JPH04233926A - Hybrid polymer, and aqueous dispersion and coating composition obtained therefrom - Google Patents

Abstract

PURPOSE: To obtain a core/shell structure water-dispersible hybrid polymer and a process for producing the same.

CONSTITUTION: There is provided a core/shell structure hybrid polymer which is based on a polymer (core) of an unsaturated acid group functionalized poly(epoxyester) onto which at least one addition polymer-based chain (shell) has been grafted. There are also provided an aqueous dispersion of these hybrid polymers and a coating composition obtained therefrom. The coating composition is especially suited for use as clear coatings, pigmented coatings and primers/surfacers.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION This invention broadly relates to water-dispersible hybrid polymers with a core/shell structure.
lymer). The hybrid polymer is
It contains (A) a polymer (core) and (B) a chain (shell) based on one or more addition polymers grafted thereon. The present invention also broadly relates to these hybrid polymers.
and coating compositions based thereon. The coating composition is particularly suitable for use as a primer/surfacer, clearcoat and pigmented topcoat.

0002

BACKGROUND OF THE INVENTION Hybrid polymers containing a polymer backbone onto which chains based on one or more addition polymers are grafted are used in coating compositions, so in a general sense: Known to those skilled in the art. For example, West German patent application A-2304680, US Pat. No. 3,932,562 and US Pat. No. 4,025.
See Specification No. 471.

Aqueous forms of such coating compositions are also known. For example, Belgian patent no. 8545
No. 23, European Patent Application A-0116225, European Patent Application A-0287144, US Patent No. 4028294, US Patent No. 411690
1 specification, U.S. Patent No. 4151131 specification,
US Pat. No. 4,212,776, US Pat. No. 42
12781 specification, US Patent No. 4285847 specification, US Patent No. 4297261 specification, US Patent No. 4303565 specification, US Patent No. 43081
No. 85, U.S. Pat. No. 4,443,568, U.S. Pat. No. 4,564,648, Japanese Patent Application Publication No. 63-309516, and Bauer, Ronald S. (Bauer, Ronald S.) article “Recent Advances in Water-Based Epoxy Resins”
t Developments in Water B
orne Epoxy Resins)” [Journal of Waterborne Coatings (Jou
rnal of Waterborne Coatin
gs), Vol. 5 (1982), pp. 5-17].

0004

SUMMARY OF THE INVENTION A particular type of such hybrid polymers has now been found which, when dispersed in an aqueous medium, produces stable dispersions of relatively low viscosity even at concentrations of 40% by weight and above. . The hybrid polymer itself has a relatively low acid number, comparable to polymers used in organic solvents.

Furthermore, aqueous coating compositions based on these aqueous dispersions can be formulated at extremely high solids contents, and coating compositions can be formulated from these aqueous dispersions to Films can be obtained which exhibit a good combination of physical and mechanical properties, such as good durability and chemical, water and acid resistance.

[0006] Such preferred hybrid polymers
, as well as aqueous dispersions and coating compositions therefrom, are not explicitly known or suggested from the prior art mentioned above.

According to the invention, (A) a polymer (core, c
ore) and (B) one or more addition polymer-based chains grafted thereon, comprising: i. The polymer (A) contains an unsaturated fatty acid group-functional poly(epoxy ester), and the unsaturated fatty acid group-functional poly(epoxy ester) has (1) an epoxy-terminated poly(epoxy ester);
2) It is a reaction product with an unsaturated fatty acid component, at least in part consisting of a conjugated double bond-containing unsaturated fatty acid.i
i. Chains (B) based on addition polymers are about 20 to 10
having an acid value of 0; and iii. One or more addition polymer-based chains (B) are grafted onto the polymer (A) by addition polymerization of free-radically polymerizable monomers in the presence of an unsaturated fatty acid group-functionalized poly(epoxy ester). A hybrid polymer is provided.

The hybrid polymer comprises A) about 40-90% by weight of polymer (core), and B) about 10-60% by weight of addition polymer-based chains (based on the total weight of the hybrid polymer). shell). It has been found that within these ranges, the hybrid polymer has the best blend of favorable properties from each component. Preferred properties of poly(epoxy esters) include, for example, good adhesion to many substrates, good mechanical resistance, and a good balance of stiffness and flexibility. Preferred properties of addition polymers include, for example, good chemical resistance.

The hybrid polymers according to the invention can be readily dispersed in water upon at least partially neutralizing the acid groups of the chain (B) based on the addition polymer. The aqueous dispersion is made by at least partially neutralizing the acid groups and dispersing the so neutralized hybrid polymer in an aqueous medium.

The aqueous dispersions of hybrid polymers according to the invention are suitable for a variety of applications, but are especially suitable for use as aqueous coating compositions. They can be formulated to yield films with the desired combination of chemical, water, and acid resistance, as well as excellent durability, required for the end use, so they are suitable for use with primer/surfacers. , particularly suitable for use as clear coatings and pigmented top coatings.

These and other features and advantages of the present invention will be more readily understood by those skilled in the art upon reading the following detailed description and the detailed examples contained therein. Dew.

As indicated above, the present invention relates to certain water-dispersible hybrid polymers, aqueous dispersions of such hybrid polymers, and coating compositions based thereon.

The hybrid polymer, in its general concept, consists of (A) a polymer (core), and (B) the addition thereon of a monomer capable of free radical polymerization in the presence of the polymer core. Contains chains (shells) based on one or more addition polymers grafted by polymerization.

Polymer (A) comprises (1) epoxy-terminated poly(epoxy ester);
2) Contains an unsaturated fatty acid group-functionalized poly(epoxy ester) which is the reaction product of an unsaturated fatty acid component, at least in part consisting of a conjugated double bond-containing unsaturated fatty acid.

The epoxy-terminated poly(epoxy ester) preferably has a number average molecular weight (Mn) in the range of about 150 to 2000, and is composed of n moles of bisepoxide and 4
Contains the reaction product with n-1 mol of dicarboxylic acid having ~40 carbon atoms, where n=2-10. The Mn of the resulting poly(epoxy ester) preferably ranges from about 400 to 20,000, more preferably from about 2,000 to 20,000.

Suitable bisepoxides include a wide range of aliphatic, aromatic, arylaliphatic compounds.
ic) and cycloaliphatic bisepoxides and mixtures thereof. Many suitable specific examples are given in Epoxy Resins - Chemistry and Technology.
-Chemistry and Technology
) 2nd edition [Dekker Inc.,
New York, 1988] 2
It can be found with reference to pages 12-231.

As a preferred example, diglycidyl ether of bisphenol A; from epichlorohydrin and bisphenol A, with an oxirane end group and about 300 to 20
Epoxy oligomers with Mn in the range of about 300-2000 from epichlorohydrin and hydrogenated bisphenol A with oxirane end groups and Mn in the range of about 300-2000; 1,3 -bis(2,3-epoxy-1-propoxy)benzene [1
,3-bis(2,3-epoxyprop-1-ox
y) benzene]; 1,4-butanediol diglycidyl ether; diglycidyl ether of polypropylene glycol; diglycidyl ether of dimerized linoleic acid; epoxy dicyclopentylphenyl glycidyl ether; bis(2 ,3-epoxycyclopentyl)
Ether; Bis(2,3-epoxy-6-methylcyclohexylmethyl)adipate; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-6-methyl Mention may be made of cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate; and dicyclopentadiene dioxide.

When the hybrid polymer is used in primer/surfacer applications, aromatic bisepoxides (eg, those based on bisphenol A) are preferred because of their excellent corrosion resistance. Particularly preferred are the diglycidyl ethers of bisphenol A mentioned above and epoxy oligomers from epichlorohydrin and bisphenol A.

However, clear coating and/or
Alternatively, when used in pigmented top coatings, cycloaliphatic bisepoxides, including those based on hydrogenated bisphenol A, are preferred because of their excellent UV resistance.

Examples of preferred dicarboxylic acids having 4 to 40 carbon atoms include adipic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, hexahydrophthalic acid, succinic acid, sebacic acid, dodecanedicarboxylic acid. Mention may be made of acids, azelaic acid and dimerized fatty acids. Particularly preferred are dimerized fatty acids containing 10 to 40 carbon atoms, especially 18 to 36 carbon atoms.

The epoxy-terminated poly(epoxy ester) is prepared by reacting at least a portion of its epoxy groups with one or more unsaturated fatty acids (an unsaturated fatty acid component, at least a portion of which contains a conjugated double bond). Functionalized with unsaturated fatty acid groups.

As examples of suitable unsaturated fatty acids, mention may be made of various mono- and polyunsaturated fatty acids, preferably those having 12 to 26 carbon atoms. Particularly suitable examples include monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid and ricinoleic acid; diunsaturated fatty acids such as linoleic acid,
triunsaturated fatty acids such as linolenic acid, eleostearic acid and lycanic acid; tetraunsaturated fatty acids such as arachidonic acid; pentaunsaturated fatty acids such as sardine acid;
Mention may also be made of other unsaturated fatty acids prepared from animal and vegetable oils. Usually natural fatty acids or mixtures thereof containing at least 80% of the fatty acids mentioned above are used.

As mentioned above, the unsaturated fatty acid component contains at least a portion, preferably 10 mol % or more, especially 3
It must contain 0 mole percent or more of a conjugated double bond-containing fatty acid, such as conjugated linoleic acid. The actual amount of conjugated double bond-containing fatty acids is determined primarily by addition polymer-based chains (B
) on the polymer (A) and also on the end use of the hybrid polymer.

Generally, if a more reactive monomer (eg, an acrylic monomer) and an initiator are used, the fatty acid component will contain 10 to 80 mole % of fatty acids containing conjugated double bonds.
In particular, the content is preferably 30 to 60 mol%. Under the most reactive conditions, more than 80 mole % of conjugated double bond-containing fatty acids results in gelation. On the other hand, if a less reactive monomer (for example, a methacrylic monomer) is used, the fatty acid component will contain 50 to 10 double bond-containing fatty acids.
It is preferable to contain 0 mol%.

If the hybrid polymer is ultimately used in clear coatings and/or pigmented top coatings, the unsaturated fatty acids should contain at least 30 mole percent of fatty acids containing conjugated double bonds. moreover,
If more reactive monomers and initiators are used, the fatty acid component may contain 30 to 50 mole percent conjugated double bond-containing fatty acids.
If less reactive monomers and initiators are used, the fatty acid component preferably contains 50 to 65 mole percent of conjugated double bond-containing fatty acids.

A person skilled in the art can easily and appropriately select a desired unsaturated fatty acid component based on these indicators and general knowledge.

A part of the unsaturated fatty acid component has the general formula (I)
can be replaced by monofunctional compounds. R-X (I) where R is a hydrocarbon group having 1 to 40 carbon atoms, more preferably an alkyl group, aralkyl group, aryl group or cycloalkyl group having 1 to 24 carbon atoms; represents a group reactive with an epoxy group, preferably an amino group or a carboxyl group;
In particular, it represents a carboxyl group.

Particularly preferred monofunctional compounds are monocarboxylic acids. As suitable monocarboxylic acids, mention may be made of the various aromatic, arylaliphatic, aliphatic and cycloaliphatic monocarboxylic acids, preferably having 2 to 24 carbon atoms. Particularly preferred examples include pivalic acid, propionic acid, benzoic acid and stearic acid.

The unsaturated fatty acid is reacted with the epoxy-terminated poly(epoxy ester) in a carboxyl/epoxy equivalent ratio of at least about 1/4, preferably at least about 1/2. The combination of unsaturated fatty acids and monofunctional compounds is preferably about 1/4 to 1/1, more preferably about 1/2 to 1/1, especially about 1/1 so that essentially no epoxy functionality remains. /1 (carboxyl group +
X group)/epoxy group equivalent ratio.

The unsaturated fatty acid functional poly(epoxy ester) is prepared in a conventional manner by reacting the bisepoxide, dicarboxylic acid, unsaturated fatty acid component and optional monofunctional compound in the amounts described above. be able to.

Preferably, the reaction is carried out in an organic solvent (10
~30% by weight) should be carried out at a temperature of about 60-200°C. The organic solvent for the reaction should be miscible with water. Suitable examples include glycol ethers and propylene glycol ethers, such as methoxypropanol, butoxyethanol, isopropoxypropanol, propoxypropanol, diethylene glycol dimethyl ether.
Mention may be made of N-methylpyrrolidone and N-methylpyrrolidone. It is also possible to use small amounts of water-immiscible organic solvents, such as ethyl methyl ketone and methyl isobutyl ketone.

It is also possible to use catalysts for the reaction between epoxy groups and carboxyl groups and other functional groups. Suitable examples include acid catalysts such as p-toluenesulfonic acid; basic amines; ammonium and phosphonium catalysts such as tetramethylammonium chloride, benzyltrimethylammonium methoxide and triphenylbenzylphosphonium chloride; and other well-known catalysts such as Cr(III)-2-ethylhexanoe-
zinc chloride, and zinc acetylacetonate.

The hybrid polymer is produced by addition polymerization of free-radically polymerizable monomers in the presence of the unsaturated fatty acid functional poly(epoxy ester) described above. Thereby, the addition polymer-based chains are believed to be grafted onto the poly(epoxy ester) backbone through the unsaturated functionality resulting from the unsaturated fatty acids.

A variety of free-radically polymerizable monomers are suitable for use in the production of addition polymer-based chains. As particular examples, ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid;
(Cyclo)alkyl (meth)acrylates having 1 to 12 carbon atoms in the (cyclo)alkyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate
Propyl (meth)acrylate, Isopropyl (meth)acrylate, Butyl (meth)acrylate, 2-
Ethylhexyl (meth)acrylate, octyl (meth)acrylate, isobornyl (meth)acrylate,
Dodecyl (meth)acrylate and cyclohexyl (meth)acrylate; dicarboxylic acids such as maleic acid (
(and its anhydrides), fumaric acid, and itaconic acid (and its anhydrides); (cyclo)alkyl esters of the abovementioned dicarboxylic acids having 1 to 12 carbon atoms in the (cyclo)alkyl group, such as dimethyl maleate , diethyl maleate, diethyl fumarate, dipropyl maleate,
Dibutyl maleate, dibutyl fumarate, 2-ethylhexyl maleate, 2-ethylhexyl fumarate,
Octyl maleate, isobornyl maleate, dodecyl maleate and cyclohexyl maleate; (meth)acrylates containing ether groups, such as 2-methoxy-ethyl methacrylate, 2-ethoxy- Ethyl methacrylate and 3-methoxy-propyl methacrylate;
Hydroxyalkyl (meth)acrylates, e.g. 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, p-hydroxycyclohexyl (meth)acrylate, hydroxy Polyethylene glycol (meth)acrylate, hydroxypolypropylene glycol (meth)acrylate, and their alkoxy derivatives; aromatic monovinyl compounds such as styrene, vinyltoluene, α
- methylstyrene and vinylnaphthalene; other substituted (meth)acrylic compounds such as (meth)acrylamide, (meth)acrylonitrile, N-methylol (meth)acrylamide and N-alkyl (meth)acrylamide; and others Mention may be made of monounsaturated compounds such as vinyl chloride, vinyl acetate, vinyl propionate and vinylpyrrolidone.

A preferred monomer mixture for producing chains based on addition polymers is described in European Patent B-0000601.
No. 4,245,074 (U.S. Pat. No. 4,245,074). As a first specific example, the following monomer mixture: 35 to 55 mol % styrene and/or α-methylstyrene; 20 to 50 mol % of the general formula (I
I) Compound

[0036]

[Formula 1] (Here, R1 is a hydrogen atom or a methyl group, and R
2 is an alkyl group having 4 to 10 carbon atoms); and 0 to 30 mol % of other monoethylenically unsaturated compounds as mentioned above.

As a second specific example, the following monomer mixture: 35-55 mol % styrene and/or α-methylstyrene; 20-50 mol % acrylic acid and/or methacrylic acid; and 0-55 mol % acrylic acid and/or methacrylic acid; Mention may be made of 30 mol % of other monoethylenically unsaturated compounds as mentioned above, in which the reaction product during or after the polymerization has the following general formula (III):

[0038]

embedded image wherein R2 is as defined above.

The specific monomers and/or monomer mixtures should be selected in such a way and in amounts to yield addition polymer-based chains having an acid value of about 20 to 100 (mg KOH/g). be. It is generally found that if the acid number of the addition polymer-based chain is less than about 20, stable dispersions cannot be easily prepared, and if the acid number exceeds about 100, water resistance becomes unacceptable. It has been discovered. It is particularly preferred that the acid number is within the range of about 30-80.

The monomer and/or monomer mixture may also include (A) about 40-90% by weight of polymer (core), based on the total weight of the hybrid polymer; (B) about 10-6% by weight of the polymer (core);
They should be selected in such a way and in amounts that result in a hybrid polymer containing 0% by weight of chains (shells) based on addition polymers. As stated above, it has been found that within these ranges, the hybrid polymer has the best blend of favorable properties from each component.

Of course, the particular choice of monomer and/or monomer mixture will also depend on various other factors, such as the end use of the hybrid polymer. Those skilled in the art can judge these and other factors and can therefore further adjust the monomer selection.

Copolymerization of ethylenically unsaturated monomers in the presence of unsaturated fatty acid group-functionalized poly(epoxy esters) is usually carried out in the presence of a radical initiator under an inert (eg nitrogen) atmosphere. It will be held in Polymerization temperature is usually about 60
-200°C, preferably about 100-160°C.

Suitable radical initiators include dibenzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-
Butyloxy-2-ethylhexanoate, t-butylperbenzoate, t-butylcumyl peroxide,
Mention may be made of di-t-butylperoxy-3,5,5-trimethylcyclohexane and 1,3-bis(t-butyl)peroxyisopropylbenzene. Mixtures of the above are also suitable. Radical initiators are generally used in amounts of about 0.05 to 10% by weight, preferably about 1 to 5% by weight, based on the total weight of the monomer mixture.

The hybrid polymer so produced can be readily dispersed in an aqueous medium upon neutralization of at least a portion of the carboxyl groups of the chains based on the addition polymer. Suitable neutralizing agents for carboxyl groups include various organic and inorganic bases such as tertiary amines. The preferred degree of neutralization is about 50-130% on an equivalent basis.

After neutralization, the hybrid polymer can be readily dispersed in an aqueous medium by conventional methods, preferably at elevated temperatures of about 50-100°C. Using the hybrid polymers according to the invention, stable aqueous dispersions of 40% by weight or more can be made in many cases.

[0046] Typically, the aqueous dispersion of the present invention will contain about 3
It contains solids in the range of 0-60% by weight, preferably about 35-55%.

As indicated above, the preferred use of these aqueous dispersions is in the formulation of coating compositions. When so used, the coating composition may also contain a curing agent for the hydroxyl groups of the hybrid polymer.

Suitable hydroxyl-reactive curing agents include generally N-methylol- and/or N-methylol ether-containing aminoplasts. It has 4 to 6 methylol groups per molecule, and at least three of the methylol groups are methanol, butanol and/or formaldehyde and methanol or butanol of N,N'-ethylene diurea. Particularly favorable results can be obtained by using methylol melamines which have been esterified with -ol condensation products. Other suitable curing agents include water-dispersible blocked isocyanates, such as those blocked with methyl ethyl ketoxime, and isocyanate group-containing adducts of polyisocyanates and hydroxycarboxylic acids such as dimethylolpropionic acid. include.

Curing agents that react with hydroxyl groups are generally used in amounts such that the ratio of hydroxyl groups on the hybrid polymer to reactive groups on the curing agent is within the range of about 0.7 to 1.5. .

Depending on the field of application, the coating composition may also contain various other additives customary in the coatings industry, such as pigments, colorants, pigment dispersants, as well as thixotropic agents and other rheological control agents. - It can contain a lubricant. The coating may also optionally contain accelerators for the curing reaction, such as acid compounds such as p-toluenesulfonic acid and blocked derivatives thereof.

The coating composition can be applied onto any known substrate such as wood, synthetic and metal surfaces. Suitable application methods include rolling, spraying, brushing, sprinkling, dipping and electrostatic spraying.

The coating composition under various conditions:
For example, it can be dried and cured at ambient temperature. 20-60 at elevated temperature usually 100-160 °C
Accelerated hardening can also be achieved by baking for a minute.

As mentioned above, these coating compositions are suitable for use in a variety of applications. However, they can be formulated to yield films with excellent durability for end use, as well as a desirable combination of chemical, water and acid resistance, so that primer/surfacer , particularly suitable for use as clear coats and pigmented top coatings.

The foregoing more general discussion of the invention is further illustrated by the following detailed examples.

[0055]

EXAMPLES Preparation of Dispersions In Examples 1-15 below, a number of stable aqueous polymer dispersions were prepared in accordance with the present invention. Various properties of these dispersions were measured and the results are shown in Table 1 below.

In these examples, the average particle size of the dispersions was determined by dynamic light scattering after diluting the dispersions with water to about 0.1% solids by weight.

The viscosity of the dispersion is Brookfield (B
Rookfield) viscometer.

The solids content of the dispersion is determined by ASTM method 1644-
59, the sample was heated to 130°C for 30 minutes and measured.

[0059]

[Example 1] Stirrer, thermometer, reflux condenser, and dropping roller
In a 2 liter reaction flask with Epoxy resin [Epiko from Shell]
Bisphenol, commercially available under the trademark te 828.
diglycidyl ether of Le A] 138.0 g, first unsaturated fatty acid [containing 65% conjugated linoleic acid, commercially available from Akzo under the trademark Nouracid DE-656] 52.4 g, 1 -Methoxy-
2-propanol 60.0g and Cr(III)
0.3 g of -2-ethylhexanoate was mixed uniformly.

Into the dropping funnel, add 30.4 g of styrene, 20.7 g of butyl methacrylate, and 25 g of methacrylic acid.
．． 1 g, glycidyl ester of 1,1-dimethyl-1-heptanecarboxylic acid (Cardura from Shell)
40.2 g of tert-butyl perbenzoate (commercially available under the trademark E), 3.6 g of t-butyl perbenzoate, and 1-methoxy-
A homogeneous mixture of 40.1 g of 2-propanol was charged.

After ventilation, the reaction flask and dropping funnel were placed under a nitrogen atmosphere. The contents of the reaction flask were then heated to reflux temperature (135-145 °C) and at that temperature
After maintaining the temperature for a certain period of time, the temperature of the reaction flask was increased to 125°C.
Add the contents of the dropping funnel and heat the reaction mixture to 125°C.
I kept it there for another 4 hours.

The contents of the reaction flask were then cooled to 100° C. and 11.7 g of N,N-dimethylethanolamine were added, followed by 441 g of deionized water as well.
I added it over time.

[0063]

Example 2 The same operations as in Example 1 were repeated except for the following points.

In the reaction flask, dimerized fatty acid 5
6.2g, sebacic acid 39.8g, first epoxy resin 147.8g, first unsaturated fatty acid 56.2g
, 1-methoxy-2-propanol 65.0 g, and Cr(III)-2-ethylhexanoate 0.3
g was mixed uniformly.

Into the dropping funnel, add 25.3 g of styrene, 17.3 g of butyl methacrylate, and 20 g of methacrylic acid.
．． 9 g, glycidyl ester 33.5 g, t-butyl perbenzoate 3.0 g, and 1-methoxy-2
- Propanol 35.1 g of a homogeneous mixture was charged.

After cooling the contents of the reaction flask to 100°C, 9.7 g of N,N-dimethylethanolamine was added, followed by 399.7 g of deionized water as well.
I added it over time.

[0067]

Example 3 The same operations as in Example 1 were repeated except for the following points.

In the reaction flask, dimerized fatty acids 9
2.9 g, 61.1 g of the first epoxy resin, 77.4 g of the second epoxy resin (diglycidyl ether of bisphenol A, commercially available from Shell under the trademark Epikote 1001), 77.4 g of the first epoxy resin; Saturated fatty acids 2
3.2g, secondary unsaturated fatty acids (87% ricinoleic acid)
(commercially available from Akzo under the trademark Nouracid CS-80) 25.4 g, 1-methoxy-
2-propanol 60.0g and Cr(III)
0.3 g of -2-ethylhexanoate was mixed uniformly.

[0069] 29.05 g of styrene was added to the dropping funnel.
, methyl methacrylate 7.0g, acrylic acid 2
5.15 g, glycidyl ester 56.7 g, dicumyl peroxide 2.1 g, and 1-methoxy-2
- Propanol 40.1 g of a homogeneous mixture was charged.

Polymerization of the acrylic monomer was carried out at 130° C. for 4 hours.

After cooling the contents of the reaction flask to 100° C., 10.9 g of N,N-dimethylethanolamine was added, and then 542 g of deionized water was also added.
I added it over time.

[0072]

Example 4 The same operations as in Example 3 were repeated except for the following points.

In the reaction flask, dimerized fatty acids 9
9.2g, first epoxy resin 65.2g, second epoxy resin 82.7g, first unsaturated fatty acid 14.
9g, second unsaturated fatty acid 38.0g, 1-methoxy-2-propanol 65.0g, and Cr(III
)-2-ethylhexanoate (0.3 g) was mixed uniformly.

Into the dropping funnel were 24.2 g of styrene, 5.8 g of methyl methacrylate, and 20 g of acrylic acid.
9g of glycidyl ester, 1.8g of dicumyl peroxide, and 35.1g of 1-methoxy-2-propanol.

After cooling the contents of the reaction flask to 100° C., 9.1 g of N,N-dimethylethanolamine was added followed by 380 g of deionized water over a period of 2 hours.

[0076]

Example 5 The same operations as in Example 3 were repeated except for the following points.

In the reaction flask, dimerized fatty acid 1
05.4g, first epoxy resin 69.4g, second epoxy resin 87.9g, first unsaturated fatty acid 5
．． 3g, second unsaturated fatty acid 52.0g, 1-methoxy-2-propanol 70.0g, and Cr(I
II) 0.3 g of -2-ethylhexanoate was mixed uniformly.

Into the dropping funnel were 19.4 g of styrene, 4.6 g of methyl methacrylate, and 16 g of acrylic acid.
8g of glycidyl ester, 1.4g of dicumyl peroxide, and 30.1g of 1-methoxy-2-propanol.

After cooling the contents of the reaction flask to 100° C., 7.3 g of N,N-dimethylethanolamine was added, followed by 262 g of deionized water as well over a period of 2 hours.

[0080]

[Example 6] The same operation as in Example 5 was repeated except for the following points.

In the reaction flask, dimerized fatty acid 1
01.3g, first epoxy resin 63.1g, second epoxy resin 97.8g, first unsaturated fatty acid 5
．． 3g, second unsaturated fatty acid 52.5g, 1-methoxy-2-propanol 70.0g, and Cr(I
II) 0.3 g of -2-ethylhexanoate was mixed uniformly.

After cooling the contents of the reaction flask to 100° C., 7.3 g of N,N-dimethylethanolamine was added, followed by 262 g of deionized water over a period of 2 hours.

[0083]

[Example 7] The same operation as in Example 5 was repeated except for the following points.

In the reaction flask, dimerized fatty acids 9
7.0g, first epoxy resin 56.7g, second epoxy resin 107.8g, first unsaturated fatty acid 5
．． 4g, second unsaturated fatty acid 53.1g, 1-methoxy-2-propanol 70.0g, and Cr(I
II) 0.3 g of -2-ethylhexanoate was mixed uniformly.

After cooling the contents of the reaction flask to 100° C., 7.3 g of N,N-dimethylethanolamine was added, followed by 248 g of deionized water as well over a period of 2 hours.

[0086]

Example 8 The same operations as in Example 3 were repeated except for the following points.

In the reaction flask, dimerized fatty acids 9
2.9g, first epoxy resin 61.1g, second epoxy resin 77.4g, first unsaturated fatty acid 23.
2g, second unsaturated fatty acid 25.4g, dipropylene glycol monomethyl ether 60.0g, isopropanol 21.3g, and Cr(III)-2-ethylhexanoate 0.4g were uniformly mixed. did.

Into the dropping funnel were 28.7 g of styrene, 6.9 g of methyl methacrylate, and 24 g of acrylic acid.
8g, glycidyl ester 56.1g, dicumyl peroxide 3.5g, and isopropanol 8.0
A homogeneous mixture of g.

The contents of the reaction flask were heated to reflux temperature (approximately 1
After heating to 30° C. and maintaining reflux for 3 hours, the contents of the addition funnel were added to the solution while maintaining the reaction mixture at reflux temperature.
Added over an hour. The temperature of the reaction mixture was then kept at reflux for a further 3 hours.

After cooling the contents of the reaction flask to 100° C., 10.8 g of N,N-dimethylethanolamine was added, and then 553 g of deionized water was also added.
I added it over time.

[0091]

Example 9 The same operations as in Example 8 were repeated except for the following points.

[0092] Into the dropping funnel, add 52.9 g of styrene, 2
-Hydroxyethyl methacrylate 17.2g, butyl methacrylate 36.1g, acrylic acid 8.7g
, dicumyl peroxide, 5.1 g, and isopropanol, 8.0 g.

After cooling the contents of the reaction flask to 100° C., 10.9 g of N,N-dimethylethanolamine was added, followed by 553 g of deionized water.
I added it over time.

[0094]

Example 10 The same operations as in Example 9 were repeated except for the following points.

In the reaction flask, dimerized fatty acid 1
21.0g, first epoxy resin 110.2g,
First unsaturated fatty acid 23.3g, second unsaturated fatty acid 25.5g, dipropylene glycol monomethyl ether
64.0 g of alcohol, 17.2 g of isopropanol, and 0.4 g of Cr(III)-2-ethylhexanoate.
g was mixed uniformly.

After cooling the contents of the reaction flask to 100° C., 8.7 g of N,N-dimethylethanolamine was added, followed by 500.5 g of deionized water as well.
I added it over time.

[0097]

Example 11 In a 2 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 140.7 g of dimerized fatty acid, a third epoxy resin [Ciba-Geigy Co., Ltd. -Geigy) A
3,4-epoxycyclohexylmethyl-3,4-, commercially available under the trademark raldite CY-179.
Epoxycyclohexylcarboxylate] 90.
2g, first unsaturated fatty acid 23.4g, second unsaturated fatty acid 25.7g, methyl isobutyl ketone 49.
3g, dipropylene glycol monomethyl ether 2
0.0 g and 0.4 g of Cr(III)-2-ethylhexanoate were uniformly mixed.

[0098] Into the dropping funnel, add 54.6 g of styrene, 2
-Hydroxyethyl methacrylate 13.6g, butyl methacrylate 37.3g, acrylic acid 11.3g
A homogeneous mixture of 3.2 g of dicumyl peroxide, 3.2 g of dicumyl peroxide, and 20.0 g of dipropylene glycol monomethyl ether was added.

After ventilation, the reaction flask and dropping funnel were placed under a nitrogen atmosphere. The contents of the reaction flask are then 1
After heating to 20°C and holding at that temperature for 3 hours, the temperature of the reaction flask was brought to 130°C, the contents of the addition funnel were added, and the reaction mixture was kept at 130°C for an additional 3 hours.

After cooling the contents of the reaction flask to 100° C., 14.0 g of N,N-dimethylethanolamine was added, and then 677 g of deionized water was also added.
I added it over time.

[0101]

Example 12 In a 2 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and two addition funnels, a second dimerized fatty acid (P from Unilever) was added.
(marketed under the trademark ripol 1009) 2
35.5g, third epoxy resin 149.6g,
First unsaturated fatty acid 38.9g, second unsaturated fatty acid 42.6g, methyl isobutyl ketone 82.5g,
and Cr(III)-2-ethylhexanoate 0.
7g were mixed uniformly.

70.0 g of diethylene glycol monobutyl ether was placed in the first addition funnel.

[0103] Styrene 86.8 was added to the second dropping funnel.
g, 2-hydroxypropyl methacrylate 31.2
g, butyl methacrylate 59.3g, acrylic acid
A homogeneous mixture of 14.4 g and 8.3 g of dicumyl peroxide was charged.

After ventilation, the reaction flask and dropping funnel were placed under a nitrogen atmosphere. The contents of the reaction flask are then 1
After heating to 20°C and holding at that temperature for 3 hours, the contents of the first addition funnel were added, bringing the temperature of the reaction flask to 1.
The temperature was 30°C. The contents of the second addition funnel are then added at a constant rate over a period of 2 hours, after which the reaction mixture is
After cooling the contents of the reaction flask to 100°C, which was kept at 130°C for an additional 3 hours, 14.3g of N,N-dimethylethanolamine was added, followed by 755g of deionized water, also added over 2 hours. added.

[0105]

Example 13 The same operations as in Example 12 were repeated except for the following points.

In the reaction flask, 237.4 g of the second dimerized fatty acid, 150.8 g of the third epoxy resin.
g, first unsaturated fatty acid 78.4 g, 1-methoxy-2-propanol 82.6 g, and Cr(III
)-2-ethylhexanoate (0.7 g) was mixed uniformly.

After ventilation, the reaction flask and dropping funnel were placed under a nitrogen atmosphere. The contents of the reaction flask are then 1
After heating to 20°C and holding at that temperature for 3 hours, the contents of the first addition funnel were added, bringing the temperature of the reaction flask to 1.
The temperature was 30°C. The contents of the second addition funnel are then added at a constant rate over a period of 1 hour, after which the reaction mixture is
After cooling the contents of the reaction flask, which was kept at 130°C for an additional 3 hours, to 100°C, 14.3g of N,N-dimethylethanolamine was added, followed by 922g of deionized water, which was also added over a period of 2 hours. added.

[0108]

Example 14 The same operations as in Example 13 were repeated except for the following points.

In the reaction flask, 254.3 g of the second dimerized fatty acid, 161.6 g of the third epoxy resin.
g, first unsaturated fatty acid 84.0 g, 1-methoxy-2-propanol 84.9 g, and Cr(III
)-2-ethylhexanoate (0.7 g) was mixed uniformly.

A second addition funnel was charged with 166.7 g of the homogeneous monomer mixture.

After cooling the contents of the reaction flask to 100°C, 11.9 g of N,N-dimethylethanolamine was added, followed by 834.2 g of deionized water as well over a 2 hour period.

[0112]

Example 15 The same operations as in Example 13 were repeated except for the following points.

After cooling the contents of the reaction flask to 100° C., 10.8 g of N,N-dimethylethanolamine was added followed by 733.3 g of deionized water over a period of 2 hours.

[0114]

[Table 1] Comparative Examples 1 to 4 below do not use unsaturated fatty acids (
This is a comparative example showing the effect of the absence of unsaturated functionality.

[0115]

[Comparative Example 1] The same operation as in Example 2 was repeated except for the following points.

In the reaction flask, dimerized fatty acids 5
6.2g, sebacic acid 39.8g, first epoxy resin 147.8g, stearic acid 56.2g, 1-
Methoxy-2-propanol 65.0g, and Cr
0.3 g of (III)-2-ethylhexanoate was mixed uniformly.

The contents of the reaction flask were then cooled to 100° C. and 9.7 g of N,N-dimethylethanolamine were added, followed by 399.7 g of deionized water as well.
I added it over time.

The resulting aqueous dispersion was unstable as layer separation occurred.

[0119]

[Comparative Example 2] The same operation as in Example 8 was repeated except for the following points.

In the reaction flask, dimerized fatty acid 1
02.7g, first epoxy resin 67.6g, second epoxy resin 85.6g, dimethylolpropionic acid 24.1g, dipropylene glycol monomethyl ether 60.0g, isopropanol 21.3g,
and Cr(III)-2-ethylhexanoate 0.
4g were mixed uniformly.

The resulting aqueous dispersion was unstable as layer separation occurred.

[0122]

[Comparative Example 3] The same operation as in Example 8 was repeated except for the following points.

In the reaction flask, dimerized fatty acid 1
06.9g, first epoxy resin 70.3g, second epoxy resin 89.0g, propionic acid 13.8
g, dipropylene glycol monomethyl ether 60
．． 0 g, isopropanol 21.3 g, and Cr(I
II) 0.4 g of -2-ethylhexanoate was mixed uniformly.

The resulting aqueous dispersion was unstable as layer separation occurred.

[0125]

[Comparative Example 4] The same operation as in Example 13 was repeated except for the following points.

In the reaction flask, 237.5 g of the second dimerized fatty acid, 150.9 g of the third epoxy resin.
g, stearic acid 78.2g, 1-methoxy-2-
Propanol 82.6g, and Cr(III)-2
-0.7 g of ethylhexanoate was mixed uniformly.

After cooling the contents of the reaction flask to 100° C., 14.3 g of N,N-dimethylethanolamine was added followed by 1019.3 g of deionized water over a period of 2 hours.

The resulting aqueous dispersion was unstable as layer separation occurred.

The following Comparative Examples 5 to 7 are comparative examples showing the influence of using an unsaturated fatty acid substantially free of conjugated double bonds.

[0130]

[Comparative Example 5] The same operation as in Example 2 was repeated except for the following points.

In the reaction flask, dimerized fatty acid 5
6.3 g, sebacic acid 39.9 g, first epoxy resin 148.1 g, oleic acid 55.7 g, 1-methoxy-2-propanol 65.0 g, and Cr(I
II) 0.3 g of -2-ethylhexanoate was mixed uniformly.

The contents of the reaction flask were then cooled to 100° C. and 9.7 g of N,N-dimethylethanolamine were added, followed by 399.7 g of deionized water as well.
I added it over time.

The resulting aqueous dispersion was unstable as layer separation occurred.

[0134]

[Comparative Example 6] The same operations as in Comparative Example 5 were repeated except for the following points.

In the reaction flask, dimerized fatty acid 5
5.3g, sebacic acid 39.9g, first epoxy resin 145.5g, second unsaturated fatty acid 60.0g
, 1-methoxy-2-propanol 65.0 g, and Cr(III)-2-ethylhexanoate 0.3
g was mixed uniformly.

The resulting aqueous dispersion was unstable as layer separation occurred.

[0137]

[Comparative Example 7] The same operation as in Example 13 was repeated except for the following points.

In the reaction flask, 233.7 g of the second dimerized fatty acid, 148.5 g of the third epoxy resin.
g, second unsaturated fatty acid 84.5 g, 1-methoxy-2-propanol 82.6 g, and Cr(III
)-2-ethylhexanoate (0.7 g) was mixed uniformly.

The resulting aqueous dispersion was unstable as layer separation occurred.

Preparation of Coating Compositions In Examples 16 to 34 below, a number of unpigmented and pigmented coating compositions according to the invention were prepared including a dispersion, a melamine hardener, and optional desorption. Prepared by uniformly mixing ionized water, optional 2-butoxyethanol, optional diethylene glycol monobutyl ether (DEGMBE) and optional titanium oxide (pigment) as shown in Table 2. did.

The melamine curing agent used in these examples was manufactured by American Cyanamid.
Cymel 327 is a 90% solids melamine resin sold under the trademark Cymel 327 by Cymel 327.

[0142] The deionized water contains approximately 0% of the coating composition.
．． 1 Pa・s [Ford Cu
p) No. Effluent viscosity for 30 seconds at 4 (run-o
spray viscosity
viscosity).

The solids content of these coating compositions was determined in the same manner as described above for the dispersions. The results are also shown in Table 2.

Each of these coating compositions was applied to a zinc phosphate pretreated steel plate (Bonder 132) and heated in a baking oven at 140°C (Examples 16-
29) or 150°C (Examples 30-34) for 30 minutes. Various properties of the coating thus obtained were measured. The results are shown in Table 3.

[0145] Persoz hardness
ss), French Industrial Standard NF T30-016
Measured according to the following. The result is shown in seconds. The acceptable minimum for automotive painting is about 180 seconds.

[0146] The flexibility of the coating was determined according to ASTM D2
794-69, a ball weight of 0.908 kg, a ball diameter of 15.9 mm and a diameter of 16.3 mm (
It was measured using a ball impact tester using aperture. The result is expressed in kg·cm. For primer/surfacer, the minimum acceptable flexibility for the coated side is approximately 35 kg cm;
The maximum measurable value is 85 kg·cm. For pigmented or clear topcoats, the minimum acceptable flexibility on the coated side is about 20 kg.cm.

[0147] Also used as a coating is Eri
A test was carried out using a dent test, and the results were expressed in mm. A test value higher than 6 indicates a flexible cord.
a value of 2 indicates a brittle coating.

[0148] The gloss of the coating conforms to the American Industrial Standards AST.
Measurements were taken at 60° and 20° according to MD-523. A gloss value higher than 80 at 60° on a steel substrate is
Quite expensive.

[0149]

[Table 2] Table 2 Coating composition formulation Dispersion
Hardening agent Water 2-BuO-** DE
GMBE Thirty Oxide Solid Content Example Type*
Amount (g) (g) (g) EtOH (g
) (g) Tongue (g) (wt%)
16 1 100.0 15.3
2.0 2.0 -
- 43.3 17 2
100.0 16.2 3.4
2.0 - -
44.9 18 3 100.0
13.7 3.0 1.7
- - 38.9 19
4 100.0 16.2 5.
0 2.1 - -
45.3 20 5 100
．． 0 18.9 6.6 2.3
- - 49.7
21 6 100.0 18.9
8.1 2.3 -
- 49.3 22 7
100.0 19.3 10.5
2.4 - -
49.1 23 8 100.0
13.7 2.5 1.7
− − 40.5 24
9 100.0 14.0 -
1.8 - -
41.0 25 10 100
．． 0 14.8 3.2 1.8
- - 42.1
26 2 100.0 16.2
27.6 2.0 -
57.5 54.9 27 4
100.0 16.2 24.0
2.1-57.5
56.0 28 8 100.0
13.7 21.9 1.7
-50.5 53.6
29 11 100.0 12.7
3.0 1.6 -
- 36.4 30 12
100.0 19.9 12.5
- 4.6 -
40.5 31 13 100.0
18.0 7.9 -
4.1 - 39.4 32
14 100.0 19.0
2.3 - 4.1 -
43.1 33 15
100.0 20.3 7.3 -
4.3-43
．． 8 34 13 100.0 1
8.0 15.6 - 4.
1 43.4 52.7 *The type is indicated by the number of the example in which the dispersion was prepared** 2-Butoxyethanol

[0150]

[Table 3] Table 3
Coating characteristics Coating thickness
Perso hard Flexibility (kg/cm) Elixe
Gloss (Example) (μm)
Degrees (seconds) Coat side Back side N value (mm)
60° 20° 16
40 273 >85
>85 9.1 89 63
17 41
272 >85 >85
8.6 93 72
18 38 263
>85 >85 8.7
94 73 19
37 260 >8
5 >85 8.5 93
70 20 38
246 >85 >8
5 8.8 88 75
21 41
285 >85 >85 8
．． 8 90 76 22
39 299
>85 >85 8.5
92 78 23
36 269 >85
>85 8.4 99 8
1 24 37
302 >85 >85
8.3 100 85
25 40 248
>85 >85 8.2
96 82 26
40 265 >
85 70 8.4 85
66 27 3
9 250 >85
80 8.0 86 68
28 39
245 >85 >85
8.1 90 75
29 43 286
>85 48 7.7
96 73 30
39 292
30 2 5.4 9
1 73 31
41 297 35
8 6.3 96
72 32 44
285 34
8 6.7 96 75
33 44
298 31 7
5.8 96 73 3
4 40 287
32 6 6.0
95 70 Clearcoat Testing The coatings of Examples 29-33 are particularly suitable for use as clearcoats and, as shown below,
It was further tested for acid resistance and durability. A comparison was also made to a standard acrylic clearcoat (the "control", which was a conventional thermosetting acrylic system used industrially on automotive manufacturing lines).

The zinc phosphate treated steel sheet was first coated with a conventional epoxy primer to a dry thickness of 30 μm, cured at 170° C. for 20 minutes, and then subsequently coated with a conventional polyester/melamine primer. It was coated with a facer to a dry thickness of 40 μm and cured at 140° C. for an additional 20 minutes.

[0152] The pre-coated panels are coated with a water-based basecoat (eg as described in European Patent Application A-0287144) in an atmosphere having a relative humidity of 65% until a dry film thickness is reached. It was sprayed to a thickness of 15 to 20 μm. The test panels obtained were pre-dried in a baking oven at a temperature of 60°C for 15 minutes and then overcoated with a clear coat to a dry film thickness of 40-45 μm and cured for a further 30 minutes at 150°C. did.

Acid resistance was tested according to the spot test using a 52% sulfuric acid solution. The results are shown in Table 4,
It is expressed on a scale of 0 to 5 (5 indicates no change, 0 indicates no acid resistance).

Durability was tested in a weather tester using a carbon arc and a 17/3 cycle for 2000 hours. Gloss was then measured at 60° (as above) according to ASTM D-523. These results are also shown in Table 4.

[0155]

Table 4 Only a limited number of preferred embodiments according to the invention are described above. However, those skilled in the art will appreciate that many substitutions, modifications and alterations may be made without departing from the scope of the invention.

Claims (26)

[Claims] 1. A hybrid polymer comprising (A) a polymer, and (B) one or more addition polymer-based chains grafted thereon, comprising: i. The polymer (A) contains an unsaturated fatty acid group-functional poly(epoxy ester), and the unsaturated fatty acid group-functional poly(epoxy ester) has (1) an epoxy-terminated poly(epoxy ester);
2) It is a reaction product with an unsaturated fatty acid component, at least in part consisting of a conjugated double bond-containing unsaturated fatty acid.i
i. Chains (B) based on addition polymers are about 20 to 10
having an acid value of 0; and iii. One or more addition polymer-based chains (B) are grafted onto the polymer (A) by addition polymerization of free-radically polymerizable monomers in the presence of an unsaturated fatty acid group-functionalized poly(epoxy ester). A hybrid polymer characterized by: 2. Based on the total weight of the hybrid polymer, about 40-90% by weight of polymer (A), and about 1
2. Hybrid polymer according to claim 1, containing from 0 to 60% by weight of chains (B) based on addition polymers. 3. The epoxy-terminated poly(epoxy ester) has a number average molecular weight (M
n mole of bisepoxide having 4 to 40 carbon atoms, where n = 2 to 10. 1. Hybrid polymer according to 1. [Claim 4] The poly(epoxyester) is about 4
4. The hybrid polymer according to claim 3, having an Mn in the range of 00 to 20,000. [Claim 5] The poly(epoxyester) is about 20
4. The hybrid polymer according to claim 3, having an Mn in the range of 00 to 20,000. [Claim 6] The bisepoxide is bisphenol A.
4. A hybrid polymer according to claim 3, wherein the hybrid polymer is selected from diglycidyl ether of 7. The bisepoxide is selected from cycloaliphatic bisepoxides and epoxy oligomers from epichlorohydrin and hydrogenated bisphenol A.
Hybrid polymers as described. 8. The hybrid polymer according to claim 3, wherein the dicarboxylic acid contains a dimerized fatty acid. 9. The hybrid polymer according to claim 1, wherein the unsaturated fatty acid contains at least 10 mol % of conjugated double bond-containing fatty acids. 10. The hybrid polymer according to claim 9, wherein the unsaturated fatty acid contains at least 30 mol % of conjugated double bond-containing fatty acids. 11. The hybrid polymer of claim 1, wherein the unsaturated fatty acid has 12 to 26 carbon atoms. 12. A part of the unsaturated fatty acid has the general formula (I
)R-X (I), where R is a hydrocarbon group having 1 to 40 carbon atoms and X is a functional group reactive towards epoxy groups. The hybrid polymer according to claim 1, wherein
. 13. The hybrid according to claim 12, wherein R is an alkyl group, aralkyl group, aryl group or cycloalkyl group having 1 to 24 carbon atoms, and X is an amino group or a carboxyl group. Polymer. 14. The hybrid polymer of claim 13, wherein the monofunctional compound contains a monocarboxylic acid. 15. The unsaturated fatty acid contains at least about 1/2
The hybrid polymer according to claim 1 or 12, which is used at a carboxyl group/epoxy group equivalent ratio of 4.
. 16. The unsaturated fatty acid is at least about 1/2
16. A hybrid polymer according to claim 15, wherein the hybrid polymer is used in a carboxyl/epoxy equivalent ratio of 2. 17. The combination of unsaturated fatty acids and monofunctional compounds is used in an equivalent ratio of (carboxyl groups + X groups)/epoxy groups of about 1/4 to 1/1. Hybrid polymer. 18. A water-dispersible hybrid polymer comprising a hybrid polymer according to claim 1, wherein the acid groups of the hybrid polymer are at least partially neutralized. 19. An aqueous dispersion based on the water-dispersible hybrid polymer according to claim 18. 20. An aqueous coating composition based on the aqueous dispersion of claim 19. 21. The aqueous coating composition of claim 20, wherein the coating composition further contains a curing agent for the hydroxyl groups of the hybrid polymer. 22. Based on the aqueous coating composition of claim 20, and wherein the bisepoxide of the unsaturated fatty acid group-functionalized poly(epoxy ester) is bisphenol A
and an epoxy oligomer of epichlorohydrin and bisphenol A. 23. The aqueous coating composition of claim 20, wherein a bisepoxide of an unsaturated fatty acid functional poly(epoxy ester) is hydrogenated with a cycloaliphatic bisepoxide and epichlorohydrin. Clearcoat selected from epoxy oligomers made from bisphenol A. 24. The aqueous coating composition of claim 20, wherein a bisepoxide of an unsaturated fatty acid functional poly(epoxy ester) is hydrogenated with a cycloaliphatic bisepoxide and epichlorohydrin. A pigmented topcoat selected from epoxy oligomers made from bisphenol A. 25. Chains based on one or more addition polymers (B
) onto the polymer (A) by addition polymerization of free-radically polymerizable monomers in the presence of an unsaturated fatty acid functional poly(epoxy ester). A method for producing a hybrid polymer according to any one of the above. 26. At least partially neutralizing the acid groups of the hybrid polymer according to any one of claims 1 to 17, and dispersing the thus neutralized hybrid polymer in an aqueous base. A method for producing an aqueous dispersion by