Waterborne technology:

its greatest limitation is your imagination

Sandy Morrison , Member of SpecialChem Technical Expert Team

Introduction

Waterborne paints have a long and successful history in certain niche applications (see
this month's editorial), but the twin issues of environmental legislation and the low cost of
water as a solvent have encouraged their much wider use. Today's waterborne systems
can - in the same way as their early predecessors - offer application and performance
advantages over solventborne technology, but now in a much wider range of situations.

How have paintmakers dealt with the problems inherent in waterborne technology? Are
these limitations fundamental and unavoidable - or are 'fundamental limits' mainly
created by a lack of imagination? This column attempts to answer these questions, while
the accompanying editorial looks at market statistics and the (very) early history of
waterborne coatings.

Breaking the boundaries

It has been estimated that in western economies, as much as 90% of the volume of DIY
paints sold are now waterbornes. Outside this field, the picture is a mixed one.
Waterborne coatings successfully dominate the market for interior wall paints and
exterior masonry coatings, but elsewhere they must compete with high solids,
solventless and radiation curable systems as environmentally friendly, regulation-
compliant coatings.

Insert any one of the three pictures of houses in this section No caption required

Some problems have been regarded as inevitable when using waterborne coatings - but
some which appeared to be insoluble turn out not to be. So what are the prospects for
breaking out of these supposed boundaries?

Foaming v wetting: an end to a paradox?

Two of the best known and almost universal problems which have limited the
performance of waterborne paints are foaming and poor adhesion. Both arise from the
same cause: water has a far higher surface tension than any other solvent used in
coatings. Solutions have tended to be in conflict with each other, since highly effective
surfactants that will promote adhesion are often excellent foam generators, whereas
defoamers may cause surface wetting problems and many are slowly deactivated during
storage of the wet paint by the surfactants.

Recent developments in molecular engineering have created various types of complex

surfactants which are able to enhance both foam control and substrate wetting. What all
these materials have in common is that two or more surfactant moieties are firmly bound
into the same molecule, and the defoaming effect takes place at a molecular level, rather
than being affected by the particle size of the defoamer. Storage stability is also
enhanced by the fact that defoaming no longer depends on maintaining an optimum
particle size. The simplest types, called 'gemini surfactants' comprise two surfactant
molecules bound together by a spacer molecule. Other companies offer more complex
'star' molecules and dendrimers.

Improving substrate penetration and bonding

Also related to the issue of substrate wetting is the limited penetration of emulsified
resins into porous substrates, though the first cause of this is that emulsion particle size
is much larger than that of the molecules themselves. Waterborne alkyds, with their finer
particle size and slow oxidative drying, are frequently incorporated into emulsion paints
to improve the penetration of woodfinishes, though this is at the expense of drying time.

One approach to defeating the particle size problem is a substituted styrene-acrylate

resin in which the emulsion particles incorporate an aliphatic hydrocarbon which is a true
solvent for the resin. As the water evaporates, what is in effect a high-solids solvent-
borne paint is formed. Coatings based on this product are reported to penetrate twice as
deep into porous masonry as conventional acrylic emulsions, and as a result, provide
improved adhesion.1 The system does not require additional coalescing solvents and
paints can be formulated with a VOC content of 75 g/l or less.

Alkyd/acrylic hybrids have been developed in which the alkyd resin core is protected
during storage by an acrylic layer, but which allow the (water-insoluble) alkyd to
penetrate wooden substrates after drying and cure by oxidation. Current versions of this
technology appear to suffer from the unfortunate combination of limited wet-edge time
but extended hard-dry times. However, improved drying has been claimed for a
modification in which secondary hydroxyl groups are present in the ester linkages of the
alkyds.

If you cannot improve penetration, a useful alternative is to increase adhesion.

Isocyanates are capable of developing a covalent bond with hydroxyl groups on the
surface of wood and this process can improve the adhesion of wood primers. However,
when isocyanates are added to waterborne systems, they immediately begin to react
and so applying this concept to waterborne primers presents some difficulties. Some
experiments have been carried out using an application system with continuous
isocyanate addition to minimise these problems. Panels coated with this primer showed
improved adhesion (especially wet adhesion). This improvement was retained when the
primer was overcoated, but after prolonged ageing, differences in performance were less
marked. Thus, the isocyanate addition reduces the risk of early damage to the paint on
the coated articles.2

'Insoluble' coalescence problems: 1- achieving high gloss

While disruption of film formation can occur when coatings are deposited from solution, it
is usually easily avoided by appropriate formulation. The matter becomes much more
difficult when dealing with waterborne dispersion resins. As is well known, coalescence
of the individual particles requires them to have a soft surface so that the particles will
fuse together at the surface, a requirement which conflicts with the general desire for the
coating to have a hard and tack-free surface. Standard solutions to this problem include
core-shell particles (discussed in more detail below), volatile coalescents, reactive
diluents and the use of crosslinking resins.

Theoretical studies have shed light on further problems. If surface drying proceeds
rapidly, a surface 'skin' of partly coalesced particles may form which inhibits further
evaporation and leads to irregular film formation. The concept of the Péclet number
(used in fluid dynamics) has been applied to this situation. Its value increases with the
viscosity of the continuous phase, film thickness, evaporation speed and particle size. At
low values, the particles are able to diffuse rapidly enough (due to Brownian motion) to
ensure uniform drying; at high values they will be drawn towards the surface, causing
premature skinning.3

Further work by the same researchers showed that the presence of 'free' surfactant and
other low MW water-soluble materials can interfere with smooth film formation even at
temperatures well above the Tg of the resin.

Thus it should be no surprise that high gloss air-drying waterborne finishes are rarely
able to match the gloss levels of traditional alkyds, and if they do, the haze or
distinctness-of-image is usually inferior. A recent study provides further light on this
problem.

Fundamentally, the apparent gloss is dependent on surface roughness and overall

refractive index of the film. Attempts to reduce the surface roughness of gloss emulsions
to match that of alkyds were unsuccessful, even with low pigmentation, high film
thickness and variations in rheology. Electron microscopy revealed a key difference: the
surface of the alkyd film was a continuous resin layer, whereas particles of titanium
dioxide protruded above the surface of the emulsion paint. Application of an
unpigmented layer of waterborne resin produced gloss levels matching those of an
alkyd, and in this situation, the gloss was affected significantly by the refractive index of
the binder (styrene acrylic having a higher RI and gloss than pure acrylic).

However, few people will be willing to adopt this basecoat/clearcoat concept in

decorative applications. A water-based alkyd-acrylate resin has now been developed
which forms a continuous resin layer during drying and is able to match the gloss and
distinctness-of-image of traditional alkyds.4

'Insoluble' coalescence problems: 2 - the road to zero VOC

The fundamental requirement for film coalescence to occur is that the surface of the
polymeric particles must be sufficiently soft to merge into one another as the film
contracts. On the other hand, a hard film surface is necessary to resist damage, dirt
pickup and solvent penetration.

If paints are formulated using 'standard' dispersions without coalescents, the low Tg
which used to achieve coalescence results in soft films, poor resistance to staining and
dirt pickup and an increased risk of film formation defects. Yet in practice several
different ways have been found to minimise or avoid this problem and produce good film
properties in single-pack air-drying near-zero VOC paints.

A simple but limited approach is to use emulsions such as VAE (vinyl acetate-ethylene)
copolymers which are naturally hydrophilic. Water itself acts as a 'cosolvent' during film
formation, so that for a given minimum film forming temperature (MFFT), the Tg of VAE
emulsions is significantly higher (by about 8°C) than that of styrene-acrylic emulsions.
Similarly, in the case of polyurethane dispersions, the presence of water within the
emulsified particles themselves assists in achieving coalescence.

Several coalescents have been developed with sufficiently high boiling points and low
volatility to ensure that they are not legally classed as VOCs - though the question of
whether they are released into the atmosphere over a very long period is hard to
answer.

• 2,2,4-trimethyl-1,3-pentanediol (isobutyric acid, 1-isopropyl-2,2-dimethyltrimethyl

ester) has a boiling point of 280°C, which means that it is legally not classed as a
VOC, but may be so classed in some environmental standards.
• Archer RC is a zero-VOC coalescent for waterborne inks, paints and sealants.
The material is based on propylene glycol monoesters of sunflower and corn oil
fatty acids. It crosslinks during drying rather than evaporating, adding to the
resistance properties of the coating. Archer claims the product calls for little or no
reformulation, since its HLB value is similar to that of the common coalescent
TMB (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate).
• Cognis markets EFC-100, a propylene glycol mono-oleate with a very high
boiling point as a coalescent. The company claims that although the product
remains permanently in the film, it has little effect on hardness and provides
scrub, stain and blocking resistance that are at least as good as standard volatile
coalescents. In addition, because the product is very hydrophobic, it modifies the
rheology of the system, and in some cases may increase gloss.5

A further approach is to make the coalescent and/or part of the polymer system radiation
curable. Camphorquinone is an effective photoinitiator for curing coatings under natural
sunlight, due to its high absorption at around 450 nm. It has been shown that some
radiation-curable acrylate monomers can be used to replace normal cosolvents with little
or no reformulation. After curing in sunlight, paints containing no other cosolvents
showed hardness values up to 30% higher than those of a conventional emulsion paint
with cosolvents.6

Polyurethane dispersions have traditionally been manufactured using N-methyl

pyrrolidone as a solvent in order to keep the viscosity at a manageable level during the
polymerisation. The NMP remains after the polymer is emulsified and contributes to
VOC levels. Manufacturers are seeking to avoid the use of NMP entirely because of
concerns over its toxicology. Alternatives include the acetone process (where it is
possible to strip off this high-boiling solvent afterwards) or the use of acrylic monomers
as solvents (forming urethane/acrylic hybrids).

Two-pack waterborne PU systems can similarly be produced which need no cosolvent,

by adding hydroxy-functional reactive diluents when forming secondary dispersions of
hydroxy acrylates as the polyol component of the system.

Corrosion protection

At first sight, the use of waterborne coatings for corrosion protection appears perverse;
water is, after all, a key factor in creating corrosion. Nevertheless, one of the great
success stories for waterborne coatings has been the development of the cathodic
electrodeposition process, now the near-universal method of protecting vehicle bodies
against corrosion. It provides a coat of controllable and fairly uniform thickness on both
visible and inaccessible parts of the bodywork with very little use of solvents or waste of
paint.

After initial pretreatment such as phosphating, the body of a vehicle passes through a
tank of waterborne coating while an electric current 'plates' the coating onto the metal.
The coatings are cured by stoving, after rinsing off excess coating which has not been
consolidated into the film. Modern electrocoating formulations are able to provide
effective protection without use of the lead chromates which traditionally served as
anticorrosive pigments.

In more general anticorrosive markets, progressive improvements have been made. A

report from the USA notes that tests of systems based on acrylic and styrene-acrylic
resins in the early 1980s gave poor results, whereas tests in 2000-2002 gave good
results for waterborne acrylics (outperforming waterborne epoxies and a polyurethane)
and indicated that the best waterborne acrylic formulations were now competitive with
solventborne acrylics and epoxies.7

Outperforming solventborne systems

Some of the coatings with the highest resistance to exterior weathering are based on
polyvinylidene fluoride (PVDF), but established PVDF technologies for both liquid and
powder coatings require stoving. These coatings contain about 70% PVDF and 30%
acrylic resin and owe their high performance to the formation of an interpenetrating
polymer network (IPN) on stoving. Waterborne PVDF emulsion coatings are now
available, which are said to achieve similar results without stoving. The key to this
technology is that the emulsion particles themselves must contain IPNs; emulsions
based on core-shell particles will only perform effectively after stoving.8

Unwanted-effect coatings

Reactions between water and aluminium pigments, which can readily blow the lid off a
paint container, can be due to hydrogen generation. Effect pigment suppliers now offer
'protected' grades which resolve the problem; and it does not arise with pearlescents.
This problem can be considered as solved, with waterborne metallic basecoats being
widely used in automotive coatings, but the author can recall some interesting
laboratory-scale failures in the early days of this technology.

A more difficult problem which produces unwanted effects is the staining due to
bleeding-out of coloured compounds in the wood. The kiln-drying process helps to 'set'
resinous materials but has little effect on materials such as tannins. Since these are
water-soluble they (and other staining materials) are more problematic with waterborne
coatings that with solventborne ones.
A range of solutions has been examined, and in general improvements can be achieved
by incorporating barrier pigments (aluminium flake) or reactive pigments (zinc
compounds). A number of more sophisticated approaches have also been developed for
waterborne coatings, relying on the use of cationic materials to immobilise the tannins.

A waterborne cationic epoxy primer has been developed which provides good resistance
against tannin staining over wood and also over nicotine stains when applied over
existing interior paintwork. The binder was formulated as an epoxy-amine adduct
neutralised with an organic acid in order to make it water-soluble, then water-insoluble
epoxy resin was added under agitation to increase the molecular weight. This was
applied as a clear primer to maximise its barrier properties and protected the
subsequently applied acrylic emulsion paint against staining.9 A similar concept has
been applied successfully using styrene-acrylate emulsions. Amine groups are
incorporated into the polymer, and neutralised with volatile organic acids to produce the
coating.10

In addition to improving the physical barrier properties of the coating, improvements can
be obtained by incorporating functionalities such as urethanes which will crosslink with
the extractable components of the wood.11

This approach is highly desirable when using coatings whose cure may be affected by
high levels of extractables (a known problem with radiation curable systems). It has been
claimed that the use of a waterborne primer containing a waterborne dispersion of
crosslinkable urethane and low levels of a suitable crosslinker (preferably an aziridine
rather than an isocyanate) provides more effective stain sealing than a corresponding
solventborne coating.12

Good stain blocking has also been achieved by the addition of exfoliated fine particle
size hydrotalcite, using an anionic dispersing agent for the exfoliation so as to produce
material with a very high surface area that has a cationic exterior. Additions of as little as
0.5% hydrotalcite have been shown to be effective, when added to a self-crosslinking
dispersion resin formulation.

Breaking the solids content barrier

Normally, the solids content of waterborne emulsions is limited by instability as the solids
content increases. While there is no regulatory need to reduce the content of water in a
coating, increasing the solids content allows drying times to be reduced and higher film
build coatings to be applied.

A distinctive form of hybrid resin technology allows very high solids waterborne coatings
to be produced, the resin itself having a solids content of 70-80%. The concept is to
produce a conventional emulsion polymer (normally acrylic) and then to disperse a
second, different resin at a much smaller particle size within the free water of the
dispersion. By careful process control, it is possible to achieve a much lower
viscosity/solids curve than for normal emulsions.

These resins have been found to provide faster drying, good substrate penetration and
adhesion. Water resistance is good, and initial natural exposure trials indicate that the
coatings should have a long useful life.13 These systems have initially been developed
for exterior wood coatings, but their use for masonry coatings is being examined.
Products based on this technology were commercialised in 2003, with a VOC content of
below 25 g/litre.

Key waterborne coating technologies

Having considered some of the once-insoluble challenges which waterborne technology

has successfully overcome, it is also useful to briefly examine some of the key
technologies which are allowing waterbornes to develop yet further towards challenging
and surpassing solventborne technologies.

Core-shell technology

The most significant general concept used to enhance the properties of waterborne
coatings is that of core-shell technology. Many researchers have confirmed that a better
balance of blocking resistance and low-temperature film formation can be achieved by
using either core-shell polymers with a soft shell or mixtures of hard and soft emulsions
rather than homogeneous copolymerised emulsions with the same overall monomer
composition.

The morphology of heterogeneous emulsion particles can in fact take on many more
forms than a simple core-shell structure or a random mixture of components in each
particle. If an initial homopolymerisation is carried out, followed by addition and
polymerisation of a second monomer, the distinctness of the boundary between the core
formed in the first polymerisation and the shell formed in the second depends (among
other factors) on the extent to which the core particles are crosslinked during
polymerisation. If, on the other hand, the different polymers are mixed before dispersion
so that composite particles are produced, separation of the polymers will be driven
mainly by differences in hydrophobicity and surface tension.

Multi-lobed ('raspberry') and other more complex structures can be produced. The
composition of the monomer feed can also be continuously varied during the
polymerisation process to yield 'gradients' of composition from core to shell. An
extension of this technology is to use inorganic nanoparticles to form the core or as part
of the core.
 "Core-shell" particles may have a range of very different
morphologies

A recently announced development is the production of emulsions which incorporate

within the particles monomers that have an affinity for pigments. This helps to ensure
that pigment particles remain unflocculated and are more uniformly distributed in the
paint film. It is claimed that these emulsions give improved corrosion and abrasion
resistance as well as the increased opacity and higher gloss which would be expected.14

This construction can be created readily, since a mixture of hydrophobic and hydrophilic
materials dispersed together will tend to form droplets in which the hydrophobic material
is encased by the more hydrophilic one - especially if the latter has surfactant-like
properties.

Polyurethane dispersions and their hybrids

Waterborne polyurethane dispersion (PUD) coatings were first introduced in the 1970s
and are now produced in non-reactive physical drying, 2-pack and UV curable forms.
The properties of the final coating can be varied from very hard to extremely flexible. The
backbone of a PUD may be made from many different materials, including polyesters,
polyethers and polysiloxanes, but recently a number of authors have claimed that a
better overall balance of properties can be obtained (at higher cost!) by using a
polycarbonate backbone.

Their high cost can be reduced by mixing with other resins. Simple blending of
polyurethane dispersions (PUDs) with acrylic emulsions provides useful coatings with a
good cost/property balance, but much better performance can be obtained by preparing
true urethane/acrylate hybrids. Two types are known:

• Type 1: Acrylic monomers are added to an existing PUD and polymerised in the
mixture.
• Type 2: Initial urethane polymerisation, which normally requires a solvent to
maintain a low viscosity, is carried out, using part of the acrylate monomer in
place of a solvent. Dispersion occurs automatically when the prepolymer is
added to water. Chain extension can be carried out at this point to increase the
MW, followed by acrylate polymerisation.

In either case, the individual emulsified particles contain intimate mixtures of the two
polymers. Frequently, the particles are swollen and plasticised by water molecules,
which assists coalescence.

Although PUDs are supplied as fully crosslinked high MW resins which need no curing
agent, the addition of a polyisocyanate will provide harder films and improved chemical
resistance. (If the PUD has no hydroxyl functionality, the isocyanate simply self-
crosslinks by moisture curing.) Another way to produce tougher films is to incorporate
acrylate functionality, add a photoinitiator and cure under UV irradiation. Such coatings
have the advantage of having a low crosslink density, making them much more flexible
than standard UV curable coatings, while also producing reasonable hardness and
mechanical properties in shadow areas which are not fully cured.

Self-crosslinking PUDs have been developed which have good storage stability, but
which undergo a rapid carbonyl-amine crosslinking reaction during drying, if the coatings
are formulated with a volatile amine as pH stabiliser.15

Extending the scope of epoxies

Type I waterborne epoxies, developed in the 1970s, use liquid epoxies emulsified by
water-soluble polyamide curing agents. In the later type II systems, the curing agent is
mixed into a dispersion of solid epoxy which contains some solvent. Each has strengths
and weaknesses. Type I coatings form mixed emulsion particles at the outset and
require little cosolvent. They produce hard coatings, but with insufficient flexibility and
impact resistance for use over metal substrates. Type II systems dry more rapidly and
are more flexible, but usually require high levels of cosolvent as it is necessary for the
curing agent to become dispersed within the epoxy emulsion particles.

Recently, an epoxy resin has been developed which has a very low particle size in
dispersion and a relatively high fraction of low MW material, both of these factors making
coalescence easier to achieve and producing a system which is intermediate between
Type I and Type II.16 Initial tests indicate that it is possible to produce anticorrosive
primers, gloss finishes and concrete coatings with good performance at very low
cosolvent contents.

Dow has developed a range of fine particle size (below 1 µm) epoxy dispersions
produced by a patented mechanical dispersion process which are solvent-free and
stabilised by nonionic surfactants which are epoxy functional and so crosslink into the
final coating. The very fine particle size ensures homogeneous curing when used with a
water-soluble curing agent, and high gloss and resistance properties can be obtained.

The range of applications open to these coatings has been further extended by the
development of hydrophobic polymeric amines which provide increased colour stability
as well as improved acid resistance.

The furniture industry

As noted in this month's editorial, the furniture industry represents an important but
difficult market for waterborne coatings. A major European project known as the COST
E18 initiative has been operating for several years, with the objective of improving the
performance, durability and environmental profile of coated wood structures. Two issues
have led to the furniture industry being closely studied in COST:

• The industry is highly fragmented, with as many as 60 000 SMEs in Europe that
may have difficulty in carrying out detailed research or making major investments
in new plants;
• Natural wood is used in high quality furniture, and is one of the most difficult
substrates to deal with in terms of maintaining the appearance of traditional
finishes while retaining good physical and chemical resistance properties.

While the use of waterborne coatings in the industry rose from 5% in 1997 to 16% in
2003 and the use of radiation-curable coatings also increased, the industry has a major
problem in trying to comply with the European VOC emission targets overall.

A COST report from early in 2006 indicates that by that time, waterborne technologies
had improved to the point at which single-component coatings could replace
nitrocellulose, and waterborne UV and PU coatings their solventborne counterparts. An
investigation of energy consumption in drying indicated that the increase in power was
not as great as might be imagined, though care had to be taken in selecting the most
appropriate oven drying system.17

Cleaner and greener: miscellaneous applications

Finally, it may be interesting to consider some of the byways of waterborne coatings

technology, once again illustrating the point that we never know what is possible until it
has been done. Dow Chemical has recently developed a method by which solvent-free
very fine particle size dispersions of polyolefins can be produced (these materials cannot
be produced via emulsion polymerisation and have very high melting points).
Coalescence requires heating of the applied film to the melting point of the polymers,
though no crosslinking reactions are involved. These materials can be applied by many
industrial processes and are expected to prove useful in applications such as textile
coatings, carpet backings and lamination adhesives and can also be foamed.18

HMG paints (UK) recently introduced a waterborne grass-marking paint for use in
creating promotional signage at sports events. Paint Away has been formulated to resist
the inevitable British rain, provide strong colours which will show up well on TV
broadcasts, yet can be dispersed by a special cleaner which does not harm the grass.

Electrolube (UK) has developed a waterborne conformal coating (for protection of

electronic components) which eliminates the low flashpoint solvents often used in these
materials. It meets the high demands for resistance to solvents, humidity and wide
temperature operating range, though it does not provide as high a level of insulation
resistance as standard solventborne types. It can also be soldered through without
releasing toxic gases.

Radiation curing coatings may be considered a 'competitor' for waterborne coatings, but
it should be noted that solventless UV systems have a number of limitations which can
be resolved by the use of waterborne versions. Waterborne radcure coatings avoid the
need to use high levels of monomer diluents, which in turn allows films to be produced
with lower crosslink density, less shrinkage on cure and better substrate adhesion.
Oxygen inhibition may be reduced, and controllable matting is much more easily
achieved.

But, no matter how good the performance of a paint, no matter how environmentally
friendly it is, waste is inevitably produced and must be disposed of. Various schemes
have been used to recycle waste decorative emulsion paint in particular, ranging from
simply collecting the paint and offering it to charitable and community associations to
blending it and attempting to recycle it into new paint. Recently, however, researchers at
Rutgers University (USA) have shown that it is possible to blend waste paint solids with
either HDPE or PMMA (methyl methacrylate). Aside from a loss of transparency, the
paint addition had little effect on the properties of HDPE and acted as a toughener and
flexibiliser for the PMMA.19

Waterborne limits drift with time

As this review has I hope shown, waterborne technology has broken down most of the
apparent limits to its wider adoption, and known technologies are even now taking these
developments further.

The ultimate and intractable limit is that water is a slow-evaporating solvent with an
inconveniently high freezing point. Drying time has been speeded up by (for example)
producing solids contents higher than the theoretical limit. So who will be first to
introduce a waterborne coating with an MFFT below zero? Don't say it will never
happen; think about how to make it happen!

References

1. F Duval, A Fream, Polym Paint Colour Jnl, Jan 2004 pp 36, 38

2. J G Nienhuis, M A J Akkerman, Surf Coat Intl B, June 2002 pp123-129
3. J L Keddie et al, Surf Coat Intl A, 2004/02 pp 70-73
4. R Dersch et al, paper presented at Nürnberg Congress, May 2007
5. A A Khan et al, PRA Waterborne & High Solids Coatings Conference 2006,
paper 15
6. D Burget, 7th Nürnberg congress, 7-8 April 2003 paper VI.1, pp 73-83
7. S L Chong, Y Yao, US Dept of Transport report FHWA-RD-03-032 (online)
8. K A Wood, Europ Coat Jnl 09/2005 pp 48, 50-53; Arkema press release, June
2006
9. R Feola, M Gobec, China Coat Jnl, 2/2007 pp 26, 28-33
10. J Fischer, W van Drunen, Europ Coat Jnl, 2007/05 pp 168-170
11. D Twene, D Mestach, Surface Coat Intl A, Nov 2004 pp 384-389
12. USP 7 157 120
13. J H Olsen, PRA Woodcoatings Congress Oct 2004 paper 41; USP 6 277 910
14. M Bleuzen et al, Europ Coat Jnl, 2007/5 pp 144,146, 148-9
15. A van den Elshout, Surface Coatings International A, A06, July 2003 pp 229-232
16. Ancarez AR 550 resin
17. M Roux et al, PRA Waterbone & High Solids Coatings Conference 2006, paper 3
18. C F Diehl, PRA Waterbone & High Solids Coatings Conference 2006, paper 6;
 SpecialChem online seminar, 21 June 2007
19. M Drukenbrod, SpecialChem, 22 March 2007