JPH06228494A - Resin composition for water-based coating - Google Patents

Abstract

PURPOSE:To obtain a composition, comprising a specific resin, etc., and a specified glycidyl group-containing compound, excellent in dispersibility and storage stability and useful as a cationic electrodeposition coating, etc. CONSTITUTION:The composition comprises (A) a resin, prepared by reacting (i) an epoxy resin, etc., having >=3 epoxy group-containing functional groups of formula I [(m) is 2-4] with (ii) a primary or a secondary amine compound having >=1 primary hydroxyl groups and (iii) a phenolic compound having >=1 phenolic hydroxyl groups and substantially without containing primary or secondary amino group and epoxy group, (B) a resin having >=2 phenolic hydroxyl groups substantially without containing the primary and secondary amino groups and (C) a compound having >=2 glycidyl groups based on a glycidylamino group of formula II (R is H or glycidyl) directly bound to the carbon atom in the aromatic ring as principal components. Furthermore, the blending ratio of the components (A) to (C) is preferably 15-50wt.% component (A) and 85-50wt.% total amount of the components (B) and (c).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for water-based coatings, and particularly when applied as a resin composition for cationic electrodeposition coatings, a block isocyanate compound (curing agent) or organic tin that has been used until now. There is no need to use a compound (curing catalyst), etc. As a result, heating loss, resistance to catalyst poisoning, etc. are improved, and the adhesion of coating film, weather resistance,
The present invention relates to a resin composition for water-based paints having improved low temperature curability and the like.

[0002]

2. Description of the Related Art Conventionally, a resin composition for a cationic electrodeposition coating composition mainly comprises a polyamine resin (base resin) such as an amine-added epoxy resin and a block polyisocyanate compound (curing agent). Widely used. This resin composition has a good anticorrosion property of the coating film, however, as an essential problem, the curing start temperature of the coating film is high (170 ° C. or higher), and in order to lower the curing start temperature, the organic tin is used. When a compound (curing catalyst) is used, the tin compound may poison the exhaust combustion catalyst of the baking furnace,
When heated at a high temperature to cure the coating film, the block polyisocyanate compound is thermally decomposed, causing tars and soot, and further causes yellowing, bleeding and curing inhibition in the top coating film, and also reduces weather resistance. It has a serious defect such as the above, and these improvements are strongly desired.

On the other hand, cationic electrodeposition coatings utilizing a self-crosslinking resin by ring-opening reaction of epoxy groups without using a curing agent are disclosed, for example, in Japanese Patent Publication Nos. 49-31736 and 49-23807. Although proposed in JP-A-48-69896 and JP-A-47-13432, it is difficult to achieve both the bath stability of the electrodeposition coating composition and the curability of the coating film. Atsuta For example, among these, the most common glycidyl ether type polyepoxy compound has excellent curability of the coating film, but has a drawback that it is inferior in bath stability.

The inventors of the present invention have conducted extensive studies to develop a cationic electrodeposition coating composition that eliminates the above defects, and as a result,
It was found that a specific epoxy compound having an alicyclic skeleton directly bonded to an epoxy group is useful as a curing agent for a cationic electrodeposition coating instead of a block polyisocyanate compound, and has been proposed previously. However, there are some points to be improved, such as a decrease in acid concentration in the bath due to high amine concentration, and insufficient corrosion resistance for untreated steel sheet due to high residual amine concentration in the cured coating film. Wakatsuta.

The object of the present invention is that there is no need to use a block polyisocyanate compound or an organic tin compound, the amine concentration in the paint is low, the corrosion resistance to untreated steel sheet is excellent, and the acid concentration stability in the bath is good. In addition, it is an object of the present invention to provide a cationic electrodeposition coating composition which has excellent water dispersibility and has a small heat loss during heat curing.

According to the present invention, (A) an epoxy resin (A) having at least three epoxy group-containing functional groups represented by the following formula (I) per molecule (A)
1-1) and / or novolak phenol type glycidyl ether group-containing resin (A-1-2) represented by the following formula (II) having at least 3 glycidyl ether groups per molecule, and primary hydroxyl group 1 A primary or secondary amine compound having at least one per molecule (A-
2) and a resin essentially free from primary or secondary amino groups and epoxy groups, obtained by reacting a phenol compound (A-3) having at least one phenolic hydroxyl group per molecule;

[0007]

[Chemical 4]

[In the formula, m is an integer of 2 to 4]

[0009]

[Chemical 5]

[In the formula, R ₁ and R ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aromatic group or a halogen atom, and R ₃ is a hydrogen atom, 1 to 1 carbon atoms. 10 alkyl group, aromatic group, allyl group or halogen atom, R ₄ is hydrogen atom or carbon atom 1 to
4 is an alkyl group, R ₅ is a hydrogen atom, having 1 to 1 carbon atoms.
0 is an alkyl group, an aromatic group, an allyl group or a halogen atom, n is an integer of 0 to 38, and at least a part of the benzene ring in the formula may be substituted with a naphthalene ring] (B ) At least two phenolic hydroxyl groups per molecule, or at least two phenolic hydroxyl groups and at least one primary hydroxyl group based on an alkanolamine,
And a resin essentially free of primary and secondary amino groups; and (C) a glycidyl group based on a glycidylamino group represented by the following formula (III) directly bonded to a carbon atom of an aromatic ring. Compounds having two or more in one molecule

[0011]

[Chemical 6]

There is provided a resin composition for an aqueous coating material, characterized in that [wherein R is a hydrogen atom or a glycidyl group] as a main component.

The resin composition for aqueous paint of the present invention will be described in more detail below.

Component (A) : An epoxy resin (A-1-1) having at least three epoxy group-containing functional groups represented by the general formula (I) in one molecule and / or a glycidyl ether group in one molecule. A general formula (I
I) a novolac phenol type glycidyl ether group-containing resin (A-1-2), a primary or secondary amine compound (A-2) having at least one primary hydroxyl group in one molecule, And a primary hydroxyl group and a cationic group obtained by reacting a phenol compound (A-3) having at least one phenolic hydroxyl group in one molecule, but essentially primary or secondary Resins containing no primary amino group or epoxy group.

The above-mentioned component (A-1-1), component (A-1-2), and component (A-2) used for preparing the component (A).
The components and the component (A-3) will be described first.

Component (A-1-1) : the following formula

[0017]

[Chemical 7]

An epoxy group-containing functional group represented by the formula: wherein m is an integer of 2 to 4 is used at least 3 per molecule.
It is an epoxy resin that has one.

Examples of the epoxy resin (A-1-1) component include, for example, JP-A-60-170620, JP-A-62-135467, and JP-A-60-1666.
Those known per se, such as those described in JP-A-75, JP-A-60-161973 and the like can be used.

Further, the component (A-1-1) also includes a compound in which the residue of the polymerization initiating component, that is, the active hydrogen-containing organic compound residue is bonded to the terminal of the above formula (I), Examples of the active hydrogen-containing organic compound that is the precursor thereof include alcohols, phenols, carboxylic acids, amines, thiols and the like.

Of these, the alcohols may be either monohydric alcohols or polyhydric alcohols having a valence of 2 or more, and specific examples thereof include methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol. Aliphatic monohydric alcohol; aromatic monohydric alcohol such as benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, Pentanediol, 1.6
Examples include polyhydric alcohols such as hexanediol, neopentyl glycol, neopentyl glycol oxybivalate, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol. It

Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydrylquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resin,
Examples thereof include cresol novolak resin.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils; fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. , Terephthalic acid and the like, and compounds having both a hydroxyl group and a carboxylic acid such as lactic acid, citric acid and oxycaproic acid can also be used.

Further, as a compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, allyl polyol resin, styrene-allyl alcohol copolymer resin. , Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Polycaprolactone polyol resin etc. can also be used. Further, the compound having active hydrogen may have an unsaturated double bond in the skeleton together with active hydrogen,
Further, the unsaturated double bond may have an epoxidized structure.

The component (A-1-1) can be obtained, for example, by using the above active hydrogen-containing organic compound as an initiator,

[0026]

[Chemical 8]

A vinyl cycloalkene oxide represented by the formula (4), for example, 4-vinylcyclohexene-1-oxide, alone or in the presence of another epoxy group-containing compound, is subjected to ring-opening ( Co) polymerization is carried out to form a polyether resin, and then the vinyl group based on the vinyl cycloalkene oxide present in the side chain in the resin is epoxidized with an oxidizing agent such as peracids or hydroperoxides, It can be obtained by introducing a functional group represented by (I).

4-Vinylcyclohexene-1-oxide can be obtained, for example, by partially epoxidizing vinylcyclohexene obtained by the dimerization reaction of butadiene with peracetic acid. In addition, vinyl cyclopentene or vinyl cyclobutene is partially epoxidized with peracetic acid to give vinyl cyclopentene-1-
Oxides or vinylcyclobutene-1-oxide can be obtained. The other epoxy group-containing compound is not particularly limited as long as it is a compound having an epoxy group, but in production, a compound having one epoxy group in one molecule is preferable, and specific examples include ethylene oxide and propylene. Formulas such as oxide, butylene oxide:

[0029]

[Chemical 9]

Α-olefin epoxide represented by the formula (wherein n is 2 to 25); an oxide of an unsaturated compound such as styrene oxide; allyl glycidyl ether, 2
-Glycidyl ethers of compounds having a hydroxyl group such as ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether; and glycidyl esters of organic acids such as fatty acids.

[0031]

[Chemical 10]

[0032]

[Chemical 11]

In the above formulas, R ₁₁ represents a hydrogen atom or a methyl group, R ₁₂ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ₁₃ represents 2 having 1 to 10 carbon atoms. Represents a valent hydrocarbon group.

In the above, the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ₁₂ is a linear or branched alkylene group such as methylene, ethylene, propylene or tetra. Methylene, ethyl ethylene,
Examples include pentamethylene and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ₁₃ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene,

[0035]

[Chemical 12]

Examples thereof include groups.

Further, the following general formula

[0038]

[Chemical 13] [Wherein R ₁₁ and R ₁₂ have the same meanings as defined above], for example, the following formula partially by-produced by partial epoxidation of glycidyl acrylate, glycidyl methacrylate or vinylcyclohexene.

[0039]

[Chemical 14]

A compound having an alicyclic unsaturation as represented by the formula (1) can also be used as the other epoxy group-containing compound. Furthermore, 4-vinylcycloheptene (vinyl norbornene) or the like can be used.

The ring-opening (co) polymerization reaction of an epoxy group in the presence of the vinylcycloalkene oxide of the above formula (IV), for example, 4-vinylcyclohexene-1-oxide alone or in the presence of another epoxy group-containing compound is active. It is preferable to carry out in the presence of a hydrogen-containing organic compound and using a catalyst. Examples of the catalyst that can be used include amines such as methylamine, ethylamine, propylamine and piperazine; organics such as pyridines and imidazoles. Bases; organic acids such as formic acid and propionic acid acetate; inorganic acids such as sulfuric acid and hydrochloric acid; alkali metal alcoholates such as sodium methylate; alkalis such as KOH and NaOH; B
Examples thereof include Lewis acids such as F ₃ ZnCl ₂ , AlCl ₃ and SnCl ₄ or their complexes; and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts are 0.001 relative to the reactants.
It can be used within the range of 10 to 10% by weight, preferably 0.1 to 5% by weight. The ring-opening (co) polymerization reaction temperature is generally -70 to 200 ° C, preferably -30 ° C to 100 ° C. The reaction can be carried out using a solvent, and it is preferable to use an ordinary organic solvent having no active hydrogen as the solvent.

The functional group represented by the above structural formula (I) is introduced by epoxidizing the vinyl group contained in the side chain of the polyether resin (ring-opening (co) polymer) thus obtained. It is possible to obtain the component (A-1-1). Epoxidation can be carried out using peracids, hydroperoxides and the like. Examples of peracids include formic acid,
Peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used, and as hydroperoxides, hydrogen peroxide, tert-butyl peroxide, cumene peroxide and the like can be used. The epoxidation reaction can be carried out using a catalyst, if necessary.

A vinyl alkene oxide of the formula (IV),
For example, the vinyl group in 4-vinylcyclohexene-1-oxide is epoxidized to generate the functional group represented by the structural formula (I). In this epoxidation reaction, when the alicyclic oxirane group-containing compound or the like is present as another epoxy group-containing compound, the vinyl group contained in the compound may also be epoxidized,
This is different from the structural formula (I).

Whether or not a solvent is used in the epoxidation reaction and the reaction temperature can be appropriately adjusted depending on the apparatus used and the physical properties of the raw materials.

As the component (A-1-1), a commercially available product can be used, and examples thereof include EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.). This is 4-
A vinyl cyclohexene-1-oxide ring-opening polymer in which a vinyl group is epoxidized, and the degree of polymerization is 4 to on average.
It is 15.

The amount of the epoxy group-containing functional group represented by the structural formula (I) may be 3 or more per 1 molecule of the component (A-1-1), but the epoxy equivalent is preferably 140 to 100. It is in the range of 1000, and more preferably 170 to 300.

Component (A-1-2) : The following formula having at least 3 glycidyl ether groups per molecule

[0049]

[Chemical 15]

[In the formula, R ₁ and R ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aromatic group or a halogen atom, and R ₃ is a hydrogen atom, 1 to 10 carbon atoms. Is an alkyl group, an aromatic group, an allyl group or a halogen atom, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. Group, an allyl group or a halogen atom, n is an integer of 0 to 38, and at least a part of the benzene ring in the formula may be substituted with a naphthalene ring.] Novolak phenol glycidyl ether Group-containing resin.

In the above formula (II), "alkyl group"
Is linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl groups. The "aromatic group" may be either monocyclic or polycyclic, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.

"Halogen atom" includes fluorine, chlorine, bromine and iodine atoms.

Therefore, in the general formula (II), R
_{As 1} and R ₂ , a hydrogen atom, a methyl group, a chlorine atom and a bromine atom are preferable, and a hydrogen atom, a methyl group and a bromine atom are particularly preferable. Further, as R ₃ and R ₅ , a methyl group, a tert-butyl group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom are preferable, and among them, a methyl group, a tert-butyl group, a phenyl group and a bromine atom are preferable. . Furthermore, R ₄ is preferably a hydrogen atom, and n is particularly preferably 1-8.

The number average molecular weight of the component (A-1-2) is generally about 400 to 400 based on the vapor pressure osmometry.
It is preferably in the range of about 8000, especially 600-2000. The number average repeating unit number (n + 2) can be determined from the number average molecular weight. In addition, (A-1
-2) The component preferably has 3 or more, particularly 3.5 to 10, glycidyl ether groups per molecule,
Further, the epoxy equivalent of the component (A-1-2) is preferably in the range of about 180 to about 2000, particularly 200 to 600.

The component (A-1-2) is, for example, the following formula (VII):

[0056]

[Chemical 16]

A difunctional phenyl compound (a-1) represented by the formula: wherein R ₁ , R ₂ and R ₃ are as defined above.
And the following general formula (VIII)

[0058]

Embedded image R ₄ —CHO (VIII) [wherein R ₄ has the same meaning as above] and / or the following general formula (IX)

[0059]

[Image Omitted] R ₄ —CO—R ₁₄ (IX) [wherein R ₄ has the same meaning as defined above] and a phenol type novolak obtained by polycondensation reaction with a ketone compound (a-3). It can be produced by further reacting the resin (a-4) with epihalohydrin (a-5) to introduce a glycidyl ether group into the phenol type novolac resin (a-4).

During or after the reaction for obtaining the phenol type novolak resin (a-4), if necessary, the following formula (X)

[0061]

[Chemical 19]

[Wherein R ₈ represents an alkyl group, an aryl group, an aralkyl group, an allyl group or a halogen atom having 1 to 10 carbon atoms; and R ₁ and R ₂ have the same meanings as defined above] 1 The functional phenol compound (a-6) may be used together as an end cap.

Specific examples of the group R ₈ in the above formula (X) include a methyl group, an ethyl group, a propyl group, an n-butyl group,
Examples thereof include t-butyl group, pentyl group, hexyl group, nonyl group, ethylene group, propylene group, phenyl group, benzyl group, chlorine atom, bromine atom and iodine atom, and preferably methyl group, t-butyl group, Nonyl group, phenyl group, chlorine atom and bromine atom, especially methyl group, t
-Butyl, phenyl and bromine atoms are preferred.

The term "difunctional" used for the above-mentioned phenolic compound as the component (a-1) is defined by the general formula (VII).
In the above, it means that two hydrogen atoms are directly bonded to the ortho position and / or the para position based on the hydroxyl group. The hydrogen atom undergoes a dehydration condensation reaction with the carbonyl group (C = O) in the components (a-2) and (a-3) to produce a phenol type novolac resin (a-4).

Further, the term "monofunctional" used for the phenol compound of the component (a-6) means that in the general formula (X), one hydrogen atom is present at the ortho or para position based on the hydroxyl group. It means a direct bond. The hydrogen atom undergoes a dehydration condensation reaction with the carbonyl group (C = O) in the component (a-2) or (a-3) to form the terminal of the phenol type novolac resin (a-4).

Examples of the bifunctional phenol compound (a-1) represented by the above formula (VII) include phenol, p-propenylphenol, o-benzylphenol, 6-n-amyl-n-cresol and o-. Cresol, p-cresol, o-ethylphenol, o-phenylphenol, p-phenylphenol, p-ter
t-pentylphenol, p-tert-butylphenol, o-chlorophenol, p-chlorophenol,
4-chloro-3,5-xylenol, o-allylphenol, nonylphenol, o-bromophenol, p-
Examples include cumylphenol.

Examples of the aldehyde compound (a-2) represented by the formula (VIII) include acetaldehyde and formaldehyde. Further, m- (or p-) hydroxybenzaldehyde may be used as the aldehyde compound (a-2), and after the reaction with the component (a-1), the hydroxybenzaldehyde may be glycidyl etherified with epihalohydrin (a-5). . In addition, the benzene nucleus of the said hydroxybenzaldehyde may be substituted by the C1-C10 alkyl group.

The ketone compound represented by the formula (IX) (a-
Examples of 3) include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Furthermore, by using 2-acetylphenyl-2-hydroxyphenylpropane, an organic group containing a glycidyloxyphenyl group can be introduced into the resin of formula (II). That is, in this way, in the formula (II)

[0069]

[Chemical 20] At least part of

[0070]

[Chemical 21]

It can be

Further, examples of epihalohydrin (a-5) include epichlorohydrin and epibromhydrin.

The phenol type novolak resin (a-4) is obtained by subjecting the above component (a-1) to the polycondensation reaction of the component (a-2) and / or the component (a-3).
This polycondensation reaction can be carried out according to a conventional method for producing a phenol type novolak resin known per se. Specifically, it can be performed by a batch method or a continuous method described in JP-A No. 51-130498.
For example, the respective components are blended in such a ratio that the number of repetitions (n) in the formula (I) is within the range of 1 to 38, and the number average molecular weight and the epoxy equivalent are within the above range, and By reacting, the component (a-4) can be obtained. In this reaction, it is also possible to use a catalyst such as an inorganic acid such as hydrochloric acid, phosphoric acid and sulfuric acid; an organic acid such as paratoluenesulfonic acid and oxalic acid; a metal salt such as zinc acetate.

In the production of the component (a-4), the above component (a-1), the component (a-2) and //
Alternatively, during or after the polycondensation reaction with the component (a-3), the monofunctional phenol compound (a-6) represented by the formula (VII) can be reacted as an end-capping agent.

Specific examples of the monofunctional phenol compound (a-6) represented by the above formula (X) include 2-t-butyl-4-methylphenol, 2,4-xylenol,
2,6-xylenol, 2,4-dichlorophenol,
2,4-dibromophenol, dichloroxylenol,
Dibromoxylenol, 2,4,5-trichlorophenol, 6-phenyl-2-chlorophenol and the like can be mentioned.

The component (a-6) and the above component (a-1),
The polycondensation reaction with the component (a-2) and / or the component (a-3) can be carried out in the same manner as above. (A-
The novolac type phenol resin obtained by using the 6) component together is also included in the category of the (a-4) component.

The component (A-1-2) can be obtained by reacting the phenolic hydroxyl group in the component (a-4) with the component (a-5) to form a glycidyl ether.
Specifically, for example, the component (a-4) is dissolved in the component (a-5), an aqueous solution of an alkali metal hydroxide is continuously added to this solution, and water and unreacted water in the reaction system are added. Of (a
-5) Obtained by distilling off the component. The component (a-5) can be separated from the distilled liquid and reused. This reaction is preferably carried out in the presence of an ether solvent such as dioxane or diethoxyethane.

The component (A-1-2) can be produced as described above, but a commercially available product may be used. As a commercially available product, for example, polyglycidyl phenol type novolac resin may be used. As an etherified product, D
EN-438 and DEN-439 (trade name, manufactured by Dow Chemical Japan Co., Ltd.): EPICRON N as a polyglycidyl etherified product of cresol type novolac resin.
-695 [Dainippon Ink Co., Ltd., trade name], ESCN
-195XHH [Sumitomo Chemical Co., Ltd., trade name], EOC
N-102S, EOCN-1020 and EOCN10
4S [Nippon Kayaku Co., Ltd., trade name]: BREN-S [Nippon Kayaku Co., Ltd., trade name]: long-chain alkyl-modified phenol type novolak as a polyglycidyl ether of brom-modified phenol type novolak resin Examples of the polyglycidyl ether of the resin include ESMB-260 (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

Component (A-2): A primary or secondary amine compound having at least one primary hydroxyl group in one molecule.

This compound serves to react with the above-mentioned component (A-1-1) and / or component (A-1-2) to form a primary hydroxyl group and a basic group.

The amino group of the component (A-2) and (A-1-
The cationic resin is produced by the reaction with the glycidyl group of the component 1) and / or the component (A-1-2), and the primary hydroxyl group and basic group in the cationic resin are the same as those of conventional bisphenols. Compared with the above-mentioned ones produced by the reaction with the A-type epoxy resin, the water dispersibility and throwing power are remarkably excellent even at partial neutralization and high pH, and the curability of the coating film formed and There is no reduction in corrosion resistance.

Examples of the component (A-2) include the following compounds.

(1) Primary alkanolamines such as monoethanolamine, monopropanolamine and monobutanolamine.

(2) N-methylethanolamine, N
-Ethylethanolamine, diethanolamine, di-
Secondary alkanolamines such as n- (or iso) -propanolamine and dibutanolamine.

(3) Addition product of the above-mentioned primary alkanolamine and α, β-unsaturated carbonyl compound (secondary alkanolamine): For example, monoethanolamine and N, N-dimethylaminopropylacrylamide Addition product, addition product of monoethanolamine and hydroxyethyl (meth) acrylate, addition product of monoethanolamine and hydroxypropyl (meth) acrylate, monoethanolamine and hydroxybutyl (meth)
Adducts with acrylate, etc.

(4) Primary and secondary alkanolamines such as hydroxyethylaminoethylamine.

(5) Condensation product of one or more selected from hydroxyamine, hydroxyethylhydrazine and hydroxybutylhydrazine with a ketone compound such as dimethylketone, methylethylketone, methylisobutylketone, dibutylketone, dipropylketone ( Secondary alkanolamines).

(6) Formula (XI)

[0089]

[Chemical formula 22] [In the formula, n is an integer of 1 to 6 and R ₂₁ has 4 to 3 carbon atoms which may contain a hydroxyl group and / or a polymerizable unsaturated group.
And a primary hydroxyl group, a secondary amino group and an amide group are present together in one molecule.

The amine compound represented by the general formula (XI) can be obtained, for example, by subjecting N-hydroxyalkylalkylenediamine and a monocarboxylic acid having 5 to 37 carbon atoms to a dehydration condensation reaction. Examples of the diamine include primary hydroxyl groups such as hydroxyethylaminoethylamine, N-hydroxyethylpropylenediamine, N-hydroxyethylbutylenediamine, N-hydroxyethylpentylenediamine, and N-hydroxyethylhexylenediamine. The first and second diamines are preferable, and examples of the monocarboxylic acid include coconut oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil. Mixed fatty acids such as oil fatty acid and tung oil fatty acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, eleostearic acid, 12-hydroxystearic acid , Beheny Such as acid, and the like.

The reaction between the above diamine and monocarboxylic acid to obtain the amine compound represented by the above formula (XI) is
Usually, it can be carried out by mixing the both components in an approximately equimolar ratio, and removing a specified amount of reaction product water using an organic solvent such as toluene or methyl isobutyl ketone.
The amine compound is obtained by removing the residual organic solvent by a pressure reduction method or the like. The amine compound thus obtained generally has an amine value (secondary amine) of 88 to 35.
0, especially in the range of 120 to 230, and having a hydroxyl value (preferably primary hydroxyl group) of 44 to 350, especially 6
It is preferably in the range of 0 to 230.

The above (1) to (A-2) as the component
Among (6), the primary alkanol secondary amines of (2), (3) and (6) are preferred. In particular, it is preferable to use the amine compound represented by the formula (XI) (particularly hydroxyethylaminoethyl fatty acid amide) and diethanolamine together in order to improve the smoothness of the coated surface and the corrosion resistance. The ratio of the amine compound (particularly hydroxyethylaminoethyl fatty acid amide) to diethanolamine is 30 to 30 based on the total weight of both components.
It is preferable to use 80% by weight and the latter in a proportion of 70 to 20% by weight.

Component (A-3): A phenol compound having at least one phenolic hydroxyl group in one molecule.

The phenol compound having a phenolic hydroxyl group as the component (A-3) contains at least one structural unit represented by the following formula (XII), and (A-
The number average molecular weight of the component 3) is usually preferably in the range of 94 to 20,000.

[0095]

[Chemical formula 23]

[Wherein R ₃₃ and R ₃₄ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom] (A-3) Specific components include bis (4-hydroxyphenyl) -2,2-propane, 4,4'-dihydroxybenzophenone and bis (4
-Hydroxyphenyl) -1,1-ethane, bis (4-
Hydroxyphenyl) -1,1-isobutane, bis (4
-Hydroxy-tert-butylphenyl) -2,2-
Propane, bis (2-hydroxynaphthyl) methane,
1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4'-dihydroxydiphenyl ether, 4, Polyvalent phenol compounds such as 4'-dihydroxydiphenyl sulfone, phenol novolak, cresol novolak; phenol, nonyl phenol, α- or β-naphthol, p-tert.
Examples include monophenol compounds such as octylphenol, o- or p-phenylphenol and the like.

In the present invention, the following formula (XIII) is used as the component (A-3).

[0098]

[Chemical formula 24]

[In the formula, R ₃₁ and R ₃₂ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms; and R _{33 to} R ₃₆ are the same or different, each being a hydrogen atom and having 1 to 10 carbon atoms. Alkyl group, aryl group, aralkyl group,
Representing an allyl group or a halogen atom], a compound having a phenolic hydroxyl group-containing functional group represented by
The corrosion resistance of the coating film can be further improved. The number average molecular weight of the component (A-3) having a phenolic hydroxyl group-containing functional group represented by the formula (XIII) is not particularly limited, but is generally 200 to 20,000, particularly 800 to 3
It is preferable that it is within the range of 000.
The component 3) has 0.3 to 2 phenolic hydroxyl group-containing functional groups represented by the formula (XIII) per molecule, and particularly 0.3.
It is preferable to contain 5 to 1.5, more preferably 0.8 to 1.2.

Examples of the compound having a phenolic hydroxyl group-containing functional group represented by the above formula (XIII) include:
Examples thereof include bisphenol resins such as bis (4-hydroxyphenyl) -2,2-propane (bisphenol A) and bis (4-hydroxyphenyl) -2,2-methane (bisphenol A).

Further, as the compound (A-3 component) having a phenolic hydroxyl group-containing functional group represented by the formula (XIII), the compound represented by the following general formula (XIV) can be more preferably used.

[0102]

[Chemical 25]

[Wherein q is an integer of 0 to 7 and R ₃₈ is a residue of an active hydrogen-containing compound] As the active hydrogen-containing compound which is the precursor of R ₃₈ in the above formula (XIV), For example, amines such as secondary amines; phenols such as phenylphenol and nonylphenol; organic acids such as fatty acids; thiols; alkyl alcohols,
Examples thereof include alcohols such as cellosolve, butyl cellosolve, and carbitol; inorganic acids; and the like. Among these, particularly preferred are secondary amines having primary hydroxyl groups such as dialkanolamines; amine compounds represented by the above formula (XIV); phenols such as nonylphenol, phenylphenol, phenol and hydroquinone monomethyl ether. Fatty acids such as stearic acid, oleic acid and soybean oil fatty acids; lower organic acids such as acetic acid, formic acid and hydroxyacetic acid.

In the component (A-3), a compound of the above formula (XIV) having both ends of either R ₃₈ or --OH may be mixed, but a phenolic hydroxyl group-containing functional group per molecule. It is preferred to contain 0.5 to 1.5, especially 0.8 to 1.2, groups and have a number average molecular weight in the range of 500 to 20,000.

The component (A-3) having a phenolic hydroxyl group-containing functional group represented by the above formula (XIV) is, for example,
A bisphenol type glycidyl ether, a bisphenol type diphenol and an active hydrogen-containing compound (for example, a secondary alkanolamine) are optionally added in the presence of a catalyst or a solvent at 30 to 300 ° C., preferably 70 to 18 ° C.
Obtained by reacting at a temperature of 0 ° C. Also,
In this reaction, for example, dimer diol,
Polyols such as ethylene glycol, propylene glycol and butylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyester polyols such as polycaprolactone; polycarboxylic acids; polyisocyanates; monoisocyanates; Oxides of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide; allyl glycidyl ether, polypropylene glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, etc. Glycidyl ethers of compounds having hydroxyl groups; groups of organic acids such as fatty acids Glycidyl ester; alicyclic oxirane-containing compound; such may be Coexistence of. Further, δ-4-caprolactone, an acrylic monomer or the like may be graft polymerized without any problem.

The component (A) used in the present invention is the above-mentioned component (A-1-1) and / or component (A-1-2), component (A-2) and component (A-3). It is obtained by reacting. This reaction can be carried out by reacting the component (A-1-1) and / or the component (A-1-2) with the component (A-2) and the component (A-3) simultaneously or sequentially. it can. For example, these components may be mixed and reacted at the same time; or the component (A-1-1) and / or the component (A-1-2) may be reacted with the component (A-2), and then the component (A-3). React the components; (A-1
-1) component and / or (A-1-2) component with (A-
It can be carried out by a method such as reacting the component (3) and then reacting the component (A-2), whereby the component (A) is obtained.

Component (A-1-1) and / or (A-
The reaction between the component 1-2) and the component (A-2) is (A-1-
1) the reaction of the glycidyl group of the component and / or the component (A-1-2) with the primary and / or secondary amino group of the component (A-2), these amino groups being after the reaction Changes to a tertiary amino group. In addition, (A-1-
1) component and / or (A-1-2) component and (A-
The reaction with the component 3) is a reaction between the glycidyl group of the component (A-1-1) and / or the component (A-1-2) and the phenolic hydroxyl group of the component (A-3). An ether bond is formed.

Component (A-1-1) and / or (A-
Since most or all of the glycidyl groups in the component 1-2) are consumed in the above reaction, it is general that no glycidyl groups remain in the component (A) thus obtained in principle. Therefore, the (A) component is the first and second
It is substantially free of primary amino groups and glycidyl groups.
The reaction ratio of each of these components can be varied within a wide range depending on the intended use of the intended product. For example, (A-1-
1) component and / or (A-1-2) component of glycidyl group per 1 mol, the amino group of (A-2) component and (A-
3) The total number of moles with the phenolic hydroxyl group of the component is 0.7
It is preferable to carry out the reaction so as to be in the range of 5 to 1.5 mol, particularly 0.8 to 1.2 mol. If the total number of moles is less than 0.75 moles, the viscosity of the reaction product may increase, while if it is more than 1.5 moles, a large amount of unreacted amine groups remain, which adversely affects the electrodeposition coating characteristics. May be given.

The content of the component (A-1-1) and / or the component (A-1-2) is (A-1-1) component and / or (A-1-2) component, ( 0.5 to 75 based on the total amount of the component (A-2) and the component (A-3).
%, Particularly preferably in the range of 5 to 50% by weight, and
If it is less than 5% by weight, the water dispersibility may be insufficient, while if it is more than 75% by weight, the amine value may be high and the corrosion resistance of the coating film may be lowered.

The amount of the component (A-2) used is preferably such that the hydroxyl group equivalent of the component (A) to be produced is in the range of 250 to 2000, preferably 300 to 700. If the hydroxyl equivalent of component (A) is less than 250, the amine value may be high, and the corrosion resistance of the coating film may be reduced. is there. The component (A-3) is the component (A-1-1) and / or the component (A-1-2).
0.05 to 1.5 mol, especially 0.2 per molecule of the component
It is suitable to use in the range of up to 1.2 mol. (A
If the amount of the component (-3) is less than 0.05 mol, the water dispersibility tends to decrease, whereas if it exceeds 1.5 mol, the smoothness of the coated surface may decrease.

Further, the component (A-1-1) and / or the component (A-1-2), the component (A-2) and the component (A-
The reaction temperature of the component 3) is usually 50 to 300 ° C., especially 7
It is preferably in the range of 0 to 200 ° C. This reaction can be carried out in the presence of organic solvents such as alcohols, ketones and ethers.

The component (A) thus obtained has a number average molecular weight of generally 1,000 to 20,000, particularly 1,500 to 1.
It is preferably in the range of 0000.

Further, in order to adjust the hydroxyl equivalent and amine value of the component (A) within the above ranges, the other cationizing agent (A-4) exemplified below is used together with the component (A-2). You can also This cationizing agent (A-4)
May be added at the beginning of the reaction, during the reaction, or at any stage after the reaction.

Other cationizing agents (A-4) include, for example, methylamine, ethylamine, n- or i.
Primary amines such as so-propylamine; secondary amines such as diethylamine, dipropylamine, dibutylamine; polyamines such as ethylenediamine, diethylenetriamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylamine, dimethylaminopropylamine. Etc., and can be used in combination with ammonia, hydrazine, N-hydroxyethylimidazoline compound, and the like. It is preferable that no primary or secondary amino group remains in the product after the reaction.

As another cationizing agent (A-4), the primary hydroxyl group-containing primary and secondary diamines used for preparing the compound of the formula (XI) in the component (A-2) are used. Replace with primary and secondary diamines containing secondary hydroxyl groups 1
An amine compound having a secondary hydroxyl group, a secondary amino group and an amide group in the molecule can also be used.

Further, tertiary amines such as triethylamine, triethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N, N'-diethylethanolamine and N-ethyldiethanolamine (A-4). It can be used as a component, which can be preprotonated with an acid and reacted with an epoxy group to give a quaternary salt.

In addition to amino compounds, sulfides such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide and thiodiethanol, and boric acid,
A salt with carbonic acid, an organic monocarboxylic acid or the like may be reacted with an epoxy group and used as a tertiary sulfonium salt.

Further, a salt of a phosphine such as triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, triphenylphosphine and the like and an acid as described above is reacted with an epoxy group to be used as a quaternary phosphonium salt. You can also do it.

In the present invention, it is necessary to introduce a cationic group using the component (A-2), but (A-
It is optional to use the other cationizing agent (A-4) together with the component 2).

The thus-obtained cationic resin (A) containing a primary hydroxyl group can be used as a resin for cationic electrodeposition coating composition. Further, since the resin (A) has excellent water dispersibility, it is useful for improving the water dispersibility of an organic substance or an inorganic substance having insufficient water dispersibility. It is also useful as a water dispersibility improver and a pigment dispersant.

Component (B) : Resin (B-1) having at least two phenolic hydroxyl groups per molecule and at least one phenolic hydroxyl group and at least one primary hydroxyl group based on alkanolamine per molecule (total). It is preferred that the resin (B-2) has both at least 2) and essentially no primary and secondary amino groups.

By using these, it is possible to improve the curability, corrosion resistance, water resistance and the like of the coating film formed. The number average molecular weight of the component (B) is not particularly limited, but is generally about 200 to about 20,000, particularly about 2
It is preferably in the range of 0 to about 10,000.

Component (B-1) : A resin having at least two phenolic hydroxyl groups in one molecule.

The component (B-1) has a phenolic hydroxyl group of 1
It can have at least 2, preferably 2-38, more preferably 2-15 per molecule. The following resin is preferably used as the resin (B-1).

Examples of the resin (B-1-1) having two phenolic hydroxyl groups per molecule include bis (4-hydroxyphenyl) -2,2-propane (bisphenol A) and bis (4-hydroxy). Phenyl) -2,2-methane (bisphenol F), 4,4'-dihydroxybiphenyl, 4,4 '-(1-α-methylbenzylidine)
Bisphenol, 2,2'-bis (4-hydroxy-3
-Methylphenyl) propane, methylenebis-p-cresol, 4,4'-ethylidenebisphenol, bis-
4-hydroxy-3,5-dimethylphenyl) methane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, dihydroxybenzophenone, 1,1
Examples include -bis (4-hydroxyphenyl) cyclihexane.

As the resin (B-1-2) having three phenolic hydroxyl groups per molecule, for example, 4,4 ′,
4 ″ -methylidene trisphenol, 4,4 ′-[(4
-Hydroxyphenyl) methylene] bis [2methoxyphenol], 4,4 '-[(4-hydroxyphenyl)]
Methylene] bis [2,6-dimethylphenol], 4,
4 ', 4 "-ethylidene trisphenol, 4,4-
[1- [4- (2- (4-hydroxyphenyl) -2-
Examples include propyl) phenyl] ethylidene] bisphenols.

Examples of the resin (B-1-3) having more than 3 phenolic hydroxyl groups per molecule include a phenol type novolak resin represented by the following formula (XV).

[0128]

[Chemical formula 26]

[Wherein R ₅₁ and R ₅₂ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group or a halogen atom;
₅₃ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; R ₅₄ and R ₅₆ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₅₅ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; and p is an integer of 1 to 38] In the formula (XV), The “alkyl group” is linear or branched,
Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl groups. Further, the “aryl group” may be either monocyclic or polycyclic, and examples thereof include a phenyl group and a naphthyl group. Particularly, a phenyl group is preferable, and an “aralkyl group” is an aryl-substituted group. Alkyl groups include, for example, benzyl and phenethyl groups,
Of these, a benzyl group is preferable.

The “halogen atom” includes fluorine, chlorine, bromine and iodine atoms.

Therefore, in the above formula (XV), R ₅₁
As R ₅₂ , a hydrogen atom, a methyl group, a chlorine atom and a bromine atom are preferable, and a hydrogen atom, a methyl group and a bromine atom are particularly preferable. Further, as R ₅₃ and R ₅₅ , a methyl group, a tert-butyl group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom are preferable, and among them, a methyl group, a tert-butyl group, a phenyl group and a bromine atom are preferable. . Furthermore, R ₅₄ and R ₅₆ are preferably hydrogen atoms, and p is especially preferably 1-8.

The number average molecular weight of the component (B-1-3) is generally about 400-based on the measurement by vapor pressure osmometry.
It is preferably in the range of about 20,000, especially 600 to 10,000. The number average repeating unit number (p + 2) can be determined from the number average molecular weight. Also, (B
-1-3) The component preferably has 3 to 15 phenolic hydroxyl groups per molecule, and (B-3)
The phenolic hydroxyl group equivalent weight of the component is preferably in the range of generally about 120 to about 2000, particularly 140 to 600.

The component (B-1-3) has, for example, the following formula (XVI):

[0134]

[Chemical 27]

A difunctional phenyl compound represented by the formula: wherein R ₅₁ , R ₅₂ and R ₅₃ are as defined above, and a compound represented by the following formula (XVII)

[0136]

Embedded image R ₅₄ —CHO (XVII) [wherein R ₅₄ has the same meaning as above] and / or the following formula (XVIII)

[0137]

Embedded image R ₅₄ —CO—R ₅₆ (XVIII) [wherein R ₅₄ and R ₅₆ are as defined above] can be obtained by polycondensation reaction.

During or after the reaction for obtaining the phenol type novolak resin of the above formula (XV), if necessary, the following formula (XIX)

[0139]

[Chemical 30]

[Wherein R ₅₇ represents an alkyl group, an aryl group, an aralkyl group, an allyl group or a halogen atom having 1 to 10 carbon atoms; and R ₅₁ and R ₅₂ have the same meaning as defined above] 1 A functional phenol compound may be used together as an end cap.

Specific examples of the group R ₅₇ in the above formula (XIX) include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, nonyl group, ethylene group and propylene group. Group, phenyl group, benzyl group, chlorine atom, bromine atom, iodine atom and the like,
Of these, a methyl group, a t-butyl group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom are preferable, and a methyl group, a t-butyl group, a phenyl group and a bromine atom are particularly preferable.

The term "difunctional" used in the above bifunctional phenyl compound refers to the general formula (XVI):
It means that two hydrogen atoms are directly bonded to the ortho position and / or the para position based on the hydroxyl group. The hydrogen atom undergoes a dehydration condensation reaction with the carbonyl group (C = O) in the aldehyde compound and the ketone compound to form a phenol type novolak resin.

The term "monofunctional" used in the monofunctional phenol compound means that in the general formula (XIX), one hydrogen atom is directly bonded to the ortho position or the para position based on the hydroxyl group. Means The hydrogen atom undergoes a dehydration condensation reaction with the carbonyl group (C = O) in the aldehyde compound or ketone compound to form an end of the phenol type novolak resin.

Examples of the bifunctional phenol compound represented by the above formula (XVI) include phenol, p-propenylphenol, o-benzylphenol and 6-n.
-Amyl-n-cresol, o-cresol, p-cresol, o-ethylphenol, o-phenylphenol, p-phenylphenol, p-tert-pentylphenol, p-tert-butylphenol, o-chlorophenol , P-chlorophenol, 4-chloro-
3,5-xylenol, o-allylphenol, nonylphenol, o-bromophenol, p-cumylphenol and the like can be mentioned.

Examples of the aldehyde compound include acetaldehyde and formaldehyde. In addition, m- (or p-) hydroxybenzaldehyde may be used as the aldehyde compound, and the hydroxybenzaldehyde may be glycidyl etherified with epihalohydrin after the reaction with the bifunctional phenyl compound. In addition, the benzene nucleus of the said hydroxybenzaldehyde may be substituted by the C1-C10 alkyl group.

Examples of the ketone compound represented by the formula (XVIII) include acetone, methyl ethyl ketone,
Examples include methyl isobutyl ketone. Furthermore, 2
By using -acetylphenyl-2-hydroxyphenylpropane, an organic group containing a phenolic hydroxyl group can be introduced into the resin of the formula (XV). That is,
Thus, in formula (XV)

[0147]

[Chemical 31] At least part of

[0148]

[Chemical 32]

It can be

A phenol type novolak resin (B-3) is obtained by subjecting the above bifunctional phenyl compound to a condensation polymerization reaction of an aldehyde compound and / or a ketone compound. This polycondensation reaction can be carried out according to a conventional method for producing a phenol type novolak resin known per se. Specifically, a batch system or JP-A-51-1304
It can be carried out by the continuous method described in Japanese Patent Publication No. 98 or the like. For example, the respective components are blended in such a ratio that the repeating number (p) in the formula (XV) is within the range of 1 to 38, and the number average molecular weight and the epoxy equivalent are within the above range, and By reacting (B
-3) The component is obtained. In this reaction, it is also possible to use an inorganic acid such as hydrochloric acid, phosphoric acid and nitric acid; an organic acid such as paratoluenesulfonic acid and silicic acid; and a metal salt such as zinc acetate.

In the production of the component (B-1-3), if necessary, during or after the polycondensation reaction of the bifunctional phenyl compound with the aldehyde compound and / or the ketone compound, the above formula (XVIII) A monofunctional phenol compound represented by can be reacted as an end-capping agent.

As the monofunctional phenol compound represented by the above formula (XVIII), specifically, 2-t-butyl-4-methylphenol, 2,4-xylenol, 2,2
6-xylenol, 2,4-dichlorophenol, 2,4
-Dibromophenol, dichloroxylenol, dibromoxylenol, 2,4,5-trichlorophenol, 6
-Phenyl-2-chlorophenol and the like.

The polycondensation reaction between the monofunctional phenol compound and the above-mentioned bifunctional phenyl compound component, aldehyde compound and / or ketone compound can be carried out in the same manner as above. A novolak type phenol resin obtained by using a monofunctional phenol compound component in combination (B-
3) It is included in the category of components.

Further, as the component (B-1), the above (B
At least 1 selected from (1-1) to (B-1-3)
A product obtained by reacting a mono- or polyglycidyl compound with various components at a temperature of 30 to 300 ° C., preferably 70 to 180 ° C. in the presence of a catalyst or a solvent if necessary (B-1 -4) is also included.

Examples of the mono- or polyglycidyl compound include bisphenol diglycidyl ether; oxides of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide; allyl glycidyl ether, polypropylene glycol diglycidyl ether. , 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and other glycidyl ethers of compounds having a hydroxyl group; and glycidyl esters of organic acids such as fatty acids.

Further, in the production reaction of the component (B-1-4), the following components can be further coexisted as long as the reaction product has two or more phenolic hydroxyl groups per molecule. is there. For example, polyols such as dimer diol, ethylene glycol, propylene glycol, butylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; polyester polyols such as polycaprolactone; polycarboxylic acids; polyisocyanates. A monoisocyanate; an alicyclic oxirane-containing compound and the like can coexist. Further, δ-4-caprolactone, an acrylic monomer or the like may be graft polymerized without any problem.

Component (B-2): In one molecule, a total of two or more phenolic hydroxyl groups in which a hydroxyl group is directly bonded to a benzene ring and primary hydroxyl groups introduced from an alkanolamine, and essentially A resin that does not have primary or secondary amino groups.

Component (B-2) is a resin (B-1) having two or more phenolic hydroxyl groups in one molecule, a polyglycidyl compound and an alkanolamine, if necessary in the presence of a catalyst and a solvent. It can be obtained by reacting at a temperature of 30 to 300 ° C, preferably 70 to 180 ° C.

As the resin (B-1) having two or more phenolic hydroxyl groups in one molecule and the polyglycidyl compound, the same ones as described above can be used. As the alkanolamine, it is preferable to use at least one compound selected from the compounds described in (1) to (6) exemplified in the description of the component (A-2).

Further, in the production reaction of the component (B-2), the following components are further coexisted as long as the reaction product has a total of two or more phenolic hydroxyl groups and alkanolamine-derived hydroxyl groups per molecule. It is also possible. For example, polyols such as dimer diol, ethylene glycol, propylene glycol, butylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; polyester polyols such as polycaprolactone; polycarboxylic acids; polyisocyanates. A monoisocyanate; an alicyclic oxirane-containing compound and the like may be present together. Further δ-4-
Graft polymerization of caprolactone, acrylic monomer, etc. can be used.

Component (C) : a compound having two or more glycidyl groups in one molecule based on a glycidylamino group represented by the following formula (III), which is directly bonded to a carbon atom of an aromatic ring.

[0162]

[Chemical 33]

[Wherein R is a hydrogen atom or a glycidyl group] The component (C) has an aromatic ring and a glycidyl group in one molecule, and the glycidyl group is a glycidyl group represented by the above formula (III). It is introduced in the form of an amino group and the nitrogen atom (N) in formula (III) is directly bonded to the carbon atom of the aromatic ring.

The component (C) is generally prepared by dehydrohalogenating (condensing in the presence of a catalyst such as an alkali metal hydroxide aqueous solution) with epihalohydrin (preferably epichlorohydrin) at the amino group (-NH ₂ ) of the aniline derivative. ) It can be obtained by reacting. This reaction can be carried out in a manner known per se.

In this reaction, theoretically, in molar ratio,
When 1 mol of epihalohydrin is reacted with 1 mol of the amino group, one glycidyl group is introduced into the amino group, and one hydrogen atom remains bonded to the amino group. This hydrogen atom corresponds to the hydrogen atom as R in the above formula (III). Then, in this reaction, when 2 moles of epihalohydrin are reacted, two glycidyl groups are introduced into the amino group.
Glycidyl groups correspond to R in formula (III). Here, "aniline derivative" has a broad meaning,
Is intended to include one or a compound having two or more benzene rings or directly bonded to an amino group on the ring carbon atom of an aromatic ring such as naphthalene ring (-NH _2), for example, aniline, o- toluidine, m- Toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, p-cresidine, 2,4-xylidine,
Monoaniline derivative in which one amino group (—NH ₂ ) is directly bonded to a ring carbon atom of a benzene ring or naphthalene ring such as 3,4-xylidine, o-anisidine, p-anisidine, and naphthylamine: phenylenediamine, 2, 4-toluylene diamine, diaminobenzanilide, dianisidine, diaminodiphenyl ether, 3,5-diaminochlorobenzene, 3,3'-dimethylbenzidine, 1,5
- dianiline derivatives naphthylenediamine a benzene ring or a naphthalene amino group to the carbon atom of the ring such as an amine (-NH ₂₎ is bonded two directly; and the like.

In addition to the above monoaniline derivative and dianiline derivative, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; organic acids such as paratoluenesulfonic acid and oxalic acid; and metal salts such as zinc acetate are used as catalysts to form aldehydes. Kinds (eg formaldehyde, acetaldehyde, etc.)
Also, a polycondensate in which a plurality of aromatic rings are bound by a methylene group or the like by reacting a ketone or a ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be used as the aniline derivative. This polycondensate preferably has an aromatic ring repeating unit in the range of 2 to 40, particularly 2 to 20. Specific examples of such polycondensates include diaminodiphenylmethane, 3,3-dimethyl-4,4-diaminodiphenylmethane, 3,3-diethyl-4,4-diaminodiphenylmethane, and the like. It is not limited to only.

Part of the glycidyl group of the component (C) obtained as described above is a phenol such as bisphenol A, bisphenol F, phenylphenol, nonylphenol or phenol; dimer acid, stearic acid, oleic acid, It may be modified by reacting one or more selected from higher fatty acids such as soybean oil fatty acid; organic acids such as acetic acid, formic acid, hydroxyacetic acid; alcohols such as alkyl alcohol, cellosolve and carbitol;
Of these, phenols and higher fatty acids are particularly preferable. For this modification, it is preferable to use a catalyst such as zinc borofluoride or tetramethylammonium chloride.

The component (C) used in the present invention has a number average molecular weight of about 200 to 8,000, especially 500 to 5,000 as measured by a vapor pressure permeation method, and an epoxy equivalent of 100 to 2,000, especially 100 to 2,000. It is preferably in the range of 600. As the component (C), it is possible to use a commercially available product, for example, GAN [Nippon Kayaku Co., Ltd., N, N-diglycidylaniline], GOT.
[N, N-diglycidyl-O-toluidine manufactured by Nippon Kayaku Co., Ltd.], MY720 [manufactured by Nippon Ciba Geigy, N, N,
N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane], MY722 [manufactured by Nippon Ciba Geigy,
N, N, N ', N'-tetraglycidyl-3,3'-dimethyl 4,4'-diaminodiphenylmethane] and the like.

Resin composition for water-based coating: The composition for water-based coating of the present invention has the above-mentioned (A), (B) and (C).
It contains a component as a main component, for example,
It can be prepared by neutralizing the basic group of the component (A) with an acid and dispersing this together with the components (B) and (C) in an aqueous medium. The component (A) may be neutralized at any time before, during or after mixing the above components. When the component (B) has a basic group, it may be neutralized in the same manner as the component (A). There is no particular restriction on the mixing order of the above components, and the components can be mixed in any order, for example, all components are mixed and dispersed at once; (A) and (B) components are mixed and then (C).
Mixing the components; mixing components (A) and (C) and then component (B); mixing components (B) and (C) and then component (A), etc. Can be done in any way. The neutralizing agent that can be used for neutralizing the component (A) is preferably, for example, formic acid, acetic acid, lactic acid, butyric acid, protic acid and the like.

The compounding ratio of the above components (A), (B) and (C) is not particularly limited and can be varied within a wide range depending on the application of the resin composition, etc. Based on the total solid content weight, the component (A) is 10 to 60.
% By weight, in particular 15-50% by weight, and (B) and (C) components in total 90-40% by weight, in particular 85-50%.
It is preferably in the range of% by weight. Moreover, per 1 mol of the total of the hydroxyl groups contained in the components (A) and (B),
Component (C) has a glycidyl group (epoxy group) of 0.3 to
It is preferably in the range of 3, especially 0.6 to 2 mol.

The resin composition for water-based coating composition of the present invention comprises, in addition to the above-mentioned components (A), (B) and (C), if necessary, an extender pigment, an anticorrosive pigment, a dispersant, an cissing inhibitor,
A hardening accelerator etc. can be contained. Of these, the pigment is preferably blended as a pigment dispersion paste (Y) described below.

Pigment dispersion paste (Y): The pigment dispersion paste (Y) is prepared by mixing and dispersing at least one resin selected from the component (A) and a pigment (coloring pigment, extender pigment, anticorrosion pigment, etc.). In addition, a plasticizer, a wetting agent, a surfactant, a defoaming agent, or the like may be added if necessary.

Mixing and dispersion of each of these components can be carried out by using a ball mill, a sand mill, a Crowles dissolver, a continuous disperser or the like. For example, the pigment is dispersed in a desired size and the above (A) is used. Wetting with the components is preferred. The particle size of the dispersed pigment is preferably 10 microns or less (about 6 to 8 in Hermann grind gauge). This dispersion is preferably performed in water. In this case, it is preferred that a part or all of the basic groups in the component (A) be neutralized with the acidic compound as described above and protonated to prepare an aqueous dispersion. The amount of the acidic compound added is such that the neutralization value of these resins is usually 5 to 200, particularly 10 to 10 in terms of KOH (mg / g).
It is preferable to adjust it to be within the range of 150. The water content in the aqueous liquid separation of the pigment-dispersed paste (Y) is not particularly limited, but is usually preferably in the range of about 20-80% by weight.

There are no particular restrictions on the type of the above-mentioned pigment in the pigment dispersion paste (Y). For example, coloring pigments such as carbon black, titanium white, lead white, lead oxide and red iron oxide; antimony oxide, zinc oxide and basic carbonic acid. Extending pigments such as lead, basic lead sulfate, barium carbonate, calcium carbonate, aluminum silica, magnesium carbonate, magnesium silica, clay, talc; strontium chromate, lead chromate, basic lead chromate, red lead, silicic acid. lead,
Examples thereof include anticorrosion pigments such as basic lead silicate, lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silicochromate, yellow lead, cyanamide lead, calcium leadate, lead suboxide, and lead sulfate. Usually, the mixing ratio of these pigments and the component (A) is preferably in the range of 2/1 to 7/1 in terms of solid content weight ratio.

The resin composition for aqueous paints of the present invention is adjusted by a method known per se, for example, by neutralizing the resin composition with an acid component as described above, diluting it with water, and adjusting it to a desired concentration. By doing so, a cationic electrodeposition paint can be obtained.

The cationic electrodeposition coating composition prepared by using the resin composition for water-based coating composition of the present invention can be subjected to cationic electrodeposition coating on a suitable conductive substrate (subject to be coated) by an ordinary method. The membrane is, for example, 80 to 250 ° C., preferably 12
It can be heat-cured at a temperature of 0 to 160 ° C.

Particularly, when it is desired to sufficiently cure the electrodeposition coating film of the cationic electrodeposition coating composition using the resin composition for water-based coating composition of the present invention at a low temperature of 160 ° C. or lower, a lead compound, a zirconium compound, It is effective to add one or more catalysts selected from cobalt compounds, aluminum compounds, manganese compounds, copper compounds, zinc compounds, iron compounds, chromium compounds, nickel compounds, tin compounds and the like. Specific examples of these metal compounds include, for example, chelate compounds such as zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, and manganese acetylacetonate; compounds having a β-vidroxyamino structure and lead (II) oxide. Killing reaction product; lead 2-ethylhexanoate, lead naphthenate, lead octylate, lead benzoate, lead acetate, lead lactate, lead formate, lead glycolate, zirconium octylate, and other carboxylates.

The metal content of the above metal compound is generally 10% by weight or less, preferably 0.5 to 0.5%, based on the resin solid content.
It can be used in an amount such that it is 5% by weight.

The resin composition for aqueous paints of the present invention comprises (A)
In the resin skeleton of the component, there is a clear distinction (localization) between the hydrophilic part due to the acid-neutralized tertiary amino group and hydroxyl group and the other hydrophobic part (eg epoxy group part). Therefore, there is an advantage that the component (B) and the component (C) can be easily dispersed. Further, in the resin composition for water-based paints of the present invention, the epoxy group of the component (C) is a hydroxyl group introduced by a phenolic hydroxyl group or an alkanolamine in the component (B) and a hydroxyl group in the component (A). The resulting coating film has almost no shrinkage stress, and the smoothness and corrosion resistance are remarkably improved because the weight loss upon heating is extremely small. Furthermore, since the component (A) has excellent dispersibility, it can be used in a small amount, and as a result, the basic concentration of the resin composition for water-based coatings becomes low, resulting in poor acid resistance and corrosion resistance of the coating film. Be improved.

The method for forming an electrodeposition coating film on a conductive substrate using a cationic electrodeposition coating composition based on the composition of the present invention is not particularly limited, and ordinary cationic electrodeposition coating conditions are used. Can be done. For example, a pigment, a curing catalyst, and other additives are added to the electrodeposition coating as needed, and the bath concentration (solid content concentration) is 5 to 40% by weight, preferably 10 to 25% by weight, and the bath pH is 4 to 8, Preferably 5
A cationic electrodeposition bath within the range of 7 is prepared. At this time, it is preferable to use the object to be coated as a cathode and the stainless steel or carbon plate as the anode. The electrodeposition coating conditions are not particularly limited, but generally bath temperature: 20 to 3
0 ° C., voltage 100 to 400 V, preferably 200 to 30
0 V, current density: 0.013 A / dm ² , energization time: 1
The electrode area ratio (A / C): 2/1 to 1/2, the distance between the electrodes: 10 to 100 cm, and electrodeposition in a stirring state are preferable.

The above cationic electrodeposition coating composition of the present invention comprises (A)
Since the component is a cationic resin, the component (B) is a low basic resin, and the component (C) is a non-basic resin, water dispersibility, storage stability, bath stability, corrosion resistance on untreated steel sheet, Excellent smoothness. The electrodeposition coating composition can be applied to a base material having a conductive metal at least on the surface. Examples of the substrate include, but are not limited to, automobile bodies, home appliances, office equipment, building materials, and structures.

[0182]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. All parts and% are, as a general rule, parts by weight and% by weight.

I. Sample preparation 1. Production Examples of Components (A) and (B) Components were produced by reacting based on the components and blending amounts shown in Table 1. Of these, in Production Examples 1 to 4, only the component (A),
Production Examples 5 to 7 are examples in which the components (A) and (B) are produced simultaneously.

In Production Examples 1 to 4, a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was attached to Table 1.
The solvent shown in and the components (A-1-1) to (A-3) are charged, gradually heated with mixing and stirring, and reacted at 150 ° C., and it is confirmed that the epoxy equivalent becomes 0,
The component (A) was obtained.

In Production Examples 5 to 7, a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was used, and Table 1 was used.
Is charged and the components (A-1-1) to (A-2) are charged, gradually heated while mixing and stirring, and allowed to react at 120 ° C., and the epoxy equivalent of the first stage end point shown in Table 1 is obtained. After confirming that, add other ingredients,
It was made to react at 0 degreeC, it confirmed that the epoxy equivalent became 0, and the mixture of (A) and (B) component was obtained.

[0186]

[Table 1]

[0187]

[Table 2]

In Table 1, BREN-S: brom-modified novolac phenol polyglycidyl ether having an epoxy equivalent of 285 (Nippon Kayaku Co., Ltd.)
DEN-438: Novolac phenol polyglycidyl ether with an epoxy equivalent of 180 (Dow Chemical Japan Co., Ltd.)
EOCN-102S: cresol novolatsk phenol polyglycidyl ether having an epoxy equivalent of 215 (Nippon Kayaku Co., Ltd.)
Polypropylene glycol diglycidyl ether: Epoxy equivalent 380 EHPE-3150: Alicyclic epoxy resin with epoxy equivalent 180 (manufactured by Daicel Chemical Industries, Ltd.) Bisphenol A glycidyl ether: Epicoat 8
28 (manufactured by Yuka Shell Epoxy Co., Ltd.) (* 1) A-2-1: thermometer, stirrer, reflux condenser,
Add 285 stearic acid to a reaction vessel equipped with a water separator.
Parts, 104 parts of hydroxylethylaminoethylamine, and 80 parts of toluene are charged, and gradually heated with mixing and stirring to remove toluene as necessary and 18 parts of reaction water are separated and removed while raising the temperature, and then residual toluene is removed under reduced pressure. An amino compound obtained by Amine value 15
0, freezing point 76 ° C.

(* 2) A-3-1: A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 105 parts of diethanolamine, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, and bisphenol. A product obtained by adding 456 parts of A and 330 parts of ethylene glycol monobutyl ether and reacting at 150 ° C. until the residual amount of epoxy groups becomes 0. Solid content 80%.

(* 3) A-3-2: 170 parts of phenylphenol and 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190 are placed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Bisphenol A 456 parts, tetramethylammonium chloride 0.2 and ethylene glycol monobutyl ether 3
A product obtained by adding 46 parts and reacting at 150 ° C. until the residual amount of epoxy groups becomes 0. Solid content 80%.

(* 4) A-3-3: A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was equipped with 280 parts of oleic acid, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, and bis. Phenol A4
A product obtained by adding 56 parts, 0.2 parts of tetramethylammonium chloride and 374 parts of ethylene glycol monobutyl ether and reacting at 150 ° C. until the residual amount of epoxy groups becomes 0. Solid content 80
%.

(* 5) A-3-4: A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 370 parts of the amine compound (A-2-1), and an epoxy equivalent of 1
90 bisphenol A diglycidyl ether 760
Part, 456 parts of bisphenol A and 397 parts of ethylene glycol monobutyl ether, and the reaction product is obtained by reacting at 150 ° C. until the residual amount of epoxy groups becomes zero. Solid content 80%.

(* 6) A-3-5: A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 0.2 part of tetmethylammonium chloride and 190 equivalents of bisphenol A diglycidyl ether. 760
And 684 parts of bisphenol A and 361 parts of ethylene glycol monobutyl ether are added and reacted at 150 ° C. until the residual amount of the epoxy group becomes 0. Solid content 80%.

2. (B) Component Production Example (B-1): In a flask equipped with a stirrer, a thermometer and a reflux condenser, SHIONOL BRG-556 (manufactured by Showa High Polymer Co., Ltd., trade name, novolak polyphenol, phenolic hydroxyl group equivalent) 100 parts of 122) and 25 parts of ethylene glycol monobutyl ether were charged and heat-dissolved to obtain (B-1).

(B-2): A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with SYONOL CRG-9.
51 (manufactured by Showa High Polymer Co., Ltd., trade name, Gresol Novolac polyphenol, phenolic hydroxyl equivalent 110)
0 parts and ethylene glycol monobutyl ether 25
Parts were charged and heated to dissolve to obtain (B-2).

(B-3): The above-mentioned A-3-1 was directly used as (B-3).

(B-4): The above-mentioned A-3-5 was directly used as (B-4).

3. Production Example (C-1 ) of Component (C): 100 parts of N, N-diglycidyl-O-toluidine (GOT, manufactured by Nippon Kayaku Co., Ltd.) was added to a flask equipped with a stirrer, a thermometer and a reflux condenser. 25 parts of ethylene glycol monobutyl ether was charged and dissolved by heating to obtain (C-1). The solid content was 80% and the epoxy equivalent was 117.

(C-2): N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (Nippon Ciba Geigy Corp.) was placed in a flask equipped with a stirrer, a thermometer and a reflux condenser. (MY720) (100 parts) and ethylene glycol monobutyl ether (25 parts) were charged and dissolved by heating to obtain (C-2). The solid content was 80% and the epoxy equivalent was 115.

(C-3): N, N, N ', N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphine was added to a flask equipped with a stirrer, a thermometer and a reflux condenser. Enylmethane (manufactured by Ciba-Geigy Japan, MY722) 1
00 parts and ethylene glycol monobutyl ether 2
5 parts were charged and heated to dissolve to obtain (C-3). The solid content was 80% and the epoxy equivalent was 125.

(C-4): N, N, N ', N'-tetraglycidyl-m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Inc.) in a flask equipped with a stirrer for comparison, a thermometer and a reflux condenser. , TETRA-X) 10
0 parts and ethylene glycol monobutyl ether 25
Parts were charged and heated to dissolve to obtain (C-4). The solid content was 80% and the epoxy equivalent was 101.

(C-5): For comparison, a flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 250 parts of MDI (4,4'-diphenylmethane diisocyanate), dissolved by heating at 80 ° C, and then heated. ,
80 parts of a mixture of 130 parts of 2-ethylhexyl alcohol and 134 parts of diethylene glycol monoethyl ether.
Keeping at ℃, add over 60 minutes, then add 12
After raising the temperature to 0 ° C and confirming that the absorption derived from the isocyanate group has disappeared by IR (infrared analysis), ethylene glycol monobutyl ether 128.5
Parts were blended to obtain (C-5). Solid content 80%,
The blocked isocyanate equivalent was 257.

II. Examples and Comparative Examples The above samples were mixed and dispersed based on the compounding amounts shown in Table 2 below to prepare compositions of the present invention and compositions for comparison.

[0204]

[Table 3]

In Table 2, 1) Mixing and dispersion of each component was performed using a disper.

2) The blending amount of each component includes a solvent and the like.

3) The name of the component A is as described in the production examples in Table 1, of which A-5 to A-7 also include the component B.

4) The component (B-5) of Comparative Example 1 was a compound containing no phenol group and having a high amine value. The amine compound was placed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. (A-2-1) 371 parts, diethanolamine 105 parts, epoxy equivalent 190 bisphenol A diglycidyl ether 950 parts, bisphenol A 342 parts and ethylene glycol monobutyl ether 442 parts were added, and the residual amount of the epoxy group was 150 ° C. 0
The solid content was 80%.

5) (A-8) of Comparative Example 2 is (A-1-
The component (A), which does not contain the components 1) and (A-1-2), is manufactured by the following method.

A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with diethanolamine 21.
Parts, 950 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 340 parts of polypropylene glycol diglycidyl ether having an epoxy equivalent of 340, and 456 parts of bisphenol A are charged and gradually heated with mixing and stirring to react at 120 ° C. Equivalent is 98
After confirming that it was 0, 492 parts of ethylene glycol monobutyl ether was added and maintained at 100 ° C., and 158 parts of diethanolamine and the amino compound (A-2-
1) 43 parts was added and reacted until the increase in viscosity stopped, to obtain a comparative resin (A-8) having a solid content of 80%, an amine value of 57, and a primary hydroxyl group equivalent of 532.

6) (C-4) in Comparative Example 3 is the component (C) in which the structure represented by the formula (III) is not directly bonded to the carbon atom of the aromatic ring.

7) In (C-5) of Comparative Example 4, 250 parts of diphenylmethane diisocyanate was charged into a flask equipped with a stirrer, a thermometer and a reflux condenser, heated to 80 ° C. and treated with 2-ethylhexyl alcohol. 1
30 parts and diethylene glycol monoethyl ether 13
The mixture with 4 parts was added dropwise over 60 minutes and then 120
The temperature was raised to 0 ° C., and it was confirmed by IR that the absorption of free NCO groups had disappeared, and then 128.5 parts of ethylene glycol monobutyl ether was added to obtain.

Preparation Example of Pigment Dispersion Paste (Y-1 ) 20 parts of titanium white (Typepec CR93 manufactured by Ishihara Sangyo Co., Ltd.) and 10 parts of carbon (manufactured by Mitsubishi Kasei Co., Ltd.) MA-7) 2 parts, aluminum tripolyphosphate (manufactured by Teikoku Kako Co., Ltd., K White 84) 4 parts, clay (manufactured by Sieglite Chemical Co., Sieglite) 24
Parts, 0.4 parts of acetic acid and 39.6 parts of deionized water were added and kneaded, then 200 parts of glass beads were added and dispersed by a paint shaker, and coarse particles in a particle gauge were 58% and solid content was 58%. To obtain a pigment dispersion paste (Y-1).

Preparation of Electrodeposition Paint 75 parts of the pigment dispersion paste (Y-1) and 333 parts of each emulsion obtained in Table 2 were mixed, and then deionized water 31 was added.
0 part was added to obtain an electrodeposition coating composition having a solid content of 20%.

Performance Test The following are the measurement results of the dispersion particle size and MEQ stability of the resin composition (emulsion) obtained above, and the heating loss and salt spray resistance of the coating film formed using the above electrodeposition coating material. It is summarized in Table 3.

[0216]

[Table 4]

In Table 3, (1) Dispersed particle diameter: the diameter of emulsion (after 12 hours from the production) particles having a solid content of 30% obtained based on the composition in Table 2 above, The measurement was performed using Nanosizer N-4 manufactured by Coulter.

(2) MEQ stability: Emulsion having a solid content of 30% (containing no pigment paste) obtained based on the composition of Table 2 after 12 hours from the production (initial) ) And the one after closed storage at 30 ° C. for 20 days are precisely weighed by about 10 g each, and 1/10 N-KOH
Using an alcoholic solution, titration was carried out by a potentiometric titrator, the amount of acid content was quantified, and MEQ was obtained according to the following formula. Those with little fluctuation after storage relative to the initial value are good.

[0219]

[Equation 1] MEQ (milliequivalent) = [KOH alcoholic solution titer (ml) × 10] / [sample amount (g) × 0.
3) (3) Heat loss: The weight of the zinc phosphate-treated steel sheet is set to W _0, and the above electrodeposition coating is electrodeposited on the treated sheet under the above-described conditions so that the film thickness is 20 μm based on the cured coating film. After coating, the coating film was dried in a vacuum dryer at 80 ° C. for 1 hour under reduced pressure. The weight of this item is W ₁ . Then 1 in the dryer
The weight after heating at 80 ° C. for 30 minutes and baking is W ₂ . These were substituted into the following formula to obtain the weight loss on heating.

[0220]

[Equation 2] Heat loss (%) = [(W ₁ −W ₂ ) / (W ₁ −
W ₀ )] × 100 (4) Salt spray resistance: The above electrodeposition paint was electrodeposited on an untreated steel plate under the above-described conditions so that the film thickness was 20 μm based on the cured coating film, and at 160 ° C. The coating was cured by heating for 10 minutes. This coated plate was subjected to a salt spray resistance test in accordance with JIS Z2871 (time 600 hours), and the clique width (one side) from the cut (linear cut reaching the base) of the coating film was within 2.00 mm, and other than the cut portion. When the blistering of the coating film was 8F (ASTM) or less, it was judged as pass (◯), and when it was more than 8F (ASTM), it was judged as fail (x).

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C25D 13/06

Claims (1)

[Claims] 1. (A) An epoxy resin (A-1-1) having at least 3 epoxy group-containing functional groups represented by the following formula (I) and / or at least 3 glycidyl ether groups per molecule. Novolak phenol type glycidyl ether group-containing resin (A-1-2) represented by the following formula (II), and a primary or secondary amine compound (A having at least one primary hydroxyl group per molecule) (A -2), and a phenol compound having at least one phenolic hydroxyl group per molecule (A-
A resin essentially free of primary or secondary amino groups and epoxy groups, obtained by reacting 3); [In the formula, m is an integer of 2 to 4] [In the formula, R ₁ and R ₂ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aromatic group or a halogen atom, and R ₃ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. Group, an aromatic group, an allyl group or a halogen atom, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₅ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group, An allyl group or a halogen atom, n
Is an integer of 0 to 38, and at least a part of the benzene ring in the formula may be substituted with a naphthalene ring] (B) At least two phenolic hydroxyl groups per molecule, or a phenolic hydroxyl group and an alkanol A resin having a total of at least two primary amine-based hydroxyl groups and essentially free of primary and secondary amino groups; and (C) the following directly bonded to a carbon atom of an aromatic ring: A compound represented by the formula (III) and having two or more glycidyl groups in one molecule based on the glycidylamino group. [Wherein R is a hydrogen atom or a glycidyl group] as a main component, and a resin composition for an aqueous coating composition.