Acrylic and acrylic/styrene copolymer dispersions

Sunday, 01. March 1998

Quelle/Publication: European Coatings Journal

Ausgabe/Issue: 3/1998

Modern binders for emulsion paints Latex paints can be formulated from a variety of polymer dispersions. This article compares the
properties of acrylic and acrylic!styrene dispersions when used as binders in such paints. The films formed from these dispersions
absorb little water. Acrylic/styrene films are more permeable to water vapour than straight acrylic ones. There is no difference in the
performance of acrylic and acrylic/styrene latices in mat paints formulated for use outdoors. 1 Introduction Emulsion paints and
textured finishes are usually based on aqueous dispersions of acrylic ester or vinyl ester copolymers. This paper will look at acrylics
only and compare the properties of acrylic and acrylic/styrene copolymers. In 1929 in Ludwigshafen/Germany, Fikentscher developed
a process for the emulsion polymerization of acrylic esters. Aqueous dispersions of these copolymers, called latices, have been used
in Europe for exterior emulsion paints since the mid- 1950s. The paints at that time exhibited good saponification resistance but poor
resistance to chalking. In the mid- 1960s, the first acrylic/styrene binders appeared on the European market. Acrylic and
acrylic/styrene binders have been in continuous competition ever since. Why were acrylic/styrene binders developed? Vinyl ester
polymers dominated the emulsion paints market up until the mid-60s. Premature dirt pick-up, higher water absorption and destruction
of the binder by saponification on alkali substrates were just some of the problems associated with vinyl esters. Pure acrylic
dispersions did offer a technical solution, but their higher price was out of proportion to the potential gains. The market demanded a
cheaper binder, yet with all the advantages of pure acrylics - low water absorption, high alkali resistance and low dirt pick-up of the
coating. These requirements led to the development of a new dispersion based on butyl acrylate and styrene. A further advantage of
this fine-particle anionic dispersion was high pigment-binding capacity; this marked a new era for highly pigmented mat interior
emulsion paints characterized by good wet scrub resistance. Low water absorption proved to be an important property when it came
to textured finishes. Acrylic/styrene dispersions quickly grew in popularity in the masonry paints segment, as accelerated and
long-term trials confirmed the advantages predicted. Even today, almost 30 years after the start of the first field trials, there are
buildings that still have their original coats (see Figure 1 of building in Ludwigshafen/Germany, painted in 1969 and photographed in
1997). It is in masonry paint applications that the acrylic-versus-acrylic/styrene question arises continually. To answer this question,
the differences and similarities between both types of acrylic dispersions will be discussed in the following. 2 Acrylic copolymer
dispersions There are two types of acrylic copolymer dispersions produced industrially: those consisting of only acrylates - the
so-called pure or straight acrylic dispersions - and those made up of acrylate and styrene. The monomers used in pure acrylic
dispersions are acrylic or methacrylic esters; those used in acrylic/styrene polymers are styrene and (chiefly) acrylic esters. Table 1
shows the range of monomers used in both types of copolymer. The monomers available allow a wide range of copolymers with
greatly differing properties to be produced. It is therefore certainly untrue that all pure acrylic polymers have similar properties.
Coatings based on EA/MNA copolymers, for instance, are prone to chalking; those based on nBA/MMA are stable. The situation is
similar with acrylic/styrene polymers. If one wants to produce an EHA/styrene polymer and a BA/styrene polymer having the same
glass transition temperature, the EHA/styrene copolymer has to contain a higher proportion of styrene to compensate for the lower
glass transition temperature of EHA. But because styrene has poor UV stability, use of a polymer containing less styrene (here
BA/styrene) is preferable for formulating paints for use outdoors. Acrylic/styrene copolymers have the advantages of high pigment
binding capacity, low water absorption and high resistance to saponification. Of course, exterior paints can be made from pure acrylic
binders, which are resistant to weathering and UV. They also generally absorb less water than vinyl esters. Pure acrylics are prefered
for "binder-rich" formulations, i.e. those having a low pigment content (e. g., varnishes, wood stains and gloss emulsion paints).
Figure 2 shows the types of coatings in which the two classes of binders are used and the volume concentration of pigment they
contain. Two typical copolymer dispersions - one a pure acrylic (Ak), the other an acrylic/styrene (Ak/S) were used for the
experiments. They are described by their constituent monomers, minimum filmforming temperature (MFFT) and their water
absorption ( Table 2). Tests were carried out on films formed from the pure dispersion and various masonry paints in which the
dispersion was present as the binder. The paints were applied to a substrate and allowed to weather naturally; they were examined
for evidence of chalking and colour change at specific intervals. 3 Tests on polymer-dispersion films Polymers used as binders in
architectural coatings exposed to the weather must meet several performance criteria. Apart from its decorative role, the coating must
protect the masonry work from moisture and so preserve the fabric of the building. The main factors to consider when formulating
such a coating are: * the moisture protection afforded, * resistance to fading. Moisture protection (i.e., the resistance the coating
offers to the penetration of moisture) is the main technical criterion for masonry paints. This is because water, in all its physical states,
is still the main cause of damage to buildings. The "hydraulics" of a coating can be described well in terms of two variables: * water
absorption, * water vapour transmission rate (WVTR). Low water absorption is important in rainy climates, including European
latitudes. Water absorption by capillary action can be minimized by careful formulation and application of the coating. The use of
organic binders has a measurable effect on water absorption and WVTR; the extent depends on the constituents of the binder (type
of main and auxiliary monomers, emulsifiers and additives present) and the polymerization process. Water absorption and vapour
transmission are therefore important selection criteria for dispersion binders for masonry paints. 3.1 Film testing procedures The
water absorption and water vapour transmission rate of paint films and dispersion films were determined. Preparation of the specimen
was made as described in the following. 3.1.1 Water absorption in polymer films Pure dispersion was mixed with 1 % of "Lusolvan
FBH" and 0.5% of "Luconyl Red 3396". The mixture was allowed to "mature" for 24 hours. Then the mixture was poured into a
shallow silicone rubber tray, dried for three days at room temperature and then for seven days at 50 °C; the dry film thickness was
approximately 0.5 mm (± 0.1 mm). Six test specimens were taken from the film for each type of dispersion. The paints were applied
on a sheet of glass by a film applicator. The film was dried as above and six test specimens obtained for each type of dispersion. The
dry film thickness was also similar. The films were immersed in water for a number of cycles. Each cycle consisted of weighing the
film, immersing in water for 24 hours, removing excess water with absorbent material, weighing, drying for 48 hours at 50 °C and
finally re-weighing. 3.1.2 Preparation for the measurement of water vapour transmission Three unprimed discs of fritted glass were
coated with 2 g of paint; this corresponded to a coating weight of 300 g/m². The specimens were dried for three days at room

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 temperature and then for seven days at 50 °C. Water immersion was made as described in chapter 3.1.1. 3.2 Results of the water
obsorption and water vapour transmission tests Polymer films immersed in water turn hazy as they absorb moisture. The rate of
water absorption, and the amount of water absorbed after a given time, can be taken as a measure of the film's resistance to
moisture. Absorbed water makes the films more extensible but worsens mechanical properties such as wet scrub resistance. The
loss of wet scrub resistance, which depends on the amount of water absorbed, is caused by a loss of cohesion within the polymer
film. The rate of water absorption largely depends on two factors: a) the type and composition of the polymer, b) the osmotic pressure
caused by salt solution between the polymer particles. The first factor is to do with the presence of hydrophilic, non-ionic groups on
the polymer chain, which become solvated by water molecules. Therefore, the more hydrophilic the polymer, the higher the water
absorption under otherwise uniform conditions [2]. The second factor concerns water-soluble substances in the polymer dispersion
such as emulsifiers and/or protective colloids. However, the influence of these components on water absorption diminishes over time
as they are gradually washed out of the dry film by dew or rain water; this fact can be confirmed in the laboratory by repeated
immersion in water for 24 hours followed by drying for 48 hours at 50°C. The way the wet films of dispersion are dried affects the
results considerably. In this case, the films were dried for three days at room temperature followed by seven days force drying at
50°C. Figure 3 shows how the water absorption of polymer films decreases after repeated immersion in water. The relative drop in
water absorption of the acrylic/styrene film was approx. 16%, that of the pure acrylic film about 6%. Repeated immersion in water
causes the film to become more hydrophobic, the acrylic/styrene film more so than the pure acrylic film. According to Künzel, there
should be a balance between water absorption and water vapour transmission rates [3]. The effect of repeated immersion in water on
the film's WVTR was also determined (Figure 4). The WVTR of the acrylic film was found to decrease, while that of the acrylic/styrene
film remained almost constant. In his detailed comparison of pure acrylic and acrylic/styrene films, Wagner [2] took dispersions that
differed only in the type and proportion of the main monomer; all the other variables - emulsifiers, auxiliary monomers, additives and
polymerization process - were identical. Our dispersions Ak and Ak/S are commercial products differing not only in monomers but
also in the cited variables. Moreover, all the dispersions Wagner used had roughly the same film forming temperature. Figure 5
compares the water absorption and WVTR of the polymer films obtained from them. Notice that, the longer the carbon chain of the
alcohol in the ester monomer, the greater the films' water-vapour permeability; their water absorption on the other hand decreases.
And if one compares a pure acrylic with its "corresponding" acrylic/styrene (MMA/EHA with S/EHA for example), the pure acrylic is
found to absorb more water but transmit less water vapour. Both types of dispersion Ak and Ak/S were used to formulate masonry
paints (Table 3). Pigment volume concentrations of 35%, 45% and 55% were obtained by varying the binder fraction; in each case,
the amount of thickening agent was equivalent to about 1 %, expressed as solids on solids. The paints used in the tests were
produced in two colours: the first a titanium dioxide containing formulation tinted with yellow iron oxide, the second a mixture of red
and yellow iron oxide only. Figure 6 shows water absorption data for the paint films after a number of immersion cycles in water. Like
the dispersion films, the paints were observed to absorb less water after each immersion cycle. The acrylic/styrene paints absorbed
less water than the pure acrylic ones. Figure 7 shows the paint films' water vapour transmission rates. The pure acrylic paint with 55%
PVC exhibits the highest WVTR; as is the case with the others, WVTR falls after the first immersion cycle. The fact that the WVTR of
the 55% PVC pure acrylic is higher than for formulations with lower PVCs indicates that the critical pigment volume concentration
(CPVC) has been exceeded. With the Ak/S paints, the WVTR of the 55% PVC film is higher than the others only in the case of the
untreated film; the WVTR declines there after, but, for a given number of immersion cycles, is roughly equal for each PVC value. This
means that at 55 % PVC (unlike the pure acrylic paint), the CPVC for the acrylic/styrene paints has not yet been reached. Until the
hydrophilic substances in the film have been removed, little can be concluded about the film's "true" water vapour permeability. As
has been clearly shown, the rate at which film can transmit water vapour is dependent on the amount of water-soluble substances
present. Repeated immersion in water removes these substances and lowers the WVTR Reliable WVTR values are only obtained
after at least five immersion cycles. Moreover, such laboratory experiments cannot tell the whole story; they can only be used to
support long-term weathering trials. 4 Weathering of masonry paints So far experiments were made with films in laboratory. In further
trials, masonry paints were formulated to assess the effect of natural weathering on the binder. The paints were based on the
formulation given in section 3.2. The following variables were taken into account: a) The type of dispersion (acrylic versus
acrylic/styrene), b) the type of pigment (titanium dioxide versus iron oxide), c) pigment volume concentration, d) the type of fillers The
same pigments as in section 3.2 were used to colour the finishes. Table 4 summarizes two important pigment properties: A 83: 17
blend of calcite (calcium carbonate) and talc (i.e., the same proportions as in the formulation in Table 3) was used as extender in
those tests where the type of filler was not the variable (i e., a) to c) above). Fibre-cement board was chosen as the alkali substrate
on which to test the paint. The board was first primed with a water-based emulsion primer (to even out any differences in absorbency
and prevent efflorescence due to the leaching of alkali salts from the substrate) followed by two coats of the test paint to a total coat
weight of 300 g/m². The panels were placed in a south-facing exposure rack inclined at 45 ° at Limburgerhof/Germany. Experience
has shown that this is equivalent to the weathering of coatings on vertical exterior surfaces, but 2 to 2 1/2 times faster. At set intervals
the coatings were photographed and examined for evidence of chalking (DIN 53159) and colour change (DIN 6174). 4.1 Effect of the
binder type and pigment volume concentration This series should investigate the effect of binder type and PVC in mat masonry
paints. A useful measure of weathering resistance is the extent of chalking. Weathering is the process whereby UV and moisture
destroys the binder at the surface of the coating, thereby exposing the particles of pigment and filler. Chalking was assessed on a
scale of 1 (heavy chalking) to 10 (no chalking). As a rule, no colour change occurs at ratings between 10 to 6. Paints were formulated
with pure acrylic and acrylic/styrene binders and PVCs of 35%, 45% and 55%. Coated test panels were kept outdoors for a nineyear
period. At a PVC of 45%, the effect of the binder type is small; after two years exposure, the chalking had reached a rating of only 8, i
e. there was no noticeable colour difference between the acrylic and acrylic/styrene formulations (Figure 8). PVC has a greater
influence than the binder type. By comparing chalking of paints with different PVCs one can see a difference after two years. The
change is roughly the same for each binder type, i.e. the differences between Ak and Ak/S are small After this time, chalking falls to a
rating of 9 for a PVC of 35% and to 7 for a PVC of 55% (Table 5). Chalking, and with it colour fade, becomes more pronounced after
nine years. Ratings for each value of PVC are 5 or 6; the pigment loading therefore makes little difference. Again, the effect of the
binder is small. Similar results were observed with the red-brown, full-shade paint. A paint with a supercritical PVC applied to a
vertical substrate (a wall in practice) tends to chalk, and therefore fade, earlier than when applied to a south-facing inclined surface
like the exposure rack. The reason is that the inclined surface collects airborne dirt more easily. And because the dirt protects the
binder from UV radiation, the coating exhibits less chalking in the initial stages of weathering. However, this effect evens out after
many years of weathering. 4.2 Effect of pigment/extender ratio on weathering properties Weathering trials were carried out on paints
with PVCs of 45 and 55%, but containing different ratios of pigment and extender. What is the point of such tests? Coloured pigments

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 with good hiding power (e. g., iron oxides) are often mixed with a high proportion of extender to reduce the cost of the formulation.
However, extenders can also add to a paints hiding power by protruding from the surface of the dry film, where they scatter incident
light. The reason for the increased hiding - known as dry hiding - is due to the larger difference in the refractive indices of air and
extender compared with that between air and binder (compare R.I. values in Table 6). The phenomenon of dry hiding is put to good
effect in highly extended interior wall paints. Masonry paints that contain a lot of extender are prone to premature fading. This,
however, does not necessary mean that much chalking occurs in the initial stages of the binder's photochemical disintegration: the
exposed particles of pigment and extender may be still firmly anchored in the binder. Because of this, only fading was investigated;
this was done by determining photometrically the total colour difference DeltaE after five years' weathering. The results are given in
Table 7. Paints with the higher proportion of extender (90%) faded the most. After seven years' weathering, most of the test samples
had been photographed. Figures 9 and 10 confirm what Kresse [4] suggested: that the extender can cause fading in formulations
containing less than 30% pigment. Once again, the findings were independent of the type of binder. 4.3 Effect of the filler type Most
masonry paints contain fillers. These substances do not only make the formulation more economic to produce, they also impart
desirable properties - for example, improve rheology; increase abrasion resistance; optimize the spacing of titanium dioxide particles;
produce certain surface texture; and, as already mentioned, impart dry hiding. Most extenders are mineral substances with a wide
variety of chemical compositions. Table 8 lists some common minerals used as extenders. In this test, the only variable is the type of
extender: the same binders, PVC and colour shades were adopted from the previous trials; a pigment/extender ratio of 30:70 was
chosen. The results of the weathering trials were very informative. The results after three years are summarized in Table 9 and
Figures 11 to 14. Except for calcite, dolomite and barytes, which caused little chalking (ratings of 8 and 9), the rest of the extenders
produced significant chalking in most cases. There was also a slight difference in the chalking of the cream and red-brown paints,
depending on the type of extender used: the red-brown paints, which contained no titanium dioxide, exhibited less chalking when
extended with mica, quartz or talc Weathering of paint films for four and a half years on the 45 ° exposure rack equivalent to about
ten years on a vertical wall confirms the earlier results. An important pont to note is that extenders high in silica lead to pronounced
chalking; no such effect occurs in those containing no silica - calcite and dolomite. Such a comparison is certainly not without
difficulties. For example, the extenders have very different specific surface areas despite of having the same particle size. Moreover,
paints containing only mica or talc are uncommon in practice; on the other hand, coatings highly loaded with quartz sand used to be
quite normal in the past. 5 Summary of results Films and masonry paints produced from acrylic/styrene copolymers absorb less water
than ones produced from pure acrylic copolymers, but are more permeable to water vapour. Only slight fading of acrylic/styrene
paints during outdoor exposure was observed at subcritical PVCs. No difference was observed between acrylic/styrene and pure
acrylic copolymers. So when is it best to use pure acrylic dispersions and when best to use acrylic/styrene dispersions? As the
weathering trials proved, there is no difference in the outdoor performance of acrylic and acrylic/ styrene latex paints with PVCs in the
range 35-55%. What is important, however, is the use of an optimal PVC and pigment/extender ratio. Testing formulations with
supercritical PVCs present problems on inclined substrates due to the protective effect of atmospheric dirt that collects in the pores of
the coating. The critical PVC of pure acrylics is slightly lower than that of acrylic/styrenes. Pigments and fillers should be in a well
balanced ratio. Only slight fading was found for a ratio of 30 parts pigment and 70 parts filler. The choice of extender is important too:
calcite, dolomite and barytes cause no fading. The type of binder (pure acrylic or acrylic/styrene) used is unimportant, provided the
paints are properly formulated. The authors would like to thank A. Schmidt, J. Bizik and K. Zander for their help with the tests.
References [1] J. Brandrup, E. H. Immergut, Polymer Hand Book, Interscience Publication, New York (1966) [2] O. Wagner, FARBE
& LACK (1991), No. 2. p. 109-113 [3] H. Kunze (Beurteilung des Regenschutzes von Außenbeschichtungen, Institut für Bauphysik
der Fraunhofer Gesellschaft (1978), Mitteilung 18 [4] P. Kresse FARBE & LACK (1991). No. 5, p. 399 8 tables, 14 figures (see pdf or
tiff)

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