A New Generation Waterborne All Acrylic (WB AA) System

Author: Dr. Richard H. Hall, Nicole E.M. Presented by: Dr. Richard H. Hall
Mangnus-Verhagen, Technical Project Manager
Maarten J.J. Weber Surface Coatings Resins
Company: Akzo Nobel Resins b.v.
Synthesebaan 1 Tel: +31 (0)164 276561
P.O. Box 79 Fax: +31 (0)164 276502
4600 AB Bergen op Zoom e-mail: Rick.Hall@AkzoNobel.com
The Netherlands

Hall, Rick (Dr.) obtained his doctorate from Queen's University, Belfast, Northern Ireland in 1
After 10 years at the National Chemical Laboratory, Pretoria, South Africa and 18 months at
Technical University of Twente, Enschede, the Netherlands, he joined Akzo Nobel Resins. He
present a Technical Project Manager, specializing in waterborne and UV projects.

A New Generation Waterborne All Acrylic (WB AA) System

Summary:

The Waterborne All Acrylic (WB AA) system is an isocyanate-free, easily mixable, two pack c
system with a low co-solvent level. It was originally developed for topcoats in the general me
market but is finding many applications on other substrates such as wood and plastic. It is b
on amino functional acrylic emulsions and epoxy functional acrylic dispersions. The range ha
recently been extended with an amino resin with much improved stability, Setalux 8455 AQ-
and an APE-free epoxy resin, Setalux 8552 AQ-50. Now, all WB AA resins, except one, are A
free. This presentation will concentrate on recent developments and new evaluation results.

Introduction:

Solventborne coatings are easy. Every coatings company has a vast wealth of experience in
formulating solventborne coatings and while these companies are all busy with improvement
price reduction the techniques and ways of working are generally well known. In general, the
a good degree of application freedom and there is an abundance of resins and additives that
be used to improve the formulation.

That is to say, solvent-borne coatings are easy compared to their waterborne counterparts. W
waterborne coatings, more compromises have to be made and physical properties become m
important. To start with, oil with water has to be mixed and the mixture has to remain stable
There are not so many suitable additives for waterborne formulations. Indeed, there are less
waterborne resins available.

Nevertheless, most companies producing resins are applying a very large part of their resear
effort in developing waterborne resins. Those companies that are not concentrating on water
resins are developing 100% resins such as powder resins or UV resins. The trend cannot be
stopped. Solvents are taboo or are quickly becoming so if all the predictions are to be believe

Many projects to develop a waterborne system begin by attempting to bring a successful

solventborne resin system into water and this is how it began with the development of the
Waterborne All Acrylic (WB AA) system.

The Solventborne All Acrylic (SB AA) system:

The solventborne AA system is a well-established system, having been introduced in 1983. T
second and third generation systems, namely Setalux 8402 XS-55/Setalux 8403 SS-55 and
Setalux 8502 BX-60/Setalux 8503 SS-60, respectively, are commercially available at present
Projects are currently running to improve the system.

The SB AA system is an isocyanate-free two component system based on two acrylic resins,
with built-in tertiary amino- and carboxylic acid functionality and the second component with
epoxy functionality. It must not be confused with conventional two component epoxy-acid
systems. These are also usually based on amino-, carboxylic acid- and epoxy functionality.
However, whereas epoxy-acid systems have high amounts of both carboxylic acid- and epox
functionality and low amounts of amino-functionality, the AA system has high amino- and ep
functionality and low carboxylic acid functionality.

The two resin types used in the SB AA system are prepared by radical polymerization of the
relevant acrylic monomers in solvent and are represented in Figure 1.

Figure 1. The resins of the Solventborne All Acrylic (SB AA) system

The Waterborne All Acrylic (WB AA) system:

In the early 1990´s it was decided to develop a waterborne version based on the third gener
solventborne system. The preparation of the epoxy component was readily achieved using th
emulsion polymerization technique without making too many compromises with the monome
composition. It is stabilized with a non-ionic surfactant.

The amino component proved to be more difficult to prepare but was eventually developed u
the secondary emulsion technique. The polymer is prepared in solvent by radical polymerizat
the solvent is removed, a small amount of co-solvent is added to the resin and the mixture is
directly emulsified by dosing it into water containing amine. Again, as few as possible
compromises were made with the monomer composition. The resins of the WB AA system ar
represented in Figure 2.

Figure 2. The resins of the Waterborne All Acrylic (WB AA) system

The first generation Waterborne All Acrylic system,namely Setalux 8450 AQ-36 and Setalux
AQ-50, was introduced in 1996 [1] and the major differences between the third generation
solventborne AA resins and the first generation waterborne AA resins are represented in Tab

  SB AA WB AA
3rd Generation 1st Generation
epoxy 402% butyl acetate 502% water
resin as solvent as solvent

non-ionic
surfactant
amino 452% butyl acetate ca. 62% water
resin as solvent as solvent

ca. 2% butyl glycol

as solvent

tertiary amine

Table 1. Comparison of SB AA and WB AA resins

Since its introduction in 1996 several comparisons of the coatings characteristics of the first
generation WB AA system with SB AA and SB and WB two-pack acrylic polyol-polyurethane
systems have been presented [2, 3, 4]. Further, details of the curing mechanism have also
presented [5].

In 1998 two new WB epoxy resins were introduced and are known as second generation prod
namely Setalux 8551 AQ-45 and XL 1074. The major difference is that they are stabilized wi
anionic surfactant and the difference between Setalux 8551 AQ-45 and XL 1074 is a differen
Tg.

The WB AA system was developed for the industrial applications as topcoats on primed meta
first generation epoxy was developed for application on WB epoxy-amine primers and the se
generation epoxy for application on cataphorese primers. However, more and more applicatio
are being developed on other substrates such as wood and PVC.

The 1st generation WB AA amino emulsion (Setalux 8450 AQ-36)

Since the introduction of the WB AA amino resin it became apparent during the scaling up pr
that there was an inconsistency in the stability of the viscosity of the amino functional emuls
Several batches had a tendency to increase in viscosity in a relatively short space of time. Th
characteristic was not constant and could initially only be detected by studying the stability o
resin at 40°C over a period of 4 weeks. The viscosity instability was very severe. Unstable re
were semi-solid within months (Figure 3).
Figure 3. Viscosity instability of Setalux 8450 AQ-36

The coatings properties were not affected by the phenomenon but it was first required to hea
resin before formulating a paint. It was also shown that dilution of the resin further retarded
increase in viscosity.

Subsequent investigation showed that the resin was very susceptible to traces of butyl aceta
fact, the increase in viscosity resulted from the hydrolysis of the ester to form acetic acid.

As explained above, Setalux 8450 AQ-36 is prepared by first preparing the acrylic polymer in
solvent. The solvent is butyl acetate, the original solvent used in the SB amino product. The
acetate is then removed by distillation, approximately 5% butyl glycol is added to the very v
"100%" polymer and the mixture is emulsified in water with in the presence of an amine.
However, it is virtually impossible to remove all traces of butyl acetate from the highly viscou
resin, even at elevated temperature and deep vacuum and traces of butyl acetate are always
present in the emulsion.

The pH of the amino emulsion is approximately 10 and it is well known that butyl acetate is v
susceptible to hydrolysis under these conditions. What was not suspected was the degree of
susceptibility to low amounts of butyl acetate or acetic acid. This was clearly demonstrated b
preparing the intermediate in xylene and then contaminating the resulting amino emulsion w
known amounts of either butyl acetate or acetic acid (Table 2).

It can clearly be seen that the level of butyl acetate must be contained below 0.5% (weigh-w
butyl acetate-solid resin). Addition of similar amounts of n-butanol had no affect on the visco
Similarly, contamination with the same amounts of methacrylic acid had little effect on the
viscosity. Only with much increased addition of methacrylic acid did the viscosity increase.
   Click for large image

Table 2.
Viscosity of Setalux 8450 AQ-36, contaminated with butyl acetate or acetic acid and stored a
40°C

Acetic acid is miscible in water at all levels and methacrylic acid is much less soluble in water
can be surmised that with the gradual build up of small amounts of acetic acid in the water p
of the emulsion forces part of the water-soluble polymer into the solid phase and this results
increase in viscosity. This was confirmed by analysis of several batches of the amino emulsio
There was a clear relationship between viscosity and the level of water-soluble polymer.

Since the discovering of the effect of residues of butyl acetate on the amino emulsion, levels
butyl acetate and acetic acid have been monitored by analysis at various stages of the prepa
process and in the final amino emulsion. In this way it was possible to deliver the amino emu
without a tendency to increase in viscosity.

The third generation WB AA amino emulsion (Setalux 8455 AQ-36):

In order to eliminate the possibility of excess contamination with butyl acetate it was decided
eliminate butyl acetate from the process all together and, at the same time, to remove butyl
from the system. Various solvents and co-solvents were evaluated and eventually it was dec
to use 1-methoxypropan-2-ol as both solvent for the intermediates and as co-solvent. This h
resulted in the development of the third generation amino emulsion, Setalux 8455 AQ-36 (Th
no second-generation amino emulsion). It must be emphasized that only the solvent and co-
solvent have been changed as shown in Table 3.

Characteristics Setalux 8450 AQ- Setalux 8455

36 AQ-36
1st Generation 3rd Generation
Polymer Identical Identical
composition
Amino equiv. Identicalca. Identicalca.
Weight 655 (on solids) 655 (on solids)
Total solvent Identical (2-3%) Identical (2-3%)
content
Organic (co) Butyl glycol 1-Methoxy-
solvent Butyl acetate propan-2-ol
Table 3. Comparison of Setalux 8450 AQ-36 and Setalux 8455 AQ-36

This minor but very essential change results in viscosity stability of the amino emulsion. Seta
8455 AQ-36 has been extensively tested as follows:

 5 cycles freeze-thaw
 8 weeks at 40°C
  3 days at 60°C

After the tests at elevated temperatures Setalux 8455 AQ-36 showed only a slight increase i
viscosity. All the samples, after the above tests, have been shown to perform similarly to fre
prepared samples. Tests are currently running to study further the aging process of the emu
and its effect on performance.

The 3rd generation WB AA epoxy dispersion (Setalux 8552 AQ-50):

Setalux 8550 AQ-50 is stabilized with a non-ionic surfactant and Setalux 8551 AQ-45 and XL
are stabilized with an anionic surfactant. The surfactant used in Setalux 8550 AQ-50 is a non
phenol type (alkylated phenol ethoxylate, APE) surfactant. Many clients do not wish to work
products containing such surfactants. It was therefor decided to develop an APE-free analog
Setalux 8550 AQ-50. This was readily achieved by simply replacing the original surfactant wi
alcohol ethoxylate type. Again, it must be emphasized that this is the only difference as show
Table 4.

All the various components of the Waterborne All Acrylic system are now APE-free except for
Setalux 8550 AQ-50.

Characteristics Setalux 8550 AQ- Setalux 8552 AQ-50

50
1st Generation 3rd Generation
Epoxy equiv. Identical Identical
Weight
Amino equiv. Identical ca. Identical ca.
Weight 620 (on solids) 620 (on solids)
Total solvent Identical (0%) Identical (0%)
content
Type of APE Non-APE
surfactant
Table 4. Comparison of Setalux 8550 AQ-50 and Setalux 8552 AQ-50

The WBAA epoxies has been extensively tested as follows:

 3 cycles freeze-thaw
 13 weeks at 40°C
 3 days at 60°C

As expected the Setalux 8551 AQ-45 and XL 1074, stabilized only with an anionic surfactant
not survive a single cycle freeze-thaw. The other epoxy dispersions, Setalux 8550 AQ-50 and
Setalux 8552 AQ-50 stabilized with non-ionic surfactants, came through with no problems. A
epoxy dispersions had good viscosity and particle size stability after 13 weeks at 40°C. After
days at 60°C a very thin film formed at the surface. This film can easily be removed. Tests a
running to study the aging process of the epoxy dispersions and its effect on the performanc
the system.
Performance in coatings formulations
The following combinations:
 Setalux 8450 and Setalux 8550 (1st Generation)
 Setalux 8455 and Setalux 8550 (3rd and 1st Generation)
  Setalux 8455 and Setalux 8552 (3rd Generation)

were tested in a white topcoat as shown in Table 5.

  Click for large image

Parameters   Application
Non-volatiles
50.% recipe Spray viscosity   : 25-28 seconds DIN 4, 23°C
23°C
1.25
Density Spray pressure   : 500 kPa
kg/dm3
PVC 18.5%  
85/100
Pigment/binder  
(solids)
VOC 83 g/litre at  
appl.
viscosity
Perc. cosolvent 2.3 % at Amine : epoxy ratio : 43 : 57
appl.
viscosity
Table 5. Starting point formulation for WB AA
The stability of the paint based on Setalux 8450 AQ-36 and Setalux 8455 AQ-36 resins but w
the epoxy resin is given in Table 6. Setalux 8450 AQ-36 contained between 0.5 and 1% but
acetate and this is responsible for the increase in viscosity of the base paint. If Setalux 8450
36 with less than 0.5% butyl acetate is used there is much better viscosity stability in the pa
The choice of additives is very important and it is advisable not to use acidic additives unless
absolutely necessary. Use of acidic additive often result in an increase in viscosity of the base
paint. In the recommended formulation the base paint is remarkably stable.
 
Viscosity (DIN cup 4, 23°C in seconds
Time Setalux 8450 Setalux 8455
Start 60 60
After 1 week 80 60
After 2 weeks 120 60
After 3 weeks 180 60
Table 6. Stability of paint without epoxy resin as shown by increase in viscosity.
The potlife of the formulation (with epoxy resin and additional additives) is given in Table 7
Table 8. It can be seen in Table 7 that up to 24 hours there is only a small increase in visco
with all three combinations. The presence of the residue of butyl acetate in the first combina
has little effect and it might be concluded that a potlife of 24 hours is possible with all
combinations.
 
Viscosity (DIN cup 4, 23°C in seconds
Setalux 8450 Setalux 8455 Setalux 8455
Time
Setalux 8550 Setalux 8550 Setalux 8552
Start 25 25 25
After 1 hour 23 24 26
After 3 hours 25 25 25
After 5 hours 26 25 25
After 8 hours 25 25 27
After 16 hours 25 25 26
After 24 hours 32 28 27
After 36 hours 45 35 30
After 48 hours 60 50 35
After 72 hours GEL GEL GEL
Table 7. Potlife of formulations (with epoxy resin) as shown by increase in viscosity.
However, the formulations were allowed to stand at ambient temperature for 1 hour, 2 hours
as shown in Table 8 and then applied on glass. The gloss level, haze and hardness were