Technical Paper

Air Drying Waterborne Alkyd Resin Emulsions

by
Michael Gobec - Vianova Resins AG - Austria
Dr. Walter Weger - Vianova Resins AG - Austria
Mario Pschaidt - Vianova Resins - U.S.A.

As a result of some fairly recent developments, the great

versatility of synthetic resin chemistry is now reflected in the
area of eco-friendly binders. The benefits are apparent in both
the binders' chemical composition and range of applications.

Since their launch in the late 1950s, waterborne synthetic resins

have grown in popularity to the point where they are now used
in virtually all types of coatings. Water reducible binders were
originally used mainly for dip coatings because of their low
flammability, as in the case of electrodeposition coatings for the
automotive industry. But increasingly strict environmental
legislation has led to a further expansion in the use of these
binders. Even today, because of the versatility permitted by a
wide range of raw materials and synthesis, the development of
waterborne binders has by no means reached its limit. Among
the many aqueous systems, alkyd-resin emulsions have steadily
gained in popularity; they already cover a wide field of forced
and air dried coatings. But before we discuss the current
products that make up this binder class, a brief look at the
chemistry of alkyd-resin emulsions is necessary.

Structure of Alkyd-Resin Emulsions

The molecules of modern resin emulsions consist of a
hydrophobic alkyd-resin segment onto which high-acid polymer
segments have been grafted and then neutralized to make them
hydrophilic. During the emulsification process, these molecules
associate in a particular way to form emulsion droplets with a
core shell structure
(Figure 1).
The hydrophobic alkyd-resin segments form the core, and the
hydrophilic but unsaponifiable polymer segments form the shell.
This structure gives these self-emulsifying alkyd-resins a
significantly longer storage life. Previously, alkyd-resins with
high acid numbers and large proportions of organic cosolvent
had only limited stability, since the ester bonds were soon
hydrolyzed in water as a result of the anchimeric effect (Figure
2).
Self-emulsifying, alkyd-resin emulsions are more complicated to
produce. First, methacrylic acid and its esters are grafted onto
drying fatty acids (stage 1). Then, a low molecular weight alkyd-
resin with a high hydroxyl value and a low acid number is
produced (stage 2). Finally, the end product is manufactured
(stage 3) by a partial esterification of the two intermediates
(stages I and 2). Through suitable control of the reaction, all the
primary carboxyl groups of the fatty acids are esterified, while
the majority of the tertiary, sterically hindered carboxyl groups
of methacrylic acid remain free and are then neutralized with
ammonia and diluted with water (see Figure 3).
If polyethylene glycol constituents are incorporated into alkyd-
resin emulsions, then hydrolytic splitting must be prevented.
The following are advantages of alkyd-resin emulsions produced
in this way.

• Low acid numbers.

• Better stability with certain basic

pigments.

• Improved drier compatibility.

The cross section of an emulsion droplet in a core-shell emulsion

is shown in Figure 4. On the inside, the alkyd-resin core is
surrounded by an intermediate layer of alkyl chains of the fatty
acid links; on the outside, grafted onto these chains, are the
hydrophilic-polymer segments and the polyethylene-glycol
chains forming a swollen shell.
The hydrophilic polymer segments and the polyethylene glycol
portions are responsible for rheology, interaction with pigments
and driers, and substrate wetting; the nature of the alkyd-resin
core is cru-cial to film formation, wetting and stability. Water
dilutability is achieved by neutralizing the carboxyl groups with
ammonia.

Self-Emulsifying Alkyd Resins

Vianova Kunstharz AG (a subsidiary of Hoechst AG) supplies self-
emulsifying alkyd-resins in the form of 35% to 45% aqueous
emulsions. The content of organic cosolvents is low; in some
cases, there is no organic cosolvent. When the emulsions are
diluted, no water mountain occurs since that step has already
been accomplished. Furthermore, the alkyd-resin emulsions are
not irreversibly damaged by freezing. If the emulsions or paint
produced from them have been frozen, they can be thawed and
restored to a usable state by slowly stirring at temperatures up
to a maximum of 120°F (50°C). The shear stability of these alkyd-
resins provides a number of additional benefits, including:
• good pigmentation properties;
• high gloss;
• rapid drying;
• good corrosion resistance with certain anti-corrosive pigments;
and
• good storage stability.

These alkyd-resin emulsions also exhibit marked

pseudoplasticity, including viscosity decreases with a rise in
shear rate and increases with a rise in pH level. Cosolvents, as
well as the nonvolatile portion, have an adverse effect on viscos-
ity values. This group is represented by Resydrol AY 586w and its
thixotropic version, 548w TIX. The development of these binders
was guided by the following three objec-tives.

• They must permit the manufacture of coatings with a solvent

content of less than 5%.
• They should be suitable for a variety of applications, ranging
from decorative paint to anticorrosion and industrial coatings.
• The coatings produced from these emulsions must have good
flow, high gloss and good weathering resistance.

In Figure 5, paint based on 586w is compared with paint based on

a conventional, long-oil alkyd. Even after outdoor weathering,
paint based on 586w shows good gloss retention see
(Figure 6) and thus compares well with conventional, solvent-
based systems.
Externally Emulsified Alkyd Resins
Self-emulsifying alkyd resins have a relatively low solids content;
hence, the paint body is slightly poorer than that obtained with
conventional alkyd-resins. In addition, ammonia is required as a
neutralizing agent. These two factors became the starting point
for developing externally emulsified alkyd resins. The creation of
externally emulsified resins was guided by the desire to achieve
ecological benefits and to produce a high-solids content, which
is customary with conventional alkyd resins for decorative paint.
The quality of the binder and, therefore, the quality of the paint
is significantly influenced by the type and amount of emulsifier
used, as well as by the emulsification process itself. Our Vianova
research team has developed its own emulsification process.
The sole emulsifiers used are nonionic, nonylphenol ethoxylate-
free products with sufficient double bonds for crosslinking/ This
prevents the emulsifier from causing flooding and floating, and
leads to high initial gloss, good gloss retention and good
repaintability.
Nevertheless, drying both to the touch and complete is impaired
by the emulsifier. For this reason, medium-oil alkyd-resins of this
type with an oil content of about 50% are highly suitable for
decorative paint, unlike conventional types that dry too hard and
brittle. Since no neutralization is required for the emulsification
process, there is no need to use agents such as amines or
ammonia. The same applies to auxiliary solvents and
coalescents.
Paint production is carried out with a pigment paste. Additol®
VXW 6208 has been developed for dispersion of white pigments
in finishes and primers. This dispersing agent is a nonionic,
modified, acrylic copolymer in aqueous solution. Colored paint
can be produced by tinting a low pigmented white paint with
color pastes based on
Colanyl®. The emulsification of solvent-free alkyd resins with
special emulsifiers is an ecologically sensible method of
converting alkyd-resins into an aqueous supply form without
changing their structure.