Aqueous resin composition

An aqueous resin composition comprising a neutralization product of an isocyanurate group-containing maleinized alkyd resin having an acid value of 5 to 65 in an aqueous medium, said maleinized alkyd resin being prepared by maleinizing an alkyd resin having an acid value of not more than 10 and a hydroxyl value of not more than 10 which is the product of condensation reaction of PA0 (A) 20 to 60% by weight of at least one of drying or semi-drying oils and fatty acids, PA0 (B) 10 to 45% by weight of at least one tris(hydroxyalkyl) isocyanurate, PA0 (C) 0 to 45% by weight of at least one polyhydric alcohol other than the component (B), PA0 (D) 10 to 45% by weight of at least one polybasic acid, and PA0 (E) 0 to 15% by weight of at least one monobasic acid and an aqueous emulsion resin composition obtained by emulsion polymerization of a radical polymerizable unsaturated monomer in an aqueous medium in the presence of the aforesaid neutralization product. The above aqueous resin compositions can give a coating having excellent corrosion resistance and fast-drying property.

This invention relates to an aqueous resin composition, and more 
specifically, to an aqueous resin composition containing an isocyanurate 
group-containing maleinized alkyd resin which can give a coating having 
excellent corrosion resistance and fast-drying property. 
Alkyd resins have been used in quantities from old as resins for air-drying 
paints, and it is well known that they are also useful as primers for 
inhibiting corrosion. Nowadays, the properties (e.g., drying property, 
corrosion resistance, etc.) required of coated films are on a higher 
level, and it is desired to develop alkyd resins having excellent 
corrosion-inhibiting ability without adding a hazardous rust preventive 
pigment such as strontium chromate. 
We therefore extensively worked on alkyd resins which would meet the above 
requirements. Our work led to the discovery that the corrosion resistance 
of an alkyd resin can be improved by imparting a moderate degree of 
basicity to it, and its drying property (curability) can be improved by 
strenghthening its intramolecular cohesive force. As an alkyd resin which 
simultaneously meets these requirements of basicity and intramolecular 
cohesive force, we discovered an alkyd resin containing large amounts of 
isocyanurate groups. This resin formed a coated film having excellent 
corrosion resistance without using a rust preventive pigment, but we 
furthered our investigation to determine the possibility of using the 
isocyanurate group-containing alkyd resin as a vehicle for a water-base 
paint containing little or no organic solvent so as to make it 
pollution-free and also to save resources. 
As the most general method, we prepared a water-solubilized alkyd resin by 
imparting an acid value to the main skeleton of the resin by condensing an 
isocyanurate group-containing monomer, such as 
tris(2-hydroxyethyl)isocyanurate, as a polyhydric alcohol component with a 
polybasic acid such as phthalic acid and trimellitic anhydride, and 
examined its corrosion resistance. The corrosion resistance of this resin, 
however, was found to be insufficient. 
There is known a resin composition obtained by neutralizing an alkyd resin 
having an isocyanurate group-containing compound as a polyhydric alcohol 
component, and dispersing it in water (Japanese Laid-Open Patent 
Publication No. 41221/1981). Since the alkyd resin used in the above resin 
composition is prepared by using polyoxyethylene glycol having a molecular 
weight of 600 to 20,000, a coated film prepared from the resin composition 
has poor water resistance and is difficult to use as an air drying paint. 
Furthermore, since the carboxyl group and the isocyanurate group showing 
basicity both exist close to each other in the main skeleton of the resin, 
they effect each other, and the properties of the two groups cannot be 
exhibited fully. Hence, the resulting resin composition has insufficient 
water dispersibility, curability and corrosion resistance in practical 
application. 
In view of the aforesaid state of the art, we made investigations about a 
method of rendering an isocyanurate group-containing alkyd resin aqueous 
without impairing the improved properties (corrosion resistance and 
curability) attributed to the isocyanurate group which imparts basicity to 
the resin and has a strong intramolecular cohesive force and while 
maintaining the water resistance and other properties at practical levels. 
These investigations had led to the discovery that the best method of 
achieving it is to impart the desired acid value to an alkyd resin by 
maleinizing the fatty acid group in the alkyd resin. 
According to this invention, there is provided an aqueous resin composition 
comprising a neutralization product of an isocyanurate group-containing 
maleinized alkyd resin having an acid value of 5 to 65 in an aqueous 
medium, said maleinized alkyd resin being prepared by maleinizing an alkyd 
resin having an acid value of not more than 10 and a hydroxyl value of not 
more than 10 which is the product of condensation reaction of 
(A) 20 to 60% by weight of at least one of drying or semi-drying oils and 
fatty acids, 
(B) 10 to 45% by weight of at least one tris(hydroxyalkyl) isocyanurate, 
(C) 0 to 45% by weight of at least one polyhydric alcohol other than the 
component (B), 
(D) 10 to 45% by weight of at least one polybasic acid, and 
(E) 0 to 15% by weight of at least one monobasic acid. 
In the alkyd resin provided by this invention, the carboxyl groups 
introduced by maleinization add to the fatty acid moiety having strong 
oiliness. Hence, in a dried coated film, the carboxyl groups are 
surrounded by oily groups and spaced from the isocyanurate group located 
at the main chain of the skeleton of the alkyd resin. Consequently, the 
alkyd resin can be dissolved or dispersed in an aqueous medium without 
adverse effects exerted by the isocyanurate group which exhibit weak 
basicity. On the other hand, the isocyanurate groups can exhibit the 
aforesaid properties without being adversely affected by the carboxyl 
groups. Furthermore since the fatty acid and the maleic anhydride in the 
alkyd resin in accordance with this invention are bonded through a C--C 
bond, it has resistance to hydrolysis and is easily dissolved or dispersed 
in the aqueous medium. 
The isocyanurate group-containing maleinized alkyd resin used in this 
invention is characterized in that it has an acid value as a result of 
maleinizing the fatty acid group of an alkyd resin having an isocyanurate 
group at the main chain. To obtain such a maleinized alkyd resin, the 
starting alkyd resin should have a relatively low content of hydroxyl and 
carboxyl groups. If the starting alkyd resin to be maleinized contains 
much hydroxyl groups in the main skeleton, the hydroxyl groups would react 
with maleic acid during maleinization to form a half ester and thus to 
introduce the carboxyl group into the main skeleton of the alkyd resin. As 
a result, the resulting maleinized alkyd resin would be susceptible to 
hydrolysis by the so-called anchimeric effect (see J. Paint Technol., 47, 
No. 602, 40, 1975) and have poor stability. 
In the present invention, an alkyd resin having an acid value of not more 
than 10, preferably not more than 7, and a hydroxyl value of not more than 
10, preferably not more than 7, is used as a starting resin to be 
maleinized. If the acid value and hydroxyl value exceed 10, the properties 
(the improvement of corrosion resistance and curability, etc.) of the 
isocyanurate group cannot be exhibited for the reason mentioned above. In 
order to limit the acid value and hydroxyl value of the alkyd resin to the 
above range, the components (A) to (E) should be preferably reacted so 
that the ratio of the number of hydroxyl groups to that of carboxyl groups 
is adjusted to from 1.10:1.0 to 1.0:1.10, preferably from 1.05:1.0 to 
1.0:1.05. 
The components (A) to (E) which constitute the alkyd resin to be maleinized 
will be described below. 
The component (A) is at least one fatty component selected from the group 
consisting of drying fatty oils, semidrying fatty oils, drying fatty acids 
and semidrying fatty acids. Generally, these fatty components are animal 
and vegetable oils and monobasic acids derived therefrom. Drying fatty 
oils and acids generally have an iodine value of at least 130, and 
semidrying fatty oils and acids usually have an iodine value of 100 to 
130. Typical examples of such fatty oils and acids include drying oils or 
semidrying oils such as linseed oil, safflower oil, soybean oil, sesame 
oil, poppy oil, perilla oil, hemp seed oil, grape kernel oil, corn oil, 
tall oil, sunflower oil, cotton seed oil, walnut oil, rubber seed oil, 
tung oil, oiticica oil and dehydrated castor oil; and fatty acids and 
"Hidiene" fatty acids derived from these oils. These materials may be used 
singly or as a mixture of two or more. It is preferred to use linseed oil, 
soybean oil, soybean oil fatty acid and linseed oil fatty acid which can 
be easily maleinized and have good dispersibility in water. 
In view of the ease of maleinization and the drying and curing properties 
of the resulting coated film, the amount of the component used is 20 to 
60% by weight, preferably 30 to 50% by weight, more preferably 35 to 50% 
by weight, based on the total amount of the components (A) to (E). If the 
amount of the component (A) is less than 20% by weight, a coated film 
formed from the final aqueous resin composition has reduced water 
resistance and corrosion resistance. On the other hand, if it is larger 
than 60% by weight, the hardness and corrosion resistance of the coated 
film are reduced. 
The component (B) is a tris(hydroxyalkyl)isocyanurate which is a component 
for introducing the isocyanurate group into the alkyd resin. Examples of 
usable tris(hydroxyalkyl)isocyanurates are 
tris(2-hydroxyethyl)isocyanurate and tris(hydroxymethyl)isocyanurate. They 
may be used either singly or in combination. The amount of the component 
(B) is 10 to 45% by weight, preferably 15 to 40% by weight, more 
preferably 20 to 35% by weight, based on the total amount of the 
components (A) to (E). If the amount of the component (B) is less than 10% 
by weight, a coated film formed from the final aqueous resin composition 
shows no appreciable improvement in corrosion resistance and curability. 
If it exceeds 45% by weight, the water resistance of the coated film is 
reduced. 
The component (C) is a polyhydric alcohol other than the component (B). It 
may include those which are usually employed in the production of alkyd 
resins. Generally, mainly aliphatic polyhydric alcohols containing 2 to 6, 
preferably 2 to 4, hydroxyl groups and preferably 2 to 10 carbon atoms per 
molecule can be advantageously used. Specific examples include ethylene 
glycol, propylene glycol, butanediol, diethylene glycol, pentanediol, 
neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, 
pentaerythritol, sorbitol, 1,4-cyclohexanedimethanol and tricyclodecane 
dimethanol. They may be used singly or in combination. The use of 
1,4-cyclohexane dimethanol, tricyclodecane dimethanol and pentaerythritol 
is preferred because such polyhydric alcohols can give a rigid resin. 
The amount of the component (C) is 0 to 45% by weight, preferably 1 to 20% 
by weight, especially preferably 3 to 15% by weight, based on the total 
amount of the components (A) to (E). 
The component (D) is any polybasic acid which is usually employed in the 
production of alkyd resins. Generally, mainly aliphatic or aromatic 
polycarboxylic acids containing 2 to 4, preferably 2 to 3, carboxyl groups 
and preferably 6 to 10 carbon atoms per molecule can be used 
advantageously. Specific examples include aromatic polycarboxylic acids 
such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic 
acid, and pyromellitic acid; tetrahydrophthalic acid; aliphatic 
polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, 
azelaic acid, 3,6-endomethylene, tetrahydrophthalic acid, and 
methylcyclohexenetricarboxylic acid; and anhydrides of these 
polycarboxylic acids. Of these, isophthalic acid and terephthalic acid are 
preferred. In combination with the isocyanurate compound (B), the 
component (D) serves to give an aqueous resin composition having markedly 
improved water dispersibility and film properties (particularly, 
flexibility). 
The amount of the component (D) is 10 to 40% by weight, preferably 15 to 
30% by weight, based on the total amount of the components (A) to (E). 
The component (E) is a monobasic acid other than the fatty acids described 
hereinabove as the component (A). Specifically, there can be cited any 
monobasic acids which are usually employed in the production of alkyd 
resins, such as benzoic acid, p-tert-butylbenzoic acid, methylbenzoic 
acid, and non-drying oil fatty acids (e.g., coconut oil fatty acid, and 
olive oil fatty acid). Benzoic acid is especially preferred because of its 
low price. The amount of the component (E) is 0 to 15% by weight, 
preferably 1 to 8% by weight, based on the total amount of the components 
(A) to (E). 
PREATION OF AN ISOCYANURATE GROUP-CONTAINING ALKYD RESIN 
An alkyd resin can be produced from the components (A) to (E) [the 
components (C) and/or (E) are optional components] in a manner known per 
se. For example, the components (A) to (E) may be dehydrocondensed at 
about 150.degree. to about 250.degree. C. for a about 3 to about 10 hours 
in an atmosphere of an inert gas such as nitrogen in the absence or 
presence of a suitable solvent such as an aromatic hydrocarbon (e.g., 
benzene, toluene and xylene) and optionally in the presence of a 
condensation catalyst such as dibutyltin oxide, zinc acetate and sulfuric 
acid. 
The resulting alkyd resin desirably has an acid value and a hydroxyl value 
both of not more than 10, preferably not more than 7. If the acid value 
and/or the hydroxy value becomes higher than 10, the aforesaid properties 
of the component (B) may not be exhibited fully. 
In order to control the acid value and the hydroxy value of the resulting 
alkyd resin within the aforesaid range, it is convenient to blend the 
components (A) to (E) such that the ratio of the total number of hydroxyl 
groups to that of carboxyl groups is adjusted to from 1.10:1.0 to 
1.1:1.10, preferably from 1.05:1.0 to 1.0:1.05. 
MALEINIZATION OF THE ALKYD RESIN 
According to this invention, the resulting isocyanurate group-containing 
alkyd resin is then maleinized. Maleinization is carried out by the 
addition of maleic anhydride to the fatty acid group in the alkyd resin. 
Specifically, a mixture of the alkyd resin and maleic anhydride is reacted 
at about 150.degree. to about 230.degree. C. for about 1 to 5 hours in the 
absence or presence of a suitable solvent, such as an aromatic hydrocarbon 
solvent (e.g., benzene, xylene or toluene). 
The degree of maleinization is adjusted so that the acid value of the 
maleinized alkyd resin (this denotes the acid value in the state in which 
the acid anhydride group is ring-opened) is within the range of 5 to 65, 
preferably 10 to 50, more preferably 15 to 45. If the acid value exceeds 
65, a coated film formed from the finally obtained aqueous resin 
composition has reduced water resistance and weatherability. On the other 
hand, if the acid value is lower than 5, the maleinized alkyd resin has 
poor solubility or dispersibility in water. 
In order to confine the acid value of the resulting maleinized alkyd resin 
within the above range, it is preferred that 5 to 55 parts by weight, 
preferably 10 to 42 parts by weight, of maleic anhydride be used per 1,000 
parts by weight of the alkyd resin. 
The resulting maleinized alkyd resin has a number average molecular weight 
of generally in the range of about 800 to about 100,000, especially 
preferably about 1000 to about 30,000. 
According to this invention, the isocyanurate group-containing maleinized 
alkyd resin prepared in the above-described manner is then converted into 
a form soluble or dispersable in an aqueous medium by neutralizing it with 
a basic substance selected from ammonia and amines. 
Illustrative of the amine used for neutralization are tri(lower 
alkyl)amines such as trimethylamine, triethylamine and tripropylamine; 
di(lower alkyl)amines such as dimethylamine and diethylamine; and di(lower 
alkyl) (lower alkanol)amines such as 2-dimethylaminoethanol and 
2-diethylaminoethanol. 
The aqueous medium used to dissolve or disperse the neutralized alkyd resin 
may be water or a mixture of water with a water-miscible organic solvent. 
Examples of the water-miscible organic solvent include Cellosolve-type 
solvents of the general formula HO--CH.sub.2 CH.sub.2 --OR.sub.1 in which 
R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon 
atoms, such as ethylene glycol, butyl Cellosolve and ethyl Cellosolve; 
carbitol-type solvents of the general formula HO--CH.sub.2 CH.sub.2 
--OCH.sub.2 --CH.sub.2 --OR.sub.2 wherein R.sub.2 is the same as R.sub.1, 
such as diethylene glycol, methyl carbitol and butyl carbitol; glyme-type 
solvents of the general formula R.sub.3 O--CH.sub.2 CH.sub.2 --OR.sub.4 
wherein R.sub.3 and R.sub.4 each represent an alkyl group having 1 to 3 
carbon atoms, such as ethylene glycol dimethyl ether; diglyme-type 
solvents of the general formula R.sub.5 O--CH.sub.2 CH.sub.2 OCH.sub.2 
--CH.sub.2 OR.sub.6 wherein R.sub.5 and R.sub.6 are the same as R.sub.3 
and R.sub.4, such as diethylene glycol dimethyl ether; Cellosolve 
acetate-type solvents of the general formula R.sub.7 O--CH.sub.2 CH.sub.2 
OCO--CH.sub.3 wherein R.sub.7 represents a hydrogen atom or a methyl or 
ethyl group, such as ethylene glycol monoacetate and methyl Cellosolve 
acetate; alcohol-type solvents of the general formula R.sub.8 OH wherein 
R.sub.8 represents an alkyl group having 1 to 4 carbon atoms, such as 
ethanol and propanol; and diacetone alcohol, dioxane, tetrahydrofuran, 
acetone, dimethylformamide and 3-methoxy-3-methyl-butanol. These organic 
solvents may be used singly or as a combination of two or more. The amount 
of the organic solvent is preferably not more than 100 parts by weight per 
100 parts by weight of the maleinized alkyd resin used in this invention, 
and is less than the amount of water. Specifically, it can be used in an 
amount of not more than 100 parts by weight, preferably not more than 80 
parts by weight, per 100 parts by weight of water. 
Preferably, the maleinized alkyd resin in this invention is present in this 
aqueous medium in a solids concentration of about 5 to about 60% by 
weight, especially 10 to 50% by weight. 
The resulting aqueous resin composition of this invention can be used 
advantageously as a coating composition by incorporating extender 
pigments, coloring pigments, dryers, rustproofing agents, ultraviolet 
absorbers, antifoamers, etc. which are normally used as paint additives. 
A coated film prepared from the aqueous resin composition of this invention 
cures fully at room temperature. But when it is heated in the presence or 
absence of an amino resin, etc., it cures to a film of good quality within 
a shorter period of time. 
It has further been found in accordance with this invention that when a 
radical-polymerizable unsaturated monomer is emulsion-polymerized in the 
presence of the aqueous resin composition of this invention used as a 
dispersion stabilizer, there can be obtained an aqueous emulsion resin 
composition which can give a coated film having very good properties such 
as further improved drying property and water resistance. 
Thus, according to this invention, there is also provided an aqueous 
emulsion resin composition obtained by emulsion polymerization of a 
radical polymerizable unsaturated monomer in the presence of a 
water-solubilized or water-dispersed product of the neutralization product 
of the aforesaid isocyanurate group-containing maleinized alkyd resin. 
Since the isocyanurate group-containing maleinized alkyd resin has a great 
grafting effect, it induces excessive grafting reaction with the 
radical-polymerizable unsaturated monomer during the emulsion 
polymerization to form a grafted product of the maleinized alkyd resin. At 
the same time, the radical polymerizable unsaturated monomer itself is 
emulsion-polymerized to form polymer particles. 
The resulting aqueous emulsion resin composition is characterized by having 
excellent corrosion resistance attributed to the inclusion of the basic 
isocyanurate group in the main skeleton of the maleinized alkyd resin used 
as a dispersion stabilizer, and hardness and excellent drying property 
attributed to the presence of the grafted product of the maleinized alkyd 
resin. Furthermore, unlike a conventional water-soluble alkyd resin of the 
trimellitic acid or phthalic anhydride added type, the maleinized alkyd 
resin has excellent stability to hydrolysis. Furthermore, since the maleic 
acid component addes to the fatty acid moiety having strong oiliness, and 
is present remote from the basic isocyanurate group, the water 
dispersibility of the resin composition is not impaired, and moreover, 
good dispersing property can be imparted to the grafted product of the 
maleinized alkyd resin formed by the polymerization of the radical 
polymerizable unsaturated monomer. Accordingly, the aqueous emulsion resin 
composition prepared from it has very good stability. 
Suitable radical polymerizable unsaturated monomers used for the synthesis 
of the grafted product of the maleinized alkyd resin are those monomers 
whose hydrophilicity is not so strong as is not in general emulsion 
polymerization. 
The oxidation-curable groups contained in the maleinized alkyd resin are 
liable to undergo radical chain transfer and tends to reduce the molecular 
weight of the resin particles. In order, therefore, to strengthen the 
inside of the resin particles and to improve the film properties, it is 
preferred to use a polyfunctional unsaturated monomer as at least a part 
of the radical polymerizable unsaturated monomer. 
The radical polymerizable unsaturated monomer generally has a Q value, 
determined by the Q-e theory, of at least 0.1, and can be selected broadly 
according to the properties required of the final aqueous emulsion resin 
composition. Unsaturated monomers having a Q value of 0.3 to 5 are 
especially suitable. 
Typical examples of the radical polymerizable unsaturated monomers are 
shown below. 
(a) Vinyl aromatic compounds 
Styrene, .alpha.-methylstyrene, vinyltoluene, p-chlorostyrene and 
vinylpyridine. 
(b) Acrylic or methacrylic acid esters 
C.sub.1-26 alkyl esters of acrylic or methacrylic acid, such as methyl, 
acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl 
acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl 
methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl 
methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate 
and lauryl methacrylate; addition condensation products between glycidyl 
acrylate or glycidyl methacrylate and C.sub.2-26 carboxyl-containing 
compounds (e.g., acetic acid, propionic acid, oleic acid, stearic acid or 
lauric acid); C.sub.2-12 alkoxyalkyl esters of acrylic or methacrylic 
acid, such as methoxybutyl acrylate, methoxybutyl methacrylate, 
methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate and 
ethoxybutyl methacrylate; C.sub.2-8 hydroxyalkyl esters of acrylic or 
methacrylic acid, such as hydroxyethyl acrylate, hydroxyethyl 
methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate, or 
condensation products of these hydroxyalkyl esters with 
carboxyl-containing compounds having 2 to 26 carbon atoms; allyl acrylate 
and allyl methacrylate; mono- or di(C.sub.1-10 alkyl) aminoalkyl esters of 
acrylic or methacrylic acid, such as diethylaminoethyl acrylate, 
diethylaminoethyl methacrylate, methylaminoethyl acrylate and 
methylaminoethyl methacrylate; and C.sub.5-12 alkenyloxyalkyl esters of 
acrylic or methacrylic acid, such as allyloxyethyl acrylate and 
allyloxyethyl methacrylate. 
(c) Diolein compounds 
Diolefins having 2 to 8 carbon atoms, such as butadiene, isoprene and 
chloroprene. 
(d) Amides of acrylic or methacrylic acid 
Acrylamide, N-methylol acrylamide and N-butoxymethyl acrylamide. 
(e) Other unsaturated monomers 
Acrylonitrile, methacrylonitrile and methyl isopropenyl ketone. 
These unsaturated monomers may be used singly or in combination with each 
other. 
Among these unsaturated vinyl monomers, the vinyl aromatic compounds (a) 
and the acrylic or methacrylic esters (B) are especially suitable. 
Especially preferred unsaturated vinyl monomers are styrene, 
.alpha.-methylstyrene, vinyltoluene, and C.sub.1-12 alkyl esters of 
acrylic or methacrylic acid. 
The polyfunctional unsaturated monomer which can be used in combination 
with the radical polymerizable unsaturated monomer is a monomer having two 
or more non-conjugated double bonds in the molecule. Examples of the 
polyfunctional unsaturated monomer include esters formed between 
polyhydric alcohols having 2 to 4 functional groups and 2 to 10 carbon 
atoms (such as ethylene glycol, 1,6-hexanediol, trimethylolpropane and 
pentaerythritol) and acrylic or methacrylic acid; esters formed between 
glycidyl acrylate or glycidyl methacrylate and acrylic or methacrylic 
acid; esters between polycarboxylic acids having 2 to 4 functional groups 
and 6 to 10 carbon atoms (such as isophthalic acid, terephthalic acid, 
adipic acid and trimellitic acid) and glycidyl acrylate, glycidyl 
methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 
hydroxypropyl acrylate or hydroxypropyl methacrylate; esters formed 
between polyepoxy compounds having 2 to 4 functional groups (such as 
bisphenol A diglycidyl ether) and hydroxyethyl acrylate, hydroxyethyl 
methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic 
acid or methacrylic acid; adducts formed between isocyanates having 2 to 4 
functional groups and 2 to 12 carbon atoms (such as 1,6-hexamethylene 
diisocyanate, isophorone diisocyanate, lysine diisocyanate, xylylene 
diisocyanate and hydrogenated toluene diisocyanate) and hydroxyethyl 
acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl 
methacrylate, acrylic acid or methacrylic acid; C.sub.6-7 alkenyl esters 
of acrylic or methacrylic acid such as allyl acrylate and allyl 
methacrylate; esters formed between tris(2-hydroxyethyl)isocyanurate or 
tris(hydroxymethyl)isocyanurate and acrylic or methacrylic acid; adducts 
formed between tris(glycidyl)isocyanurate and acrylic or methacrylic acid; 
urethane compounds formed between polyisocyanate compound having 2 to 4 
functional groups and hydroxyethyl acrylate, hydroxyethyl methacrylate, 
hydroxypropyl acrylate or hydroxypropyl methacrylate; esters formed 
between phosphoric acid and hydroxyethyl acrylate, hydroxyethyl 
methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate; and 
divinylbenzene. There can also be used adducts formed between epoxy 
polymers having a number average molecular weight of not more than 2,000, 
preferably not more than 200 or acrylic or methacrylic polymers having 
hydroxyl, epoxy or carboxyl groups, and acrylic acid, methacrylic acid, 
glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, 
hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl 
methacrylate. 
Preferred among these polyfunctional unsaturated monomers are esters formed 
between polyhydric alcohols having 2 to 4 functional groups and 2 to 8 
carbon atoms and acrylic or methacrylic acid; esters formed between 
glycidyl acrylate or glycidyl methacrylate and acrylic or methacrylic 
acid; and divinylbenzene. 
The unsaturated monomers are properly selected according to the properties 
desired of the final aqueous emulsion resin composition, and may be used 
singly or as a combination of two or more. 
Up to 50% by weight, preferably up to 30% by weight, of the aforesaid 
unsaturated monomer may be replaced by a hydrophilic unsaturated monomer. 
Examples of the hydrophilic unsaturated monomer that can be used in this 
invention include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylonitrile, 
methacrylonitrile, acrylic acid, methacrylic acid, glycidyl acrylate, 
glycidyl methacrylate, acrylamide, N-n-butoxymethyl acrylamide, and 
vinylpyridine. These monomers may be used singly or in combination with 
each other. 
The aqueous emulsion resin composition in accordance with this invention 
may be prepared by conventional known methods. For example, it can be 
prepared by well dispersing the radical polymerizable unsaturated monomer 
in a water-solubilized or water-dispersed product of the isocyanurate 
group-containing maleinized alkyd resin in the presence of an aqueous 
medium, and subjecting the dispersion to emulsion polymerization with or 
without stirring at a temperature below the boiling point of the aqueous 
medium, optionally using a polymerization initiator such as an azo 
compound, a peroxide, a or a redox system, or activated energy rays such 
as ultraviolet rays, gamma-rays and electron beams. A part of the 
resulting resin may be in the gelled state. But since this gellation 
occurs microscopically, it does not at all cause inconvenience to the 
formation of a coated film. 
In the above reaction, the ratio of the maleinized alkyd resin to the 
radical polymerizable unsaturated monomer may be varied widely depending 
upon the type of the alkyd resin and/or the unsaturated monomer, etc. 
Usually it may be from 5:100 to 100:5, preferably from 10:100 to 100:10. 
As stated above, the polyfunctional unsaturated monomer can be used as at 
least a part of the radical polymerizable unsaturated monomer. The amount 
of the polyfunctional monomer is not more than 50% by weight of the total 
weight of the unsaturated monomers used. However when the ratio of the 
maleinized alkyd resin to the radical polymerizable unsaturated monomer is 
from 100:100 to 100:5 and the proportion of the unsaturated monomer is 
small, the unsaturated monomers may be wholly one or more polyfunctional 
monomers, and this is preferred in view of the properties of the resulting 
coated film. 
The resulting aqueous emulsion resin composition of this invention can be 
used mainly as an air-drying type coat-forming material after adding 
conventional paint additives such as coloring agents, extender pigments, 
dryers, rust-proofing agents, ultraviolet absorbers and antifoamers, etc. 
and adjusting its solids concentration to, for example, 5 to 50% by 
weight. Needless to say, it can also be used as a baking-drying type coat 
forming material. It can also be used as a resin finishing agent. 
The aqueous emulsion resin composition of this invention exhibits excellent 
performance by itself, but in order to improve its performance further, it 
may be used in admixture with another water-soluble or water-dispersible 
resin.

The following Examples and Comparative Examples illustrate the present 
invention in greater detail. All parts and percentages in these examples 
are by weight unless specifically indicated. 
EXAMPLE 1 
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Linseed oil fatty acid 
407 parts 
tris(2-Hydroxyethyl) isocyanurate 
250 parts 
1,4-Cyclohexane dimethanol 
138 parts 
iso-Phthalic acid 245 parts 
Benzoic acid 47 parts 
Dibutyltin oxide 2 parts 
Xylene 30 parts 
______________________________________ 
The above ingredients were put in a reactor, and with stirring in an 
atmosphere of nitrogen, they were heated to 240.degree. C. The reaction 
was carried out for 6.5 hours, until the acid value of the resin reached 
5.5 (the hydroxyl value 5.4). Subsequently, the temperature was lowered to 
200.degree. C., and 25 parts of maleic anhydride was added to maleinize 
the alkyd resin at 200.degree. C. for 2.5 hours. After the reaction, the 
reaction mixture was distilled under reduced pressure to remove the 
unreacted maleic anhydride and xylene, and then the temperature was 
lowered to 140.degree. C. At this temperature, 15 parts of tap water was 
added to the reactor, and ring-opening reaction was carried out for 1 
hour. Then, 330 parts of n-butyl Cellosolve was added. There was obtained 
a maleinized alkyd resin varnish having a heating residue of 75%, a resin 
acid value of 25.0, a Gardner viscosity (as a 60% n-butyl Cellosolve 
solution) of T to U, and a number average molecular weight of about 5,000. 
The varnish was neutralized with 2.0 equivalents of triethylamine, and then 
dispersed in tap water. 
The following pigments were added to 26.3 parts, as the resin solids, of 
the dispersion, and dispersed for 1 hour using a paint conditioner. 
______________________________________ 
Mapicoyellow XLO (a tradename for iron 
26.3 parts 
oxide made by Titanium Kogyo Co., Ltd.) 
Talc No. 1 34.3 parts 
Tancal No. 3000 a tradename for 
34.3 parts 
calcium carbonate made by Sakuhara 
Chemical Industry Co., Ltd.) 
______________________________________ 
To the resulting pigment dispersion was added another portion of the 
aforesaid neutralized resin solution which contained a dryer, and the 
weight ratio of the entire resin solids to the pigments was adjusted to 
1.0:1.8. Then, while adding water, the mixture was stirred by a high-speed 
dispersing device. The dryer was cobalt naphthenate added in an amount of 
0.05 part as metal based on 100 parts by weight of the resin solids. 
EXAMPLE 2 
______________________________________ 
Linseed oil fatty acid 
407 parts 
tris(2-Hydroxyethyl) isocyanurate 
250 parts 
1,4-Cyclohexane dimethanol 
138 parts 
Terephthalic acid 245 parts 
Benzoic acid 47 parts 
Dibutyltin oxide 2 parts 
Xylene 30 parts 
______________________________________ 
The above ingredients were put in a reactor and reacted for 7.0 hours and 
under the same conditions as in Example 1, until the acid value of the 
resin reached 6.9 (the hydroxyl value 6.5). Then, 25 parts of maleic 
anhydride was added, and the alkyd resin was maleinized under the same 
conditions as in Example 1. The reaction mixture was then distilled under 
reduced pressure to remove the unreacted maleic anhydride and xylene. 
Then, 15 parts of tap water was added, and the same ring-opening reaction 
as in Example 1 was carried out to give a maleinized alkyd resin varnish 
having a heating residue of 75%, a resin acid value of 30.2, a Gardner 
viscosity (as a 60% n-butyl Cellosolve solution) of U-V, and a number 
average molecular weight of about 5,500. 
In the same way as in Example 1, the varnish was neutralized and pigments 
were further dispersed. 
EXAMPLE 3 
______________________________________ 
Linseed oil fatty acid 
399 parts 
tris(2-Hydroxyethyl) isocyanurate 
302 parts 
1,4-Cyclohexane dimethanol 
90 parts 
iso-Phthalic acid 228 parts 
Benzoic acid 67 parts 
Dibutyltin oxide 2 parts 
Xylene 30 parts 
______________________________________ 
The above ingredients were put in a reactor and reacted for 6.5 hours under 
the same conditions as in Example 1, until the acid value of the resin 
reached 6.1 (hydroxyl value 6.3). The temperature was then lowered to 
200.degree. C., and the resulting alkyd resin was maleinized at 
200.degree. C. for 2 hours. After the reaction, the reaction mixture was 
distilled under reduced pressure to remove the unreacted maleic anhydride 
and xylene. The residue was cooled to 140.degree. C., and then 15 parts of 
tap water was added, and ring-opening reaction was carried out for 1 hour. 
Then, 330 parts of n-butyl Cellosolve was added to give a maleinized alkyd 
resin varnish having a heating residue of 74.9%, a resin acid value of 
25.4, a Gardner viscosity (as a 60% n-butyl Cellosolve solution) of V and 
a number average molecular weight of about 4,500. 
In the same way as in Example 1, the varnish was neutralized to form an 
aqueous dispersion, and pigments were dispersed. 
COMATIVE EXAMPLE 1 
______________________________________ 
Linseed oil fatty acid 
396 parts 
Pentaerythritol 140 parts 
1,4-Cyclohexane dimethanol 
144 parts 
iso-Phthalic acid 248 parts 
Benzoic acid 178 parts 
Dibutyltin oxide 2 parts 
Xylene 30 parts 
______________________________________ 
The above ingredients were put in a reactor and reacted under the same 
conditions as in Example 1 for 7 hours, until the acid value of the resin 
reached 3.7. Then, 25 parts of maleic anhydride was added, and under the 
same conditions as in Example 1, the alkyd resin was maleinized. The 
reaction mixture was distilled under reduced pressure to remove the 
unreacted maleic anhydride and xylene. Tap water (15 parts) was added, and 
ring-opening reaction was carried out as in Example 1. Then, 330 parts of 
n-butyl Cellosolve was added to give a maleinized alkyd resin varnish 
having a heating residue of 75%, a resin acid value of 27.8, a Gardner 
viscosity (as a 60% n-butyl Cellosolve solution) of Y and a number average 
molecular weight of 5,000. 
The resulting varnish was neutralized to form an aqueous dispersion, and 
pigments were dispersed, in the same way as in Example 1. 
COMATIVE EXAMPLE 2 
______________________________________ 
Dehydrated castor oil fatty acid 
336 parts 
tris(2-Hydroxyethyl) isocyanurate 
306 parts 
Trimethylolethane 88 parts 
Neopentyl glycol 15 parts 
iso-Phthalic acid 304 parts 
Polyethylene glycol 51 parts 
(molecular weight 6,000) 
Xylene 30 parts 
______________________________________ 
An alkyd resin having an acid value of 16 was prepared by reacting the 
above ingredients in a reactor under the same conditions as in Example 1 
(the reaction time was 4.5 hours). Then, 330 parts of n-butyl Cellosolve 
was added to give an alkyd resin varnish having a heating residue of 75%, 
a resin acid value of 15.0, a Gardner viscosity (as a 60% n-butyl 
Cellosolve solution) of Z and a number average molecular weight of about 
10,000. 
In the same way as in Example 1, the varnish was neutralized to form an 
aqueous dispersion, and pigments were dispersed. 
COMATIVE EXAMPLE 3 
______________________________________ 
Linseed oil fatty acid 
411 parts 
tris(2-Hydroxyethyl) isocyanurate 
254 parts 
1,4-Cyclohexane dimethanol 
139 parts 
iso-Phthalic acid 266 parts 
Benzoic acid 19 parts 
______________________________________ 
The above ingredients were put in a reactor and reacted under the same 
conditions as in Example 1 to give an alkyd resin having an acid value of 
15.8 (the reaction time was 4.5 hours). Then, 15 parts of maleic anhydride 
was added, and the alkyd resin was maleinized at 200.degree. C. for 2.5 
hours. After the maleinization, the reaction mixture was distilled under 
reduce pressure to remove the unreacted maleic anhydride and xylene. Then, 
15 parts of tap water was added, and ring-opening reaction was carried 
out. Thirty parts of n-butyl Cellosolve was added to give a maleinized 
alkyd resin varnish having a heating residue of 75.1%, a resin acid value 
of 30.1, a Gardner viscosity (as a 60% n-butyl Cellosolve solution) of Z 
and a number average molecular weight of 5,500. 
In the same way as in Example 1, the varnish was neutralized to form an 
aqueous dispersion, and pigments were dispersed. 
TESTS FOR PROPERTIES AND THE RESULTS 
Each of the pigment dispersion obtained in Examples the above Examples and 
Comparative Examples was coated by a bar coater on a mild steel sheet 
polished with a sand paper No. 320, and dried at 20.degree. C. and a 
humidity of 75% for 7 days. 
The properties of the coated films were tested and the results are shown in 
Table 1. 
TABLE 1 
__________________________________________________________________________ 
Com- Com- Com- 
parative 
parative 
parative 
Film properties 
Example 1 
Example 2 
Example 3 
Example 1 
Example 2 
Example 3 
__________________________________________________________________________ 
Film thickness after 
32 33 33 34 33 32 
drying (microns) 
Pencil 
1 day 
5B 5B 4B 5B 4B 4B 
hardness 
3 days 
4B 4B 3B 4B 2B 3B 
(*1) 7 days 
HB HB HB B B B 
Adhesion test (*2) 
Good Good Good Good Good Good 
Water resistance (*3) 
Slightly 
Slightly 
Slightly 
Slightly 
Wholly 
Slightly 
whitened 
whitened 
whitened 
whitened 
blistered 
whitened 
Salt spray resistance 
1.5 mm 
1.0 mm 
0.5 mm 
4.0 mm 
Wholly 
5.0 mm 
(*4) blistered 
(from width of blister 
from the cut part) 
__________________________________________________________________________ 
(*1): Film thickness 
The coating was performed at a temperature of 20.degree. C. and a humidit 
of 75%, and the hardness of the coated film after the lapse of 1, 3, and 
days, respectively, was measured. 
(*2): Adhesion test 
One hundred squares each having an area of 1 mm.sup.2 were provided on a 
test specimen by crosscutting. An adhesive cellophane tape was applied to 
the crosscut surface, and then violently peeled off. 
(*3): Water resistance 
The sample specimen was dipped in tap water at 20.degree. C. for 2 days, 
and then the state of the coated film was examined. 
(*4): Corrosion resistance 
The coated film was cross-cut by a razor edge so that the cuts reached the 
substrate. The specimen was then subjected to a salt spray tester for 120 
hours, and the state of the coated surface of the specimen was examined 
(in accordance with JIS Z-2371). 
EXAMPLE 4 
The maleinized alkyd resin varnish (213 parts) obtained in the same way as 
in Example 1, 3 parts of n-butyl Cellosolve, 7.2 parts of triethylamine 
and 778 parts of tap water were stirred to form a solution. To the 
solution was added a solution of 1 g of ammonium persulfate in 20 parts of 
tap water. Then, a mixture of 404 parts of n-butyl methacrylate and 10 
parts of 1,6-hexanediol diacrylate was added at a time, and the mixture 
was well stirred and heated to 80.degree. C. The mixture was left to stand 
for 2 hours at this temperature to form an emulsion composition. 
EXAMPLE 5 
The same maleinized alkyd resin varnish (333 parts) as obtained in Example 
1, 11.2 parts of triethylamine and 640 parts of tap water were stirred to 
form a solution. Then, a solution of 2.5 parts of 
azobisdimethylvaleronitrile in 50 parts of 1,6-hexanediol diacrylate was 
added, and the mixture was well stirred and heated to 80.degree. C. The 
mixture was reacted at this temperature for 4 hours to form an emulsion 
composition. 
EXAMPLE 6 
The same maleinized alkyd resin varnish (213 parts) as in Example 2, 3 
parts of n-butyl Cellosolve, 8.7 parts of triethylamine and 777 parts of 
tap water were stirred to form a solution. Then, to the solution was added 
a solution of 1 g of ammonium persulfate in 20 parts of tap water, and 
then, a mixture of 202 parts of n-butyl methacrylate, 202 parts of 
styrene, and 10 parts of 1,6-hexanediol dimethacrylate was added at a 
time. The mixture was stirred and heated to 80.degree. C. It was left to 
stand at this temperature for 2 hours to form an emulsion composition. 
EXAMPLE 7 
The same maleinized alkyd resin varnish (333 parts) as in Example 2, 13.4 
parts of triethylamine and 638 parts of tap water were well stirred to 
form a solution. Then, a solution of 2.5 parts of 
azobisdimethylvalenonitrile in 50 parts of trimethylolpropane triacrylate 
was dissolved in the resulting solution. The mixture was well stirred and 
heated to 80.degree. C. The mixture was reacted at this temperature for 4 
hours to form a microgel emulsion composition. 
EXAMPLE 8 
The same maleinized alkyd resin varnish (213 parts) as in Example 3, 7.2 
parts of triethylamine and 778 parts of tap water were well stirred to 
form a solution. To the solution was added a solution of 1 g of ammonium 
persulfate in 20 parts of tap water. Thereafter, a mixture of 202 parts of 
styrene, 202 parts of 2-ethylhexyl methacrylate, and 10 parts of 
1,6-hexanediol diacrylate was added at a time. The mixture was well 
stirred and heated to 80.degree. C. It was then kept at this temperature 
for 2 hours to form an emulsion composition. 
EXAMPLE 9 
The same maleinized alkyd resin varnish (333 parts) as used in obtained in 
Example 3, 11.3 parts of triethylamine and 881 parts of tap water were 
well stirred to form a solution. To the solution was added a solution of 
3.8 parts of azobisdimethylvaleronitrile in 75 parts of 1,6-hexanediol 
diacrylate. The mixture was well stirred, and heated to 80.degree. C. It 
was reacted at this temperature for 4 hours to form a microgel emulsion 
composition. 
COMATIVE EXAMPLE 4 
160 parts of 1,2-vinyl maleinized polybutadiene having a number average 
molecular weight of about 3,000 and an acid value of 100, ring-opened with 
water, (the composition of polybutadiene: 1,2-linkage 91% by weight, 
1,4-trans 9% by weight), 56 parts of n-butyl Cellosolve, 28 parts of 
triethylamine and 757 parts of tap water were well stirred to form a 
solution. To the solution was added a solution of 1 g of ammonium 
persulfate in 20 parts of tap water. Then, 414 parts of n-butyl 
methacrylate was added. They were well stirred and the mixture was heated 
to 80.degree. C. It was left to stand at this temperature for 2 hours to 
form an emulsion composition. 
COMATIVE EXAMPLE 5 
______________________________________ 
Styrene-allyl alcohol copolymer 
547 parts 
(molecular weight 1140; OH group 
content 7.5% by weight) 
Linseed oil fatty acid 
635 parts 
Xylene 61 parts 
Dibutyltin oxide 1.1 parts 
______________________________________ 
The above ingredients were put in a reactor, and heated at 230.degree. C. 
for 9 hours to perform esterification and give a resin having an acid 
value of 5.3 and a number average molecular weight of about 2,500. Then, 
206 parts of maleic anhydride was added to the resin, and the mixture was 
heated at 200.degree. C. for 3 hours. The reaction mixture was purified 
under reduced pressure, and 50 parts of water was added and the 
ring-opening reaction was performed at 100.degree. C. for 2 hours, to give 
a resin varnish having an acid value of 133. 
Then, 160 parts of the varnish, 56 parts of n-butyl Cellosolve, 36 parts of 
triethylamine and 749 parts of tap water were well stirred to form a 
solution. To the solution was added a solution of 1 g of ammonium 
persulfate in 20 parts of tap water. A mixture of 404 parts of n-butyl 
methacrylate and 10 parts of 1,6-hexanediol dimethacrylate was added at a 
time, and the mixture was well stirred and heated to 80.degree. C. It was 
left to stand at this temperature for 2 hours to give an emulsion 
composition. 
COMATIVE EXAMPLE 6 
______________________________________ 
Linseed oil fatty acid 
396 parts 
Pentaerythritol 140 parts 
1,4-Cyclohexane dimethanol 
144 parts 
iso-Phthalic acid 248 parts 
Benzoic acid 178 parts 
Dibutyltin oxide 2 parts 
Xylene 30 parts 
______________________________________ 
The above ingredients were put in a reactor, and reacted at 240.degree. C. 
for 7 hours with stirring in an atmosphere of nitrogen, until the acid 
value of the resin reached 3.7. Thus, an alkyd resin having a hydroxyl 
value of 3.5 was obtained. The temperature was lowered to 200.degree. C., 
and 25 parts of maleic anhydride was added. The alkyd resin was maleinized 
at 200.degree. C. for 3 hours. After the reaction, the reaction mixture 
was distilled under reduced pressure to remove the unreacted maleic 
anhydride and xylene. The temperature was then lowered to 140.degree. C. 
At this temperature, 15 parts of tap water was added to the reactor, and 
ring-opening reaction was performed for 1 hour. Then, 330 parts of n-butyl 
Cellosolve was added to give a maleinized alkyd resin varnish having a 
heating residue of 75%, a resin acid value of 27.8, a Gardner viscosity 
(as a 60% n-butyl Cellosolve solution) of Y and a number average molecular 
weight of 5,000. 
The resulting varnish (213 parts), 3 parts of n-butyl Cellosolve, 8 parts 
of triethylamine, and 778 parts of tap water were well stirred to form a 
solution. To the solution was added a solution of 1 part of ammonium 
persulfate in 20 parts of tap water. Then, a mixture of 404 parts of 
n-butyl Cellosolve and 10 parts of 1,6-hexanediol dimethacrylate was 
added, and the resulting mixture was well stirred, and then heated to 
80.degree. C. The mixture was kept at this temperature for 2 hours to give 
an emulsion composition. 
COMATIVE EXAMPLE 7 
The maleinized alkyd varnish obtained in Comparative Example 6 (333 parts), 
12.2 parts of triethylamine, and 639 parts of tap water were well stirred 
to form a solution. Then, a solution of 2.5 parts of 
azobisdimethylvaleronitrile in 50 parts of 1,6-hexanediol diacrylate was 
added. They were well stirred, and then heated to 80.degree. C. The 
mixture was reacted at this temperature for 4 hours to give a microgel 
emulsion composition. 
The properties of the emulsion compositions obtained in Examples 4 to 9 and 
Comparative Examples 4 to 7 are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Com- Com- Com- Com- 
parative 
parative 
parative 
parative 
Example 
Example 
Example 
Example 
Example 
Example 
Example 
Example 
Example 
Example 
4 5 6 7 8 9 4 5 6 7 
__________________________________________________________________________ 
Film prop- 
Film 32 34 34 33 35 33 34 36 33 35 
erties after 
thickness 
drying for 7 
(microns) 
days (*5) 
Pencil 
B 2B HB B B B B HB B 2B 
hardness 
Water No No No No No No No No No No 
resistance 
change 
change 
change 
change 
change 
change 
change 
change 
change 
change 
Adhesion 
Good Good Good Good Good Good Good Good Good Good 
test 
Salt-spray 
2.5 2.0 2.0 1.5 2.0 1.5 12.0 13.0 7.0 6.0 
resistance 
(mm) 
__________________________________________________________________________ 
(*5): The aqueous resin composition containing a dryer in an amount of 
0.05% by weight as metal based on the resin solids was coated on a 
polished mild steel sheet by a bar boater, and dried at a temperature of 
20.degree. C. and a relative humidity of 75% for 7 days. 
The other properties were tested by the same methods as shown in the 
footnote to Table 1.