Jaap Akkerman | Toine Biemans | Cathrin Corten |

Rudolf Hager | Ingrid Heußen | Claas Hövelmann

Joachim Krakehl | Martin Leute | Dirk Mestach |
Oliver Seewald | Adrian Thomas | Jacques Warnon

Resins for Water-borne Coatings

Cover: Vladyslav Bashutskyy, Adobe Stock
 

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Jaap Akkerman, Dirk Mestach et al.
Resins for Water-borne Coatings
Hanover: Vincentz Network, 2021
European Coatings Library
 
© 2021 Vincentz Network GmbH & Co. KG, Hanover
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European Coatings Library

Jaap Akkerman | Toine Biemans | Cathrin Corten |

Rudolf Hager | Ingrid Heußen | Claas Hövelmann
Joachim Krakehl | Martin Leute | Dirk Mestach |
Oliver Seewald | Adrian Thomas | Jacques Warnon

Resins for Water-borne Coatings

Contents
Foreword
1 A brief introduction
2 Water-borne resins and coatings: history, markets and definitions
2.1 History of water-borne coatings and resins
2.1.1 The past
2.1.2 The present: from polymer science to resins
2.1.3 The present: water-borne resins and coatings
2.1.4 The future
2.2 Markets and applications
2.2.1 The market for water-borne coating resins
2.2.2 Coatings market definitions
2.3 Definitions
2.3.1 Definitions of water-borne paints
2.3.2 Definitions of water-borne resins
2.3.3 Volatile Organic Compounds
2.3.4 Polymer dispersion terminologies
2.4 References
3 Polymer dispersions and emulsions
3.1 General introduction
3.2 Preparation of polymer dispersions
3.2.1 Stability of polymer dispersions
3.2.2 Free radical (co)polymerization mechanism
3.2.3 Free radical emulsion (co)polymerization
3.2.4 Raw materials: emulsion polymerization
3.2.5 Process variation and morphology control
3.2.6 Crosslinking of polymer dispersions
3.2.7 Polymer dispersions made by other processes
3.3 Parameters and mechanisms of polymer dispersions
3.3.1 Particle size and particle morphology
3.3.2 Glass transition temperature
3.3.3 Film formation – coalescence
3.3.4 Minimum film formation temperature (MFFT)
3.3.5 Coalescing aids, cosolvents and plasticizers
 3.3.6 Stabilization mechanism
3.3.7 Rheology of polymer dispersions and paints
3.3.8 Guideline formulations and performance
3.4 Coating applications and formulations of polymer dispersions
3.4.1 Paint formulation with polymer dispersion resins
3.4.2 Styrene copolymer dispersions
3.4.3 Styrene acrylic dispersions
3.4.4 Pure acrylic dispersions
3.4.5 Polyvinyl acetate and vinyl acetate copolymer
dispersions
3.4.6 Polybutadiene dispersions
3.4.7 Cationic polymer dispersions
3.5 References
4 Alkyd resins
4.1 Water-soluble alkyds
4.1.1 Molecular structure of the alkyd resins
4.1.2 Cosolvents
4.1.3 Applications
4.1.4 Examples
4.2 Externally emulsified alkyds
4.2.1 Molecular structure of the alkyd resins
4.2.2 Anionic and non-ionic modification
4.2.3 Surfactants
4.2.4 Technology
4.2.5 Emulsification in theory and practice
4.2.6 Applications
4.2.7 Examples
4.3 Internally emulsified alkyds
4.3.1 Anionic and non-ionic modification
4.3.2 Molecular structure
4.3.3 Applications
4.3.4 Examples
4.4 References
5 Epoxy resins
5.1 Historical background
5.2 Basics
5.3 Reaction and crosslinking
 5.4 Epoxy dispersions
5.5 Application
5.6 Trends
5.6.1 Epoxy hybrids
5.6.2 BPA substitutes, biobased epoxy resins
5.6.3 References
6 Polyurethane resins and coatings
6.1 One-component polyurethane coatings
6.1.1 Synthesis of polyurethane dispersions
6.1.2 Raw materials for the production of polyurethane
dispersions
6.1.3 Production process
6.1.4 PUD producers
6.1.5 Applications and formulations of polyurethane
dispersions
6.1.6 Automotive OEM applications/formulations
6.1.7 Industrial wood applications
6.1.8 Architectural: deco/DIY applications/formulations
6.1.9 Automotive plastics applications/formulations
6.1.10 Teletronics – industrial plastics
6.1.11 Vehicle refinishing
6.1.12 Metal applications/formulations
6.2 Two-component polyurethane coatings
6.2.1 Polyols and polyisocyanates
6.2.2 Coating applications of two-component polyurethanes
6.2.3 Coatings formulation with acrylic emulsion resins
6.2.4 Coatings formulation with polyester emulsions
6.3 References
7 Silicone resins
7.1 Silicone chemistry
7.1.1 Structure of silicones
7.1.2 Silicone resins
7.1.3 Silanes, siloxanes and siliconates
7.2 Silicone resin-based binders for coatings
7.2.1 Silicone resin emulsions
7.2.2 Performance profile of a binder
7.3 Other silicone ingredients for water-borne coatings
 7.3.1 Hydrophobic primers
7.3.2 Hydrophobic additives
7.3.3 Special effect additives
7.3.4 Silicone-based pH adjuster
7.4 Silicone resin emulsion paints and plasters
7.4.1 Definition of silicone resin emulsion paintsand plasters
7.4.2 Properties of silicone resin paints and plasters
7.4.3 Ingredients and formulation principles
7.4.4 Selected formulations and properties
7.5 Summary and outlook
7.6 References
8 Alkali silicates
8.1 Historical background
8.2 Chemical compositions
8.3 Molecular structure of water-borne alkali silicates
8.4 Production of alkali silicates
8.5 Water-borne silicates
8.5.1 Classification according to EU Regulations
8.5.2 Sodium silicates
8.5.3 Potassium silicates
8.5.4 Lithium silicates
8.6 Curing or hardening processes of alkali silicates
8.6.1 Dehydration
8.6.2 Reaction with alkali taking substances
8.6.3 Reaction with mineral acids and acidic salts
8.6.4 Reaction by increasing molar ratio
8.6.5 Reaction with CO
8.6.6 Reaction with esters
8.6.7 Gel formation by reaction with polyvalent metal ion
containing compounds or base metals
8.6.8 Reaction with base metal powders
8.6.9 Reaction with the constituents of the substrate (e.g. in
case of wall coatings)
8.6.10 Reaction with water soluble polyvalent metal salts
8.6.11 Reactions with alkaline solutions of salts from
polyvalent amphoteric metals
8.7 Water-borne alkali silicate containing surface coatings
 8.7.1 Silicate emulsion paint
8.8 Organo-silicate paint
8.9 Various applications of soluble silicates
8.10 References
9 Amino resins as hardeners
9.1 Structure of amino resins
9.2 Types and properties of amino resins
9.2.1 Melamine resins
9.3 Combination partners for amino resins
9.3.1 Crosslinking reactions
9.4 Water-borne stoving enamels based on amino resins
9.4.1 Selecting amino resins
9.4.2 Combination resins for water-borne stoving enamels
9.4.3 Hybrid systems
9.4.4 Neutralization agents
9.4.5 Cosolvents for water-borne stoving enamels
9.4.6 Mixing ratios and crosslinking
9.4.7 Acid catalysts
9.4.8 Film properties
9.4.9 Pigmentation
9.4.10 Additives
9.5 Formaldehyde free melamine-based resins
9.6 Formulation examples
9.7 Conclusion and comparison water-borne to solvent-based
stoving enamels
9.8 References
10 REACH and other regulations
10.1 Legislation on volatile organic compounds
10.2 Legislation on chemical substances ‘REACH’ and ‘CLP’
10.3 Conclusions
11 Outlook
Authors
Index
Foreword
There is no doubt that water-borne resins for coatings have
a bright future. The environmental and health related issues
have caused a slow but unstoppable change from solvent-
borne resins and coatings to water-borne. It started slowly
with some pioneering countries in Europe in the 1980s and
became more imbedded in legislation when the solvent
emission directives were introduced in 2007 and 2010. In
the last decade other stricter regulations appeared that in
general led to the increasing preference for water-borne
resins and coatings. In fact, the change can be called a
“solvent-to-water-transition” similar to the “energy
transition” that we are facing to reduce CO2 emission.
Simultaneously the legislation on the Registration,
Evaluation, Authorisation and Restriction of Chemicals
(REACH) highly influenced the resins and coatings market,
not only for water-borne but for all resins and coatings. One
could even say that the water-borne resins and coatings
technologies even suffer more from REACH than solvent-
borne for two simple reasons: water-borne resins and
coatings use far more additives and these additives cannot
easily replaced by alternatives that are not phased out by
REACH.
What are the largest problems to overcome during the
“solvent-to-water-transition” in the coming decennia? We
mention a few but not by necessarily in order of priority.
First there is the overall performance of the water-borne
alternatives for solvent-borne paints. There are more
obvious and more well-developed transitions in, for
instance, joinery and furniture coatings where spraying,
heating, radiation curing, or two-component systems are
currently used with much success. The transition in the
automotive OEM industries is happening as well, but
strongly depends on investments into new production lines
suitable for the use of water-borne coatings. In this market
segment, the conditions are favourable for water-borne
coatings as the application can be controlled easily and
higher temperature curing is often used. In both examples
the performance of water-borne coatings is up to par or
even better.
In other markets such as architectural or vehicle-refinish
coatings, the transition is also happening but is not so
obvious since water-borne coatings have different
performance and not always up to par, when it comes to the
performance.
The second problem is the presence of water in coatings
where conditions such as relative humidity and temperature
affect drying. When it rains outside, coating walls or wood is
not possible and can only be overcome by excluding
outdoor conditions, such as scaffolding with rain cover and a
heater.
The third problem is the pseudoplastic rheology of water-
borne paints especially in architectural paints. This is not
only the case in the can, but also during application,
resulting in poor open time and in the final film formation
leading to limited flow. Water-borne paints often still suffer
from limited flow and gloss and this may lead to inferior
appearance. “Telegraphing” is an often-occurring problem
as this copying the surface roughness is caused by a lack of
change in surface tension as described by Filip Oosterlinck
et al. in Surface Coatings International in 6/2009. For these
reasons, professional painters often still use the alternative
high solids solvent-borne alkyd paints for application and
aesthetic reasons.
The fourth problem is the sustainability of water-borne
resins and paints when compared to solvent-borne types.
Especially, in the choice between water-borne acrylics and
alkyds. The use of renewable raw materials and life cycle
analysis have not clearly steered the resin development in
one clear direction.
The fifth problem with water-borne resins and coatings is the
relatively low solid content leading to the need to apply
more layers. As a consequence, this requires more
application work and also road transport of more paint. And
therefore, this can have a negative influence on the life
cycle analysis.
All these issues will be discussed with the best of our know-
how, however, not always supported by hard evidence.
Resin producers and paint makers know the stodgy reality
where some phenomenon or problems cannot be
understood and only be solved by hard trial and error efforts
with often unexplained solutions (“don’t ask me why but it
works”). The so-called “tacit” know-how is often our day to
day reality. Because of this issue the writing of this book was
a challenge and may lead to disagreement with other
specialists. We absolutely liked this challenge.
If one overlooks the last 40 to 50 years, the “solvent-to-
water-transition” had a large impact of the research and
development budgets of resin and paint companies. A lot, if
not most developments have been done to keep-up with the
evolving legislation.
We wish you a pleasant and instructive reading on behalf of
all co-authors.
Jaap Akkerman and Dirk Mestach
Goes and Bergen op Zoom, The Netherlands, January 2021
1 A brief introduction
The discussion on water-borne resins and their application in
coatings immediately leads to a division in chapters on resin
technologies. This is also the approach in the present book.
Every resin technology is very often specifically used in a
specific application area. Per resin technology the important
application areas are discussed and wherever possible
guidelines for formulation of the paint including starting
point formulations are supplied. Comparison of
performances to the alternative solvent-borne are made and
shortcomings as well as better properties are discussed.
Important for any formulator of paints is to understand the
resin technology he or she is using. For that reason, it is
even important to know how the resins are made including
all chemistry that is used and the physics transforming a
hydrophobic resin into a water-borne resin. If this is not
known, the formulator cannot ask the important and correct
questions to the resin company's technical support staff.
Then the wrong resins or the wrong raw material
components may be used in the paint. Attention is paid to
the must-have information that a paint formulator needs to
receive from the resin technical service people.
In Chapter 2 the history of water-borne resins and coatings
is discussed. The various businesses and their importance in
the market are shown. Next to that the most important
definitions are reviewed critically.
In Chapter 3 water-borne dispersions are discussed.
Important is the definition of dispersion polymers in
comparison with emulsion polymers (discussed in Chapter
6). They use completely different technologies, production
processes and even monomers. The process will influence
for instance the morphology or surface of the dispersed
particle. It is also important to understand that the
dispersed particles, whether in the form of a dispersion or
emulsion, will only lead in a perfect film if coalescence is
possible during the application and drying of the film. The
various chemically based classes of dispersion polymers are
discussed: their chemical composition almost directly will
lead to the application area. It can happen that a
“dispersion” polymer actually proves to be an emulsion
polymer. It is also important to realize that not all resin
suppliers use the same definition. This may lead to incorrect
choice of the resin that you will use to start the
development of a paint formulation.
Chapter 4 focuses on water-borne alkyds. They are divided
into three categories: dissolved, externally emulsified and
internally emulsified alkyds. Each of these will be discussed
in detail, including the demand on the resin properties, the
different requirements and possibilities regarding resin
functionalization and processing technology. Also, recipes
and applications are presented.
In Chapter 5 water-borne epoxies will be reviewed. An
overview of properties and application areas and their
relationship to the structure and crosslinking of epoxy resins
is followed by a summary of emulsification methods for the
preparation of anionic-, cationic- and non-ionic epoxy resin
dispersions. The use of electrophoretic dip coating as the
sole application method for water-borne epoxy resins in the
automotive industry is described. The chapter ends with a
discussion of future trends in the area of water-borne epoxy
resins with an emphasis on the benign replacement of
bisphenol A (BPA) and examples of biobased epoxy resins.
In Chapter 6 water-borne polyurethane (PU) paint
formulations are discussed that use PU dispersions (one and
two-component) or hydroxyl functional emulsion resins that
are cured with polyisocyanate crosslinkers (two component).
PU dispersion resins often have very special applications
and in most cases are used in combination with other resins,
as will be shown in application examples. Attention will be
paid to their various and complex production processes. The
well and broadly used two component hydroxyl functional
emulsion resins cured with polyisocyanates are
subsequently discussed and illustrated with several
guideline formulations in a variety of applications.
In Chapter 7 silicone resins and their use in silicone resin
emulsion paints and plasters are described. The key
features of silicone resin-based coatings are low water
absorption and at the same time high water vapour
permeability. With these physical principles the coatings are
extremely durable and last for decades. Guide formulations
for paints and plasters are presented and the performance
is discussed. Aside of the silicone resins other silicone
components are presented which are used in coatings for
special effects e.g. anti-scratch or easy-clean.
In Chapter 8 soluble silicates and their properties are
discussed. Soluble silicates, also commonly known as water
glass or alkali silicates, are the only type of glasses, which
are soluble in water again. The different production routes
as well as the different structures in solution and types of
water glass are shown, which have an influence on the
chemical properties of the products. By curing, they form
very stable inorganic covalent bonds, which match
especially with inorganic fillers, pigments and substrates.
Different curing methods are presented, as well as the broad
range of different applications where soluble silicates are
the means of choice. Especially in combination with organic
emulsions they show a very high potential for versatile
hybrid coatings.
In Chapter 9 melamine resins as the most important type of
amino resins are presented. Formulations of water-borne
stoving enamels with melamine resins in combination with
alkyds, polyesters and acrylics are discussed and
formulation examples for different applications are given.
In Chapter 10 the REACH situation and other regulations will
be discussed. During the last twenty years several
important regulations have been implemented, which have
had and continue to have a direct impact on the coating
sector in Europe. Among these we may indicate the
European Directives to reduce the emissions of volatile
organic compounds (VOC), the ‘REACH’ regulation for the
control of chemical substances and the European Regulation
on biocidal products. Other topics are currently on European
or national authorities’ agendas, like the nanomaterials, the
emissions of dangerous substances into the indoor air in
buildings and sustainable development.
The closing Chapter 11 will take you through an outlook in
the future. What problems – as described in the foreword –
need to be solved, are there still solvent-borne resins and
what new resin technologies or chemistries will appear on
the horizon.
This book does not cover in detail all the individual coating
raw materials required to produce a good coating. Only if
the coating raw material is essential and specifically critical
in interaction with the resin, it is discussed.
2 Water-borne resins and
coatings: history, markets
and definitions
Jaap Akkerman and Dirk Mestach
This chapter deals with the history of water-borne resins and
its coatings. In order to understand water-borne resins that
are used in the water-borne coating formulations, not only
the history is important, but also the markets and
application areas in these markets.
In order to use the same language, the definitions used in
Europe and the deviating ones used elsewhere are
discussed.

2.1 History of water-borne coatings

and resins
2.1.1 The past
Paint made its earliest appearance about 40,000 years ago.
It was one of the earliest inventions of mankind as it truly
can be traced to the dawn of history, to artefacts from pre-
historic humans, and all cultures. Tribes in Europe, Australia,
and Indonesia painted images of hunters and herders on
cave walls and had expanded their colour palette to include
many colours. Some cave paintings drawn with red or yellow
ochre, hematite, manganese oxide, and charcoal were made
by early Homo sapiens as long as 40,000 years ago [1] .
They used eggs, blood, milk or tree sap as “resins” in order
to improve the adhesion and durability. Water was the only
solvent available at that time. They then applied the paint
with fingers, brushes, or by blowing them through hollow
bones, very much like today’s airbrushes.
Ancient coloured walls at Dendera, one of the best-
preserved temple complexes in Egypt, which were exposed
for years to the elements, still possess their brilliant colour,
as vivid as when they were painted more than 2,300 years
ago. The Egyptians mixed their colours with a binding
substance, such as casein, egg whites, bees wax and
vegetable gums such as Gum Arabic, the hardened sap of
various species of the acacia tree and applied them
separately from each other without any blending or mixing
them. They appear to have used only six basic colours:
white, black, blue, red, yellow, and green. First the area was
covered entirely with white, then the design was traced in
black, leaving out the lights of the ground colour.
The Egyptians continued the advancements and began
painting on fresh lime plaster, where the pigments became
fixed by carbonization and drying of the lime. Greeks and
Romans expanded upon these techniques, to create a
painting style not matched till the Renaissance – when
Italian artists made paint with plant oils to create works of
astonishing colour and depth that still captivate viewers
today. The Greeks also developed lead white paint, which
was the most popular white paint in use until titanium
dioxide replaced it in the nineteenth century. White lead is
the basic lead carbonate, 2PbCO3·Pb(OH)2 [2] and occurs
naturally as a mineral. Lead-based paint has been the
source of health issues for painters and others for centuries.
Before the industrial revolution “whitewash” also known as
calcimine, kalsomine, calsomine, or just lime paint, a type of
paint made from slaked lime (calcium hydroxide, Ca(OH)2 or
chalk calcium carbonate, (CaCO3), was one of the main
paint types used. Whitewash cures through a reaction with
carbon dioxide in the atmosphere to form calcium carbonate
in the form of calcite, a reaction known as carbonization. It
was usually used for exterior applications, however, it has
been also applied for interior applications, for example in
kitchens. Whitewash could be tinted for decorative use
however it can rub off to a small degree [3] . Various
materials were added to the lime to improve the quality of
the coating. Portland cement was added to improve the
durability in harsh environments. Casein, a protein
extracted from milk, was added to improve adhesion and
durability. Actually, the origins of modern water-borne paints
begin with these casein paints.
At the onset of the industrial revolution, in the mid-18th
century, paint was being ground in steam-powered mills,
and an alternative to lead-based pigments had been found
in a white derivative of zinc oxide. Interior house painting
increasingly became the norm as the 19th century
progressed, both for decorative reasons and because the
paint was effective in preventing the walls being affected by
moisture. Linseed oil was also increasingly used as an
inexpensive “resin”. The paint and coatings industry,
however, had to wait for the industrial revolution before it
became a recognized element of the economy.
The first US paint patent dating from 1865 to Flinn (US
50,068), covers a composition based on zinc oxide,
potassium hydroxide, resin, milk and linseed oil. In 1867,
Averill of Ohio patented the first prepared or “ready mixed”
paints in the United States. In the mid-1880s, paint factories
began springing up in populated and industrial centres
across the nation. In 1866, Sherwin-Williams in the United
States started as a large paint-maker and invented a paint
that could be used directly from the tin without additional
preparation.
The casein paints were continually improved. By the 1930s
they contained pigments with a high refractive index (high
covering power), similar to those used in oil paints. The
casein paints were traded as a powder or in the form of a
paste. In order to trade the paste form, it was necessary to
protect the paint against hydrolysis and infestation by
micro-organisms. A major advantage of casein binders was
their low cost. The paints were easy to apply and provided
covering in one layer. A disadvantage of the casein paints
was, that they are porous and therefore easily fouled.
Adding drying oils resulted in a more compact film and
improved durability as well. A drawback was that the drying
process became slower. When the amount of oil in the paint
was increased, the casein paint evolved into an “emulsion
paint”. In the 1920s, however, alkyd resins were first
developed [4] [5] . In many cases, the drying oil was
partially or completely replaced by an alkyd to accelerate
the drying of the paint film. The role of the casein in the
paint shifted from “resin” to emulsion stabilizer and
thickener. The drying oil and the alkyd became the real
binders.
2.1.2 The present: from polymer science to resins
The development of modern paint is closely associated with
the event of polymer science. However, as early as the
1830s people like Braconnot and Schönbein developed
derivatives of the natural polymer cellulose such as celluloid
and cellulose acetate. In 1844, Goodyear, amongst others,
discovered that adding sulphur to natural rubber,
polyisoprene, transformed the material from a flexible, non-
sticky material to a hard solid (“ebonite”) [6] , depending on
the amount of sulphur used. In 1907 Baekeland invented
the first synthetic polymers: phenol-formaldehyde
condensation resins called Bakelite [7] and Novolac [8] .
Despite advances made, the molecular nature of polymers
was not well understood until the work of Staudinger in
1922[9] . He was the first to propose that polymers
consisted of long chains of atoms held together by covalent
linkages. He presented this at a meeting of the Swiss
Chemical Society, coining the term “macro-molecules” [10] .
He was awarded the Nobel Prize for this in 1953.
Meanwhile, also the very first inventions were made that
would eventually lead to the development of water-borne
paints. In 1912 Gottlob patented the dispersion
polymerization of isoprene (German patents 254 & 255),
using egg albumin or starch as emulsifier. Polyvinyl acetate
was patented by Klatte and Rollet in Germany in 1914.
Rather than using naturally occurring stabilizers, the first
synthetic surfactants developed in Germany during World
War I(WWI) were used. These were short-chain alkyl
naphthalene sulfonates, similar to the materials are still
used today.
It was not until the end of the World War I, when a lot of
paint raw materials such as linseed oil were in short supply,
that artificial resins became available on the market. In
1920 Kienle of General Electric develops unsaturated alkyds
[11] that were commercialized under the name “Glyptal”
resins (from glycerol phthalate). A patent is applied for, but
the patent is ruled invalid in 1935 due to existing prior art,
which enables other companies to produce and sell alkyds
(after 1935). Kienle was probably responsible for the
combination of the word alkyd – from the condensation of
alcohols and acids. Alkyd modified oil paints and then alkyd
paints were eventually used on cars and household
appliances.
In 1929 Carothers (DuPont) publishes papers on linear
polyesters [12] , He is generally credited with formalizing
the concept of functionality, although Kienle had almost
certainly been thinking along the same lines. By 1930 Flory
[13] starts work on molecular weight distributions
(experimentally and theoretically) and shows that step-
growth polymerizations follow the Gaussian distribution for
molecular weight. In the years leading up to the second
World War, a range of additional synthetic resins was
appearing.
In 1933 Schlak patents the first epoxy resins: diglycidyl
ethers made from epichlorhydrin and bisphenol A [14] . Also,
Castan (Switzerland) and Greenlee (USA) file patents on
epoxy resins. Epoxies resins only became commercially
available in about 1947. They impart outstanding resistance
properties and find many applications, including one- and
two pack air drying systems. The latter includes a
polyamine, polyamide or polyamino-amide as a crosslinker.
This results in durable and resistant films used in heavy
duty coatings.
Urea formaldehyde resins started to be combined with alkyd
resins. Several US automobile producers, such as Ford and
Chrysler, started using alkyd enamel topcoats. Urethane
resins produced by Bayer for elastomers and foams are first
being introduced in 1937. Later on, polyurethane paints
were produced by Bayer based on solvent-borne polyols
(“Desmophen”) and polyisocyanates (“Desmodur”), often
referred to as “D-D” coatings, for example on German
military planes. In 1939 DuPont introduced thermosetting
acrylics developed by Strain [15] .
During the years of the second World War, there were a
couple of important developments in the field of water-
borne paints. In the US, the classic cheap interior wall paints
based on casein were improved by combining them with
both drying oil and alkyd resin. The acid number of the resin
was high enough to be neutralized with ammonia in order to
make them dispersible in water. In order to obtain fast
drying it was necessary that the binder had a high
molecular weight (degree of polymerization). The first
drying was caused by the evaporation of the water in the
paint. The through-drying was due to the oxidative
crosslinking of the alkyd resin and the drying oil. A
disadvantage of this type of paint was the fact that only low
gloss coatings could be made, limiting the use to interior
wall paints. In Germany in the meantime, due to the
shortage of linseed oil, polyvinyl acetate and polyvinyl
propionate latexes were used for the preparation of wall
paints.
One of the most important developments was the emulsion
polymerization process for the synthesis of styrene-
butadiene latexes. Even though in Germany, Luther and
Hück patented a method for making a styrene-butadiene
dispersion already in 1932 [16] , the biggest progress was
made in the US. Being cut off from their supplies of natural
latex by the occupation by Japan of big parts of south-east
Asia, a project was set-up that was the second largest in the
US during WW2, after the Manhattan project aimed at
developing the atomic bomb. The so-called GR-S
(government rubber styrene), was developed originally for
the production of car tires and tracks used for military
vehicles. GR-S according to the “Mutual Recipe” consisted of
75 % butadiene, 25 % styrene with a rosin soap as
emulsifier and a small amount of mercaptan. At the end of
WWII, it was found that the production capacity that was
installed could also be used for paint applications, mainly in
the US. Later, polyvinyl acetate dispersions became
available which were also increasingly used. In 1953 the
first all-acrylic dispersion was introduced commercially
under the tradename “Rhoplex” AC-33 in the USA or
“Primal” AC-33 in Europe.
In the 1970s, satin gloss latex paints were introduced. For
these paints, new types of fine-particle size polymer
dispersions were developed. These were combined with new
coalescing agents. In recent years, a large variety of high-
quality acrylic dispersions have been introduced on the
market, including types with a controlled particle
morphology or types that contained functional groups for
(self) crosslinking. At the end of the 1960s, the first
polyurethane dispersions were patented [17] by Bayer
although it would at least take until the 1980s before they
saw widespread use.
For several years, alkyd emulsions have also made a “come-
back”. In the 1950s, water-reducible alkyd paints were
introduced for industrial applications [18] . These alkyd
paints contained both alkyd resins in dispersed and
dissolved form and were combined with amino-
formaldehyde resins for thermo-setting applications.
Vianova, a heritage company of the current Allnex,
pioneered the use of “core-shell” alkyd emulsions under the
trade-name “Resydrol”, where the alkyd core was stabilized
by an acrylic carboxylic acid functional shell. Also, other
internally stabilized types of alkyd emulsions appeared on
the market. One particular driver was that alkyds are easily
produced from renewable oils or fatty acids. Also, other
alkyd building blocks, such as the polyols or polacids can be
derived from sustainable building blocks.
The following chapters will discuss the different aspects of
modern resins for water-borne coatings.

2.1.3 The present: water-borne resins and

coatings
The modern development of water-borne resins and
coatings may be roughly divided in the years before 1970,
the years between 1970 and 1990 and the years after 1990.
This choice is maybe arbitrary, since this differs depending
on the end use application and region.
Before 1970, water-borne coatings and resins were only
applied in those areas and applications where they
performed better than solvent-borne paints, be it on
performance or on cost. Performance wise there are not
many examples except for the widely used interior and
exterior wall paints. Here classical acrylic, styrene or
styrene-butadiene dispersions were used in formulations
with a low binder content. Chalk and water-glass binders
and coatings are other well-known examples used in both
interior and exterior wall paints. Other main application of
early water-borne coatings is the electrophoresis coatings
used in industry: both in automotive OEM as well as
industrial metal coatings.
In the years between 1970 and 1990, environmental
awareness resulted in a slow but steady reducing of the
amounts of organic solvents. Solvent emissions could be
avoided either by lowering the content of volatile organic
solvents (VOC) such as high solids coatings or using water-
borne or solvent-free solutions such as radiation cured or
powder coatings. Legislation initiatives started in Europe
around 2000, amongst others in the Netherlands. The
KWS2000 (“KoolWaterStoffen” or hydrocarbon) decree was
an initiative to reach a reduction of 100 KT/year solvent
emissions, by transfer from low or medium solid solvent-
borne coatings to water-borne or high solid coatings in the
architectural paint markets [19] . In spite of these initiatives,
it took until 2007 to 2010 before a VOC legislation was
implemented in the European Union [20] . During this period
frantic research efforts were initiated in most resin and paint
companies as well as in Universities and Research Institutes.
The many disadvantages of the older generation water-
borne resins and paints still had to be overcome. This will be
discussed in Chapter 3.
The results of these efforts can be observed in the next
period starting from 1990. If we focus on architectural
paints, a continuous stream of new water-borne resins and
paints appeared on the market with for instance for water-
borne trim paints VOC’s of 120 to 150 g/l (incl. water) as
from 1990 till recently VOCs of 30 to 50 g/l (incl. water). This
was also the case for high solids resins and paints and has
led to low VOC alkyd paints for instance with VOCs of 250 to
300 g/l (a 300 g/l VOC became the limit for trim paints in
2010). For wall paints, the VOCs can be as low as close to 0
g/l for interior application and up to 5 to 30 g/l (incl. water)
for high resistance or outdoor wall paints where the limit is
30 g/l (incl. water).
For automotive coatings – from primer to topcoat – the
choice between water-borne and high solid resin technology
strongly depends on the production lines that are able to
use water-borne coatings. The market is still in transition
depending on the characteristics of these production lines.
On most automotive OEM production lines, a water-borne
cataphoretic electro deposition (CED) coating is applied to
new car bodies. Use of water-borne base coat application is
state of the art though the VOCs of these coatings can still
be quite high (420 g/l excl. water). Solid colour topcoats are
water-borne in a number of automotive OEM factories. Clear
coats are less commonly using water-borne technology,
though some car producers have water-borne production
lines. Clear coats are in most cases still solvent-borne (ultra)
high solids (<VOC 420 g/l).
For vehicle refinish coatings, water-borne technology is
more common than in automotive, though clear coats and
solid colours tend to be more solvent-borne high solids than
water-borne. Base coats are almost all water-borne based on
acrylic or polyurethane dispersions or combinations thereof
with a VOC from 350 to 400 g/l excl. water (limit 420 g/l
excl. water).

2.1.4 The future

The recent years of 2010 to 2020 have shown a further
increase of low emission paints with a move to either water-
borne or high solids, depending on the specific end-use
application. Additionally, the sustainability as well as life
cycle analysis (LCA), carbon footprint and use of renewable
and recycled raw materials, has strongly influenced the
developments over the last years.
These trends do not always match with the move to water-
borne or high solids. Earlier published results from the
1980s of LCA studies [21] in the Netherlands show at least
that water-borne acrylic dispersions are not more LCA
friendly as the then actual high solid alkyd paints. More
recent investigations show comparable results, when
parameters that are put in the calculations are correctly
used and peer reviewed. The dominant contribution on all
segments in the LCA calculations is by far the titanium oxide
(when used in the formulation, however most coatings are
using TiO2). Another trend is the carbon footprint calculation
that is more focused on one – very important – parameter
and thus only partly sustainable. If one adds bio-based to
the equation, the situation becomes even more
complicated. It may favour alkyds, both high solids as well
as alkyd emulsions [22] .
Another recent trend in resin chemistry is the focus on
either bio-based alternatives for existing monomers used as
drop-in in the resins or new bio-based building blocks
(having different chemical structures) that can be
alternatives when providing similar performance in the
paint. However, a main obstacle remains the high raw
material cost of these bio-based alternatives and the
uncertainty of supply.
The near future may also have surprising events ahead that
can lead to the ban or limitation in use of certain raw
materials or even cause major transitions in application of
water-borne or high solid paints or even more vital raw
materials. The use of titanium dioxide – at the moment of
writing this book – is under pressure, being registered as a
carcinogenic raw material. This may in worst case lead to a
radical change in use of colour in any paint application.
Chapter 10 is addressing all H&S issues in the coatings and
resin world.
This book ends with a special chapter on the coming
innovations and outlook for the coming decades.

2.2 Markets and applications

2.2.1 The market for water-borne coating resins
Since the early days of water-borne coatings, the coating
resins used and their applications have come a long way.
The substitution of solvent-borne coatings by water-borne
equivalents was mainly due to legislation on the emissions
of organic solvents (Clean Air Act [23] , U.S. Environmental
Protection Agency-EPA [24] , the solvent emissions directive
– SED [25] ). Nevertheless, in some market-segment,
solvent-borne coatings are still the dominant technology
(only 22 % of all coatings in Europe are water-borne).
Automotive, protective and wood coating applications are
important growth areas for water-borne coating resins. In
Europe and North America, however, it is estimated that the
growth will be moderate due to strong regulations for
coating resins. The Asia Pacific water-borne coatings market,
however, is projected to witness the highest growth. Factors
such as huge and increasing population, rapidly growing
construction activity, and increase in the number of
automobiles, wooden furniture, and electronic appliances
are driving the growth. Acrylic resins are the fastest-growing
class of coating resins. They are used in a wide range of
applications for their chemical and mechanical
characteristics and aesthetic properties. Currently, the
strongest demand for water-borne acrylic coating resins
comes from the automotive, architectural and construction
markets. Next to acrylics, also water-borne epoxy and
polyurethane coating resins are high growth segments in
the resins market.
The market size data of the global market for water-borne
coating resins was estimated to be 24,000 million euros and
forecasted to reach over 37,000 million euros in 2025,
growing at a CAGR of 5.3 % from 2019 [26] . The estimated
breakdown [27] going from the global paint volume – CACR
(compound annual growth rate) of 1.8 % – to the global
water-borne coating resins volume (24 % of the total value
and a CACR of 5.3 %) – shows the substantial value of the
water-borne resins and their high growth rate (Table 2.1).

Table 2.1: Estimated global value of paints and resins, based on several
sources
Market 2017–2019 2023–2025 CAGR#

Global coatings 99.6 100   115.2 100 %   1.8 %

market **
%

Global resins market*** 28.8 29 %   36.0 31 %   4.7 %

Global water-borne 60.7 61 % 100 % 80.3 70 % 100 % 5.7 %

coatings market****

Global water-borne 24.0 24 % 40 % 37.0 32 % 46 % 5.3 %

resin market*****
 Table 2.1: Estimated global value of paints and resins, based on several
sources
Market 2017–2019 2023–2025 CAGR#
exchange rate $ to euro 0.9 **** data Vincentz Network 
* based on several sources and years   *****
**www.decisiondatabases.com/ip/ www.coatingsworld.com/contents/view_market-
5588-paint-marker-industry-market-report research/2019-07-29/  cont. coating-resins-market-
*** www.coatingsworld.com/contents/view_market- worth-379-billion-by-2023-marketsandmarkets/
research/2019-01-30/  cont. coating-resins-market- # stated CAGR (compound annual growth rate) 
worth-379-billion-by-2023-marketsandmarkets/

Table 2.2 shows the spread of the global volumes over the
different regions. Asia Pacific (mainly China) produced in
2017 (in volume) by far the most water-borne coatings: 24.6
billion Euros. This region also shows the largest growth both
in sales volume as well as in 6.6 % CACR. The growth of
water-borne coatings is substantially slower in Europe and
the Middle East & Africa. [28]

Table 2.2: Spread of global water-borne coatings and their growth, market
size, by region in 2017 and 2022 
Region EUR  % of EUR  % of  growth  CACR
billion global billion global [%] [%]

2017 2022

Asia-Pacific 24.6 39 % 34.3 41 % 39 % 6.6 %

Europe 18.5 30 % 22.0 27 % 19 % 3.2 %

North America 11.4 18 % 15.8 19 % 39 % 6.4 %

South America 3.5 6% 5.3 6% 51 % 8.6 %

Middle East & 4.4 7% 5.3 6% 20 % 3.4 %

Africa

Total 62.4 100 % 82.7 100 % 33 % 5.4 %

 

The global market of water-borne coatings is spread across

all market-segments as can be seen in Figure 2.1. The most
important segment for water-borne coatings and resins is
the architectural coatings market, more specific in both
interior as well as exterior wall or façade paints. This market
dominates the total global sales as well as volume (Table
2.1) by over 60 % in paint sales and 40 % in resin sales.
Water-borne wall paint types started to appear over 50
years ago, qualities as well as application areas were and
are differing strongly per country. For instance, in France
interior wall paints have for a long time been solvent-borne
– see for example the VOC values for solvent-borne wall
paints (Chapter 2.3.3) – and the PVC (pigment volume
concentration) of both interior as well as exterior wall paints
vary largely depending on the country and application: for
example in the Netherlands the high end wall paints have
substantially lower PVC than in the neighbouring countries.
Another application in architectural coatings are the trim
paints used in the USA. In Europe the use of water-borne
trim paints is of more recent date. Recently architectural
coatings are divided in wall paints and deco/DIY (do-it-
yourself) or trim paints. Deco paints are trim paints for
professional painters and DIY obviously for the do-it-yourself
painter. Often similar or almost similar brands are sold in
deco via warehouses or company-shops whereas the DIY
paints are sold under different brands in shops and outlet
stores.
Second largest business segment is automotive coatings
with a substantial percentage of 9 % in value of water-borne
coatings. It is a fast-growing market due to mainly
expansion of car production in Asia, more specifically in
China.
If one looks at the global spread of resin types or
technologies the figures are almost evenly divided over the
technologies. The biggest part is “others” which suggests
that there are a lot of smaller polymer technologies present
in the water-borne resin market. Most water-borne
technologies will be discussed in this book and not
discussed here. It is important to realize that the global
market technologies mentioned in Figure 2.2 are clusters of
applications.
Figure 2.1: Global markets water-borne coatings
 
Figure 2.2: Breakdown in water-borne resin types volumes
 

So far, the sales of water-borne resins have been discussed.

The comparison of volumes is as important, especially if a
technological comparison is made. Tables 2.3, 2.4 and 2.5
show available data of 2016 volumes for Europe, both as
total and as water-borne systems. As can be seen, the
volume percentage of water-borne paints [29] in
architectural coatings is substantial, up to 81 %. The high
levels for architectural systems come from the dominance of
water-borne wall paints. Trim paints account only for 35 % of
the water-borne coatings. The highest growth rate for water-
borne will probably occur in this segment as some of the
application issues are solved.
The volume percentage of water-borne paints in the
segments industrial and automotive OEM coatings are as
low as 22 % (Table 2.4). For industrial applications, only
automotive OEM has a high score, most probably due to the
full water-borne sub-segment electrophoreses coatings. All
other segments score low levels of water-borne paint (2 to
40 %). Overall the score is only 22 %. Combining Tables 2.3
and 2.4 gives the European volume of architectural,
industrial and automotive OEM coatings, it adds up to 9.0
billion kilos of coatings of which 5.4 billion kilos (60 %) are
water-borne (Table 2.5). Unfortunately, for the global
volumes no comparable data are available.

Table 2.3: Volumes of deco/DIY paints in Europe in 2016, breakdown for

architectural in total and water-borne
Segment Overall Segment Water- Water-borne Water-
[t] share borne [t] share/total borne
[%] [%] share [%]

Interior wall 3,275,000 56 % 3,105,000 95 % 66 %

Exterior 1,305,000 22 % 1,180,000 90 % 25 %

wall

Wood/trim 1,255,500 22 % 440,000 35 % 9%

 Table 2.3: Volumes of deco/DIY paints in Europe in 2016, breakdown for
architectural in total and water-borne
Segment Overall Segment Water- Water-borne Water-
[t] share borne [t] share/total borne
[%] [%] share [%]

Totals, 5,835,500 100 % 4,725,000 81 % 100 %

tonnes
Source: European Coatings Journal 11/2017, p. 12–14

Table 2.4: Volumes of industrial and OEM paints in Europe in 2016, breakdown
for OEM and industrial coatings in total and water-borne
Segment Overall Segment Water- Water- Water-
[t] share borne borne borne
[%] [t] share/ share
total [%]
[%]

Automotive OEM 281,250 9% 175,000 62 % 24 %

Automotive refinish 190,500 6% 44,000 23 % 6%

Other transportation 87,500 3% 22,000 25 % 3%

Protective & marine 736,000 23 % 45,500 6% 6%

Industrial wood 522,000 16 % 130,500 25 % 18 %

Agricultural, construction & 110,000 3% 38,000 35 % 5%

earthmoving (ACE)

Precoated metal (Coil) 190,000 6% 3,500 2% 0%

Metal packaging (Can) 201,500 6% 80,500 40 % 11 %

Other (general metal and 920,000 28 % 176,500 19 % 25 %

plastic)
 Table 2.4: Volumes of industrial and OEM paints in Europe in 2016, breakdown
for OEM and industrial coatings in total and water-borne
Segment Overall Segment Water- Water- Water-
[t] share borne borne borne
[%] [t] share/ share
total [%]
[%]

Totals, tonnes Industrial 3,238,750 100 % 715,500 22 % 100 %

and OEM
Source: European Coatings Journal 11/2017, p. 12–14

Table 2.5: Combination of Tables 2.3 and 2.4

Total and water-borne volumes of deco/DIY, industrial and OEM
coatings in Europe in 2016 

Totals, tonnes deco/DIY 5,835,500 64 % 4,725,000 81 % 87 %

Totals, tonnes industrial and 3,238,750 36 % 715,500 22 % 13 %

OEM

Total European volumes in 9,074,250 100 % 5,440,500 60 % 100 %

tonnes

Table 2.6 shows a breakdown of the most important sub-

segments, classified in the various main segments. The
presence in water-borne is in this case an estimate of the
authors. Several sub-segments appear in different segments
due to totally different applications of the same
technologies.
Not the least important issue is to mention the most
important resin producers that are leading producers in
water-borne resins and their specific resin technologies
(Table 2.7, p. 28).
Table 2.6: Global markets and their detailed applications (based on author’s
experience and estimates)
Markets in Main applications Applications used in Present in
review this book water-
(see Figure borne
2.1) coatings

Architectural decorative deco yes

Do-it-yourself/DIY DIY medium

trimpaints or wood trim paints medium

coatings

wall or façade paints wall paints full

plaster wall paints full

plastic, concrete and plastic, concrete or medium

metal metal

Automotive new vehicles automotive limited

electrophoresis car automotive high

bodies

car refinishes car refinishes medium

plastic coatings (OEM automotive limited

parts)

OEM original equipment automotive limited

manufacturing

Protective marine protective limited

protective protective limited

anti-corrosion protective limited

Table 2.6: Global markets and their detailed applications (based on author’s
experience and estimates)
Markets in Main applications Applications used in Present in
review this book water-
(see Figure borne
2.1) coatings

General metal coatings metal coatings medium

industrial
ACE coatings metal coatings limited

glass coatings glass coatings limited

OEM original equipment metal coatings medium

manufacturing

plastic coatings plastic coatings medium

coil coatings coil coatings limited

Wood industrial wood joinery yes

joinery joinery full

kitchen cabinets kitchen cabinets medium

flooring, parquet flooring medium

Packaging packaging packaging limited

interior can coatings can coatings limited

exterior can coatings can coatings limited

Other aircraft and aerospace aerospace coatings limited

coatings

paper coatings paper coatings high

intumescent coatings fire retarding coatings medium

 Table 2.6: Global markets and their detailed applications (based on author’s
experience and estimates)
Markets in Main applications Applications used in Present in
review this book water-
(see Figure borne
2.1) coatings
Deco and DIY involve in most cases the same resins and formulations except for legislative matters.
Only then the applications are mentioned
When possible, OEM is not used since it involves many different industries

2.2.2 Coatings market definitions

Coating market definitions are as varied as there are
countries or continents. Instead of using larger segments as
presented below, more specific applications to focus the
application are used. Table 2.6 illustrates the used
terminology in this book.

Wall paints
Wall paints can be divided into exterior and interior wall
paints.
Exterior wall paints are also called façade paints. They are
applied on the outside of façades of brick walls, masonry,
concrete, PVC and other plastic panels or metal cladding, as
well as plastering. Depending on the type of surface they
need different performance parameters. Very important,
especially in warm, humid climates is resistance to dirt-
pickup and bacterial growth. Also important are aestetics
where the wall paint is able to hide formation of small
cracks of the substrate.
For interior wall paints, the focus is mainly on low cost, as
well as on hiding and dirt resistance or easy cleaning. The
substrate can be concrete, plaster or wall paper. Both
interior and exterior wall paints are mainly applied with
rollers, large brushes and spray guns. Main critical factors
are the pigment volume concentration (PVC), levelling and
the possibility to use point-of-sale colouring, using mixing
machines. Formulations should be economic since large
surfaces are involved as well as there is fierce competition
in this market-segment.

Trim paints
Trim paints are applied by professional or non-professional
painters on all “fittings on a building” such as panels, doors,
window frames. The substrate being the full range of wood
types, plastics, concrete and metal.
Main critical factors: very broad area of country-specific
applications, mixing machines, colouring, colour
acceptance, formulations, huge variation of quality and
performance due to VOC limits based on “ready for use”
amongst other things.OEM coatings

OEM coatings
(original equipment manufacturer, e.g. automotive coatings)
are coatings used at the original equipment manufacturer
and are applied under very well controlled conditions.
Application can be by automated spray robots or by dipping
in electrophoresis baths, followed mostly by curing at
elevated temperatures often referred to as baking or
stoving. Substrates are metal and plastic. Important
application areas are the automotive as well as automotive
related industries such as bumpers and fenders.
Vehicle-refinish coatings
Vehicle-refinish coatings are all coatings used for the repair
of damaged cars: fillers, primers, metallic base coats, solid
colour topcoats and clear coats. Main substrates are metal,
aluminium, repair-putties and plastics. Main critical factors
for water-borne topcoats is the fact that it is still difficult to
obtain excellent appearance unless the VOCs are still
substantial.

Industrial wood coatings

Industrial wood coatings are industrially applied. Main
application areas are window and door frames (often
referred to as joinery) and parquet flooring. Windows and
door frames are mainly coated by means of spraying, flow
coating or dipping. The changeover to water-borne in the
joinery segment is almost completely realized. The drying
conditions can be from primitive to complete high speed
lines under controlled conditions.
Industrially finished parquet coatings are almost always
applied and dried on high speed lines using radiation cured
coatings. Individual layers are water-borne, the topcoat
however is almost always a 100 % solid UV-curing coating.
Many “parquet” materials are not at all based on solid wood
but on foils that are printed and glued to an MDF or other
fibre-board like substrate. In most case a thick clear coat is
then applied on the printed foil to protect it from abrasion.

Protective coatings
Protective coatings are the cluster of marine, metal
constructions and other applications where anti-corrosion
applications are important. Substrates can be steel,
aluminium or other metal substrates. The change to water-
borne coatings in this segment is still limited or in a transfer
phase. Recently air-drying polyurethane dispersions and
very hydrophobic acrylic dispersions have entered the
market and they have an acceptable performance.

Industrial coatings
Industrial coatings, sometimes also referred to as general
industrial coatings, are basically the collection of coatings
that do not fit in the previously described segments. End-
use applications are for instance metal machines,
agricultural construction and earthmoving equipment (ACE),
kitchen appliances or household equipment and anti-
corrosion applications. The British Coatings Federation (BCF)
[31] defines this market segment as follows: “An industrial
coating is a paint or coating defined by its protective, rather
than its aesthetic properties, although it can provide both.”
The most common use of industrial coatings is for corrosion
control of steel or concrete. Overall the change to water-
borne coatings is still limited or in a transition phase. Most
water-borne coatings still have substantial to high VOC.

Plastic coatings
Plastic coatings are often a sub-segment of automotive OEM
coatings. A very well know application are bumpers and
wheel covers. The pretreatment of polypropylene plastics is
far more critical if water-borne coatings are used. The sub
segment plastic coatings for equipment (TV, mobile phones
etc.) is often put under industrial coatings.
Packaging coatings
Packaging coatings are defined as a means to give
functional as well as aesthetic properties to various products
related to consumer goods, personal care, healthcare, food
& beverages, and other such industries [32] . It is a large
mixed bag of coatings and applications and will only be
discussed on specific known applications. One of the main
areas is can coatings: both interior and exterior. Often this
segment is not included in market overviews. An example of
the complexity of these coatings is the coating of
multicolour printed plastic food bags such as for crisps. For
direct or indirect food contact coating, ingredients must
meet the FDA regulations and in addition migration tests
need to be done by the end-user (formulated and applied,
cured coating) to determine migration of certain ingredients
from the coating into the food.

Other coatings
Other coatings businesses are certainly not less important.
Figure 2.1 shows the substantial market share they have of
16 %. Main areas are aerospace coatings, intumescent
coatings, resin flooring coatings, paper coatings, etc. It
becomes visible that these market-segments tend to look
for water-borne resins, developed for other applications and
then adapt these resins for their specific use. For paper
coatings, for example, a lot of styrene butadiene dispersions
are being used. Aerospace coatings on the other hand use
both one- and two-component water-borne systems for the
interior (coatings and fillers). The exterior coating is
expected to remain solvent-based for a longer period of
time.
2.3 Definitions
This paragraph discusses various definitions of terms like
applications, markets and parameters used that are prone
to discussion or sometimes used inappropriately.
Nevertheless, some have more than one definition or are
not the same in various countries. The definitions that are
used in this book need to be crystal clear in order to keep
the subject and information the same for all readers.
Whenever possible also the alternative definitions or
accuracy of a definition will be mentioned. The combination
of defined paints and the defined resins that lead to the
proper product and performance is discussed in the
forthcoming chapters.

Table 2.7: Most important resin manufacturers in the worldwide water-borne

coating resins market [30]
Company Water-borne resins Most important brand
technologies names

Alberdingk acrylate dispersions types AC and Alberdingk, Albodur, Albolink

Boley AS, PUD type U

Allnex acrylics, epoxies, alkyds, Setaqua, Resydrol, Acropol,

polyurethanes, acrylic- Ucecoat
polyurethane hybrids, cationic
electro deposition, amino resins

Arkema acrylics Encor, Synaqua

Axalta acrylics PercoHyd, Standox, Lucite

BASF acrylics Propiofan, Acronal, Joncryl,

Styrofan, AQAGloss, Glascol,
Luhydran
 Table 2.7: Most important resin manufacturers in the worldwide water-borne
coating resins market [30]
Company Water-borne resins Most important brand
technologies names

Covestro acrylics, polyurethanes Bayhydrol types U, UH, PAC, PU

acrylic-polyurethane,hybrids, etc., NeoCryl, NeoPac,
alkyds Haloflex. NeoRez, NeoRad,
Uradil

DIC acrylics, epoxies, polyurethane Watersol, Burnock

DOW acrylics, polyurethanes Primal, Roshield, Rhoplex,

Chemical Avance, Aquaset
Company

Evonik epoxies, silanes Ancarez, Dynasilan,

Corp.

Hexion epoxies EPI-REZ, Epicote

Huntsman epoxies Araldite

Corp.

King water-thinned resins K-Flex

Industries

Lubrizol acrylics, PUD, polyvinylidene Carboset, Aptalon, Permax

chloride PVDC dispersions

Reichold acrylics, epoxies, alkyds Beckosol, Kelsol, Urotuf, Arolon

Specialty acrylics, styrene acrylics RayCryl, RayFlex, RayCote

Polymers

Worlée alkyds, acrylic WorléeSol, WorléeCryl

 
2.3.1 Definitions of water-borne paints
The definition of water-borne paint seems to be straight
forward. It could very well be the following one:
“ A water-borne paint is a paint containing and using water
in order to apply the mixture of solid materials such as
pigments, resin, hardener and additives, in order to form a
proper wet and dry film and leading to the performance that
is required when applied and dried ” [33]
Some critical remarks.
“…using water…”: almost all water-borne paints need still
limited to considerable amounts of solvent be it cosolvents,
coalescing agents, plasticizers or other solvent. Meaning
they still emit solvents and therefore have a VOC value. The
function of these solvents is critical to the formation of a
proper film after evaporation of the water. Water is in fact
the carrier of the paint for the application and not taking
part in the actual film formation. Exceptions are real water
dissolved resins, their use is rare. In that case water acts as
a solvent.
“…containing water…” is too limited, we should add a
proper and accurate definition of the amount of water. Since
water is not to be seen as a classical solvent and its function
to dilute the resin/paint to the proper viscosity, it is
depending on the application “excluding water” or
“including water” in the VOC calculation.
There are well known examples of a classical solvent-borne
alkyd paint that is diluted with water until the VOC
requirements are met. The water actually forms a water in
oil emulsion. They still emit the same large amount of
solvent when applied in the proper layer thickness. Another
example may be the water-borne base coat formulations
used in metallic automotive paints that have very high VOCs
(over 400 g/l, excluding water) and are in fact high solid
metallic paints containing water.
Taking this into account the definition should be sharper:
“ A water-borne paint is a paint containing water and only
contains other volatile components such as solvents, to a
level that meets the actual and local volatile emission
legislation. Additional to that the water-borne paint, when
applied at the proper and final layer thickness/solids, must
also lead to a legally acceptable emission. Exempt solvents
as are used in the USA should be part of the emitting
solvents.”
Note: The second sentence of the definition covers the
practice and fact that VOC legislation may largely miss its
objective. If multiple layers need to be applied to have the
proper amount of solid and dried film on the substrate. It is
well known in architectural water-borne paints, having a
VOC of 120 g/l (incl. water) has a total emission that equals
that of a high solid alkyd paint with a VOC of 250 g/l simply
because of the fact that the volume solid of the high solid
alkyd paint is a factor of 1.8 to 1.9 higher than the water-
borne paint [34] . Several alternative terms for water-borne
are used in the literature and communication, such as
water-based, water-dilutable and water-reducible. In this
book water-borne is the preferred terminology. This is well
motivated by Martens: a resin as well as a paint is based on
the main functional component of the resin/paint. A resin or
paint is for instance acrylic- or alkyd-based and not borne.
The main and very important component is not water or
solvent – it is there to apply the paint – but the generally
accepted chemistry of the binder. Martens writes: “This (the
water-based coating) is a misnomer in that the base is
normally the binder. … It is recommended that the term
“water-based” be dropped. … Calling a coating water-based
is equivalent to calling a coating toluene (note by authors: it
should be xylene-borne) based or mineral-spirits based ….”

2.3.2 Definitions of water-borne resins

“ A water-borne resin is a polymer diluted, emulsified or
dispersed in water and not containing volatile organic
materials such as solvents. It should not contain non-volatile
materials such as monomer residuals not incorporated in
the polymer, higher than the allowed levels, according to
the local legislation”. [33]
Volatile materials may be solvents or additives used during
production that are not or not completely removed during
production. Examples are for instance the remaining
solvents such as N-methyl pyrrolidone or N-ethyl pyrrolidone
present in older polyurethane dispersions. Neutralizing
agents such as triethyl amine that has an unfavourable
labelling are not allowed in various Eco-labels. Higher
boiling point amines such as di isopropyl ethyl amine serve
a similar function but are not yet regulated to the extent of
triethyl amine.
Water-borne resins are basically made in three different
processes (Figure 2.3): water-borne dispersions, water-borne
emulsions and water-borne solutions.
Water-borne resin dispersions are made in situ by addition
polymerization of the selected monomer mix in water with
the help of a stabilizing additives (emulsifiers) or polymer
stabilizers. Water-borne resin emulsions are made in two
steps by first making the resin both by addition
polymerization or polycondensation using organic solvents
and then either adding water called primary emulsification
(phase-inversion) or adding the hot resin in water called
secondary or direct emulsification. Water-borne resin
solutions are resins made really dissolved in water with the
help of ionic or non-ionic functionalities build into the
polymer backbone followed in the case of ionic polymers by
neutralization. These resins are only used in specific areas
such as electrophoresis in metal treatment and some other
automotive coatings.

2.3.3 Volatile Organic Compounds

Volatile organic compounds or contents (VOC) regulations
and definitions differ between USA, Europe, China and other
countries or continents [36] . The following part focusses on
the European situation.
The VOC is defined as follows:
“ Volatile organic compound means any organic compound
having an initial boiling point less than or equal to 250 °C
measured at a standard pressure of 101.3 kPa”.
The present European VOC legislation is complicated and
can be misleading since it uses two VOC definitions [35] . A
VOC value expressed in g/l excl. water is used for vehicle
refinishing coatings and a VOC value expressed in g/l incl.
water or g/l ready to use is used for architectural coatings.
For industrial coatings there is no VOC legislation, but here
the emissions of solvent and carbon dioxide are regulated.
A better tool for legislations may be the total emission of
volatile materials per square meter of applied film of the
required film thickness [37] . Too many water-borne paints
will fulfil the VOC legislation but not the emission as
described here. Positive developments are legislations as
observed in Germany and France covering the full emissions
over a longer period of time (up to 28 days after application
of the paint) as well as total applied dry film.
Table 2.8 illustrates the complexity of the European VOC
regulation, since there are many different application areas
having different limiting VOC values. The ready for use or
incl. water VOC makes it even more difficult to compare
different paint applications for instance the actual emission
per square meter of a paint job. In practice application this
may lead to the situation that the actual VOC of a water-
borne coating may be as high or only slightly lower than the
solvent-borne predecessor.

Table 2.8: VOC directive for architectural paints per application area, Directive
2004/42/CE: “ready for use”
Category type Type Phase 1 Phase 2
(2007) (2010)
VOCmax VOCmax
content [g/l] content [g/l]

Paints for interior walls and water-borne 75 30

ceilings

Ibid (Gloss <25 @ 60°) solvent- 400 30

borne

Paints for interior walls and water-borne 150 100

ceilings

Ibid (Gloss ≥25 @ 60°) solvent- 400 100

borne

Paints for exterior walls of water-borne 75 40

mineral substrates.

solvent- 450 450

borne

Interior and exterior paints for water-borne 150 130

wood or metal, trim and cladding

solvent- 400 300

borne

Interior and exterior transparent water-borne 150 130

coatings and varnishes, semi-
transparent coatings, stains and
wood stains and opaque wood
stains for wood & metal

solvent- 500 400

borne
Interior & exterior minimal build water-borne 150 130
wood stains

solvent- 700 700

borne

Primers for use on wood, walls water-borne 50 50

and ceilings

solvent- 450 350

borne

Binding primers to stabilise water-borne 50 50

substrates or impart hydrophobic
properties

solvent- 750 750

borne

One-component coatings water-borne 140 140

(performance)

solvent- 600 600

borne

Two-component reactive coatings water-borne 140 140

(performance)

solvent- 550 500

borne

Multi-coloured coatings water-borne 150 100

solvent- 400 100

borne

Decorative effect coatings water-borne 300 200

 solvent- 500 200
borne

Table 2.9: VOC directive for vehicle refinishes coatings, Directive 2004/42/CE
Category subtype Coatings VOCmax content
[g/l]

Preparatory and preparatory 850

cleaning

pre-cleaner 200

Body filler/stopper all types 250

Primer surfacer/filler and general metal 540

primer

wash primer 780

Topcoat all types 420

Special finishes all types 840

2.3.4 Polymer dispersion terminologies

Some important terminologies that are encountered when
talking to a resin supplier about polymer dispersions are:
self-crosslinking, thermoplastic, morphology-control,
polymer stabilization, Tg (glass transition temperature), etc.
These will be discussed in the next chapters.
2.4 References
[1] Craughwell, Thomas J., 1956 (2012). 30,000 years of inventions. New
York: Tess Press

[2] Inorganic Chemistry, Egon Wiberg, Arnold Frederick Holleman, Elsevier

2001, ISBN 0-12-352651-5

[3] Robinson, George W. (2015-01-13). Bert Combs The Politician: An Oral

History. UniversityPress of Kentucky. ISBN 9780813150192.

[4] Kienle, R.H. and Hovey, A.G., J. Amer. Chem. Soc. Vol. 51, 1929, p.509;
Kienle US patent 1,893,873, General Electric Company 1933

[5] Hopkins, H., US Patent 1,974,742, Dupont 1934

[6] US Patent 3633A, 1844 to Charles Goodyear

[7] Baeckeland, L.H., Ind. Eng. Chem. Vol. 1, No. 3, 1909; Bakelite: The
World’s First Synthetic Plastic”. National Historic Chemical Landmarks.
American Chemical Society. Archived from the original on July 22, 2012.
Retrieved June 25, 2012

[8] Novolac, patented in 1907: “Method of Making Insoluble Products of

Phenol and Formaldehyde”
https://polymerdatabase.com/polymer%20classes/Phenolic%20type.html

[9] Staudinger, H.: Foundation of Polymer Science. National Historic

Chemical Landmarks. American Chemical Society. Archived from the
original on January 12, 2013. Retrieved June 25, 2012.

[10] H. Ber. Deut. Chem. Ges. 1920, 53, 1073

[11] Kienle, R. H. and Ferguson, C. S. present a paper at an ACS meeting in

September, entitled “Alkyd Resins as Film-Forming Materials. This was
published in 1929 in Ind. Eng. Chem., Vol 21, 1929, p. 349

[12] Carothers, J., Am Chem Soc, 51, 2560 (1929)

[13] Flory, P.J., Principles of polymer chemistry, Cornell Univ. Press, 1953

[14] German Patent 676,117.

[15] U.S. Patent 2173005 to DuPont,1939

[16] I.G. Farbenindustrie in Germany, US patent 1,864,078 (June 21, 1932)

[17] Dieterich, D., “Aqueous Emulsions, Dispersions And Solutions Of

Polyurethanes; Synthesis And Properties,” Progress in Organic
Coatings, 9 p. 281–340, (1981)

[18] Hofland, A., Progress in Organic Coatings Volume 73, Issue 4, April
2012, Pages 274–282

[19] Wat is KWS 2000?, Veenstra, S., 1991, Published in Journal Lucht :
kwartaalblad over alle facetten van luchtverontreiniging. Volume 8. Issue
2. Page 53–78. ISSN: 0925-9953

[20] Official VOC legislation document

www.coatings.org.uk/vocproductregulations.aspx

[21] Geurink,P., Akkerman, J.M., SLF Conference paper, 1988, Stockholm

[22] Dieterich, D., “Aqueous Emulsions, Dispersions And Solutions Of

Polyurethanes; Synthesis And Properties,” Progress in Organic
Coatings, 9 p. 281–340, (1981)

[23] www.epa.gov/clean-air-act-overview

[24] www.epa.gov

[25] ec.europa.eu/environment/archives/air/stationary/solvents/legislation.htm

[26] Coatings World, 07.29.19:

www.coatingsworld.com/contents/view_market-research/2019-07-
29/coating-resins-market-to-reach-42-billion-by-2023-
marketsandmarkets/ and www.coatingsworld.com/contents/view_market-
research/2019-01-30coating-resins-market-worth-379-billion-by-2023-
marketsandmarkets/ and www.decisiondatabases.com/ip/5588-paint-
marker-industry-market-report

[27] Data of several sources (shown in Table 2.2 and ref 26) are combined
since no reports are known covering all mentioned data

[28] European Coatings Journal, 11/2018, p. 12

[29] European Coatings Journal, 11/2017, p. 12-14

[30] www.coatingsworld.com/issues/2016-07-01/view_features/resins-
supplier-directory-18886/7878

[31] BCF British Coatings Federation:

www.coatings.org.uk/Sectors/Industrial_Coatings.aspx

[32] www.alliedmarketresearch.com/packaging-coatings-market

[33] The authors best guess based on experiences in the European market

[34] Geurink, P., Akkerman, J.M., SLF Conference paper, 1988, Stockholm

[35] Akkerman, J.M., Vincentz European Coatings Academy China,

Shanghai 2017

[36] https://en.wikipedia.org/wiki/Volatile_organic_compound

[37 ] www.coatingsworld.com/issues/2016-07-01/view_features/resins-
supplier-directory-18886/7878 www.cepe.org/wp-
content/uploads/2019/03/CEPE-Guideline-for-VOC-Determination-of-
the-Decorative-Paint-Industry.pdf

[38] C.R. Martens, Waterborne Coatings, 1981, Litton Educational

Publishing, Inc., p. 1

 
3 Polymer dispersions
and emulsions
Jaap Akkerman and Dirk Mestach

3.1 General introduction

Water-borne polymer dispersions are resins that are
dispersed as ‘solid’ particles in water and are stabilized by
ionic charges, ionic or non-ionic molecules, oligomers or
polymers [1] . The resins are predominately organic
polymers that are synthesized directly in water by means of
emulsion polymerization . In this process the resin is
most of the time obtained by free radical addition
(co)polymerization in situ in the aqueous phase of
ethylenically unsaturated monomers in the presence of
surface-active components (surfactants or emulsifiers). A
typical polymer particle is composed of a large number of
polymer chains with molecular weights in the range of 105 to
107 g/mol. Coating resins obtained by this process are
referred to as polymer dispersions in the rest of this chapter,
even though they are sometimes also referred to as latexes,
lattices or emulsion polymers.
In Chapter 3.2 the preparation of polymer dispersions is
discussed in detail. Attention is given to the most frequently
used monomers. New developments in the process for
making polymer dispersions are also discussed. Followed by
the important parameters of polymer dispersions that are
key information for the paint formulation and are normally
supplied by the resin producer. Then the different
classification of polymer dispersion resins – including new
and special types – are discussed.
In Chapter 3.3 the most important properties and
characteristics that have to be known to coating formulators
are explained, as well as curing mechanisms and calculation
methods of coating formulations. The classification of
polymer dispersions and emulsions is based on the chemical
nature of the monomers that are used and their particular
processing and properties.
In Chapter 3.4 the following classes of polymer dispersions
are discussed: styrene copolymer dispersions, vinyl acetate
and vinyl acetate ethylene dispersions, pure acrylic
dispersions, cationic dispersions and other dispersions. For
each class of dispersions or emulsions the application and
one or more guideline formulations and their particular
properties are discussed. When possible, the examples are
compared to the solvent-borne counterparts.

3.2 Preparation of polymer

dispersions
3.2.1 Stability of polymer dispersions
When a polymer dispersion is used in a paint, an important
requirement is the stability of the system. For example, the
binder should not sediment or coagulate and the viscosity
should not change over time. The polymer particles in a
dispersion remain stable because they exhibit colloidal
behaviour.
The colloidal behaviour of a polymer dispersion is mainly
determined by the surface properties of the polymer
particles. These properties depend on the method of
preparation of the polymer dispersion as well as on the type
and concentration of the initiator used (in case emulsion
polymerization is used), ionogenic groups in the polymer
and possibly the emulsifier used during the synthesis.
On the surface of the polymer particle prepared by emulsion
polymerization, end-groups are present originating from the
decomposition products of the initiator. These groups may
be ionic or non-ionic, depending on the type of initiator
used. If these end groups have an electric charge, they
contribute to the stability of the polymer dispersion.
Table 3.1 provides an overview of initiators commonly used
in emulsion polymerization and the surface groups formed
by their decomposition.

Table 3.1: Overview basic chemistry of initiators

Surface Structure Origin
group

Strong acid -OSO3 - H+ decomposition of persulphates

Weak acid -COO- H+ hydrolysis of sulphate terminal

groups followed by oxidation of
formed hydroxyl groups

  -COO- H+ hydrogen peroxide – oxidation of the

originally formed hydroxyl end
groups
 Table 3.1: Overview basic chemistry of initiators
Surface Structure Origin
group

  -COO- H+ functional azo-initiators

(e.g. 4,4'-azobis(4-cyanovaleric acid)

Alkaline functional azo-initiators

(azo(bis isobutyramidine))

Non-ionic -OH hydrogen peroxide

  -OH hydrolysis of sulphate group

Adsorbed or “grafted” emulsifier molecules also contribute

to the total number of surface groups. Depending on the
type of emulsifier (anionic, cationic or non-ionic) the surface
load varies. The specific types of emulsifiers are discussed
in one of the following chapters.
In some cases, a protective colloid (e.g. polyvinyl alcohol,
polyvinyl pyrrolidone or polyacrylic acid) is used in the
preparation of the polymer dispersion. These polymers can
also contribute to the overall surface charge by adsorption
or grafting.
In case of polymer dispersions obtained through “secondary
emulsion” techniques, a distinction should be made
between self-emulsifying polymers and polymers that
require external emulsifiers. Self-emulsifying polymers have
hydrophilic groups build into the polymer. These groups may
be charged (e.g. acid groups) or maybe non-ionic
(polyethylene oxide derivatives).

Electrostatic stabilization
In an ionizing medium such as water, the acidic or alkaline
surface groups, depending on their pKa or pKb and the pH of
the water phase, exist in their dissociated form. As a result,
the polymer dispersion particles build-up a net electrical
charge.
Schematically, a polymer particle can be displayed as a
sphere with the electrical charges evenly distributed across
the surface. The electro-neutrality condition is met by the
presence of counter ions in the continuous phase, see Figure
3.1.

Figure 3.1: Negatively charged dispersion particle with electric double layer.
 

As a result of the surface charge of the polymer particle, an

electrical double layer is formed. The particle possesses an
electrostatic surface potential (Ψs ) that can be both
negative or positive depending on the nature of surface
groups. The potential decreases exponentially with the
distance to the surface according to the equation:

In this equation Ψr is the surface-potential at a distance (r-

a), where a is the radius of the sphere and s is the surface.
The constant K is given by the expression:

with:
I the ionic strength of the continuous phase

e the basic electrical charge (1.6022∙10-19 Coulomb)

NA Avogadro’s number (6.0231∙1023 mol-1)

ε dielectric constant of the dispersion medium

 

K determines how the electrostatic surface potential

decreases with the distance to the particle surface.
Derjaguin, Verwey, Landau and Overbeek [4] , [5]
developed a theory for the electrostatic contribution to
colloidal stability (DVLO theory). Combination of the
potential energy for electrostatic repulsion (Vr) and the van-
der-Waals attractions forces (Va ) between the particles,
gives a value for the total interaction potential energy (Vt).
Vt = Va + Vr
Taking into account the short distance Born repulsion, this
gives a function for the potential energy as a function of the
distance to the particle surface. A schematic representation
of this function is given in the Figure 3.2.
Figure 3.2: Illustration of a potential energy against distance of surface
separation curve to show the main features used in discussing colloid stability

Source: A reproduction from R.H. Ottwill [6]