JPH0633001A - Cationic electrocoating deposition coating composition - Google Patents

Abstract

PURPOSE:To provide the subject new composition composed of a specified composition, excellent in bath stability, dispersibility in water and throwing power and capable of forming a coating film excellent in curability, corrosion resistance and weather resistance without requirement for using a toxic lead compound as a curing catalyst. CONSTITUTION:The objective composition is composed mainly of a composition containing (A) a cationic resin synthesized by reacting (i) an epoxy resin having two or more epoxy-containing functional groups of the formula ((m) is 2 to 4) with (ii) an amino compound having a hydroxyl group in combination with a secondary amino group and an amide group and (iii) an amino compound having a primary hydroxyl group in combination with a primary or secondary amino group, (B) a curing agent composed of an epoxy resin having averagely two or more epoxy-containing functional groups of a structure in which an epoxy group is directly bonded to an alicyclic skeletone or a crosslinked alicyclic skeleton and (C) a curing promotion catalyst composed of a metal compound selected from hydroxids of metal elements of atomic number 25 to 30 or 40 to 42 and metal salts (provided that lead salts are exluded) of organic acids.

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 present applicant has previously made a resin composition for a cationic electrodeposition coating using as an curing agent an epoxy resin 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. Proposed a product (Japanese Patent Laid-Open No. 2-2558)
74 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 lowers, the corrosion preventing ability of the auxiliary equipment lowers, and the throwing power of the coating becomes insufficient.

[0008]

The object of the present invention is to solve the above-mentioned problems (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 present invention is to develop a new cationic electrodeposition coating composition having good curability and corrosiveness, and also good water dispersibility and throwing power. As a result, all the objects were achieved and the present invention was completed.

That is, the present invention provides the following formula (1) in one molecule (A).

[Chemical 3] 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 (B) having 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 per molecule on average of 2 or more. A composition comprising an epoxy resin and (C) at least one metal compound selected from hydroxides of metal elements having an atomic number of 25 to 30 or 40 to 42 and metal salts of organic acids (excluding lead salts). The present invention relates to a cationic electrodeposition coating composition characterized by containing as a main component.

The present invention will be described in more detail below.

The present invention will be described in more detail below.

Component (A-1) : An epoxy resin used in the preparation of the component (A) of the present invention, which has at least two epoxy group-containing functional groups represented by the following structural formula (1) in one molecule.

[0013]

[Chemical 4]

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

The epoxy resin (A-1) may 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, JP-A-2-265975 by the applicant of the present invention describes in detail the composition of the epoxy resin, the manufacturing method and the like. Therefore,
All the descriptions relating to the epoxy resin described in this publication can be applied to the epoxy resin as the component (A) of the present invention as it is.

The above-mentioned component (A-1) includes the above-mentioned structural formula (1) in which the residue of the polymerization initiating component, that is, the active hydrogen-containing organic compound residue 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 divalent or higher aliphatic or alicyclic polyhydric alcohols; phenols, fatty acids, Aliphatic (or alicyclic or aromatic) dibasic acid or polybasic acid; oxyacid; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, 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; Further, the compound having active hydrogen may have a structure in which an unsaturated double bond is epoxidized in the skeleton together with active hydrogen.

The epoxy resin as the component (A-1) is
For example, using the active hydrogen-containing organic compound as an initiator,
4-vinylcyclohexene-1-oxide alone,
Or in the coexistence of this with other epoxy group-containing compounds,
Initiating (co) polymerization with the epoxy group contained in each to form a polyether resin, and then epoxidizing the vinyl group present in the side chain in the resin with an oxidizing agent such as peracids or hydroperoxides. Can be manufactured.

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 an epoxy group, but a compound having one epoxy group in one molecule is preferable in production. Specifically, ethylene oxide, propylene oxide, butylene oxide and the formula:

[0020]

[Chemical 5]

Α-olefin epoxide represented by the formula: n is an integer of 2 to 25; an oxide of an unsaturated compound such as styrene oxide; allyl glycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl. Examples thereof include glycidyl ethers of compounds having a hydroxyl group such as glycidyl ether and phenylglycidyl ether; glycidyl esters of organic acids such as fatty acids.

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.

[0023]

[Chemical 6]

[0024]

[Chemical 7]

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
Examples thereof include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene groups and the like. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ₅ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene,

[0027]

[Chemical 8]

Examples thereof include a group.

Further, the following general formula

[0030]

[Chemical 9]

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

[0032]

[Chemical 10]

A compound having an alicyclic unsaturated group as shown by can also be used as the other 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 4-vinylcyclohexene-1-oxide alone or in combination with another epoxy group-containing compound, uses a catalyst in the presence of an active hydrogen-containing organic compound. It is preferable to carry out. 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. An alkali metal alcoholate such as sodium methylate; an alkali such as KOH or NaOH; a Lewis acid such as BF ₃ SnCl ₂ , AlCl ₃ , SnCl ₄ or a complex thereof; an organometallic compound such as triethylaluminum or diethylzinc; I can give you.

These catalysts usually have a pH of 0.
It can be used in 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.

[0036] 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 [component (A)] having a functional group represented by the above formula (1) is obtained. Epoxidation can be carried out using peracids or hydroperoxides. Examples of peracids include peroxyacid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, and the like.
Further, as the 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 in the ring-opening (co) polymer is epoxidized based on 4-vinylcyclohexene-1-oxide, whereby the functional group represented by the above structural formula (I) is produced. 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. ) 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 apparatus 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 (3) in the raw material and / or the generated substituent represented by the above formula (1) As a result of causing a side reaction with an epoxidizing agent or the like, a modified substituent is generated and may be mixed in the component (A).

[0039]

[Chemical 11]

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

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

It is sufficient that at least two epoxy group-containing functional groups represented by the formula (1) are 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 compound represented by the following general formula (2) is preferable.

[0045]

[Chemical 12]

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
Represents a hydroxyl group and / or a hydrocarbon group having 4 to 36 carbon atoms which may have a polymerizable unsaturated bond.

The amino compound of the above formula (2) is, for example, as shown in the following reaction formula 1, about 1 mol of N-hydroxyalkylalkylenediamine (3) and about 1 mol of C5-C37, preferably. It can be produced by adding 8 to 23 monocarboxylic acids (4).

[0048]

[Chemical 13]

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

As the diamine (3) 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 (4), 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.

When the carbon number of the alkyl group of R ₁ of the diamine (3) is 3 or more, 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 (4) is smaller than 4, the improvement of the smoothness of the coated surface cannot be expected so much.

The reaction of the N-hydroxyalkylalkylenediamine (3) with the monocarboxylic acid (4) is carried out by mixing the both components in an approximately equimolar ratio and using an organic solvent such as toluene or methyl isobutyl ketone in a specified amount. The reaction product water is removed, and the residual organic solvent is removed by a reduced pressure method or the like. The component (A-2) preferably has an amine value (secondary amino group) of generally 350 to 88, particularly 230 to 120, and a hydroxyl value of 350.
It is preferable that it is within the range of -44, especially 230-60.

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) reacts with the component (A-1) to introduce a primary hydroxyl group and a basic group into the cationic resin (A).

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

1. 1. Primary alkanolamines such as monoethanolamine, monopropanolamine, monobutanolamine; N-methylethanolamine, N-ethylethanolamine, diethanolamine, di-n (or is
2. secondary alkanolamines such as o) -propanolamine, dibutanolamine; Addition product of the above-mentioned primary alkanolamine and α, β-unsaturated carbonyl compound (secondary alkanolamine): For example, addition product of monoethanolamine and N, N-dimethylaminopropylacrylamide, monoethanolamine 3. Addition product of hydroxyethyl (meth) acrylate, addition product of monoethanolamine and hydroxypropyl (meth) acrylate, addition product of monoethanolamine and hydroxybutyl (meth) acrylate, etc .; 4. Primary and secondary alkanolamines such as hydroxyethylaminoethylamine; Mixture (secondary alkanolamine) of at least one selected from hydroxyamine, hydroxymethylhydrazine and hydroxyethylhydrazine and a ketone compound (eg, dimethylketone, methylethylketone, methylisobutylketone, dibutylketone, dipropylketone, etc.) .

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-
It is obtained by reacting 1) component] with an amino compound [(A-3) component].

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), for example, 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).

[0061]

[Chemical 14]

In the formula, EP represents the skeleton portion 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, in general, the (A-1) component and the (A-2) component are (A-
1) per mole of the epoxy group-containing functional group in component (A)
-2) It is preferable to use the secondary amino group in the component in an amount of 0.02 to 0.5, particularly 0.1 to 0.4 mol, and the components (A-1) and (A- 3) component is (A
-1) Per mol of the epoxy group-containing functional group in the component,
It is preferable to use the primary or secondary amino group in the component (A-3) in a ratio of 0.4 to 0.98 mol, particularly 0.4 to 0.8 mol. Furthermore, (A-
The total number of moles of the 2) component and the (A-3) component is (A-
1) 0.75 per mol of functional group containing epoxy group
It is preferable to be in the range of 0.1 to 1.1 mol, particularly 0.8 to 1.0 mol.

(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 resin (A) is excellent in water dispersibility, plasticity and compatibility,
The smoothness of the coated surface is also good. It is speculated that this is due to the plasticizing effect of the hydrocarbon chain of R _{2 in} the component (A-2) and the polarization of the hydroxyl group. Moreover, the 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, but 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 is also included.

Component (A-4) : A phenol compound used in preparing 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-dihydroxyphenyl) methane, tetra (4
-Hydroxyphenyl) -1,1,2,2-ethane,
Examples thereof include polyhydric phenol compounds such as 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenyl sulfone, phenol novolac and cresol novolac.

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

[0072]

[Chemical 15]

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 a 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- and -O are attached to both ends of the formula.
H is shown as being bonded to each other, but both ends are R _6-.
Alternatively, even if only one of -OH is mixed, it does not matter.

Further, 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. These 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 and butylene glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and 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) is replaced with (A-
The method of reacting the components 2) and (A-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 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 generally, per 1 mol 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, the primary or secondary amino group in the component (A-3) is 0.3 to 0.98 mol, and particularly 0.4 to 0.9.
It is preferable to use it in a molar ratio of 0.02 to 0.4 mol, particularly 0.1 to 0.3 mol of the phenolic hydroxyl group in the component (A-4). And (A-
2), (A-3) and the total of the above-mentioned number of moles of the component (A-4) is 0.75 to 1.5 moles, especially 0 per mole of the epoxy group-containing functional group in the component (A-1). It is preferably 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 above, and the reaction temperature is, for example, 50 to 3
00 ° C, especially 70-200 ° C, is suitable. The reaction order is not particularly limited, and all the components may be charged at the same time for the 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
When the polyepoxide and the polyphenol, which are the raw materials of the component (A-4), are allowed to exist in the system in which the component (A-1) is reacted with the component (A-2) and / or the component (A-3), Since the production of the component (A-4) itself and the addition reaction to other components are simultaneously performed, the structural step of the component (A-4) can be omitted, which is convenient. Further, the component (D) is blended in an excessive amount, and the component (A-1) and the components (A-2) and (A-3) are added.
After reacting with the component, the unreacted product of the component (A-4) can be reacted with another polyepoxide.

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 resin (A), (A-1) to (A
By using the component (A-4) in addition to the component (-3), hydrophobicity and 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, (A-4)
When the components are 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 the total amount including that, it is 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 can 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. Examples thereof include polyamines such as ethylamine, methylaminopropylamine, dimethylaminoethylamine and dimethylaminopropylamine. Furthermore, ammonia, hydrazine, N-hydroxyethyl imidazoline compound, etc. can be used together.

Further, triethylamine, triethanolamine, N, N-dimethylethanolamine, N, N-
Tertiary amines such as methyldiethanolamine, N, N-diethylethanolamine and N-ethyldiethanolamine can also be used. 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 may be prepared by reacting a salt of a sulfide such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide, thiodiethanol and boric acid, carbonic acid or an organic monocarboxylic acid with an epoxy group.

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 basic group of the cationic resin (A) can be protonated with an acidic compound and dissolved or dispersed in water.

Examples of the acidic compound 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 It is preferable that the number calculated as (solid content) is generally within the range of 3 to 200, particularly 5 to 180, but it is possible to uniformly disperse it in water by adding a surfactant and the like, and If the stability is excellent, the neutralization number of less than 3 is acceptable. The pH of the aqueous solution or dispersion of the cationic resin (A) is preferably 4-9, and more preferably 6-7.

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

That is, the epoxy group-containing functional group in the component (B) is composed of an alicyclic skeleton and / or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton is 4 to 10
Member, preferably a 5- or 6-membered saturated carbocyclic ring or a condensed ring in which two or more of the rings are condensed, and the bridged alicyclic skeleton constitutes the cyclic or polycyclic ring. A linear or branched C _1-6 (preferably C
_1-4) alkylene group [e.g. -CH ₂ -, - CH ₂ CH
_{2 -, - CH (CH 3} ) -, - CH 2 (CH 3) CH 2
_{-, - C (CH 3)} 2 -, - CH (C 2 H 5) CH 2 -
Etc.] containing a ring to which a bridge (endmethylene, endoethylene, etc.) is bonded.

[0091] Directly bonded to a ring carbon atom in an alicyclic skeleton or a bridged alicyclic skeleton [see, for example, the following formulas (6) and (7)]
Alternatively, two carbon atoms of the epoxy group and adjacent two constituting the ring in the alicyclic skeleton or the bridged alicyclic skeleton are adjacent to each other.
Have a common carbon atom [for example, the following formula (8),
(See (9)] is important. Specific examples of such an epoxy group-containing functional group include those represented by the following formulas (6) to (9).

[0092]

[Chemical 16]

In the formula, R ₃₁ , R ₃₂ , R ₃₃ , R ₃₅ , R ₃₆ and R
₃₇ , R ₄₀ and R ₄₁ are each 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 contains 1 or more epoxy group-containing functional groups selected from the above formulas (6) to (9).
An average of at least 2, preferably 2 or more per molecule,
More preferably, it can have 4 or more.

Of the above, the epoxy group-containing groups represented by the formulas (6) and (8) are preferable, and particularly the following formula (9):

[0096]

[Chemical 17]

An epoxy group-containing functional group represented by: and the following formula (10)

[0098]

[Chemical 18]

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, and can be changed according to the production method thereof, the intended use of the final resin composition, etc. Speaking specifically, 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 100,000.
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, for example, in 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 can be obtained by a method known per se, and its main production methods are listed below, but the invention is not limited thereto.

First production method: Part of the double bond of the 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 of ring-opening polymerization of an alicyclic compound having two or more epoxy groups in the same molecule based on the epoxy groups to such an 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.

Details of these manufacturing methods are described in the above-mentioned JP-A-2-255874.

The above-mentioned component (B) is suitable for applications requiring a high level of performance such as cationic electrodeposition coatings used for automobile bodies, in which an epoxy group-containing functional group per molecule is used. 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.
It is in the range of from 00 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,
It is in the range of 000.

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 heat-cured. 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 a part of the component (B) added in advance to the component (A).

Component (C) : A catalyst for accelerating the cross-linking and curing reaction between the components (A) and (B), which is a hydroxide of a metal element having an atomic number of 25 to 30 or 40 to 42, That is, Mn, Fe, Co, Ni, Cu, Zn,
Hydroxide of metal selected from Zr, Nb and Mo (C
-1) and metal salts of organic acids (excluding lead salts) C-
It is at least one metal compound selected from 2).

The above Mn, Fe, Co, Ni, Cu, Z
Among the metal hydroxides (C-1) selected from n, Zr, Nb and Mo, particularly preferred are copper (II) hydroxide, cobalt hydroxide and zinc hydroxide.

As the organic acid for forming the organic acid metal salt (C-2), one carboxyl group is contained in one molecule.
Or, an organic compound having two is included, and specifically,
Examples thereof include saturated or unsaturated monocarboxylic acids having 1 to 18 carbon atoms, aromatic dicarboxylic acids, alicyclic dicarboxylic acids having 5 to 18 carbon atoms, and aliphatic dicarboxylic acids having 2 to 10 carbon atoms. As the above monocarboxylic acid, for example,
Aromatic monocarboxylic acids such as benzoic acid and methylbenzoic acid; formic acid, acetic acid, propionic acid, butyric acid, caproic acid,
Examples thereof include saturated or unsaturated aliphatic monocarboxylic acids such as octylic acid, oleic acid, linoleic acid, and natural fatty acids. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Acid, biphenyldicarboxylic acid and the like, and as the alicyclic dicarboxylic acid, for example, hexahydroterephthalic acid, hexahydroisophthalic acid and hexahydrophthalic acid, and the like, further, as the aliphatic dicarboxylic acid, For example, oxalic acid, adipic acid,
Examples thereof include sebacic acid, succinic acid, maleic acid, fumaric acid, itaconic acid and dimer acid. And as a metal which forms a salt with these organic acids, the above (C-
1) Atomic number described for the component 25-30 or 40-
The metal element of No. 42, aluminum, etc. are mentioned, and among them, Fe, Ni, Cu, Zn and Al are preferable.

Thus, as the metal salt of such an organic acid, a salt of formic acid and zinc, nickel or copper; zinc octylate; zinc linseed oil fatty acid; aluminum octylate;
Preferred examples include iron (II) oxalate dihydrate.

As the component (C), one or more selected from the above metal hydroxide (C-1) and organic acid metal salt (C-2) can be used. The compounding amount is generally 0.1 to 10% by weight, particularly 0.2 to 10% by weight based on the total weight of the components (A) and (B).
It is preferably within the range of 5% by weight.

Component (D) : Inorganic bismuth compound. This 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. Specific examples of the inorganic bismuth compound that can be used include basic bismuth carbonate, 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. Generally, the amount of the metal is 15% by weight based on the total weight of the components (A) and (B). % Or less, particularly preferably in the range of 1 to 10% by weight.

The cationic electrodeposition coating composition of the present invention comprises, for example, the above-mentioned components (A), (B) and (C) as essential components and, if necessary, the component (D),
It can be prepared by dissolving or dispersing these in an aqueous medium. More specifically, first (A)
And (B) component are mixed and then dispersed in an aqueous medium, and then (B) component, (D) component, color pigments such as carbon black, titanium white and red iron oxide, extender pigments such as clay and talc. , And other additives (for example, a dispersant, a cissing inhibitor, etc.) and the like.

The resin composition for cationic electrodeposition coating composition of the present invention can be subjected to cationic electrodeposition coating on a conductive substrate,
Although the film thickness of the coating film is not particularly limited, it is generally suitable within a range of 3 to 200 μm based on the cured coating film, and the coating film is, for example, 70 to 250 ° C., preferably 120 ° C.
It can be heat-cured at a temperature between 160 ° C.

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 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 3
00V; and energizing time 0.5 to 5 minutes, preferably 2
It can be performed under the condition of ˜3 minutes.

After the electrodeposition coating, the object to be coated is lifted 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".

[0121]

Example I. Production Example 1. Amino compound (A-2) (A-2-): 285 parts of stearic acid, 104 parts of hydroxyethylaminoethylamine and 80 parts of toluene are placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a water separator. Parts of the reaction mixture were gradually heated with mixing and stirring to remove toluene as necessary, and 18 parts of the reaction water was separated and removed while raising the temperature, and then the remaining toluene was removed under reduced pressure to obtain an amine compound having an amine value of 150 and a freezing point of 76 ° C. (A-2
-) 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. 80 parts were charged, 18 parts by weight of the reaction water was separated and removed by gradually heating while mixing and stirring to remove toluene as necessary and raising the temperature, and then residual toluene was removed under reduced pressure to obtain an amine value of 149 and a freezing point of 45 ° C. To obtain the amino compound (A-2-).

(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 heat with mixing and stirring to remove toluene as needed, and then remove and remove 18 parts of reaction water while raising the temperature, and then remove residual toluene under reduced pressure to remove an amine compound having an amine value of 148 and a freezing point of 69 ° C. (A-2 -) 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-): 170 parts of phenylphenol, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts of bisphenol A, and tetramethyl were placed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Ammonium 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 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, and mixed and stirred,
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 group 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. The content rate of the component (A-1) is 10.4%.

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

[0131]

[Table 1]

II. Examples Example 1 In 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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 1.8 parts of copper (II) hydroxide (first grade reagent) (1.2 parts as metallic copper), 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-1) 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%.
Then, to this 333 parts of emulsion was added 75.6 parts of the above-mentioned pigment paste (P-1) and deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20%.

Example 2 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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black and 4.5 parts of cobalt hydroxide (2.9 parts as metallic cobalt) were added and dispersed in a ball mill for 24 hours, and deionized water was added to the mixture to obtain a solid content of 50%. A pigment paste (P-2) was obtained.

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%.
Next, 81 parts of the above-mentioned pigment paste (P-2) and deionized water were added to 333 parts of this emulsion to give a solid content of 2
A 0% 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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 2.8 parts of zinc hydroxide (1.9 parts as metallic zinc), and 5 parts of bismuth hydroxide (purity 98%) were added, and the mixture was dispersed in a ball mill for 24 hours and then removed. Ionized water was added to obtain a pigment paste (P-3) 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%.
Subsequently, 77 parts of the above-mentioned pigment paste (P-3) 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 4 To 94 parts of cationic resin (A-) (75 parts of solid content),
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 with stirring. Furthermore, 20 parts titanium white, 1 part carbon black, 0.8 parts copper (II) hydroxide (first grade reagent) (0.5 parts as metallic copper), ferrous oxalate 10.7
(3.0 parts as metal amount), 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 (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, 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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 0.8 parts of copper (II) hydroxide (first grade reagent) (0.5 parts as metallic copper), 6.3 parts of aluminum octylate (0.3 parts as metallic amount). 5 parts), 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-5) 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, 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 of cationic resin (A-) (75 parts of solid content),
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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 0.8 part of copper (II) hydroxide (first grade reagent) (0.5 part as metallic copper), bismuth hydroxide (purity of 98)
%) And dispersed in a ball mill for 24 hours, and then mixed with deionized water to prepare a pigment paste having a solid content of 50% (P-6).
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%.
Then, to this 333 parts of emulsion, 73.6 parts of the above-mentioned pigment paste (P-6), 75.3 zinc formate (0.5 parts as metal amount) and deionized water were added, and the solid content was 20%.
% Of the cationic electrodeposition coating composition was obtained.

Example 7 110 parts of cationic resin (A-) (solid content: 75 parts)
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).

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 with stirring. Furthermore, 20 parts of titanium white, 1 part of carbon black, 2.8 parts of zinc hydroxide (1.9 parts as metallic zinc), and 5 parts of bismuth hydroxide (purity 98%) were added, and the mixture was dispersed in a ball mill for 24 hours and then removed. Ionized water was added to obtain a pigment paste (P-7) 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%.
Next, to 333 parts of this emulsion, 72 parts of the above pigment paste (P-7) and 100 parts of copper formate (metal
98 parts) and deionized water were added to obtain a cationic electrodeposition coating composition having a solid content of 20%.

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 the coating film was pulled up from 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.

[0154]

[Table 2]

In Table 2, Comparative Example 1 is the pigment paste (P-
Example 1 was used except that 1.8 parts of copper (II) hydroxide in 1) was changed to 2.8 parts of lead hydroxide (lead content of metal 90%) and bismuth hydroxide was removed. It is a coating composition produced in the same manner as 1.

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 using Nanosizer N-4 manufactured by Beckman Coulter Inc. immediately after production and after being stored at 30 ° C. for 1 month.

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

Curability: After wiping the coated surface 10 times with gauze impregnated 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, with the coated surface facing upward, a 500 g impact is 30 cm
When the film was dropped from the height of No. 1 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 this is tested 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, and then intermediate coating (known thermosetting intermediate coating mainly composed of polyester resin and melamine resin)
(Thickness: approx. 30μ) and baked, and then topcoat paint (known thermosetting solid color topcoat paint consisting mainly of acrylic resin and melamine resin) (thickness: approx. 40μ) and heat curing The coating film of the test plate, which was made up to a minimum, was cross-cut to reach the substrate. This was subjected to a salt spray resistance test for 24 hours under the same conditions as the above salt spray resistance, 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 property: 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-mentioned Examples and Comparative Examples, the cationic electrodeposition coating composition of the present invention is equivalent to 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 the front page (72) Inventor Toshio Fujibayashi 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (7)

[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 (B) having 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 per molecule on average of 2 or more. A composition comprising an epoxy resin and (C) at least one metal compound selected from hydroxides of metal elements having an atomic number of 25 to 30 or 40 to 42 and metal salts of organic acids (excluding lead salts). A cationic electrodeposition coating composition, characterized by containing as a main component. 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 composition for 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 may have a hydroxyl group and / or a polymerizable unsaturated bond. A resin composition for a cationic electrodeposition coating composition according to claim 1 or 2, which is a compound represented by a hydrocarbon group having 4 to 36 carbon atoms. 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. 5. The atomic number of the component (C) is 25 to 3
The cationic electrodeposition coating composition according to claim 1 or 2, wherein the hydroxide of the metal element of 0 or 40 to 42 is selected from copper (II) hydroxide, cobalt hydroxide and zinc hydroxide. 6. A metal salt of an organic acid as the component (C),
The cationic electrodeposition sample composition according to claim 1 or 2, which is a salt of formic acid and a metal selected from zinc, nickel and copper. 7. A metal salt of an organic acid as the component (C),
A dicarboxylic acid metal salt or a fatty acid metal salt.
Alternatively, the cationic electrodeposition coating composition according to item 2.