Alkyd resins have been widely used in the coatings industry because of their excellent gloss,

corrosion resistance and adhesion to various substrates. Changes in consumer preferences and
VOC regulations have mandated that the industry reduce the VOC of coatings. In some cases,
this necessitates a switch from solvent-based to water-based technology.
Comprised of aromatic moieties and lipophilic fatty acids, alkyd polymers are waterinsoluble hydrophobic polymers. To create waterborne alkyd systems several techniques have
been developed for incorporating the alkyd resin into aqueous systems. The most recent
practices focus on stabilizing the alkyd in water utilizing either a dispersion or an
emulsification process.
This article discusses the current technology available in the industry and introduces a new
polymer that does not contain solvent, or surfactant-related moieties. The new polymer offers
markedly improved corrosion resistance while offering typical alkyd benefits. The resin can
be supplied as a dispersion with near-zero VOC.

Current Technology
Many desirable alkyd properties result from the excellent film formation and oxidative curing
process that alkyds offer. If an alkyd paint is compared to an acrylic latex paint, the molecular
weight of the alkyd polymer at the time of coating application is much lower than the latex. It
is this low molecular weight that gives the alkyd molecules the mobility they need to flow out
to achieve high gloss and excellent adhesion. After application to the substrate, the molecular
weight of the alkyd polymer increases through crosslinking by an oxidation reaction of the
fatty acid. The corrosion resistance that alkyds are known for is a result of excellent wetting
of the substrate and the subsequent crosslinking reaction.
A disadvantage of alkyd polymers is their VOC content. A traditional solventborne alkyd
polymer is supplied as a solution polymer. The viscosity of the solution is, therefore, a
function of the molecular weight. To reduce viscosity, the molecular weight can be reduced
and high solids systems can be pursued. The high solids approach can be successful in some
applications, but does not satisfy the need of all applications due to unfavorable coating
properties caused by low polymer molecular weight. Another approach is to replace the
solvent with a non-VOC using exempt solvents or water. Since exempt solvents can be costly,
flammable and often odorous, there is strong interest in using water as the solvent for many
coatings. Since alkyds are hydrophobic, the alkyd polymer must be modified to exist in the
polar, aqueous environment.
The modification of alkyds for use with water is not a new concept; the first water-compatible
alkyds utilized in coatings were water-reducible alkyds. Water-reducible alkyds are supplied
at 70-75% solids in hydrophilic glycol ether solvents. Formulators neutralize the carboxylic
groups in the alkyd with a base and disperse the alkyd polymer in water. Water-reducible
alkyds display excellent corrosion resistance; however, they suffer two major drawbacks: a
high VOC of 250-300 g/L and a short shelf life due to poor hydrolytic stability.
One approach used to improve alkyd hydrolytic stability in water is emulsification. Using
surfactants, an alkyd emulsion is produced via an emulsification process to yield a surfactantstabilized dispersion of the water-insoluble alkyd polymer. To accomplish this, a significant

level of surfactant, typically 5-10 weight percent of alkyd polymer, is needed. This approach
does not require organic co-solvents and has been shown to protect the alkyd from
hydrolysis. The drawback to this approach is the high level of migratory surfactant that is
utilized. The surfactant can lead to water resistance issues such as blistering and reduced
corrosion resistance.
Another approach to improve the hydrolytic stability of a water-reducible alkyd and lower the
VOC creates an acrylic-modified alkyd dispersion wherein a hydrolysis-resistant acrylic
polymer is placed in the shell neighboring the aqueous phase while protecting the core
alkyd from hydrolysis. To disperse the alkyd polymer in water, salts are created with the acid
from the alkyd and a base. Despite the success in extending shelf life and lowering the VOC
to about 100 g/L, some acrylic-modified alkyd dispersions demonstrate poor corrosion
resistance. This may be due to inefficient grafting of the acrylic onto alkyd, resulting in the
formation of high-Tg and high-acid-value acrylic homopolymers. These polymers can result
in poor substrate wetting and higher-than-expected water sensitivity.
In most alkyd dispersion manufacturing processes, organic alcoholic co-solvents are needed
to achieve a workable viscosity. Removing the organic solvents from the process to achieve
zero VOC leads to a high viscosity unless other modifications are made. One such
modification is the use of a hydrophilic polyalkylene oxide moiety covalently bound to the
alkyd polymer. The bonding of this component to the polymer adds an internal non-migratory
surfactant that was shown to lower the dispersion viscosity, allowing for reduced VOCs (US
Patent 5,698,625). The inclusion of this hydrophilic component reduces hydrophobicity
relative to a traditional alkyd.
Almost all contemporary commercial waterborne zero-VOC alkyd products available contain
either chemically bound or physically blended surfactants to either lower the dispersion
viscosity or to form an alkyd emulsion. The presence of these water-sensitive components in
the coatings inevitably leads to a compromise in coating properties such as corrosion
resistance and QUV resistance. Therefore, to widen the use of zero-VOC alkyd products for
outdoor application, new technology must emerge in order to produce a zero-VOC alkyd
dispersion that does not contain water-sensitive surfactants.

Novel Technology
To overcome the shortcomings of surfactant-containing zero-VOC waterborne alkyd
products, we developed a novel process to create a zero-VOC alkyd dispersion without using
water-sensitive surfactants. It is well known that alkyd dispersions offer favorable corrosion
and QUV resistance because of the absence of surfactants, while alkyd emulsions offer lower
viscosity because of spherical morphology in water. Therefore, the ideal product would have
the major positive attributes of both technologies: good coating performance and low
viscosity. This novel proprietary process creates an alkyd dispersion with emulsion-like
morphology without the use of surfactants. By creating a surfactant-free dispersion, the resin
can offer strong outdoor coating performance at low dispersion viscosity. When compared to
existing alkyd emulsions and existing VOC-containing alkyd dispersions, this novel
technology demonstrates much improved corrosion resistance, comparable gloss and dry
times, and can be supplied at resin solids of 45% or greater with no added surfactant or
solvent.

Results and Discussion

The target application areas for a zero-VOC, surfactant-free waterborne alkyd range from
industrial to architectural and include metal and wood substrates. In this work the product is
targeting the replacement of solvent-based alkyds. The results discussed focus primarily on
metal substrates.
In our tests, five types of alkyd technologies were compared. For the water-based alkyd
technologies the formulation contained approximately 10 g/L of VOC from additives. In
future work the authors intend to lower this value further. No additional solvent is added to
the water-based samples.
Technologies included in this testing and their formulated VOCs include:

SBA - a Solvent-Based chain-stopped short oil Alkyd resin (<450 g/L);

ADS - an Alkyd Dispersion Short oil (<75 g/L);

ADM - an Alkyd Dispersion Medium oil (<25 g/L);

AES - an Alkyd Emulsion Short oil (<10 g/L);

EXR - Experimental Resin (<10 g/L).

Resin samples ADS and ADM contain some solvent from the resin manufacturing process
and, therefore, have VOCs higher than AES and EXR.
Sample EXR represents a surfactant-free, zero-VOC alkyd dispersion produced by the
proprietary process. In the QUV results section, two zero-VOC alkyd dispersions that were
tested differed in raw material economics and offer a choice of cost vs. performance. These
samples are labeled EXR and EXR2.
The solvent-based alkyd is a high-solids chain-stopped alkyd for industrial use and is
formulated to <432 g/L. The solvent-based paint formula appears in Table 1.
All of the water-based alkyd resins were tested using the formula in Table 2. Water was
adjusted to equalize the resin solids across all paints. It is worth noting that the water-based
alkyd formulation is cobalt-free.
Gloss
Alkyd resins are well known for producing very high gloss. Figure 1 shows that the
traditional solvent-based alkyd produced a 20 gloss over 90 units. Most of the other resins
were near or over 80 units, with the exception being the short oil alkyd dispersion (ADS).
The gloss capability of the experimental technology meets expectations for an alkyd at 85
units. The alkyd emulsion performed very well for 20 gloss, as it surpassed the solvent-based
alkyd.
QUV Performance

Paints were tested for QUV-A performance using alternating cycles of light and moisture
every four hours. Test results are shown in Figure 2. In this case two experimental zero-VOC
alkyd dispersions were tested. As can be seen in the figure, EXR showed greater gloss loss
than the solvent-based alkyd. To demonstrate that QUV performance is not a limitation of the
composition, but rather a function of polymer composition, EXR2 was run and shows very
good gloss retention through 500 h. There is a cost difference between EXR and EXR2,
therefore the final QUV performance is a cost vs. performance decision and not a limitation
of the technology.
Dry Time
For industrial applications dry time is a critical feature. It is often very difficult to match the
dry time of certain solvent-based coatings using water-based technologies. This is especially
true when drying under adverse conditions. The dry time results for ambient conditions are
presented in Figure 3. The alkyd emulsion showed the longest tack-free time and the second
longest through-cure time. The solvent-based chain-stopped alkyd showed the fastest tackfree and through-dry. The experimental resin fell in the middle of the group, offering a tackfree time that was better than the alkyd emulsion, but a little slower than the short oil alkyd
dispersion. Despite not drying as fast as the solvent-based alkyd, the experimental technology
offered a reasonable through-cure of 80 min. The alkyd dispersion short oil (ADS) shows the
potential for water-based systems to match the dry time of the solvent-based chain-stopped
alkyd under ambient conditions.
Adhesion
Figure 4 shows the adhesion performance of the paint samples tested on cold rolled steel
(CRS), untreated aluminum (Al) and galvanized metal (Galv) panels when tested using
ASTM D 3359.
The adhesion of each sample to the various metals was comparable for all samples on cold
rolled steel and galvanized metal. On aluminum only the medium oil alkyd dispersion (ADM)
showed any adhesion to the untreated aluminum.
Corrosion Resistance
The new alkyd dispersion technology demonstrates one of its greatest performance attributes
in corrosion resistance. As can be seen in Figure 5, the alkyd emulsion (AES) and both of the
older technology alkyd dispersions (ADS and ADM) show significant failure in this photo.
This photo was taken after 142 h of ASTM B117 salt spray testing. The dry film thickness
was controlled to 2 mils +/- 0.1. The experimental alkyd dispersion (EXR) performed
comparable to the solvent-based alkyd (SBA) when comparing the unscribed field
performance. Around the scribe the solvent-based alkyd slightly outperformed EXR. The
significant blistering seen in the alkyd emulsion sample after 24 h is also worth noting.

Conclusion
A novel alkyd dispersion has been developed that offers performance similar to traditional
solvent-based alkyds at VOC levels near zero. Gloss, dry time and adhesion are comparable
to solventborne alkyd samples. QUV results for the new process can be controlled depending

on the cost vs. performance that is required. Corrosion resistance performance surpasses
existing water-based alkyd technology and is comparable to existing solvent-based
technology.
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By Jeff Arendt, Technical Account Coordinator, Arkema Coating Resins, Cary, NC

By Jun Kim, Senior Research Chemist, Arkema Coating Resins, Cary, NC

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