JPH06200193A - Composition for cationic electrodeposition coating - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific cationic resin, a specific epoxy resin, and a specific composition comprising an imidazole compound, etc., as main components, excellent in bath stability, corrosion resistance and weather ability without using a poisonous lead compound, and useful for automobiles, etc. CONSTITUTION:The objective composition contains as main components (A) a cationic resin obtained by reacting (i) an epoxy resin having two or more epoxy group-containing functional groups of the formula (m is 2-4) in the molecule with (ii) an amino compound having a hydroxy group, a secondary amino group and an amide group in the molecule, and (iii) an amino compound having a primary hydroxy group and a primary or secondary amino group in the molecule, (B) an epoxy resin having on the average two or more of epoxy group- containing functional groups in the molecule, each of the functional groups having a structure in which the epoxy group is directly bonded to an alicyclic skeleton and/or a bridge-having alicyclic skeleton, and (C) a composition consisting of one or more kinds components selected from imidazole compounds, benzotriazole compounds and the reaction products of the compounds with an epoxy resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cationic electrodeposition coating composition which is excellent in bath stability, forms a coating film having good curability, corrosion resistance and weather resistance, and does not require the use of toxic lead compounds. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, resin compositions containing a polyamine resin such as an amine-added epoxy resin and a blocked polyisocyanate compound as main components have excellent anticorrosion properties and are widely used in cationic electrodeposition paints. There is. However, the composition has various drawbacks as listed below, and it is strongly desired to eliminate them.

When heated at a high temperature, the blocked polyisocyanate compound is thermally decomposed to generate tars and soot,
Moreover, the top coating film turns yellow, causes bleeding and curing failure, and also has reduced weather resistance, and the coated surface is liable to whiten.

If an organotin compound is added as a catalyst in order to lower the curing start temperature of the coating film, the exhaust combustion catalyst may be poisoned.

When a large amount of a lead compound such as lead hydroxide is blended as a catalyst for accelerating the curing of a coating film or for improving anticorrosion property, it is necessary to take the utmost care in safety and hygiene in handling the lead compound, and moreover, pollution. It is not preferable for prevention.

For the purpose of eliminating the above-mentioned and disadvantages,
The applicant has previously used a resin having a hydroxyl group and a cationic group as a base resin, and having an epoxy group-containing functional group having a structure in which an epoxy group is bonded to an alicyclic skeleton and / or a bridged alicyclic skeleton. A resin composition for a cationic electrodeposition coating using an epoxy resin as a curing agent has been proposed (JP-A-2-2).
55874 publication). The use of such a curing agent eliminated the above-mentioned drawbacks, but, however, the curing reaction between the resin having a hydroxyl group and a cationic group as the base resin and the epoxy resin having the epoxy group-containing functional group as the curing agent was performed. Lead compounds still have to be used for promotion, and the above-mentioned drawbacks have not been completely eliminated.

Further, the amine-added epoxy resin as the base resin has a cationic group mainly a tertiary amino group, and therefore has insufficient water dispersibility and requires a large amount of a neutralizing agent (acidic compound). Therefore, there are disadvantages that the pH of the electrodeposition bath is lowered, the anticorrosion preventing ability of the auxiliary equipment is lowered, and the throwing power of the coating is insufficient.

[0008]

The objects of the present invention are as described in the above items 1 to 3 without using a blocked polyisocyanate compound as a curing agent or an organotin compound and a lead compound as a curing catalyst. The defect has been resolved,
It is an object of the present invention to develop a novel composition for cationic electrodeposition coating which has excellent curability and anticorrosion property and can form a coating film having good water dispersibility and throwing power.

Therefore, according to the present invention, the following formula (1) is contained in one molecule of (A).

[0010]

[Chemical 3]

In the formula, m is an integer of 2 to 4, and an epoxy resin (A-1) having at least two epoxy group-containing functional groups represented by is added to one molecule of a hydroxyl group, a secondary amino group and Cationic resin [(A) component obtained by reacting an amino compound (A-2) having an amide group and an amino compound (A-3) having a primary hydroxyl group and a primary or secondary amino group in one molecule ], (B) Epoxy resin having an average of two or more epoxy group-containing functional groups having a structure in which an epoxy group is directly bonded to the alicyclic skeleton and / or the bridged alicyclic skeleton per molecule [(B) component], And (C)
At least one component [component (C)] selected from an imidazole compound, a benzotriazole compound and a reaction product of these with an epoxy resin, and optionally (D) an inorganic bismuth compound [component (D)] Provided is a composition for cationic electrodeposition coating composition, which comprises the composition as a main component.

The present invention will be described in more detail below.

(A) Cationic resin: Component (A-1) : An epoxy group-containing functional group represented by the following structural formula (1) in one molecule, which is used for preparing the component (A) of the present invention. Epoxy resin having at least two.

[0014]

[Chemical 4]

In the formula, m is an integer of 2 to 4, preferably 4.

The epoxy resin (A-1) can be one known per se, for example, JP-A-60-1.
70620, JP-A-62-135467,
JP-A-60-166675, JP-A-60-161
Those described in Japanese Patent Application Laid-Open No. 973, Japanese Patent Application Laid-Open No. 2-265975 and the like can be used. In particular, Japanese Patent Application Laid-Open No. 2-265975, filed by the applicant, describes in detail the composition of the epoxy resin, the manufacturing method, and the like. Therefore, all the descriptions regarding the epoxy resin described in the publication can be directly applied to the above epoxy resin as the component (A) of the present invention. Replace with detailed description.

The above-mentioned component (A-1) also includes the above structural formula (1) in which the residue of the polymerization initiating component, that is, the residue of the active hydrogen-containing organic compound is bonded to the terminal. Examples of the active hydrogen-containing organic compound that is a precursor thereof include alcohols such as aliphatic monohydric alcohols, aromatic monohydric alcohols, and aliphatic or alicyclic polyhydric alcohols; phenols; fatty acids, aliphatics, and fats. Aromatic or aromatic dibasic or polybasic acids; oxy acids; polyvinyl alcohol, polyvinyl acetate partial hydrolysates, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, allyl polyol resin, styrene-allyl Alcohol copolymer resin, alkyd resin, polyester polyol resin,
Polycaprolactone polyol resin; and the like. The compound having active hydrogen may have a structure in which an unsaturated double bond that may be present in the skeleton together with active hydrogen is epoxidized.

The epoxy resin as the component (A-1) is
For example, using the active hydrogen-containing organic compound as an initiator,
The following formula

[0019]

[Chemical 5]

In the formula, m has the above-mentioned meaning, and a compound represented by, for example, 4-vinylcyclohexene-1-oxide is contained alone or in the presence of another compound containing an epoxy group. To form a polyether resin by carrying out ring-opening (co) polymerization with an epoxy group, and then epoxidizing the vinyl group present in the side chain of the resin with an oxidizing agent such as peracids or hydroperoxides. Can be manufactured by.

The compound of the above formula (3) is, for example, the following formula

[0022]

[Chemical 6]

In the formula, m has the above-mentioned meaning, and can be produced by partially epoxidizing vinylcycloalkenes represented by For example,
4-Vinylcyclohexene-1-oxide is obtained, for example, by partially epoxidizing vinylcyclohexene obtained by the dimerization reaction of butadiene with peracetic acid.

The other epoxy group-containing compound which can be copolymerized is not particularly limited as long as it is a compound having at least one epoxy group, but a compound having one epoxy group in one molecule is preferable in production. . Specifically, lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and formulas

[0025]

[Chemical 7] In the formula, n is an integer of 2 to 25, α-olefin epoxide; an oxide of an unsaturated compound such as styrene oxide; allyl glycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Examples thereof include glycidyl ethers of compounds having a hydroxyl group such as phenylglycidyl ether; glycidyl esters of organic acids such as fatty acids; and the like.

The other epoxy group-containing compound further includes an alicyclic oxirane group-containing vinyl monomer having an unsaturated bond, and specific examples thereof include the following.

[0027]

[Chemical 8]

[0028]

[Chemical 9]

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 formula, the divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R ₄ is
For example, a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene,
Examples thereof include ethylethylene and pentamethylene groups. Further, the carbon number represented by R ₅ is 1 to 10
Examples of the divalent hydrocarbon group include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene,

[0031]

[Chemical 10]

Examples thereof include a group.

Further, the following general formula

[0034]

[Chemical 11] In the formula, R ₁₁ and R ₁₂ have the same meanings as described above, and a compound represented by the formula (eg, glycidyl acrylate, glycidyl methacrylate, etc.), and the following formula partially by-produced by partial epoxidation of vinylcyclohexene.

[0035]

[Chemical 12]

A compound having an alicyclic unsaturated group as shown by can be used as another epoxy group-containing compound. Furthermore, 4-vinylcycloheptene (vinyl norbornene) or the like can also be used.

The ring-opening (co) polymerization reaction of an epoxy group, which is carried out in the presence of a compound of the formula (3), for example, 4-vinylcyclohexene-1-oxide alone or in combination with another epoxy group-containing compound, is carried out by reacting an active hydrogen-containing organic compound It is preferable to carry out in the presence of a catalyst. Examples of the catalyst include amines such as methylamine, ethylamine, propylamine and piperazine; organic bases such as pyridines and imidazoles; organic acids such as formic acid, acetic acid and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid. ; Alkali metal alcoholates such as sodium methylate; KO
Inorganic alkalis such as H and NaOH; BF ₃ SnCl ₂ ,
Examples thereof include Lewis acids such as AlCl ₃ and SnCl ₄ or complexes thereof; organometallic compounds such as triethylaluminum and diethylzinc; and the like.

These catalysts are usually present at 0.
It can be used within the range of 001 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 to 100.
Within the range of ° C. This reaction is preferably carried out using a solvent, and as the solvent, a usual organic solvent having no active hydrogen can be used.

[0039] By epoxidizing is then vinyl group directly linked to the carbon atoms of the alicyclic structure of the side chain of the thus obtained polyether resin (ring-opened (co) polymer) (-CH = CH ₂₎ An epoxy resin [(A-1) component] having a functional group represented by the above formula (1) is obtained. The above epoxidation can be carried out using peracids or hydroperoxides. Examples of peracids include peroxy acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, and the like, and as hydroperoxides,
For example, hydrogen peroxide, tert-butyl peroxide, cumene peroxide, etc. can be used.
The epoxidation reaction can be carried out in the presence of a catalyst, if necessary.

The vinyl group is epoxidized based on the compound of the formula (3) (for example, 4-vinylcyclohexene-1-oxide) in the ring-opening (co) polymer to give the above structural formula (1). ) The functional group represented by In this epoxidation reaction, when the alicyclic oxirane group-containing compound and the like coexist as other epoxy group-containing compounds, the vinyl group contained in the compound may also be epoxidized. ) Is different from the functional group shown by.

Whether or not a solvent is used in the epoxidation reaction and the reaction temperature can be appropriately adjusted depending on the equipment used and the physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, at the same time as the epoxidation of the vinyl group in the raw material polymer, the substituent represented by the following formula (6) in the raw material and / or the substituent represented by the above formula (1) is epoxidized. As a result of causing a side reaction with an agent or the like, a modified substituent is generated, and (A-1)
May be mixed in the ingredients.

[0042]

[Chemical 13]

The ratio of these modified substituents contained varies depending on the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the vinyl group, the reaction conditions and the like.

Commercially available products can be used as the component (A-1), and examples thereof include EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.). This is 4
A vinyl group in a ring-opening polymer of -vinylcyclohexene-1-oxide is epoxidized, and its average degree of polymerization is in the range of 15 to 25.

At least two epoxy group-containing groups represented by the formula (1) may be present in one molecule of the component (A-1), and the component (A-1) is preferably 140-1.
It may have an epoxy equivalent weight in the range of 000, more preferably 170-300.

Component (A-2) : An amino compound used in the preparation of the cationic resin (A) and having a hydroxyl group (preferably a primary hydroxyl group), a secondary amino group and an amide group in one molecule.

As such an amino compound (A-2), a compound represented by the following general formula (2) is preferable.

[0048]

[Chemical 14] In the formula, n is an integer of 1 to 6, R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₂ is a carbon which may have a hydroxyl group and / or a polymerizable unsaturated bond. It represents a hydrocarbon group of the number 4 to 36.

The amino compound represented by the above formula (2) is, for example, as shown in the following reaction formula 1, about 1 mol of N-hydroxyalkylalkylenediamine (7) and about 1 mol of carbon atoms of 5 to 37, preferably. It can be produced by adding 8 to 23 monocarboxylic acids (8).

[0050]

[Chemical 15]

In the formula, R ₁ , R ₂ and n have the same meanings as described above.

As the diamine (7) used in this reaction, for example, hydroxyethylaminoethylamine, N-hydroxyethylethylenediamine,
N-hydroxyethyl propylene diamine, N-hydroxyethyl butylene diamine, N-hydroxyethyl pentylene diamine, N-hydroxyethyl hexylene diamine, N- (2-hydroxy) propyl ethylenediamine, N- (2-hydroxy) propyl propylene diamine , N- (2-hydroxy) propyl butylene diamine, N- (2-hydroxy) propyl pentylene diamine, N- (2-hydroxy) propyl hexylene diamine, and the like. Among them, hydroxyethyl aminoethyl amine, N-hydroxy Ethyl propylene diamine is preferred.

As the monocarboxylic acid (8), for example, 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 fatty acid, Mixed fatty acids such as 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, behenic acid And so on. Of these, stearic acid, oleic acid, 12-hydroxystearic acid and mixed fatty acids containing these acids are particularly preferable.

If the alkyl group of R ₁ of the diamine (7) has 3 or more carbon atoms, the reactivity of the hydroxyl group may decrease. Further, when the carbon number of R ₂ of the monocarboxylic acid represented by the above general formula (8) is smaller than 4, improvement in the smoothness of the coating surface is not so desired.

The reaction of N-hydroxyalkylalkylenediamine (7) with monocarboxylic acid (8) is carried out by mixing the two components in an approximately equimolar ratio and using an organic solvent such as toluene or methyl isobutyl ketone in a specified amount. It can be carried out by removing the water produced by the reaction and removing the residual organic solvent by a reduced pressure method or the like.

The amino compound as the component (A-2) is
It is suitable that the amine value (secondary amino group) is generally in the range of 350 to 88, especially 230 to 120, and the hydroxyl value is further preferably in the range of 350 to 44, especially 230 to 60. .

Component (A-3) : An amino compound used in the preparation of the cationic resin (A) and having a primary hydroxyl group and a primary or secondary amino group in one molecule.

The component (A-3) serves to introduce a primary hydroxyl group and a basic group into the cationic resin (A) by reacting with the component (A-1).

Examples of the component (A-3) include the following compounds.

Primary alkanolamines such as monoethanolamine, monopropanolamine, monobutanolamine; N-methylethanolamine, N-ethylethanolamine, diethanolamine, di-n (or is)
o) -Secondary alkanolamines such as propanolamine and dibutanolamine; an adduct of the above-mentioned primary alkanolamine and an α, β-unsaturated carbonyl compound (secondary alkanolamine): for example, monoethanolamine Addition product of N, N-dimethylaminopropyl acrylamide, addition product of monoethanolamine and hydroxyethyl (meth) acrylate, addition product of monoethanolamine and hydroxypropyl (meth) acrylate, monoethanolamine and hydroxybutyl ( Additions with (meth) acrylates; primary and secondary alkanolamines such as hydroxyethylaminoethylamine; at least one compound selected from hydroxyamine, hydroxymethylhydrazine and hydroxyethylhydrazine, and a ketone compound (E.g., dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, dipropyl ketone, etc.) a mixture of (secondary alkanolamine).

Of these, the particularly preferred component (A-3) is N-methylethanolamine, N-ethylethanolamine, diethanolamine, di-n (or is).
o) -Secondary alkanolamines such as propanolamine.

Cationic resin (A) : In addition to the epoxy resin [(A-1) component] described above, an amino compound [(A-
2) component] and an amino compound [(A-3) component] are reacted.

The reaction between the component (A-1) and the component (A-2) is carried out by reacting the secondary amino group in the component (A-2) with the component (A-1) as shown in the following reaction formula 2. It is presumed that this is done between the alicyclic epoxy group in the component. In addition, (A-
The component 3) has a primary or secondary amino group (A-
1) reacting with an epoxy group-containing functional group in the component to give (A-
It seems that primary hydroxyl group and amino group are introduced into the component 1).

[0064]

[Chemical 16]

In the formula, EP represents the skeleton of the epoxy resin. However, in the above formula, only one epoxy group of the epoxy group-containing functional group is shown for simplification, but it is understood that at least one other epoxy group-containing functional group is bonded to EP. Should be. And R ₁ , R ₂ and n have the same meaning as described above.

The cationic resin (A) thus obtained has excellent water dispersibility even with a small amount of the neutralizing agent, as compared with the conventional resin produced by the reaction with the bisphenol type A epoxy resin. , The electrodeposition bath equipment is not easily corroded, the water dispersibility and throwing power are remarkably excellent even at a high pH, and the curability and corrosion resistance of the formed coating film are not deteriorated at all. It has excellent advantages.

(A-1), (A-2) and (A-3)
The reaction ratio of the components is not particularly limited, and can be arbitrarily selected according to the application of the resulting coating resin. However, generally, in the component (A-2), the secondary amino group in the component (A-2) is 0.02 to 0.5 per mol of the epoxy group-containing functional group in the component (A-1). , Particularly preferably used in a ratio of 0.1 to 0.4 mol, and (A-3)
In the component, the primary or secondary amino group in the component (A-3) is 0.4 to 0.98 mol, and particularly 0.9 per mol of the epoxy group-containing functional group in the component (A-1). It is preferable to use it in such a ratio as to fall within the range of 4 to 0.8 mol. further,
The total number of moles of the component (A-2) and the component (A-3) is
It is preferable that the amount is 0.75 to 1.1 mol, particularly 0.8 to 1.0 mol, per 1 mol of the epoxy group-containing functional group of the component (A-1).

(A-1), (A-2) and (A-3)
The reaction temperature of the components is generally 50 to 300 ° C., especially 70 to
A range of 200 ° C is suitable. If necessary, an alcohol-based, ketone-based, ether-based, or other organic solvent may be used in this reaction system. Further, the reaction order of the component (A-2) and the component (A-3) with respect to the component (A-1) is not particularly limited, and, for example, both components may be added at the same time or before and after separately and reacted. it can.

The cationic resin (A) is usually (A-
2) Amino group, amide group and hydroxyl group derived from the component,
It has a primary hydroxyl group and an amino group derived from the component (A-3), and has an amine value of 30 to 150, especially 80 to 130; a hydroxyl group equivalent of 230 to 800, especially 3
00-500; The number average molecular weight is preferably 800 to 70,000, and particularly preferably 1,000 to 50,000. The cationic resin (A) is excellent in water dispersibility, plasticity and compatibility, and has good smoothness on the coated surface. This is (A-2)
It is presumed that it is due to the plasticizing effect of the hydrocarbon chain of R _{2 in} the component and the polarization due to the hydroxyl group. Moreover, the cationic resin (A) does not reduce the corrosion resistance.

The cationic resin (A) can be obtained by reacting the components (A-1) to (A-3) as described above. The components (A-1) to (A-3) may be further reacted. A cationic resin obtained by reacting a phenol compound (A-4) having at least one phenolic hydroxyl group in one molecule can also be used as the cationic resin (A).

Component (A-4) : A phenol compound used in the preparation of the cationic resin (A) and having at least one phenolic hydroxyl group in one molecule.

Specific examples of such a phenol compound (A-4) include bis (4-hydroxyphenyl) -2,2.
-Propane, 4,4'-dihydroxybenzophenone,
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-
Polyhydric phenol compounds such as dihydroxyphenyl) methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenylsulfone, phenol novolac and cresol novolac can give.

Further, phenol, nonylphenol,
Monophenol compounds such as α- or β-naphthol, p-tert-octylphenol, o- or p-phenylphenol can also be used.

In order to form a coating film having a better anticorrosion property, as the component (A-4), particularly bisphenyl A type [bis (4-hydroxyphenyl) -2,2-propane] or bisphenol F is used. It is preferable to use a bisphenol resin such as type [bis (4-hydroxyphenyl) -2,2-methane]. Among the bisphenol resins, particularly, the number average molecular weight is at least 200, preferably in the range of about 800 to about 3000, and 2 or less on average per molecule, preferably 0.8 to 1.2. Those represented by the following formula containing a phenolic hydroxyl group of are suitable.

[0075]

[Chemical 17]

In the formula, q is an average number of 0 to 7, and R
₂₁ represents a residue of an active hydrogen compound.

Examples of the active hydrogen-containing compound which is the precursor of R _{21 in} the above formula include amines such as secondary amines; phenols such as nonylphenol;
Examples thereof include compounds such as organic acids such as fatty acids; thiols; alcohols such as alkyl alcohol, cellosolve, butyl cellosolve, and carbitol; inorganic acids. Among these, the most preferable are dialkanolamine which is a secondary amine having a primary hydroxyl group, nonylphenol, phenylphenol, and monophenol such as phenol. In particular, when a primary hydroxyl group-containing amine is used, curability is improved, and otherwise stability is improved.

In the above formula, R ₂₁ --and-
OH is shown as bonded to each other, but both ends are R ₂₁
It does not matter even if only one of − and −OH is mixed.

As the component (A-4), for example, 1 mol of a bisphenol A diglycidyl ether type polyepoxide having a molecular weight of 200 or more, preferably 380 to 2000, and a molecular weight of 200 or more, preferably 200.
1 mol of a polyphenol of bisphenol A within the range of up to 2000 and a compound having active hydrogen (for example, secondary dialkanolamine, monophenol and the above (A
-2) one or more kinds selected from the component) 1 mol, if necessary, in the presence of a catalyst or a solvent, a temperature of 30 to 300 ° C, preferably 70 to 180 ° C. Can be used. The above reaction molar ratios are merely examples and are not limited to these and can be arbitrarily selected.

Further, as the component (A-4), polyols such as dimer diol, ethylene glycol, propylene glycol, butylene glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; and polycaprolactone. Polyester polyols; 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 Has hydroxyl groups such as ether, methyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether Glycidyl esters of organic acids as fatty acids;; glycidyl ether compound alicyclic oxirane-containing compounds such as those obtained by reacting, (A-4)
It can also be used as an ingredient. Further, such compounds in which δ-4-caprolactone, an acrylic monomer and the like are graft-polymerized can also be used.
In preparing the cationic resin (A) using the component (A-4), the component (A-1) includes (A-2) and (A-).
The method of reacting the component 3) can be performed in the same manner as described above. Further, it is speculated that in the component (A-4), the phenolic hydroxyl group in the component causes a ring-opening reaction with the epoxy group-containing functional group in the component (A-1) to form an ether bond. The reaction ratio of each of these components can be arbitrarily selected according to the intended use of the resulting cationic resin (A) and the like, but in general, per mole of the epoxy group-containing functional group in the component (A-1). , The secondary amino group in the component (A-2) is 0.02 to 0.5 mol, particularly 0.1 to 0.4 mol;
-3) The primary or secondary amino group in the component is 0.3 to
0.98 mol, in particular 0.4 to 0.9 mol; and (A-
It is preferable to use the phenolic hydroxyl group in the component 4) in an amount of 0.02 to 0.4 mol, and particularly 0.1 to 0.3 mol. And, the total of the above-mentioned number of moles of the components (A-2), (A-3) and (A-4) is 0.75 to 1. per mole of the epoxy group-containing functional group in the component (A-1). 5
It is preferably in the range of 0.8 mol to 1.2 mol, especially in the range of 0.8 to 1.2 mol.

The reaction using each of these components can be carried out in the same manner as described above, and the reaction temperature is, for example, 50 to 3
A temperature of 00 ° C., particularly 70 to 200 ° C., is suitable.
The reaction order is not particularly limited, and all the components may be charged at the same time for reaction, or each of the other components may be added to the component (A-1) in any order and the reaction may be sequentially performed. For example, the component (A-1) is first reacted with the component (A-4), and then the components (A-2) and (A-3) are reacted, or with the raw material of the component (A-4). A polyepoxide and a polyphenol are added to the component (A-1) (A-
When the component (2) and / or the component (A-3) is allowed to exist in the system for reacting, the component (A-4) itself and the addition reaction to other components are simultaneously carried out. This is convenient because the manufacturing process of the components can be omitted. Moreover, after excessively blending the component (D) and reacting the component (A-1) with the components (A-2) and (A-3), the unreacted product of the component (A-4) and other Can also be reacted with the polyepoxide of.

The cationic resin (A) using the component (A-4) generally has an amine value of 20 to 150, particularly 35 to 50.
100; hydroxyl equivalent is 300 to 1000, especially 350 to
700; number average molecular weight is 800 to 15,000, especially 10
It is preferably in the range of 00 to 6000.

In the cationic resin (A), (A-
By using the component (A-4) in addition to the components (1) to (A-3), the hydrophobic property and the compatibility with other resin components are further improved. Further, the portions to which the components (A-2) and (A-3) are added have strong hydrophilicity and basicity. Therefore,
When the component (A-4) is used in combination, the hydrophobic part and the hydrophilic part are co-polarized, so that the dispersibility with other resins is extremely excellent.

The component (A-1) can remarkably improve the water dispersibility and throwing power of the resin even if it is contained in the cationic resin (A) of the present invention in a trace amount. Therefore, as the content of the component (A-1) in the cationic resin (A), the component (A-1), the component (A-2) and the component (A-3), and the component (A-4) are used. If it is specified, based on the total amount including it, 0.5-
It is preferably in the range of 95% by weight, preferably 3 to 75% by weight, more preferably 5 to 50% by weight.

In producing the cationic resin (A), the following cationizing agent may be further reacted, if necessary, during or after the production. Examples of such a cationizing agent include primary amines such as methylamine, ethylamine, n-, or iso-propylamine; secondary amines such as diethylamine, dipropylamine, dibutylamine; ethylenediamine, diethylenetriamine, ethylamino. Polyamines such as ethylamine, methylaminopropylamine, dimethylaminoethylamine and dimethylaminopropylamine; and the like. Furthermore, ammonia, hydrazine, N-hydroxyethyl imidazoline compound, etc. can be used together.

It is also possible to use tertiary amines such as triethylamine, triethanolamine, N, N-dimethylethanolamine, N, N-methyldiethanolamine, N, N-diethylethanolamine, N-ethyldiethanolamine and the like. it can. These can be previously protonated with an acid and reacted with an epoxy group to form a quaternary salt.

In addition to the amino compounds described above,
A tertiary sulfonium salt obtained by reacting a salt of a sulfide such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide or thiodiethanol with boric acid, carbonic acid or an organic monocarboxylic acid with an epoxy group may be used. .

Further, a tertiary phosphine such as triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine and triphenylphosphine, and formic acid,
A quaternary phosphonium salt formed by reacting a salt with an acid such as acetic acid, lactic acid or glycolic acid can also be used as a cationizing agent.

The cationic resin (A) can have its basic group protonated with an acidic compound and dissolved or dispersed in water. Examples of the acidic compound that can be used here include water-soluble organic carboxylic acids such as formic acid, acetic acid, glycolic acid and lactic acid. These can be made water-dispersible or water-soluble by reacting with a basic group in the above-mentioned cationic resin (A) to be protonated. The amount of the acidic compound reacted with the cationic resin (A) is preferably within a range in which the reaction product can be stably dispersed or dissolved in water, and is preferably as small as possible, and particularly, the neutralization value is KOH (mg / g Generally 3 to 2 in terms of solid content)
It is preferable that the amount of the compound is 00, particularly 5 to 180, but if a surfactant or the like can be added to uniformly disperse in water and the stability of the dispersion is excellent, neutralization is performed. A value of less than 3 is acceptable. The pH of the aqueous solution or dispersion of the cationic resin (A) is 4 to
It is preferably in the range of 9, particularly 6 to 7.

(B) Epoxy resin : alicyclic skeleton and /
Alternatively, an average of two or more epoxy group-containing functional groups having a structure in which an epoxy group is directly bonded to a bridged alicyclic skeleton per molecule,
It is preferably an epoxy resin having three or more, and is a curing agent component for forming a crosslinked cured coating film mainly by an etherification reaction with the base resin of the above-mentioned component (A).

The epoxy group-containing functional group in the component (B) comprises an alicyclic skeleton and / or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton has 4 to 10 members, preferably 5 members. A 6-membered saturated carbocyclic ring or a condensed ring in which two or more rings are condensed, and the bridged alicyclic skeleton has two carbon atoms constituting the above cyclic or polycyclic ring. A linear or branched C _1-6 (preferably C _1-4 ) alkylene group in between [for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH (C
_{H 3) -, - CH 2} (CH 3) CH 2 -, - C (CH 3) 2 -, -
CH (C ₂ H ₅ ) CH ₂ — and the like] bridge (endmethylene, endoethylene, etc.) is contained therein.

On the other hand, epoxy group

[0093]

[Chemical 18]

Is one of the carbon atoms in the epoxy group directly bonded to a ring carbon atom in the alicyclic skeleton or the bridged alicyclic skeleton [for example, the following formulas (10) and (11)] Or] two carbon atoms of the epoxy group and two adjacent carbon atoms constituting the ring in the alicyclic skeleton or the bridged alicyclic skeleton are common [eg, the following formula: (1
2), (13)] is important.

Specific examples of such an epoxy group-containing functional group include those represented by the following formulas (6) to (9).

[0096]

[Chemical 19]

In the formula, R ₃₁ , R ₃₂ , R ₃₃ , R ₃₅ , R ₃₆ and R
₃₇ , R ₄₀ and R ₄₁ each represent H, CH ₃ or C ₂ H ₅ , and R ₃₄ , R ₃₈ and R ₃₉ each represent H or CH ₃ .

The component (B) used in the present invention is represented by the above formula (1)
1) the epoxy group-containing functional group selected from 0) to (13)
An average of at least 2, preferably 3 or more per molecule,
More preferably, it can have 4 or more.

Of the above, the epoxy group-containing groups represented by the formulas (10) and (11) are preferable, and particularly the following formula (1)
4)

[0100]

[Chemical 20]

And an epoxy group-containing functional group represented by the following formula (15)

[0102]

[Chemical 21]

Epoxy group-containing functional groups represented by are preferred.

The epoxy equivalent and molecular weight of the component (B) used in the present invention are not strictly limited. Although it can be changed depending on the production method and the intended use of the final resin composition, generally speaking, the epoxy equivalent is usually 100 to 2,000, preferably 150 to 500,
More preferably, it can be in the range of 150 to 250, and the number average molecular weight is usually 400 to 100,00.
Suitably, it is in the range of 0, preferably 700 to 50,000, more preferably 700 to 30,000.

The epoxy resin [component (B)] having two or more such epoxy group-containing functional groups in one molecule is described in, for example, JP-B-56-8016 and JP-A-57-47.
365, JP-A-60-166675, JP-A-63-221121, and JP-A-63-23402.
It is described in documents such as Japanese Patent Publication No. 8 and can be used those known per se.

Alternatively, the component (B) having an epoxy group-containing functional group is obtained by a method known per se, and the main production methods thereof are listed below, but the invention is not limited thereto.

First production method: Part of the double bond of an alicyclic compound having two or more carbon-carbon double bonds in one molecule is partially epoxidized, and the epoxy group is subjected to ring-opening polymerization, A method of epoxidizing the double bond remaining in a polymer. Second production method: a method in which an alicyclic compound having two or more epoxy groups in the same portion is subjected to ring-opening polymerization based on the epoxy groups to the extent that all of the epoxy groups are not erased.

Third manufacturing method: a method of polymerizing a compound having an epoxy group-containing functional group and a polymerizable unsaturated bond in the same molecule.

Since the details of these manufacturing methods are described in the above-mentioned Japanese Patent Laid-Open No. 2-255874, the details will be replaced by the description with reference to them.

The above-mentioned component (B) is suitable for applications requiring a high degree of performance such as cationic electrodeposition coatings used for automobile bodies, in which an epoxy group-containing functional group is contained per molecule. It has 3 or more on average, more preferably 4 or more on average, most preferably 5 or more on average, and the epoxy equivalent is preferably 1 or more.
In the range of from 0 to 2,000, more preferably from 150 to 500, especially from 150 to 250, and the number average molecular weight is preferably from 400 to 100,000, more preferably from 700 to 50,000, particularly preferably from 700 to 30,0
It is in the range of 00.

The amount of the component (B) used depends on the type of the component (A) used, and does not impair the stability of the cationic electrodeposition coating composition or the minimum amount necessary for the coating film obtained to be thermoset. It can be appropriately changed within the range of the maximum amount, but generally, the weight ratio of the solid content of the component (B) to the component (A) is 0.2 to 1.0, particularly 0.25 to 0.85, and more desirably. Is preferably selected to be within the range of 0.25 to 0.65.

The composition of the present invention may contain the component (B) partially added to the component (A) in advance.

Component (C) : A catalyst for accelerating the cross-linking and curing reaction between the component (A) and the component (B), which is an imidazole compound, a benzotriazole compound, and a reaction product of these with an epoxy resin. Is at least one or more components selected from

Examples of the above-mentioned imidazole compound include compounds represented by the following formula:

[0115]

[Chemical formula 22]

In the formula, R ₄₀ is a linear or branched C
_{1 to 25} (preferably C _{1 to 17} ) alkyl group or aryl group (especially phenyl group), wherein R ₄₁ and R ₄₂ are each a lower alkyl group which may be substituted with a hydrogen atom, a hydroxyl group or a nitrile group ( For example, methyl, hydroxymethyl, 2-cyanoethyl group) or aralkyl group (for example, benzyl group), and R ₄₃ represents a hydrogen atom or a lower alkyl group optionally substituted with a hydroxyl group (for example, hydroxymethyl group). Specifically, for example, they are commercially available from Shikoku Kasei Kogyo Co., Ltd. under the trade names of series such as Curezor OR, Curezol CN, Curezol CNS, Cuizazole AZINE, Curezol OK, and Curezol HZ. The following are mentioned as particularly preferable ones. That (in parentheses is a trade name of Shikoku Chemicals Co., Ltd.).

[0117]

[Chemical formula 23]

[0118]

[Chemical formula 24]

Examples of the benzotriazole compound include those represented by the following formula

[0120]

[Chemical 25]

In the formula, R ₄₄ and R ₄₅ are each a hydrogen atom or a linear or branched C _1-10 (preferably C
_{1 to 6} ) representing an alkyl group are included, and particularly 1,2,3-benzotriazole in which R ₄₄ and R ₄₅ in the above formula (17) are hydrogen atoms is preferable.

Further, in the above formula (16), an imidazole compound in which R ₄₀ is a hydrogen atom and the above formula (1)
In the benzotriazole compound of 7), the active hydrogen of the secondary amino group can react with the epoxy group of the epoxy resin to form an adduct, and such a reaction product is also the component (C) of the present invention. Can be used as
Then, as the epoxy resin capable of forming an adduct, for example, a bisphenol type, a phenol novolac type, a gresol novolac type, and an aliphatic type epoxy resin having at least one epoxy group in one molecule are mentioned. Those having a number average molecular weight in the range of about 300 to about 2,000 are suitable.

The reaction ratio of the epoxy resin to the imidazole compound or the benzotriazole compound is such that the epoxy group of the latter is 0.3 to 1 per secondary amino of the former.
It can be one.

As the component (C), the above-mentioned imidazole compound, benzotriazole compound or a reaction product of these with an epoxy resin may be used alone or in combination of two or more kinds. The amount used can be varied over a wide range depending on the types of the components (A) and (B) and other conditions.
In the case of the imidazole compound and the benzotriazole compound, based on the total amount of both components (A) and (B), generally 0.1 to 10% by weight, particularly 0.2 to 5% by weight, and In the case of a reaction product with an epoxy resin, a range of generally 0.3 to 30% by weight, particularly 1 to 15% by weight is suitable.

(D) Inorganic bismuth compound : The inorganic bismuth compound is not an essential component in the composition of the present invention, but is useful for further improving the corrosion resistance of the coating film formed from the composition of the present invention. Specifically as the inorganic bismuth compound that can be used, for example, basic bismuth carbonate,
Examples thereof include bismuth carbonate oxide, bismuth nitrate, bismuth nitrate hydroxide, basic bismuth nitrate, bismuth oxide, bismuth hydroxide and bismuth sulfate. Of these, bismuth hydroxide is particularly preferable. The blending amount of the component (D) is not strict and can be arbitrarily selected according to the purpose, but with respect to the total amount of the component (A) and the component (B),
Generally, the amount of metal is preferably 16% by weight or less, more preferably 1 to 10% by weight.

Cationic electrodeposition coating composition : The cationic electrodeposition coating composition of the present invention may be, for example, the above-mentioned (A),
It can be prepared by using the components (B) and (C) as essential components, and optionally using the component (D) and dissolving or dispersing them in an aqueous medium.
More specifically, first, the components (A) and (B) are mixed and then dispersed in an aqueous medium, and then the component (C) and, if necessary, the component (D), and further carbon black. , Titanium white, red iron oxide, and the like, extender pigments such as clay and talc, and other additives (for example, dispersants, cissing inhibitors, etc.) and the like.

The resin composition for cationic electrodeposition coating composition of the present invention can be applied by cationic electrodeposition coating on a conductive substrate. The thickness of the coating film is not particularly limited, but in general,
The range of 3 to 200 μ is suitable based on the cured coating film,
The coating film is, for example, 70 to 250 ° C., preferably 120.
It can be heat-cured at a temperature between ℃ and 160 ℃.

The cationic electrodeposition coating of the cationic electrodeposition coating composition of the present invention can be carried out by a method known per se. For example, the solid content in the bath is adjusted to 5 to 40% by weight, preferably 10 to 25% by weight and the pH is adjusted to 5 to 8, preferably 5.5 to 7, and the bath temperature is set to 20 to 35%.
C, preferably 25 to 30 C; current density (DC current)
0.005 to ^{2 A} / cm ² , preferably 0.01 to 1 A /
cm ² ; voltage 10 to 500 V, preferably 100 to 30
0V; and energizing time 0.5 to 5 minutes, preferably 2 to
It can be performed under the condition of 3 minutes.

After electrodeposition coating, the article to be coated can be pulled up from the electrodeposition bath and washed with water, and then the water contained in the electrodeposition coating film can be removed by a drying means such as hot air.

The electrodeposition coating film thus formed using the resin composition for cationic electrodeposition coating composition of the present invention can be cured by heating as described above.

Next, the present invention will be described more specifically by way of examples. In the examples, "part" is "part by weight" and "%" is "% by weight".

[0132]

Example I. Production Example 1. Amino compound (A-2) (A-2-): 285 parts of stearic acid in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a water separator.
104 parts of hydroxyethylaminoethylamine and 80 parts of toluene were charged, and gradually heated with mixing and stirring to remove toluene as needed, and 18 parts of reaction water was separated and removed while raising the temperature, and then residual toluene was removed under reduced pressure. Then, an amino compound (A-2-) having an amine value of 150 and a freezing point of 76 ° C. was obtained.

(A-2-): In a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a water separator, 288 parts of tall oil fatty acid having an acid value of 195, 104 parts of hydroxyethylaminoethylamine and toluene. After charging 80 parts and gradually heating while mixing and stirring to remove toluene as necessary, 18 parts of reaction water was separated and removed while increasing the temperature,
The residual toluene was removed under reduced pressure to obtain an amino compound (A-2-) having an amine value of 149 and a freezing point of 45 ° C.

(A-2-): 300 parts of 12-hydroxystearic acid, 104 parts of hydroxyethylaminoethylamine and 80 parts of toluene were placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a water separator. Charge
Gradually heating while mixing and stirring to remove toluene as needed, 18 parts of water of reaction was separated and removed while increasing temperature, and then residual toluene was removed under reduced pressure to obtain an amine value of 148,
An amino compound (A-2-) having a freezing point of 69 ° C. was obtained.

2. Phenol compound (A-4) (A-4-): Diethanolamine 1 was added to a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
05 parts, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts of bisphenol A and 330 parts of ethylene glycol monobutyl ether were added and reacted at 150 ° C. until the residual amount of epoxy groups became 0, and the solid content was 80%. (A-4-) of was obtained.

(A-4-): In a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 170 parts of phenylphenol, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts of bisphenol A, tetra. Methylammonium chloride 0.2
Parts and ethylene glycol monobutyl ether 346
Parts were added, and the mixture was reacted at 150 ° C. until the residual amount of epoxy groups became 0, to obtain (A-4-) having a solid content of 80%.

(A-4-): 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 bisphenol A456.
Parts, 0.2 parts of tetramethylammonium chloride and 374 parts of ethylene glycol monobutyl ether, and reacted at 150 ° C. until the residual amount of epoxy group becomes 0,
(A-4-) having a solid content of 80% was obtained.

3. Cationic resin (A) (A-): EHPE-3150 (epoxy equivalent 180 manufactured by Daicel Chemical Industries, Ltd.) 900 in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
Parts, 200 parts of ethylene glycol monobutyl ether,
315 parts of diethanolamine and amino compound (A-
2-) Charge 370 parts, gradually heat and dissolve while mixing and stirring, and react at 140 ° C., epoxy equivalent is 158
After confirming that the amount was 5, 2052 parts of bisphenol A was added and reacted at 150 ° C. for 5 hours, and it was confirmed that the residual amount of epoxy group was 0.

Then, 420 parts of diethanolamine, 4370 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 740 parts of the amino compound (A-2-) and 2092 parts of ethylene glycol monobutyl ether were added and reacted at 150 ° C. for 5 hours to obtain an epoxy group. After confirming that the remaining amount was 0, a cationic resin (A-) having a solid content of 80%, an amine value of 61, and a primary hydroxyl group equivalent of 540 was obtained. (A-1) Component content rate is 8.6%.

(A-): A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 397 parts of ethylene glycol monobutyl ether and EHPE-315.
0 (Epoxy equivalent 180, manufactured by Daicel Chemical Industries, Ltd.)
900 parts, 370 parts of amino compound (A-2-), 315 parts of diethanolamine and 1651 parts of monophenol compound (A-4-) were added, while mixing and stirring.
The temperature was raised to 150 ° C., and the reaction was continued until the residual amount of epoxy group became zero. Further, 3610 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, bisphenol A
Add 1596 parts, 525 parts diethanolamine and 1433 parts ethylene glycol monobutyl ether,
The reaction was carried out at 150 ° C. until the residual amount of epoxy groups became 0, to obtain a cationic resin (A-) having a solid content of 80%, an amine value of 65 and a primary hydroxyl group equivalent of 455. (A-1) Component content rate 10.4%.

Reactions were carried out in the same manner as A- using the formulations shown in Table 1 below to obtain A- to A-.

[0142]

[Table 1]

II. Examples Example 1 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB) of the A component and the B component.

On the other hand, 13.8 parts of the above resin (A-)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Further, 20 parts of titanium white, 1 part of carbon black, 4 parts of Curezol C ₁₁ Z (manufactured by Shikoku Chemicals Co., Ltd.) and 5 parts of bismuth hydroxide (purity 98%) 5
Parts were added, and the mixture was dispersed by a ball mill for 24 hours, and then deionized water was added to obtain a pigment paste (P-1) having a solid content of 50%.

To 125 parts of the above mixture (AB), 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Then, to this 333 parts of emulsion was added 75.6 parts of the above pigment paste (P-1) and deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 2 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB).

On the other hand, 13.8 parts of the above resin (A-)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Further, 20 parts of titanium white, 1 part of carbon black and 4 parts of QUIAZOL IB2MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) were added, dispersed with a ball mill for 24 hours, and then deionized water was added to prepare a pigment paste having a solid content of 50% ( P-2) was obtained.

To 125 parts of the above mixture (AB), 12.0 parts of a 10% formic acid aqueous solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%. Next, 81 parts of the above pigment paste (P-2) and deionized water were added to 333 parts of this emulsion to give a solid content of 20.
% Of the cationic electrodeposition coating composition was obtained.

Example 3 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB).

On the other hand, 13.8 parts of the above resin (A-)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 4 parts of QUIAZOL 2PZ (manufactured by Shikoku Chemicals Co., Ltd.) and 5 parts of bismuth hydroxide (purity 98%) were added, and the mixture was dispersed in a ball mill for 24 hours, followed by deionized water. By mixing, a pigment paste (P-3) having a solid content of 50% was obtained.

To 125 parts of the above (AB) mixture, 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Then, to 333 parts of this emulsion, 77 parts of the above-mentioned pigment paste (P-3) and deionized water were added to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 4 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB).

On the other hand, 13.8 parts of the above resin (A-)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 4 parts of Cyuazole C ₁₁ Z-CN (manufactured by Shikoku Chemicals Co., Ltd.) and bismuth hydroxide (purity 98
%) And dispersed in a ball mill for 24 hours, and then mixed with deionized water to prepare a pigment paste (P-4) having a solid content of 50%.
Got

To 125 parts of the above mixture (AB), 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Then, to 333 parts of this emulsion, 95 parts of the above pigment paste (P-4) and deionized water were added to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 5 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB).

On the other hand, 13.8 parts of the above resin (A-)
4.4 parts of 0% formic acid aqueous solution was added, and 15 parts of deionized water was added while stirring. Further, 20 parts of titanium white, 1 part of carbon black, 4 parts of 1,2,3-benzotriazole (trade name, manufactured by CVI CHIREST Co., Ltd.), and 5 parts of bismuth hydroxide (purity 98%) were added, and a ball mill was used to obtain 24 parts. After time dispersion, deionized water was added to obtain a pigment paste (P-5) having a solid content of 50%.

To 125 parts of the above mixture (AB), 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Then, 83.2 parts of the above pigment paste (P-5) and deionized water were added to 333 parts of this emulsion to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 6 To 94 parts (75 parts of solid content) of the cationic resin (A-),
EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-vinylcyclohexene-) as a curing agent (component B)
Cyclohexane skeleton with 1-oxide Epoxy resin, 80% of epoxy equivalent 175-195)
31 parts of butyl cellosolve solution (25 parts of solid content) were blended to obtain a mixture (AB).

After dissolving 164 parts of Curezol 2MZ (manufactured by Shikoku Chemicals Co., Ltd.) in 218 parts of methyl ethyl ketone,
Epoxy resin [trade name Epicoat 828
Ciel Chemical Co., Ltd.] After dropping 380 parts over 1 hour,
It hold | maintained at 80 degreeC for 2 hours, and obtained the reaction product (E-1).

On the other hand, 13.8 parts of the resin (A-6) and 18.6 parts of the resin (E-1) were mixed, 4.4 parts of 10% formic acid was added, and 15 parts of deionized water was added while stirring. Was compounded. Further, 20 parts of titanium white, 1 part of carbon black and 5 parts of bismuth hydroxide (purity 98%) were added, dispersed in a ball mill for 24 hours, and then deionized water was added to the mixture to prepare a pigment paste (P-6 having a solid content of 50%). ) Got.

To 125 parts of the above (AB) mixture, 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Subsequently, 73.6 parts of the above-mentioned pigment paste (P-6) and deionized water were added to 333 parts of this emulsion to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 7 110 parts of cationic resin (A-) (75 parts of solid content)
8 of EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd., having a cyclohexane skeleton using 4-vinylcyclohexene-1-oxide, epoxy resin, epoxy equivalent 175 to 195) as a curing agent (component B).
31 parts of a 0% butyl cellosolve solution (solid content: 25 parts) was blended to obtain a mixture (AB).

148 parts of methyl ethyl ketone 1,2,3-
Benzotriazole [Product name CVI Crest Co., Ltd.]
After dissolving 143 parts, 1 part of 228 parts of epoxy resin [trade name of Epicoat 828 Shell Chemical Co., Ltd.] is heated to 85 ° C.
After dropping over a period of time, the reaction product (E-2) was obtained by holding at 85 ° C. for 1 hour.

On the other hand, 13.8 parts of the above resin (A-) and 14.3 parts of the above resin (E-2) were mixed to obtain 10% formic acid 4.4%.
15 parts of deionized water was added with stirring.
Furthermore, 20 parts of titanium white, 1 part of carbon black and 5 parts of bismuth hydroxide (purity 98%) were added, dispersed with a ball mill for 24 hours, and then deionized water was added to obtain a solid content of 50%.
To obtain a pigment paste (P-7).

To 125 parts of the above mixture (AB), 10%
12.0 parts of an aqueous formic acid solution was added, and deionized water was added while stirring to obtain 333 parts of an emulsion having a solid content of 30%.
Then, to 333 parts of this emulsion, 72 parts of the above-mentioned pigment paste (P-7) and deionized water were added, and the solid content was 2
A 0% cationic electrodeposition coating composition was obtained.

III. Performance test results Using the cationic electrodeposition coating composition thus obtained, the bath temperature was set to 3
Adjusted to 0 ℃, 200-300V on zinc phosphate treated steel plate
Was applied for 3 minutes to perform cationic electrodeposition coating, and was taken out of the bath and washed with water, and then heated at 160 ° C. for 30 minutes to cure the coating film (film thickness 15 to 23 μm). The performance test results of the coating film are shown in Table 2 below.

[0167]

[Table 2]

In Table 2, Comparative Example 1 is the pigment paste (P-
In the same manner as in Example 1 except that 4 parts of quinazole C ₁₁ Z in 1) was changed to 2.8 parts of lead hydroxide (lead content of metal 90%) and bismuth hydroxide was removed was used. It is a coating composition manufactured in-line.

In Comparative Example 2, as the component (A), ethylene glycol monobutyl ether 10 was added to a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
0 part, diethanolamine 210 parts, amino compound (A
-2-) 740 parts and bisphenol A 684 parts and epoxy 1140 parts of bisphenol A diglycidyl ether having the above-mentioned equivalent of 190 were charged, and the temperature was raised to 100 ° C. to generate ethylene glycol monobutyl ether 594.
The solid content of 80 parts was confirmed by confirming that the residual epoxy group was 0
%, Amine value 81, primary hydroxyl group equivalent 462, and the same pigment paste as in Comparative Example 1 was used, and otherwise the same as in Example 1.

The test method is as follows.

Particle size: The particle size of the emulsion particles was measured immediately after production and after standing and stored at 30 ° C. for 1 month using Nanosizer N-4 manufactured by Coulter.

Coating state: The coating state was visually evaluated. ◯ means good.

Curability: After wiping the coated surface 10 times with gauze soaked with methyl ethyl ketone, the degree of coloring of the case was observed. Those not markedly colored were marked with ◯.

Impact resistance: Using a DuPont type impact resistance tester, the coated surface is faced up, and a 500 g impact is applied at 30 c.
When the film was dropped from a height of m and the generation of cracks or peeling on the coating film could not be confirmed, it was evaluated as ◯.

Salt spray resistance: This is a salt spray resistance test, in which the coating film is cross-cut so as to reach the substrate, and the test is performed according to JIS Z2371 (5% saline solution is sprayed at 35 ° C.). When the creep width (one side) from the cross-cut part after 1000 hours is within 2 mm,
And

Thread rust resistance: Cationic electrodeposition coating as described above, followed by intermediate coating (known thermosetting intermediate coating mainly composed of polyester resin and melamine resin) (film thickness of about 30 μ) After baking, a top coat paint (a known thermosetting solid color top coat paint containing acrylic resin and melamine resin as a main component) is further applied (film thickness of about 40 μ) to form a coating film on a test plate which is heat-cured. The coating film was cross-cut to reach the substrate.
This was subjected to a salt spray resistance test under the same conditions as the above salt spray resistance for 24 hours, washed with deionized water, and then placed in a container kept at a temperature of 40 ° C. and a relative humidity of 85% for 480 After a lapse of time, it is taken out and the length of the thread rust from the cut portion is measured to determine the maximum length.

Environmental pollution: A paint containing a lead compound, which is a heavy metal and may cause environmental pollution, was marked with X, and a paint containing no lead compound was marked with ◯.

As is clear from the performance test results of the above Examples and Comparative Examples, the cationic electrodeposition coating composition of the present invention is the same as that using a lead compound without using a toxic lead compound. It is a cationic electrodeposition paint that can form a coating film having higher performance and has less safety and health problems.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Takahisa Kasukawa 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. (72) Hiroshi Ichinose 4--17-1, Higashi-Hachiman, Hiratsuka, Kanagawa West Paint Co., Ltd.

Claims (4)

[Claims] 1. (A) The following formula (1) in one molecule: In the formula, m is an integer of 2 to 4, an epoxy resin having at least two epoxy group-containing functional groups (A-
In 1), an amino compound (A-2) having a hydroxyl group, a secondary amino group and an amide group in one molecule, and an amino compound (A-2) having a primary hydroxyl group and a primary or secondary amino group in one molecule (A -3) Cationic resin obtained by reacting (B) An epoxy group-containing functional group having a structure in which an epoxy group is directly bonded to an alicyclic skeleton and / or a bridged alicyclic skeleton is 2 on average per molecule. A cation containing the above-mentioned epoxy resin, and (C) a composition comprising at least one component selected from imidazole compounds, benzotriazole compounds, and reaction products of these with epoxy resins, as a main component. Composition for electrodeposition paint. 2. The cationic resin (A) comprises an epoxy resin (A-1), an amino compound (A-2) and an amino compound (A-3), and at least one phenolic hydroxyl group in one molecule. Phenolic compound (A-
The cationic electrodeposition coating composition according to claim 1, which is a cationic resin obtained by reacting 4). 3. The amino compound (A-2) has the following general formula (2): In the formula, n is an integer of 1 to 6, R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₂ is a carbon which may have a hydroxyl group and / or a polymerizable unsaturated bond. The resin composition for a cationic electrodeposition coating composition according to claim 1 or 2, which is a compound represented by the formula 4 to 36, which represents a hydrocarbon group. 4. A cationic electrodeposition coating composition containing the components (A), (B) and (C) according to claim 1 and a composition comprising (D) an inorganic bismuth compound as main components. Composition.