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Learning from the past
Waterborne hybrid uses principles of solventborne
alkyds to maximise gloss.
Examination of paint films has shown that solventborne
alkyds achieve their very high gloss by forming a continuous
clear top resin layer during drying. This appearance could
only be matched with waterborne emulsions by applying a
clearcoat. A water-based alkyd-acrylate hybrid has been
developed which behaves similarly to solventborne alkyds,
giving an alkyd-like gloss and haze with low solvent content.
Rolf Dersch,* Roelof Balk, Uwe Dittrich, Thomas Frechen,
Sebastian Roller, Bernhard Schuler, Harm Wiese.
The substitution of solventborne paints by water-based
alternatives has been a major issue in the coatings industry
for at least 30 years. Most prognoses about the time scale of
the substitution process have turned out to be wrong. The
volume of solventborne paints is still huge, even though their
market share has decreased over the years.
Now the situation has changed. With the European VOC
directive 2004/42/CE having come into force, limits for
VOCs have been set, in fact a whole body of legislation has
been created, based upon the category of paint and with
different values for solvent- and water-based paints.
Whereas the 2007 limits can often be met by reformulation,
it will be difficult to meet the 2010 limits. We assume that a
major part of solventborne paints will be replaced by
water-based paints and we at BASF want to participate in
that substitution process.
To be successful in this process it is necessary to overcome
the technical deficiencies of current emulsion-based paints
regarding application properties such as brush drag, body,
levelling and open time, or properties of the coating such as
gloss level, hardness, stain blocking and resistance to
household chemicals.
The main target of these investigations was to match the
gloss and haze of solventborne alkyd paints. For emulsion
gloss paints, gloss is typically between 40 and 60 units at
20° and 70 to 85 at 60°. Solventborne alkyds, the
benchmark, attain 70 to 85 units at 20° and more than 85 at
60°.
Initial gloss measurements
Basically gloss is dependent on two factors:
- Roughness of the surface;
- Refractive index of the paint film.
When comparing an acrylic based gloss paint and a
solventborne alkyd the following gloss values were obtained:
- Acrylate-based paint: 50/78 for 20°/60° angles,
respectively
- Solventborne alkyd: 83/92
Topographic images and mean surface roughness (RMS)
could be obtained by atomic force microscopy. The values
were 53 nm for the acrylic and 14 nm for the alkyd, which
corresponded well with the gloss values.
What variables influence gloss?
The question is, how can surface roughness be reduced and
thereby gloss improved? Factors that were investigated
during the study included flow of the paints, film formation
and pigment-binder ratio. Variations were implemented on
two emulsion gloss paints, one based on an all-acrylic, the
other based on a styrene acrylic dispersion, and a
solventborne alkyd paint from a paint store for comparison
(see Table 1).
Rheology
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Rheology is crucial for levelling of a paint after application
and smoothness of the film surface - at least in the wet
stage. Rheology can be adjusted by choice of thickeners in
the formulation of the emulsion gloss paint.
High shear viscosity of the paints was more than doubled
and also the pseudoplasticity was varied to some degree,
but gloss remained the same for all the all-acrylic based
paints. In the case of the styrene acrylic, only the paint with
the lowest viscosity displayed a somewhat lower gloss. All
the others showed equal gloss and haze data.
Film formation
In general, solventborne alkyds need a much longer time to
dry than water-based paints. Additionally, films are formed
from solution, whereas in the case of emulsion gloss paints,
latex particles have to coalesce to become a more or less
uniform film after evaporation of water.
For emulsion gloss paints, longer drying time means that
polymer and pigment particles have more time to rearrange
into a close regular packing with less surface irregularities.
Drying time of the emulsion gloss paints was influenced by
varying film thickness -from 100 to 400 µm film applicator
gap - and humidity during drying - from 40% to 90% - both at
23°C. Results for the all-acrylic are shown in Figure 1. There
was no change in gloss or haze, even when the extrema -
100 µm, 40% relative humidity and 400 µm, 90% relative
humidity- were compared.
Pigment volume concentration (PVC)
It is well known that PVC definitely has a strong impact on
gloss. For the all-acrylic based paint, as expected, the gloss
decreased and haze increased when the PVC was raised
(Figure 2). Thus reduction of PVC could be a way to
improve gloss and haze. But even at a PVC of 10%, gloss
was far below the alkyd level and hiding power became
unacceptable.
Morphology of high glosscoatings
To gain more insight into morphology, the different paint
films were investigated using electron microscopy.
Topographic images of the paint films could be obtained by
scanning electron microscopy (SEM). Whereas the
solventborne alkyds displayed smooth surfaces free of
defects, the all-acrylic and the styrene acrylic based gloss
paints were full of surface irregularities, corresponding to
their reduced gloss.
In Figure 3 (top) the SEM topographic images of the styrene
acrylic and the solvent-based alkyd paint are contrasted. On
the bottom row the backscattered electron images are
shown: Using this technique, titanium dioxide particles are
depicted as white spots in the black binder matrix.
In the case of the solventborne alkyd, the white spots were
smaller, which means the titanium dioxide was better
dispersed. Furthermore, the coarse surface irregularities of
the styrene acrylic based film could be attributed to large
titanium dioxide agglomerates.
In a further step, paint films were embedded in an epoxy
resin, cut vertically to the surface and the ultra-thin cuts
were subsequently analysed by transmission electron
microscopy (TEM). (Figure 4)
Again, images of the styrene acrylate are presented on the
left; the solventborne alkyd is on the right. Black spots are
titanium dioxide particles. White spots are holes resulting
from titanium dioxide particles pulled out by the cutting
process. The surrounding binder is grey.
When focusing on the surface, i.e., the borderline between
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paint film and epoxy resin, a remarkable difference becomes
obvious: whereas the styrene acrylic based paints show
many titanium dioxide particles at the surface and partially
sticking out of the binder matrix, in the case of the
solventborne alkyd the whole surface is covered with a layer
of binder.
The secret of the high gloss of solventborne alkyds
Basically there are three factors leading to the superior
gloss of solventborne alkyds (compared to acrylates):
- (Somewhat) better dispersion of titanium dioxide;
- High refractive index of the alkyd resin;
- Complete coverage of pigment particles at the surface with
binder, leading to a smooth surface which is homogeneous
with respect to refractive index, thus minimising diffuse
reflection of light.If the clear layer of binder on top of the film
is the key to superior gloss, it should be possible to boost
gloss just by applying a layer of binder onto the emulsion
gloss paint film. Thus, different binders were cast onto the
all-acrylic based gloss paint as substrate:
- The all-acrylic dispersion;
- The styrene acrylic dispersion;
- A styrene acrylic dispersion II (with a higher content of
copolymerised styrene);
- An acrylate solution polymer;
Gloss results are summarised in Table 2. Without any
additional layer, gloss was 50/78 at 20° and 60°
respectively. With the all-acrylic dispersion on top it rose to
78/88. With the styrene acrylics, gloss exceeded that of the
alkyds.
Surface roughness of all the double layer coatings was
below that of the two alkyds. The sample with the acrylate
solution polymer had the lowest mean surface roughness,
only about 2 µm, but almost the lowest gloss. It seems that
below 10 µm surface roughness the refractive index
becomes more and more important. With regard to refractive
index, styrene acrylates and alkyd resins have a clear
advantage.
It is not necessary to have a thick binder layer on top. When
the film applicator gap was reduced to 30 µm, corresponding
to a dry film thickness of approximately 7 µm, gloss
remained unaffected.
Unfortunately, emulsion gloss paints showed no tendency to
separate into a pigmented base and a clear top layer during
drying.
Wb alkyd-acrylate hybrid - a true high-gloss alternative
The main problems encountered with alkyd-acrylate hybrids
are:
- Incompatibility leading to grit, coagulum, viscosity increase
on storage or just low gloss and/or
- Retardation of the polymerisation or high residual
monomer content, when the alkyd is employed during
emulsion polymerisation.received his Ph.D. in 1982. He
joined BASF in 1984 and is now a Research Associate in
the Polymer Physics Department of the Polymer Research
Division, responsible for electron microscopy of polymers
As a final outcome of the multitude of approaches and
experiments, a new water based hybrid can be presented,
"AQAGloss", which is a true alternative to replace
solventborne alkyds.
The main target of the project was to match the gloss of
solventborne alkyds. As can be seen from Table 3, the
target has been fully achieved: gloss and haze were almost
identical to the benchmark, even though data were obtained
with a rather simple starting point formulation (Table 4).
Films of the new paint have also been analysed by means of
electron microscopy in the way described above. On the top
row of Figure 5 secondary beam (topographic) images are
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shown. The new gloss paint surface on the right is smoother
than the styrene acrylate based on the left; pigment particles
are well covered with binder.
The ultra-thin cuts on the bottom look somewhat different as
a result of RuO4 staining (the styrene acrylate binder in
particular displayed an inhomogeneous structure.). In the
image for the new paint on the right, the binder layer on the
surface is clearly visible. Thus this gloss paint not only
matches the gloss of solventborne alkyds, but as with
alkyds, the superior gloss level is achieved by a binder layer
on top, which develops during drying.
"AQAGloss" paint properties
The hybrid paint was applied on different substrates and
tested in comparison to several water-based paints from
paint stores based on polymer dispersions or hybrids.
Regardless of the substrate, it exceeded all competitive
paints in gloss or haze performance. But there are other
important paint properties besides gloss. Professional
painters will appreciate the:
- Excellent body
- Superior brush drag
- High film build
- Easy application by PU-foam applicator
- Low foaming tendency
- Safe working hygiene and easy cleanability
For DIY painters it will be important that:
- The paint is water-based
- Contains only a low amount of solvents
- No heavy metal driers
- No oximes
- It is easy to apply
- Equipment can be cleaned with water.
On the exposure test fence, the new gloss paint films
displayed better gloss retention and reduced yellowing
compared to solventborne alkyds. Water uptake was lower
than with the styrene acrylic and the paint films remained
free of blisters. Furthermore, resistance to household
chemicals was greatly improved.
Application properties closer to alkyds than to acrylics
The secret of the high gloss of solvent borne-alkyds is a
clear layer on top, which separates during drying leading to
a smooth and homogeneous surface. With a new
water-based alkyd-acrylate hybrid, a similar morphology has
been realised, resulting in an alkyd-like gloss and haze.
Application properties, stain blocking and water resistance
were closer to alkyds than acrylics. The solvent content of
the new formulation was far below the limits of the
EU-Decopaint directive, and in addition driers (Co- or
Mn-based) and oximes could be omitted.
Results at a glance
- Tests carried out on waterborne gloss emulsions showed
that it was not possible to match the high gloss and low
haze of traditional alkyds by modifying the formulation or
application conditions.
- Examination of paint films by electron microscope revealed
that the the high gloss of solvent borne-alkyds is produced
by a continuous clear resin layer on top, which separates
during drying to give a smooth and homogeneous surface.
- A new water-based alkyd-acrylate hybrid has been
developed which shows a similar morphology to alkyds,
resulting in alkyd-like gloss and low haze.
- Application properties, stain blocking and water resistance
were closer to alkyds than acrylics.
- The solvent content of the new paints was well below the
limits of the EU-Decopaint directive, and alkyd driers and
oximes could be omitted.
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The authors:
-> Dr. Rolf Dersch studied chemistry at the University of
Marburg, where he received his PhD in 1979. In the
following year he joined BASF in the polymer research
laboratory. In 1985 he moved to marketing polymer
dispersions, where he is now responsible for the
development of binders for architectural coatings.
-> Dr. Roelof Balk studied chemistry and physics in Leiden,
the Netherlands, and obtained his PhD in organometallics at
the University of Amsterdam. He joined BASF in 1988.
Since 2004 he has worked on acrylic dispersions with a
main focus on the development of binders for coating
applications.
> Dr. Uwe Dittrich joined BASF in 1984. After holding a
variety of positions in R&D in Germany, Japan and USA, he
is presently involved in marketing of architectural coatings.
-> Dr. Thomas Frechen studied physics at the
Albertus-Magnus University of Cologne, Germany, and
received his Ph.D. in 1982. He joined BASF in 1984 and is
now a Research Associate in the Polymer Physics
Department of the Polymer Research Division, responsible
for electron microscopy of polymers.
-> Dr. Sebastian Roller studied chemistry at the University of
Freiburg and obtained his PhD at the University of
Dortmund. Since 2006, he has worked as laboratory
manager at BASF polymer research in Ludwigshafen on
development of water-based binders for coatings.
-> Dr. Bernhard Schuler studied chemistry at the University
of Heidelberg, where he obtained his Ph.D. in 1989. After
post-doctoral research work at the University of California at
Berkeley he joined BASF in 1990. Since January 2004 he
has been head of global product development, Polymers for
Architectural Coatings and Construction Polymers.
-> Dr. Harm Wiese studied chemistry at the TU Darmstadt
and received his PhD in physical chemistry in 1987. After a
postdoctoral year at IBM Rueschlikon/Switzerland with Prof.
Heinrich Rohrer, he joined BASF AG's Polymer Physics
Department in 1989. In 1994, he moved to Emulsion
Polymers Research. Since January 2004, he is heading the
group "Polymer colloids for coatings" in the polymer
research division.
* Corresponding Author. Contact: Dr. Rolf Dersch, BASF
Aktiengesellschaft, ED/DA - H 201, D-67056 Ludwigshafen,
Germany, rolf.dersch@basf.com
This paper won the European Coatings Award 2007 for the
best contribution to the Nürnberg Congress 2007, 7 - 9 May,
Nuremberg, Germany.The award is endowed by the
European Coatings Journal, the jury consists of Dr. Barbara
Brune (ECJ), Dr. Dirk Meine (ECJ) and David Sykes (PRA)

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Figure 1a-c: Variables influencing surface roughness: gloss and haze comparisons at
different film thicknesses and relative humidity .

Figure 2: Factors influencing surface roughness: effects of changes to PVC in

all-acrylic paint.

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Figure 3: SEM images of gloss paints: styrene acrylic (left) and solvent-borne alkyd
(right); surface view (top) and backscattered electron images showing titanium dioxide
particles as white spots (bottom).

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Figure 4: TEM images of ultra-thin cross-sections through paint films: styrene acrylic
(left) and solvent-borne alkyd (right) at different magnifications. Titanium dioxide
appears as black specks, and voids due to film damage as white spots .

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Figure 5: Morphology of paints based on styrene acrylic (left) and the new alkyd-acrylic
hybrid binder (right): SEM images of the surface (top), TEM images of vertical
cross-sections through the coating (bottom).

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