Progress in Organic Coatings 53 (2005) 112–118

Effect of surfactants used for binder synthesis

on the properties of latex paints
Lauren N. Butler 1 , Christopher M. Fellows ∗, 2 , Robert G. Gilbert
Key Centre for Polymer Colloids, School of Chemistry F11, University of Sydney, Sydney, NSW 2006, Australia

Abstract

Surfactants are commonly used during emulsion polymerization to produce stable dispersions of polymer particles for applications such as
paints, adhesives and other coating applications. Surfactants can improve properties such as shelf-life, freeze–thaw stability and mechanical
stability. However, the addition of surfactants can also have a negative effect on end-use properties, such as the water resistance of the coating.
The type and amount of surfactant used is an important determinant of system behaviour during polymerization, film formation, and throughout
the lifetime of the formed coating.
The molecular architecture of binder particles is of crucial importance to latex paint properties. The type of surfactant used to stabilize
binder particles had an effect on the adhesion of the paint to both alkyd-coated and ZincalumeTM panels. The binders containing the polymeric
surfactant showed better adhesion to these substrates, as they were better able to wet the surface of the substrates. However, polymeric
surfactants also gave a greater amount of blistering when exposed to water and longer recovery times after exposure. The more hydrophobic
the stabilization system, the greater the abrasion resistance observed, presumably due to the reduced extent of film plasticization by water.
Accelerated weathering tests showed that these systems, designed to have low water sensitivity, gave good protection properties in regards
to corrosion and blistering. UV exposure resulted in severe degradation of all films except where the binder contained acrylic acid, which is
proposed to act as a photo-stabilizer.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Paint properties; Latex paints; Binder; Surfactants

1. Introduction However, the addition of surfactants can have a negative ef-

Surfactants are commonly used during emulsion polymer-
ization to produce latexes, stable dispersions of polymer par-
ticles in an aqueous environment [1]. The latexes produced
from this process are used in applications such as adhesives,
paints, and other coating applications. In these applications,
the prevention of sedimentation and phase separation during
the manufacture and storage of the particles is desirable. The
use of surfactants improves latex properties such as shelf-
life stability, freeze–thaw stability and mechanical stability.
∗ Corresponding author.
E-mail address: fellows@chem.usyd.edu.au (C.M. Fellows).
1 Present address: Advanced Nano Technologies, 112 Radium St., Welsh-
fect on film properties such as the water resistance of the
coating [2,3].
Thousands of different commercial surfactants are avail-
able for use in emulsion polymerization. The type used will
determine the behaviour of the system during polymerization,
during film formation, and under end-use conditions. There
are three main categories of surfactants—ionic, polymeric
and electrosteric. Ionic surfactants are low-molecular weight
molecules that contain a charged hydrophilic end group. They
impart particle stability by electrostatic repulsion and due to
their small size are readily adsorbed and desorbed from the
particle surface. Polymeric surfactants consist of a long hy-
drocarbon chain as the hydrophobic group and a polar poly-
mer chain as the hydrophilic end group. This type of surfac-

pool, WA 6106, Australia.

tant stabilizes particles by means of steric repulsion between
2 Present address: School of Biological, Biomedical, and Molecular Sci- polymeric chains. Electrosteric stabilizers can be best de-
ences, University of New England, NSW 2351, Australia. scribed as a polymeric surfactant with ionizable groups in

0300-9440/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2005.02.001
 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118 113

Table 1
Paint formulation
Component Amount
Letdown
Latex (g) 397.4
Water
Anti-foaming agent (g) 1.0
Ammonia aqueous 25% To pH∼9
Mill base (g)
Water 175.0
Thickener 10.0
Propylene glycol 200.0
Fungicide 1 5.0
Sodium benzoate 5.0
Anti-foaming agent 10.0
Non-ionic polymeric surfactant 15.0
Fig. 1. Entry to particles. Sulfato radicals (−OSO3 • ) formed in aqueous Titanium dioxide 1250.0
phase by decomposition of persulfate initiator can add either hydrophilic Fungicide 2 25.0
monomer (A), such as acrylic acid, which is common in aqueous phase, or Premix (g)
hydrophobic monomer (M), such as butyl acrylate, which is largely localized Water 15.0
in polymer particles and monomer droplets. Polymer radicals will not enter a Propylene glycol 10.5
particle until they have become sufficiently hydrophobic by adding a critical Non-ionic polymeric surfactant 1.0
number of molecules of hydrophobic monomer. Rheology controller 0.4
Texanol 9.5
the hydrophilic section, allowing both electrostatic and steric Modified polyurethane thickener 1 (g) ∼3.8
repulsion to stabilize particles. The source of the ionizable Modified polyurethane thickener 2 (g) ∼8.0
Wetting agent (g) ∼3.0
group is usually a polymerizable electrolyte with acid or base
Ammonia aqueous 25% To pH 9
functionality, such as acrylic acid.
The aim of this work is to examine how a range of
different surfactant systems affect common emulsion paint using the recipe in Table 1. The paints were prepared in four
properties. For the sake of uniform conditions, binder par- stages, all with the same mill-base. The grind size for this
ticles comprising primarily poly(methyl methacrylate-co- paint system was <10 ␮m (ISO 1524:2000 grind gauge).
butyl acrylate) (MMA-co-BA) were polymerized to the same
size and surfactant post-added to eliminate the effect of 2.2. Testing paint properties
binder particle size on film formation and resultant film
properties. Formed films prepared from paint formulation were tested
The surfactants used in this study include two polymeric for gloss, hardness, abrasion resistance, adhesion, wet adhe-
surfactants, nonyl phenyl ethoxylates of ethoxylate lengths sion, blistering, prohesion, and UV degradation, as detailed
of 30 (Igepal CO887) and 50 (Igepal CO977), which were below. The viscosity of each paint formulation prepared was
used individually and as a 1:1 mixture by weight. A range also measured.
of electrosteric stabilizers were formed via the addition of a For gloss testing, the paints were applied to a glass panel
percentage of water-soluble monomers such as acrylic acid using a 0.006 in. doctor blade. The specular gloss of the film
(AA) or methacrylic acid (MAA) to the final polymerization was measured following AS/NZS 1580.602.2:1995 [5] after
stage. These monomers may be incorporated into the poly- both 1 day and 1 week of drying at room temperature and
meric radicals that initiate polymerization inside the polymer humidity.
particles, and provide a grafted layer of electrosteric stabilizer For hardness testing the paints were applied to a glass
on the particle surface, as illustrated in Fig. 1 [1]. panel using a 0.006 in. doctor blade. The hardness of the film
was checked by the scratch test (AS/NZS 1580.405.1:1996
[6]) and the pendulum dampening method (ISO 1522:1998)
2. Experimental after both 1 day and 1 week of drying at room temperature
and humidity.
2.1. Paint formulation To test abrasion resistance the paints were applied to Scrub
black test panels (Leneta Co. size 6.5 in. × 17 in.) using a
Seven latexes were prepared as described previously, 0.004 in. doctor blade in duplicate. Two panels for each sam-
of approximate particle radius 55 nm and solid content ple were tested with different drying times—24 h and 1 week
of approximately 45% [4]. These latexes, plus a standard at room temperature. The panels were placed in a scrub ma-
poly(butyl acrylate-co-methyl methacrylate) latex (BASF, chine (Gardner Straight Line Washability and Abrasion Ma-
0.2 ␮m diameter) were formulated for a gloss exterior paint chine), which uses a scrubbing brush that moves back and
114 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118
forward at a constant rate and force over a substrate. A scrub
paste consisting of water, thickener, sand and detergent (10 g)
was added to the brush as well as 5 g of water. The abrasion is
measured by how many cycles have been performed before
a thin black line covering the entire film can be seen.
The paints were applied to ZincalumeTM and aged alkyd-
coated panels using a paintbrush and dried at room temper-
ature for adhesion testing. The adhesion of the film to the
substrate was measured using the pull-off test method for ad-
hesion (AS 1580.408.4:1993 [7]) after various drying times.
For one set of ZincalumeTM panels dried at room temper-
ature for 2 h, the adhesion of the film to the substrate was
measured before and after the panels were immersed in wa-
ter for 30 min. The recovery of the film was measured by a
third adhesion test 30 min after removal from immersion.
To measure the degree of blistering, the paints were ap-
plied to ZincalumeTM panels using a paintbrush and dried
at room temperature for 2 h. The panels were placed onto
a 250 mL paint can (with rim removed) containing 100 g of
water at 50 ◦ C for 30 min. The panels were rated by size and
number of blisters following a test method for evaluation
of degradation of paint coatings AS/NZS 1580.481.1.9:1998
[8]. The rating of the panel was subjective, as the panels
needed to be examined in comparison to the pictures in the
standard. The recovery of the film was checked by repeating
the rating every 5 min after removal.
Prohesion testing was carried out on ZincalumeTM pan-
els of dimensions 100 mm × 145 mm. These were primed by
paintbrush with a water-based red-oxide primer and allowed
to dry at room temperature for 2 h. The paints were applied
to the primed panels using a paintbrush and dried at room
temperature for 2 h, then a second coating of the paint was
applied and the panels were dried at room temperature for a
further 24 h. The panels were placed into a Salt-Spray cab-
inet. This cabinet uses a 4-h cycle of moist air provided by
spraying a prepared salt solution (10 g of sodium chloride
and 80 g of ammonium sulfate in 20 L of water) followed by
4 h of dry air. The panels were rated over time by size and
number of blisters following AS/NZS 1580.481.1.9:1998 [8].
These tests were repeated using panels of ZincalumeTM and
galvanized steel that had not been primed.
To measure the sensitivity of the paints to UV degradation,
ZincalumeTM panels of dimensions 75 mm × 150 mm were
primed by paintbrush with a water-based red-oxide primer
Table 2
Gloss levels and hardness of paint films
Binder Gloss at 20◦ Gloss at 60◦
Standard 32.5 69.4
2% MAA 35.7 68.9
4% MAA 3.8 31.7
2% AA 47.2 73.0
4% AA 48.6 75.2
Igepal CO887 27.7 67.6
Igepal CO977 3.8 30.1
Igepal mixture 5.1 37.0
and allowed to dry at room temperature for 2 h. The paints
were applied to the primed panels using a paintbrush and
dried at room temperature for 2 h, then recoated and dried at
room temperature for a further 24 h. The panels were placed
into a QUV-condensation cabinet using fluorescent UVA-340
lamps. The QUV test method is designed to simulate the ex-
posure to sunlight responsible for the degradation of paint
films. This cabinet uses a 3-h cycle of UV, in which panels
reach a temperature of 60 ◦ C, followed by 3 h of water vapour
condensation on the panels, in which temperatures around
45 ◦ C are reached. The panels were rated over time by mea-
suring the gloss following the AS/NZS 1580.602.2:1995 [5]
test method. The percentage reduction in gloss over time was
calculated.
The readiness of the formulations to be applied by paint-
brush (application of viscosity at a high shear rate of 104 s−1 )
was measured using an ICI cone-and-plate viscometer fol-
lowing the AS 1580.214.3:1993 [7] test method.
The ease of flow and stirring of the paint (viscosity at a
medium shear rate of 102 s−1 ) was measured using a Rototh-
inner (Brookfield model VT-1). A 250 mL paint can, with rim
removed, was filled with the paint and the spindle was low-
ered into the paint to the machine’s preset level as described
in AS/NZS 1580.214.4:1996 [9].
3. Results
Gloss is a function of how well dispersed pigment is within
the binder, and hence of how the components in the paint sys-
tem react to the dispersant. On drawing down the paints onto
a glass substrate, variations in surface roughness between
films were immediately observed (Table 2). During the mill
grinding stage, the pigment-particle agglomerates are broken
down by the mill and are stabilized by the dispersant, which
is the sodium salt of a polymeric carboxylic acid. It can be
seen that binders incorporating low percentage AA stabilizers
are most effective at achieving even dispersal of the pigment
particles, followed by the low percentage MAA stabilizer,
the standard formulation, and Igepal CO887, with the least
glossy paints those containing Igepal CO977 and 4% MAA.
It would be expected that a more viscous paint would give
rise to a rougher final surface, and the binders prepared with
the more hydrophobic stabilizers do interact with the asso-
Sward-rocker hardness (no. of cycles) Pencil hardness
29
3B
31
39
31
2B
35
32
29
3B
29
 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118 115

ciative thickener to give more viscous formulations (Table 7), Table 3

but the gloss results do not correlate well with the low-shear Results from abrasion testing
viscosity. It is possible that the more hydrophobic binder sys- Binder Number of scrub cycles
tems may react in a negative manner with the dispersant in the 24 h 1 week
paint formulation, leading to a formulation in which pigment Standard 198 187
particles are not dispersed as homogeneously. Igepal CO887 316 295
The hardness of the films was measured using both the Igepal CO997 241 284
Sward-rocker and pencil hardness tests (Table 2). The results Igepal mixture 260 337
of the pencil hardness test are that all the films tested will 2% MAA 220 215
4% MAA 128 156
be scratched with either a 2B or 3B pencil. This suggests 2% AA 128 150
that the elastic limits of the films are nearly identical. This is 4% AA 131 135
reasonable, as the binder in the system (primarily (poly(BA- Error = ±10 scrub cycles.
co-MMA)) is essentially the same for all preparations, and
suggests that the opacifier particles are well-dispersed within
a matrix of this polymer. However, the tests used are relatively standard paint formulation, while all other paints were more
insensitive to the small differences in hardness expected to resistant to abrasion than the standard paint. It is most likely
arise from the variations in composition and in future work that swelling of the more hydrophilic films with water causes
more quantitative measurements of film hardness will be ob- a loss of tensile strength and elastic modulus.
tained using a nano-indenter. Abrasion testing was performed using two drying con-
The addition of AA and MAA to the binder will increase ditions (24 h and 1 week) in order to check the effect of
the glass transition temperature (Tg ) and minimum film form- the coalescent agent on abrasion resistance. As the coales-
ing temperature (MFFT) of the binder, as these monomers cent agent evaporates from the film, the abrasion resistance
form glassy polymers at room temperature. The results from should increase as the MFFT is lowered and the film becomes
the Sward-rocker test imply differences in the MFFT of the more elastic. In most cases, however, the change in abrasion
binders, with the 4% AA and 4% MAA preparations display- resistance over 1 week was not significant. The number of
ing a significant increase in hardness compared to the other scrub cycles decreased over time only for the latex contain-
binder systems. No appropriate controlled humidity environ- ing Igepal CO887. Strong increases in abrasion resistance
ment was available for determining reproducible MFFT val- over time were seen for the Igepal CO977-containing latexes
ues of the paint formulations. 4% MAA latex and 2% AA latex. It is possible that these car-
The abrasion test (Table 3) was performed under wet con- boxylic acid preparations, which can bind a greater amount
ditions, so the main factors affecting the results will be the of water than the latexes with a reduced hydrophilic compo-
pigment binding ability of the latex and the hydrophilicity of nent, will show a more improved MFFT with loss of bound
the latex, the particle size and type of polymer in the latex water over this time.
being held constant. Poor pigment-binding ability would be Adhesion is the measure of the degree of wetting of paint
expected to give rise to both low gloss and poor abrasion resis- to a substrate and the strength of bonds formed between the
tance. However, little correlation was seen between the results polymer and substrate. The two substrates, ZincalumeTM and
of these two tests. A more likely explanation for the differ- Alkyd coated panels, have surfaces consisting of an acrylic
ences in the binders that could account for the abrasion results coating and a mixture of alcohol and polyester functionalities,
are the varying hydrophilicities of the binder film caused by respectively. The test method rating scheme is along a scale
modifying the particle surface; paints prepared with binders from 1 to 5, with ‘0’ corresponding to the case where no paint
with a high proportion of polymerizable carboxylic acid (2 is removed and ‘5’ to complete removal of paint from the
and 4% AA, 4% MAA) were more easily abraded than the substrate. The results of adhesion tests are given in Table 4.

Table 4
Adhesion test results
Binder Drying time

24 h 2h 6h 48 h 2 + 30 min immersion

Adhesion on alkyd-coated panel Adhesion on ZincalumeTM

Standard 0 4 1 0 1
Igepal CO887 2 2 2 0 3
Igepal CO997 2 2 2 0 5
Igepal mixture 4 5 5 0 5
2% MAA 5 2 1 1 3
4% MAA 5 3 1 0 4
2% AA 4 5 5 0 5
4% AA 5 4 3 0 4
116 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118
For adhesion to the alkyd panel, the results suggest that
those latexes that contain the polymeric surfactant have bet-
ter adhesion than those that contain electrosteric stabilizers.
Since adhesion is a function of the degree to which the adher-
ing latex can wet the surface, insufficient surface wetting due
to the higher surface tension of the latexes that contain elec-
trosteric stabilizers may explain these results. The standard
latex formulation, containing conventional surfactant, clearly
shows the best adhesion. The poor performance of the NPE
mixture may also be related to poor surface wetting. Longer
NPEs inhibit coalescence [10] while the mixture would be
expected to stabilize w/o emulsions to a greater extent than
the NPE50 alone, leading to inclusions localizing the surfac-
tant to a greater extent within the forming film than on the
film-substrate interface.
The adhesion of the paints on ZincalumeTM improves over
time for all systems. After 2 h of drying, the paints that contain
AA take a considerable amount of time to develop strong ad-
hesion with the ZincalumeTM , as does the paint formulated
with a mixture of NPE30 and NPE50. This poor adhesion
could be a function of poor wetting of the substrate by these
latexes, or be related to a lack of favourable adhesive inter-
actions between the carboxylic acid groups on the surface of
the particles and the poly(acrylate) binder of the primer. The
latexes containing polymeric surfactants gave reasonable ini-
tial adhesion to the ZincalumeTM panels, as they did to the
alkyd panels.
The wet adhesion was poor for all systems except the stan-
dard. The standard latex is likely to contain a wet-adhesion
promoter, as is the case for most commercial latexes, but no
wet-adhesion promoter was added to the test formulations.
A common method of wet-adhesion promotion is addition
of dimethylaminoethyl methacrylate [11] during the final
stages of binder production. The wet-adhesion promoter is
able to form either strong hydrogen bonds with the surface
through the amino functionality in the wet-adhesion promoter
or chemical bonds with any acidic functionality in the sub-
strate surface. Both the alkyd coatings and ZincalumeTM have
primarily carboxyl or hydroxyl polar surface groups.
3.1. Chemical properties of paint films
The prohesion test is used to examine how a paint film
reacts to a salty environment in terms of corrosion, blister-
ing, chalking and discoloration of films. Normally this test
is performed with a more concentrated salt solution (0.5 M
NaCl). However, it has been found that the less concentrated
solution of NaCl and (NH4 )2 SO4 used in this study gives re-
sults that correlate more readily to exterior exposure [12,13].
Primed ZincalumeTM and galvanized steel both initially give
white deposits of zinc oxide that were difficult to distinguish
from the paint films.
All the latexes formulated into paints had latex films that
give an approximately 10% gain in weight when immersed
in water. This test should not therefore be able to distinguish
the latexes on the basis of water uptake but on the interac-
Table 5
Blistering test results
Latex Size/density of blisters Recovery time (min)
Standard 3/1 15
2% MAA 0/0 N/A
4% MAA 2/3 5
2% AA 2/2 5
4% AA 2/4 5
Igepal CO887 2/5 17
Igepal CO977 2/5 10
Igepal mixture 2/4 15
tion that the binder has during the formulation of the paint
that promotes water uptake. The results are shown in Table 5.
The rating scheme for this test is AS/NZS 1580.481.1.9:1998
[8], where 0 = no blisters and 5 = dense, large blisters. The
rating of the panel was subjective, as the panels needed to
be examined in comparison to the pictures in the standard.
Most of the panels began to blister at the edges, making it
difficult to give a rating for density as the density refers to
the entire area of the film. A duplicate of each paint sys-
tem was tested to account for any differences in film thick-
ness.
On the primed ZincalumeTM and galvanized steel, all the
latexes that contained the polymeric surfactants showed signs
of blistering. The samples containing the lower amounts of
acid showed no signs of blistering on the ZincalumeTM af-
ter 8 weeks exposure. However, the level of blistering in all
samples was minimal.
The worst blistering is seen for the standard formulation
and the formulations using polymeric surfactants, suggest-
ing that these latexes are effective at binding and trapping
water in the film and are slow in releasing that water. The
blistering observed with latexes containing carboxylic acid
followed the order of hydrophilicity, that is, as the latex be-
came more hydrophilic, more water was apparently trapped
at the film/substrate surface.
3.2. Accelerated weathering
The conditions experienced by the paint films under the
QUV test are much harsher than that in the natural environ-
ment. During the condensation cycle, the water droplets on
the surface of the film can act as lenses, magnifying the ef-
fects of the UV light. Water may also be absorbed into the
film and wash away small chain fragments. This test method
is used as a guide to indicate which paints would be more
likely to fail under UV light.
The results from the QUV test are shown in Table 6, dis-
played as the percentage of loss in 60◦ gloss. Fairly rapid
degeneration is seen for the standard formulation, for formu-
lations prepared with polymeric surfactant, and for formu-
lations prepared with MAA (after an initial period of rela-
tive stability). The latexes containing polymeric surfactants
started blistering after one month of exposure. The latexes
containing MAA also degraded on a macroscopic scale much
 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118 117

Table 6
Percentage gloss change at 60◦ from QUV test for duplicate panels
Latex Time (day)
3 7 14 21 28 35

Standard −14/−18 −18/−18 −18/−18 −20/−27 −27/−26 −27/−29

2% MAA −3/−1 −5/−3 −18/−15 −28/−23 −34/−28 −55/−40
4% MAA −9/−1 −17/−15 −35/−40 −54/−56 −55/−65 −78/−76
2% AA −5/−8 −7/−1 −6/−4 −14/−13 −8/−11 −14/−14
4% AA −4/6 −2/0 −4/7 −3/−2 −6/−7 −16/−6
Igepal CO887 −7/−3 −9/−9 −20/−17 −23/−21 −57/−59a −53/−58a
Igepal CO977 −9/−15 −15/−20 −27/−27 −35/−26 −66/−50a −57/−53a
Igepal mixture −7/−9 −11/−13 −30/−21 −37/−24 −49/−48a −47/−53a
a Indicates that blisters were present on the panels.

more quickly than the other panels while samples containing
AA show small gloss losses over time.
Poly(butyl acrylate-co-methyl methacrylate) undergoes
photo-degradation either through oxidation of the tertiary
carbon to give stable hydroperoxides or through oxidation
of methylene groups adjacent to ester functionalities to give
less stable hydroperoxides, with the latter reaction predom-
inating when the amount of butyl acrylate is higher [14].
Co-monomers such as styrene and dialkyl acrylamides have
been reported to act as photo-stabilizers, as they sacrificially
undergo photo-oxidation reducing the amount occurring in
the system [15]. Titanium dioxide has been known to in-
crease the amount of photo-degradation that occurs in paint
films [16]. The titania used in these paints has an alumina
and tri-methylol propanol layer on the surface to increase
photo-stability and dispersibility.
The low percentage gloss loss in the paints containing AA
suggests that this monomer may act as a photo-stabilizer in
the system, although the mechanism of this is unclear. While
carboxylic acid functionality on the surface of the particles
could complex transition metals, which could act as radical
scavengers, there is no obvious source for such transition
metal ions in these systems. Further experiments on photo-
degradation are required to validate this effect of poly(AA)
and test possible mechanisms.
3.3. Viscosity
During formulation, it was noticed that different latices re-
sponded differently towards the rheology modifiers, as shown
in Table 7. Product quality specifications for a water-based
Table 7
High and mid-shear viscosities of the paints formulated (P)
Latex ICI cone and plate
Standard 1.4
2% MAA 1.6
4% MAA 1.6
2% AA 1.7
4% AA 1.2
Igepal CO887 1.7
Igepal CO977 1.3
Igepal mixture 1.3
gloss white exterior paint are an ICI cone and plate viscosity
of 1–1.3 P and Rotothinner viscosity of 5–7 P [17]. The im-
plications of having the high- and mid-range viscosities out
of this range is that the paint will drip and splatter on appli-
cation if viscosity is too low, or give poor levelling if it is too
high. Having high viscosities will also result in the appear-
ance of pinholes in the film caused by micro air bubbles in
the paint, as the system will be too viscous for bubbles to rise
to the surface and the defoamer can only effectively remove
large bubbles.
The differing high- and mid-range viscosities of the vari-
ous paints give an indication of how the surface charge of the
binder affects the response of the rheology modifiers. The rhe-
ology modifiers consist of modified polyurethane chains with
hydrophobic domains on a hydrophilic backbone that have an
associative thickening action. When placed into paint, thick-
ening occurs by the rheology modifiers forming a complex
network structure that increases the viscosity. The hydropho-
bic domains connect with the binder particles to create this
network [18].
The results appear to indicate that the systems with the
more hydrophobic surfaces have higher viscosities. For ex-
ample, latices containing Igepal CO887 are more viscous then
those containing Igepal CO977 and latices containing 2%
MAA more viscous than those with 4% MAA. The greater
hydrophobicity of the binder particle surfaces probably im-
proves the ability of the associative thickeners to establish a
network between binder particles. The results for the latices
containing AA are opposite to this trend, suggesting that AA-
containing polyelectrolytes in the aqueous phase are formed
during the polymerization of the binder, which can act them-
selves as rheology modifiers. As the amount of AA is in-
creased, these polyelectrolytes will have a greater average
molecular weight and have a more pronounced affect on the
Rotothinner viscosity of the system.
5.8
19.3
19.1
6.4 4. Conclusions
7.6
16.3 The molecular architecture of binder particles – specif-
12.2 ically, the type of stabilizer used – has been shown to be
11.2
of crucial importance to paint properties. Frequently, there
118 L.N. Butler et al. / Progress in Organic Coatings 53 (2005) 112–118
is a trade-off between desirable properties, with a particu-
lar stabilizer providing improvements in some properties and
impairing others (e.g., acrylic acid in this study gave reduced
blistering and increased UV resistance, but also reduced ad-
hesion).
The following trends have been observed:
(1) The more hydrophobic the stabilization system, the
greater the abrasion resistance as the incorporation of
water into the film can soften the paint film.
(2) The most hydrophobic stabilization systems also gave
poor gloss, for reasons that are as yet unclear.
(3) The binders containing the polymeric surfactant showed
better adhesion to both alkyd-coated panels and
ZincalumeTM , possibly due to better wetting of the sur-
face of the substrates. However, polymeric surfactants
gave more blistering and longer recovery times after ex-
posure than electrosteric surfactants.
(4) UV exposure resulted in severe degradation of all films,
except for those with binders that contained acrylic acid,
which is proposed to act as a photo-stabilizer. The accel-
erated weathering tests performed showed that all these
binder systems, designed to have low water sensitivity
[4], gave adequate protection from corrosion and blister-
ing when formulated into paints.
Surfactants in current binder systems affect all of particle
size, freeze–thaw stability, paint rheology and water sensitiv-
ity. A surfactant which adversely affects one of these prop-
erties may be beneficial for another. A possible way around
this nexus of problems is through the advent of new latex
synthesis methods [19,20], which obviate the need for sur-
factant during particle formation, and thus enable formulators
to choose surfactants for optimizing desirable properties, by
decoupling particle size from the other properties.
Acknowledgement
The Key Centre for Polymer Colloids is established and
supported by the Australian Research Council’s Key Cen-
tres Program. Dr. Butler’s Ph.D. studies were supported by
the Australian Research Council’s Australian Postgraduate
Award—Industry program and Wattyl Australia Pty. Ltd.
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