introduction
Over the last 30 years, the market for spray-applied, polyurethane or polyurea
elastomeric coatings has grown to 68,000 tons. They are used for a wide variety of
spray applications to improve the corrosion, water and abrasion resistance of
numerous substrates including metal, concrete, wood, and plastic. Typical applica-
tions for these spray polyurethane/polyurea systems include pipes and tanks for
wastewater infrastructure, roofing protection, bridge deck waterproofing, and truck
bedliners for personal and industrial use. Most often, these elastomeric coatings
are based on aromatic raw materials, but recently there has been an increase in the
development of aliphatic systems which show much improved weather stability.

Spray-applied, aromatic polyurethane elastomeric coatings

Spray-applied, fast-curing elastomeric polyurea and polyurea hybrids based on
aromatic starting materials have been commercially available for over 20 years. As
mentioned above, one of the application areas that has found wide acceptance is for
the after-market application of spray-in bedliners for pick-up trucks. These aromatic
systems are limited somewhat in that they are typically only available in darker
colors, due to their susceptibility to UV degradation (e.g. color change and loss of
gloss). The darker pigmentation is used to mask the effect of sunlight. Mainly for
cost considerations, polyureas and polyurea hybrids are most often based on resins
consisting of aromatic isocyanate functional materials (such as diphenylmethane
diisocyanate (MDI) adducts or MDI prepolymers), and polyol/polyamine materials
(such as amine- or hydroxyl-terminated polyethers, aromatic diamine chain extend-
ers, or aliphatic diamines). Table 5.24 lists some typical properties of spray-applied,
aromatic polyurethane elastomeric coatings used in bedliners.
These aromatic polymer building blocks are prone to oxidation, which is acceler-
ated by exposure to sunlight. Since the gradual color change (yellowing) is retarded
and masked by incorporating carbon black into the elastomeric spray coating, the
only detectable degradation is loss of gloss. A common method that the coatings
industry uses to detect oxidation is to determine the loss of gloss after exposure to
sunlight. Figure 5.61 shows the retention of gloss as a function of time when exposed
in South Florida. The 60° gloss readings fall from initial values of about 80 to less
than 10 within 2 months when no UV stabilizer is added, and within 9 months when
a typical UV stabilizer package is added.
Despite the dramatic loss of gloss shown above, it is also very important to note that
the physical properties (e.g. tensile strength and elongation) of the same aromatic
elastomeric coatings were still greater than 95 % of their original values after exposure.
Table 5.24: Typical properties of a spray-applied, aromatic polyurethane/polyurea system [83]

Processing
Gel time 15 sec
Tack-free time 2 min
Physical properties ASTM method
Density (pcf) D792 67
Shore A, D D2240 85A
Tensile strength (psi) D412 1330
Elongation [%] D412 580
Die C (PLI) D624 330
Split tear strength (PLI) D1938 140
Taber abrasion [mg loss/1000 H-18] D4060 190

Spray-applied, aliphatic polyurethane elastomeric coatings

Because the traditional polyether or aromatic isocyanate polymers are not UV-
resistant, other chemical approaches and building blocks must be used to provide
non-yellowing membranes. Most of these approaches involve the use of aliphatic
isocyanate prepolymers or adducts in place of the aromatic isocyanate prepolymers.
These, in combination with light-stable coreactants (e.g. polyesters or aliphatic
di- or polyamines) can yield the necessary weathering performance. Specific market
areas require light- and weather-stable, tough, elastomeric, thick film coatings that
can be pigmented to various shades. For example, the automotive industry would
like to use this approach to manufacture truck bedliners that match or complement
the color of the remainder of the vehicle. Additional markets with an interest in
these color and gloss retention characteristics would include marine, agricultural
and construction machinery and amusement parks, to name a few.
New approaches have been developed to address this issue [83, 84]. They include the use
of light stable spray elastomers based on aliphatic polyisocyanates, either used alone
(i.e. single layer) or in combination with aromatic elastomers (i.e. top layer of ali-
phatic over an aromatic base elastomeric coating layer in a composite approach).
Low monomer containing prepolymers that have been used to provide light-stable
elastomers include those based on poly(caprolactone) or poly(carbonate) diols
Figure 5.61: Florida weathering of an aromatic polyurea truck bedliner

capped with IPDI or H12MDI. These products, in combination with aliphatic diami-
nofunctional or triaminofunctional resins, produce instant-set durable polyurea
coatings with excellent physical properties. These aliphatic isocyanate prepolymer-
based polyurea systems are relatively expensive and can entail other problems. For
instance, sometimes they cure too quickly for certain applications. The cure speed
and cost of these systems can be reduced by replacing the aliphatic amines with
amine-terminated polyethers or aromatic amine chain extenders. However, this
often lowers resistance to UV exposure. Nevertheless, the UV resistance of these
“light-stable” systems is still significantly better than in corresponding systems
based on aromatic polyisocyanates.
Recently, newer approaches have been taken which have used aliphatic polyisocya-
nate adducts or prepolymers. These products (based on HDI or IPDI) are currently
used in standard, high-performance polyurethane coatings in the automotive OEM,
refinish, construction, and general industrial markets (e.g. “Desmodur N 3400”,
“Desmodur XP 2410”, “Desmodur XP 2580”).
These products are generally already stripped of monomeric diisocyanate, yet
have relatively low viscosities. They are commonly used in spray coatings within
well-established industrial hygiene guidelines. They usually have more than three
isocyanate groups per molecule, which can lead to more rigid polymers with
plastic-like physical properties, rather than the true elastomeric character required
for this application.
Polyester polyols often serve as coreactants for aliphatic isocyanate adducts. The
molecular design possibilities for these polyesters are very broad and easily custom-
ized to compensate for the higher functionality of the aliphatic polyisocyanate adducts
used. This is achieved by selecting polyesters with the appropriate molecular weight,
functionality, and glass transition temperature (Tg). Polyesters can, however, suffer
a weakness toward hydrolysis. One way to improve the hydrolysis resistance of
polyester-based elastomers is to incorporate urea linkages into the polymer.
Commonly, urea linkages are formed when amines are introduced as coreactants
along with the polyester in the formulations. There are several amine choices avail-
able. Aromatic amines can be used here with some sacrifice in color stability. The
use of primary and secondary aliphatic di- and triamines can help here as well, but
the difference in reactivity between these amine (NH2) reactive groups and the poly-
ester (OH) is very large. If too much of these highly reactive amines are used, they
will react preferentially and the resulting urea can precipitate from the reacting mass,
bringing with it unreacted isocyanate. This in turn leaves an excess of polyester in
the system that can later exude from the elastomer. Therefore, it may be critical to
catalyze the polyol/isocyanate reaction to match that of the amine/isocyanate reaction
to obtain complete polymer curing and optimum physical properties.

An alternative aliphatic amine type is polyaspartic ester (see also 3.7.7 and 5.2.5.6).
This relatively new class of amino coreactants consists of hindered secondary
amines, produced by the reaction of primary amines with maleic acid esters [85].
The reactivity of polyaspartic acid esters (polyaspartics) varies depending on the
structure of the base amine. Slower reactivity is due mainly to steric hindrance
from pendant groups on the amines [86]. Polyaspartics can be combined with pri-
mary amines and polyesters to provide a balanced reactivity profile, leading to
excellent physical properties when combined with the aliphatic isocyanates.
The physical properties of several aliphatic isocyanate-based spray elastomer sys-
tems using different polyesters with polyaspartics can be seen in Table 5.25. All
of them have lower elongation properties than the traditional MDI-based hybrid
elastomers. The user has to define adequate physical properties for the applica-
tion. If the system is to be applied on a rigid substrate, like painted steel for truck
bedliners, it is doubtful that 500 % elongation is needed in the polymer. If the glass
transition temperature of the cured aliphatic elastomeric coating is centered to the
service temperature range and has a broad enough transition phase, it should meet
the needed performance goals.
Although a smooth reaction profile can be achieved with these new aliphatic poly-
urethane/polyurea elastomers, the gel times are still not adequately fast to con-
sistently provide the necessary sag resistance at 1 to 2 mm per coat. One way to
improve sag resistance is to increase the system viscosity by using thixotropic
additives. These cause the system viscosity to be high when no shear is applied.
The viscosity drops dramatically when shear is applied by means of agitation or
by forcing the material through an orifice (e.g. a spray gun).
Table 5.25: Mechanical properties of aliphatic elastomeric coatings

System basis Tensile Elongation Split tear Shore
strength at at break strength hardness
break (psi) [%] (PLI)
Control (aromatic) 1,300 580 140 85A
Hard branched 2,500 60 200 50D
polyester
Hard linear polyester 1,400 100 50 85A
Soft linear polyester 500 300 15 60A
Table 5.26: Yellowing (∆E) comparison of elastomeric coatings
1,500 hours exposure Aromatic Hybrid Aliphatic
Weather-o-meter 55.6 10.6 3.3
QUV-A (313 bulb) 51.5 22.8 6.2
QUV-B (340 bulb) 45.6 17.4 4m

The resistance to UV degradation of the aliphatic isocyanate-based elastomeric

coatings is much improved compared to that of aromatic coatings. Table 5.26 shows
the comparison of white aromatic isocyanate-based spray elastomers to two types
of aliphatic isocyanate-based coatings. The hybrid aliphatic isocyanate-based
system contains aliphatic isocyanate adduct, polyester, and an aromatic amine chain
extender. It resists yellowing much better than the aromatic isocyanate-based
system, but it is not as good as the system based on aliphatic isocyanate, polyester,
and polyaspartate. The improved gloss and color stability shown by aliphatic poly-
urethane/polyurea systems opens up a myriad of color and design possibilities,
allowing this technology to be used in additional demanding market segments (see
Figure 5.62).
Spray application technology

When spray applying an elastomeric polyurethane /polyurea coating, the appli-
cation equipment selected is a big factor in getting the product to market. Thor-
oughly understanding the application and the capabilities of your customer will
help greatly with this selection. The most successful product introductions usually
involve the cooperative support of raw material suppliers, equipment specialists,
and end-users.
Typically, for most applications, multicomponent mixing/spray equipment of some

type is used. Typically, these application devices can be divided into two basic
categories – low-pressure and high-pressure. They allow a relatively thick coat of
the spray elastomer to be applied in a minimum number of passes. Low-pressure
equipment (100 to 1,000 psi) can be used for production and larger scale trials. It
can have a broader range of varying mixing ratios and produce a higher output.
Low-pressure equipment can be fitted with material heating capabilities that can
aid sprayability when using higher viscosity materials. This type of equipment can
also use low-pressure guns with disposable plastic static mixer inserts. Some
equipment manufacturers will use and/
or recommend using an impingement
mix gun for fine finish applications.
High-pressure/high-output equipment
(1,000 to 4,000 psi) can also be used
for production and large trials. It can be
equipped with fixed or varying ratios,
heating capabilities and generally use
impingement-style spray guns. These
spray guns can produce a coarse to Figure 5.62: Examples of spray-applied
aliphatic polyurethane/polyurea
fine finish. A higher volume of mate- elastomeric coatings showing possible
rials is normally required when using colors and surface textures.

this equipment. Due to the much higher

pressures, an equipment manufacturer
or spray equipment specialist should be
consulted when considering high-pres-
sure spray equipment.
A new approach to applying systems
like this is to use a cartridge-fed spray
gun. A cartridge gun, which is now used
in the adhesives market, is similar to a
Figure 5.63: Spray application of a poly-
caulking gun. It has the capability to
urethane/polyurea coating using portable handle different size dual-component
cartridge application equipment cartridges and may be used manually
or pneumatically actuated (see Figure
5.63). This device uses a piston to drive a plunger into the cartridge, displacing the
product through a static mixer. Attached to the end of the static mixer is a spray
nozzle that blows the product from the static mixer tip and propels it at the intended
substrate [87]. This positive displacement device, in combination with the static mixer
and spray tip configuration, works very well when evaluating formulations in the
lab, small-scale trials or repair applications. These types of guns are relatively
inexpensive, and can be purchased with basic mixing ratios, as well as varying
size cartridges. The disposable tubes and static mixers can come equipped with a
spray tip that will allow the applicator to create effects ranging from a textured to
somewhat smooth surface. This cartridge application option has also greatly aided
laboratory developments of fast-curing sprayable elastomeric coatings because it
is a very simple and cost-effective means of applying experimental systems. The
benefits of this application method do not end there, however, as applicators are
finding niche markets where this application method can work very well.
No matter what application technique is used to apply these sprayable polyure-

thane/polyurea systems, proper care should always be given to protecting the appli-
cator and bystanders. Proper recommendations for worker safety and health infor-
mation should be obtained from the resin product suppliers. These companies can
provide appropriate training and recommendations for items such as respirator
usage, eye and skin protection, and proper ventilation. Industry organizations such
as the U.S. Center for the Polyurethanes Industry (CPI) can also provide valuable
information regarding the safe application of these types of systems [88].
Current and future applications for spray-applied, aliphatic polyurethane

elastomeric coatings
The use of aliphatic, spray-applied truck bedliners are now a commercial reality in
the OEM sector, and are being applied in a limited number of assembly plants [89].

This means that pickup truck owners

who opt for the coating have a tough,
durable and non-fading bedliner protect-
ing their vehicle from the day of deliv-
ery. Additional automotive manufactur-
ers in North America and other parts of
the world are evaluating aliphatic poly-
urethane spray-applied elastomeric coat-
ings and are moving toward adopting the
technology for their lines as well. In
addition to these OEM manufacturers, Figure 5.64: Aftermarket-applied
suppliers are also beginning to introduce protective liner for pickup truck bed
aliphatic based polyurethane/polyurea
sprayable coatings to the aftermarket for
trucks (see Figure 5.64), as well as in
other industrial applications [90].
The usefulness of this weather-stable
technology is by no means limited to
truckbeds. Two-component aliphatic
elastomeric polyurethane coatings are
also being considered for almost any
other application that requires resis-
tance to corrosion, chipping or abra- Figure 5.65: Thick film polyurethane/
sion, in addition to UV durability. Pos- polyurea coatings can be used to provide
light- and color-stable protection for a
sible additional end uses include floors, wide variety of industrial applications
bridges, marine applications, roofing, (such as amusement parks) where frequent
industrial equipment and construction repainting is not an option
applications (see Figure 5.65). Addi-
tional development work continues to ready the technology for incorporation into
applications with even higher performance demands such as structural composites
and fire-resistant coatings (see Figure 5.63).
5.5 Plastic coating

Plastics have become indispensable, whether in industrial applications in the auto-
motive [91], electronics and household appliance sectors or in the leisure segment.
In short, countless items we use every day are made from plastics. Over the last
20 years, it has also become established practice to apply coatings on plastics to
enhance their appearance and technical properties [92–94]:
• to achieve certain shades and color effects
• to protect plastics from weathering, chemicals and mechanical impact [95]
• to give plastics certain haptics.

A large number of systems are suitable for coating plastics. Acrylic coatings, for
example, have proved particularly suitable for finishing rigid plastic components
such as housings for home stereo equipment. The choice of suitable coating systems
becomes more restricted with increasing flexibility of the substrate and stringency
of the quality requirements.
Coatings based on polyurethane raw materials satisfy the technical requirements
to a high degree [96]. In the automotive industry, which has always set very high
standards in terms of lightfastness, weather stability, flexibility, chemical resistance
and scratch resistance, polyurethanes have become the systems of choice for coat-
ing plastics. In analogy to its use in automotive applications, polyurethane technol-
ogy is being used increasingly in industrial plastic coating.
5.5.1 Market evaluation
Plastic substrates
The world market for plastics currently stands at about 215 million tons. About 8 %
(17 million tons) is used by the automotive industry [97–99], around 70 % of which
are coated. Thermoplastics (mostly with low heat resistance) are used in the man-
ufacture of both exterior and interior automotive components such as fenders,
mirror housings and instrument panels. These plastics include polypropylene (PP),
polycarbonate (PC), acrylonitrile butadiene styrene (ABS), polybutylene tere-
phthalate (PBT) and their blends. Polystyrene (PS), polyvinyl chloride (PVC) and
polyethylene terephthalate (PET) are also used.
Plastic coatings
In 2005, some 95,000 tons of coating raw materials were used for coating plastics.
More than half of this amount was used in the automotive industry. Coating systems
with a high baking temperature (above 120 °C) are not suitable for use on plastics
with low heat resistance. In Europe nowadays, two-component polyurethane coatings
with drying temperatures around 80 °C are mainly used because of constantly increas-
ing quality demands. A comparable trend can also be observed outside of Europe.
Ultimately, the pressure to reduce solvent emissions, which has already been men-
tioned several times, will lead to a further increase in the use of waterborne coatings,
currently about 30 to 40 % for exterior and 60 % for interior components (Western
Europe). In 2005, polyurethane coatings (solventborne, waterborne and UV-curing)
accounted for more than 60 % of the formulations used in plastic coating worldwide,
with annual growth of about 10 %.
5.5.2 Coating process
When coating plastics, the formulation and application technology must be matched
to the substrate. Pretreatment, formulation design and the choice of raw materials
are therefore of great importance.

Plastic coating 183
Pretreatment
As plastic surfaces are often contaminated with release agents, oil, grease or dirt,
they must be cleaned before coating, e.g. using an acid or alkaline medium in a
power washing unit (Figure 5.66).
A cleaning solution heated to 60 °C is pressure-sprayed onto the plastic components.
After rinsing with water, the components are dried and blown down with ionized
air to prevent dust contaminating the coating process. In the case of plastics with a
Figure 5.66: Flow chart of a three-stage power washing process
Figure 5.67: Coating line for a three-coat plastic coating system

low surface tension (e.g. polypropylene = PP), additional surface activation may be
necessary [99, 101, 102]. Without this treatment, the coating may not adhere properly.
Surface activation can be achieved by flame [99], corona [103] or plasma [99, 101] pretreat-
ment or by fluorination.
Flame treatment involves passing a flame briefly over the component. Polar groups
form on the surface as the result of oxidation. In the corona method, a high voltage
electrode is passed over the earthed plastic component. The corona formed results
in a bombardment with ions or electrons that activates the surface in a similar way
to flame treatment. In the plasma process, usually performed in dilute gases, the
surface is activated by the effect of ions released from the gas, i.e. not only air ions
as is the case with the corona process. The plasma process is used less often due to
the high capital investment required.
Corona pretreatment is used above all to activate planar surfaces (e.g. films), while
flame treatment is the standard process for three-dimensional components such as
Table 5.27: Coating concepts for plastics
Film Application (all coats) Drying
thick-
ness
[µm]
Three-coat system - solventborne:
Primer 20–30 30–70 % rel. humidity at 10 min at RT, 30 min
15–30 °C at 80 °C
Basecoat 10–15 - waterborne: 45–60 % rel. 5 –10 min at RT, 5 min
humidity at 18–25 °C at 80 °C
Clearcoat 25–50 10 min at RT, 30 min
at 80 °C
Two-coat system I See above
Primer 20–30 10 min at RT, 30 min
at 80 °C
Topcoat 30–50 10 min at RT, 30–45
min at 80 °C
Two-coat system II See above
Basecoat 10–15 5 min at RT, 5 min at
80 °C
Clearcoat 25–50 5 min at RT, 30 min at
80 °C
One-coat topcoat 30–50 See above 10 min at RT, 30–45
min at 80 °C

Plastic coating 185
fenders. The advantage of the corona and plasma processes is that the activation of
planar surfaces is largely uniform.
In addition to the surface activation methods described above, it is also possible to
use adhesion primers or adhesion promoters based on chlorinated polyolefins [99, 104].
These also ensure good coating adhesion on non-polar polypropylene substrates [105].
However, the use of organochlorine compounds is being viewed increasingly criti-
cally. The application of primers is often combined with other methods of pretreat-
ment to enhance the general reliability of the plastic coating process.
Coating concepts
Three different coating concepts are normally used for plastics:
• three-coat systems (primer/basecoat/clearcoat)
• two-coat systems (primer/topcoat or basecoat/clearcoat)
• one-coat topcoats
Growing environmental awareness and increasingly stringent VOC legislation have
resulted in a general switch from solventborne to waterborne coating systems,
particularly in Europe. It can be assumed that waterborne coating systems will be
used increasingly in North America and the Asia-Pacific area as well. Typical film
thicknesses and application conditions are summarized in Table 5.27.
In a three-coat system (Figure 5.67), the primer is applied directly on the cleaned
and possibly pretreated plastic component. After a flash-off time of 5 to 10 min-
utes, the coating is dried for about 30 minutes at 80 °C. Dry film thicknesses of
20 to 30 μm can be achieved. The basecoat is applied on the primer to give a dry
film thickness of between 10 to 15 μm. After a flash-off time of about five minutes,
the clearcoat is applied and then force-dried together with the basecoat for 30 to
45 minutes at 80 °C. The target dry film thickness for the clearcoat is between 25
and 50 μm.
The three-coat system is mainly used in coating automotive components based on
PP blends, e.g. fenders. The two-coat system (normally system II shown in Table
5.27) is used in the coating of thermoplastic resins such as ABS and PC. This pro-
cess is widely used for the coating of automotive and motorcycle components,
especially in Asia. One-coat topcoats are used primarily on plastics in non-automo-
tive applications, e.g. electronic housings, household appliances and toys.
5.5.3 Raw material selection

The selection of raw materials is as important as the application conditions. The
film properties must be matched to the substrate, especially in terms of flexibility.
Hard coatings on a flexible plastic substrate have been proven to result in splinter-
ing and the risk of injury in the event of a crash. This is not true of coatings whose
flexibility has been matched to the substrate [106].

The impact penetration test according to DIN 53443 is suitable for investigating this
relationship. High-speed photographs of an impact penetration test of coated PBT/
PC show how a brittle topcoat results in splintering of the component. If a flexible
coating such as a two-component polyurethane formulation is used, the mechanical
properties of the plastic remain unaffected (Figure 5.68a and b).
On account of the major influence of temperature on the mechanical properties of
both coated and uncoated plastics, the impact penetration test is normally performed
in a temperature range of -40 to +30 °C. At temperatures down to -40 °C, uncoated
PBT/PC components show no significant change in their energy absorption, as can
be seen in Figure 5.69. The ability of the coated component to absorb energy with-
out fracturing is an indication of its splintering tendency. For example, a hard topcoat
on a flexible primer reduces the energy absorption to 40 Nm at 0 °C, which would
indicate a risk of brittle fracture in the plastic. In contrast, a flexible two-component
polyurethane topcoat retains its energy-absorbing properties at -20 °C.
Figure 5.68a: A hard coating causes splintering
Figure 5.68b: A flexible two-component polyurethane coating prevents splintering

Figure 5.68a/b: High-speed photographs of an impact penetration test of coated
“Pocan” (PBT/PC)
Figure 5.69: Impact penetration test of coated “Pocan”

Plastic coating 187
Even better results are achieved using a waterborne polyurethane primer [107]. The
notching effect of a brittle topcoat is buffered by the polyurethane primer. It should
be emphasized that waterborne primers allow the use of relatively hard topcoats,
e.g. solventborne OEM clearcoats – an aspect which is important in the context of
online and inline coating of plastics.
Polyurethane systems for coating plastics are often based on aliphatic polyisocya-
nates such as “Desmodur N” (trimer or biuret). Adding a flexible polyester polyol
such as “Desmophen 670” allows the flexibility of the paint film to be matched to
the plastic substrate. Mixing with flexible polyacrylates (“Desmophen A575”) or
the use of flexible polyisocyanates (“Desmodur N 3800”) also yields coatings suit-
able for plastics. The transfer of solventborne two-component polyurethane tech-
nology to waterborne systems has been achieved with equivalent polyols such as
“Bayhydrol PT 241” and polyisocyanates such as “Bayhydur 3100”, as well as with
the latest generation of hydrophilically modified polyisocyanates such as “Bayhy-
dur XP 2487/1”.
Coating concept – primer
The use of primers is state of the art in plastic coating [108]. Primers cover defects
on the surface of the molded component and improve adhesion to the substrate.
Good sandability, stone-chip resistance and overcoatability are required here and
are achieved using polyurethane systems. “Desmodur N 75” combined with poly-
ester or polyether polyols is used for a solventborne formulation. Corresponding
waterborne primers are formulated using polyester polyols such as “Bayhydrol
PT 241” combined with a hydrophilically modified “Desmodur N” trimer, e.g.
“Bayhydur 3100”.
Conductive primers are required for the electrostatic coating of plastic components.
They are formulated using conductive pigments [99, 109]. The most important of these
is carbon black, not least because of its low price.
Coating concept – basecoat
The basecoats used on plastics are expected to meet similar requirements to those
used on metal bodies [99, 108]. The special aspects of matching color and effects have
already been discussed. Apart from greatly reducing the solvent content, the use
of waterborne basecoats has a further advantage. The parallel alignment of the
metallic flakes is more pronounced due to the greater shrinkage of waterborne
coatings and provides better reproducibility.
Coating concept – clearcoat
The clearcoats used on plastics must be of high quality and match the flexibility of
the substrate. These requirements are satisfied by two-component polyurethane sys-
tems, even at the low drying temperatures normally used in coating plastics. In
contrast to the mostly hard melamine-crosslinked systems (thermosetting acrylics =

TSA), the two-component polyurethane coatings are characterized by the fact that
their flexibility can be varied infinitely to match the flexibility of the substrate through
the choice of raw materials. Even a flexible two-component polyurethane system,
force-dried at just 80 °C, meets all standards for leveling, gloss (wet look) and resis-
tance to weathering, etching and chemicals. This is not true of one-component TSA
and one-component TPA (thermoplastic acrylic) coatings, even if they are baked at
higher temperatures.
Two-component polyurethane clearcoats are characterized by a more or less pro-
nounced reflow effect. This means that scratches heal due to a recovery effect [110].
As a result, there is relatively little scratching on components finished with this
kind of clearcoat, even after many years of use. In order to satisfy the demand for
higher flexibility coupled with good resistance properties, many two-component
polyurethane formulations are based on combinations of flexible polyester polyols
such as “Desmophen 670” with hard chemically resistant polyacrylates such as
“Desmophen A 665”. Suitable polyisocyanates are “Desmodur N” trimers and biu-
rets (e.g. “Desmodur N 3390” and “Desmodur N 75”).
Work is under way to develop special blocked polyisocyanates, which deblock at
low temperatures between 80 and 100 °C, thus facilitating one-component formula-
tions with high resistance properties for plastic coating [111]. The application condi-
tions for waterborne systems are more strictly defined than those for solventborne
coatings, in particular due to the differences in drying behavior [108].
5.5.4 Coating concepts for automotive add-on components

When coating plastic components for automotive applications, various processes
can be used (Figure 5.70). Unless contrasting colors are used, it is particularly
important that the coatings applied on the different components, whether interior
or exterior, and on the car body all match in terms of color and effect.
• Offline: The add-on component is coated by the supplier and then fitted to the
coated vehicle by the car manufacturer. This is the current state of the art in
the automotive industry.
• Inline: The uncoated add-on component is fitted to the car body after applica-
tion of the cathodic electrodeposition primer and passes through the remaining
stations of the online coating process. In other words, the primer surfacer,
basecoat and clearcoat are applied in the usual way. Dust may cause problems
as it is virtually impossible to avoid dust contamination after application of the
CED primer. Many of the plastics used are at the limits of their heat resistance
and fracture strength at the baking temperatures of 130 to 160 °C. In addition,
the differing coefficients of thermal expansion of plastics and metal must be
considered when fitting the add-on components. These are challenging process
conditions for the plastic substrates.

Plastic coating 189
• In an online process, the plastic components are fitted to the uncoated car body
and pass through the entire coating process. The plastic component has to with-
stand the relatively high baking temperature used for the CED coating without
deformation. Until now, this level of thermal resistance was found in only a few
plastics such as sheet molding compounds (SMC), polystyrene/polypropylene
oxide (PS/PPO) or reinforced reaction injection molded polyurethane (PUR-
RRIM). However, because of their mechanical properties, these plastics are of
only limited suitability for manufacturing components such as fenders.
Given the difference in conditions between offline and online coating, a difference
in shade is virtually unavoidable, even if it is only slightly visible in the best case.
In the case of online and inline coating, the differences in conductivity between
plastic and metal play a major role, even if a conductive primer has been applied
on the plastic component. Just slight variations in the electric field density may
cause variations in shade in an electrostatic coating.
Two-component polyurethane systems are widely used in the offline coating of
automotive add-on components. Inline and online coating are the object of ongo-
ing development work. Two-component polyurethane technology is also ideal for
these processes.
Due to further tightening of VOC legislation, especially in Western Europe, most
of the primer surfacers and basecoats used on car exteriors are now waterborne
Figure 5.70: Coating concepts for the automotive industry: online, inline, offline

systems. In 2006, a waterborne clearcoat was used for the first time in the OEM
finishing of automotive add-on components. Usage of waterborne coatings in auto-
motive applications is expected to grow.
5.5.5 Soft-feel coatings

Haptics in car interiors
For some years, efforts to reduce the weight of cars have gone hand in hand with
an increased use of plastics, also in the vehicle interior [112–113]. The surfaces of
molded plastic components, even if they have a grain pattern, appear inferior. The
required surface finish can be produced using a soft-feel coating [114–116], which gives
plastic components a pleasant
leather-like feel (haptics), see Figure
5.71. The coating not only provides
protection against scratching and
graying caused by UV exposure, but
also prevents irritating noises such
as the squeaking of component
assemblies.
Polyurethane soft-feel coatings also

reduce fogging inside vehicles,
which is caused by the emission of
Figure 5.71: A waterborne two-component low molecular weight constituents
polyurethane soft-feel coating from the plastics used. In contrast to
Figure 5.72: The reactions in a waterborne two-component polyurethane soft-feel coating

Plastic coating 191
back-foamed plasticized PVC lami-

nating films, soft-feel coatings con-
tain few low molecular weight con-
stituents that can contribute to fog-
ging. In addition, the coating acts as
a barrier layer, thereby slowing the
migration of low molecular weight
substances.
Waterborne formulations are usu- Figure 5.73: Industrial soft-feel coating with
ally based on highly flexible, non- waterborne two-component polyurethanes
functional polyurethane dispersions
such as “Bayhydrol PR 240” and “Bayhydrol PR 340”. Chemical resistance can
be improved by adding hydroxyfunctional polyester/ polyurethane polyols such
as “Bayhydrol PT 355”, crosslinked with polyisocyanates, e.g. the hydrophilically
modified “Desmodur N” trimer “Bayhydur 3100” (see Figure 5.72).
In practice, the gloss of soft-feel coatings is set very low by the addition of matting
agents. This reduces reflection on instrument panels, thus increasing driving safety.
Furthermore, the matte surface underscores the luxurious appearance. Thanks to
significantly reduced solvent emission during application and almost comparable
film properties, waterborne soft-feel coatings are preferred to solventborne formu-
lations. They were first used in the automotive industry in 1992 and are in use
worldwide [116, 117].
High-quality surfaces in general industrial applications

Soft, leather-like to velvet dry coatings are also very suitable for finishing plastics
in general industrial applications (see Figure 5.73). Cell phones and MP3 players
are coated with soft-feel coatings, as are hair dryers, food mixers and coffee
machines. The applications are as varied as the consumer goods industry. Office
furniture, chairs and cabinet handles, computer accessories (external hard disk
drives, computer mice, monitors, notebooks), televisions and remote controls are
all available in this warm and pleasant finish.
Solventborne soft-feel coatings yield a surface with a rather sticky or rubbery feel.
Waterborne systems can be formulated to give dry and velvety soft, but also more
leather-like, haptics. The surface grain also plays an important part. A deep grain
reduces the contact surface so a softer coating formulation is needed to produce a
corresponding effect.
Because of their soft formulations, both solventborne and waterborne soft-feel
coatings are usually less durable than other hard, highly crosslinked industrial coat-
ings. To ensure that they still have good resistance properties, all soft-feel coatings

are formulated with polyurethanes. The additional hydrogen bridge bonds of this
chemistry make it the only crosslinking technology capable of uniting elasticity
and robustness.
5.5.6 Industrial plastic coating

The coating of plastic components in the entertainment electronics and consumer
goods industries has become indispensable. Successful marketing today includes
product differentiation, which depends not only on technical performance data, but
increasingly on design characteristics. High-quality finishes are in demand and are
an important component of medium- and high-value products. Pearl effects, irides-
cent colors and, more recently, multicoat systems for high-gloss wet-look finishes
are all used alongside traditional metallic finishes [109]. Soft-feel coatings are in
demand for control elements, and this demand is growing with the continuing trend
for mobility in many applications. The further miniaturization of devices facilitates
a mobile lifestyle, and is accompanied by much more stringent specifications in
terms of surface resistance properties. Portable devices must satisfy high require-
ments with regard to scratch resistance so as to preserve their appearance in con-
tinuous use. Steam jet and hot water immersion tests as well as resistance to sol-
vents, skincare products, UV radiation, and climatic influences are further chal-
lenges for the coatings formulator.
Many substrates are used, with PP, PS, ABS, ABS/PC and PC/PBT dominating in
the production of molded components. PVC and PET are important materials for
the production of decorative films (e.g. used in the furniture industry). PVC is also
used widely in the manufacture of floor coverings. Polyurethane coatings adhere
well on these substrates, and also on others pretreated by standard processes. Poly-
urethane coatings are therefore also used as primers for polyurethane foams, glass
fiber reinforced polyesters and, for example, PPO blends.
The plastic housings of televisions, office equipment, home entertainment electron-
ics, plastic toys, hair dryers, and kitchen appliances are usually coated with non-
crosslinking acrylate systems. The resistance requirements in these applications are
relatively low, and the coatings are used above all to produce an attractive appear-
ance. However, it is not usually possible to achieve high gloss levels.
Objects which are subject to intensive mechanical wear, such as cell phones, por-
table computers, remote controls, medical instruments, computer mice, wheel rim
covers, digital cameras, CD/MD/MP3 players, plastic handles or plastic furniture
must be far more durable. Two-component polyurethane systems dominate in these
applications. They are also used for aesthetic reasons, as only these coatings yield
high-gloss films. Typical examples here are controls, buttons, optical displays or
LCD and plasma flat screens. The plastic containers used in the cosmetics industry
are also expected to be highly durable, making two-component polyurethane coat-
ings popular here as well.

Plastic coating 193
Polyurethane systems can also be formulated as textured coatings. The microstruc-

ture can be varied, even to produce suede-like surfaces. Both solventborne and
waterborne polyurethane formulations are used in industrial plastics coating. The
latter are of growing interest if there is a need to comply with statutory emission
limits or if specifically required by the end customer.
5.5.7 UV technology in plastic coating
Important uses for UV-curing polyurethane systems on plastics are roll-to-roll appli-
cation for flooring (PVC, natural rubber, polyolefin, linoleum), automotive compo-
nents such as polycarbonate diffuser disks for head lights, cell phone casings made
of polycarbonate or polycarbonate blends, plastic household goods, and optical data
carriers such as compact discs (CDs) or digital versatile discs (DVDs). While floors
are usually roller-coated with solvent-free polyurethane or waterborne coatings,
diffuser disks and cell phones are spray-coated with solventborne formulations. Spin
coating followed by UV curing is used for CDs and in the bonding of polycarbonate
discs during DVD production.
Due to the high productivity of UV curing, the number of applications using solvent-
free, solventborne, or waterborne UV-curing polyurethane systems [119] is growing
strongly worldwide. Polyurethane is superior for applications requiring tough, flex-
ible or particularly weather-resistant UV-curing coatings (see Figure 5.74).
5.5.8 In-mold coating
The aim of in-mold coating (IMC) technology is to perform production and surface
modification of molded components in a single step. The following methods are
included under the term IMC:
• inserting molded components (mostly plastics, but also wood, for example) into
a mold and subsequently injecting coating
• back-molding of films (inserting film
and injecting plastic)
• back-foaming of films (inserting film
and injecting foam)
• initially applying coating in the mold,
then closing the tool and injecting
plastic
• injecting plastic, opening the tool a
crack, injecting coating, closing, and
pressing the coating onto the substrate
• injecting plastic, cooling, and then
injecting coating into the gap created
by shrinkage
• injecting plastic, cooling, displacing Figure 5.74: Non-slip coating based on
into second cavity, injecting coating UV-curing “Desmolux” urethane acrylates

IMC in the narrower sense usually refers to the methods by which a liquid coating
system is applied to a plastic component still in the mold, produced immediately
prior to this in an injection molding method. This is “direct coating” in the case of
a coating application or “direct skinning” if polyurethane skins or foams are applied.
Possible applications for these technologies include:
• uses in the interior of automobiles (e.g. switches, glove compartment lids)
• uses on the exterior of automobiles (e.g. exterior mirrors, plastic lenses)
• electronics (e.g. cell phones, entertainment electronics)
• household appliances
• furniture, sports, leisure equipment
Compared to conventional manufacture in two separate steps, IMC methods
exhibit major advantages in terms of efficiency, surface design and ecology. In
particular, due to the omission of a spatially separate coating application, there are
cost advantages in terms of investment, operation and maintenance. Further sav-
ings potential results from the significantly reduced transport and logistics expen-
diture. In order to perform the IMC procedure economically, it is important to
synchronize the timing of the injection molding and coating processes.
As IMC represents an imaging coating method, the surface structure of the coating
can be adjusted reproducibly via the graining of the mold. Mold surfaces which
are polished to a high gloss yield high-gloss paint films. In contrast, a rough mold
surface produces matte films. In addition, the haptics of the coating can be varied
specifically over a wide range using different surface structures. Grained surfaces,
for example, in combination with soft polyurethane coatings produce soft-feel
haptics. The film thickness of the coating is determined via the mold gap. It can
be varied from a few millimeters in the case of polyurethane skins and foams to
around a hundred micrometers in the case of polyurethane coatings.
In IMC methods, where the liquid coating is cured in a closed mold, only solvent-free
coating systems can be used. This avoids the emission of solvents and the development
of overspray, representing a clear ecological advantage over conventional coating
methods. Suitable coating systems are low viscosity two-component polyurethane
systems with a solids content of 100 %, as well as radically curing one-component
systems. Depending on the required property profile, polyacrylate, polyether, poly-
ester or polycarbonate can be combined with aliphatic or aromatic polyisocyanates.
The coating components can be preheated to reduce the viscosity. To avoid pot
life problems with the highly reactive coating systems, reaction injection molding
(RIM) equipment has proven reliable for the homogeneous mixing of the coating
components and injection of the coating. Curing times of less than 60 seconds can be
achieved at temperatures of about 80 ºC with suitably catalyzed polyurethane systems.
The wide variety of polyurethanes makes it possible to control the properties of IMC
coatings over a broader range. Depending on requirements regarding resistance and

Plastic coating 195
haptics, hard coatings with good chemical resistance or soft coatings can be formu-
lated which are very flexible even at low temperatures and yield more pleasant
haptics. Nevertheless, the method still has some limitations, which is why it has not
yet prevailed on the market. The following aspects require further development:
• process-oriented mold design at sliders and openings is not completely solved,
restricting design freedom
• depending on the method, sealing the tools from exit of the (thin) fluid coating
• creation of undercuts and shear edges
• refinishing (e.g. removal of coating sprue)
• process-dependent production of thin coats (less than 100 µm)
• control of a complex process
The advantages of IMC technology have led to increased interest in the market and
have initiated intense development activity. Raw material and coating manufacturers,
plastic processors and tool producers are
involved in interdisciplinary projects.
Test and prototype tools are seeing increasing
investment. Figure 5.76 describes the two-
cavity process. The plastic component is manu-
factured by injection molding in the first cavity
(1 to 3). It is then pushed into a second cavity
(3 to 5), where it is coated (6) with a two-com-
ponent polyurethane system. With optimal
coordination of the processing properties of
both plastic and coating and corresponding pro-
cess timing, it is possible to produce a plastic
component in one cavity while a second com-
ponent, molded before, can be coated at the Figure 5.75: Two-cavity tool for
same time in the second cavity, thereby enabling the in-mold coating process
Figure 5.76: The two-cavity process: the component is produced by injection molding in the
first cavity (1–3). It is then pushed into the second cavity (3–5), where it is coated with a two-
component polyurethane system (6).

the highest possible productivity (see Figure 5.75). It can be assumed that the IMC
method in combination with polyurethane coatings will become increasingly impor-
tant in the production of coated plastic parts due to the economic, ecological and
qualitative advantages.
5.5.9 Polyurethane gelcoats
Introduction
In recent years, the composites market has grown to a volume of 2 million tons.
Gelcoats play an essential role in that market by representing a unique methodology
to decorate composites in ways that would not otherwise be possible with conven-
tional coating systems. Gelcoat processing, performance and application techniques
are all very specialized. To better understand the partnership shared by gelcoats and
composites, a fundamental understanding of composite technology is useful.
Composites overview
Many products have component structural parts that are required to exhibit a com-
bination of light weight and high strength. The wing of an aircraft is a classic exam-
ple of just such an application. Conventional building materials typically provide
strength at the price of weight and mass. Lightweight materials, on the other hand,
are often incapable of meeting rigorous performance demands. Fortunately, this
strength/weight dilemma can be successfully addressed through the use of compos-
ites. By definition, composites are materials made up of at least two components
whose combined physical strength is greater than that of either component individu-
ally. They are also typically lighter and stronger than alternative materials that could
be selected for a particular structural application. Composites are often referred to
as “reinforced plastics” because they consist of a fibrous reinforcing network that is
embedded in a cured resin matrix. The resin is typically polyurethane, polyester or
epoxy, and the reinforcing fibers can be glass strands (fiberglass) or carbon fiber.
Gelcoat history
Due to the way in which they are processed, glass-reinforced composites cannot
always be decorated in a manner typically associated with conventional coatings.
Production processes used to manufacture composites, as well as other physical
and performance requirements demand that alternative methods be employed.
Therefore, when there is a need for a pleasing aesthetic appearance to a structural
composite part, gelcoats are the technology of choice (see Figure 5.77). In addition
to appearance, gelcoats are expected to:
• provide a low-maintenance protective surface finish
• enhance durability appropriate to the part end use
• reduce fiber pattern on the surface of the component
• provide a finished surface of sufficient quality out of the mold so that the need
for coating is eliminated

Plastic coating 197
Figure 5.77: Gelcoat and composite substrate
When the composites industry was in its early stages, laminating resin was mixed
in the shop with thixotropes to provide a resin-rich surface on the part. However,
these proved to be inadequate when demands grew for reduced air entrapment and
colored finishes. This led to the development of more sophisticated gelcoats based
on unsaturated orthophthalic polyester reacted with styrene, and catalyzed with
peroxides [120]. The advantages they offered include:
• reduction of the number of components mixed at the manufacturing site (only
peroxide needs to be added to a pre-formulated batch)
• correct dispersion of additives such as surfactants and pigments
• excellent air release characteristics
• exacting color match [121]
Although there were cost penalties associated with these newer style gelcoats,
they were offset by savings realized in labor and waste elimination of improperly
mixed materials.
The marine industry was among the first markets to adopt this technology on a large
scale for structural component construction. Therefore, early gelcoat development
efforts focused on systems that could function well in environments where resistance
to water is essential. This eventually led to the use of isophthalic-based polyesters.
The formulation change provided greater water resistance, lower rates of water
absorption, and improved blister resistance. Toughness was also enhanced as the
tensile elongation at break of isophthalic-based polyesters is greatly improved.
As the use of composites grew for other applications, gelcoat development also
evolved to meet the performance and application demands for those markets.
Improved resins and UV-resistant additives were introduced that provided gelcoats
with the ability to better maintain color and gloss retention, even when subjected
to severe weathering conditions. Today’s gelcoat systems, which can be applied by
brush, roller or spray, can even be formulated to provide fire resistance.

Gelcoat challenges
Although gelcoat technology has made significant technological strides and has
grown to an 80,000 ton market in North America, it faces serious new challenges.
Among the most critical are those related to the use of styrene in gelcoat formula-
tions. Health and environmental concerns have led to legislation that demands
reduced styrene emission levels, forcing gelcoat manufacturers to develop systems
that contain in the range of 30 % styrene. The emission issue poses significant chal-
lenges to both gelcoat formulators and gelcoat end users alike. No substitute for
styrene has yet been found to act as an acceptable coreactant for unsaturated poly-
ester. This severely limits the options formulators have at their disposal in develop-
ing a gelcoat that will meet government regulations and performance and applica-
tion requirements. Some end users even face the prospect of a mandatory shutdown
of their production lines if they exceed defined styrene emission limits.
Polyurethane gelcoat technology
The problems noted are forcing the gelcoat industry to look in new directions.
Poised to meet these challenges and ready to take the industry on its next evolution-
ary step are polyurethane gelcoats. Unlike conventional gelcoats, polyurethane
gelcoats are based on a near-zero VOC formulation. Thus, not only are concerns
about styrene emissions eliminated, but the technology offers an overall environ-
mentally friendly product.
Health and environmental issues are not the only reasons to consider polyurethane gel-
coats. High performance is inherent to the nature of polyurethanes, and systems based
on aliphatic isocyanates offer outstanding weathering characteristics and long-term
durability. This is critically important for markets such as marine, wind turbines and
transportation that use gelcoats for outdoor applications. Those gelcoats must be resis-
tant to chalking, down-glossing, fading, and yellowing. The latter is especially impor-
tant to the marine market where white is the predominant color used (see Figure 5.78).
Another benefit to the high performance of polyurethane gelcoats is the potential
for reduced warranty costs. Whether the gelcoat application is marine pleasure craft
or tub and shower surrounds, the use of
higher quality materials results in the likeli-
hood of fewer field problems or failures.
Polyurethane gelcoats bring a toughness that
cannot be matched by polyester/styrene
chemistry. This may result in fewer field war-
ranty claims and increased customer satisfac-
tion. Not to be forgotten is the potential for
reduced in-plant warranty claims. For exam-
Figure 5.78: Marine gelcoats offer ple, damage can occur when a boat hull gel-
outstanding water resistance coated with a conventional polyester/styrene

Plastic coating 199
formulation is demolded in the factory. The toughness and resilience exhibited by

polyurethanes can help to resist this kind of damage.
Application of conventional gelcoats has traditionally been a time-consuming and
labor-intensive process. This translates to higher manufacturing costs, and has the
industry seeking better methodologies. Polyurethane gelcoats are typically rapid-
curing systems, but are also extremely versatile. Formulation adjustments and the
use of catalysts allow the cure rate to be modified to meet the specific needs of the
end use application. Controlled application time along with automated application
equipment offers an opportunity to increase productivity and reduce costs.
Polyurethane gelcoats attain their optimum properties when used in conjunction with
polyurethane composite materials. By combining these two polyurethane systems into
a single part, exceptional performance and a high degree of toughness can be expected
that is not achievable with any other currently available technology.
Chemistry of polyurethane gelcoats

There are two chemistries that can be utilized when producing a polyurethane
gelcoat. Both approaches have advantages and disadvantages.
One approach is to modify an existing unsaturated polyester gelcoat by the addition
of a urethane acrylate. The system may be cured by conventional peroxide curing
methods. This benefits the user by increasing the elongation of the resin system,
potentially reducing the number of warranty claims due to cracking. However, there
is no reduction or elimination of styrene from the formulation, which is a major
drawback of conventional unsaturated polyester gelcoats.
A second approach is to use two-component polyurethane chemistry. This approach
can utilize either urethane or urea chemistries. The main benefits of the two-com-
ponent system are the elimination of styrene and improved flexibility and weather
stability. A drawback of this approach is the likelihood of higher raw material costs.
However, costs becomes less of an issue when process and performance improve-
ments are considered. For example, cost savings can be realized by faster curing
times, potential to eliminate post-mold coating, and higher factory output and fewer
warranty claims.
A typical two-component urethane could be comprised of a branched short-chain
polyester polyol and an aliphatic polyisocyanate based on hexamethylene diiso-
cyanate (HDI). The polyester polyol binder will contribute to a high-quality, hard,
and weather-stable film. The aliphatic polyisocyanate will contribute weathering
and chemical resistance while maintaining excellent gloss retention.
A standard two-component polyurea coating is the reaction product of an amino-
functional polyol (e.g. “Desmophen NH”) and an aliphatic polyisocyanate based
on HDI (e.g. “Desmodur N 100” or “Desmodur XP 2410”). The aminofunctional

system offers the benefit of decreased

cure times and the ability to customize
pot life. This system will also yield a
hard, weather-stable and chemically
resistant film [122].
For both the urethane and polyurea sys-
tems, formulations could also contain
pigments, fillers, extenders, diluents,
plasticizers and surfactants. The pig-
Figure 5.79: Gelcoats provide durable and
attractive finishes ments contribute to visual appearance,
color and masking of the backing mate-
rial. The remaining additives can be used to modify viscosity, volumes of reactive
compositions, flow properties of the formulated coating, bulk volumes, and costs.
Conclusion
The use of gelcoats continues to grow along with the rapidly expanding number of
applications for composite materials. At the same time, industry challenges such
as legislated styrene emissions reductions and demands for improved performance
and reduced warranty costs will force gelcoat technology into new directions. Poly-
urethane gelcoats stand ready to meet these challenges head-on and offer solutions
to an evolving market.
5.6 Application on glass

Glass plays an important role in our daily life. It is available in a wide range of colors,
shapes and designs, and is used in everything from containers for beverages, through
household and consumer articles, to flat glass for glazing in buildings and cars. The
following two examples show the importance of glass coatings which contribute to
significant improvements in quality, especially if polyurethane systems are used.
5.6.1 Coatings for glass containers

Colored glass is produced either by the addition of pigments or by coating with
pigmented organic materials.
Pigmenting glass
The production and shaping of glass is generally performed at temperatures in the
range of 800 to 1,500 °C. Colored glass is produced by adding metal oxides to the
glass melt. The color results from the incorporation of the metal ions into the glass
matrix [123]. One of the most important applications for colored glass is in the manu-
facture of containers for beverages. In addition to the standard browns and greens
used for glass bottles, the market is increasingly requiring special colors. These
shades, ranging from yellow to orange or blue and red, can only be achieved using

Application on glass 201
the toxic salts of heavy metals such as cadmium and cobalt, or with very expensive
additives such as gold. Ecological and economic considerations therefore make it
virtually impossible to use glass colored in these ways in the food industry.
It is estimated that, during the processing and especially shaping of glass, there is a
breakage rate of about 40 %. Such material must be sorted by color so that it can be
remelted separately and reused – a costly and laborious process. The same problem
is encountered with the different-colored disposable containers for beverages. They
have to be sorted into clear, green and brown glass for recycling [124].
Coating glass
Coating glass with pigmented organic materials has considerable advantages com-
pared to pigmenting. For example, glass objects coated in different colors can be
recycled without sorting by melting and burning off the organic layer at tempera-
tures between 400 and 600 °C. This process yields clear glass.
Moreover, the coatings impart new properties which enhance the usefulness of the
glass. They provide improved resistance to mechanical and chemical influences and
protection against shattering. They also give designers new scope for using color
and special effects. Glass can be coated with UV-curing acrylates [125] or high viscos-
ity solvent-free or solventborne polyurethane systems [126]. Each of these technolo-
gies requires specific coating units and equipment. Examples here are special spray
coating equipment, UV lamps, and off-gas incinerators. Apart from differing in the
application processes, the coatings also vary particularly in terms of their service
properties, e.g. chemical resistance, weather stability and mechanical stabilization
of the glass.
In addition to the systems described here, environmentally friendly, waterborne
polyurethane systems are available. These consist of hydrophilically modified
blocked polyisocyanates (“Bayhydur BL”) and hydroxyl-bearing polyurethane
dispersions (“Bayhydrol”) [127]. The formulations have a co-solvent content of less
than 10 %. Conventional application processes such as dipping or spraying are used.
The coatings are baked for 30 minutes at about 170 °C.
These formulations have proved to be highly resistant to the heavy wear associ-
ated with the sterilization, repeated rinsing (alkali resistance) and weathering
of returnable bottles, and are thereby very suitable for glass coating. With their
combination of hardness and durability, the coatings ensure excellent protection
of the glass over a long period of time. As the coatings can be pigmented easily,
different colors and effects can be achieved economically and ecologically.
This waterborne technology has opened up new perspectives for glass coating,
because it is environmentally friendly and at the same time satisfies the perfor-
mance requirements specified by the industry (see Figure 5.80, page 202).

5.6.2 Glass fiber sizing

In the form of fibers, glass has special mechanical properties that are exploited in,
for example, the reinforcement of plastics.
Sizing application
Glass fibers are produced in the melt.
Individual glass filaments are drawn out,
coated and then combined into a single
fiber. This application process and the
coatings used as referred to as ‘sizing’.
The sizing protects the fibers against
abrasion and breakage and gives them
special product-specific properties.
Figure 5.80: Decorative glass coating with These include stiffness, cutting proper-
waterborne one-component polyurethane ties, and in the case of chopped strands,
systems flow properties (see Figure 5.81).
The chopped strands with a length of
3 to 5 mm are incorporated by extru-
sion into the plastic to be reinforced.
Temperatures of more than 250 °C are
reached for short periods during this
process. The sizing essentially consists
of a polymer (binder), an adhesion pro-
Figure 5.81: Chopped strands with a moter, slip agents, antistatics, and other
“Baybond” polyurethane dispersion sizing additives. Water serves as the dispersion
medium.
The reinforcing properties depend on
how well the glass filaments adhere to
the plastic matrix. The binder used in
the sizing must therefore be compat-
ible with the plastic so as to ensure an
adequate bond. Depending on the appli-
cation of the glass fibers, various poly-
mers, e.g. polyvinyl acetates, polyester
resins, epoxy resins and polyurethane
dispersions, can be used in the sizing
formulation. For example, polyure-
Figure 5.82: High-performance, glass fiber
reinforced plastic in engine construction;
thane-sized glass fibers are preferred
component of an intake manifold made using for reinforcing thermoplastics such as
a “Baybond” polyurethane dispersion sizing polyamide.

Application on glass 203
Polyurethane-based glass fiber sizings are stable to the shear forces that occur
during the application process. They also have outstanding film-forming properties
and very good colorfastness on exposure to heat.
Polyether and polyester polyurethane dispersions based on aliphatic diisocyanates
are mainly used to formulate polyurethane glass fiber sizings. Both non-functional
and crosslinkable dispersions are available [128, 129]. Thanks to their good compatibil-
ity with the plastic matrix, polyurethane sizings ensure very good adhesion and
thus positively influence the reinforcing properties in the end product, such as
impact strength, tensile strength and flexural strength. The main applications for
glass fiber reinforced thermoplastics are in the automotive and electrical industries
(see Figure 5.82). Some of the binders used for glass fiber sizings are also used to
formulate sizings for carbon fibers.
5.7 Use on textiles and leather

In 2005, approximately 100,000 tons of polyurethane raw materials (calculated as
solid resin) were processed worldwide in textile and leather coating and coagulation.
Annual growth is about 3 %. Most textile coatings are used in the Far East with around
75 %, followed by Europe with about 20 %, and 5 % in North and South America.
The reasons for the growing significance of polyurethanes in this segment lie in the
excellent service properties of the finished articles and the variability of this class of
raw materials. Polyurethanes can be used in the form of solutions, virtually solvent-
free high solids, granules or waterborne dispersions for the coating of textiles.
Due to the higher price of polyurethanes compared to PVC, for example, they are
used only in applications which specifically require their superior technical proper-
ties: high abrasion resistance, flexibility, high brittleness temperature, tensile
strength and tear strength. As even thin coats of polyurethane fulfill their technical
function, the price disadvantage can often be reduced significantly or even offset
completely in some cases.
5.7.1 Textile coating

The first polyurethane systems for coating textiles, which came onto the market in
the 1950s, were two-component systems [130, 131]. These were applied by the direct
coating method (Figure 5.83, page 204) to produce materials for clothing for men,
women and children, for work clothing, accessories and luggage [132].
Applications
With the introduction of one-component polyurethane systems and the transfer
coating process, new applications were found in the early 1970s, for example the
production of articles with a leather-like appearance. In the transfer coating process,

the topcoat is applied on release paper (silicon- or propylene-coated paper), which

can also have a grain, and then transferred to the textile using an adhesive coat
(Figure 5.84).
In the1980s and 1990s, the demand for clothing with greater wear comfort increased.
This required high water vapor permeability and good wind protection. Special
microporous and hydrophilically modified polyurethanes were developed for this
purpose [133-135].
Polyurethane-coated articles are now found in the following areas:
• clothing: outerwear, shoes
• protective textiles: work clothing, rainwear, windproof clothing
• materials for bags and luggage: bags, suitcases
• industrial textiles: filters, seals, awnings
• environmental textiles: drainage mats, erosion nets
• automotive interiors: seat covers, door and side panels, headliners
• medical and hygiene articles: adhesive plasters, bandages, mattress covers
• sports textiles: grips, balls, backpacks, sports clothing
Figure 5.83: The direct coating process
Figure 5.84: The transfer coating process

Use on textiles and leather 205
Manufacturers worldwide offer an extremely wide range of products for a variety of

different applications. Because of the combinability of polyurethane coating raw
materials, textiles coated with these products can be adapted easily to suit the dictates
of fashion. Moreover they are comfortable to wear. Typical service properties include:
• variable formulation and application
• textured, leather-like surfaces (see Figure 5.85)
• good wear properties
• warm and pleasant feel
• resistance to washing and dry cleaning
• good adhesion to the substrate
• high elongation at break and elasticity
• high low-temperature flexibility (without plasticizer)
• good abrasion resistance
• high scratch resistance
• high flexibility
• resistance to water and solvents
• resistance to oils and grease
• good water vapor permeability and windproof properties
• low specific weight
The type of textile coated, the polyurethane system used, the coating process and the
finish products applied determine the quality and service properties of the end product.
Textile substrates
The importance of polyurethane coatings increased with the growing variety of

textile materials. Today, coatings are applied mainly on woven and knitted goods
made from various natural and
synthetic fibers and their blends,
as well as on non-wovens made
from synthetic fibers and micro-
fibers.
Formerly, when only direct coat-
ing was possible, the napping of
a cotton fabric was the decisive
factor in the quality of the coated
goods. Only with the introduc-
tion of thermoplastic one-com-
ponent polyurethane systems and
suitable release papers could
simpler, lighter and cheaper fab- Figure 5.85: Example of a textured surface
rics be coated by the transfer produced by the transfer coating process

process. It is even possible to produce softer articles in this way. Now, the napping
of a cotton fabric can be substituted by a foamed polyurethane intermediate coat. For
many years, it was standard to use PVC, latex and acrylate for this purpose. Poly-
urethane systems are foamed by the addition of blowing agents (chemical compounds
which split off nitrogen on exposure to heat) [136] or, in the case of dispersions, by the
mechanical incorporation of air (mechanical foaming). Polyurethane-coated cotton
fabrics without napping are used to manufacture, for example, light coats for men
and women. Similarly produced light to heavy polyamide fabrics are used to manu-
facture work clothing, backpacks and camping equipment. Polyester and polyamide
fabrics coated with polyurethanes are suitable for tarpaulins and technical articles.
Products and methods
As any chain branching caused by triols, amines or isocyanates on the polyurethane
structure can result in undesirable hardening of the coating film and a reduction in
the flexibility and softness of the coated fabric, the polyurethanes developed for
textile coating applications have a largely linear chain structure [137-139]. On the other
hand, greater chain branching improves the resistance to solvents and water.
The polyurethanes developed for textile coating differ not only in their technical
properties, but also in their preparation. Figure 5.86 shows that there are four types
of product on the market: granules, solutions (one- and two-component systems), high
solids and waterborne dispersions.
Solventborne systems
After being dissolved, granules are either processed directly from solution, or films
are made from solution and then applied on textiles by lamination. One-component
Figure 5.86: Classification of polyurethane textile coatings and processes

polyurethanes yield films with the desired properties without chemical crosslinking,
i.e. solely as the result of physical interactions such as hydrogen bonds. These films
are of medium hardness, highly elastic, relatively difficult to dissolve and thermo-
plastic. As they are based on aromatic isocyanates, the one-component systems
require the use of highly polar solvents or solvent mixtures such as dimethyl for-
mamide/methyl ethyl ketone [140, 141].
Using cycloaliphatic isocyanates such as isophorone diisocyanate, lightfast one-
component polyurethane ureas were developed in the 1970s. Soft solvents such as
alcohols and toluene are normally used with these systems. The aliphatic polyure-
thanes not only have good lightfastness, but can be processed easily and safely to
yield coatings with outstanding flexibility. Special, usually harder polyurethane
ureas are used as finishes on polyurethane coatings when necessary. These finish
films, normally 5 to 8 µm thick, improve the feel, appearance, and fashion aspects
of the coating, as well as its scratch resistance. They are applied by spraying, print-
ing or knifing by doctor blade. The high solid systems mentioned are two-component
polyurethanes consisting of blocked polyisocyanate prepolymers reacted with cyclo-
aliphatic diamines. 1-Methoxypropylacetate-2 is normally used as the solvent [142].
A well-known example of a multilayer system of polyurethane solutions and high
solids based on “Impranil” is the “+Teamgeist” ball used in the 2006 Soccer World
Cup (see Figure 5.87).
1. Aliphatic topcoat made from polyurethane solution:
Print protected underneath clearcoat, prevents abrasion of the printed surface.
2. Aliphatic intermediate coat based on two-component high solid polyurethane:
Protects the ball from exter-
nal influences and ensures
exceptionally high elasticity.
3. Syntactic foam based on two-
component high solids:
Consists of polyurethane con-
taining millions of gas-filled
microspheres. This gives the
ball its outstanding resilience,
which significantly improves
the flight properties.
4. Adhesive coat made from
polyurethane solution:
Bonds the various layers to
the textile substrate
5. Special polyester/cotton fabric: Figure 5.87: Multilayer “Impranil” finish on the
Serves as the substrate “+Teamgeist” ball used in the 2006 Soccer World Cup

Before application, the diamine is added to the prepolymer at room temperature.

These mixtures have a long pot life and the crosslinking reaction starts at tempera-
tures above 60 °C. Depending on the type of prepolymer used, temperatures of 150
to 175 °C are required for full crosslinking.
Waterborne polyurethane systems
Waterborne dispersions with good storage stability are produced from linear one-
component polyurethanes. They contain internal emulsifiers – incorporated into the
molecular chain – as well as ionic groups which produce an additional hydrophilic
effect, or corresponding nonionic segments. Depending on the type of ionic groups
incorporated, a distinction can be made between anionic and cationic dispersions,
whereby the latter are practically of no importance in textile coating.
Another alternative manufacturing process uses external emulsifiers. In just a few
cases, such dispersions contain small amounts of solvent (co-solvent). They are
used as adhesive coats or topcoats, and as foamed intermediate coats applied by
the mechanical foam method (see above).
The use of waterborne one-component polyurethane dispersions and products with
a low solvent content such as two-component polyurethane high solid system offers
considerable potential for reducing the solvent content. The resulting ecological
advantages mean that this type of polyurethane coating is being used more frequently.
Effect of the application methods
Special techniques exist for the application of granules. One is the melt calendering
process using thermoplastic polyurethane granules. Another is coagulation, in
which the coating material is precipitated in water from a one-component solution
in dimethyl formamide. A third option is film lamination using the thermal transfer
method [143]. In addition to the material used, the coating method [144–146] also influ-
ences the properties of the finished article. For example, the application rate and
the feel of the finished product change with the type and hardness or flexibility of
the application instrument (knife-over air, knife-over roll) when applying a poly-
urethane solution straight to the pile of the fabric by direct coating.
By contrast, the transfer process yields particularly soft coatings. The coating mate-
rial is applied as a solution on release paper. It is cured by heating and then lami-
nated onto the textile using a thin adhesive coat. Even high solids and dispersions,
adjusted to the necessary coating viscosity of about 5,000 mPas with just a small
amount of thickener, can be applied by transfer coating. Dispersions containing no
emulsifiers thickened in this way and then foamed mechanically yield very soft
materials for outerwear.
5.7.2 Polyurethane synthetic leather and microporous coatings
An essential characteristic of leather is its microporosity. It has the ability to adsorb
and release water vapor. Efforts to develop a synthetic material with the appear-

ance and properties of leather started some 45 years ago [147]. About ten years later,
“Corfam” (DuPont) was the first poromeric synthetic leather on the market [148]. The
manufacture of this product was later licensed to Clarino in Japan where develop-
ment continued to enhance the product with a microfiber non-woven. Brands such
as “Alcantara”, “Amara” and “Amaretta” are now of importance worldwide.
One of the first steps in this development was the polyurethane/dimethyl formamide
(DMF) coagulation process [149, 150]. The substrate – a woven fabric, a non-woven, or
in special cases a knitted fabric – is coated with a solution of polyurethane that has
already started to gel. It is then passed through a number of baths containing DMF
in decreasing concentrations and lastly through a bath of pure water. As the result
of phase transfer, a polyurethane sponge forms from the polyurethane solution in
DMF. The precipitation reaction is slow and occurs from the outside inwards. The
non-solvent water penetrates the layer and displaces the solvent DMF. Once the
DMF has been fully replaced by water, the product is dried.
As the result of the heat which is generated by mixing DMF and water, the product
is voluminous and porous but, although it has a pleasant feel, it does not yet look
like leather. Additives (e.g. cellulose powder), pigment pastes and emulsifiers can
be mixed into the polyurethane to control the microporosity. Silicones serve as
antifoamers, and flow promoters can also be added. Depending on the method of
application, only the top side of the product is coated, or it is dipped to coat it on
both sides [151]. The DMF can be recovered from the process water (i.e. water/DMF
= 75 : 25) by distillation.
Depending on the intended end-use, the product can be printed, embossed, buffed,
transfer-coated, impregnated or tumbled. In this way, materials with a micropo-
rous structure can be produced for the manufacture of shoe uppers, shoe linings,
upholstery, bags and luggage, clothing, cleaning and polishing cloths and filters
(see Figure 5.88). An overview of the production of porous textile structures is
referred to in the literature [152].
There have been various efforts to pro-
duce thick, porous textile structures
as synthetic leather without the use
of solvents. The development of new,
high solid and fine polyurethane disper-
sions has made it possible to produce
mechanical foams and apply them on a
textile substrate in a thickness of some
millimeters in just one process step [153].
If high-quality raw materials such as
polycarbonates and polytetramethylene Figure 5.88: Shoe uppers – a typical appli-
glycols (PTMG) are used as the polyol cation for polyurethane synthetic leather

components, synthetic leathers with high resistance properties can be produced [154].
The advantage of this method is that it can be run on conventional textile coating
units and, in contrast to the DMF coagulation method, does not require solvents.
High solid polyurethane dispersions make it possible to economically produce
synthetic leather by this process (see Figure 5.89).
Methods of coagulation
There are other processes for generating microporosity. These include the removal
of salts from films or the spray application of polyurethane solutions in highly
volatile solvents. However, neither method has been adopted by industry [155]. The
selective vaporization coagulation process has been more successful [156]. In this pro-
cess, a non-solvent with poor vaporization properties, such as water, is mixed into
a polyurethane solution in, for example,
methylethyl ketone. The result is a paste
which can be used to coat the substrate.
As the coated substrate passes through
the drying tunnel, the solvent evapo-
rates first. The amount of non-solvent
increases steadily, with the result that
the polyurethane coagulates and then
precipitates as a microporous product.
Finally, the non-solvent evaporates and
leaves a microporous coating. How-
Figure 5.89: Structure of a synthetic leather ever, the application rate is limited to
based on a waterborne, solvent-free system. about 20 to 50 g/m². The end products
From bottom to top: textile substrate; inter- are mainly used in the clothing industry
mediate foam coat based on a 60 % “Impra- (see Figure 5.90). There are other appli-
nil DLU” dispersion; compact, waterborne
topcoat with visible grain cations for polyurethanes in the textile
and clothing segments. These include
textile finishes [130, 157, 158], binders for
pigment printing [164], and the tanning [130,
159–163]
and finishing [130, 164–168] of leather.
5.7.3 Leather coating

Leather is a substrate of natural origin
that is used in the production of shoes,
clothing, and furniture, as well as in
other diverse applications. The high
Figure 5.90: SEM showing a microporous
polyurethane coating in cross section; the
wear comfort of leather is based on the
porous layer has been applied on a polyester excellent adsorption and desorption of
fabric (below) moisture. In chemical terms, leather is

collagen or a polypeptide obtained from animal hides. The soaked hides are fixed
by tanning to stabilize the collagen fibers and ensure that the leather remains flex-
ible at the temperatures of use. The tanning quality depends on the temperature at
which a leather dries, shrinks and cures. Above 90 °C, most tanned leathers cure
irreversibly to brittleness.
In nearly all cases, leather is too thick for processing. For this reason, it is separated
into two layers. While the top layer still shows the natural grain, the bottom layer or
split leather has a rough surface and is often used to produce suede. Leather is coated
for different purposes. Generally, the surface treatment of dry leather is called
finishing. This may result in coloring, altered haptics, water and dirt resistance,
and improvements of abrasion and scratch resistance. Starting from the leather
substrate, the finishing layers are the impregnation, primer and finish. The drying
temperatures for the individual coats should not be too high to avoid damaging the
leather (see above).
In addition to polyacrylates, butadiene copolymers and nitrocellulose, one- and
two-component polyurethanes are used when particularly good performance is
required. Polyurethane dispersions are usually crosslinked either with water-dis-
persible polyisocyanates, polyaziridines or methylol compounds [169]. The best prop-
erties are yielded by two-component polyurethane finishes. Isocyanate prepolymers
crosslinked with diamines have a short pot life and therefore have to be mixed by
a special method. Both the products and the mixing method are known by the name
“Levacast” [170].
Standard methods of applying the leather finishing products are spraying, curtain
coating, transfer coating (analogous to textile coating), and film lamination. The
demand for suede depends on prevailing fashion trends. However, since large amounts
of split leather are produced, methods have been developed to produce artificial
graining on the surface of split leather.
One method is direct coating followed
by embossing. Alternatively, a grain pat-
tern can be produced by reverse coating
with negative graining on the release
paper, lamination and removal of the
paper (see Figure 5.91). In a third
method, a matrix of silicon rubber is
used as the negative pattern. The artifi-
cial grain produced by one of these
methods has the advantage that there are
no defects (e.g. scars caused by barbed
wire or damage from skin parasites that
are found on natural grained leather). Figure 5.91: Steering wheel with polyure-
Also, it is uniform and entirely reproduc- thane transfer coating on split leather

ible. These artificially grained split leathers are hard to distinguish from natural
grained leather.
5.8 Coating and finishing of paper and films

In the coating and finishing of thin substrates such as paper or films, a distinction
is made between the following segments:
• paper manufacturing
• the coating of printed products
• the production of packaging materials
• the production of decorative films for furniture and interior design
• the modification and finishing of technical films
5.8.1 Paper manufacturing

Polyurethane raw materials still play a comparatively subordinate role in paper
manufacturing [171]. The chemical crosslinking of paper components – cellulose or
starch – with polyisocyanates significantly strengthens the structure of the paper.
This results in an improvement in the wet strength – an important factor in the
papermaking process. Properties such as the printability and tear resistance of the
end product – the paper – can also be improved. Hydrophilically modified polyiso-
cyanates are suitable for this purpose. Depending on the use of the paper, food
safety regulations must be observed. The polyisocyanates are normally added to
the pulp but may also be applied as a surface coating [172, 173].
Polyurethane dispersions can also be used in the production of paper [174]. They are
particularly suitable for improving the properties of paper for inkjet and thermal
printing [175-177]. A special application for polyurethane raw materials is in the manu-
facture of carbonless copying paper. A colorless leuco dyestuff is encapsulated in the
heterogeneous phase by reacting polyisocyanates with water, i.e. through the forma-
tion of urea. These capsules are applied on the reverse side of a carrier paper. On use,
this comes into contact with an acidified paper. The pressure exerted by writing or
typing destroys the capsule walls and the color develops by reaction of the dyestuff
on the acidic paper [173]. A modern process which is also based on the use of leuco
dyestuffs is thermal printing. Urethane and urea derivatives of aromatic isocyanates
are used for the thermally activated color development process [178] (see Figure 5.92).
5.8.2 Paper coating

Printed products are overcoated with a clearcoat both for technical reasons and to
enhance their appearance. Such an overprint varnish accentuates the print color and
increases its brilliance. It also protects the print from mechanical and chemical
damage. In response to growing quality requirements, chemically crosslinking sys-
tems such as two-component polyurethane coatings are being used increasingly for

Coating and finishing of paper and films 213
this application. They are applied by roller coating and by flexographic and rotogra-
vure printing. The coatings are dried in heat and air, e.g. in infrared, jet or float
dryers. In order to ensure high production rates, the two-component systems are
formulated such that physical drying takes place in the drying unit and chemical
crosslinking occurs once the coated products are stacked or rolled. This process is
used to apply HDI-based aliphatic polyisocyanates combined with physically drying
polyacrylate polyols, especially for lightfast coatings. On account of their high
curing speed, radiation-curing polyurethane systems in particular are established as
binders for overprint varnishes. Many of the raw materials used in polyurethane
overprint varnishes are also suitable for the formulation of printing inks [179].
The coating of packaging materials
To a large extent, flexible packaging materials, prefabricated as films, have
replaced rigid packagings made from glass or metal. Coatings play an important
role in printing, coating, laminating and embossing the film substrates [179-183]. Poly-
urethane raw materials are normally used to formulate the coatings, printing inks
or lamination adhesives. For example, polyurethanes are added to nitrocellulose
in the production of composite packaging [182]. Two-component systems, e.g. two-
component white, are also used in high-quality laminates.
In general, the statements made with
regard to printed products also apply to
the coating of packaging materials made
from plastic films or aluminum foil. In
this segment, the following properties
are exploited or optimized:
• high scrub resistance
• high chemical resistance
• broad variability of flexibility
• good adhesion, although polyolefin
films should be pretreated
e.g. by corona discharge
• resistance to sterilization
• resistance to freezing
• sealability
• diffusion barrier properties
In order to satisfy this wide range of
requirements, the broad variety of prod-
ucts available – both polyols and poly-
isocyanates – can be exploited, as can Figure 5.92: High-quality applications for
the many combination options. In the thermal paper

design of packaging, haptic properties are increasingly viewed as distinguishing

features [183]. In the area of plastic coating, polyurethane dispersions are used to
produce a soft-feel effect.
5.8.3 The production of decorative films for furniture and

interior design
In the furniture and interior design segments, around half of all wood and wood
material surfaces are finished by direct coating. Alternatively, decorative films are
applied. For the finishing of MDF materials, polyurethane dispersions are used in
the heat activation process (see 6.5.6).
Suitable substrates for decorative and finishing films for furniture are specially
impregnated paper, thin paper and thermoplastic films. The coating is applied in
a continuous process by roller with a spreading knife or by gravure rolling. It is
then dried in float dryers. High demands are made with regard to the lightfast-
ness and chemical resistance of the coatings used to produce decorative films [184].
As these films are also applied on shaped components such as the fronts of furniture
or rounded edges, the coatings must also have a certain flexibility and good blocking
resistance. As polyurethane coatings combine these properties, they differ from the
acid-curing coating systems which have been widely used until now in the furniture
industry. The polyurethane systems used are usually two-component formulations
based mainly on polyacrylate polyols and aliphatic HDI based polyisocyanates. In
the case of decorative films, the polyurethane coatings are formulated so that they
are tack-free when films are wound to prevent sticking, but crosslink on the roll.
This is possible because of the rapid physical drying of the coating.
5.8.4 Finishing of technical papers and films

There is a wide range of applications for polyurethane systems in the processing
of film-like materials. Significant uses include:
• Production of abrasive paper
As a rule, phenolic resins are used as the embedding compound for the abrasive
material. However, polyurethane binders yield products with much higher water
resistance. They are therefore used primarily in the manufacture of abrasives
for wet sanding processes. Two-component systems based on polyester polyols
and crosslinked with aromatic isocyanates are normally used.
• Embossed release paper
Embossed release paper is used, for example, as the negative for grain emboss-
ing in the manufacture of synthetic leather. The contact side must be chemically
inert and non-adhesive. The product must also yield good image reproduction.
These requirements are satisfied by crosslinking polyurethane topcoats as well
as by other systems such as radiation-curing coatings.

Coating and finishing of paper and films 215
• Scratch-resistant finishes for films used in machine and automotive production

The coatings used in this application must not only satisfy strict requirements
in terms of scrub and scratch resistance but must also be suitable for deep-
drawing. For this reason, fast-drying polyurethane resins are favored, which
can be crosslinked easily with aliphatic polyisocyanates if necessary. Also in
development are systems based on polyurethane dispersions and water-reducible
polyisocyanates.
• Stamping foils
Stamping foils are widely used to decorate plastics components, for example in
cosmetics packaging. They originated in the graphics industry and were optimized
technically for the aforementioned application. The significance of polyurethane
coating raw materials in these applications lies in their use as finishes. They make
it possible to satisfy specific requirements in terms of the resistance properties
and to achieve adequate blocking resistance and an accurate image during the
stamping process. It is therefore necessary to use very hard coatings based on
aromatic TDI polyisocyanates.
The finishing of technical film and foils with polyurethane materials goes beyond
the few examples given here. Each application requires a special technology and
demands different property profiles. Frequently, only polyurethane raw materials in
all their chemical versatility allow the formulation of such customized coatings.
5.9 Construction applications

Polyurethanes have many uses in the construction sector. They are used as adhesives
and sealants, for floor and wall coatings, in sealing membranes for roofs and bal-
conies, as well as for thermal insulation foam [185].
5.9.1 Floor coatings
The demands made on floors vary greatly depending on the intended use. Prefab-
ricated plastic coverings and coating materials are being used increasingly along-
side parquet, ceramic tiles and carpets. The use of polyurethane is favored mainly
because of its high resistance to mechanical and chemical influences and the favor-
able cost/benefit ratio. An additional advantage is the exceptionally broad design
scope offered by this technology. Floors are of particular importance in ensuring
the functionality of industrial facilities. The quality of a floor is instrumental in the
smooth operation of production and the correct storage of products.
The requirements made of industrial floors are therefore correspondingly high and
various. Depending on the type of facility and the prevailing conditions, the fol-
lowing characteristics may be required:
• mechanical and dynamic strengtha (resistance to compression, impact and abra-
sion, crack-free)
a
Primarily dependent on the raw materials

• chemical resistancea
• electrical resistanceb
• thermal resistancea (long-term and short-term)
• colorfastness and weather stabilitya
• insulation propertiesa (acoustic and thermal)
• evenness (DIN 18 202) [186]
• non-slip propertiesc
• ease of care, cleanabilitya, c
• ease of repaira
• service life, cost/benefit ratio
Many of these properties are defined in, for example, Germany’s DIN 28 052 [187]
and in sum make up the service profile of a floor. The primary function of floors is
to absorb and distribute static and dynamic loads. Irrespective of its actual structure,
a floor can be defined as consisting of two layers:
1. A load-bearing layer such as a monolithic concrete slab or a combination of a
concrete slab and screed floor overlay
2. A wear layer which is rigidly bonded to the load-bearing layer. This must
withstand chemical and mechanical influences and satisfy other user-specific
demands, e.g. non-slip properties, ease of cleaning and optical properties as
listed in more detail above
A floor coating is such a wear layer. In order to achieve a fully functional bond,
the properties of the individual layers must be harmonized. The wear layer is often
based on synthetic resins, particularly reactive systems, such as polymethyl meth-
acrylate (PMMA), epoxy resin (EP) or polyurethane. Figure 5.93 shows the current
market situation for these binders. Epoxy resins hold the largest share at 65 %,
followed by polyurethane coatings with 25 %.
The floor coating may be in the form
of a sealant, a thin coating of up to
0.3 mm or a covering of up to 3 mm
thick. Other options include syn-
thetic resin mortars or decorative
synthetic resin screeds applied in
thicknesses of 3 to 10 mm (colored
sand mortar). In the latter case, the
wear layer additionally has a load-
bearing capacity. Sealers, thin coat-
Figure 5.93: World floor coatings market,
2005, total: 275,000 tons raw materials
ings and coatings are formulated
solvent-free or with a low solvent
Primarily dependent on the raw materials
content. Synthetic resin mortars are
a
b
Primarily dependent on the formulation
c
Primarily dependent on the application always formulated solvent-free.

Construction applications 217
5.9.1.1 Technology of polyurethane floor coatings

The wide variability of polyurethane technology is also exploited fully in the floor
coating segment.
Table 5.28 provides an overview of the main properties. Polyurethane coatings can
be customized to yield property profiles that suit the individual floors.
As shown, polyurethane coatings may range from highly elastic (for membranes,
floors in sports facilities) to hard and highly resistant to chemicals (for chemical
production plants). Typical applications of polyurethanes are:
• one- and two-component primers and sealers
• floor coatings for sports facilities
• membranes, e.g. waterproofing membranes
• industrial floor coatings ranging from tough yet flexible to hard depending on
the requirements of construction and water protection regulations
• one- and two-component synthetic resin mortars and colored sand mortars
Instrumental in the success of polyurethane systems in these applications are the
following properties:
• hard curing even at low temperatures
• good adhesion
• adjustable hardness and, as a result
– excellent chemical resistance with hard coatings
– crack-bridging with elastic and tough yet flexible formulations
– seamless application, also with elastic and tough yet flexible formulations
Table 5.28: Variability of the properties of polyurethane floor coatings

Property Standard Range
Pot life [min] 2–120
Tensile strength [N/mm2] DIN EN ISO 527 1–60
Elongation at break [%] DIN EN ISO 527 6–1,000
Modulus of elasticity [N/mm ] 2
DIN EN ISO 527 0.1–2,500
Compression strength [N/mm2] DIN EN ISO 604 ≤100
Tear propagation resistance [N/mm] DIN ISO 34-1 1–100
Shore hardness DIN 53 505 A 20 – D 80
Abrasion resistance [mg] DIN EN ISO 5470-1 5–150
Adhesion to iron [N/mm ] 2
DIN 53531-2 ≤30
Glass transition temperature [°C] DIN EN ISO 6721-1 -40 to +100
Water vapor diffusion resistance DIN EN ISO 12572 500–100,000
factor µ

– variable water vapor diffusion values (for application on anhydrite and

magnesite overlays)
• good resistance to hydrolysis and low water absorption
• very good weather stability and colorfastness in formulations containing selected
aliphatic products
Polyurethane floor coatings have been in widespread use for more than 40 years
and a large number of reference objects are proof of their outstanding quality and
long service life.
Chemical principles
The most important base products in the formulation of polyurethane floor coatings
are isomer blends and prepolymers of diphenylmethane diisocyanate (MDI).
Oligomers and adducts of hexamethylene diisocyanate (HDI) and isophorone
diisocyanate (IPDI) as well as prepolymers of toluene diisocyanate (TDI) and
isophorone diisocyanate (IPDI) are also used.
The preferred coreactants are polyhydroxy compounds, but aromatic and sterically
hindered aliphatic amines, such as polyaspartates [188, 189] and polyether amines, and
latent hardeners, such bisoxazolidines [190], are also available. The latter are con-
verted into reactive products by the effect of moisture. Classic one-component
polyurethane systems are also used in which the polymer is formed by the reaction
of the isocyanate with moisture. These systems are used mainly to produce thin
coatings, as foaming occurs in thicker coverings.
It is also possible to use waterborne polyurethane systems based on special polyol
dispersions. These formulations can be applied in a wide range of thicknesses.
However, thick coatings require the addition of cement and/or hydrated lime (three-
component systems) to capture the carbon dioxide produced by the effect of water
[191]
. These coatings are characterized by a very high chemical resistance (“Desmo-
lith”). Low and high molecular weight products, both linear and branched, with
Table 5.29: Example of a polyurethane floor coating
Component 1 Percent by weight
Step 1 “Desmophen 1150” 19.0
Molecular sieve paste 3Å 7.5
Inert filler 32.1
Inert inorganic pigment 5.0
Step 2 “Desmophen 1150” 19.0
Step 3 Deaeration agent 0.4
Component 2
“Desmodur VL” 17.0
100.00

differing chemical structures are available as the polyhydroxy compounds. Poly-

ester polyols, for example, ensure good solvent resistance, polyether polyols ensure
resistance to acids and alkalis, and derivatives of acrylic and methacrylic acids
ensure high weather stability. Table 5.29 shows the typical formulation of a self-
leveling two-component polyurethane floor coating.
Aspects of application technology
When processing these materials at the construction site, it is essential to be able to
control potential disruptive influences, especially the moisture which is unavoidable
on a construction site. This can result in foaming when applying thick coatings.
Systems with a short pot life – normally applied by spraying – and those containing
amines instead of polyhydroxy compounds present few problems in this respect. It
is a different matter if systems with a long pot life are used. Here, the hydrophilicity
or hydrophobicity of the systems and the associated degree of absorption of ambient
moisture play a crucial role. Polyether polyols modified with fatty acid to ensure
hydrophobicity are among the substances that have been found ideal in this respect.
It is necessary to use molecular sieves, which scavenge the water from the fillers,
pigments and other components in the formulation. Such floor coating systems fully
satisfy the requirements for on-site application [192].
The coatings are formulated in, for example, a dissolver or butterfly mixer, prefer-
ably under vacuum. The extenders, pigments, molecular sieve and surfactants are
mixed into the polyol component. Working under vacuum makes it easier to remove
air from the formulation, thus reducing the risk of microblistering due to exiting
air during hardening. Before filling the coating material into work containers, a
suitable deaeration agent is added to ensure a smooth pore-free surface.
In Germany, conformity with the requirements generally valid for floor coatings
must be ensured before application. These are contained in the “Richtlinie für
Schutz und Instandsetzung von Betonbauteilen” (Guideline for the Protection and
Refurbishment of Concrete Structural Elements) compiled by the “Deutscher
Ausschuß für Stahlbeton” (DAfStb – German Committee for Steel-Reinforced
Concrete) [193]. They include the removal of loose particles, laitance and dirt and
application only on a load-bearing substrate which is dry to slightly moist (nor-
mally ≤ 4 % water) and has a surface tensile strength of at least 0.8 N/mm (walk-
able surfaces) or 1.5 N/mm (trafficable surfaces). The ambient temperature should
be between 8 and 40 °C and the object temperature at least three degrees above
the dew point.
The polyol and polyisocyanate components are mixed on site using a cage or blade
mixer. As a rule, the floor covering system consists of a primer, a scratch filler to
level any unevenness (if needed) and the actual floor coating. These formulations
are applied using a roller or a notch trowel. The floor covering system can be com-

pleted with the application of a decorative, abrasion-resistant topcoat based on

“Desmodur N” and a polyester.
5.9.1.2 Examples of applications
The property profile of polyurethane floor coatings can be varied across a wide
range. Depending on the raw materials used, the coatings may be tough but flexible
or hard. Typical applications are described in the following paragraphs.
Floor coverings for sports facilities
The coatings used on the floors of sports
facilities provide either point or full-sur-
face elasticity in accordance with DIN
18 032 [194]. Different qualities can be
achieved thanks to the variable hardness
of the topcoat and the substrate, which
may consist of polyurethane-bonded
rubber granule mats, possibly incorpo-
Figure 5.94: Flexible flooring based on rating glass or textile fabrics. These sat-
two-component polyurethane isfy the requirements for physiotherapy
use but can also be formulated to be
suitable for multipurpose floors [195–197]
(see Figure 5.94).
Decorative floor coatings
Hotels, department stores, and public
buildings among others are increasingly
enhanced architecturally. Decorative
floor coatings play an important role
here. A wide range of colors and very
Figure 5.95: Individually designed, decora- attractive optical effects are in demand.
tive floor coating based on polyurethane [187] Individually designed floor coatings
using two-component polyurethane
systems based on aliphatic isocyanates
combined with hydrophobic polyols
have gained importance in recent years
[198]
(see Figure 5.95).
In the application of decorative floor
coatings, a solid-color primer based on
epoxy resins or one-component polyure-
thane prepolymers is applied first. The
Figure 5.96: Application of a decorative liquid two-component polyurethane
floor coating casting resin is then applied to yield the

colors, patterns, and motifs required. The applicators walk across the liquid coating
wearing spiked shoes (see Figure 5.96).
The coating is then topped with a highly abrasion-resistant, transparent polyure-
thane sealer.
Penetrating sealers and sealing compounds

Penetrating sealers and sealing compounds strengthen the surface of a substrate,
preventing abrasion of concrete or cement screed. The properties required include
exceptional toughness and abrasion resistance, coupled with high resistance to
water, chemicals and solvents. These systems can be formulated with moisture-
curing one-component polyisocyanate prepolymers, waterborne two-component
polyurethane sealing compounds or two-component polyaspartates, applied at the
rate of 100 to 300 g/m².
Coatings for car park decks
In the past, it was standard to apply only a sealing compound to car park decks
for protection. However, compliance with DIN 1045 [200] should be ensured. This
requires that steel-reinforced concrete components, which may crack across their
entire cross-section if exposed to water with a high chloride content (e.g. caused
by road salt), must have special protection. This largely applies to statically
indeterminate, area-covering structural elements such as car park decks. Given the
stresses to which these are exposed, cracking is virtually unavoidable.
A crack-bridging coating is recommended as special protection for steel-reinforced
concrete. Specifications for suitable coatings are stipulated in the “Richtlinien für
Schutz und Instandsetzung von Betonbauteilen” (Rili, Guidelines for the Protection
and Refurbishment of Concrete Structural Elements) issued in October 2001 by the
“Deutsche Ausschuß für Stahlbeton” (German Committee for Steel-Reinforced
Concrete – DafStb) [193]. These cover in particular the requirements for durable
crack-bridging of existing and newly formed expansion cracks caused by tem-
perature- and stress-related movements of the structure. They specify minimum
crack-bridging of 0.3 mm in a temperature range of -20 to +70 °C. Coatings which
meet the requirements of these guidelines are applied at a film thickness of 3 and
4.5 mm respectively.
Both one- and two-coat systems can be used. In the case of two-coat systems, each
coat may fulfill different functions. For example, the first coat provides crack-bridg-
ing, in particular at low temperatures, while the topcoat protects against abrasion,
chemicals, weathering and mechanical impact. One-coat systems must combine all
these functions in a single coat. To ensure crack-bridging at -20 °C and adequate
tensile strength, tear propagation resistance and abrasion resistance, the binder used

for the system must be selected carefully

and fine tuning is required during for-
mulation. Today, both types of system
– one- and two-coat – are primarily
polyurethane-based. The one-coat vari-
ant is normally the more economical of
the two [201–203].
Industrial floor coatings
Tough to hard floor coating systems
Figure 5.97: Two-component polyurethane are considered indispensable in fac-
floor coating that satisfies the special hygiene
tories and warehouses, for example,
and cleaning requirements of the food industry
in the automotive, food processing,
pharmaceutical and chemical industries and in wholesale markets. The coatings
have to meet a wide range of requirements in terms of mechanical properties,
safety and optical properties [204]. Individual customer requirements may also be
considered. Thanks to their toughness, polyurethane systems are also suitable
for use on bituminous substrates. They can also be customized via the choice of
raw materials for use on magnesite and anhydrite screeds compliant with DIN
ISO EN 13 813 [205], bearing in mind the construction physics and water vapor
diffusion resistance.
Antibacterial floor coatings
In recent years, floor coatings with additional functionalities have been used
increasingly in areas with special requirements. A typical example is coating mate-
rials for hospitals, schools, kindergartens and care homes, which have special
requirements regarding hygiene and the cleaning properties of surfaces. The
required properties such as an antibacterial finish are ensured by incorporating
suitable additives into the polyurethane coating material.
Secondary containment
The operators of production units in which substances hazardous to water are used
are obliged under § 19 of Germany’s Water Resources Act (WHG) to implement
suitable protection measures. These comprise concrete containment basins that are
often coated with systems which have to satisfy particularly stringent requirements
in terms of crack-bridging, elasticity and chemical resistance[207]. Applied in a mul-
ticoat system, polyurethane coatings can provide resistance to all 15 main chemical
classes defined in Germany’s construction and testing guidelines. A one-coat system
(without primer) already provides resistance to eight of these chemical classes. The
incorporation of carbon fibers, for example, yields antistatic floor coatings which
are required in areas where solvents are stored and handled [211–213].

5.9.2 Wall coatings

Whereas wall coatings previously had a primarily decorative function, surface pro-
tection is today increasingly the main purpose. The prevailing conditions must
always be borne in mind when selecting a coating system. Exterior walls (masonry)
differ significantly from interior walls with respect to coating requirements [214–216].
Masonry paints
Masonry paints must display the following characteristics:
• mechanical strength
• weather stability
• resistance to aggressive substances
• impermeability to driving rain
• gas diffusion properties
• ease of cleaning (lotus effect) [217]
As masonry is often exposed to wide fluctuations in temperature, the coatings used
must display a certain elasticity. Other key criteria for a good coating system are
adequate colorfastness and chalking resistance on exposure to weathering and a
minimal tendency to microcracking. In large metropolitan and industrial regions,
the coating systems come into contact with aggressive substances such as sulfur
dioxide (SO2), nitrous oxides (NOx), ozone and smog. It is particularly important
that the coatings do not age and lose their protective function. Another, not insig-
nificant feature is ease of cleaning of, for example, graffiti.
Impermeability to driving rain is a fundamental requirement of any masonry paint.
If moisture penetrates a wall, it can cause substantial damage such as frost crack-
ing, efflorescence and reduced insulation properties. The coatings must also have
a good barrier effect to acid gases without restricting the water vapor diffusion
too much. If the water vapor diffusion is too low, any moisture trapped in the
masonry cannot escape. This can easily result in damage inside the building, such
as mold growth.
Interior wall paints
Interior wall paints mainly have a decorative function. As a rule, ease of application
and a low organic solvent content are key requirements. The resistance properties
required depend very much on the area of use. In the case of paints used in private
homes, it is normally sufficient to ensure medium resistance to standard household
cleaning agents. In buildings such as hospitals, laboratories, food-processing plants
and nuclear facilities, stricter requirements prevail in respect of the resistance prop-
erties, for example, resistance to cleaning agents, steam cleaning, disinfectants and
decontamination chemicals. These strict requirements can only be satisfied by using
a highly crosslinked coating system.

5.9.2.1 Coating systems

A large number of wall and masonry paints covering a broad spectrum of price and
quality levels are available on the market. Generally speaking, masonry paints can
be divided into two types:
• systems that dry only physically, such as emulsion paints based on vinyl copo-
lymers and silicates
• reactive resin systems based on, for example, epoxy resins (EP) or polyurethanes
For most standard applications, emulsion paints based on polyvinyl acetate (PVA)
or acrylates have become the systems of choice.
Waterborne vinyl copolymers

Vinyl copolymers are the dominant binders for the formulation of wall and masonry
paints. Pure acrylates represent a particularly high-quality variant. Like the other
vinyl copolymers, they dry physically. In other words, film formation results exclu-
sively from the evaporation of the solvent, which may be water. It is above all the
range of relatively low-price systems that has led to the widespread use of pure
acrylates in wall and masonry paints. This type of system is easy to handle and can
be applied in various film thicknesses. Subsequent overcoating with the same
system is possible. Adhesion is normally adequate on various mineral substrates.
The dry paint films are colorfast, UV-stable and provide an adequate barrier to
atmospheric carbon dioxide. However, pure acrylate paints do have a few disad-
vantages resulting from the absence of crosslinking that must be accepted:
• low solvent resistance
• vulnerability to graffiti
• thermoplasticity
• medium abrasion resistance
The quality of such coatings can be increased by adding polyurethane dispersions.
Epoxy (EP) systems

Epoxy (EP) systems yield very high-quality wall paints. They are two-component
systems that form a film and cure as the result of a chemical reaction that produces
a three-dimensional network. The films are hard, have outstanding chemical resis-
tance, adhere well on different substrates and act as an effective barrier to carbon
dioxide. Solventborne, solvent-free and waterborne systems are available. The fol-
lowing properties of EP systems may be disadvantageous:
• inadequate through-curing at low ambient temperatures
• poor recognizability of the end of pot life in waterborne systems
• no UV stability resulting in yellowing of films

Polyurethanes
Like EP systems, polyurethanes cure to form a three-dimensional network yielding
thermoset films. However, in contrast to the EP systems, one-component systems
that cure by reaction with atmospheric humidity can be formulated. The systems
available on the market also include solventborne, solvent-free and waterborne
two-component formulations. The raw materials used are polyesters, polyethers and
polyacrylates, which are combined with a polyisocyanate crosslinker. Polyesters
include “Desmophen 651” or similar products. “Desmophen A 160” or equivalent
products are among the polyacrylates used. Preferred polyisocyanates are “Des-
modur N” or comparable crosslinkers from other manufacturers. In recent years,
waterborne two-component polyurethane systems also achieved greater market
acceptance. They are formulated with hydroxyl-bearing polyacrylates such as
“Bayhydrol A 242” and hydrophilically modified polyisocyanates such as “Bay-
hydur 3100” or comparable products.
Polyurethane coatings have good resistance to solvents, graffiti and chemicals,
as well as very good weather stability and colorfastness. They are hard yet have
a distinct degree of elasticity. From the construction physics aspect, they provide
mineral substrates with optimum protection, have adequate water vapor permeabil-
ity and are effective barriers to acid gases such as carbon dioxide. Critical features
of polyurethane coatings that might be considered disadvantages include:
• higher material costs compared with vinyl copolymers
• a certain sensitivity to high moisture levels in the substrate - varies widely among
the polyurethane systems available on the market
• the need to maintain a maximum film thickness on application to prevent film
defects such as blistering
On account of their higher price, high-quality polyurethane systems are only used
when special requirements are made in terms of the resistance properties that cannot
be satisfied by “normal” emulsion paints. This may be of particular interest if, for
example, high secondary costs (scaffolding) make long-term protection properties
an important requirement [218]. Typical applications of polyurethane coatings are
therefore on the exterior of apartment blocks, towers and stacks; on the interior
walls of pharmaceutical and food-processing plants with their high demands in
terms of cleaning properties; on the interior walls of schools, hospitals and other
buildings with a high visitor frequency. There is also growing recognition of the
suitability of polyurethane systems as anti-graffiti coatings.
5.9.2.2 Polyurethane wall coatings
To ensure the durability of a coating on interior or exterior walls, the careful selec-
tion and application of a multicoat concept is essential. A typical polyurethane coat-
ing concept consists of three coats: a penetration primer, a basecoat and a topcoat.

Whereas the first coat (primer) is

often applied with a brush, the pig-
mented basecoat and the topcoat are
usually applied with a roller. If the
coating system is adjusted to a suit-
able viscosity, compressed-air or air-
less spraying is also possible.
Penetration primer
Due to the alkalinity of many min-
eral substrates, such as concrete,
Figure 5.98: Polyurethane coating with high saponification-resistant binders
resistance to graffiti and ease of cleaning based on polyether or polyacrylate
are preferred for the primer. Formu-
lations are adjusted to a particularly low application viscosity to ensure good pen-
etration of the porous substrate. In the case of solventborne systems, this often
means an elevated organic solvent content.
Waterborne polyurethane systems based on “Bayhydrol” and “Bayhydur” are avail-
able for the formulation of virtually odorless and emission-free primers. As pig-
ments and extenders have a negative impact on the penetration properties of the
primer, they are generally not used.
The cured polyurethane strengthens the substrate and provides a firm base for the
subsequent coating. Depending on the type and porosity of the substrate, the appli-
cation rate varies from 60 to 100 g/m2 for compacted concrete surfaces and 80 to
250 g/m2 for highly porous substrates. Depending on the system and the ambient
conditions (temperature, humidity), the subsequent coats should be applied between
8 and 24 hours after the primer.
Basecoat
The pigmented basecoat must be matched to the roughness of the substrates in terms
of its flow properties, body and hiding power. It must also have good adhesion to
the penetration primer and to the topcoat. The application rate of the basecoat is
150 to 200 g/m2 for solventborne systems, 60 to 120 g/m2 for solvent-free formula-
tions and 60 to 100 g/m2 for waterborne coatings. The topcoat can be applied on the
basecoat after about one day.
Topcoat
The pigmented topcoat is usually a lightfast aliphatic polyurethane system cross-
linked with “Desmodur N” or a similar product. The application rate is 60 to 200 g/m2
for solventborne systems, 60 to 120 g/m2 for solvent-free systems and 60 to 100 g/m2
for waterborne formulations. Depending on the system used, the topcoats achieve

adequate initial drying (touch dryness) after 5 to 8 hours (solventborne), 8 hours

(solvent-free) or 8 to 24 hours (waterborne), provided an adequately high room
temperature and air circulation are ensured. The total film thickness is 100 to 250 µm
(solventborne), 90 to 140 µm (solvent-free) and 70 to 110 µm (waterborne).
Formulation of polyurethane wall coatings
Several different concepts using various systems have proved suitable for use on
masonry. In the first variant, a polyether polyol and an aromatic polyisocyanate
crosslinker are used in the penetration primer and the basecoat. This saponifi-
cation-resistant combination is relatively inexpensive, but has the disadvantage
that it displays a certain sensitivity to moisture during application because of the
high reactivity of the polyisocyanate. The topcoat is based on a polyester polyol
crosslinked with a lightfast aliphatic polyisocyanate. It is highly crosslinked and
therefore has very good resistance properties. The second variant uses a hydroxy-
functional polyacrylate crosslinked with an aliphatic polyisocyanate in all three
coats. This system is far less sensitive to moisture and thus allows the blister-free
application of thicker films. It has the additional benefit that it can be overcoated
even after long interruptions in the coating operation.
When selecting the pigments and extenders, it should be ensured that these have good
wetting properties. Poor pigment wetting will result in the relatively rapid occurrence
of chalking. Low emission solvent-free or waterborne co-solvent-free polyurethane
systems are particularly suitable for interior wall coatings. The solvent-free systems
are based on low viscosity polyisocyanates such as “Desmodur N 3400”, which react
with atmospheric moisture to form urea groups and yield a highly crosslinked film
with very good resistance properties. The systems may be pigmented or formulated
as clearcoats. On account of the moderate pigment wetting properties of the binder,
only medium gloss values can be achieved with the pigmented systems.
The waterborne systems usually consist of hydroxyfunctional polyacrylate disper-
sions, and perhaps hydroxyfunctional polyurethane dispersions, crosslinked with
a hydrophilically modified polyisocyanate such as “Bayhydur 3100”. An aqueous
dispersion of the hydrophilically modified polyisocyanate can be used as the pen-
etration primer. The waterborne systems can be pigmented or formulated as
clearcoats. The gloss can be varied as required. The general property profile of the
waterborne systems virtually matches that of the equivalent solventborne polyure-
thane coatings.
Aspects of construction physics
Water absorption and the effect on carbon dioxide and water vapor diffusion are the
most important properties of wall coatings with respect to construction physics [219].
Generally speaking, polyurethane coatings absorb very little water. They are there-
fore able to prevent the penetration of water, even on prolonged exposure to moisture,

and thus block the growth of microorgan-

isms. Polyurethane coatings are not particu-
larly permeable to carbon dioxide. Standard
polyurethane coating concepts yield carbon
dioxide diffusion resistance values (µ[CO2])
of more than 2 x 106 and diffusion-equiva-
lent air layers of more than 200 m. It can
therefore be assumed that such polyurethane
coatings provide reliable long-term protec-
tion against carbonation.
If properly formulated, polyurethane wall
coatings also satisfy European require-
Figure 5.99: Seamless flat roof sealing
with liquid polyurethane membranes
ments in respect of water vapor permeabil-
ity. Their water diffusion resistance
values (µ[H2O]) are between 7,500 and 50,000. The coatings are therefore relatively
impermeable to water vapor diffusion. However, as dry film thicknesses of only
100 to 150 µm are normally applied, the diffusion-equivalent air layer is between
0.75 and 3.8 m – depending on the system – and thus below the maximum value of
four meters generally required in specifications.
5.9.3 Surface sealing

Surface sealing is understood to be the application of a water-impermeable system
on construction elements, usually made of concrete. These may be roofs or balco-
nies, but also ponds, canals and bridges, for example. The following two sections
discuss the sealing of flat roofs and balconies. The other applications use highly
reactive polyurea systems or hybrids of polyurethane and polyurea.
5.9.3.1 Sealing flat roofs with liquid polyurethane membranes

Most flat roofs are sealed with sheeting materials based on (polymer-modified)
bitumen, polymeric rubber or PVC. Nevertheless, the use of a liquid membrane
would seem to be a safe and economical alternative, especially on roofs with many
breakthroughs such as vents, dome lights, gutters, etc. Typical binders for liquid
membranes are polyurethanes, unsaturated polyesters and acrylates [220].
Liquid polyurethane roof membranes are coating materials that are applied in the
liquid state and cure to form a weather-stable skin with long-term flexibility. They
are used above all in the refurbishment of leaking flat roofs but also in new construc-
tion projects. The key properties of these coatings are a long service life and low
water vapor diffusion resistance, allowing roofs which have been penetrated by mois-
ture to dry out after application of the membrane. In contrast to the use of roof sheet-
ing materials, liquid polyurethane membranes yield a seamless skin (see Figure 5.99).

Standards and regulations

The following regulations are relevant to the use of liquid membranes in the refur-
bishment of flat roofs:
• “Richtlinien für die Planung und Ausführung von Dächern mit Abdichtungen”
(Guidelines for the planning and construction of roofs with sealing), issued by
the “Zentralverband des deutschen Dachdeckerhandwerks” (Central Association
of German Roofing Contractors) [221]
• DIN 4102/part 7, “Resistance to radiating heat and fly ash” (to be replaced by
DIN EN 13501/part 5) [222]
• ETAG 005: Guideline for European Technical Approval of Liquid Applied Roof
Waterproofing Kits [223]
Chemical composition
Table 5.30 shows the composition of a one-component roof-sealing formulation for
manual application. Bisoxazolidine ensures blister-free curing of the formulation in
the necessary film thickness of about two millimeters. It reacts with atmospheric
moisture to release amino and hydroxyl groups, which react in turn with the iso-
cyanate prepolymers. This suppresses a direct reaction between the isocyanate pre-
polymers and atmospheric moisture, which would result in the formation of carbon
dioxide and cause blistering. At the same time, bisoxazolidine improves the
mechanical properties of the coating. The aluminum paste (aluminum powder in
plasticizer) reflects the sun and thus contributes to the weather stability of the
polyurethane system (aromatic isocyanate, polyether polyol).
Table 5.30: Formulation for a one-component liquid polyurethane roof membrane for
manual application
Bifunctional TDI prepolymer, Binder approx. 37 %
e.g. “Desmodur E 15”
IPDI isocyanurate Binder approx. 2 %
Bisoxazolidine Latent curing agent approx. 3 %
Barytes Filler approx. 36 %
Diphenyl cresyl phosphate Flame-retardant plasticizer approx. 10 %
Aluminum paste Light stabilizer approx. 4 %
Methoxypropyl acetate Solvent approx. 5 %
Pyrogenic silica Thixotropic agent approx. 0.5 %
Dibutyl tin dilaurate Catalyst approx. 0.1 %
Deaeration agent Deaeration agent approx. 0.4 %
Monofunctional aliphatic isocyanate Dryer approx. 2 %

230
Table 5.31: Formulation for a two-component liquid polyurethane roof membrane for
machine application
Component A:
Polyether polyol Binder approx. 53 %
Amine Binder approx. 16 %
Diphenyl cresyl phosphate Flame-retardant plasticizer approx. 17.6 %
Diazabicyclooctane Catalyst approx. 0.2 %
Carbon black paste Light stabilizer approx. 13 %
Sum of component A: 100 %
Component B:
MDI polyisocyanate Binder approx. 27 %
Bifunctional TDI prepolymer Binder approx. 66 %
Diphenyl cresyl phosphate Flame-retardant plasticizer approx. 7 %
Sum of component B: 100 %
Table 5.32 Types and properties of liquid polyurethane membranes for sealing flat roofs
Binder Type of Raw materials Remarks
application
One-component, Manual TDI polyether Systems must be made
aromatic prepolymers and weather-stable by addition
oxazolidines of aluminum pigments or
carbon black
One-component, Manual IPDI polycarbonate Systems can be pigmented
aliphatic systems and oxazoli- in any color
dines
Two-component, 2K spraying TDI and MDI prepoly- Systems must be made
aromatic mers, polyethers and weather-stable by addition
amines of aluminum pigments or
carbon black
Table 5.33 Standard primers for liquid polyurethane membranes on various substrates
Substrate Primer
Concrete MDI polyether prepolymers, e.g. “Desmodur E 21”
Asbestos MDI polyether prepolymers, e.g. “Desmodur E 23”
Roof sheeting MDI

Highly reactive two-component formulations can also be used for this application.
They are fast-drying and can therefore only be applied using special equipment.
These products may consist of, for example, a mixture of a TDI prepolymer and an
MDI polyisocyanate that is cured with a polyol/amine combination (Table 5.31,
page 230).
In this formulation, light stabilization is achieved by the addition of carbon black or
aluminum powder. Table 5.32 gives a summary of the types and properties of liquid
polyurethane membranes. One- and two-component roof sealing systems that can be
pigmented in any color and applied manually can be formulated on the basis of ali-
phatic isocyanate prepolymers such as “Desmodur I” and polycarbonate polyols.
Roof sealing concepts
If refurbishing a roof with liquid polyurethane membranes, the old sealing materi-
als which have become leaky, usually bituminous roofing felt, do not have to be
removed first. Depending on how the liquid membrane is to be applied, there are
two alternative concepts:
One-component systems for manual application:
a) primer (undercoat to strengthen substrate and bind dust)
b) basecoat (approx. 1.5 kg/m2 of liquid polyurethane membrane, applied by roller)
c) polyester matting (approx. 100 g/m2, pressed into the liquid membrane to provide
mechanical reinforcement and ensure achievement of the desired film thickness)
d) topcoat (approx. 1 kg/m2 of liquid polyurethane membrane, applied after the
basecoat has dried to cover the polyester matting)
Two-component systems for machine application:
a) primer
b) two-component polyurethane spray formulation (minimum film thickness 2 mm)
Before application of the liquid polyurethane membrane, the following conditions
must be satisfied:
• the substrate must be clean and strong enough
• the residual moisture content of the substrate and the underlying insulation
materials must not exceed four percent
The highly reactive two-component systems are applied using 2K units with gear
or piston pumps. Table 5.33 summarizes the primers normally used with liquid
polyurethane membranes. The primers and one-component liquid membranes are
applied by brushing, rolling, or 1K airless spraying.
5.9.3.2 Sealing balconies with polyurethane membranes
Balconies, terraces and galleries on the outside of buildings are highly exposed to
weathering and mechanical wear. The load-bearing concrete substrate therefore
requires a high level of protection, particularly against the penetration of moisture.
If this protection is absent, the moisture may migrate into adjacent floors and cor-

rode the rebars of the concrete balcony slab or the balcony railing anchorages
embedded in the concrete or the concrete may be spalled by freeze/thaw cycles.
The result is a reduction in the load-bearing capacity of the balcony slab with the
ultimate consequence that the balcony can no longer be used.
Liquid polyurethane membranes can provide the necessary protection and fulfill a
decorative function at the same time.
Standards and regulations
There are no special regulations covering the use of liquid membranes for sealing
balconies and galleries. The following general standards should be observed:
• “Richtlinien für Schutz und Instandsetzung von Betonbauteilen” (Guidelines for
the Protection and Refurbishment of Concrete Structural Elements) issued by the
“Deutsche Ausschuß für Stahlbeton” (German Committee for Steel-Reinforced
Concrete) in Berlin/Germany [193]
• Building regulation list B/part 1 [224]
Chemical structure
Liquid membranes used to seal balconies must display a high degree of lightfastness
and weather stability and remain elastic in fluctuating temperatures. Polyurethane
materials fully satisfy these requirements. Formulations based on IPDI polycarbon-
ate polyol prepolymers and HDI polyisocyanates are adequately lightfast and can
be used as transparent sealing systems. TDI prepolymers yield highly flexible,
two-component membranes that may either be combined with topcoats based on
IPDI or HDI polyurethane prepolymers or used as sealing systems underneath
ceramic tiles (see Figure 5.100).
As far as the coreactants are concerned, the use of polycarbonate polyols in the
polyurethane prepolymers yields particularly weather-stable, flexible membranes.
Table 5.34: Polyurethane raw materials for balcony sealing systems
Binder Raw materials
One-component, IPDI polycarbonate prepolymers such as “Desmodur XP 2406”,
aliphatic IPDI polyisocyanates, bisoxazolidines such as “Hardener
VP LS 2959”
Two-component, HDI polyisocyanates, IPDI/HDI polyisocyanates, such as
aliphatic “Desmodur N 3600” or
“Desmodur NZ1”
Polycarbonate/polyether/polyester polyols such as
“Desmophen C 1200” or
“Desmophen XP 2501”
Two-component, TDI polyether prepolymer/amines such as
aromatic “Desmodur E 15”/“Ethacure 300”

Prepolymers based on polyether/polyester

polyols are not weather-stable and therefore
cannot be used in formulating the topcoat
that is exposed to weathering. In addition to
the binder, the formulations usually contain
mineral extenders, pigments and many other
additives. Solventborne, moisture-curing,
one-component polyurethane systems and
solvent-free two-component systems have
proved ideal as balcony sealing compounds.
The most important polyurethane raw materi-
als used in the formulation of balcony sealing
systems are summarized in Table 5.34. Table
5.35 shows the guide formulation for a one-
component liquid polyurethane membrane
Figure 5.100: Aliphatic balcony
for manual application on balconies, a typical sealer with high resistance to
form of application. weathering
Balcony sealing concepts

Polyurethane balcony membranes suitable for walking on:
Depending on the expected crack formation in the concrete slab, two different
concepts can be considered.
Concrete slabs with narrow cracks (up to approx. 0.5 mm):
a) primer
b) flexible polyurethane coating based on aliphatic isocyanates
Concrete slabs with wide cracks (1 to 2 mm):
a) primer
b) intermediate coat: highly flexible polyurethane coating based on aromatic
isocyanates
c) topcoat: flexible polyurethane coating based on aliphatic isocyanates
It is also possible to apply a flexible membrane as a sealing layer between a concrete
slab and tiles. The concept is as follows:
a) primer
b) highly flexible polyurethane coating based on aromatic isocyanates
c) highly flexible polyurethane coating based on aromatic isocyanates and scat-
tered with sand
d) plastic-modified mortar (PCC mortar)
e) tiles

Table 5.35: Guide formulation for a one-component liquid polyurethane membrane for
manual application as a balcony sealing system
IPDI polycarbonate polyol prepolymer Binder approx. 64 %
IPDI isocyanurate Binder approx. 17 %
Bisoxazolidine Latent curing agent approx. 13 %
Methoxypropyl acetate Solvent approx. 3.5 %
Deaeration agent Deaeration agent approx. 0.8 %
Methylhexahydrophthalic anhydride Catalyst approx. 0.4 %
Additives approx. 1.2 %
Application techniques
Before commencing refurbishment, it must be checked that the load-bearing capac-
ity of the concrete balcony slab is still intact. Old coverings must either be removed
or well roughened before application of the polyurethane system. The concrete
surface should be shotblasted and very smooth surfaces roughened by some other
means. Greasy or oily contamination must be removed. It is important that the
residual moisture content of the substrate does not exceed 4 %.
As already mentioned, the primer serves to strengthen the substrate and bind any
dust. This ensures the good adhesion of the subsequent coats. Solvent-free epoxy
resin systems are normally used as primers. Solventborne one-component and low-
solvent two-component polyurethane formulations are also used as coating materi-
als. They are scattered with sand to improve adhesion.
Plastic chips can be scattered into the still wet sealing system for decorative pur-
poses and to ensure non-slip properties. The surface is then finished with a transpar-
ent, lightfast liquid polyurethane topcoat. Another decorative option is the incor-
poration of colored quartz sand in the transparent membrane. Generally speaking,
liquid polyurethane membranes can be applied by roller, brush or notch trowel. The
freshly applied membrane is deaerated using a spiked roller.
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33–34, 13187 Berlin

Introduction 243
6 Polyurethane adhesives
6.1 Introduction
Adhesive bonding: Comparison with other joining methods
Adhesive bonding is an essential technique, without which many products could not
be manufactured economically or with reproducible properties. It is [1, 2], however,
only one of many possibilities for joining materials to one another and competes
with other joining methods such as welding or screwing. The process used is the
one that delivers the best benefit/effort ratio, after consideration of all costs and risks.
Several advantages of adhesive bonding are immediately apparent. The parts to be
joined are not damaged by thermal stress (welding), nor are they weakened by holes
(screwing). Very different materials can be joined together. The forces acting on the
bonded surface are spread across the whole area, and adhesion bonding only margin-
ally increases the weight of the material combination. However, adhesive joints can
also entail disadvantages. Generally they cannot be separated without damage, and
combinations of different materials make recycling difficult.
Basically, adhesive bonding is not a particularly inexpensive joining method. Its
real advantages are often first realized by considering the overall value-added pro-
cess, for example, by factoring weight savings or better construction variants into
the overall equation [3]. The possibility of joining different materials yields products
that benefit from the interaction of the specific properties. Another example is shoe
manufacture. Without heat-activated polyurethane adhesives, fashion and sports
shoes would look completely different, and today’s diversity of complexly struc-
tured sports shoes would certainly not exist.
Properties of polyurethane adhesives
Polyurethane adhesives [4–7] adhere well to many substrates. This is not solely due
to physical bonding forces arising from the close contact between the adhesive film
and the substrate. The adhesion can be reinforced by hydrogen bridge bonds, which
the polymerizing polyurethane can develop to many substrates. Moreover, free
isocyanate groups present in the adhesive film can react with slight traces of mois-
ture in or on the substrate surface.
Every adhesive must be capable of flow for a certain time, so that it can be applied
to the parts to be joined. It wets the substrate surfaces and yields initial adhesion
that is not yet a load-bearing bond between the two parts. The adhesive joint attains
the necessary cohesion by subsequent hardening. This sequence also applies to
polyurethane adhesives. While they are very different in structure and use, they
have the common trait that urethane groups are either already present or are formed
during application.

244 Polyurethane Adhesives
6.2 Classification
Polyurethane adhesives are differentiated as follows:
Polyurethane reactive adhesives
As the raw materials used are of low molecular weight, at most oligomeric, poly-
urethane reactive adhesives have good flow properties. After application of the
adhesive and joining, the polymer is formed by the reaction of free isocyanate
groups (see Chapter 6.3).
The polyisocyanates used in two-component systems are of low molecular weight
or may be pre-reacted. The polyols likewise have a relatively low molecular
weight. After mixing, they set in a polyaddition reaction that forms urethane
groups. The setting rate is determined by the reactivity of the components used
and the processing conditions.
One-component systems consist of a liquid polyisocyanate polyurethane (NCO
prepolymer) that may have been prereacted to make it oligomeric. It sets by the
reaction of its free isocyanate groups with atmospheric moisture or with the mois-
ture in the substrate, resulting in the formation of urea groups. The setting rate is
not solely dependent on the reactivity of the components. The availability and dif-
fusion rate of the moisture are also determining factors.
Solventborne polyurethane adhesives based on hydroxyl polyurethanes
Solventborne polyurethane adhesives contain a usually flexible polyurethane poly-
mer dissolved in an organic solvent. In this way, the solid polymer can be applied to
the substrate. The solvent promotes the wetting properties and then evaporates, caus-
ing the adhesive to physically set. Linear hydroxyl polyurethanes based on crystalline
polyester segments are generally processed as heat-activated adhesives.
Heat activation: By briefly heating to a temperature above the softening point of
the crystalline polyester segments, the dry (not tacky) film that remains after evap-
oration of the solvent retains the tackiness and flowability required for the joining
process. In this state, the adhesive layer can be bonded to a second one using rela-
tively little pressure to form a homogeneous adhesive joint that subsequently sets
physically due to recrystallization of the polymer.
Isocyanate crosslinking: In order to prevent the thermoplastic adhesive film from
softening on exposure to heat, these adhesives are often two-component formulations
incorporating crosslinking isocyanates of higher functionality. They significantly
increase the softening temperature of the adhesive bond and enhance substrate adhe-
sion. First, the adhesive film physically sets. Chemical crosslinking follows a short
while later. The softening temperature of the crosslinked adhesive film is significantly
increased, as is its resistance to solvents, plasticizers, oil and fat migration.

Polyurethane reactive adhesives 245
Polyurethane dispersion adhesives

These contain a high molecular weight polyurethane dispersed in water that sets
due to evaporation or migration of the water. In comparison to solventborne adhe-
sives they have a lower viscosity and higher solids content. Products designed for
heat-activated bonding are dominant. They consist of mainly linear chains that
contain crystallizing polyester segments.
Heat activation: After drying, the adhesive yields a non-blocking film that must be
activated (decrystallized) for joining by brief exposure to heat. Linear polymers
have to be used to ensure the necessary flowability of the activated adhesive film.
Particularly exacting demands are placed on the flowability of the adhesive polymer
if the activated adhesive film is directly bonded with an adhesive-free substrate
surface. The adhesive joint physically sets by recrystallization.
Isocyanate crosslinking: As is the case for the corresponding solventborne adhe-
sives, the heat-activated polyurethane dispersion adhesives also develop their full
potential only through chemical crosslinking. In this case, emulsifiable crosslinking
isocyanates are used. The isocyanate groups react with reactive groups on the
polymer chain. Thus, the adhesive film first sets physically and then crosslinks
chemically. The softening temperature and resistance properties of the crosslinked
adhesive film are significantly increased, as is the case for the solventborne poly-
urethane adhesives.
Polyurethane hot-melt adhesives
These products exhibit very good adhesive properties. They are available as non-
reactive types in the form of films or powders based on linear hydroxyl polyure-
thanes with crystallizing polyester segments. Applied at temperatures ranging from
of 60 to 130 °C, they set physically by cooling and recrystallization. By contrast,
reactive hot-melt adhesives consist of a meltable polyisocyanate polyurethane that
is solid at room temperature which is solid at room temperature. They are applied
at temperatures between 100 and 140 °C, first set physically by cooling and then
chemically by reaction with atmospheric moisture. When processing these adhe-
sives, care must be taken that they are not damaged by excessively high tempera-
tures or prolonged exposure to heat.
6.3 Polyurethane reactive adhesives

Polyurethane reactive adhesives can cure to form elastomers or thermosets, whereby
the degree of crosslinking and the strength are dependent on the raw materials used.
The mechanical properties and adhesion characteristics of the adhesive films are
mainly determined by:
• the type of polyols [8] used, their molecular weight and their functionality
• the choice of polyisocyanate in terms of type, functionality and NCO content

• the concentration of urethane and/or urea groups

• the crosslinking density yielded by the interplay of the molecular weights and
functionalities of all the components
Adhesives with useful properties are only obtained by combining raw materials
with a functionality of at least two.
6.3.1 Raw materials [9]

Polyether polyols
Generally, polypropylene (ethylene) oxide ether polyols are used. These are obtained
by the catalytic addition of propylene oxide and ethylene oxide to low molecular
weight polyols (e.g. 1,2-propane diol, ethane diol, glycerol or trimethylol propane).
Polyether polyols yield polymers with good stability to hydrolysis. However, their
limited resistance to oxidation necessitates suitable stabilization. The very flexible
polymer chain does not crystallize and gives the adhesive good low temperature
flexibility but poor resistance to plasticizers. Polyether polyols have a lower viscos-
ity than most polyester polyols and are therefore used to adjust (lower) the viscos-
ity of the formulation. In laminating adhesives they produce a good compatibility
with lubricants. They are less polar than polyesters and promote the wetting of
surfaces with low surface tension. Last but not least, cost is of course an important
criterion. Polyether polyols are generally less expensive than polyesters.
“Acclaim”, “Desmophen BD” (difunctional) and “Desmophen BT” (branched) are
respectively polyether diols with molecular weights ranging from 154 to 18,000 g/mol,
trifunctional short-chain ethers with molecular weights from 300 to 725 g/mol and
long-chain polyether triols with molecular weights from 3,000 to 6,000 g/mol.
“Acclaim” polyols [10] are a new generation of polyether polyols manufactured by
Impact Technology. They enable the production of high molecular weights with very
low chain termination, i.e. with a very low monofunctional (monol) content. The
monol serves as a chain stopper which blocks chain propagation to prevent the
formation of long difunctional polymer chains. The low monofunctional content of
“Acclaim” polyols makes it possible to produce very high molecular weight poly-
mers with exceptionally good mechanical and dynamic properties, for example
high-grade silane-modified adhesives and sealants. By contrast, the chain termina-
tion rate restricts conventional KOH-catalyzed polyether polyols to equivalent
weights (= molecular weight/functionality) of about 2,000 g/mol.
Polyester polyols
Due to the many monomers that can be used, polyester polyols offer a very broad
spectrum of highly varied properties, the most important of which is very good adhe-
sion to a wide range of substrates. Polyester chains are considerably less flexible than
polyethers and consequently yield stiffer and, in particular, stronger adhesive films.

However, polyester polyols increase the viscosity and application temperature of the
adhesives. The polarity of the polyester polyols (e.g. resulting from integrated aro-
matic moieties) affects substrate adhesion and increases the barrier effect of the
adhesive film to gases.
Isocyanates
The isocyanate components can be selected from a great variety of aromatic and
aliphatic polyisocyanates. Difunctional MDI monomers (4,4’- and 2,4’-diphenyl-
methane diisocyanate) are used in the manufacture of prepolymers, laminating
adhesives, reactive hot-melt adhesives and sealants. Some monomers have been
specifically modified to yield an easily manageable liquid form at temperatures
above 20 °C. Other MDI monomers are isomeric mixtures with a high content of
2,4’-isomer in addition to the 4,4’-isomer. Given the different reactivity of the
isocyanate groups in the 2,4’-isomer, they yield prepolymers with a lower viscosity
and improved storage stability but lower reactivity than 4,4’-MDI.
Polymeric MDIs contain oligomeric fractions of higher functionality in addition to
difunctional diphenylmethane diisocyanate (MDI). They are used in two-component
reactive adhesives and for manufacturing NCO prepolymers. Polymeric MDI types
of defined and elevated acidity are particularly suitable for the prepolymer reaction.
In addition to the MDI types, toluene diisocyanate (TDI) types and aliphatic isocya-
nates are used for special applications, mainly as building blocks for special oligo-
meric hydroxyl polyurethanes. Due to their high vapor pressure and the dangers
associated with their toxicity, the use of the monomers is avoided. Low-monomer
derivatives or low-monomer NCO prepolymers of these isocyanates are used instead.
Isocyanate-terminated polyurethanes (NCO prepolymers)
NCO prepolymers [11], i.e. prepolymers containing free isocyanate groups, play a
major role in polyurethane chemistry. They occupy an important position between
the monomeric isocyanates and the polyurethane polymers. An NCO prepolymer
is a polyol reacted with an excess of polyisocyanates. If this excess is very large,
the products are referred to as semi-prepolymers. There are many reasons for using
prepolymers:
• A liquid prepolymer is easier to handle than solid monomeric isocyanates, e.g.
4,4’-diphenylmethane diisocyanate which is crystalline at room temperature.
The monomer content of the prepolymer is lower and hence also the vapor
pressure, e.g. in TDI or hexamethylene diisocyanate (HDI) prepolymers.
• The advance prepolymer reaction allows the formation of a defined polymer
structure. This is advantageous, for example, when coreactants of very different
reactivities, such as polypropylene glycol ethers containing primary and secondary
hydroxyl groups, are reacted, not simultaneously as a mixture, but consecutively.

• Incompatibilities between polyols can occasionally be reduced by prepolymer-

ization. It can be very beneficial to the processing of two-component adhesives
if the total exothermia of the crosslinking reaction is reduced by utilizing some
of the heat of reaction in a prepolymerization step.
• The pot life in two-component systems is also longer due to the generally lower
reactivity of prepolymers in comparison with monomeric polyisocyanates.
• A prepolymer as the isocyanate component of a two-component system allows
the NCO content to be balanced with the OH components to produce a favorable
mixing ratio (e.g. 1:1) for processing.
Commercial products: Many problems can arise during production of the prepolymer
which can have a negative effect on the quality or result in a complete gelling of the
formulation. These risks during in-house formulation are not negligible and can be
avoided by working with ready-to-use NCO prepolymers that are supplied as stan-
dard products by raw material manufacturers. In the absence of moisture, these prod-
ucts exhibit good storage stability and can be successfully used in many applications.
Low-monomer NCO prepolymers
Low-monomer NCO prepolymers are required for special applications. For exam-
ple, they are used as the isocyanate components in laminating adhesives. Formulat-
ing adhesives with a low content of migratable residual monomer is the key aspect
here. Low-monomer NCO prepolymers are also used as building blocks for low-
emission reactive hot melts. A further possible application field is the production
of labeling-free adhesives for the DIY home improvement market.
Manufacturing low-monomer NCO prepolymers is very complicated and requires
an infrastructure for transporting, storing, reacting and distilling monomeric diiso-
cyanates, which is mainly available to the producers of these monomers. Because of
their lower boiling point, HDI and TDI are the dominant base isocyanates in this
product group. Recently, however, MDI-based products have also become available.
6.3.2 Two-component polyurethane reactive adhesives [12, 13]

Chemical structure and processing properties
Composition: Two-component systems consist of low molecular weight or only
slightly pre-reacted polyisocyanate components (or optionally, a modified isocya-
nate or NCO prepolymer) and likewise relatively low molecular weight polyol
components. The latter are often a mixture of different polyols. Short-chain hydroxyl
compounds can also be present in the formulation, sometimes also containing NCO-
reactive amine compounds.
Mixing ratio: The two components have to be processed in a defined mixing ratio.
This is calculated as the stoichiometric ratio of the NCO equivalents present to the
equivalents of the NCO-reactive groups (OH and NH groups) present. Frequently,

an excess of isocyanate causes a deviation from the stoichiometric ratio. This iso-
cyanate excess (5 to 15 %) results in additional crosslinking, compensates problems
due to substrate moisture and improves adhesion to suitable substrates.
Pot life: After adding and mixing the OH (polyol or prepolymer with terminal
hydroxyl groups) and NCO components, the setting reaction commences with the
formation of urethane groups. The pot life is essentially determined by the reactiv-
ity and functionality of the starting materials, the fillers present in the formulation,
and the processing conditions (temperature, mixing technology). Tertiary amine
compounds and metal salts are normally used as the catalysts [14]. Metal salts in
particular, even in small amounts, reduce the pot life, sometimes considerably.
Setting and curing: The same parameters also determine the setting rate. At room
temperature, complete curing takes anything from several hours to days. This
process can be accelerated by heating and catalysis, which often also increases the
final bond strength.
Additives: Fillers such as chalk, talc, barites, quartz powder or ground shale are often
used. They increase the stiffness, but often reduce the elongation at break and the
peel resistance. Moreover, they reduce the exothermia and shrinkage on setting – and
make the adhesive less expensive. They are used above all in adhesives for rigid
materials, such as wood, plastics or metals. When bonding highly absorbent materi-
als, any unwanted penetration into the material can be prevented by adding finely
dispersed silica as a thixotropic agent. On mixing both adhesive components, small
quantities of reactive amine compounds (e.g. isophorone diamine, IPDA) in the
polyol component instantaneously form highly dispersed polyurea particles that act
as in situ or chemical thixotropic agents. This type of thixotropic modification has
the advantage that it does not increase the viscosity of the OH component. Thixo-
tropic additives ensure the adhesive’s stability when applied in beads and prevents
run off from vertical surfaces. The additives are usually incorporated into the polyol
(OH) component. They must always be carefully dried. In order to remove traces
of moisture that may remain even after drying, the addition of a drying agent to the
polyol component is recommended, e.g. zeolite (UOP (“Baylith”) L Paste, Kurt
Obermeier GmbH & Co. KG; D-57319 Bad Berleburg, Germany).
End properties of the cured adhesive: Structure, chain length and functionality of
the coreactants and the fillers used determine the characteristic properties of the
crosslinked polymer via the concentration of urethane groups and possibly urea
groups, as well as via the chemical crosslinking density. These properties are the
tensile strength, modulus, elasticity, softening temperature and chemical resistance.
Catalysis and processing temperature can also have a considerable influence.
Mixing ratio [15]
Practical experience suggests the use of about a 15 % isocyanate excess above the
calculated stoichiometric ratio.

Processing technology
Two-component reactive adhesives are preferably processed using two-component
metering and mixing units (Figure 6.1).
Filler-free two-component reactive adhesives can be metered with gear pumps as
there is no danger of abrasion. Plastic static mixers make processing particularly
economical. Gear pumps cannot be used to process systems containing fillers
because abrasion (grinding action of the filler) would quickly make them unusable.
Reciprocating piston pumps are far less sensitive for this type of formulation.
The use of double cartridges with static mixers (Figure 6.2, page 251) is suitable
for trade application of small quantities. A pre-condition is a mixing ratio of both
components that matches the specification of the double cartridges. The pot life of
Figure 6.1: Processing unit for two-component reactive systems

the adhesive must be sufficiently long. It

is very important that the adhesive com-
ponents are absolutely phase-stable (i.e.
that the fillers also do not sediment out),
because the contents of the cartridge can
no longer be homogenized.
In principle, manual processing is also
possible if the two-component reactive
adhesives are specially formulated to be
slow for this purpose. However, since Figure 6.2: Double cartridge static mixer
in this case the components are blended
in buckets or pots, it is essential to note
that the temperature of the exothermi-
cally reacting mixtures increases signifi-
cantly when processing large volumes in
mixing vessels, which can considerably
shorten the pot life. Moreover, it should
be borne in mind that two-component
polyurethane systems require a high
mixing quality to yield homogeneous
and reproducible adhesive layers. Such Figure 6.3: Example of a polyurethane
a level of mixing quality can only be integral skin foam part bonded with a two-
achieved manually in exceptional cases. component polyurethane reactive adhesive
Use of two-component polyurethane reactive adhesives

These systems are frequently used as structural adhesives which are designed to
have a shear modulus of approximately 200 to 600 MPa in fully cured adhesive
layers. Applied as structural adhesives, the systems yield energy-transmitting
bonds (Figure 6.3).
Two-component polyurethane reactive adhesives are also used for bonding large
surfaces, e.g. for manufacturing sandwich panels for refrigerated vehicles, contain-
ers and superstructures (caravans, trucks), or for laying large areas of flooring
(intended for rapid use). Further applications are as encapsulating compounds for
filter elements or electrical components.
6.3.3 Moisture-curing one-component reactive adhesives

6.3.3.1 One-component polyurethane systems
These adhesives, that are processed as more or less viscous liquids at room tem-
perature or at slightly elevated temperatures, consist of polyisocyanate polyure-
thanes (NCO prepolymers), whose chains are often pre-extended by a preliminary

reaction to form oligomers. They set by reaction of the free isocyanate groups with
atmospheric moisture or with moisture contained in the substrate to form polyurea
groups. Through-curing of the adhesive layer with atmospheric moisture proceeds
from the outside to inside at a rate determined by the reactivity of the isocyanate
groups, the catalyst and the diffusion rate of the water into the adhesive layer. Small
amounts of carbon dioxide are formed during this reaction but these do not interfere
with the adhesion process provided the free isocyanate content of the adhesive is
not too high (less than four percent NCO). The slow curing which is essential for
such adhesives means that they may only be used if the pieces to be joined can be
mechanically fixed in the required position until setting. It should also be noted
that, with the onset of curing, a skin may form on the surface of the adhesive where
it has contact with the moist ambient air. This may prevent the wetting and bonding
of the second piece to be joined. These adhesives cure to yield layers with a shear
modulus in the range of about 1 to 10 MPa.
Since they are based on the same principle, the NCO-reactive hot melts, one-com-
ponent laminating adhesives and one-component moisture-curing polyurethane seal-
ants also belong in this section. However, the first two product groups are so specific
in their formulation and processing that they will be discussed in more detail in
separate sections (see 6.3.4 and 6.6.2). One-component moisture-curing polyurethane
sealants are also described in a dedicated chapter (see Chapter 7).
Manufacturing NCO prepolymers
The description of the manufacture of NCO prepolymers falls outside the scope of
this publication. Nevertheless, some general observations will be discussed.
Prepolymer suitability of the raw materials
With unknown formulations and new raw materials, preliminary trials must be
carried out to test the prepolymer suitability. In all prepolymer reactions, care has
to be taken that the component in excess is actually present in excess throughout
the whole reaction. The component in excess must always be present, i.e. in the
case of NCO prepolymers containing free isocyanate groups, the polyisocyanate
must be initially present; in the case of OH prepolymers containing free hydroxyl
groups, the polyol must be initially present.
Water content of the raw materials
The molecular weight of water is very low: one mole (18 g) reacts with two moles
NCO groups. Therefore, the water content of the raw materials used for manu-
facturing NCO prepolymers must be very low (< 0.05 %). In the case of NCO
prepolymers containing fillers, the moisture content of the fillers has also to be
minimized. The water content of the raw materials consumes some of the isocyanate
in the prepolymer. Above all, the stability of the prepolymer is negatively affected
by the urea groups formed with the water. During storage, particularly in warm

conditions, these produce higher functional groups that greatly increase viscosity
via the formation of biurets. Consequently, the polyols and fillers should be dried
before they are used in the reaction. Polyisocyanates can also be damaged by the
action of moisture. This is evidenced by an increased content of dissolved carbon
dioxide. Dissolved gases are easily removed by applying a vacuum in the initial
phase of prepolymer manufacture. If this is not done, apparently inexplicable foam-
ing may occur during subsequent application of the prepolymer.
Stability of NCO prepolymers
Stable prepolymers are products that can be stored at room temperature for a long
period and which can also be handled for short periods above the recommended
storage temperature, without any extensive change in the NCO content and the vis-
cosity. In the case of unstable prepolymers, a large decrease in the NCO value and a
marked increase in viscosity are observed. Aromatic polyisocyanate-based NCO
prepolymers should not be subjected to temperatures above 90 °C during production,
because higher temperatures trigger side reactions (formation of allophanates and
biurets, trimerization reactions), which can negatively affect the storage stability of
the prepolymers, the viscosity and the molecular structure of the systems.
Applications
The viscosity of these moisture-curing one-component adhesives which are liquid
at room temperature is in the range of 2,000 to 10,000 mPas. There are also prod-
ucts in paste form. The adhesives can be applied manually with a spatula or using
cartridge guns, or mechanically, e.g. using a bead applicator. They can be used to
bond a wide variety of substrates and substrate combinations, e.g. in the manufac-
ture of windows, doors and sandwich elements.
For a number of years now, moisture-curing one-component polyurethane adhe-
sives have been used in an interesting field of application: structural wood construc-
tion (Figures 6.4 and 6.5). This technology has achieved great significance in
Figure 6.4: Application of adhesive in the Figure 6.5: Hall construction using
manufacture of structural wood [17] structural wood [18]

Europe because it offers considerable advantages over conventional formaldehyde-

based adhesives (formaldehyde-free, short curing times without additional thermal
acceleration and without costly pressure equipment).
6.3.3.2 One-component silane-terminated polyurethanes
One-component silane-terminated polyurethanes also cure by reaction with atmo-
spheric and ambient moisture. In contrast to the one-component polyurethane sys-
tems, however, they do not contain terminal NCO groups, but instead terminal alk-
oxysilane groups. When they react with water, methanol is formed instead of carbon
dioxide. Moreover, the substrate adhesion (e.g. to glass)) is significantly improved.
6.3.4 Polyurethane laminating adhesives [19]

This section deals with laminating adhesives that cure by NCO/OH reaction. Depend-
ing on requirements, they can be two-component or moisture curing one-component
reactive systems, which for medium and high requirements, often also contain a
solvent. Other types of polyurethane adhesives such as isocyanate-crosslinked
hydroxyl polyurethanes and polyurethane dispersions [20] will not be considered here.
Technical requirements
Films for food packaging have to fulfill a very demanding catalog of properties. The
list is extensive and many of these properties have to be met simultaneously. The
films have to be impervious to light, gases, aromas, moisture and steam, resistant to
sterilization and aggressive contents, impermeable to fat migration, printable, heat-
sealable, resistant to tearing and abrasion. There is no single film material able to
meet this catalog of requirements. Consequently, films made from different materi-
als are combined to produce composite films. The individual film layers are bonded
together using very thin layers of special laminating adhesives, which are mainly
based on polyurethane raw materials. A well-known example is the packaging of
ground coffee. The packaging material must combine the functions aroma, oxygen
and light protection, adhesion to aluminum and heat-sealability. The polyester film
that forms the outer skin provides the mechanical strength. Any labeling required
is relief-printed on the reverse side that is to be bonded. The first layer of adhesive
is applied at a coating weight of 4 to 6 g/m2 onto the print and is markedly thicker
than the subsequent layers to fill the depressions in the relief print. This is topped
with an aluminum foil that is impervious to light, aroma, and gas. Another coat of
adhesive is thinly applied (1 to 3 g/m2) on the smooth aluminum surface and bonded
to an LDPE film, which forms the heat-sealable inside of the packaging. It serves
as an inert layer to protect the aluminum from the coffee powder and enables the
packet to be hermetically sealed.
The very complex film lamination process is continuous. The film sheets are
unwound from stock rolls and the liquid adhesive is applied on the surfaces by
rollers. The next sheet of film is conveyed via a system of transport and guide rolls

and pressed together with the adhesive-coated film surface by pressure rolls (Figure
6.6). The laminate is wound onto rolls and must be stored for some time until curing
is completed. Only then can the film be utilized.
Three performance classes for laminated films
Laminated films for food packaging are classified into three performance classes
based on the property profile required for the intended use (Table 6.1).
Table 6.2 (page 256) shows the typical requirements for these three perform-
ance classes and the formulation principles used for adhesives that fulfill these
requirements.
Chemistry of laminating adhesives
The popularity of solvent-free systems has been growing for years. Nevertheless,
solventborne systems are still strongly represented in the manufacture of laminated
films for medium and maximum requirements. The reasons for this are easy to under-
stand. Solventborne systems can be applied in thicker layers. At layer thicknesses of
Figure 6.6: Principle of laminated film manufacture on a laboratory duplex unit
Table 6.1: Performance classes for laminated films

Performance class Global market share (%)
High performance 15
Medium performance 35
General performance 50

Table 6.2: Requirements for laminated films in the different performance classes
Performance Laminate/application Adhesive chemistry
classes
High 1) All laminates (film/film & film/ Exclusively solventborne adhesives

performance aluminum) for Two-component systems:
a) Aggressive products (e.g. fruit
juice, detergents) I: – OH-functional polymer with high
b) High-strength laminates with molecular weight
high tear strength – Isocyanate crosslinker with low
c) Thermal exposure >100 °C molecular weight
for sterilizability (e.g. animal
feed) and boiling resistance II: – NCO prepolymer with high
(microwave) molecular weight
2) Aluminum (film/aluminum) – OH crosslinker with low
laminates for thermal exposure molecular weight
<100 °C (pasteurizable)
Medium 1) Film/film laminates for thermal – Up to 50 % solventborne adhesives

performance exposure of < 100 °C (pasteuri- Two-component systems:
zable)
OH-functional prepolymer with high
molecular weight
Isocyanate crosslinker with low mo-
lecular weight
– Up to 50 % solvent-free adhesives
Two-component systems:
2) “Simple” aluminum composite NCO prepolymer with high molecular
for thermal exposure of weight
< 40 °C (e.g.: coffee packaging) OH crosslinker with low molecular
weight
General 1) Film/film laminates for thermal Two-component systems

performance exposure of < approx. 40 °C The proportion of solventborne sys-
(cheese packaging) and for low tems is much lower than of solvent-
mechanical stress free systems
2) Film/paper laminates Solvent-free

Two-component systems
One-component systems:
NCO-functional prepolymer with
high molecular weight (moisture-
curing)

>3 g/m2, solvent-free systems often have poorer optical properties (orange peel).
Prepolymers with high molecular weight can be used in solventborne adhesives
without causing viscosity problems. After evaporation of the solvent, the adhesive
film is much more viscous and thus exhibits greater cohesion than would be possible
with solvent-free systems. Freshly bonded film webs do not slip so easily against
each other and the risk of freshly manufactured film rolls telescoping is lower. The
solvent also allows the use of higher proportions of high viscosity aromatic polyes-
ter diols which lend greater strength to the crosslinked adhesive film. Lastly, solvent-
borne adhesives also facilitate the use of slow-reacting aliphatic isocyanates. As the
synthesis process is performed in solution, a large proportion of the polymer structure
at higher molecular weights can be yielded by prepolymerization. Any viscosity
problems can be corrected by the choice and amount of solvent used.
Due to the large number of different adhesive formulations and because the formu-
lations available on the market represent the manufacturer’s confidential proprietary
know-how, this chapter can only provide an overview of the chemical compositions.
Viewed across all systems and performance categories, laminating adhesives gen-
erally consist of approx. 30 % polyether polyols, approx. 40 % polyester polyols
and approx. 30 % polyisocyanates.
Raw material selection
Because laminated films for food packaging are in contact with the packaged food,
the materials, raw materials and adhesive formulations used have to meet appli-
cable statutory requirements and regulations.
In this context, it is not only the chemical structure of the raw material that is of
importance. When selecting auxiliaries such as stabilizers, antioxidants or catalysts,
the permissibility of their use must also be considered. Therefore, raw material
manufacturers frequently offer special product grades for this application.
Technical selection criteria are product properties such as:
• viscosity
• compatibility of the polyol when mixed with other polyols
• compatibility with the additives in the films
• strength and elasticity of the crosslinked polymer
• specific adhesion characteristics and resistance to hydrolysis
PE films contain slip agents to reduce the frictional resistance on fast-running
machines. This is why the slip agent compatibility of the adhesive is important in
producing polyethylene laminates. If it is insufficient, the laminate stability may
decrease during storage, going as far as complete failure of the laminate bond. Poly-
ether polyols and neopentyl glycol adipic acid polyester diols are highly compatible
with slip agents. Polyester diols based on diethylene glycol/adipic acid and butane

diol/adipic acid have poor compatibility. The boiling resistance is a further important
property for laminates used in high-performance applications. Here, hydrophobic
polyester diols are advantageous.
Both aromatic polyisocyanates (based on 4,4’-MDI, liquid MDI types and TDI)
and aliphatic polyisocyanates such as isophorone diisocyanate (IPDI), modified
HDI products and dicyclohexylmethane diisocyanate (H12MDI) are used as iso-
cyanate components. The universally applicable rules of structure/property rela-
tionships are also valid here. Higher functionality yields an increased polymer
crosslinking density, resulting in greater stiffness but also increased brittleness of
the adhesive film. Moreover, a higher functionality reduces the gel time of the
adhesive. The film therefore sets more quickly. However, the application window,
i.e. the pot life or open time of the liquid adhesive, is also reduced, which generally
makes processing more difficult.
Further processing of the laminated films

Further processing of the laminates through to their end use must take into account
the time required for complete crosslinking and the associated chemical processes.
A film roll can only be cut to the actual required width once crosslinking is sufficiently
advanced and there is adequate cohesion between the individual layers of the lami-
nate. Since the adhesion bond must withstand thermal stress during sealing, the
laminate can only be sealed after full crosslinking. Above all, packaging can only be
filled with food once no more residual isocyanate monomers are present (Table 6.3).
Processing problems
There are at least five different stations involved in the long processing chain from
adhesive to filled packaging: the raw material supplier, the adhesive manufacturer,
the film manufacturer, the laminate manufacturer and the packer. It is obvious that
mistakes are possible in this chain consisting of many complex individual steps.
The following points are limited to the adhesive development, manufacturing and
processing (laminate production) steps:
Table 6.3: Typical waiting periods for the further processing of laminated films
Typical waiting periods before:
Cutting the Sealing the The residual iso- Filling the
roll film cyanate monomer packaging
has disappeared
Solventborne 12–24 h 3–5 d 7–14 d 7–14 d
adhesives
Solvent-free 1–2 d 5–7 d 1–7 d 5–7 d
adhesives

Solventborne adhesives based on hydroxyl polyurethanes 259
• Insufficient laminate adhesion: One cause can be in the formulation, for example
the polyester content is too low. The problem can also be caused by an unsuit-
able or incorrectly adjusted NCO/OH ratio, e.g. due to a malfunction of the
two-component metering unit.
• Poor heat-sealability of the laminated film during heat sealing can be caused by
the use of an adhesive formulation with an excessively high content of mono-
meric isocyanate (MDI or TDI). In this case, the isocyanate migrates onto the
surface to be sealed where it reacts with atmospheric moisture to form polyureas.
These have a very high softening point and prevent the surfaces to be sealed
from melting.
Formation of aromatic amines by migration of aromatic polyisocyanates
The decisive criterion for utilizing the laminate as packaging film is the certainty
that the detection limit for aromatic amines [21] in a test foodstuff is not exceeded
under statutory test conditions. A film that does not meet these conditions is unus-
able. The cause of the problem may only be that the time between laminate produc-
tion and testing is too short. This period must then be increased. However, it may
also be that the adhesive is fundamentally unsuitable because either the reactivity
of the polyols it contains is too low, or the monomeric aromatic isocyanate content
is too high. This problem may be solved by using adhesive formulations with the
lowest possible content of residual migratable aromatic isocyanate monomers, i.e.
containing low-monomer NCO prepolymers or aliphatic isocyanates as the iso-
cyanate components.
6.4 Solventborne adhesives based on

hydroxyl polyurethanes
6.4.1 Hydroxyl polyurethanes
Production of hydroxyl polyurethanes
Hydroxyl polyurethanes are prepared by reacting polyester diols with diisocya-
nates. Preparation of a linear hydroxyl polyurethane with high molecular weight,
optimal strength and flexibility, and perfect solubility, requires the precisely con-
trolled addition of a very slight excess of the diol components. Besides the optimal
diisocyanate/diol ratio, the purity of the raw materials is a deciding factor for the
quality of the hydroxyl polyurethane.
The hydroxyl polyurethanes (e.g. “Desmocoll”) are soluble polymers with a
very low hydroxyl content (approx. 0.1 %), which differ in their application-
relevant parameters: solution viscosity, thermoplasticity and crystallization. These
three parameters depend on the structure of the hydroxyl polyurethane. They are
essentially determined by the molecular weight, the choice of polyester diol on
which the hydroxyl polyurethane is based, and the diisocyanate used. The term

“thermoplasticity” refers to the varying degrees of softening of the different prod-

ucts at increased temperature. The strength of the adhesive bond above the soften-
ing temperature can be significantly increased by the addition of polyisocyanates
as chemical crosslinkers.
The crystallinity of the individual hydroxyl polyurethanes essentially determines
the setting rate of the adhesive, giving the adhesive bonds high cohesive strength
and flexibility. Below a temperature of approx. 40 °C, the hydroxyl polyurethanes
are partially crystalline. On cooling from the amorphous state that exists when
heated, or after evaporation of the solvent from the adhesive layer, the individual
products demonstrate different crystallization properties (as can be shown by mea-
suring the Shore hardness).
Product selection and applications
The excellent adhesion of the adhesives based on hydroxyl polyurethanes to numer-
ous synthetic materials is decisive. Products based on highly crystalline polyesters
yield durable bonds even on highly flexibilized PVC, thus explaining their use in
the shoe, automotive and furniture industries. Products containing less crystalline
polyesters have a lower resistance to flexibilizers. They are characterized by their
higher flexibility and better adhesion to non-polar substrates. Therefore, they are
used for film lamination [22–24] (e.g. for manufacturing cross bottom valve sacks), for
manufacturing abrasive belts or for bonding polyurethane-based flexible foams.
Manufacturing solution adhesives
The solubility of the hydroxyl polyurethane types varies considerably due to the
significant differences in their chemical structure.
Methyl ethyl ketone (2-butanone) is an excellent solvent for all hydroxyl polyure-
thanes and is therefore also used for specifying the solution viscosity. All types are
also soluble in acetone. Some types are soluble in low-boiling esters such as methyl
acetate and ethyl acetate. Only in exceptional cases do they dissolve in aromatic
hydrocarbons. All types are insoluble in aliphatic hydrocarbons. In addition to
mixtures of dissolving solvents, certain mixtures of solvents can be used that con-
sist of a dissolving and a non-dissolving solvent (the composition of such dissolv-
ing/non-dissolving mixtures can be found in solubility parameter diagrams [25]). It
should further be noted that the solubility is also dependent on the selected solution
viscosity specification of the hydroxyl polyurethane used.
The effect of the solvent on the viscosity of the hydroxyl polyurethane solution is
considerable. The solvents also affect the storage stability of the adhesive and its
gelling at low temperatures. However, the latter is a purely physical process, which
is reversible. Gentle warming restores the original viscosity. In addition, substrate
wetting, the drying time and the activation behavior of the adhesive film are affected.

Solventborne adhesives based on hydroxyl polyurethanes 261
The adhesives are prepared by simply dissolving the raw materials supplied as
granules in suitable organic solvents. The granules are stirred into the solvent to
avoid any agglomeration of the readily soluble components.
With regard to the flammability of the solvent used, suitable measures must be
taken to prevent ignition caused by electrostatic charging of the solid when emp-
tying the packaging container. The flammability of the solvents themselves and
the danger that solvent vapors form explosive mixtures with air must be kept in
mind and the corresponding equipment must be used. Moreover, the physiological
action of the solvents must be considered. The use of many solvents is restricted,
e.g. by labeling requirements, or is completely forbidden. The relevant legislation
must be observed (in Germany, the Ordinance on Hazardous Substances – Gefahr-
stoffverordnung or GefStoff V).
To ensure optimal storage stability of the adhesive, the solvents used must be of high
quality. Their water and alcohol content must not be higher than 0.1 %. Ketones and
esters in particular can contain peroxides. An increased peroxide concentration causes
oxidation reactions that are evident from a discoloration of the adhesive solution.
Formulation of the adhesives

Solutions of hydroxyl polyurethanes are frequently used as adhesives without fur-
ther additives. Special effects can be obtained by mixing different types as well as
by using additives. When mixing different types of hydroxyl polyurethane, their
compatibility should be considered and tested prior to use. For example, the prod-
ucts with low crystallinity described above are incompatible with the types based
on highly crystalline polyesters. The property profile can be varied by mixing. In
general, hydroxyl polyurethane adhesives are manufactured without fillers. How-
ever, a filler can be added to increase the initial strength of the adhesive. This
increases the activation temperature and may also impair the viscosity stability of
the adhesive formulation. Highly disperse silicas have proven useful as fillers since
they have a thixotropic effect on the adhesive solutions.
Processing the adhesives

The adhesive solution is usually applied to both substrates (double-sided bonding).
However, there are other applications in which only one substrate surface is coated
with adhesive (single-sided bonding). After drying, the adhesive film is partially
crystalline at room temperature and non-blocking (not tacky). Bonding takes place
in a heat activation process, in the same way as is described in Chapter 6.5.5 for
polyurethane dispersion adhesives. Before joining, the adhesive film is made
amorphous by heating to a temperature above the minimum activation temperature
(MAT). The resulting tacky film can be joined during its hot tack life.

6.4.2 Isocyanate crosslinkers for solventborne adhesives

Although adhesives based on hydroxyl polyurethanes, especially those with low
thermoplasticity, are often processed as one-component systems, additional chemical
crosslinking using an isocyanate crosslinker is recommended. The isocyanate cross-
linkers for solventborne adhesives (e.g. the “Desmodur R” series) are mostly solu-
tions of trifunctional aromatic isocyanates in ethyl acetate. They are not only suitable
for hydroxyl polyurethane adhesives but also for solventborne adhesives [26, 27] based
on natural and synthetic rubber.
Crosslinking greatly improves the thermal stability of the adhesive bond. It also
enhances substrate adhesion and the resistance to hydrolysis, solvents, plasticizers,
oils and fats. The products differ in reactivity, color and resistance to discoloration
of the adhesive film.
6.5 Polyurethane dispersion adhesives

Dispersions based on polyurethanes or urethane urea polymers containing ionic
groups (preferably anionic) as the hydrophilic centers in the polymer chain and
which are essentially free of external emulsifiers are of particular interest for the
manufacture of adhesives. The incorporation of hydrophilic centers instead of
the use of external emulsifiers results in a number of advantages, especially high
shear stability and good film-forming properties. The solids contents of these dis-
persions manufactured by the acetone process or by the melt dispersion process
are in the range 40 to 50 % by weight. In comparison with solventborne systems,
polyurethane dispersion adhesives [28, 29] yield low application viscosities and high
solids contents. Branched or crosslinked polyurethanes can also be used, which,
however, can then only be activated at high temperatures and are primarily suitable
for wet-on-wet bonding.
Polyurethane dispersions are an important step in reducing solvent emissions in the
field of adhesive processing. A further aspect is also occupational safety because,
in contrast to solventborne systems, there are no fire and explosion risks and con-
sequently costly safety and recycling investments can be avoided.
6.5.1 Products
These aqueous products [30], e.g. “Dispercoll U”, closely correspond in their proper-
ties to the conventional hydroxyl polyurethanes used in solventborne applications
that are gradually being displaced for reason of environmental impact and occupa-
tional safety. Since most of these products are based on aliphatic isocyanates, the
adhesive films yielded are highly resistant to UV yellowing. The heat-activated
types produce very strong adhesive bonds, especially on substrates containing plas-
ticizer. They differ in their crystallinity or rate of crystallization and their activation

Polyurethane dispersion adhesives 263
temperature. Products that crystallize faster after heat activation are able to absorb
the resulting stresses in the adhesive joint more quickly after bonding. This property
is of interest, for example, in the lamination of furniture, which normally involves
three-dimensional structures rather than flat surfaces. After removal from the lami-
nation press, the adhesive joint must absorb the recovery forces of the decorative
film that has been severely stretched in some areas.
Products that crystallize less rapidly after heat activation have a somewhat longer
open time (hot tack life) compared with the fast-crystallizing types, with the result
that somewhat more time is available for positioning and joining the components
being bonded. This is a useful property for shoe manufacturing.
Polyurethane dispersions with low activation temperatures (approx. 40 to 50 °C)
are used to bond heat-sensitive substrates. Products with a high activation tem-
perature (80 to 100 °C) due to their amorphous polymer structure are mainly suit-
able for wet-on-wet bonding.
6.5.2 Formulation
Polyurethane dispersion adhesives are used pure or in combination with other poly-
mer dispersions. They can be easily applied by spraying, knifing or brushing. Their
low viscosity and high solids content provide the adhesive manufacturer with a
high degree of freedom in formulation.
Thickening
The rheological properties of aqueous adhesives are highly important for their
application behavior. The adhesive should be easy to apply, for example by spray-
ing. It should also wet the substrate surfaces as well as possible, i.e. penetrate porous
substrates to a certain extent, but not too much. The viscosity depends on the shear
stress. Thickeners based on hydrophilically modified polyurethanes (e.g. “Borchi
Gel L 75 N”) have proven suitable for adjusting the application viscosity. They can
be easily incorporated into the dispersion and are highly effective.
Addition of polymer dispersions
Dispersions with different polymer structures can be combined. However, several
points must be taken into account. Dispersions containing different stabilizers
(anionic/cationic) are incompatible and would coagulate on mixing. The stability
of the polymer dispersion can be highly dependent on the pH. Therefore, the pH of
the components should be matched to each other before mixing. Since the polymer
backbone of the “Dispercoll U” products consists of polyester polyurethanes, the
pH of the adhesive formulation should be between 6 and 9 to avoid hydrolysis of
the polymers. The long-term stability of the formulations must be carefully tested
because the appearance of the formulated adhesive dispersion (fish eye formation,
coagulation, phase separation) and its application properties can change.

Conservation
In principle all aqueous dispersions are at risk of bacterial contamination. Conse-
quently, the polyurethane dispersions contain a bactericide that prevents the repro-
duction of microbes. Depending on the type and amount of components used,
additional stabilization may be required when formulating the finished adhesive.
6.5.3 Isocyanate crosslinkers for dispersion adhesives
The full potential of the adhesives’ properties can only be exploited in two-com-
ponent formulations using emulsifiable isocyanate crosslinkers [31]. These are mainly
hexamethylene diisocyanate isocyanurates modified with hydrophilic ether chain
segments. The isocyanate groups react with reactive groups in the adhesive polymer
to yield a chemically crosslinked structure of high molecular weight. This is evident
from, for example, the change in the storage modulus (Figure 6.7).
The hydrophilically modified isocyanate crosslinkers are usually processed without
other additives. If, however, an additive is to be used, it must not contain any groups
that react with isocyanate or contain secondary components that react in this way.
In particular, the additive must be free of basic or other secondary components that
have a catalytic effect on isocyanate groups. Unsuitable additives, even in very low
concentrations, can cause an increase in viscosity or even solidification.
Crosslinking increases the softening temperature of the adhesive film and improves
its resistance to solvents, plasticizers, oil and fat migration, and hydrolysis. The
isocyanate groups also promote the adhesion to some surfaces. The influence of
crosslinking on the softening behavior of an adhesive film, as determined by ther-
momechanical analysis (TMA), is shown in Figure 6.8. The lower the softening at
increasing temperature, the lower the penetration depth of the probe.
Figure 6.7: Storage modulus of an adhesive film with and without isocyanate crosslinker

More intensive mixing is required to achieve homogeneous blending of hydrophilic

isocyanate crosslinkers with adhesive dispersions than to blend solventborne adhe-
sives with soluble crosslinkers because the crosslinkers are not physically soluble
in the aqueous adhesive. Instead, they have to be finely dispersed by emulsification.
Hand mixing is not sufficient. Any non-uniform distribution of the emulsified iso-
cyanate cannot be compensated by diffusion. After addition of the isocyanate cross-
linker, the adhesive has to be processed within a certain period of time (pot life)
that is not solely determined by the polyurethane dispersion used but also by the
other components in the formulation.
Emulsifiable polyisocyanates include the “Desmodur D” products. The individual
types differ in their viscosity and hydrophilic properties and can therefore be matched
to the adhesive formulations requiring crosslinking. Low viscosity facilitates blend-
ing with the polymer dispersion. Products with a low degree of hydrophilic modi-
fication are advantageous in minimizing the swelling in water of the crosslinked
adhesive film. On emulsification, the more highly hydrophilic types yield finer drop-
lets. Consequently, the adhesive has better shear stability on application and dries
to yield a smoother film. The composition of some products is in conformity with
paragraph 175.105 Adhesives of the U.S. FDA Regulations (Title 21, CFR).
The hydrophilic isocyanate crosslinkers are generally manufactured from aliphatic
polyisocyanate and therefore do not compromise the resistance to yellowing of the
crosslinked adhesive film.
Pot life of the adhesive
Like solventborne systems, mixtures of dispersion adhesives have only limited
storage stability after addition of the crosslinker components. The pot life represents
the limit of processability. The isocyanate groups of the emulsified crosslinker react
with the aqueous phase to form urea that, used as a solid filler, reduces the tack of
the activated adhesive film and thus impairs the contactability during bonding. The
Figure 6.8: TMA of an adhesive film yielded by a polyurethane dispersion with and
without isocyanate crosslinker

rate of the reaction with water depends on the pH, among other factors. When using
dispersions with a neutral pH, the NCO content declines relatively slowly. After
about 8 to 10 hours, the NCO content has dropped so much that the properties (e.g.
thermal stability) of the resulting adhesive bond are no longer attained. Here, in
contrast to two-component solventborne adhesives based on hydroxyl polyurethane
and processed with isocyanate crosslinkers, the end of the pot life is not usually
indicated by gelling of the adhesive mixture.
6.5.4 Drying
After evaporation of the water, the dispersion yields a solid and homogeneous
adhesive film on the substrate. In the case of dispersion adhesives, the drying costs
are often regarded as problematic. However, if the dryer has the correct layout,
drying rates comparable to those for solventborne systems can be achieved. The
drying units can also be utilized for heat activation of the adhesive layers. The
extensive and reproducible drying of the adhesive film must be carefully controlled,
especially at high relative humidity of the ambient air. A high residual moisture
content in the adhesive film would produce poor-quality bonds. Any moisture
trapped between impermeable substrates can damage the adhesive layer after a
while due to hydrolysis.
Open time of the adhesive film
The NCO groups of the isocyanate crosslinker slowly crosslink the polymer in the
dried adhesive film. This results in a slowly progressive decrease in tack and flow-
ability of the (heat-activated) adhesive film, with the result that the temperature
required for activation slowly increases during storage. In general the adhesive
layer should be heat-activated and processed at most 8 hours (end of the open time)
after application of the adhesive dispersion.
6.5.5 The principle of heat-activated adhesive bonding
Dispersion adhesives based on crystallizing polyester polyurethanes are generally
processed as heat-activated formulations [32]. After application, drying and cooling,
the adhesive forms a non-blocking film. Heat activation makes it tacky; the crystal-
line polyester segments of the polymer are melted in a heating tunnel or by infrared
radiation at a temperature above the minimum activation temperature. The activa-
tion process is illustrated in Figure 6.9 showing the change in modulus as a func-
tion of the temperature of the adhesive film.
1st step: Application of the adhesive and subsequent drying. A dry, non-tacky surface
is obtained. The modulus is high (low penetration).
2 step: Immediately prior to joining, the adhesive film is rapidly heated to a tem-
nd
perature above 50 °C. This melts the crystalline polyester segments and
the modulus decreases markedly (high penetration). The film becomes
flowable and the tack increases.

Heat activation is best done by rapid (short) heating (shock activation, e.g. by IR
radiation) because the substrate thus remains virtually unheated. Only a small
amount of heat is applied and the adhesive joint cools rapidly after joining. The hot
tack life is the period of time after the end of heat activation in which the film
exhibits sufficient tack and flowability for bonding. The substrate must be joined
during this time, which may be anything from seconds to minutes depending on
the polymer structure.
Figure 6.9: Heat activation of polyurethane adhesives containing crystalline polyester soft segments
Figure 6.10: Three phases of modulus development after heat activation and cooling of
the adhesive film

The processes that follow activation and bonding are illustrated in Figure 6.10. The
change in modulus is shown as a function of time. Three phases of modulus develop-
ment are observed. First, the adhesive cools shortly after activation, then the polymer
recrystallizes and, finally, the adhesive crosslinks in the presence of an isocyanate.
• Phase 1: The adhesion joint cools immediately after joining. Thus, in this phase,
the viscosity of the adhesive and the cohesive strength of the adhesive film
rapidly increase.
• Phase 2: The polyester segments of the polymer begin to recrystallize, so the
fresh adhesion joint quickly achieves such a high strength that it holds the part
being joined in the joining position until the final strength is attained.
• Phase 3: When using two-component formulations with an isocyanate crosslinker,
the strength increases further as a result of subsequent chemical crosslinking of
the adhesive film.
6.5.6 Applications and
application technology
Polyurethane dispersion adhesives have
found their way into a multitude of
industrial applications [33], e.g. in the
furniture industry, the automotive
industry, shoe manufacturing or in the
textile industry for manufacturing lam-
inated fabrics. The heat activation pro-
cess is easily implemented and suitable
for many materials as long as they are
not heat-sensitive. Depending on the
type of adhesive used, the activation
temperatures are in the range of 50 to
Figure 6.11: Three-dimensional compres- 80 °C. Special polyurethane dispersions
sion molding process for laminating are applied mainly in the wet bonding
decorative PVC films onto MDF process. The material to be bonded is
placed on the wet adhesive layer, which
is then dried to produce the bond. The
process is ideal for textiles or substrate
combinations in which at least one sub-
strate is permeable to water vapor.
An important example of the use of the
heat activation process in the furniture
industry is the production of three-
dimensional furniture front panels
Figure 6.12: 3aD press [34] by laminating decorative films onto

medium density fiberboard (MDF). In this three-dimensional compression molding

process (Figures 6.11 and 6.12), the adhesive film that has been applied and dried on
the MDF component is activated through the preheated decorative film by a heated
compression membrane. The pressure of the heated membrane molds the decorative
film to the shape of the furniture component, thus bonding them firmly.
In the automotive industry, the vacuum deep-drawing process is used to produce

laminated components for automobile interiors. A preheated laminating film is
pulled by a vacuum and bonded onto a preshaped component that is coated with
adhesive (Figure 6.13 and Figure 6.14). Adhesives with high initial bond strength
are needed for short cycle times, as the molded laminating films develop high
recovery strength. As soon as the laminated component is removed from the mold,
the adhesive film must be capable of
withstanding the stresses that result
between the film and substrate.
Flat surfaces can be processed by hot

lamination. The flat carrier material is
coated with adhesive and laminated in
a continuous process. Heat activation
occurs through the lamination film with
the help of heated pressure rollers.
In the shoe industry, polyurethane disper-

sion adhesives are used especially for
bonding soles (Figures 6.15 and 6.16).
Increasingly complex composite sole
structures are being used in the sports
shoe segment and require high-perfor-
mance adhesives. Polyurethane disper- Figure 6.13: Vacuum deep-drawing
sions are now also the state of the art in process for laminating components for
this application. Dispersion adhesives are automotive interiors with decorative films
also being used increasingly in the city
shoe segment as an alternative to solvent-
borne adhesives, not least to ensure com-
pliance with current VOC regulations.
6.5.7 Latently reactive
polyurethane dispersion
adhesives
Latently reactive polyurethane disper-
sion adhesives [36–38] offer new perspec-
tives for heat-activated adhesives. They Figure 6.14: Door panel of Audi A6 [35]

are formulations of heat-activatable polyurethane dispersions that contain highly

dispersed surface-deactivated solid isocyanates as the latent crosslinkers. Com-
pared with two-component dispersion adhesives, the latently reactive adhesive
mixtures have the advantage that, although they contain an isocyanate crosslinker,
they can be stored for long periods of time at 25 °C without any decrease in the
adhesion performance. Similarly, a coating of a latently reactive polyurethane dis-
persion adhesive is stable for a long period of time. The adhesion values obtained
with latently reactive polyurethane dispersion adhesives match the corresponding
two-component crosslinked dispersion adhesives in many respects.
Because the processing of latently reactive adhesive mixtures is not subject to pot
life restrictions, process stoppages are no longer a problem. Pre-coated parts retain
their activation properties longer than before and bond by self-crosslinking. Adhesive
application and joining of the substrates can therefore be carried out at different times
and in different places. All heat-activatable “Dispercoll U” dispersions can be used
to formulate latently reactive polyurethane dispersion adhesives. TDI dimer is used
as the isocyanate; the suitability of micronized IPDI trimer is being tested at the
present time. Being an aliphatic isocyanate, the latter has the advantage that it yields
adhesives resistant to yellowing. Deactivation is achieved by eliminating the NCO
groups on the particle surface through reaction with an aqueous amine solution. After
application and drying, the adhesive layer begins to crosslink by heat activation to a
temperature above 55 °C. The isocyanate particles dissolve in the then amorphous
polymer film and can become active as crosslinkers. The amount of dissolved iso-
cyanate depends on the activation temperature and the duration of exposure to this
temperature. The isocyanate particles must be very highly dispersed (<10 µm) so that
they dissolve well and the polymer crosslinks rapidly and uniformly.
Latently reactive adhesive dispersions are used for manufacturing MDF/PVC lami-
nates for furniture front panels and for bonding shoe soles. They are also being tested:
• as adhesion promoters
• as adhesives for improving metal/thermoplastic adhesion
• for interior components in automobile construction
Figure 6.15: Principle of shoe sole bonding with polyurethane dispersion adhesives

Outlook
In addition to their use as aqueous adhe-
sive dispersions, further forms of appli-
cation are of interest: storage-stable,
latently reactive crosslinkable pre-coats
of substrate surfaces and latently reac-
tive crosslinkable adhesive films [39]. An
important precondition for these appli-
cations is of course the storage stability
of the dried adhesive film. During stor- Figure 6.16: Applying dispersion adhesive
age, if only some of the deactivated iso- to a shoe sole
cyanate reacts, i.e. the polymer cross-
links, then the activation temperature increases. A slow crosslinking reaction of the
polymer would mean that, after a time, the adhesive film or the adhesive pre-coat
would no longer be activatable and would therefore be unusable. Experiments have
been successful in formulating mixtures that yielded pre-coats and adhesive films
with a storage stability of several months at 23 °C.
Latently reactive pre-coats or adhesive films are of interest for applications that
profit from the following typical properties:
• low activation temperature of 60 to 90 °C
• high heat stability and laminate strength
• fast activation process with short cycle times
• no release of condensation products during activation
• relatively low compression pressures needed for joining
• non-blocking adhesive film surface
• good adhesion to a large number of synthetic or metal surfaces
• non-discoloring adhesive layers
In addition to the latently reactive pre-coating of webs or the production of latently
self-crosslinking adhesive films, processing can also be done by screen or pad
printing on defined areas or three-dimensional components, e.g. in the electronics
industry.
6.6 Hot-melt adhesives

6.6.1 Non-reactive hydroxyl polyurethane hot-melt adhesives
Compared with copolyamides and copolyesters, “Desmomelt” polyurethanes offer

substantially longer open times without compromising the bond strength. They can
be used to particular advantage in complex manufacturing processes, such as lam-
ination of a second web without additional activation.

Granular and powder types are available. The granular types for extrusion pro-
cessing must be essentially free of gel particles. Powder types with a particle size
of < 600 µm are manufactured by low-temperature grinding and are applied by
scatter coating.
Chemically speaking, they are strictly linear hydroxyl polyurethanes based on
crystallizing polyester diols and aromatic diisocyanates, i.e. products with struc-
tures that correspond to the hydroxyl polyurethanes used for heat activatable
solventborne adhesives. The following technical advantages are significant for
their use:
• low activation temperature in comparison with normal hot-melt adhesives,
therefore suitable for heat-sensitive substrates
• very good adhesion like all heat-activatable hydroxyl polyurethanes
• no penetration of the adhesive into porous substrates because of its viscoelastic
properties (textile laminates retain their soft grip)
• high initial strength;
• practically unlimited shelf life of the coated substrates prior to bonding
One of the most important applications is the lamination of textiles. The adhesion
is achieved by heat activation of the scatter-coated powder, the extruded adhesive
film or the adhesive nonwoven and subsequent pressing together of both sub-
strates.
Granules
The granules are used for the extrusion of adhesive films and adhesive nonwovens
or for direct coating. The adhesive film extruded onto a substrate or the heat-activat-
able adhesive film or nonwoven between two substrates can be processed with
typical hot-melt bonding technology, such as heated calendars, membrane presses
or continuous presses. Grades with low
thermoplasticity and fast to very fast
recrystallization are available.
Despite their rapid recrystallization, the
products exhibit good activation prop-
erties. However, there is no danger of
the adhesive layer penetrating too
deeply into the fabric. The scanning
electron micrograph (SEM) below
(Figure 6.17) shows that the adhesive
film only surrounds the directly adja-
cent fiber and does not penetrate the
Figure 6.17: SEM of textile layers bonded
with hydroxyl polyurethane hot-melt adhe- fabric structure. The soft grip of the tex-
sive film tile is thus retained.

Hot-melt adhesives 273
The applications of hot-melt adhesive films or nonwovens formulated with heat-

activatable hydroxyl polyurethanes primarily include bonding of flat objects, mainly
textiles. The basic requirement for a textile bond – good resistance to washing and
chemical cleaning – is met by the extrusion grades. However, other possible sub-
strates are paper and film webs, leather and wood products. Further applications of
hot-melt films can be found in the automotive industry, for example in the finishing
of textile outer fabrics for back molding processes (that prevent the penetration or
strike-through of the expanding polyurethane foam), or skin coating of insulating
foams. Examples of direct coating are the production of shoe cap materials or the
adhesive pre-coating of surface films for case furniture.
Powders
Hot-melt adhesives in powder form are an interesting alternative to adhesive films
or for direct coating, especially for textile lamination. In addition to the general
features of hydroxyl polyurethane hot-melt adhesives, it should also be mentioned
here that the powders can be mixed if they have similar particle size distributions
and morphologies. Spray application can be used for bonding porous substrates in
the manufacture of breathable textile composites. Moreover, spraying is a simple
application method for large-scale applications.
As heat-activatable hydroxyl polyurethane powders become tacky at very low tem-

peratures, they are suitable for the gentle lamination of heat-sensitive substrates,
e.g. high-quality textiles. Thanks to their good flow properties in the activated state,
a good bond is produced even at low pressure and short pressing times. However,
the risk of strike-through into the fabric is low. The contact behavior is not solely
determined by the temperature; joining pressure and compression times are also
useful control parameters. By balancing these three parameters, the process can be
adjusted to the characteristics of a given substrate. If only low pressures can be
applied, then the poorer contactability can be compensated by increasing the press-
ing time or the pressing temperature.
Scatter coating of hot-melt adhesive powders

Powders with particle sizes of less than 600 µm can be applied easily on the
substrate using scatter coating equipment. The principle is shown in Figure 6.18.
The powder is contained in a hopper, from which a needle roller conveys a defined
powder stream. An oscillating brush removes the powder from the needle spaces
to fall onto the continuously moving web below. The web then passes through an
infrared tunnel where the powder is melted and fixed onto the substrate. In general,
the laminating press is immediately downstream. Examples of possible applica-
tions are textile lamination, leather processing and the production of shoe-stiffen-
ing materials.

6.6.2 Reactive polyurethane hot-melt adhesives
Reactive polyurethane hot-melt adhesives [40–43] are a fast-growing class of adhesives

consisting of a readily meltable polyisocyanate polyurethane (NCO prepolymer)
which is solid at room temperature. They set both physically by cooling and chem-
ically by reaction with atmospheric moisture. Compared with non-reactive hot-melt
adhesives moderate melt viscosities can be achieved. Provided that the adhesion
bond line cools to a sufficiently low temperature, the adhesive bond very quickly
reaches an adequate initial strength so that further processing of the joined parts can
be done without additional fixing. The final strength and high thermal stability of
the adhesive bond result from subsequent crosslinking of the free isocyanate groups
with moisture (from the ambient air or from the substrate) to polyurea structures.
Depending on the formulation, reactive polyurethane hot-melt adhesives cure to
form elastomers with flexible to hard and tough adhesive layers.
Structure and properties
Reactive polyurethane hot-melt adhesives are reaction products of polyester diols,
sometimes containing a small amount of polyether diols, with an excess of diiso-
cyanate to form an NCO prepolymer. Generally, 4,4’-diphenylmethane diisocya-
nate (MDI) is used as the diisocyanate. The processing characteristics and final
properties are adjusted by varying the NCO/OH ratio, the proportions of crystalline,
amorphous and liquid starting materials, and their selection in terms of melting
point, glass transition temperature and melt viscosity. The formulations can also
Figure 6.18: Scatter coating of a hot-melt adhesive powder

contain non-reactive polymers as modifiers, e.g. polyacrylates. Optimization in this

way requires extensive practical experience because it involves an empirical
approach. The function of the starting materials and their significance for the adhe-
sive properties are shown in Table 6.4.
The NCO/OH ratio is selected to ensure that the NCO prepolymer is solid or
highly viscous at temperatures below 50 °C. It must be liquid and have an ade-
quately low viscosity at the processing temperatures of between 100 and 150 °C.
These conditions yield a product with a free isocyanate content in the range
1 to 4 %. The stability of the product during storage and processing is very impor-
tant. Since the polyurethane contains free isocyanate groups, an increase in vis-
cosity under thermal stress from overly high temperatures or excessively long
exposure to high temperatures must be expected. Accordingly, processing should
be designed such that the limit of 150 °C is never exceeded. The processing equip-
ment must also ensure that the total thermal stress during melting, conveying and
application is minimized.
Table 6.4: The function of the starting materials and their significance for the properties
of the adhesive
Starting material Function/effect on the
properties of the prepoly-
mer
Polyester diol crystalline Melting point: > 50 °C • Low melt viscosity
• High initial cohesion,
depending on the crystal-
lization rate
• Significant effect on the
open time
Polyester diol amor- glas transition tempera- • High melt viscosity
phous ture: > 20 °C • High tackiness
• Short open time / high
initial tack
Polyester diol liquid Glass transition • Low melt viscosity
temperature: < 30 °C • Lower initial cohesion
Polyether diol liquid – • Longer open time
Diisocyanate – Reaction with the diol

components in molar excess
of the isocyanate to give
an isocyanate content in the
range of 1– 4 %

Now available are reactive polyurethane hot-melt adhesives based on new types
of raw materials with significantly reduced contents of free MDI monomer [44].
These are made possible by the use of low-monomer MDI-based NCO prepoly-
mers as the isocyanate building block. The lower content of free – i.e. volatile –
monomeric isocyanate is a key requirement in lowering emission values. The
processing temperature of these products is not restricted to below 150 °C solely
because of the viscosity stability, but also because the lability of the urethane group
from 150 °C causes cleavage of the volatile monomeric isocyanate content at higher
temperatures.
Polyester diol components
Several polyester diols used to manufacture reactive hot-melt adhesives are sum-
marized in Table 6.5.
Table 6.5: Polyester diols for reactive hot-melt adhesives

A B C
Chemical structure Polyester diol Polyester diol Polyester diol
Hexane diol Hexane diol Diol mixture
Adipic acid Dodecane dicar- Dicarboxylic acid
boxylic acid
crystalline crystalline amorphous
Crystallization rate rapid very rapid –
Melting point (°C) approx. 60 approx. 70 –
Figure 6.19: Temperature-viscosity curves of polyester diols for reactive hot-melt adhesives

The temperature-viscosity curves of these products are shown in Figure 6.19. In

addition to the crystallinity, the viscosity is an important control parameter for
the applicability, joint behavior and adhesion properties of the adhesive. The
significance of these parameters is demonstrated by the two sample formulations
in Table 6.6. Both adhesives are produced by reacting the polyester diols with
MDI (NCO content: 3 %).
Their tack as a function of temperature is shown in Figure 6.20 (page 277). For-
mulation 2 contains a high content of amorphous polyester and has much higher
tack than the adhesive based on the pure crystalline polyester diol (formulation 1).
However, this result should not lead to the conclusion that the highest possible
amorphous polyester diol content should be used. The amorphous product strongly
increases the viscosity of the adhesive, making processing and joining difficult.
Table 6.6: Sample formulations

Formulation 1 Formulation 2
Polyester diol A C A
Proportions (%) 100 75 25
crystalline amorphous crystalline
Crystallization rate rapid – rapid

Melting point (°C) approx. 60 – approx. 60
Glass transition temperature (°C) – approx. 30
Reaction with 4,4’-MDI to 3.0 % NCO 3.0 % NCO
Figure 6.20: Influence of polyester diols on tack

Moreover, the adhesive film with a high amorphous content has a relatively high
cold flow and is relatively brittle.
Formulation development thus requires a careful balance between the adhesive
properties and the specific processing conditions and final properties for the given
application, with the result that customized solutions are frequently needed.
Processing
When processing reactive polyurethane hot-melt adhesives, it is absolutely essential
that the necessary technical requirements are fulfilled and the user knows how to
safely handle these materials. In the melt, the products have an increased vapor
pressure of toxic monomeric diisocyanates. All necessary measures must be taken
to prevent emission of monomeric diisocyanates and all processing steps must be
reviewed in respect of occupational safety. NCO reactive hot melts must be deliv-
ered in absolutely moisture-proof containers, e.g. in drums, hobbocks or cans or in
moisture-proof film pouches, pots or cartridges.
Special melting units are used, preferably operating continuously, to melt the
amounts required for immediate use at 100 to 150 °C. The limited thermal stability
of the adhesive must be borne in mind, which restricts the processing temperature
and prolonged exposure to thermal stress. The principle of such a processing unit
is shown in Figure 6.21. The melt is applied to the substrate by spraying, roller
coating or extrusion through a slot die, as shown in Figure 6.22.
The initial strength of the bond depends on the substrate temperature, because the
increase in viscosity or the recrystallization of the adhesive film in the adhesive
Figure 6.21: Principle of a processing unit for reactive polyurethane hot melts [45]

joint is dependent on the temperature. If the substrate is too warm then the initial
strength will possibly be too low. If the substrate is too cold or rapidly conducts the
heat away, then the adhesive may solidify too quickly. It will then not adhere to the
cold carrier material or it can no longer wet the part being joined. The presence of
moisture is required to develop the final strength. The reaction therefore depends
on atmospheric and substrate humidity, as well as on the rate of diffusion of the
moisture in the adhesive film. Three to seven days are needed for complete curing,
depending on these factors.
After joining, the initial strength is produced by the increase in viscosity and recrys-
tallization when the adhesive layer cools. The crosslinking reaction with moisture
ultimately yields a heat-stable bond with good chemical resistance (e.g. resistance
to washing or chemical cleaning in the case of textile bonding). The moisture has
to be able to diffuse to the reactive NCO groups. Chemical post-curing therefore
occurs significantly more slowly than the physical setting process. Figure 6.23
shows a schematic illustration of the increase in adhesive bond strength of a reac-
tive hot-melt adhesive. The rapid increase (b) of strength in the adhesion joint is
produced by the increase in viscosity and/or recrystallization on cooling. Final
chemical curing by the isocyanate/water
reaction follows with some delay (c).
Applications
Customized reactive polyurethane hot-
melt adhesives are used in many differ-
ent applications: bookbinding, assembly Figure 6.22: Application variants for
and profile wrapping in furniture reactive polyurethane hot melts [45]
Figure 6.23: Schematic illustration of the increase in adhesive bond strength of a reactive
hot-melt adhesive

production, textile composites and laminates, production of metal doors and parti-
tion walls for offices, production of sandwich panel assemblies for camping vehicles,
production of window frames, manufacture of automotive lighting elements.
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Chemical structure 283
7 Polyurethane sealants
7.1 Terms and definitions

DIN EN 269 27 [1] defines sealants as products applied to joints as sprayable paste-
like compounds to seal them. Sealants must have good adhesion on the flanks of
the joints so that they absorb any movement of the joints without losing their seal-
ing effect. Polyurethane sealants are used in construction and industrial applica-
tions. In most sealant applications, polyurethanes compete with a variety of other
binders such as silicones, acrylates, rubber and polysulfides [2–5].
Sealants are classified in two groups on the basis of their physical properties:
• Plastic sealants: This type of sealant retains plastic characteristics after curing.
This means that it has virtually no elastic recovery after application of tensile or
compressive stress. Butyl rubber is a typical representative of this class of sealants.
• Flexible sealants: These exhibit elastic recovery. Flexible sealants primarily
include products based on polyurethane, polysulfide and silicone polymers (see
Figure 7.1).
7.2 Chemical structure

7.2.1 Isocyanate crosslinking systems
These products are available on the market as two-component and one-component
systems. The base components of two-component polyurethane sealants comprise
polyols, plasticizers, fillers, thickeners
and additives. The hardener component
contains polyisocyanates as the coreac-
tants for the polyol. These isocyanates
are often based on MDI or TDI prepoly-
mers but may be aliphatic in special
cases. Two-component systems with
relatively low application viscosities
can be used as self-leveling sealing
compounds and permit fast processing
because the smoothing step is not
required. Since the curing of two-com-
ponent systems is not dependent on the
inward diffusion of atmospheric mois-
ture, deep joints can also be poured Figure 7.1: Flexible polyurethane sealant

284 Polyurethane Sealants
without curing problems. Two-component polyurethane sealants are mainly used

as sealing compounds for horizontal floor joints, particularly when rapid avail-
ability is demanded. Floor joints in industrial facilities are an example.
One-component polyurethane sealants
Thanks to their safe and easy handling, one-component polyurethane sealants have
gained broad market acceptance. They usually contain MDI prepolymers such as
“Desmoseal M” that have a relatively low NCO content of approximately two
percent. The NCO content has to be limited because gaseous carbon dioxide is
produced through contact with atmospheric moisture during the hardening reaction.
The fewer isocyanate groups there are in the binder, the less gas is generated and
the lower the risk of blistering as the sealant cures.
The prepolymer chains are formed using linear polyether polyols, whereby a care-
fully calculated quantity of trifunctional polyether polyol is used to optimize elastic
recovery. The reaction of the NCO prepolymers with atmospheric and ambient
moisture yields an essentially linear chain extension through urea segments, with-
out the formation of additional branching sites (Figure 7.2). This type of system is
employed in building, automotive construction and shipbuilding. Here, the sealant
also functions as a flexible adhesive.
7.2.2 Silane-modified polymers
Sealants based on silane-modified polymers also crosslink by reaction with atmo-
spheric and ambient moisture. However, the reaction of their alkoxysilane end
groups, in contrast to the reactive NCO groups in one-component polyurethane
sealants, does not generate CO2 gas. Therefore there is no danger of blistering
or foaming. These products are characterized in particular by a broad adhesion
Figure 7.2: Chain extension of NCO prepolymers by reaction with water

Chemical structure 285
s pectrum. NCO groups and alkoxysilane groups react differently with the OH or
NH groups of substrates and consequently the adhesion mechanisms of silane-
modified polymers differ greatly from those of the one-component polyurethane
sealants on the same substrates.
Silane-modified polymers are used in flexible sealants, as well as increasingly in
flexible adhesives, and find applications in automotive construction, machine con-
struction, in the container industry, electronics and in the construction industry.
They can be overcoated with many common types of paints and exhibit good UV
and weathering stability as well as high elasticity even at low temperatures. Depend-
ing on the type of polymer backbone, the silane-modified polymers are subdivided
into two structurally different systems (see Table 7.1).
This structural distinction is reflected in the application and end properties of the
sealants formulated with these products.
Silane-modified polyethers:
The polymer backbone of silane-modified polyethers [6] (see Figure 7.3) is polyoxy-
propylene, which is also an important building block for polyurethanes. However,
silane-modified polyethers do not contain any urethane structures; consequently they
do not actually belong in a description of polyurethane sealants. Nevertheless, due
to their close relationship to the silane-terminated polyurethanes, comparison of the
two systems is indispensable in providing a complete representation.
Table 7.1: Structural principles of silane-modified polymers

Central polymer chain, polymer backbone
Silane-modified polyethers Polyoxypropylene
Silane-terminated polyurethanes Polyurethane
Figure 7.3: Fundamental structure of a silane-modified polyether
Figure 7.4: Basic structure of a silane-modified polyurethane

Silane-terminated polyurethanes:
Silane-terminated polyurethanes [7, 8] have also been available on the market for
several years. The basic structure is shown in Figure 7.4 (page 285). Of the various
production methods, essentially two processes are established:
• The reaction of NCO prepolymers based on high molecular weight polyether
polyols (e.g. “Acclaim”) and diisocyanates (e.g. isophorone diisocyanate) with
secondary aminoalkyl alkoxysilanes [9, 10]
• The reaction of long-chain polyether polyols with an alkoxyl-bearing isocya-
natosilane [11, 12]
The combination of polyurethane building blocks with the crosslinking and adhe-
sion mechanisms of silicones combines the strengths of both chemistries: the
cohesion strength and elasticity of the polymer backbone’s polyurethane structure
with the blister-free moisture curing and adhesion strength of trifunctional alk-
oxysilane end groups.
Thus, silane-modified polyethers consist of a highly flexible polyether chain with
two reactive alkoxysilane groups at each end. In contrast, the silane-terminated
polyurethane has a more rigid polyether-polyurethane chain as the polymer back-
bone, and at each end, there are three reactive alkoxysilane groups. In principle,
the crosslinking mechanism of both product groups is identical, but the higher
functionality of the silane-terminated polyurethanes yields greater reactivity and a
higher crosslinking density in the resulting polymer.
Some of the differences that result from the various polymer backbones and func-
tionalities are summarized in Table 7.2. The more rigid polymer chains of the
silane-terminated polyurethanes have a markedly higher viscosity at the same chain
length and tend to yield crosslinked end products with a higher shear modulus and
Table 7.2: Silane-terminated polyethers and silane-terminated polyurethanes: comparison

of some properties
Property Silane-terminated Silane-terminated
polyethers polyurethanes [13]
Unformulated raw material:
Functionality approx. 4 approx. 6
Viscosity lower higher
Reactivity lower higher
In the crosslinked formulation:
Elongation at break higher lower
Tensile strength lower higher
Elasticity lower (higher plasticity) higher (lower plasticity)

Formulation 287
hardness. It is thus possible to use them in formulating both sealants and flexible
adhesives (harder than sealants). The flexible silane-terminated polyethers are
lower in viscosity (yet have the same chain length), are less reactive as a result of
their lower functionality, and yield less highly crosslinked sealants that tend to be
softer and have a higher elongation at break.
7.3 Formulation
7.3.1 NCO-reactive one-component polyurethane sealants
The typical composition of a one-component polyurethane sealant is shown in the
following Table 7.3. In such a formulation, the simpler ground chalk powders can
be used as fillers. Silane-terminated polyurethanes, on the other hand, require rein-
forcing fillers (with a large surface area) to develop adequate strength. However,
this advantage of the NCO-terminated products is countered by the disadvantage
that their NCO groups can react with many antioxidants, meaning that the design
of the formulation has to take into account the storage stability of the uncrosslinked
sealant mixture and the stabilization of the crosslinked product.
7.3.2 Silane-terminated polyurethanes
The formulation of sealants or adhesives requires harmonization of a large number
of additives that all play a significant role in optimizing the processing and end
properties [14].
The storage stability of the formulations depends greatly on achieving the lowest
possible moisture content. The amount of silane added as a water scavenger is
important for the elimination of any possible traces of moisture. However, an excess
can be detrimental, because these silanes interfere with the subsequent crosslink-
ing process and, after crosslinking, can cause an increase of the modulus. The
aminosilanes, added as adhesion promoters, also have a stabilizing effect, because
their alkoxysilane groups are present in the mixture in much higher proportions
than those bonded to the silane-terminated polyurethane. This excess consequently
prevents the alkoxysilane groups bonded to the polyurethane from reacting with
trace quantities of reactive components.
The viscosity and rheological properties of the formulations are determined by the
addition of thixotropic agents, fillers, plasticizers and, if necessary, solvents. The
mechanical properties of the crosslinked formulations are determined by the silane-
terminated polyurethane, plasticizers, fillers and silanes. Their adhesive properties
depend on the aminosilane adhesion promoter. It should be noted here that the basic-
ity of these aminosilanes can increase the crosslinking rate. Plasticizers, fillers, the
amount of catalyst, and light stabilizers [15, 16] also affect the adhesive properties.
Silane-terminated polyurethane prepolymers (“Desmoseal S”) can be used to pro-
duce low-modulus sealants with a high elongation at break or high-modulus adhe-
sives, depending on the formulation.

Table 7.3: Typical composition of an NCO-reactive one-component polyurethane sealant

Function Product Parts by
weight
NCO prepolymer “Desmoseal M” 30
Plasticizer DIDP, DINP 30
Filler Chalk (ground types), pigments 30
Additives Catalysts: e.g. DBTL, DBTA 10
Antioxidants
Adhesion promoters: e.g. “Dynasylan” Glymo
Total 100
DIDP = diisodecyl phthalate, DINP = diisononyl phthalate, DBTL = dibutyl tin dilaurate,
DBTA = dibutyl tin diacetate; “Dynasylan” Glymo: www.degussa.com
7.4 Processing
The ready-to-use, normally solvent-free sealant is supplied in cartridges or flexible
pouches and applied to the joint using a manual or compressed-air spray gun. Seal-
ants are also supplied for the DIY home improvement market in special cartridges
that can be emptied without the use of spray guns. In industrial applications, e.g.
on a production line, the sealants are supplied in large containers and pumped
through hose lines to metering and application units.
References
[1] E. Baust, W. Fuchs, Praxishandbuch Dichtstoffe, Herausgeber: Industrieverband
Dichtstoffe e.V. (IVD). Public Relations Verlag und Werbung GmbH, 2004
[2] A. Damusis (Editor), Sealants. Reinhold Publishing Corporation, New York, Amster-
dam, London, 1967
[3] J. Panek (Editor), Building Seals and Sealants. ASTM Special Technical Publication
606, 1976
[4] I. R. Panek, I.-P. Cook, Construction Sealants and Adhesives. John Wiley and Sons,
Inc., New York 1984
[5] W. Endlich, Kleb- und Dichtstoffe in der modernen Technik, Verlag W. Giradet, Essen 1980
[6] K. Isayama, I. Hatano (Kanegafuchi Kagaku Kogyo, Kabushiki Kaisha, Japan) Vul-
canizable silylether terminated Polymer, Patent Application, US 3,971,751, 1976
[7] G. L. Brode, L. B. Conte Jr. (Union Carbide Corporation), Vulcanizable silicon ter-
minated Polyrethane Polymers, Patent Application, US 3,632,557, 1972
[8] B. A. Ashby, (General Electric Company), Moisture curable siloxy terminated polyether,
Patent Application, US 3,408,321, 1968
[9] Ch. Zwiener, L. Schmalstieg, J. Pedain, (Bayer AG), Alkoxysilan- und Aminogruppen
aufweisende Verbindungen, Patent Application, EP 0 596 360 A1, 1993

References 289
[10] U. Walter, L. Schmalstieg, R. Lemmerz; O. Wilmes (Bayer AG), Polyurethane pre-

polymers having alkoxysilane end groups, a method for the production there of and
their use for the production of sealants, Patent Application, EP 1 124 872, 2001
[11] S. D. Rizk, H. W. S. Hsieh, J. J. Prendergast, (Essex Chemical Corp.), Silicon-termi-
nated Polyurethane Polymer, Patent Application, 4,345,053, 1982
[12] T. Higuchi, Y. Nakano, N. Kunii, Y. Yamaguchi, S. Kozawa, (Asahi Glas Company Ltd.
Japan), Moisture-curable resin composition, Patent Application, EP 0 372 561 A2, 1989
[13] O. Ganster, W. Henning, R. Musch, M. Matner: Neue Rohstoffe für lösemittelfreie
Kleb- und Dichtstoffe Adhäsion Kleben & Dichten, 3/2003
[14] Starting formulation Bayer MaterialScience CAS-EMEA-BD ADH MMX 1088-5
[15] G. Mathur, J. E. Kresta, K. C. Frisch, Stabilization of Polyether-Urethanes and Polyether
(Urethane-Urea) Block Copolymers. Advances in Urethane Science and Technology
Vol. 6, Technomic Publishing Co., Inc., 1978
[16] H. J. Fabris, Thermal and Oxidative Stability of Urethanes. Advances in Urethane
Science and Technology Vol. 6, Technomic Publishing Co., Inc., 1978

290 New areas of application for polyurethanes
8 New areas of application

for polyurethanes
The most important areas of application for polyurethanes in the coating, adhesive
and sealant segments have been demonstrated in the foregoing chapters. This list
could certainly be continued, but the aim here is not to provide a detailed descrip-
tion of all the areas of application. Rather, it is to illustrate the wide variety of
possible uses of polyurethanes as starting points for new applications, including
those outside established areas of use. This spin-off effect will be described below
on the basis of selected examples.
Polyurethane as a latex substitute
The prophylactic measures taken worldwide in the early 1990s to guard against
HIV, hepatitis B and C, and later also bird flu, led to a sharp rise in the use of latex-
based protective gloves. However, glove users frequently complained of allergic
reactions. Latex contains allergens that lead to skin hypersensitivity. This fact trig-
gered an intensive search for alternative materials.
Such allergic reactions are not known to be caused by films based on polyurethane
dispersions. These can be processed in a similar way to latex, and today are widely
used in the manufacture of gloves for laboratory and medical applications. The
gloves are produced by application and coagulation of the polyurethane dispersion
on a ceramic hand mold. They are dipped into hot water to remove the salts formed
and then oven-dried at elevated temperatures.
Apart from their non-allergic properties, polyurethane gloves are comparable to
latex gloves in terms of wearing comfort. They are characterized by high tensile
strength and stress resistance, and are odor-free. In recent years, targeted optimiza-
tion of polyurethane dispersions has produced a significant rise in the resistance of
such gloves to alcohol-based disinfectants.
The advantages of polyurethane dispersions have made them clear alternatives to
latex. Polyurethane dispersions are also widely used in the manufacture of condoms.
The advantage of polyurethane condoms is that they cause practically no allergies,
and in contrast to latex condoms can also be used with oil-based products.
Polyurethanes for medical applications
Polyurethanes have played a significant role in medical technology for a long time.
The excellent mechanical properties of polyurethanes are also valued in this special-
ized area of use. For example, the suitability of polyurethanes for artificial heart

New areas of application for polyurethanes 291
valves was already being investigated by the end of the 1950s. Moreover, many
polyurethanes exhibit very good biocompatibility, which is a basic requirement for
use on injured skin. They can also be used in implant materials which can remain
in place over several hours, but could last for weeks or even years.
Today, polyurethane coatings are also found, for example, in modern wound treat-
ment. Certain polyurethane gels are used in many products for this application, wich
exhibit a remarkable degree of adhesion on uninjured skin but are completely non-
sticky on contact with the moist wound. Such dressings can therefore be removed
easily and painlessly, without causing any new damage to the healing wound [1].
However, the potential uses of polyurethanes in medical technology are far from
being exhausted. In particular, one- and two-component polyurethane coating sys-
tems offer an unlimited structural variety that is not accessible using thermal man-
ufacturing processes such as extrusion. There is an enormous demand for improved
materials in the field of medical technology.
Polyurethanes for cosmetic applications
Aqueous polyurethane dispersions also came into use in the cosmetics industry at
the end of the last century. The film-forming and gentle properties of polyurethane
dispersions made possible their use on hair. With the reduction in the amount of
organic solvents added, the hair care product segment (hairsprays, hair styling prod-
ucts, etc.) has been developed as a new area of application for polyurethanes [2].
The good compatibility of polyurethanes has recently made it possible to develop
systems for use on human and animal skin. Although polyurethane polymers still
play a subordinate role to the other polymers used in the cosmetics segment, such as
polyvinylpyrrolidones, polyvinyl alcohols, polyacrylates and silicones, their market
share is expected to grow significantly in view of the increasingly demanding require-
ments, e.g. elastic properties, shape memory effects, surface feel, gloss, water resis-
tance, reduction of organic solvent content, etc. Polyurethane dispersions in the form
of spray-dried powders are also being used increasingly in development work.
Polyurethanes for
holographic applications
The concept of holographic data stor-
age is already 40 years old. However,
its technical implementation had failed
until now due to a lack of available and
affordable materials. Only very recently
have polymer materials been developed
that are suitable for data storage and for
the recording of visible holograms. Poly- Figure 8.1: Cosmetics – a new area of
urethanes are also viewed as promising application for polyurethanes

292 New areas of application for polyurethanes
materials in this regard, and it is expected that such affordable holographic materials
will find use in a broad range of applications in the future by virtue of their unique
optical properties.
References
[1] Bayer scientific magazine “research” 1999, 11: “A gel for severe wounds”
[2] C. Wood, et al., SÖFW-Journal, 126. Jahrgang, 11-2000, 26–34

Combinatorial material development 293
9 Combinatorial material development

and high-throughput testing
9.1 Combinatorial material development

Polyurethane chemistry is characterized by its broad variability. The isocyanates
have extremely varied physicochemical properties, and can be combined with resins
that have a similarly wide range of properties. Many different reaction pathways
are available depending on process management, such as the choice of process
temperature or catalysis of the crosslinking reaction. The resulting products span
a wide spectrum of technical properties. At the same time, they have a broad range
of different applications in the areas of coatings, adhesives and sealants, which in
turn are used in many different industry segments, e.g. from construction to textile
coatings and automotive engineering.
Before the developer can fine tune the property profile of a formulation, the first step
is to pretest and evaluate a large number of possible candidates for the coating or
adhesive to be produced (screening phase). This is where combinatorial material
development comes into play [1]. The concept for this approach is borrowed from
biotechnology and pharmaceutical research. In screenings, only selected properties
are evaluated, but for large test sets of substances or formulations. The most promis-
ing candidates (“hits”) from such a study can then be further developed and optimized
using conventional methods. The screening processes in this initial phase are designed
so that they can be carried out very efficiently in the laboratory using automated
microscale techniques, working either in parallel or rapid serial. This accelerates the
process of preselecting the development candidates, which can be quickly ranked
against reference materials and assessed against a broad range of parameters under
reproducible conditions. The microscale approach further enables the testing of
unusual and expensive materials while minimizing the problems and costs of disposal.
The challenge in the implementation of such screening processes is selecting the
right test parameters at this early stage to provide meaningful evaluations and
predictions of subsequent material properties. Almost always, certain abstractions
must be employed, and the test design must be finely tuned to the problem being
investigated and the existing body of knowledge. Combinatorial material develop-
ment not only involves the many possible combinations of different materials, but
also systematic variations of the process and other parameters such as concentra-
tions, film thicknesses, storage and processing temperatures, environmental influ-
ences, etc. This is referred to as a multidimensional parameter space [2]. As a rule,
combinatorial experimental series are designed and implemented with the aid of
specialized software and computer-supported instrumentation [3].

294 Combinatorial material development and high-throughput testing
9.2 Statistical experimental design and

high-throughput analysis in the laboratory
Statistical experimental design
The basis for combinatorial high-throughput analysis is always an experimental
design in which the material and process variations are defined, often using statis-
tical experimental design plans (design of experiment, DoE) [1,2]. Depending on the
available knowledge of the system under study, the experimental design may just
have a screening focus, or it may address the systematic, simultaneous optimization
of several parameters. Screening designs have been used, for example, to identify
efficient catalysts for one-component PU coating systems based on blocked poly-
isocyanates. In a screening design for this purpose, coating formulations with dif-
ferently blocked isocyanates are systematically combined in all possible variations
with catalysts, cured and tested for selected properties.
In an optimization design, on the other hand, material and process parameters which
are often continuously selectable (concentration, temperature, residence time, etc.)
are tuned according to defined schemata and in defined combinations. The test results
obtained are then used to derive a precise model for the optimization of the system.
This experimental procedure is used, for example, in tuning the glass transition
temperature, identifying the optimal concentration of photoinitiator in UV-curing
coating systems, and optimizing the temperature profile for thermal curing [4–6].
Parallelized processes
Work in a high-throughput testing laboratory is usually carried out on sets of several
coating or adhesive preparations arranged in matrices, which are racks with a stan-
dardized format, thus permitting parallelized processing. This typically involves the
use of microtiter plates [9] with standardized external dimensions on which a number
(e.g. 24 or 96) of vials in which the preparations are formulated and processed are
laid out in a matrix pattern. Commercially available laboratory automation systems
are designed to handle such microtiter plates. The particular advantage of parallelized
processes lies in the simplified handling of a large number of test samples and in the
fact that the compact layout of the sample matrix ensures that all samples in a series
are subjected to exactly the same external conditions, like temperature, for example.
Automation
Laboratory automation plays a crucial role in high-throughput testing, serving above
all to accelerate the process and prevent errors in repeated procedures. Computer-
controlled apparatus extends operation beyond the working hours of laboratory
personnel, so that testing can continue overnight or on the weekend. Laboratory
automation means that multiple repetitions of preparations and tests to increase the
statistical certainty of the data can be carried out with comparatively little effort
(see Figure 9.1).

Blocked isocyanates with a lower baking temperature 295
The correct choice of high-throughput analysis methods is of particular importance.

An analysis method is only suitable if it provides results that have predictive value
for the problem at hand and if it can be automated through the use of instrumenta-
tion. It is sometimes necessary to forego the use of standardized tests. The results
provided by such test series are generally evaluations of the preparations relative
to one another, i.e. weighted rankings.
Especially well-suited for the characterization of polyurethane coating systems in
the context of high-throughput testing studies are mechanical measurements, in
particular of hardness and modulus of elasticity (for assessment of physical drying
properties or sandability) but also of viscosity (pot life) and swellability (solvent
resistance, relative crosslinking density); differential calorimetry (curing state,
glass transition); spectroscopy (crosslinking kinetics), as well as automated color,
gloss and film thickness measurements.
9.3 Blocked isocyanates with a lower baking
temperature – an example of combinatorial
development
The pairing of combinatorial material development with high-throughput testing
can be used as an approach to a wide range of problems, and has proved to be an
efficient and effective tool for polyurethane coatings, adhesives and sealants. It has
delivered substantial contributions, especially in the catalysis of one-component
coating systems (based on blocked polyisocyanates), in the development of novel
Figure 9.1: More than 100 coatings can be formulated per day in the high-throughput
testing laboratory and their films can be tested for various resistance properties

blocking agents, in the area of two-component systems (catalysis, process manage-

ment during curing) and in the development of formulations and guide formulations
(screening of photoinitiators and reactive thinners) [4–6]. It can also conceivably be
used in screening tests for potentially new applications.
In the following paragraphs, the capabilities of the high-throughput testing labora-
tory are illustrated by means of selected uses in the area of polyurethane coatings.
Combinatorial material development and automated high-throughput analysis are
used in, for example, the search for blocking agents for one-component polyure-
thane coating systems with a baking temperature of approx. 120 °C. Through com-
bination of experimental design with miniaturized, automated and parallelized
coating preparation and analysis, it is possible to identify the suitability of highly
efficient new blocking agents.
A particularly suitable screening test for the relative determination of the degree of
crosslinking in polyurethane coatings is based on the elution of a dye from a coating
film as depicted in Figure 9.2 [7]. A chemically inert dye – for example, a fluorescent
dye – is added to the coating formulation. Once the paint film has been applied and
cured, it is covered with an organic solvent that swells the film and elutes the dye.
The concentration of the dye in the solvent is correlated with the degree of swellabil-
ity and thus the degree of crosslinking of the coating film. The dye concentration
is determined by fluorescence analysis. A weak fluorescence signal indicates a high
degree of crosslinking, and conversely a low degree of crosslinking is indicated by
a strong fluorescence signal.
Figure 9.2: Principle for determining the relative degree of crosslinking of polymer films
by the elution of a fluorescent dye incorporated in the polymer

Blocked isocyanates with a lower baking temperature 297
This test was carried out for one-component polyurethane coatings baked at vari-
ous temperatures. The dependence of the fluorescence signals on the baking tem-
perature for each individual coating is depicted in Figure 9.3. At baking tempera-
tures below the crosslinking temperature, the coatings swell severely, and a high
dye concentration is measured. At baking temperatures above the crosslinking
temperature, the swellability of the polyurethane films and thus the eluate con-
centration are correspondingly lower. An easily split off blocking agent shifts the
crosslinking temperature to a lower value without affecting the pronounced step
in the signal plot.
The crosslinking temperatures measured by this method correlate well with the
results yielded by traditional techniques such as dynamic mechanical analysis
(DMA) [8], although not necessarily in absolute values but rather relative to a refer-
ence value (e.g. a formulation with a blocking agent that has been established as
the standard). The absolute values for the crosslinking temperatures are method-
specific, since they depend very much on experimental conditions such as the
baking time, and to a significant extent on the substrate used. The minimum cross-
linking temperature is defined as the temperature at which a significant drop in the
extracted dye concentration is observed. This is analogous to the procedure using
DMA, where this temperature is attributed to the rise in elastic modulus.
As an example, Figure 9.4 shows some of the results from a study to test novel
blocking agents [4]. The blocking agents tested included hydroxyfunctional com-
pounds (alcohols), aminofunctional aromatic compounds (heterocycles) and ami-
nofunctional aliphatic compounds (amines).
Figure 9.3: Determination of the crosslinking temperature for baking coatings by means
of the elution method

In this study, coating formulations were prepared from the polyacrylate polyol
“Desmophen A 870” and blocked polyisocyanates at an NCO/OH ratio of 1:1 and
catalyst loading of 1% by weight DBTL or bismuth 2-ethylhexanoate, calculated
on the solids content. As a control, the reaction was also performed without a
catalyst, using the hexamethylene diisocyanate trimer “Desmodur N 3300” as the
isocyanate component and the polyacrylate polyol “Desmophen A 870” as the
polyol component. Figure 9.1 (page 295) shows a typical layout for a single matrix
of coating formulations as a test unit used in this study.
For the systematic investigation of blocking agents, more than 60 blocked isocya-
nates based on “Desmodur N 3300” were prepared. For comparison, these same
isocyanates blocked using known standard blocking agents such as 3,5-dimethyl-
pyrazole (DMP), diisopropylamine and caprolactam were also tested.
High-throughput screening as described was completed for all the polyurethane
coatings prepared within a few days. The results provided by this study made
important contributions to understanding structure-property relationships in the
crosslinking and catalysis of one-component polyurethane coatings based on
blocked polyisocyanates (see Chapter 3.5).
Figure 9.4: Test results for the baking behavior from high throughput tests of one-
component polyurethane coatings with various blocking agents and catalysts

References 299
An impressive feature of this method is that, once a suitable experimental design

has been found, a huge number of tests can be carried out within a short period of
time. Thus, over the course of the catalysis studies, approximately 2,000 coating
formulations were tested in more than 20,000 individual tests within 20 weeks. In
another program, an optimization study was carried out for UV-curing coating
formulations by performing a total of some 15,000 solvent stability, hardness and
color measurements within a six-week period [6].
The use of high-throughput technology in the development of coatings, adhesives
and sealants opens up new perspectives. It offers possibilities for rapidly perform-
ing extensive screening operations for optimizing formulations, testing the efficacy
of novel substances, e.g. catalysts, and preselecting products, also for new applica-
tions, by means of basic suitability tests.
The method is not intended to replace practical formulation work in the laboratory,
but rather should be considered as an extension of this. High-throughput technology
should be viewed as an additional tool that helps perform material development
projects more efficiently and bring them more rapidly to a successful conclusion.
References
[1] For overviews of combinational material research, see: R.F. Service, Science 277, 474
(1997). B. Jandeleit, D. J. Schaefer, T. S. Powers, H.W. Turner and W. H Weinberg,
Angew. Chem. Int. Ed. 38, 2494 (1999). R.A. Potyrailo, E. J. Amis (eds.), High-
Throughput-Analysis, Kluwer Academic New York 2003
[2] J. N. Cawse (ed.), Experimental Design for Combinatorial and High Throughput
Materials Development, John Wiley & Sons, New Jersey, 2003
[3] E.g. the software packages JMP® (SAS Institute Inc.), STATISTICA® (StatSoft® Inc.),
Design Expert® (Statease®), MODDE® (Umetrics®), and others
[4] H. Bach, Ch. Gürtler, S. Nowak, European Coatings Journal 03, 22 (2004)
[5] H. Bach, Ch. Gürtler, S. Nowak, Farbe &Lack, 108, 30 (2002)
[6] S. Nowak et al., Increasing Efficiency in Coatings Development Using High- Through-
put-Testing, talk given at ACHEMA 2006, May 18 (2006)
[7] Test method for optimizing film forming polymers, PCT Int. Appl. WO 02/42745 A2
20020530, (2002)
[8] T. Engbert, E. König, E. Jürgens, Farbe&Lack, 7/1996, 51, (1996)
[9] Defined in ANSI/SBS 1-2004, 3-2004, 4-2004

300 Occupational hygiene in the manufacture and processing
10 Occupational hygiene in the

manufacture and processing
of polyurethane coatings and
adhesives
10.1 Occupational health and safety

10.1.1 Monomeric and polymeric isocyanates
Generally speaking, polyisocyanate coating and adhesive raw materials are prod-
ucts of higher molecular weight manufactured by polyaddition or polymerization
reactions from low molecular weight monomeric diisocyanates. These starting
materials are toluene diisocyanate (TDI), 1,6-diisocyanatohexane (hexamethylene
diisocyanate, HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate
(MDI) and 4,4’-dicyclohexylmethane diisocyanate (H12MDI).
In contrast to the non-volatile polyisocyanates they are used to manufacture, all these
compounds have a measurable vapor pressure. With its particularly low vapor pres-
sure, diphenylmethane diisocyanate (MDI) and the group of products based upon it
occupy a special position in terms of occupational safety, which is why their process-
ing will be discussed separately. Table 10.1 shows the vapor pressure and other
physical data of the monomeric diisocyanates named above. On account of the health
risks ascribed to monomeric diisocyanates, efforts are made during manufacture to
ensure the lowest possible residual monomer content in the polyisocyanates for
coatings and adhesives. This applies particularly to products based on TDI, HDI and
IPDI because of the relatively high volatility of these monomers.
The vapors of these diisocyanates have an irritant effect on the eyes, nose, throat
and respiratory tract. Depending on the concentration and the duration of exposure,
a hypersensitivity (sensitization) to diisocyanates may result. On renewed exposure
to diisocyanates, this may trigger breathing difficulties of varying severity or even
asthma-like attacks (isocyanate asthma), the latter even at diisocyanate concentra-
tions far below the occupational health exposure limits.
Prolonged exposure of the skin usually results in tanning and irritant effects. Skin
sensitization and the occurrence of allergic symptoms (reddening of the skin,
swelling, inflammation) are also possible, especially in the case of cycloaliphatic
diisocyanates.

Starting material Type Molecular Boiling point Melting Vapor pressure Saturation con-
weight [°C/mbar] point at 25 °C [mbar] centration at 25 °C
[°C] [ppm] [mg/m3]
Toluene diiso- aromatic 174.1 252 – 254/1,013 < 14 2.5 x 10-2 24.3 176
cyanate, TDI (isomer
mixture)
1,6-Hexamethylene aliphatic 168.2 255/1,013 -67 1.4 x 10-2 13.6 95
diisocyanate, HDI 112/7
Isophorone diiso- cycloaliphatic 222.3 158/13 approx. -60 1.2 x 10-3 1.2 10.8
cyanate, IPDI
4,4’-Diphenylmeth- aromatic 250.3 > 350/1,013 39–43 < 1 x 10-5 < 0.01 < 0.1
Occupational health and safety
ane diisocyanate,
MDI
4,4’-Dicyclohexyl- cycloaliphatic 262.4 Decomp./1,013 approx. 25 2.1 x 10-5 0.02 0.23
Table 10.1: Physical data of monomeric diisocyanates
methane diisocya-
nate, H12MDI
301
24.10.2007 17:36:52 Uhr

10.1.1.1 Labeling
Labeling of a substance is composed of the hazard symbol and numbered phrases,
referred to as risk phrases, which draw attention to the hazard potential inherent in
a substance that requires labeling. There are also safety phrases which indicate ways
of avoiding these risks and suitable preventive measures.
The monomeric diisocyanates HDI, IPDI, H12MDI, TDI and MDI are listed in
Annex I of EU Directive 67/548/EEC (Dangerous Substances Directive) [1]. They
are thus subject to standardized mandatory classification and labeling EU-wide.
Changes to the classification of Annex I substances are possible via an ATP (Adap-
tation to Technical Progress), if required by new scientific findings or as the result
of politically motivated reevaluations. Adaptations to directives are published in
the Official Journal of the European Union. They enter into force shortly after their
publication but require adoption into the national legislation of the member states
within the time limits defined in the Directives.
This caveat also applies to all the labeling requirements, exposure limits and regu-
lations mentioned below, which can change due to new toxicological evaluations,
amendments to the laws or the adoption of new EU Directives. Directive 67/548/
EEC (as at 2006, including the 29th ATP) classifies TDI as very toxic (hazard
symbol: T+, skull and crossbones), HDI, H12MDI as toxic (hazard symbol: T, skull
and crossbones), IPDI as toxic (hazard symbol: T, skull and crossbones) and dan-
gerous to the environment (hazard symbol: N, tree and fish) and MDI as harmful
(hazard symbol: Xn, St. Andrew’s cross).
All the above listed diisocyanates are labeled the same with respect to their irritant
effects (R 36/37/38: Irritating to eyes, respiratory system and skin). Moreover, atten-
tion must be drawn to the risk of sensitization. The phrases “May cause sensitization
by inhalation” (R 42) and “May cause sensitization by skin contact” (R 43) are used
for this purpose. In the case of IPDI and TDI, there are differences in the classifica-
tion with respect to the acute inhalation toxicity and risks to the environment. The
requirement in force since 1998 to indicate the carcinogenic potential of TDI (R 40:
“Limited evidence of a carcinogenic effect”) is not based on new toxicological find-
ings. Instead, the positive results obtained some years ago in feeding studies that
were controversial in terms of their quality and conclusive value are now weighted
more heavily than the negative findings of more recent inhalation studies.
In February 2007 the EU Technical Progress Committee (TPC) approved the pro-
posed labeling changes of the 30th ATP to Directive 67/548/EEC. Accordingly, like
TDI, MDI will also carry the phrase R 40. The hazard symbol remains unchanged
as Xn. The labeling change is not based on any new toxicological findings but
results on purely formal grounds with reference to the now 13–year-old study
results carried out with an artificially produced MDI aerosol (see Chapter 10.1.3.5).

Occupational health and safety 303
However, the reclassification will not lead to changes in occupational health and
safety measures from those that are already good practice today. According to
industry association information, the amended directive is scheduled to be imple-
mented in June 2009.
Besides the labeling of the diisocyanates, Directive 67/548/EEC also specifies sub-
stance-specific concentration limits for labeling preparations that contain diiso-
cyanate.
Polyisocyanate products are classified analogously to preparations in accordance
with the provisions of the Directive 1999/45/EEC (Dangerous Preparations Direc-
tive) [2]. Thus, polyisocyanate products based on the aliphatic diisocyanates HDI,
IPDI and H12MDI, are labeled as harmful with the hazard symbol Xn if the residual
monomer content is above 0.5 %. In the case of preparations containing polyiso-
cyanate products based on the aromatic diisocyanates TDI and MDI, this labeling
is required above a residual monomer content of only 0.1 %. If results are available
from tests on polyisocyanate products, then these are to be regarded as more sig-
nificant than the conventional calculation method and are to be preferred for clas-
sification of the product. In principle, labeling with the phrase R 42 is required for
all isocyanates, even for polymeric isocyanates, unless there are indications that a
substance of this type does not cause any sensitization of the respiratory system.
Phrase R 43 must be applied if there are positive results from animal testing.
Authorities increasingly use the maximization test according to Magnusson and
Kligman [3] as the basis for the classification and labeling of substances and prepa-
rations with respect to their potential skin-sensitizing effect. In this special animal
test, aliphatic polyisocyanate products based on hexamethylene diisocyanate or
isophorone diisocyanate reveal slight skin-sensitizing potential, even when the
residual monomer content is below the threshold of 0.5 %. If no other labeling
requirement applies (e.g. Xn, harmful), such products are labeled with the hazard
symbol Xi and the hazard designation “irritant” as well as with the phrase (R 43)
“May cause sensitization by skin contact”.
In accordance with the requirements of the Preparations Directive 1999/45/EC, the
containers of all polyisocyanate coating and adhesive raw materials that contain
isocyanate groups must be specially labeled with the phrases “Contains isocyanates.
See information supplied by the manufacturer”. This requires the user to procure
all available safety information pertaining to the product to inform himself of the
risks that may be associated with the use of the product and what precautions to
take to minimize these risks. To this end, manufacturers provide safety data sheets,
product information sheets and, if appropriate, instructions for use.
To provide the user with fast information, the European Council of the Paint, Printing
Inks and Artists’ Colours Industry (CEPE) has developed the following text for label-
ing containers holding coating products containing isocyanate groups: “Contains

isocyanates. Hardeners and ready-to-use coatings may irritate the skin and respiratory
tract and cause sensitization and allergic reactions. Ensure constant ventilation with
fresh air during and also after handling the product. Do not inhale the vapors. Respi-
ratory protection must be worn when spraying. People with allergies and with respi-
ratory diseases should not be allowed to work with these coating materials.”
At the moment, the labeling regulations for chemicals differ widely around the
world. With the introduction of the Globally Harmonized System of Classification
and Labelling of Chemicals (GHS), it can be expected that labeling will be harmo-
nized in the medium term.
10.1.1.2 Exposure limits
The European Union and its member states define maximum workplace exposure
limits for harmful gases, vapors and, increasingly, also for substances that form
dust. Such a limit gives the maximum permissible concentration of a substance in
ppm (milliliters of gas or vapor per cubic meter of air) or, in the case of suspended
particles, in mg/m³ which, in the light of available knowledge, does not constitute
a health risk or unreasonable burden during long-term work with the product, even
for many years, based on an average eight-hour working day. The exact definition
of the exposure limit can vary from country to country. In addition to the eight-hour
limit, there are also short-term exposure limits, which restrict the maximum expo-
sure levels, for example, in discontinuous processes.
Many European states have specified workplace exposure limits for monomeric
diisocyanates. A common exposure limit is 0.005 ppm (5 ppb). Sometimes, how-
ever, there are deviations from this. Due to the diverse molecular weights of the
diisocyanates, individual concentration thresholds resulted despite uniform expo-
sure limits in ppm, which are expressed in mg/m3 (see Table 10.2).
Notwithstanding the specification of individual substance-dependent air exposure
limits, some states have decided to specify an exposure limit for a generic isocya-
nates group. This exposure limit is based on the concentration of NCO groups in
the workplace air. A typical value is 0.02 mg/m3 NCO.
Table 10.2: Typical air exposure limits for diisocyanates
Diisocyanate Air exposure limit
ppm mg/m³
Toluene diisocyanate 0.005 0.035
Hexamethylene diisocyanate 0.005 0.035
Isophorone diisocyanate 0.005 0.046
4,4’-Dicyclohexylmethane diisocyanate 0.005 0.054
4,4’-Diphenylmethane diisocyanate 0.005 0.05

Air exposure limits are valid only for individual substances but not for mixtures of
substances, as are usually found when working with polyurethane coating systems.
It is possible to make only a very limited assessment of the health effects of such
mixtures of substances based solely on the air exposure limits for the individual
components. Measurements of the concentration of monomeric diisocyanate in the
air during brush application of two-component polyurethane systems under stan-
dard working conditions either yield no values at all or, at most, values well below
the exposure limit. However, measurements of the concentrations of individual
hazardous substances in the air at the workplace – including solvents if present in
elevated concentrations – can serve only to check that levels are within the indi-
vidual air exposure limits; they cannot provide any indication of possible interac-
tions between the various substances in their effect on humans, e.g. synergisms.
Recently, what is referred to as the evaluation index was introduced to assess the
workplace situation. This sets the measured concentrations of the individual hazard-
ous substances in the air at the workplace in relation to their respective exposure
limits. This index (IEL) is defined as the sum of the quotients calculated from the
measured air concentrations (C) of the individual substances and the corresponding
exposure limits (EL) – in Germany, the workplace exposure limits (AGW, Arbeits
platzgrenzwert). This is expressed by the formula shown in Figure 10.1.
Of course, this evaluation index is only a rough basis for the assessment of the work-
place situation as it, too, represents a purely additive approach. It is unable to take
any potential synergisms or antagonisms between individual substances into account.
Therefore, if ventilation and extraction are inadequate to reduce the concentrations
of all the volatile substances to a harmless level, respiratory protection should
always be worn.
Apart from the solvents present and the minimal content of residual monomers,
the higher molecular weight polyisocyanates have no measurable vapor pressure,
i.e. during all processing steps – apart from spray application – the workplace air
concentration will contain no more than traces of monomeric diisocyanates (and
volatile solvents).
Due to the very low vapor pressure of polyisocyanates, so far no air exposure
limits have been established for individual polyisocyanates. However, during
spray application, even low volatile polyisocyanates are released into the air at
the workplace. In the past, many manu-
facturers of polyisocyanates therefore
recommended keeping a guide value of
0.5 mg/m3 polyisocyanate.
The generic approach for specifying
workplace exposure limits via the con-
centration of NCO groups can also be Figure 10.1: Evaluation index

extended to polyisocyanates. However, this method only inadequately takes into

account the significant differences in the toxicological properties of high molecular
weight polyisocyanate oligomers and polymers on the one hand compared with, on
the other hand, those of monomeric diisocyanates. A possible consequence is an
unjust overestimation of the risk of exposure to polyisocyanates.
For this reason, in 2002 Germany decided to take a differentiated approach with
the Technical Rules for Hazardous Substances (TRGS) 430 “Isocyanates – Expo-
sure and Monitoring” [4]. Based on the results of acute or subchronic inhalation
studies, the manufacturer or importer of a polyisocyanate assigns the substance an
exposure assessment value (EBW, Expositionsbeurteilungswert). This is to be pub-
lished in the safety data sheet of the polyisocyanate product in question. If the EBW
has neither been determined nor published in the safety data sheet, then it is auto-
matically replaced by the workplace exposure limit for the monomeric diisocyanate
on which the polyisocyanate is based.
10.1.1.3 Isocyanate analysis
Derivatization methods are primarily used to determine the isocyanate concentra-
tion in the air at the workplace. In these methods, a suitable reagent, generally an
amine, is used to convert the isocyanate into a stable derivative that can be identi-
fied and quantified by means of chromatography. The trapping reagent is present
as a solution either in a wash bottle (impinger) or on impregnated glass fiber filters.
Several commonly used methods are listed below:
• Toluene diisocyanate, hexamethylene diisocyanate, DFG method no. 2 – impin-
ger (solution of N-4-nitrobenzyl-N-n-propylamine hydrochloride (nitro reagent)
in toluene) or glass fiber filter, coated with N-4-nitrobenzyl-N-n-propylamine
hydrochloride (nitro reagent) [5]
• Polyisocyanates based on aliphatic diisocyanates, DFG method no.1– glass fiber
filter, coated with N-4-nitrobenzyl-N-n-propylamine hydrochloride (nitro reagent) [6]
Polyisocyanates based on aromatic diisocyanates, DFG method no. 2 – glass fiber
filter, coated with N-4-nitrobenzyl-N-n-propylamine hydrochloride (nitro reagent)[7]
OSHA42 – glass fiber filter, coated with 1-(2-pyridyl) piperazine (1-2PP) [8]
OSHA 47 – glass fiber filter, coated with 1-(2-pyridyl) piperazine (1-2PP) [9]
The derivatized isocyanates are separated by chromatography (HPLC) and quan-
tified photometrically
In addition to the cited methods, there are also modifications, e.g. using different
trapping reagents. Various portable and stationary equipment is available for the
continuous monitoring of isocyanates in the air. These all work on the principle of
the colorimetric evaluation of a color generated on a paper strip. These types of
instruments are simple to use and do not require specially trained analysts. They
yield rapid results and are therefore particularly suitable for identifying leaks and
in emergency situations. However, they are not suitable for measuring aerosols and

are often not recognized for workplace measurements performed to determine con-
formity with legal requirements.
Provided that the appropriate expertise is available, measurements using trapping
reagent methods deliver reliable results for assessing the exposure situation in the
workplace down to levels of less than 0.5 ppb.
In Germany, measuring laboratories are accredited to perform workplace analyses
to meet the requirements of the hazardous substance law according to Article 9
Para. 6 of the German Ordinance on Hazardous Substances (GefStoffV) [10] by the
country’s Agency for the Accreditation of Measuring and Testing Installations
(DAR) [11]. Accreditation for measuring laboratories is voluntary. However, the
employer who commissions a measuring laboratory can assume that the results
determined by this measuring laboratory are correct if the measuring laboratory is
accredited as described here. On the European and international levels, the Multi-
lateral Recognition Agreement (MLA) of the European Coooperation for Accredi-
tation (EA) [12] supports the mutual recognition of accreditations of inspection
bodies and the certification of personnel in all MLA signatory countries.
10.1.2 Coreactants for polyisocyanates
The standard coreactants for polyisocyanate resins are polyols such as polyester or
polyether polyols that may be solvent-free, dissolved in the solvents commonly
used in coatings or supplied in the form of an aqueous dispersion. As a rule, these
products are largely harmless from an industrial hygiene standpoint. The classifica-
tion, packaging and labeling of these products are governed Europe-wide by the
relevant EU Directives, in Germany by the German Ordinance on Hazardous Sub-
stances and by the relevant legislation of other countries.
10.1.3 Processing of polyurethane coatings
10.1.3.1 General protective measures
Independently of whether national legislations require an assessment of the work-
place and documentation of the results, each workplace should be investigated and
assessed in terms of present or potential hazards to the skin and respiratory tract.
Valuable guidance for individual activities in this regard is offered by the catalog of
exposure scenarios [13] contained in the Technical Rules on Hazardous Substances
(TRGS) 430 “Isocyanates – Exposure and Monitoring” [4]. However, this catalog is
by no means suitable for replacing the necessary isocyanate exposure measurements.
The suitability of the various options for ensuring the best possible respiratory
protection depends on the object. In accordance with EU Directive 98/24/EC [14],
the employer has the obligation to ensure that the risk to the health and safety of
the employee from a hazardous chemical substance is eliminated or reduced to the
minimum. The directive specifies a ranking of the protective measures. The use of
individual protective equipment should only be mandatory if other measures such as

the appropriate design of the workplace, extraction and ventilation are not sufficient
to protect employees from contact with hazardous substances. It goes without saying
that operations such as spray coating, where excessive ventilation would go counter
to the aims of the process, cannot be performed without wearing personal protective
equipment. In such cases an exceptional regulation specifically applies.
The conditions governing the suitability of the individual safety measures and types
of equipment are described in the information provided by the manufacturers of
respiratory equipment.
In addition, the following requirements must be observed when handling reactive
polyurethane coating materials:
• As well as observing the general safety measures for coatings application, it must
be ensured that people with allergies – especially asthmatics – and those who
suffer from bronchial catarrh or other, particularly chronic respiratory diseases
are not involved in work that might additionally impair their respiratory function.
People with allergies must not be exposed to reactive polyurethane coatings. If
there are doubts as to the suitability of an individual to work with these coatings,
a medical examination must be required. If there are any problems, a physician
must be consulted.
• In the event of coughing, pressure in the chest or asthma-like symptoms during or
after work with the coatings, avoid any further exposure and consult a physician.
• The wearing of safety goggles is strongly recommended. If, nevertheless, the
spray mist gets into the eyes, rinse immediately with plenty of water and then
consult a physician.
• Skin complaints are not an occupational hygiene problem when working with
polyurethane coatings. However, careful cleaning of the skin is recommended. The
application of a barrier cream before starting work will allow the easy removal of
paint spatters with soap and water. Strong solvents are unsuitable for cleaning the
skin as they remove the natural moisture and may cause adverse skin reactions.
• To avoid exposure to solvents, freshly coated objects should be left to dry in
well-ventilated rooms.
• When baking thermally curing polyurethane coatings, the gases from the baking
oven must be extracted to prevent the build-up of harmful vapors in the work
area. If necessary, the exhaust gases from the oven must be scrubbed in accor-
dance with the air pollution control regulations (e.g. [15]).
Suitable respiratory protection includes filter masks, half-masks with replaceable
filter cartridges and air-fed hoods. It should be borne in mind that a filter mask pro-
vides protection for only a limited period, depending on the concentration of harmful
substances in the air. It has also been found that a filter for organic vapors does not
provide adequate protection against aerosols (spray mist) containing isocyanate [16].

It must be combined with a particle filter,

or a combination filter providing both
functions should be used.
The wearing of suitable overalls closed
at the neck and wrists and gloves is also
recommended. This should prevent skin
contact with the coating products. Suit-
able materials for gloves as well as first-
aid measures are described in the mate-
rial safety data sheets for the individual Figure 10.2: Protective measures during
spray coating
products (see Figure 10.2).
10.1.3.2 Spray application
When spraying two-component polyurethane coating and adhesive systems, a number
of hazardous circumstances must be considered. Firstly, the volatile components such
as the solvents and the small amount of residual monomers are present in much higher
concentrations in the air at the workplace, e.g. the spray booth in a body shop, than
is possible as a result of simple evaporation. In addition, the non-volatile components
such as the polyol, the polyisocyanate hardener, pigments, extenders and auxiliaries,
are distributed finely in the air in the form of an aerosol (spray mist). Depending on
the spraying conditions, a more or less large proportion of the coating droplets are
smaller than the threshold particle size of 7 μm assumed for lung penetration ( [17] and
the annually published air exposure limit list [18]).
In response to the fact that respirable aerosols, i.e. those that can penetrate the
alveoli of the lungs, and even inert fine dusts represent a health hazard, general
exposure limits have been defined for inhalable and respirable dusts respectively.
Table 10.3 (page 310) summarizes the air exposure limits for some common solvents
as well as the dust exposure limits. Because of the varying limits in the individual
European states, the table gives ranges of the limiting values for the workplace for
individual substances.
In the assessment of hazard potential, inhalable and respirable particles are ranked
high above solvents such as xylene and alkyl benzenes that are classified as harmful.
The hazard to spray applicators from solvents and spray mists is common to all coat-
ing systems, including the classic formulations. Polyurethane coatings present an
additional potential hazard in the form of the residual monomeric isocyanate in the
coating and the polymeric isocyanate with the as yet unreacted isocyanate groups.
Even in the case of modern waterborne coatings, the inhalation of the spray mist
presents a risk, although this is generally not due to solvents. Waterborne two-com-
ponent reactive systems, recently introduced to the market, must also be treated with
caution in respect of the risk of inhaling monomeric and polymeric isocyanates. This

Table 10.3: Air exposure limits for solvents and dusts (2006)
Substance Limit value [mg/m3]
Xylene 110–440
Ethylbenzene 220–440
C3-Alkyl benzene (cumene) 88–440
Ethyl acetate 525–1,400
Butyl acetate 480–960
2-Butoxyethanol 50–125
Methoxypropyl acetate 275
Methyl isobutyl ketone 83–410
General dust exposure limits
Breathable dust 10
Alveolar dust 3
means that personal safety measures must not be ignored, even when spray-applying
waterborne systems. Studies in rats of the subacute and subchronic inhalation toxic-
ity of polyisocyanate resins based on hexamethylene diisocyanate [19] showed that
aerosol concentrations of 3 to 4 mg/m3 of these substances were tolerated without
harm for both three and up to thirteen weeks (exposure for more than six hours per
day, five days per week). It was observed that much higher concentrations caused
an increase in lung weight and nonspecific inflammatory changes to the respiratory
tract. The latter are attributed to the primary irritant potential of the products. There
was no evidence of other organ damage.
Due to the many different components in spray mists, it is not yet possible to quan-
tify the concentrations of spray mists that may be harmful to man. It is therefore
essential to require the best possible protection against the inhalation of spray mists.
This requirement applies not only to spray mists of two-component polyurethane
coatings. It should also be made for all spray mists derived from coatings, even if
the hazard potential of the different coating systems varies.
10.1.3.3 Waterborne one-component and two-component reactive systems
It has already been stated that the novel waterborne reactive polyurethane systems
should be treated no differently from solventborne systems in terms of occupational
hygiene. Even though the risk presented by solvents has been eliminated or at least
minimized (most waterborne coating systems contain a small amount – usually just
a few percent – of a co-solvent), monomeric and polymeric diisocyanates present
the risk here, in the same way as they do in organic media. It is wrong to think that
there is no need to wear respiratory protection during spray application, just because
a waterborne system is being used.

10.1.3.4 Baking urethane resins

A special type of polyurethane coating system contains a baking urethane resin as
the hardener. This is a polyisocyanate resin with blocked isocyanate groups. These
resins should not be viewed as polyisocyanates. They are inert and non-reactive
resins at room temperature.
The isocyanate groups are blocked by reacting them with a blocking agent. This is
a monofunctional compound that contains a reactive hydrogen atom in the molecule
and reacts with isocyanates, e.g. ε-caprolactam, butanone oxime or diethyl malo-
nate. The resins can be combined with suitable coreactants to formulate baking
coatings with good storage stability. It is also possible to produce true one-compo-
nent baking coating resins with good storage stability. These are resins that contain
both hydroxyl groups and blocked isocyanate groups in the same molecule.
During thermal curing of such coating systems, e.g. coil coatings, industrial baking
coatings and automotive primer surfacers and stone-chip primer surfacers, at least
some of the blocking agent is released. It should be considered that traces of the
monomeric diisocyanate on which the product is based may be found in the gases
emitted from the baking oven. This must be borne in mind both in terms of occupa-
tional hygiene and air pollution control. As stated earlier, the gases should be extracted
to prevent a build-up of hazardous substances in the air in the workplace near the
oven that might endanger workers there. Conformity with emissions control legisla-
tion must be ensured by an adequate air supply to the oven and the implementation
of any necessary waste gas purification measures, e.g. incineration or absorption.
10.1.3.5 Special aspects of processing MDI-based products
Products based on diphenylmethane diisocyanate and its homologues, e.g. poly-
meric MDI or MDI prepolymers, occupy a special position in terms of application
technology and occupational hygiene. On the one hand, they usually contain much
higher concentrations of monomeric diphenylmethane diisocyanate. On the other
hand, the vapor pressure of this monomeric MDI is several orders of magnitude
lower than that of standard monomeric diisocyanates. MDI-based products are
normally applied without the use of solvents. Spray application usually employs
two-component metering units and airless spray equipment.
A lifelong inhalation study in rats with polymeric diphenylmethane diisocyanate
was performed over a period of two years [20] and indicated possible carcinogenic
potential. As a result of this, 4,4’-MDI and technical MDI (polymeric MDI, diphe-
nylmethane diisocyanate, isomers and homologues) in the form of inhalable aero-
sols (A-fraction) were classified as category 3 carcinogens (suspected carcinogens)
in TRGS 905 “List of carcinogenic, mutagenic or teratogenic substances” [21]. The
basis of this classification is a study in which artificial conditions had to be used in
order to yield adequate effect concentrations because of the low volatility of MDI.

The tests were therefore performed with an artificially produced aerosol that in
comparison with aerosols typically found in practice had a) a high MDI concentra-
tion (6 mg/m3) and b) a high fraction of inhalable particles (aerodynamic diameter:
95 % of the particles <5 µm).
The focus of animal testing and observations in humans still rests on the irritant
and sensitizing effects of MDI vapors and/or aerosols on the respiratory tract and
lungs. Medical knowledge at present shows that:
• a deterioration in lung function and the induction of respiratory tract sensiti-
zation is observed primarily when a concentration of 0.2 mg MDI/m³ (vapors,
aerosols) is exceeded
• if a maximum exposure limit of 0.1 mg MDI/m³ (vapors, aerosols) is not excee-
ded, such effects occur no more frequently than in unexposed control subjects
• if an exposure limit of 0.05 mg MDI/m³ (vapors) at the workplace is generally
observed, there is no increased incidence in respiratory complaints in people
with otherwise normal lung function, even if these people have worked in this
environment for ten years or more
During the course of the long-term inhalation study in rats described above, lung
tumors were found in the group exposed to the highest concentration (6 mg/m³).
These were linked to the massive exposure that also caused severe chronic irritation
of the respiratory tract and lungs of rats with partly degenerative and inflammatory
changes and the accumulation of yellowish deposits in the lung tissue. These obser-
vations allowed the conclusion that, in this case, the tumors were caused by the
irritant effect resulting from the deliberately high concentration used.
Humans would be unable to tolerate such high aerosol concentrations. Experience
shows that they would rapidly develop massive sensitization and would be forced
to avoid any further exposure. It is therefore highly unlikely for humans to be
exposed to such concentrations over a prolonged period. The classification of MDI
in the form of its inhalable aerosols as a category 3 carcinogen therefore has no
further consequences for the health of people who work with these products, pro-
vided MDI and products containing MDI are handled properly and the air exposure
limits are observed. The vapor pressure of MDI at room temperature is less than
10-5 mbar. On account of this very low vapor pressure, only negligible amounts of
MDI vapors are released into the environment during normal application of MDI-
based products or polyol/hardener formulations containing these products by roller
coating, brushing or curtain coating, even on large surfaces, or during application
in the form of knifing fillers or joint sealants. As a result, no hazardous concentra-
tions are likely to form in work areas. Workplace monitoring during the application
of coatings containing MDI also shows that, under these conditions and provided
there is minimal air circulation, the concentrations of MDI in the air will be below
the air exposure limit.

Nevertheless, special care should be exercised in monitoring the MDI concentration

and ventilation at the workplace. Particularly when spraying formulations contain-
ing MDI and when working at elevated temperatures (e.g. exposure to sunlight,
coating of heated surfaces, hot spraying , baking of coated surfaces, melt reservoirs
for hot melts), the occupational safety measures described above, such as specific
ventilation, workplace extraction, etc., must be implemented in the workplace.
Under the conditions described, MDI aerosols are formed mechanically (spray
mists) or by recondensation of MDI vapors that are supersaturated at room tem-
perature. Their concentration may significantly exceed the air exposure limit of
0.05 mg/m³. At elevated application temperatures, the vapor pressure and saturation
concentration of MDI increase considerably. If vapor extraction is inadequate, the
air exposure limit will be exceeded. If necessary, concentrations in the air must be
monitored by analysis to ensure that the air exposure limit is not exceeded and that
it is not possible to inhale MDI in the form of inhalable aerosols.
If the MDI concentration in the air exceeds the exposure limit, there is a risk of
irritation through inhalation and of sensitization. The respiratory organs must there-
fore be protected, if necessary by wearing a respirator . Particular attention is drawn
to the following list of operations, processes and sources that may cause the forma-
tion of MDI aerosols in concentrations above the air exposure limit (there is no
claim that this list is exhaustive):
• Filling containers
• Discharge under pressure from tank cars into storage tanks
• Venting of machine tanks
• Melting and transfer of pure melted MDI
• Flushing with compressed air of mixheads and machine components that
convey MDI
• Hot spraying, coating of large surfaces at elevated temperatures
• Open impregnating and coating processes (wire enameling, etc.)
• Hair-line cracks in and defective seals on pipelines, flexible pressure hoses and
connectors
Soiled equipment should be cleaned immediately after use as residues harden
quickly. They then become insoluble and stick fast to the equipment. The best way
to remove cured residues is by a mechanical process such as sandblasting. The use
of a paint stripping torch, a common practice up to now, is not recommended since
this results in the formation of toxic gases.
10.1.4 Disposal of polyisocyanate residues and cleaning

of soiled containers
Polyisocyanate residues are best disposed of at an industrial incineration facility.
If possible, the incineration temperature should be above 1,000 °C. Adequate dwell

Table 10.4: Preparation for the neutralization of polyisocyanate residues

A) Mixture of Parts by weight
Water 88
Soda (Na2CO3) 10
Detergent 2
B) Mixture of Parts by weight
Water 90
Conc. ammonia 8
Detergent 2
C) Mixture of Parts by weight
Industrial alcohol 50
(ethanol, isopropanol or butanol)
Water 45
Conc. ammonia 5
Mixture B reacts faster than Mixture A, but should only be used with adequate ventilation present due to the
ammonia content (TLV). Mixture C is flammable and must be stored and handled in explosion-proof rooms.
times and air excess must be ensured. Water vapor must not be used in the incin-
erator feed. The preparations shown in Table 10.4 are suitable for neutralizing
polyisocyanate residues.
Prolonged exposure of the polyisocyanate to these mixtures results in the formation
of insoluble solid polyureas that have no physiological effect. Complete reaction
of the diisocyanate residues with the neutralizing solution can be ensured by occa-
sionally shaking or rolling the containers over a period of about 48 hours. The
aqueous ammonia solutions can be used several times. Their pH value should not
be higher than 8. The generally stringent wastewater regulations of local and
regional authorities must be observed. The resulting polyurea can be incinerated.
Used containers are rinsed with one of the mixtures described in Table 10.4 and
then scrapped. In many countries a return system for certain used containers has
now been set up by the chemical industry. Spilled product should be taken up with
a non-flammable absorbent mineral material. In an emergency, sand, soil or bearing
in mind the fire hazard, sawdust or chippings may be used. The material is then
disposed of in an incineration facility. Any residues remaining on the floor can be
treated with one of the above described mixtures and removed.
10.2 Consumer protection aspects

10.2.1 Polyurethane coatings and indoor air quality
Repeated experience over many years confirms that properly formulated and cured
polyurethane coatings from polyurethane coating and adhesive raw materials yield

Consumer protection aspects 315
no harmful or hazardous emissions after evaporation of the commonly used solvents

e.g. [22, 23]. Thus, for example, in the comment on the specification of German reference
values for indoor air quality in reference to diisocyanates it is stated: “The working
group did not consider establishment of a guide value for diisocyanates (DI) useful,
for despite initial higher concentrations in the air during application of paints and
adhesives containing diisocyanates (concentrations within the MAK range), they
quickly decrease and long-term exposure is not likely after hardening.” [24]
Waterborne polyurethane coating systems – whether aqueous preparations of
reacted polyurethanes or waterborne two-component reactive coatings – still often
contain higher boiling solvents as flow promoters to control film formation. Exam-
ples of such additives include ethers of diethylene glycol, 1,3-butane diol or 1,4-
butane diol and N-methyl pyrrolidone. Their boiling points are much higher than
those of the solvents normally used in coatings, which is why they may be emitted
from the coating over a prolonged period. However, at most only trace concentra-
tions occur that can be easily eliminated by regular ventilation.
Rarely a hazard but occasionally a nuisance, odor problems may occur when fatty-
acid-modified polyester resins (alkyd resins) are used as the polyol components in
two-component reactive systems. These problems can be attributed to the presence
of free fatty acids in the resins or to their oxidative degradation (becoming rancid).
The only form of prevention is careful selection of the raw materials and quality
control. More details can be found in the specialist literature e.g. [25, 26]. Polyurethane
coatings – both one- and two-component systems as well as reacted polyurethane
preparations – have proved themselves over many years as decorative and protec-
tive finishes for applications where they must also be physiologically harmless, for
example, for toys, hospital furnishings and drinking water containers.
10.2.2 Do-it-yourself and polyurethanes

The German Ordinance on Hazardous Substances [10] and the Chemicals Prohibition
Ordinance [27], and at the EU level, the Marketing and Use Directive 76/769/EEC [28],
not only protect industrial applicators but also private users of coatings and adhesives.
This is achieved, on the one hand, by labeling end products as to potential hazards
associated with a coating. On the other hand, the Chemicals Prohibition Ordinance
imposes restrictions on the sale of highly toxic and toxic substances and of substances
that are classified as carcinogenic, mutagenic or toxic to reproduction.
There are as yet no restrictions on the use of specific substances in the coatings
sector. Nevertheless, it is not recommended that coatings containing isocyanate
groups (one- and two-component reactive coatings) be sold for use by nonprofes-
sionals. This applies particularly to sprayable products in one- or two-component
aerosol cans. The unsuitability of this supply form cannot be emphasized enough
since the observance of the necessary safety precautions by do-it-yourself workers

cannot be guaranteed. Especially in the case of spray coatings, do-it-yourself work-

ers who are not familiar with the specific risks of handling reactive polyurethane
coatings are jeopardizing their health. In the context of product liability legislation,
this can have serious consequences for manufacturers. Thus, the companies repre-
sented in the European Aliphatic Isocyanate Producers Association (ALIPA) [29]
explicitly exclude the do-it-yourself application of aliphatic di- and polyisocya-
nates. These products are not do-it-yourself materials. They should only be handled
by qualified professional or industrial applicators who have the required knowledge
and access to the necessary personal safety equipment. The one-component poly-
urethane sealants and in-situ foams that have been available on the home worker
market for many years are a different matter. If the manufacturers’ instructions are
followed, they represent no risk in terms of occupational hygiene when used in the
do-it-yourself applications.
As of August 2006, discussions have been taking place at the EU Commission level
on whether products containing MDI are at all suitable for end user applications due
to the potential health risks involved. The implication is that end users typically do
not properly handle and are careless with such products. The relevant industry sectors
are in contact with the EU Commission to find a solution to this problem. In contrast
to the above-mentioned reactive polyurethane systems, polyurethane dispersions are
increasingly used in DIY coating systems that dry physically or by oxidation.
10.2.3 Relevant legal provisions covering raw materials for coatings

and adhesives in contact with foodstuffs
In order to protect the consumer, the use of materials in contact with foodstuffs is
increasingly regulated by specific legal provisions.
Europe
The desire for binding European Union legislation covering food-contact applica-
tions was tackled in the 1980s. In 1989 the Council of Ministers passed the frame-
work directive 89/109/EEC [30] concerning materials and articles that are intended
to come into contact with foodstuffs. The principle underpinning this legislation
is that articles in the finished state must not transfer to foodstuffs any constituents
harmful to human health. This framework directive was replaced a few years ago by
the more precisely worded Regulation (EC) 1935/2004. This also places no specific
requirements on individual product groups, but only formulates general principles.
Declarations of conformity according to Article 16 of Regulation (EC) 1935/2004
are issued for products that come into contact with foodstuffs.
Directives 90/128/EEC and 2002/72/EC
The basic framework directive covering all materials was soon supplemented spe-
cifically for plastics with Directive 90/128/EEC [31] (also called the Plastics Direc-
tive) that covers materials and articles made of plastic which come into contact

with foodstuffs. Subsequently, the provisions of this directive replaced national

regulations, in so far as they existed. In Germany, Directive 90/128/EEC was
converted into the Ordinance on Articles for Contact with Foodstuffs [32] and
thereby adopted as German law. The Plastics Directive also includes detailed
positive lists of permitted monomers and additives (for the latter, national excep-
tions remain valid). These positive lists are regularly updated by modifying direc-
tives. Moreover, the Directive specifies migration limits for the transfer of con-
stituents to the foodstuff. Besides a general migration limit (the sum of all the
migratable substances) of 60 mg/kg, the positive list also contains specific migra-
tion limits for many substances. Conformity with these migration limits must be
proven by analytical testing.
Directive 90/128/EEC and its modifying directives were consolidated and sum-
marized by Directive 2002/72/EC. This has also already been adapted several
times to reflect technical advances (at present the 4th adaptation with Directive
2007/19/EC).
It should be noted that Directive 2002/72/EC deliberately does not cover some
plastic subgroups. An extension of the Directive to coatings or adhesives has not
yet occurred at EU level. Nevertheless, the influence of the Directive goes beyond
its actual area in that, in the evaluation of coatings and adhesives, queries are fre-
quently made as to whether a polymer raw material conforms with the positive lists
of Directive 2002/72/EC.
European Council Resolutions AP (96)5 and AP (2004)1
The European Council (a supranational body without jurisdiction) passed Resolu-
tion AP (96)5 in 1996 in respect of coatings that are intended to come into contact
with foodstuffs and updated it with the Resolution AP (2004)1 in 2004. The Euro-
pean Council resolution also contains inventories of monomers and additives. These
are similar to the positive lists of the EU Plastics Directive but also differ from
them in part. European Council resolutions are only recommendations and are not
legally binding. Nevertheless, they constitute a supranational body of rules aligned
with the specific needs of coatings.
Germany
In Germany, the responsible federal authorities (first the Federal Health Office,
BGA; later the Federal Institute for the Protection of Consumer Health and Vet-
erinary Medicine, BgVV; and since 1999 the Federal Institute for Risk Evaluation,
BfR) established a Plastics Commission some 50 years ago to advise the authorities
on drafting individual recommendations [33] for specific applications in the field of
food handling and processing. These recommendations contained lists of starting
materials and auxiliaries as well as requirements in respect of the migration of
constituents from a defined surface into foodstuffs.

At present, there is no general recommendation for coatings. The adhesive sector

is specially covered by BfR recommendation XXVIII (Crosslinked polyurethanes
as adhesive layers for packaging materials for foodstuffs).
USA
In the USA, the issue of contact with foodstuffs is the responsibility of the Food
and Drug Administration (FDA). The relevant legal provisions are contained in the
Code of Federal Regulations (CFR, Title 21, Parts 170–199). The FDA regulations
are structured completely differently from EU legislation and cover a great number
of individual application areas and product groups. Therefore it is not surprising
that significant discrepancies sometimes exist between US and EU regulations.
For adhesives, Article 175.105 Adhesives is applicable. Some polyurethanes comply
with this article. In contrast, Article 175.300 Coatings does not mention di- or poly-
isocyanates, with the result that polyurethanes are not permitted in the context of
these paragraphs. Article 177.1680 Polyurethane Resins allows polyurethane sur-
faces to only come in contact with dry commodities with oil- and fat-free surfaces,
e.g. cereals.
In addition to a listing in the relevant FDA paragraphs, individual products in the
USA can receive permission for use in food contact through the instrument of Food
Contact Notification (FCN).
10.2.4 Polyurethane coatings and drinking water
All industrial nations regulate the contact of drinking water with synthetic materi-
als or coatings by guidelines of varying stringency, coupled with legislation aimed
at safeguarding water purity. In the European Union there is at present no binding
regulation in force for plastics in contact with drinking water, with the result that
each product must be evaluated and approved in each country. However, the EU is
working on a European Acceptance System (EAS) for construction products that
come into contact with drinking water, which in the medium term is intended to
harmonize the regulations for drinking water contact across the EU.
In Germany, the responsible federal authorities first published recommendations
drafted by the Plastics Commission for individual plastics in regard to their use in
contact with drinking water (referred to as the KTW Recommendations [34]) in 1977.
This work was terminated in 1987. In addition to lists of permitted additives and
auxiliaries, these recommendations contain basic requirements for the plastic arti-
cles that come into contact with drinking water.
For the transition period up to the enforcement of the European recognition system,
Germany’s Federal Environmental Agency recommends the further application of
the KTW Recommendations for all components of the water supply system for
which no special guidelines have been published by the Federal Environmental

Agency. So far, guidelines published by the agency include an Epoxy Resin Guide-
line [35]. This guideline is not a rule of law and is therefore non-binding. It represents
today’s state of scientific and industrial knowledge of the conditions, according to
which materials and substances made of epoxy resins for the preparation and dis-
tribution of water for human consumption comply with the requirements of Article
17 Para. 1 of the Drinking Water Ordinance of 2001.
Until now, there has been no specific drinking water recommendation for polyure-
thanes. In addition to the basic requirements cited above, it is also important to
ensure compliance with the requirements contained in the BfR Foodstuffs Recom-
mendation XXXIX (Polyurethanes). Special attention should be given to ensuring
that no aromatic amines are detectable. Polyurethane based coatings are approved
for use in various countries and are being used increasingly, particularly in the
rehabilitation of drinking water pipes.
10.2.5 Behavior of polyurethane coatings in the event of fire

Polyurethane coatings are organic materials that contain carbon, hydrogen, oxygen
and, depending on their chemical character, also nitrogen. Other elements are brought
into the coating system through the use of pigments, additives and auxiliaries. Such
materials are inherently combustible. However, fire testing of multicoat polyurethane
systems on mineral substrates has led to their classification as hardly inflammable
(fire class B1) to non-combustible (fire class A2) in accordance with DIN 4102.
When carbon compounds burn or smolder, they form carbon dioxide, water and,
depending on their composition and the fire conditions (e.g. temperature and avail-
ability of oxygen), varying amounts of carbon monoxide, hydrocarbons, lower and
higher aldehydes and ketones, and soot-like decomposition products.
Products that contain nitrogen, including polyurethanes but also other natural and
synthetic materials such as leather and textiles, e.g. wool and polyamide, also
generate volatile nitrogen compounds such as ammonia, nitrogen oxide, nitriles
and, at temperatures of 800 to 1,000 °C, hydrogen cyanide (prussic acid). The latter
is a highly endothermic compound whose formation, like that of carbon monoxide,
is promoted by high temperatures.
Polyurethanes have also been observed to release traces of diisocyanates or of
unknown isocyanate-like compounds. This reaction starts at around 250 °C and
reaches its peak at 400 to 600 °C, i.e. at temperatures that are characteristic for a
smoldering fire.
This behavior is common to all products that contain nitrogen, including natural
products, and also coatings based on acid-curing alkyd resins with melamine or urea
formaldehyde resins as the crosslinkers and coatings based on amine-cured epoxy
resins. In a real fire situation, the type and concentration of harmful combustion

products depend on the prevailing conditions. These can only be simulated to a

certain extent in laboratory tests. For example, the lack of oxygen in a smoldering
fire favors the formation of hydrogen cyanide, provided the fire temperature is high
enough. However, being a combustible carbon compound, it will continue to burn
in fully developed fire conditions in the presence of oxygen.
The main risk factor presented by the combustion gases of all organic materials is
carbon monoxide. In a fire situation, it is always present in toxic concentrations.
It is therefore urgently recommended that fire-fighters wear self-contained breath-
ing apparatus.
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mit Trinkwasser vom 14.10.2005

Solvent emissions 323
11 Ecology
Paints and organic coatings are generally used to ensure the effective protection
of a substrate against corrosion, deterioration and mechanical damage. In this way,
they contribute to prolonging the service life of consumer goods, including vehi-
cles, industrial plant and buildings in particular. They thus help to preserve
resources. The latter also pertains to adhesives, which, in contrast to other joining
technologies such as welding or soldering, were the first to provide a method for
permanently joining even non-metallic substrates and the most disparate substrate
combinations. However, some unavoidable environmental impact does occur
during the life cycle of a coating or adhesive – from its manufacture through
application up to the recycling or disposal of the coated or glued object. This
impact and the strategies and legislative regulations for its control, reduction and
avoidance are largely independent of the chemistry of the binders or base polymers
used in the coating or adhesive. The information given here is largely general in
nature, and is not limited to polyurethanes.
11.1 Solvent emissions

On March 11, 1999, comprehensive regulations took effect in the European Union
aimed at reducing solvent and other organic emissions (VOC: volatile organic com-
pounds) from coating processes as well as from related applications such as adhe-
sives, printing inks and surface cleaning agents. This EU Guideline (1999/13/EC) [1],
also referred to as the Solvent Emissions Directive, governs the reduction of solvent
emissions from industrial coating processes. These regulations apply primarily to
the application, but also to the manufacture of coatings and adhesives. Moreover, the
original version of 1999/13/EC initially also covered automotive refinishing. Over
the course of the following years, this EU Guideline was adopted into the national
laws of the various EU countries. Most of the EU countries adopted 1999/13/EC
without further changes, while in some countries (for example Germany, the Neth-
erlands, Austria), the limit values introduced differed or were stricter.
In the initial step, all industrial processors of coatings and related products must
prepare a solvent balance sheet (Solvent Management Plan) showing the annual
quantities of volatile organic compounds used and the proportion thereof that is
emitted. Each of the national implementations of 1999/13/EC contains a table with
the limit values for various coating application areas in terms of the total amounts
of the volatile organic compounds used. A facility is considered to comply with
1999/13/EC if the annual usage (irrespective of the actual emission levels) is below
this limit value. All facilities that use amounts of volatile organic compounds above
this limit value are now required to reduce their usage. While new facilities must

324 Ecology
already observe the requirements of this guideline, existing facilities have an

extended deadline of October 31, 2007 at the latest.
Depending upon the respective national implementation of 1999/13/EC, there are
now several ways of fulfilling these requirements. The simplest option, especially
for smaller facilities, is to reduce the amount of volatile organic compounds used
(primarily solvents) to the extent that they are below the applicable limit values.
This can be achieved increased use of low-emitting coating and adhesive systems
such as waterborne, powder, UV-curing or high solid coatings and adhesives.
The second option is described in what is referred to as the Reduction Plan. This
defines total target emissions depending on the area of application and the size of
the facility, the sum total of which may not be exceeded. Some countries (e.g.
Germany, Slovenia and Austria) also have a simplified reduction plan for individual
applications (furniture finishes, metal and plastics coatings, adhesives, textile coat-
ings and printing inks) that specifies the exclusive use of systems with a maximum
VOC content measured in percent or in g/L. The third option for complying with
1999/13/EC is referred to as the Limit Plan. This is primarily for facilities that use
a very large amount of solvents or volatile organic compounds. Depending again
on the field of application and the size of the facility, the emission quantities are
defined in terms of mg of organic carbon per cubic centimeter of waste air, or per
square meter of coated or glued surface. Each facility is free to choose whether to
comply with the limit values through the use of low-emitting coatings such as
waterborne, powder, UV-curing or high solid coatings or adhesives, or for example
by use of a thermal waste air incineration unit.
Due to the variety of options offered to coatings processors by 1999/13/EC, generally
valid target values with respect to the VOC content of such products cannot be
defined without additional detail. In many cases, it makes sense to change over to
products with an extremely low VOC content, such as powder, UV-curing and water-
borne coating or adhesive systems. In other cases, the solution may be to slightly
reduce the solvent content of a coating or adhesive to give a high solid system.
Conventional powder coatings can only be applied to substrates of limited dimen-
sions (the size of the baking oven) that are not temperature sensitive (no wood or
plastic). Only flat substrates can be coated with (conventional) UV-curing systems.
Both technologies require a significant investment in application equipment. In many
cases, waterborne coatings or adhesives represent the simplest options for signifi-
cantly reducing VOC use. Particularly in the area of high-quality coatings and adhe-
sives, waterborne coatings and adhesives based on one-component polyurethane
dispersions (physical drying, crosslinking by oxidation or UV-curing), or aqueous
two-component coatings and adhesives represent the state of the art in many EU
countries. Depending on the area of application or the size of the facility, high solid
two-component polyurethane coatings are also used on high-value substrates.

Activity (threshold **Thresh- Emission Limit values for Limit values for Special provisions
values for the old value limits for diffuse emissions total emissions

use of solvent in (threshold exhaust (in % of the sol-
tons/year) value for gases vent used)
solvent [mg C/m3]
New Exist- New Exist-
use in
adhesive applications
facility ing facility ing

tons/year)
facility facility
Shoe manufactur- 25 g per pair The limit values for total emissions
ing (> 5) are given in grams of emitted
solvent for each completed pair
of shoes.
Wood and plastic 30 g/m2

lamination (> 5)
Solvent emissions
(1)
Adhesive coatings 5–15 50 (1) 25 When techniques that enable
(1)
(> 5) > 15 50 20 the reuse of recovered solvents
are used, the emission limit value
Table 11.1: Limit values for the maximum VOC content for various
for exhaust gases is 150.
Manufacture 100–1000 150 5 5 % of the The limit value for diffuse emis-
of coatings, solvent used sions does not include solvents
clearcoats, printing > 1000 150 3 3 % of the that are part of the coating
inks and adhesives solvent used material purchased in a sealed
(>100) container.
325
24.10.2007 17:37:01 Uhr

326 Ecology
Table 11.2: Limit values for the maximum VOC content of coatings [2]
Product subcategory Type Phase I Phase II
[g/l (*)] [g/l (*)]
(from (from
Jan. 1, 2007) Jan. 1, 2010)
a Interior matt walls and ceilings Wb 75 30
(Gloss < 25 @ 60°) Sb 400 30
b Interior glossy walls and ceilings Wb 150 100
(Gloss > 25 @ 60°) Sb 400 100
c Exterior walls of mineral Wb 75 40
substrate Sb 450 430
d Interior/exterior trim and cladding Wb 150 130
paints for wood and metal Sb 400 300
e Interior/exterior trim varnishes and Wb 150 130
woodstairs, including opaque wood- Sb 500 400
stairs
f interior/exterior minimal build wood- Wb 150 130
stairs Sb 700 700
g Primer Wb 50 30
Sb 450 350
h Binding primer Wb 50 30
Sb 750 750
i One-pack performance coatings Wb 140 140
Sb 600 500
j Two-pack reactive performance coat- Wb 140 140
ings for specific end use such as floors Sb 550 500
k Multi-colored coatings Wb 150 100
Sb 400 100
l Decorative effect coatings Wb 300 200
Sb 500 200
(*) g/l, ready to use
(Wb) Waterborne coatings, the viscosity of which is adjusted with water
(Sb) Solventborne coatings, the viscosity of which is adjusted with solvent

Solvent emissions 327
Details about low-VOC coatings for use in various applications can be found in the
sections covering automotive finishes, wood and furniture finishes, plastic coatings,
commercial vehicle finishes, general industrial coatings, and coatings for cans, coils
and glass, etc. Table 11.1 (Page 325) lists various applications and their total emis-
sion values or solvent limit values for solventborne adhesives.
Shoe manufacturers that presented an emission reduction plan by a certain date
were permitted a total emission value of 37.5 g per pair of shoes (corresponding to
1.5 times the target emission value) until October 31, 2005. They too must achieve
the target emission of 25 g by October 31, 2007.
The so-called Decopaint Directive (2004/42/EC) [2] came into force in 2004, and had
the goal of reducing organic emissions from architectural and DIY paints and coat-
ings. Due to the special conditions for automotive refinishing, which does not con-
stitute an industrial process, the regulations concerning automotive refinishing were
included in 2004/42/EC and deleted from the current version of 1999/13/EC.
The deadline for adopting 2004/42/EC into national legislation ended on Octo-
ber 30, 2005. In contrast to 1999/13/EC, which provides the processor or user with
a certain amount of freedom in selecting the products used to achieve the target
emissions, 2004/42/EC already covers the manufacture. Products that exceed the
VOC limit values can no longer be marketed once the deadline has elapsed. More-
over, the two guidelines define the term “VOC” differently. 1999/13/EC defines
VOC in terms of the vapor pressure of the compound, while 2004/42/EC uses the
boiling point. However, the national implementations of 2004/42/EC are uniform
in their definitions and limit values throughout the European Union.
2004/42/EC defined different product subcategories and VOC limit values for the
different architectural coatings as at January 1, 2007, with stricter definitions to
come into effect on January 1, 2010 (Table 11.2). Thus, in all the categories, a further
differentiation is made between aqueous and nonaqueous systems, and respective
limit values are given (in g/l VOC).
These guidelines primarily pertain to all products that are used on site as coatings
for buildings. In addition, 2004/42/EC may apply to the industrial coating of con-
struction components (made of wood or metal), e.g. ready-to-lay parquet flooring,
window frames, doors, beams, steel girders, facade elements, etc., for example, if
VOC consumption at the application facility is below the limit value set by
1999/13/EC. In this case, even if it complies with 1999/13/EC, the coating material
must now also fulfill the specifications of 2004/42/EC. According to 2004/42/EC,
from January 1, 2007, a coating material manufacturer must identify all products
used to coat buildings and for automotive refinishing with:
• the product subcategory
• the VOC content in g/L at the application viscosity

328 Ecology
Table 11.3 lists the technologies that can be used to ensure compliance with the
Decopaint Guideline 2004/42/EC in the areas of wood and metal coatings for the
construction sector.
For the automotive refinishing sector, 2004/42/EC contains a separate list with limit
values (in g/L VOC) for each individual coat (surfacer, primer, basecoat and clearcoat)
used in automotive refinishing, as well as for specialty products. In contrast to the
Table 11.3: Suitable technologies for implementing Guideline 2004/42/EC

Subcategory Application Waterborne Solventborne
d, e, i
One-compo- DIY/wood seal- one-component –

nent systems ers PAC dispersions
one-component
PUD
Joinery one-component –
PAC dispersions
one-component
PUD
High-grade two-component poly- one-component
joinery urethane (OH acrylate) polyurethane mc
Parquet flooring one-component PUD one-component
polyurethane mc
High-grade two-component PUD one-component
parquet flooring polyurethane mc
Metal primer one-component PUD one-component
coats (FA-modified) polyurethane mc
Metal topcoats one-component PUD High solid two-compo-
(FA-modified) nent polyurethane
j
Two-compo- Joinery two-component poly- -

nent systems urethane (OH acrylate)
Parquet flooring two-component PUD High solid two-compo-
(FA-modified) nent polyurethane
Metal two-component poly- High solid two-compo-
urethane (OH acrylate) nent polyurethane
Floor coatings two-component poly- Full solid two-compo-
urethane (OH acrylate) nent polyurethane
PAC: polyacrylate, PUD: Polyurethane dispersion, FA: fatty acid, : moisture-curing
mc

Waste products 329
two-stage reduction for architectural coatings, a single-stage reduction was defined

for the automotive refinishing sector, which came into effect on January 1, 2007 (see
also Table 5.18, page 160). With the exception of the waterborne basecoats (based
on polyurethane/polyacrylate dispersion combinations), the current trend here is
clearly in the direction of two-component high solid polyurethane systems.
11.2 Waste products
Much of the waste that occurs in the manufacture and application of coatings is in
the form of two industry-specific types of waste: paint slurries (for example, solid
and liquid adhesive residues) and contaminated solvents. The latter result from the
many rinsing and cleaning procedures involved in coatings application. Paint slur-
ries occur primarily during the spray application of coatings and adhesives. They
result from overspray – the coating that misses the object being sprayed. As a rule,
this overspray is captured in the washing water in the spray booth and is precipitated
by the addition of coagulants.
Recycling and disposal
A large number of legislative requirements must be observed in the recycling and
disposal of waste products. Despite the ongoing European harmonization process,
these requirements still differ from country to country. The basis of waste legisla-
tion in Germany is the Cycle Management and Waste Act. The primary approach
is the avoidance of waste in the first place, with material or energy recycling as
the secondary approach.
In principle, energy recycling is viewed as equal to material recycling, provided
certain requirements are satisfied. For example, a calorific value of 11 MJ/kg or more
and an incineration efficiency of 75 % or more are required. Only if recycling is
technically impossible or economically unfeasible can wastes be disposed of in a
manner that is environmentally compatible.
Waste types are classified by a uniform European system referred to as the European
Waste Code. Certain types of waste products are thus classified as hazardous on the
basis of their properties, and are subject to special monitoring. Designation as hazard-
ous waste entails expensive disposal methods. These wastes can only be disposed of
at specific sites and special levies are normally imposed. Waste products from the
coatings and adhesives sector that require special monitoring include in particular
solvents, old solventborne coatings and adhesives and residues containing solvents.
Polyurethane systems are not specifically mentioned in these regulations.
In the past, most paint slurries and adhesive residues were deposited in landfills.
In Germany, this option is no longer available, since both the hazardous waste
(TA-Abfall) and municipal waste (TA-Siedlungsabfall) regulations ban the land-
filling of waste with a loss on ignition of more than ten percent and more than five
percent, respectively. Thermal recycling will therefore be the technology of choice

330 Ecology
for unavoidable paint slurries and adhesive residues, provided the requirements
(see above) can be satisfied. Paint slurries and adhesive residues that cannot be
recycled must be disposed of in incinerators. Many contaminated solvents are
treated by redistillation and reused in other applications. If this is not possible
because of the nature of the contaminated solvents, they must be used in thermal
recycling or disposed of by incineration.
For economic reasons alone, the priority given to waste avoidance in German
legislation is a generally accepted goal. It is therefore a worthwhile exercise for
coatings and adhesives users to explore all options for systematically avoiding the
production of waste. Among these are various high-efficiency application tech-
niques such as dipping, curtain coating, airless spraying, HVLP spraying, electro-
static application, etc., which all yield vastly reduced amounts of paint slurry.
11.3 Wastewater
In the coatings and adhesives industries, wastewater results, for example, from
cleaning processes – particularly those associated with the manufacture and appli-
cation of waterborne coatings and adhesives – and from surface pretreatment, dip-
ping, and water-washed spray booths. This process water is polluted to a varying
extent with organic compounds and heavy metals.
The legislative regulations for wastewater are defined nationally, and even often
differ regionally within countries. In Germany, the Water Resources Act regulates
groundwater and surface waters. It also provides the basis for the requirements that
must be satisfied when discharging industrial process water. However, requirements
differ from place to place on account of the sovereignty of the individual federal
states in Germany and the different regulations imposed by the operators of munic-
ipal wastewater treatment plants.
Disposal
In the wastewater segment, too, an avoidance strategy should be pursued, primar-
ily by reducing process water volumes and increasing circuit usage. Unavoidable
wastewater from coating and adhesive lines can usually be purified using conven-
tional technologies (overspray separation, precipitation of heavy metals, coatings
and adhesives) to the extent that the limit values for heavy metals and adsorbable
organic halogen compounds (AOX) are not exceeded.
In contrast, the pollution of wastewater with solvents – measured as the chemical
oxygen demand (COD) – can be problematic. Especially in the case of waterborne
coatings and adhesives, the water-miscible cosolvents used – such as alcohols and
glycol ethers – increase the COD of the washing water in spray booths. Yet these
substances are readily biodegradable, which means that their controlled discharge
into municipal wastewater treatment facilities – generally at a higher price – is

References 331
widely accepted. Where this is not the case, the wastewater can be made suitable
for discharge by means of an on-site or external aerobic or anaerobic biological
pretreatment step. There are also other physical (adsorption, membrane technology)
and chemical (oxidation) processes for degrading organic pollutants.
References
[1] Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of
volatile organic compounds due to the use of organic solvents in certain activities and
installations, OJ L 85, 29.3.1999, 1, http://europa.eu.int/eur-lex/en/search/search_lif.
html
[2] Directive 2004/42EC of European Parliament and of the Council of 21 April 2001 on
the limitation of emissions of volatile organic compounds due to the use of organic
solvents in certain paints and varnishes an vehicle refinishing products and amending
Directive 1999/13/EC, OJ L 143, 30.4.2004, 87–96, http://europa.eu.int/eur-lex/en/
search/search_lif.html

332 Sustainable Development
12 Sustainable Development
The concept of Sustainable Development [1] gained public awareness following the
Earth Summit on Environment and Development in Rio de Janeiro in 1992 and was
addressed in more detail with regard to production and product politics at the World
Summit in Johannesburg in 2002. This concept strives for a balance between dis-
charge into the environment, the use of resources and socio-economic concerns.
However, implementation requires consensus – often difficult in practice – concern-
ing the minimization of the negative impact on humans and the environment.
Programs
The chemical industry has acknowledged its responsibility for sustainable future
development and has undertaken to follow the principles of Responsible Care in
its activities worldwide. Supplementary to this, the coatings industry has developed
its own special “Coatings Care” Program [2, 3]. The German coatings industry asso-
ciation has published its own guidelines that contain binding undertakings for its
members. These undertakings include, for example:
• according particular consideration to the preservation of resources and low
environmental impact in product development
• considering the recycling and subsequent disposal of coated objects at the product
design stage
• making efforts to reduce emissions and wastes in the manufacture of products
The German adhesive industry association (Industrieverband Klebstoffe e.V.) has
also formulated analogous guidelines [4].
Perspectives
In the future, the coatings industry will continue to be measured by its implemen-
tation of these undertakings. The need for ecological optimization of coatings and
coating processes in the context of Sustainable Development has been implemented
to a great extent by raw material manufacturers, coatings producers and users.
Through its own voluntary initiative, the industry has already set itself on course
to sustainably reduce environmental impact.
The industry is increasingly confronted with stricter controls on the manufacturing
and use of chemicals. The new European chemical legislation REACH (Registra-
tion, Evaluation, Authorisation of Chemicals) which came into force in 2007 is of
particular importance in this respect. The objective of REACH is to further improve
consumer safety and environmental protection and is supported by all stakeholders.
However, the industry has criticized the complexity, high costs and enormous

References 333
administrative effort associated with the new legislation. In the coming years,
manufacturers and users of chemicals will face many challenges that can only be
surmounted together. The coating, adhesive and sealant industry will have to adjust
to this and adapt its development programs accordingly. The polyurethane chemi-
cal industry will remain their partner in innovation for the future.
References
[1] http://www.un.org/esa/sustdev/
[2] http://www.coatingscare.org/
[3] http://www.cepe.org/
[4] http://www.klebstoffe.com

334 General references
13 General references
The priority year is given for all patents cited in the literature references at the end
of each chapter.
Bibliography
• G. Fettis, Automotive Paints and Coatings. VCH Verlagsgesellschaft mbH,
Weinheim 1995
• A. Goldschmidt, H.-J. Streitberger: BASF Handbook on Basics of Coating
Technology: Vincentz Network, 2nd Edition, Hannover 2007
• Kittel, Lehrbuch der Lacke und Beschichtungen, Hirzel S. Verlag 2004
• P. Nanetti, Coatings from A to Z, Vincentz Network, Hannover 2006
• G. Oertel, Kunststoff-Handbuch, G. W. Becker, D. Braun (Hrsg.), 3. Auflage,
Band 7: Polyurethane. Carl Hanser Verlag, München, Wien 1993
• D. Stoye, W. Freitag, Paints, Coatings and Solvents. Wiley-VCH, Weinheim 1998.
• Brock, Groteklaes, Mischke, European Coatings Handbook, Vincentz Network,
Hannover 2000

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C M Y CM MY CY CMY K

Index 337
Index
Symbole B
α-Nylon 31 bactericide 264
ε-Caprolactam 37, 39 baking gases 311
1,2,4-triazole 42 balcony sealing 231, 233
1,2-propanediol 47, 49 banned chemicals directive 315
1,3-Bis(isocyanatomethyl)cyclohexan 27 barite 129, 249
3,5-Dimethylpyrazole 39, 40, 41, 149, basecoat 41, 127, 128, 130, 138, 155, 161,
298 162, 166, 185, 187, 188, 225, 226, 328
3-(cyclohexylamino)-1-propanesulfonic BEBA 39, 41, 42
acid (CAPS) 44 bis-(4-isocyanatocyclohexyl)methan
3-Isocyanatomethyl-3,5,5-trimethylcy- (H12MDI) 26
clohexyl-isocyanat 26 bisoxazolidine 229
4-Isocyanatomethyl-1,8-diisocyanatooc- biuret 29, 30, 95, 187, 188
tan 28 blister formation 165
blistering 70, 284
A blocking agent 35, 36, 38, 40, 41, 42, 76,
abrasion resistance 80 107, 112, 136, 296, 297, 311
acetone process 54 boiling resistance 258
acid resistance 147 bonding 243, 249, 260
acrylate/melamine system 145 bonding soles 270, 271
activation 184, 185, 266, 268, 272 bookbinding 15, 23, 280
adhesion promoter 139, 271, 287 breaking elongation 205
adhesion to aluminum 254 breathing apparatus 320
adhesive pre-coat 271, 273 burn 319
air exposure limit 309 butane diol 258
airmix method 157 butanone oxime 37ff, 42, 139
Aliphatic Isocyanate Producers Associa-
C
tion (ALIPA) 316
alkoxysilane 254, 284, 286, 287 calendars 272
allophanate 29, 30, 81, 168, 253 can coating 102, 115, 116, 117, 118
amino silane 287 capability for tin plating 135
amino sulfonate 168 caprolactam 38, 42, 76, 77, 120, 139,
anti graffiti 173, 226 298, 311
antioxidants 257, 286 carbamate system 149
aroma protection 254 carbodiimid 31
artificial leather 208 carbon nanotubes 85
asparaginic acid esters 51, 104, 130, 162, car refinish 151ff
164 catalog of exposure scenarios 307
automotive 44, 78, 86, 136 ff, 151ff, 185, catalysis 40, 77, 85, 120, 159, 249, 293,
190, 203, 222, 260, 269, 293 295, 298

338 Index
catalyst 252 Deco Paint Directive 160, 162

catalytic trimerization 33 decorative film 269
cathode protection 133 deep-drawing 111, 117, 215
chain extension 53, 54, 55, 284 DFG method 306
chalk 249, 288 dicyclohexylmethane diisocyanate
chemical resistance resistance 115 (H12MDI) 19, 23, 258, 300
chopped strands 202 DIDP 288
cleaning fastness 273 dethylamin 39
cleaning resistence 205 diethylene glycol/adipic acid 257
clearcoat 138, 162, 166, 171, 173, 185, 187, disopropylamin 37, 39, 42, 298
188, 212, 227, 328 dimerization 33, 77,
slurry 149 dimethyl formamide 207, 208
coagulants 263 dimethylpyrazol (DMP) 37ff, 149, 298
coagulation process 209 DINP 288
coffee 254 diphenylmethane diisocyanate (MDI)
cohesion 257, 258 19, 23, 26, 139, 141, 300
coil coating 65, 108 ff, 311 discoloration 261, 262
cold flexibility 205
dispersion 52ff, 67ff, 82, 98, 106, 142,
combination filter 309
147, 165, 190, 263, 266, 270, 307
compatibility with lubricants 246
dispersion pressure 147
composite adhesion 259
do-it-yourself 62, 97, 315
compression pressures 272
drying 107, 135, 245, 261, 265, 266, 269,
conservation 136, 136
construction applications 215ff 271
consumer goods 317 drying booth 156
Contact Notification (FCN) 318 dual cure 57, 79, 83, 149
copper 135
corona process 118, 185
E
corrosion protection 15, 19, 47, 50, 51, easy-to-clean 86, 120, 226
86, 103, 115, 125 ff, 155 ecology 323, 324, 326, 328, 330
cresol 136 elasticity 287
crosslink density 246, 258 electron beam curing 78, 97
crosslinking density 31, 103, 147, 162, electronic industry 272
164, 249, 286 electronics 23, 136, 285
crosslinking temperature 38, 297 electrophoretic coating (CED) 138
crystallinity 83, 260, 261, 262, 277 electrostatic charge 119
cycle time 150 electrostatic discharge 261
cyclooligomerization 30 elongation at break 122, 323
cyclopentanone-2-carboxymethyl ester emission 122, 167, 278, 323
(CPME) 36ff emulsifiable crosslinking isocyanates
245, 264
D
ester amide 36
DABCO 63 etch resistance 42
Dangerous Materials Act 261 ethandiol 47
DBTA 288 ethyl acetate 260, 262
DBTL 2880 European Cooperative for Accreditation
deblocking temperature 39 (EA) 307

Index 339
evaluation index 305 glycerol 47, 49

event of fire 319 graining 190, 211
explosion dangers 262
exposure evaluation value (EEV) 306 H
exposure limit in the workplace 306 Haftung 202
extraction 308, 311, 313 Haftvermittler 202
extrusion 118, 272, 291 HALS compound 41
hazard symbol 302, 303
F
heat-sealability 254, 259
fabric 16, 205, 209, 268, 273 heat activation 263ff
fat migration 244, 254, 264 heat deformation resistance 274
filler 137, 138, 141, 155, 162, 188, 265 heating tunnel 266
film 212, 258, 269 heat stability 271
filter mask 308 hexamethylene diisocyanate (HDI) 26,
filters 204 31, 43, 81, 93, 95, 99, 103, 112, 118,
final strength 249, 268, 274, 279 139, 162, 168, 213, 214, 218, 232, 248,
fire 262 258, 300, 303
fish eye formation 263 high-throughput testing 293ff
flammability 261 Hot-Tack-Life 261
floor coating 174, 215, 216, 219, 222 hot lamination process 270
foaming 218, 219, 284 household/DIY 23
foam intermediate coating 208 hydriertes Xylylendiisocyanat (H6XDI)
Fogging 190 27
foils 83, 184 hydrocarbon resin 129
food-contact 42 hydrogen bonding 243
Food and Drug Administration (FDA) 318 hydrolysis 54, 246, 263, 264, 266
food packaging 254, 255, 257 hydrolysis resistance 45, 218
food processing 222 hydrophilically modified polyisocya-
foodstuff 117, 316, 317 nates 4ff, 69, 72, 148, 168, 212
furniture 16, 19, 23, 80, 83, 90, 93, 97, hydrophilicity 55
101, 210, 212, 214 hydrophilic modification 44, 52, 69
hydroxyl 28, 112, 129, 247, 249
G hydroxyl polyurethane 259, 260, 261,
gases from the baking oven 308 262, 266, 272, 273
gear pump 75
I
gelation 260, 266
gel time 258 imid 29, 135
German Recycling Economy Law imidazol 39, 41
(KrWAbfG) 329 Iminooxadiazindion 31
glass 16, 200, 213, 220, 254 imitation leather 209
glass coating 50, 200 impact foam method 208
glass fibre sizing 202 impervious to gas 254
glass fiber filter 306 impervious to light 254
globalization 150 impinger 306
gloss retention 47, 120, 121, 145 impregnation 211

340 Index
incineration 313 M
increase in viscosity 264, 279, 280
indoor air quality 314, 315 malonic ester 37ff
marine 86, 125, 129
infrared 101, 266, 274
market analysis 17
inhalation toxicity 302, 310
MDF 83, 91, 214, 269, 271
initial strength 261, 272, 274, 279
MDI prepolymer 128, 284, 311
inline 187, 188, 189
medical technology 290, 291
intermediate coat 127, 129, 130, 226
melt dispersion process 262
ionically-modified polyisocyanates 44 melt viscosity 83, 120, 275
IPDI trimer 43, 151, 270 metal/thermoplastic adhesion 271
isocyanate asthma 300 metal coating 102ff
isocyanate crosslinker 262, 266, 268 metallic coatings 16
Isocyanato polyurethanes 247 Methyl ketone (2-butanone) 260
isocyanato silane 286 micaceous iron ore 128
Isocyanurat 31, 162 migration 85, 259, 317
isocyanurate 162 minimum activation temperature 261, 266
isononylphenol 37 mixed crosslinkers 148
isophorone diisocyanate (IPDI) 15, 19, mixing quality 165
26, 258, 300 modulus of rigidity 286
isophorone diamine 249 moisture 75, 126, 210, 218, 219, 223, 227,
231, 252, 254, 266, 274, 279
J moisture-curing 65
jet spray dispersion 69, 85 monomer separation 33
multilateral 307
K
N
Kenics mixer 71, 146
nanoparticles 147
ketimine 53
nanotechnology 16, 85, 86, 87
knifing filler 154, 155
neutralizing amine 55
L nitrocellulose 17, 152, 153, 211, 213
NMP 98, 135
labeling 302, 303, 307, 315 non-blocking 261
laminate adhesive 204 nonionic emulsifiers 43, 52
lamination 211, 263, 269, 272, 273, 274 nonwoven 209, 272
lamination press 263 nozzle spray dispersion 148
large vehicle coating 51, 174 nylon 76
latently reactive 270, 271
latex substitute 290 O
leather 16, 203ff, 273, 319 ocupational health and safety 300 ff, 301,
legislation 44, 118, 161, 171, 185, 189, 318 303, 305, 307, 309, 311, 313
lightfastness 31, 207 offline 188
light stabilizers 287 offshore 125, 126
low-monomer NCO prepolymers 248, one-component baking coatings 105
259, 276 one-component polyurethane
low temperature flexibility 246 –, clearcoats 41, 148
low temperature grinding 272 –, baking coating 36, 42, 105

Index 341
one-sided adhesion 261 polyester 19, 23, 35, 47, 48, 96, 105, 106,
open time 258, 272 110 ff, 122, 136, 142, 167ff, 187, 191,
overbake yellowing 41 203, 206, 220, 225, 246, 307
oxadiazintrione 30 polyester diol 277
oxazolidone 30 polyether 19, 23, 35, 44, 49, 52, 66, 96,
oximcarbamate 30 133, 187, 203, 225ff, 233, 246, 285
polyether allophanate 44, 168
P polyethylene 257
polyethylene oxide polyether alcohols 43
packaging 254, 279, 307
polyethylene terephthalate (PET) 182
pad printing 272
polyhydamtions 135
paper 16, 204, 212ff, 273
polyisocyanate 19, 23, 30ff, 69, 71ff, 94,
parquet 96, 98, 215
103, 128ff, 158ff, 187ff, 218ff, 244ff,
parquet flooring 90
300 ff, 314
part being joined 268, 279
blocked 35ff, 112ff, 117, 146, 295ff, 311
partially crystalline 260, 261 polyisocyanato polyurethane 244, 245,
peel resistance 249 251
PE film 257 plymeric MDI 247
penetration primer 225, 226, 227, 263 polyoxypropylene 285
peroxide 261 polypropylene (ethylene) oxide ether
Phenol 136 polyols 246
phosgenation 25 polypropylene (PP) 182
photocatalysis 86 polystyrene (PS) 182
photopolymerization 57 polyuretdione 122
pigmentation 128 polyurethane based flexible foams 260
pigment wetting 96, 106, 167, 227 polyurethane dispersion adhesives 270
pipe coating 131 polyurethane liquid film 228, 231
pipeline construction 126 polyvinyl chloride (PVC) 182
plasma activation 184 powder clearcoat 149
plastic 78, 83, 108, 121, 181ff, 190, 213, powder coating 76, 115ff, 131
234, 250, 316, 317, 324 powder primer surfacer 143
plastic coating 15, 47, 50, 64, 65, 181ff, precoating 272
214 preparation 210
plasticizer 66, 76, 229, 244, 264, 283, prepolymer 35, 54, 244, 247, 248, 249,
287 274, 275, 284
plastifying temperature 249 primer 91, 128, 155, 156ff, 185, 187, 219,
polyacrylate 46, 55, 69, 95, 157, 167, 220, 222, 233, 234, 328
227, 298, 329 primer surfacers 119, 141ff, 155
polyacrylnitryl butadiene styrene (ABS) print color 212
182 process
polyaddition 57, 80, 128, 244 integrated 150
polyamide 36, 115, 319 processing time (pot life) 65
polyamine 50, 51, 126 process technology 71, 73, 75, 150
Polyaspartic ester 51, 130, 164, 218, 221 product label 42
polybutylene terephthalate (PBT) 182 propylene oxide 49
polycarbonate (PC) 182 potective Coatings 125
polycondensation 47 protective equipment 308

342 Index
Q setting 249, 280

shear stability 262, 265
quartz powder 249 ship building 284
shock activation 267
R
shoe 16, 23, 260
radiation curing 57, 64, 78ff, 97, 100, 174 shrinkage 249
REACH 332 silane-terminated polyurethanes 285ff
reactive adhesives 244, 245, 248, 250, silane-terminated prepolymers (STP) 35
251 silica 249
reactive diluent 49, 50, 51, 65, 78, 80 silicone chemistry 286
reactive hot melts 248, 278 single layer system 143
reactive thinners 151, 162 skin 252, 290, 291, 300, 304, 307
recovery capability 283 slip agent 257
recycling 201, 243, 262 smolder 319
reflow 147, 188 smoldering fire 319, 320
release paper 204, 208, 211, 214 softener 205
residual isocyanate 258 softening temperature 244, 245, 260, 264
resistance to acidity 145 sol-gel 85, 86
resistance to alkali 219 solidification 243
resistance to chemicals 98, 135 solubility 49, 96, 259, 260
resistance to hydrolysis 257, 262 solvent emission 101, 105, 143, 161, 173,
resistance to light 112 191, 262, 323ff
resistance to plasticizers 246, 260 Solvent Emission Directive 118, 160 ff,
resistance to stone chipping 145 323ff
resistance to yellowing 265 sound damping 139, 174
respirator 313 sound insulation 140
restoring forces 263, 269 splinter fracture 185
reverse coating process 211 spray application 115, 119, 151, 156, 165,
rigidity 85 263, 273, 305, 311, 329
rinse program 146 spray gun 65, 71, 75, 76, 146
roll coating 254, 279 spray mist 156, 308ff
roller application 115 static mixers 71, 146, 250
roof sealing 231 steel construction for hydraulic engi-
neering 125ff
S sterilization resistance 117
sandability 98 stiffness 202, 249, 258
scratching under dry conditions 147 stone chip resistance 139, 143, 157
scratch resistance 79, 85, 86, 92, 98, storage stability 36, 71, 83, 96, 120, 128,
144ff, 182, 207, 211, 215 167, 248, 253, 260, 271, 287
sealant 216, 283, 284, 288, 333 strength 254, 257, 259, 260, 262, 280
sealer 221 structural engineering 125, 126, 127, 129,
sealing 92, 96, 98 131
seam sealing 137, 140 surface inhibition 173
sensitization 300, 302, 303, 312, 313 surfacing 328
sensitization of the respiratory system 303 Sustainable Development 6, 332
serigraphy 272 synthetic rubber 262

Index 343
T two-component metering unit 65, 74,

259
T-bend test 112 two-component mixing equipment 157
tack 266, 278 two-component polyurethane
talc 129, 249 –, clearcoats 145, 155, 173, 188
tanning 210, 211 –, waterborne 69, 98, 107, 147, 167
TDI 23, 28, 50, 93, 96, 98, 103, 136, 141,
two-component polyurethane primer
215, 218, 231, 232, 247, 248, 258, 259,
155, 171
270, 283, 300, 302, 303
two-component spray application 71
TDI dimer 270
two-layer 172
temperature index 135
two-layer construction 164
tensile strength 203, 287
two-sided adhesion 261
Tetramethylxylylendiisocyanat
two layer design 185
(TMXDI) 27
textile 174, 203ff, 272 U
textile coating 15, 62, 203ff, 293
textile equipment 210 unblocking temperature 139
textile lamination 273 underbody coating 139ff
thermal print 212 urea 25, 52, 69, 106, 246, 265, 284, 319
thermal stability 262 uretdione 31, 120. 123
thermal yellowing 36, 41 urethane-urea 262
thermoplasticity 171, 224, 259, 262, 272 urethane acrylate 57, 80 ff, 97, 173, 193
thermosetting acrylics 145, 187 urethane bond 147
thickeners 263, 283 Uretonimin 31
thixotropic effect 261 UV-A hand lamps 173
thixotropy 249 UV-curing 57, 80 ff, 97, 101, 149, 173, 193
three-dimensional compression process UV-stability 224
269 UV powder 83
tiglycidylisocyanurate 122 UV protection 85, 86
TMA 264 UV resistance 111
toluene diisocyanate (TDI) 19, 26, 136, UV stability 48
139, 247, 300
top coat 47, 86, 91, 115, 127, 128, 129, 130, V
137, 138, 155, 156, 164, 166, 167, 171,
vapor pressure 247, 278, 300, 305, 311ff,
172, 185, 186, 220, 225, 226, 227
327
transfer method 203
ventilation 308
transport vehicle coating 151ff
very high solid coatings 162
trapping reagent 306
VOC 21, 24, 42, 44, 92, 118, 120, 130, 157,
TRGS 306, 307, 311
160 ff, 185, 189, 270, 323ff
triazol 37
tribo process 118
W
triisocyanatononane (TIN) 26
trimethyl-1,6-diisocyanatohexan 27 wall coating 215
trimethylolpropane 47, 49, 136 wash primer 153ff
TSA coat 145, 188 waste 329
two-component dispersion adhesives wastewater 330
270 water expansion 265

344 Index
water scavenger 219, 287

water vapor permeability 204, 228
wet adhesion process 269
windows 90, 91, 122
wire coating 134, 135
wire enameling 66, 313
wood 16, 19, 47, 50, 65, 83, 90 ff, 214,
249, 324, 327, 328
work garments 203
work safety 262, 278
woven 205
X
xylylendiisocyanat (XDI) 27
Y
yellowing 41, 117
Z
zeolite 249

TdB_Umschlag_Meier Westhues_mit Logo_englisch.qxd 23.10.2007 15:26 Seite 2
Dr. Ulrich Meier-Westhues, born 1955, studied Chemistry European Coatings Tech Files
at the RWTH Aachen, Germany. After four years with
Herberts, Wuppertal, he joined Bayer BU Coatings and
Colorants in 1989. Today he is responsible for Business
Development Polyisocyanates in the Coatings, Adhesives Ulrich Meier-Westhues
and Sealants BU of Bayer MaterialScience, Leverkusen.
Polyurethanes
Coatings, Adhesives and Sealants
Ulrich Meier-Westhues • Polyurethanes

The Mission: Acknowledged experts provide clear,
detailed discussions of the principles behind polyurethanes
and their applications in coatings, adhesives and sealants.
This compendium, aimed at the market, contains everything
that raw materials manufacturers and paint producers need
to know about this leading class of binder.
The Audience: Newcomers to the coatings, adhesives and

sealants industries, technology students, development and
application engineers, and all readers, who have an interest
in and enjoy reading about technological advances.
The Value: Readers will increase their knowledge of current

polyurethane technologies while learning from examples
how to adjust their research and development effectively
and efficiently. This will result in coatings, adhesives and
sealants that satisfy modern applications profiles.
ISBN 3-87870-334-1
ISBN 978-3-87870-334-1

Polyurethanes

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TdB_Umschlag_Meier Westhues_mit Logo_englisch.qxd 23.10.

2007 15:26 Seite 2

Ulrich Meier-Westhues • Polyurethanes

The Audience: Newcomers to the coatings, adhesives and

The Value: Readers will increase their knowledge of current

VIN Meier_eng.indb 1 24.10.2007 17:28:59 Uhr

VIN Meier_eng.indb 3 24.10.2007 17:28:59 Uhr

Bibliographic Information from the German Library

© 2007 Vincentz Network GmbH & Co. KG, Hannover

Please ask for our book catalogue

Layout: Maxbauer & Maxbauer, Hannover

VIN Meier_eng.indb 4 24.10.2007 17:28:59 Uhr

Search, free of charge, for the right raw material

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an introduction to polyurethane chemistry, followed by a discussion of the many

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4.6.2 Binders for radiation curing................................................. 79

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5.3.4 Basecoats and clearcoats..................................................... 143

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5.9.1.2 Examples of applications..................................................... 220

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8 New areas of application for polyurethanes.................... 290

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1.1 Historical aspects

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developments, e.g. nanotechnology, polyurethanes will continue to gain further

1.2 Definition of scope

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2 Economic aspects and

Figure 2.1: World consumption in 2005 of coating raw materials by region,

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2.2 Adhesives and sealants

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Material and regional distribution

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3.1 Di- and triisocyanates

Figure 3.1: Manufacture of isocyanates by phosgenation of primary amines

Figure 3.2: Manufacture of isocyanates via the urea route

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In addition to these, a number of other diisocyanates for the manufacture of coating

Bis-(4-isocyanatocyclohexyl)methane (H12MDI) Bayer MaterialScience:

2,4- and 2,6-Toluene diisocyanate (TDI) Bayer MaterialScience:

Diphenylmethane-4,4’- and/or -2,4’-diisocyanate (MDI) Bayer MaterialScience:

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Table 3.2: Di- and triisocyanate specialties (selection)

Hydrogenated xylylene diisocyanate (H6-XDI) Takeda:

2,2,4- and 2,4,4-Trimethyl-1,6-diisocyanatohexane Degussa:

Tetramethylxylene diisocyanate (TMXDI) [5] Cytec: TMXDI

Triisocyanatononane (TIN) [6] Bayer MaterialScience

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2 Economic aspects and