JP3361123B2 - Resin composition for water-based paint - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for water-based paints, and in particular, it is excellent in water dispersibility, bath stability and pigment dispersibility and is useful as a resin composition for cationic electrodeposition paints. It relates to a composition.

[0002]

2. Description of the Related Art As a base resin for a cationic electrodeposition coating, for example, a high molecular weight (about 1000 in number average molecular weight) is used.
An amine-added epoxy resin obtained by reacting the above-mentioned diepoxide with a secondary amine (for example, diethanolamine, methylethanolamine, diethylamine, etc.) is generally used. The resin is cured by a cross-linking reaction with a blocked polyisocyanate compound,
Since the coating film uses bisphenol A type diglycidyl ether, it has excellent corrosion resistance. But,
Since the amine-added epoxy resin has a tertiary amino group as a cationic group, its water dispersibility is insufficient at a degree of partial neutralization with an acid. However, there is a problem in that the corrosion performance of the equipment is deteriorated because of too low temperature.

It is widely recognized that a crosslinking agent such as a blocked polyisocyanate compound promptly reacts with the primary hydroxyl group in the base resin to crosslink and cure. However, in order to introduce a primary hydroxyl group into the base resin for cationic electrodeposition coating having bisphenol A type glycidyl ether as a basic skeleton, an alkanolamine (secondary amine) is used.
When used, the water dispersibility decreases as described above.

Further, a polyepoxide having three or more epoxy groups in one molecule (epoxy equivalent 100-100)
The reaction product of 0) with polyphenol (for example, alkylenediphenyl) has also been tried as a base resin for cationic electrodeposition coating, but it is not practical because it tends to have high viscosity or gel during the formation reaction. Further, the one obtained by adding an amine compound to this polyepoxide is not preferable because the base concentration partially increases and the corrosion resistance decreases.

Further, a base resin for a cationic electrodeposition coating composition, which is obtained by reacting a polyepoxide having an epoxy group bonded to an alicyclic skeleton with a primary hydroxyl group-containing primary or secondary amine, is also known. Although they have excellent water dispersibility by partial neutralization with acid, they have a plasticizing effect because they have an alicyclic skeleton, and it is difficult to adjust the molecular weight distribution, and high molecular weight components are also mixed. It was found that there is a drawback that the smoothness of the coated surface is reduced.

[0006]

Therefore, a primary hydroxyl group can be introduced using a secondary alkanolamine, and there is no increase in viscosity or gelation during the resin formation reaction, and
There is a strong demand for the development of a resin composition for water-based coatings, which has excellent water dispersibility in the stage of partial neutralization with an acid, and also has good coating surface smoothness and corrosion resistance of the coating film.

The object of the present invention is not to increase viscosity and gel during the synthesis reaction, and to be excellent in water dispersibility in partial neutralization, and to be excellent in smoothness of coating surface and anticorrosion property of coating film. Another object of the present invention is to provide a resin composition for an aqueous paint which is particularly useful as a resin for a cationic electrodeposition paint, and a cationic electrodeposition paint using the composition.

That is, the present invention provides the following resin compositions for coatings, cationic electrodeposition coatings, pigment pastes and the like.

(A) a compound having at least 2.5 glycidyl ether groups on average derived from a polyol having at least 3 alcoholic hydroxyl groups bonded to an aliphatic carbon atom per minute, (B) first A primary or secondary amine compound containing a primary hydroxyl group and (C)
The following general formula (1)

[0010]

[Chemical 2]

[Wherein R ₁ and R ₂ are the same or different groups selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, R _{3 to} R ₆ are hydrogen atoms and an alkyl group having 1 to 10 carbon atoms] Group, an aromatic group, an allyl group and a halogen atom, which are the same or different groups], and a primary hydroxyl group-containing cationic compound obtained by reacting a phenol compound containing a phenolic hydroxyl group-containing functional group A resin composition for water-based coatings, which comprises a resin as a main component.

Primary hydroxyl group-containing cationic resin (I)
And a curing agent (II), for example, a blocked isocyanate compound (II-1), a polyepoxide compound (II-
2) and a cationic electrodeposition coating composition (III) containing as a main component at least one compound selected from the compound (II-3) having two or more carbon-carbon unsaturated groups in one molecule. Primary hydroxyl group-containing cationic resin (I) and curing agent (I
The resin composition for self-curing coatings (I), which is obtained by partially reacting with (I).
V).

A cationic electrodeposition coating (V) containing the self-curable coating resin composition (IV) as a main component.

Primary hydroxyl group-containing cationic resin (I)
Alternatively, a pigment paste (VI) containing the resin composition (IV) for self-curing paint and the pigment (G) as main components.

Articles coated with the cationic electrodeposition coating (III) or the cationic electrodeposition coating (VI).

The resin composition, cationic electrodeposition coating composition and pigment paste of the present invention will be specifically described below.

Component (A) : A compound having at least 2.5 glycidyl ether groups on average derived from a polyol containing at least three alcoholic hydroxyl groups bonded to an aliphatic carbon atom in one molecule.

The component (A) is generally obtained by glycidyl etherification of a polyol having at least three alcoholic hydroxyl groups bonded to an aliphatic carbon atom in one molecule. The hydroxyl group present in the polyol is directly bonded to an aliphatic carbon atom, and normally, it is preferable that the hydroxyl group not directly bonded to an aromatic ring or an alicyclic ring is included. Examples of such polyols include glycerin, trimethylolpropane, trimethylolethane, diglycerin, tonoglycerin, polyglycerol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, and mannitol. Examples thereof include trihydric or higher aliphatic polyhydric alcohols. Furthermore, polylactone polyols obtained by adding lactones such as ε-caprolactone to these polyhydric alcohols can also be used.

The component (A) is, for example, an epihalohydrin (preferably epichlorohydrin) based on the above polyol.
Can be obtained by the glycidyl etherification reaction in the presence of an alkali metal hydroxide aqueous solution (catalyst). The component (A) has an average of 2.5 or more glycidyl ether groups per molecule, preferably 3 to 1 on average.
0, and the epoxy equivalent is generally 100 to
It is preferably in the range of 500, especially 100 to 300. The average molecular weight is 100 to 3 based on the measurement by GPC (gel permeation chromatography).
000, particularly preferably in the range of 200 to 1500.

In addition to the above components, the component (A) also includes those obtained by reacting the above glycidyl ether compound with an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include bisphenol A, bisphenol F, phenylphenol, nonylphenol, phenols having a phenolic hydroxyl group such as phenol, stearic acid, dimer acid, oleic acid, soybean oil fatty acid, acetic acid, formic acid, Examples thereof include carboxyl group-containing compounds such as hydroxyacetic acid; hydroxyl group-containing compounds such as alkyl alcohol, cellosolve and carbitol. The reaction between the glycidyl ether compound and the active hydrogen-containing compound is carried out by subjecting a part of the glycidyl group of the glycidyl ether compound to the ring-opening reaction of the active hydrogen-containing compound. The amount of the glycidyl ether group per molecule, the epoxy equivalent, and the average molecular weight of the component (A) obtained by this reaction are also preferably within the above range.

The component (A) itself is a known compound, and commercially available products can be used. For example, denaconal EX-313 (glycerol polyglycidyl ether); denaconal EX-421 and denaconal EX-314 (diglycerol polyglycidyl ether); denaconal EX-321 (trimethylolpropane polyglycidyl ether); denaconal EX-512 and denaconal EX. -521 (polyglycerol polyglycidyl ether); Denaconal E
X-411 (pentaerythritol polyglycidyl ether); Denaconal EX-611, Denaconal EX
-612, Denaconal EX-614, Denaconal E
X-614B and Denaconal EX-622 (sorbitol polyglycidyl ether); Denaconal EX-
651 and Denaconal EX-651A (sorbitan polyglycidyl ether); and the like [all are manufactured by Nagase Chemical Industry Co., Ltd., trade name].

Component (B): A primary or secondary amine compound containing at least one primary hydroxyl group in one molecule. This is useful for reacting with the component (A) to introduce a primary hydroxyl group and a basic group into the component (A).

A cationic resin is produced by the reaction between the amino group of the component (B) and the glycidyl group of the component (A),
The primary hydroxyl group and basic group in this cationic resin are more water dispersible and throwing power even at partial neutralization and high pH, as compared with conventional reaction products of bisphenol A type epoxy resin and amine compound. Is excellent, and the curability and corrosion resistance of the coating film formed are also good.

Examples of the component (B) include the following compounds.

Primary alkanolamines such as monoethanolamine, monopropanolamine and monobutanolamine.

N-methylethanolamine, N-ethylethanolamine, diethanolamine, di-n-
(Or iso) -Secondary alkanolamines such as propanolamine, dibutanolamine.

The above primary alkanolamine and α, β
An adduct with an unsaturated carbonyl compound (secondary alkanolamine). For example, monoethanolamine and N,
Adduct with N-dimethylaminopropylacrylamide, monoethanolamine and hydroxyethyl (meth)
Adducts with acrylates, adducts with monoethanolamine and hydroxypropyl (meth) acrylate, adducts with monoethanolamine and hydroxybutyl (meth) acrylate, etc.

Primary and secondary alkanolamines such as hydroxyethylaminoethylamine.

One or more selected from hydroxyamine, hydroxymethylhydrazine and hydroxyethylhydrazine and a ketone compound (for example, dimethyl ketone,
Methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, dipropyl ketone, etc.) (secondary alkanolamine).

An amine compound represented by the following general formula (2) in which a primary hydroxyl group, a secondary amino group and an amide group coexist in one molecule.

[0031]

[Chemical 3]

[Wherein n is an integer of 1 to 6 and R ₁₁ represents a hydrocarbon chain of 4 to 36 carbon atoms which may contain a hydroxyl group and / or a polymerizable unsaturated group] The amine compound represented by 2) is obtained, for example, by subjecting N-hydroxyalkylalkylenediamine and a monocarboxylic acid having 5 to 37 carbon atoms to a dehydration condensation reaction. Examples of the diamine compound include primary hydroxyl groups such as hydroxyethylaminoethylamine, N-hydroxyethylpropylenediamine, N-hydroxyethylbutylenediamine, N-hydroxyethylpentylenediamine and N-hydroxyethylhexylenediamine. Preferred are primary and secondary diamines. Examples of monocarboxylic acids that can be reacted with these include coconut oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid and tung oil fatty acid. Such as mixed fatty acids; 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, etc. Fatty acids are included.

The reaction of the above-mentioned diamine compound and monocarboxylic acid to obtain the amine compound represented by the general formula (2) is usually carried out by mixing both components in an approximately equimolar ratio to obtain toluene or methyl isobutyl ketone. The reaction can be carried out by removing a specified amount of reaction-produced water using an organic solvent, and the amine compound can be obtained by removing the residual organic solvent by a reduced pressure method or the like. The amine compound thus obtained has an amine value (secondary amine) of 88 to 350, particularly 1
20 to 230, and the hydroxyl value (preferably primary hydroxyl group) is preferably in the range of 44 to 350, particularly 60 to 230.

As the component (B), the primary alkanol secondary amines described above and above are preferable. In particular, it is preferable to use the amine compound represented by the general formula (2) (particularly hydroxyethylaminoethyl fatty acid amide) and diethanolamine together, since the smoothness of the coated surface and the corrosion resistance are improved. The ratio of the amine compound (particularly hydroxyethylaminoethyl fatty acid amide) and diethanolamine is within the range of 30 to 80% by weight for the former and 70 to 20% by weight for the latter, based on the total weight of both components. preferable.

Component (C): a compound containing a functional group containing a phenolic hydroxyl group represented by the above general formula (1).

The component (C) serves to further improve the corrosion resistance of the coating film. The number average molecular weight of the component (C) is not particularly limited, but is generally 500 to 20,000, especially 8
It is preferably in the range of 00 to 3000. Also,
The component (C) has an average of 0.3 to 2 phenolic hydroxyl group-containing functional groups represented by the general formula (1) per molecule.
It is preferable to have 0.5, 1.5, and especially 0.8 to 1.2.

Examples of the compound having a phenolic hydroxyl group-containing functional group represented by the general formula (1) include bis (4-hydroxyphenyl) -2,2-propane (bisphenol A) and bis (4-hydroxyphenyl). −
Examples include bisphenols such as 2,2-methane (bisphenol F).

Further, as a compound (component C) having a phenolic hydroxyl group-containing functional group represented by the general formula (1),
The compound represented by the following general formula (3) is also suitable.

[0039]

[Chemical 4]

[Wherein q is an integer of 0 to 7 and R ₂₁ represents a residue of an active hydrogen-containing compound] R in the general formula (3)
_As the active hydrogen-containing compound which is the ₂₁ precursor, for example,
Amines such as secondary amines; phenylphenol,
Phenols such as nonylphenol; organic acids such as fatty acids; thiols; alkyl alcohols, cellosolves,
Alcohols such as butyl cellosolve and carbitol;
Inorganic acid; and the like. Of these, particularly preferred are secondary amines having primary hydroxyl groups such as dialkanolamines; amine compounds represented by the general formula (2); phenols such as nonylphenol, phenylphenol, phenol, hydroquinone monomethyl ether; Fatty acids such as stearic acid, oleic acid and soybean oil fatty acids; lower organic acids such as acetic acid, formic acid and hydroxyacetic acid; and the like.

The component (C) may contain a compound of the above-mentioned general formula (3) in which both terminals are either R ₂₁ or -OH, but the phenolic hydroxyl group is averaged per molecule. 0.5 to 1.5 functional groups, especially 0.8 to 1.
It has two and has a number average molecular weight of 500 to 200.
It is preferably in the range of 00.

The component (C) having a phenolic hydroxyl group-containing functional group represented by the general formula (3) is, for example, a bisphenol type diglycidyl ether, a bisphenol type diphenol and an active hydrogen containing compound (for example, the second
Secondary alkanolamine) in the presence of a catalyst or a solvent, if necessary, at 30 to 300 ° C., preferably 70 to 180 ° C.
It can be obtained by reacting at a temperature of ° C.
In addition, in this reaction, the following components can also be present together.

For example, polyols such as dimer diol, ethylene glycol, propylene glycol and butylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyester polyols such as polycaprolactone; polycarboxylic acids; Polyisocyanates; Monoisocyanates; Oxides of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide; allyl glycidyl ether, polypropylene glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl Glycidyl of compounds having a hydroxyl group such as ether and phenylglycidyl ether Ether; alicyclic oxirane-containing compounds; glycidyl esters of organic acids such as fatty acids may be Coexistence of. Further, δ-4-caprolactone, an acrylic monomer or the like may be graft polymerized.

The cationic resin (I) having a primary hydroxyl group provided by the present invention is the above-mentioned (A),
It is obtained by reacting the components (B) and (C). The reaction order of them is not particularly limited, and for example,
Method of simultaneously reacting components (A), (B) and (C), after reacting component (A) with component (B), then (C)
This can be carried out by a method of reacting the components, a method of reacting the component (C) with the component (A), and then a reaction with the component (B), etc., whereby the cationic resin (I) is obtained.

The reaction between the components (A) and (B) is
A reaction between the glycidyl group of the component (A) and the primary and / or secondary amino group of the component (B) to form a secondary and / or tertiary amino group. Also,
The reaction between the component (A) and the component (C) is a reaction between the glycidyl group of the component (A) and the phenolic hydroxyl group of the component (C), and an ether bond is formed. The cationic resin (I) thus obtained is, in principle, (A)
The glycidyl group that the component had was consumed in the above reaction,
It contains substantially no glycidyl groups.

The reaction ratio of each of these components is not strictly limited and can be arbitrarily selected according to the purpose. For example, the total number of moles of the amino group of the component (B) and the phenolic hydroxyl group of the component (C) is 0.75 to 1.5 mol, particularly 0.8 to 1 mol, per 1 mol of the glycidyl group of the component (A). It is preferable to use each component in a ratio so as to fall within the range of 1.2 mol. If the total number of moles is less than 0.75 moles, the viscosity of the product may be high, and if it is more than 1.5 moles, a large amount of unreacted amino groups may remain to adversely affect the electrodeposition characteristics. There is. The amount of the component (A) used is generally 0.5 to 75% by weight, particularly 5 to 5% by weight, based on the total weight of the components (A), (B) and (C).
Suitably it is in the range of 0% by weight, 0.5% by weight
If the amount is less, the water dispersibility of the cationic resin (I) may be insufficient, and if it is more than 75% by weight, the amine value may be high and the corrosion resistance of the coating film may be lowered.

The amount of component (B) used is such that the hydroxyl equivalent of the resulting cationic resin (I) is 250 to 2000,
It is preferable to select it within the range of 300 to 700. When the hydroxyl equivalent is smaller than 250, the amine value of the resulting cationic resin (I) may be high and the corrosion resistance of the coating film may be lowered. When it is larger than 2000, the curability may be lowered and the corrosion resistance of the coating film may be lowered. May occur. On the other hand, the component (C) is
It is suitable to use it in the range of 0.05 to 1.5 mol, especially 0.2 to 1.2 mol. If the amount of component (C) is less than 0.05 mol, the resulting cationic resin (I) may have poor water dispersibility, and if it is more than 1.5 mol, the smoothness of the coated surface may be poor. Further, the reaction temperature is generally 50 to 30 in the above-mentioned method and in each case.
It is preferably 0 ° C., particularly 70 to 200 ° C. The reaction can also be carried out in the presence of an organic solvent such as alcohol, ketone or ether. The formed cationic resin (I) generally has a number average molecular weight of 1000 to 200.
It is preferably in the range of 00, particularly 1500-10000.

Further, in the production of the cationic resin (I), in order to adjust the hydroxyl value and the amine value within the above ranges, the other cationizing agent (D) exemplified below together with the component (B) and the above A phenol compound (E) other than the component (C) can be used. The component (D) is
It can be added at the beginning or in the middle of the above-mentioned method and the reaction thereof, or may be added after the reaction.

Examples of the other cationizing agent (D) include methylamine, ethylamine, n- or iso-.
Primary amines such as propylamine; diethylamine,
Secondary amines such as dipropylamine and dibutylamine; polyamines such as ethylenediamine, diethylenetriamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylamine and dimethylaminopropylamine, and ammonia, hydrazine, N-hydroxy. An ethylimidazoline compound or the like can also be used in combination.

As the other cationizing agent (D), the primary hydroxyl group-containing primary and secondary diamines used in the preparation of the component (B) are replaced with the secondary hydroxyl group-containing primary and secondary diamines. It is also possible to use an amine compound in which a secondary hydroxyl group, a secondary amino group and an amide group coexist in one molecule, which is replaced with a primary diamine.

Further, tertiary amines such as triethylamine, triethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N, N'-diethylethanolamine and N-ethyldiethanolamine are also used as the component (D). They can be used, and they can be used as a quaternary salt by preprotonating with an acid and reacting with an epoxy group.

In addition to amino compounds, salts of sulfides such as diethyl sulfide, diphenyl sulfide and tetramethylene sulfide thiodiethanol with boric acid, carbonic acid and organic monocarboxylic acids are reacted with epoxy groups to form a tertiary sulfonium salt. It may be salt.

Further, a salt of a phosphine such as triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, and triphenylphosphine with an acid as described above may be reacted with an epoxy group and used in combination as a quaternary phosphonium salt. .

In the present invention, it is necessary to introduce a cationic group into the resin substrate using the component (B),
It is not always necessary to use the other cationizing agent (D) other than the component.

Further, other phenol compounds as the component (E) are specifically bis (4-hydroxyphenyl) -2,2-propane, 4,4'-dihydroxybenzophenone and bis (4-hydroxy). Phenyl)
-1,1-ethane, bis (4-hydroxyphenyl)-
1,1-isobutane, bis (4-hydroxy-tert)
-Butyl-phenyl) -2,2-propane, bis (2-
Hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl) -1,1,2,
Polyhydric phenol compounds such as 2-ethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, phenol novolac and cresol novolac; phenol, nonylphenol, α-
Alternatively, monophenol compounds such as β-naphthol, p-tert-octylphenol, o- or p-phenylphenol, etc. may be mentioned.

The cationic resin (I) containing a primary hydroxyl group thus obtained is preferably used as a resin for a cationic electrodeposition coating composition. Particularly, since the resin (I) has excellent water dispersibility, the water dispersibility can be improved by blending the resin (I) with an organic substance or an inorganic substance having insufficient water dispersibility. . Therefore, the resin (I) is
It is also useful as a water dispersibility improving agent for cationic electrodeposition coatings.

The cationic electrodeposition coating composition (III) provided by the present invention is an aqueous coating composition containing a mixture of a cationic resin (I) having a primary hydroxyl group and a curing agent (II) as a main component.

As the curing agent (II), known curing agents for cationic electrodeposition coatings can be used, but in particular, for example, the blocked polyisocyanate compound (II-1),
The polyepoxide compound (II-2) and the compound (II-3) having two or more unsaturated groups in one molecule are preferable.

(II-1): Blocked polyisocyanate compound This is a polyisocyanate compound having two or more isocyanate groups in one molecule, which is blocked with an active hydrogen-containing blocking agent such as a hydroxyl group. Therefore, when heated above a specific temperature, the blocking agent dissociates to regenerate free isocyanate groups, which react with the hydroxyl groups of the cationic resin (I) to crosslink and cure. As the polyisocyanate compound, aliphatic, aromatic, or araliphatic polyisocyanates can be used, and known blocking agents can be applied. More specifically, it is described in Japanese Patent Publication No. 52-6306 and Japanese Patent Application Laid-Open No. 47-759, and in this specification, the citation of these publications is used instead of the detailed description.

(II-2): Polyepoxide compound A compound containing a specific epoxy group represented by the following structural formula (4).

[0061]

[Chemical 5]

A compound containing a specific epoxy group represented by the following structural formula (5).

[0063]

[Chemical 6]

[In the formula, R ₄₁ represents hydrogen or a methyl group] The polyepoxide compounds of (II-2) and are described in detail in JP-A-2-255874, and here, Use citations instead of specific explanations.

A phenol type novolac glycidyl ether resin represented by the following general formula (6).

[0066]

[Chemical 7]

In the above formula (6), R ₅₁ and R ₅₂ represent the same or different groups selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aromatic group and a halogen atom; R ₅₃ and R ₅₄ Represents a hydrogen atom or the same or different groups selected from an alkyl group having 1 to 4 carbon atoms; R ₅₅
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group,
Represents a group selected from an allyl group and a halogen atom;
R ₅₆ represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an aromatic group, an allyl group and a halogen atom; and n is an integer of 1 to 38. Further, a part or all of the benzene ring in the above formula (6) may be substituted with a naphthalene ring.

In the general formula (6), specific examples of the alkyl group having 1 to 8 carbon atoms, aromatic group and halogen atom which can be represented by R ₅₁ and R ₅₂ are methyl group, ethyl group and propyl group. Group, n-butyl group, t-butyl group, pentyl group, hexyl group, phenyl group, benzyl group, chlorine atom, bromine atom, iodine atom and the like. Among these, a hydrogen atom, a methyl group, a chlorine atom and a bromine atom are preferable, and a hydrogen atom, a methyl group and a bromine atom are more preferable.

Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkylene group having 1 to 10 carbon atoms, the aromatic group, the allyl group and the halogen atom which can be represented by R ₅₅ and R ₅₆ include a methyl group. , Ethyl group, propyl group, n-butyl group,
Examples thereof include t-butyl group, pentyl group, hexyl group, nonyl group, ethylene group, propylene group, phenyl group, benzyl group, chlorine atom, bromine atom and iodine atom. Preferred are methyl group, t-butyl group, nonyl group, phenyl group, chlorine atom and bromine atom, and particularly methyl group, t
-Butyl group, phenyl group and bromine atom are preferred.

Examples of the alkyl group having 1 to 4 carbon atoms which can be represented by R ₅₃ and R ₅₄ include a methyl group, an ethyl group, a propyl group and a butyl group, and a hydrogen atom is preferable. n is a number within the range of 1 to 38, but 1.5 to 8 is particularly preferable.

The number average molecular weight of the phenol type novolac glycidyl ether resin represented by the general formula (6) is generally about 400 to 400 based on the measurement by the vapor pressure osmotic pressure method.
It is preferably in the range of 8000, particularly in the range of 600 to 2000. The number average number of repeating units (n) can also be obtained from this number average molecular weight. Further, per molecule of the resin,
It is preferable to have 3.5 to 10 glycidyl groups, and the epoxy equivalent is usually about 180 to 2000, especially 20.
It is preferably in the range of 0 to 600.

The resin represented by the general formula (6) includes, for example, a bifunctional phenol compound (II-2--1) represented by the following general formula (7) and a compound represented by the formula (8): R ₅₃ CHO [ In the formula, R ₅₃ has the same meaning as described above] and / or formula (9): R ₅₃ COR ₅₄ [wherein R ₅₃ and R ₅₄ are as defined above] Have the same meaning] as a ketone compound (II-2--
3) and a phenol type novolak resin (II-2--4) obtained by polycondensation reaction with epihalohydrin (II
-2--5) to react with the resin (II-2--4)
It can be easily obtained by introducing a glycidyl ether group into.

General formula (7):

[0074]

[Chemical 8]

[Wherein R ₅₁ , R ₅₂ and R ₅₆ have the same meanings as described above] In addition, during or after the reaction for obtaining the above-mentioned phenol type novolak resin (II-2--4), it may be necessary. Accordingly, the monofunctional phenol compound (II-2--6) represented by the following general formula (10) can be used in combination as the terminal blocking agent.

[0076]

[Chemical 9]

[Wherein R ₅₆ , R ₅₁ and R ₅₂ have the same meanings as described above] C 1 to C 1 represented by R ₅₆
Specific examples of the alkyl group of 0, the alkylene group having 1 to 10 carbon atoms, the aromatic group, the allyl group and the halogen atom include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a pentyl group, Hexyl group, nonyl group, ethylene group,
Examples thereof include a propylene group, a phenyl group, a benzyl group, a chlorine atom, a bromine atom and an iodine atom. Of these, a methyl group, a t-butyl group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom are preferable, and a methyl group, a t-butyl group, a phenyl group and a bromine atom are particularly preferable.

"Bifunctionality" in the bifunctional phenol compound (II-2--1) component represented by the general formula (7) means that in the general formula (7), a hydroxyl group is used as a reference.
It means that two hydrogen atoms are directly bonded to the ortho position and / or the para position. The hydrogen atom is (II-
2-2-) and (II-2-3) are subjected to dehydration condensation reaction with carbonyl groups (C = O) in the components to form a phenol type novolac resin (II-2-4).

"Monofunctionality" in the monofunctional phenolic compound (II-2--6) component represented by the general formula (10) means that in the general formula (10), a hydroxyl group is used as a reference.
It means that one hydrogen atom is directly bonded to the ortho position or the para position. The hydrogen atom is the same as the above (II-2-
-2) or (II-2-3), and a carbonyl group (C = O) in the component, undergoes a dehydration condensation reaction to form a terminal of the phenol type novolak resin (II-2--4).

The bifunctional phenol compound represented by the general formula (7) as the component (II-2--1) is, for example, phenol, p-propenylphenol, o-benzylphenol, 6-n. -Amil-n
-Cresol, o-cresol, p-cresol, o-
Ethylphenol, o-phenylphenol, p-phenylphenol, pt-pentylphenol, pt
-Butylphenol, o-chlorophenol, p-chloropheno, 4-chloro-3,5-xylenol, o-
Examples include allylphenol, nonylphenol, o-bromophenol, p-cumylphenol and the like.

Examples of the aldehyde compound represented by the general formula (8) as the component (II-2--2) include acetaldehyde and formaldehyde. Examples of the ketone compound represented by the general formula (9) as the component (II-2-3) include acetone and
Examples include methyl ethyl ketone and methyl isobutyl ketone.

Examples of the epihalohydrin as the component (II-2--5) include epichlorohydrin, epibromhydrin and the like.

The component (II-2--4-) is the same as the above (II
It is a phenol type novolak resin obtained by polycondensation reaction of (II-2--2) component and / or (II-2-3) component with (2-1) component. This polycondensation reaction can be carried out according to a conventional method for producing a phenol type novolak resin known per se. Specifically, it can be carried out by a rotary method or a continuous method described in JP-A-51-130498. For example, each component has a repetition number (n) in the general formula (6) of 1 to 38. Within the range, and by mixing and reacting at a ratio such that the number average molecular weight and the epoxy equivalent are included in the above range (II-2-
-4) The component is obtained. In this reaction, any catalyst such as an inorganic acid such as hydrochloric acid, phosphoric acid or sulfuric acid; an organic acid such as paratoluenesulfonic acid or oxalic acid; a metal salt such as zinc acetate can be used.

In the production of the component (II-2--4-), if necessary, the above-mentioned component (II-2--1),
(II-2--2) component and / or (II-2-
During or after the condensation polymerization reaction with the component (3), the monofunctional phenol compound represented by the general formula (10) (II-
2--6) can be reacted as an endcapping agent.

Specific examples of the monofunctional phenol compound represented by the general formula (10) as the component (II-2--6) include 2-t-butyl-4-methylphenol and 2,4. -Xylenol, 2,6-xylenol,
2,4-dichlorophenol, 2,4-dibromophenol, dichloroxylenol, dibromoxylenol,
2,4,5-Trichlorophenol, 6-phenyl-2-
Examples include chlorophenol.

Component (II-2--6) and the above (II
The polycondensation reaction with the component (2-1-), the component (II-2-2) and / or the component (II-2-3) can be performed in the same manner as above. In addition, (II-2-
The novolac type phenol resin obtained by using the component (6) together is also abbreviated as the component (II-2-4).

The phenol type novolac glycidyl ether resin represented by the general formula (6) is
4) To the phenolic hydroxyl group in the component (II-2--
It can be obtained by reacting the component 5) to form a glycidyl ether. Specifically, (II-2
--4) component is dissolved with (II-2--5) component, and an aqueous solution of alkali metal hydroxide is continuously added to this solution, and water of the reaction system and unreacted (II-2--
-5) Obtained by distilling off the component. The (II-2-5) component can be separated from this distilled liquid and reused. This reaction is preferably carried out in the presence of an ether solvent such as dioxane or diethoxyethane.

The phenol type novolak glycidyl ether resin as the curing agent (II-2) can be obtained as described above, but some of them are already on the market. For example, as a polyglycidyl ether compound of cresol type novolac resin, EPICRON N-69
5 (manufactured by Dainippon Ink and Co., Inc., trade name), ESCN-19
5XHH (Sumitomo Chemical Co., Ltd., trade name), EOCN-1
02S, EOCN-1020 and EOCN-104S
(Nippon Kayaku Co., Ltd., trade name); BREN-S (Nippon Kayaku Co., Ltd., trade name) as a polyglycidyl ether of brom-modified phenol type novolak resin; long-chain alkyl-modified phenol type novolak resin Examples of the polyglycidyl ether compound include ESMB-260 (trade name, manufactured by Sumitomo Chemical Co., Ltd.);

A compound having two or more glycidyl groups in one molecule, which are based on a glycidylamino group represented by the following general formula (11) directly bonded to a carbon atom of an aromatic ring.

[0090]

[Chemical 10] In the general formula (11), R ₆₁ is a hydrogen atom and has 1 to 1 carbon atoms.
It represents a group selected from 20 alkyl groups and glycidyl groups.

The component has an aromatic ring and a glycidyl group in one molecule, and the glycidyl group is introduced by the glycidylamino group represented by the general formula (11), and the nitrogen atom in the general formula (11) is used. (N) is directly bonded to a carbon atom of the aromatic ring. The component can be generally obtained by reacting an aniline derivative with epihalohydrin (preferably epichlorohydrin) in the presence of an aqueous alkali metal hydroxide solution or the like (catalyst). The aniline derivative is a compound in which an amino group (—NH ₂ ) is directly bonded to a carbon atom of a benzene ring or a naphthalene ring, and examples thereof include aniline, o-toluidine, m-
Toluidine, p-toluidine, o-ethylaniline, m
-Ethylaniline, p-ethylaniline, p-cresidine, 2,4-xylidine, 3-4-xylidine, o-anisidine, p-anisidine, naphthylamine and other benzene rings and naphthalene rings have an amino group (-N
H ₂ ) directly bonded to one monoaniline derivative; phenylenediamine, 2-4-toluylenediamine, diaminobenzanilide, dianisidine, diaminodiphenyl ether, 3,5-diaminochlorobenzene, 3,3-
Amino group (-on the carbon atom of benzene ring or naphthalene ring such as dimethylbenzidine and 1-5-naphthylenediamine)
And a dianiline derivative in which two NH ₂ ) are directly bonded.

In addition to the above monoaniline derivative and dianiline derivative, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; organic acids such as paratoluenesulfonic acid and oxalic acid;
Using a metal salt such as zinc acetate as a catalyst, aldehydes (eg formaldehyde, acetaldehyde, etc.) and ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) are reacted, and multiple aromatic rings are bound by methylene groups, etc. It is also possible to use a polycondensate obtained by the above, and the repeating unit of the aromatic ring of this polycondensation is generally in the range of 2 to 40, particularly preferably 2 to 20. Specific examples of such polycondensates include, but are not limited to, diaminodiphenylmethane, 3,3-dimethyl-4,4-diaminodiphenylmethane and 3,3-diethyl-4,4-diaminodiphenylmethane. is not.

The components obtained as described above are phenols such as bisphenol A, bisphenol F, phenylphenol, nonylphenol and phenol in a part of the glycidyl group; dimer acid, stearic acid, oleic acid, soybean oil fatty acid. And higher fatty acids such as; organic acids such as acetic acid, formic acid and hydroxyacetic acid; alcohols such as alkyl alcohol, cellosolve and carbitol; Of these, phenols and higher fatty acids are particularly preferable. For this modification, it is preferable to use a catalyst such as zinc borofluoride or tetramethylammonium chloride.

The component has a number average molecular weight of about 200 to 8,000, particularly 500 to 5,000, as measured by vapor pressure osmometry, and an epoxy equivalent of generally 100 to 2
000, particularly preferably in the range of 100 to 600. Commercially available products can be used as such components,
For example, GAN (Nippon Kayaku Co., Ltd., N, N-diglycidylaniline), GOT (Nippon Kayaku Co., Ltd., N, N-
Diglycidyl-O-toluidine), MY720 (Nippon Ciba Geigy, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane), MY722
(N, N, N ', N'-tetraglycidyl-3,3' dimethyl 4,4'-diaminodiphenylmethane, manufactured by Nippon Ciba Geigy Ltd.) and the like.

(II-3): Compounds having two or more carbon-carbon unsaturated groups (preferably α, β-ethylenically unsaturated groups) in one molecule, such as the compounds described below and To be

An average of two or more 3-alkoxyalkyl-3- (3-alkoxyalkyl-3-) represented by the following general formula (12) per molecule.
A resin having a (meth) acryloylureido group and having a weight average molecular weight of 800 to 50,000. This resin is known per se, and is disclosed in, for example, JP-A-2-279.
No. 774, which is described in detail.

[0097]

[Chemical 11] [In the formula, R ₇₁ represents a hydrogen atom or a methyl group, and R ₇₂
Represents an alkylene group having 1 to 4 carbon atoms, and R ₇₃ represents an alkyl group having 1 to 10 carbon atoms]: a polyisocyanate compound, an active hydrogen atom capable of reacting with the isocyanate group, and the following structural formula (13): A compound having no free isocyanate group and having two or more α, β-ethylenically unsaturated groups in one molecule, which is obtained by a reaction with an α, β-ethylenically unsaturated compound having a functional group shown.

[0098]

[Chemical 12] A polyisocyanate compound and an α, β-ethylenically unsaturated compound having an active hydrogen atom capable of reacting with the isocyanate group and a functional group represented by the structural formula (13) are used so that a free isocyanate group remains. Α, β-ethylenically unsaturated group in one molecule obtained by reacting the free isocyanate group with a resin having a primary or secondary amino group and / or a hydroxyl group A compound having two or more.

The above compounds and the above compounds are known per se and are described in detail, for example, in JP-B-55-30753.

In the cationic electrodeposition coating (III), the mixing ratio of the cationic resin (I) and the curing agent (II) is not strictly limited and can be arbitrarily selected according to the purpose. The cationic resin (I) is contained in an amount of 30 to 90% by weight, particularly 50 to 8 based on the total solid content weight ratio of the both components.
0% by weight, and the curing agent (II) is 70 to 10% by weight,
In particular, it is preferably used within the range of 50 to 20% by weight.
Further, in the cationic electrodeposition coating (III), in order to improve the water solubility or the water dispersibility of the cationic resin (I), a part or all of the basic groups of the cationic resin (I) are excluded. It is preferable to neutralize with an acid component such as acid, acetic acid, lactic acid, butyric acid, and propionic acid.

On the other hand, the self-curable coating resin (IV) provided by the present invention is obtained by partially reacting the cationic resin (I) and the curing agent (II). The cationic electrodeposition coating composition (V) containing the self-curing resin (IV) as a main component can be cross-linked and cured by heating as it is without adding a curing agent. The type of the curing agent (II) used here is not particularly limited, but among them, a partially blocked polyisocyanate compound in which a partial reaction is easily performed is preferable. Therefore, the self-curable coating resin (IV) has one or more isocyanate groups present in one molecule of the polyisocyanate compound.
Free isocyanate groups of the partially blocked polyisocyanate compound in which all but the other are blocked with a blocking agent are added to the cationic resin (I) in an inert organic solvent at a temperature of 40 to 200 ° C. Can be obtained by reacting until there is little or no. The use ratio of the partially blocked polyisocyanate compound and the cationic resin (I) is not strictly limited and can be arbitrarily selected depending on the purpose in consideration of curability. The ratio of the number of moles of the blocked polyisocyanate compound to the total number of moles of the primary and secondary amino groups and hydroxyl groups contained in (I) is usually in the range of 0.4 to 1.5. Is preferred.

The self-curable coating resin (IV) is
The cationic resin (I) may have an α, β-unsaturated double bond introduced therein. Such resin (IV)
Is one of two or more isocyanate groups present in one molecule of a polyisocyanate compound, and all other isocyanate groups are α, β-unsaturated double bonds and hydroxyl groups or secondary amide groups, etc. Α, β-unsaturated diisocyanate in one molecule obtained by reacting with a compound having active hydrogen of (eg, hydroxyalkyl (meth) acrylate, methylol (meth) acrylamide, alkoxyalkyl (meth) acrylamide). It can be obtained by reacting a monoisocyanate compound having a heavy bond and one isocyanate group with any or all of the primary, secondary amino and hydroxyl groups contained in the cationic resin (I). . in this case,
The amount of the α, β-unsaturated double bond introduced is particularly preferably such that the equivalent of the α, β-unsaturated double bond in the resin solid content is in the range of 200 to 2000.

Further, the cationic electrodeposition coating material (V) provided by the present invention is mainly composed of the self-curing coating resin (IV) protonated with the acidic compound as described above, which is dissolved in water. Alternatively, it can be obtained by dispersing. The curing agent (II) is not necessary, but may be blended if necessary.

The cationic electrodeposition coatings (III) and (V) of the present invention are mainly composed of a mixture of the cationic resin (I) and a curing agent (II) and a self-curing coating resin (IV). However, an extender pigment, an anticorrosive pigment, a dispersant, an anti-repellent agent, a curing accelerator and the like can be further added, if necessary. Of these, the pigment is preferably blended using the following pigment dispersion paste (VI).

The pigment dispersion paste (VI) is usually a cationic resin (I) and a self-curable coating resin (IV).
It can be prepared by mixing and dispersing one or more kinds selected from the above and a pigment (coloring pigment, extender pigment, anticorrosion pigment, etc.) in water, and further, if necessary, a plasticizer, a wetting agent,
You may contain surfactant, a defoaming agent, etc.

Mixing and dispersion of each of these components can be carried out by using a ball mill, a sand mill, a Crowles dissolver, a continuous disperser or the like, and the pigment is dispersed in a desired size and wetted with the above resin. Is preferred. After dispersion, the particle size of the pigment is less than 10 microns (about 6-in Hermann Grind Gauge power).
8) is preferred. This dispersion is preferably performed in water. In this case, it is preferable that a part or all of the basic groups in the cationic resin (I) and the self-curable coating resin (IV) are neutralized with the acidic compound to be protonated to prepare a dispersion liquid. The addition amount of the acidic compound is preferably adjusted so that the neutralization value of these resins is generally in the range of 5 to 200, particularly 10 to 150 in terms of KOH (mg / g). The water content in the aqueous dispersion of the pigment dispersion paste (VI) is not particularly limited, but is usually about 2
It is preferably within the range of 0 to 80% by weight.

The type of the above pigment in the pigment dispersion paste (VI) is not particularly limited, and examples thereof include color pigments such as carbon black, titanium white, lead white, lead oxide and red iron oxide; antimony oxide, zinc oxide and basic carbonic acid. Extending pigments such as lead, basic lead sulfate, barium carbonate, calcium carbonate, aluminum silica, magnesium carbonate, magnesium silica, clay, talc; strontium chromate, lead chromate, basic lead chromate, red lead, silicic acid. lead,
Examples thereof include anticorrosion pigments such as basic lead silicate, lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silicochromate, yellow lead, cyanamide lead, calcium leadate, lead suboxide, and lead sulfate. The mixing ratio of these pigments to the coating resin is usually preferably in the range of 2/1 to 7/1 in terms of solid content weight ratio.

The cationic electrodeposition coatings (III) and (V) prepared as described above are subjected to cationic electrodeposition coating on a suitable conductive substrate (object to be coated), and the coating film is, for example, 8
It can be heat-cured at a temperature of 0 to 250 ° C, preferably 120 to 160 ° C. In particular, in order to sufficiently cure the electrodeposition coating film by the cationic electrodeposition coating composition of the present invention at a low temperature of 160 ° C. or lower, a lead compound, a zirconium compound, a cobalt compound, an aluminum compound, a manganese compound, a copper compound, a zinc compound, iron It is effective to add one or more catalysts selected from compounds, chromium compounds, nickel compounds, tin compounds and the like. Specific examples of these metal compounds include chelate compounds such as zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, and manganese acetylacetonate; compounds having a β-hydroxyamino structure and lead (II) oxide. Chelation reaction products of; lead 2-ethylhexanoate, lead naphthenate, lead octylate, lead benzoate, lead acetate, lead lactate, lead formate, lead glycolate, zirconium octylate, and other carboxylates; To be

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

The cationic electrodeposition coating composition provided by the present invention is excellent in water dispersibility at low neutralization even if the cationic group imparting water dispersibility in the cationic resin is a tertiary amino group. Therefore, high pH and high throwing power can be obtained. Further, since a large amount of a compound having a primary hydroxyl group can be reacted with the cationic resin (I), a large number of primary hydroxyl groups, which are useful functional groups in various curing formation, are introduced into the resin. It is possible to provide a resin composition having improved curability and suitable for cathodic electrodeposition coating.

The method for forming an electrodeposition coating film on a conductive substrate using the cationic electrodeposition coating composition of the present invention is not particularly limited, and it can be carried out under ordinary cationic electrodeposition coating conditions. For example, a pigment, a curing catalyst, and other additives are added to the electrodeposition coating as needed, and the bath concentration (solid content concentration) is 5 to 40% by weight, preferably 10 to 25% by weight.
And a cationic electrodeposition bath having a bath pH in the range of 5-8, preferably 5.5-7 is prepared. At this time, it is preferable to use the object to be coated as a cathode and the stainless steel or carbon plate as the anode. The electrodeposition coating conditions are not particularly limited, but generally bath temperature: 20 to 30 ° C., voltage:
100 to 400 V, preferably 200 to 300 V, current density: 0.01 to 3 A / dm ² , normal time: 1 to 5 minutes, pole area ratio (A / C): 2/1 to 1/2, distance between poles : 10
It is desirable that the electrodeposition is 100 cm, with stirring. The thickness of the electrodeposition coating film is not strictly limited, but in general, a range of 3 to 200 μ is suitable based on the cured coating film.
After coating, pull up the article to be coated from the electrodeposition bath, wash with water, and air-dry if necessary, 70-250 ° C, preferably 120
It is preferable to heat-cure in the range of 160 ° C.

Since the cationic electrodeposition coating composition of the present invention uses the cationic resin (I) and the self-curing resin (V), it has water dispersibility, storage stability, bath stability, corrosion resistance, smoothness, etc. It is excellent.

The cationic electrodeposition coating composition of the present invention is excellent in water dispersibility at low neutralization even if the cationic group imparting water dispersibility in the cationic resin is a tertiary amino group. Therefore, high pH and high throwing power can be obtained. Further, since a large amount of those having a primary hydroxyl group can be used as the cationic group, a large number of primary hydroxyl groups, which are useful functional groups in various curing modes, can be introduced, and the curability is improved. A resin composition suitable for cathodic electrodeposition coating can be provided.

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. The percentages and parts attached to numerical values are based on "weight" unless otherwise specified.

[0115]

Example I. Production Example (1) Amine Compound (B) (B-1) : In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a water separator, 285 parts of stearic acid and 104 parts of hydroxyethylaminoethylamine and 80 parts of toluene was charged and 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 residual toluene was decompressed to obtain an amine value of 1
An amine compound (B-1) having a melting point of 50 and a solidification point of 76 ° C. was obtained.

(B-2) : (Comparative Example) 39 parts of monoethanolamine were charged in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
While maintaining the temperature at 0 ° C, 100 parts of N, N-dimethylaminopropylacrylamide was added dropwise and reacted at 60 ° C for 5 hours.

(2) Phenol compound (C) (C-1) : Diethanolamine 105 was added to a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
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 are reacted at 150 ° C. until the residual amount of epoxy groups becomes 0, and the solid content is 80%. (C-1) was obtained.

(C-2) : 170 parts of phenylphenol, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, and bisphenol A4 were placed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser.
56 parts, 0.2 parts of tetramethylammonium chloride and 345 parts of ethylene glycol monobutyl ether were added and reacted at 150 ° C. until the residual amount of epoxy groups became 0, and (C-2) with a solid content of 80% was added. Obtained.

(C-3) : A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with oleic acid 2
80 parts, bisphenol A diglycidyl ether having an epoxy equivalent of 190, 760 parts, bisphenol A, 456 parts,
0.2 parts of tetramethylammonium chloride and 374 parts of ethylene glycol monobutyl ether were added,
The reaction was carried out at 150 ° C. until the residual amount of the epoxy group became 0, to obtain (C-3) having a solid content of 80%.

(C-4) : In a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 371 parts of the amine compound (B-1), 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts of bisphenol A and 397 parts of ethylene glycol monobutyl ether were added, and the mixture was reacted at 150 ° C. until the residual amount of epoxy group became 0, and the solid content was 80% (C-
4) was obtained.

(3) Curing agent (II) (II-1): 5 parts in 174 parts of tolylene diisocyanate
268 parts of ethylene glycol monoethyl ether was added dropwise at 0 ° C over 2 hours, and the mixture was kept warm at 80 ° C for 3 hours to 8 hours.
A curing agent (II-1) having a solid content of 0% was obtained.

(II-2): In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping funnel, 222 parts of isophorone diisocyanate and 8 parts of methyl isobutyl ketone were added.
Charge 3.4 parts, 0.1 part of dibutyltin dilaurate and 1 part of hydroquinone monomethyl ether at 100 ° C.
Add 116 parts of hydroxyethyl acrylate and add NCO
The reaction was carried out until the value was 112, and a curing agent (II-2) was obtained.

(II-3): In a flask equipped with a stirrer, a thermometer, and a reflux condenser, EPICLON N-695.
(Dainippon Ink Co., Ltd. epoxy equivalent 213 n = 7) 1
917 parts, ethylene glycol monobutyl ether 59
0 part, 440 parts of nonylphenol and 0.2 part of tetramethylammonium chloride were charged and reacted at 150 ° C. until the epoxy equivalent became 350 to obtain (II-3).

(II-4): In a flask equipped with a stirrer, a thermometer, and a reflux condenser, EPICLON N-695.
(Dainippon Ink Co., Ltd. epoxy equivalent 213 n = 7) 1
917 parts, ethylene glycol monobutyl ether 62
0 parts, tall oil fatty acid 560 parts and tetramethylammonium chloride 0.2 parts were charged, and the epoxy equivalent was 3
It was made to react at 150 degreeC until it became 70, and (II-4) was obtained.

(II-5): EHPE-3150 (Epoxy equivalent 180, manufactured by Daicel Chemical Industries, Ltd.) 100 parts and ethylene glycol monobutyl ether 25 parts were heated and dissolved at 100 ° C. to obtain a solid content of 80% and an epoxy equivalent of 180. A curing agent (II-5) was obtained.

(II-6): ESMB-260 (Sumitomo Chemical Co., Ltd.) was attached to a flask equipped with a stirrer, a thermometer, and a reflux condenser.
100 parts of epoxy equivalent 260) and 25 parts of ethylene glycol monobutyl ether were charged and dissolved by heating to obtain (II-6).

(II-7): In a flask equipped with a stirrer, a thermometer, and a reflux condenser, MY720 (Nippon Ciba Geigy Ltd. N, N, N ′, N′-tetraglycidyl-4,
4 parts of 4'-diaminodiphenylmethane) and 25 parts of ethylene glycol monobutyl ether were charged and dissolved by heating, and the non-volatile content was 80% and the epoxy equivalent was 115 (II-
7) was obtained.

( II-8): A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 666 parts of isophorone diisocyanate, 11.4 parts of parabenzoquinone and 11.4 parts of dibutyltin dilaurate.
While maintaining the temperature at 120 ° C., 471 parts of Nn-butoxymethylacrylamide was added dropwise and reacted to have an NCO value of 1
When the amount reached 10, 134 parts of trimethylolpropane were added, and the reaction was carried out at 120 ° C. When the NCO value became 0, 295 parts of ethylene glycol monobutyl ether was added to obtain a curing agent (II-8).

II. Examples Examples 1-2: primary hydroxyl group-containing cationic resin (I)
In a flask equipped with a resin composition stirrer containing water-based paint as a main component, a thermometer, a dropping funnel and a reflux condenser, the components (A) to (C) shown in Table 1 were charged and gradually mixed and stirred. It was heated to 150 ° C. and reacted at 150 ° C., and it was confirmed that the residual amount of the epoxy group became 0, and thus a resin composition for an aqueous coating containing a cationic resin (I) as a main component was obtained.

Examples 3 to 5: Resin composition for water-based coating composition containing primary hydroxyl group-containing cationic resin (I) as a main component A flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was used. The components (A) to (C) shown in 1 were charged, gradually heated with mixing and stirring, and reacted at 150 ° C., and it was confirmed that the residual amount of epoxy group became 0, and then shown in Table 1. Other components were charged and reacted at 150 ° C., and it was confirmed that the residual amount of the epoxy group was 0, and a resin composition for an aqueous coating material containing a cationic resin (I) as a main component was obtained.

[0131]

[Table 1]

In Table 1, component (A) Name: Denacol EX-512 (manufactured by Nagase Kasei Co., Ltd.,
Trade name, polyglycerol polyglycidyl ether, number average molecular weight of about 630, average number of epoxy functional groups 4.1, epoxy equivalent of 167): Denacol EX-512 (manufactured by Nagase Chemical Industry Co., Ltd.,
Trade name, polyglycerol polyglycidyl ether, number average molecular weight about 1000, average number of epoxy functional groups 6.3,
Epoxy equivalent 172): Denacol EX-611 (manufactured by Nagase Kasei Co., Ltd.,
Trade name, sorbitol polyglycidyl ether, number average molecular weight of about 630, average number of epoxy functional groups 4.0, epoxy equivalent 170): Denacol EX-622 (manufactured by Nagase Chemical Industry Co., Ltd.,
Trade name, sorbitol polyglycidyl ether, number average molecular weight about 930, average number of epoxy functional groups 4.9, epoxy equivalent 198) (B) component name B-1: See the above production example B-3: diethanolamine (C) component name C -1 to C-4: Refer to the above production example. Example 6: Cationic resin (I-6) Denacol EX-611 (epoxy equivalent: 170 Nagase was added to a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 680 parts, manufactured by Kasei Kogyo Co., Ltd.), 246 parts of ethylene glycol monobutyl ether, 315 parts of diethanolamine and 798 parts of bisphenol A are charged, gradually heated with mixing and stirring, and reacted at 150 ° C., and the residual amount of epoxy group is 0. It was confirmed.

Thereafter, 294 parts of diethanolamine, 1710 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, and 703 parts of ethylene glycol monobutyl ether were added, and the mixture was reacted at 150 ° C. for 5 hours to confirm that the residual amount of epoxy groups was 0. And solid content 80
%, Amine value 86, primary hydroxyl group equivalent 327, A component 1
8% of cationic resin (I-6) was obtained.

Example 7: Self-curable coating resin (IV-
1) In a flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 680 parts of Denacol EX-611 (epoxy equivalent 170 manufactured by Nagase Kasei Co., Ltd.), 541 parts of methyl isobutyl ketone, and 315 parts of diethanolamine.
Parts and 798 parts of bisphenol A were charged, gradually heated with mixing and stirring, and reacted at 150 ° C. It was confirmed that the residual amount of epoxy groups was 0.

Then, 189 parts of diethanolamine, 371 parts of amine compound (B-1), 1710 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, and 568 parts of methyl isobutyl ketone were added, and 150
It was confirmed that the residual amount of epoxy group was 0 by reacting at 5 ° C for 5 hours.

Next, 2239 parts of the curing agent (II-2) was added and reacted at 80 ° C. until the NCO value became 0, 1463 parts of ethylene glycol monobutyl ether was added, and 1463 parts of methyl isobutyl ketone were removed by heating under reduced pressure. , Solid content 80%, amine value 52, primary hydroxyl equivalent 110
5, A component 11%, α, β unsaturated double bond equivalent 1105
To obtain a self-curable coating resin (IV-1).

Comparative Example 1 A flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 21 parts of diethanolamine and 190 equivalents of bisphenol A diglycidyl ether having an epoxy equivalent of 190.
0 part, 340 parts of polypropylene glycol diglycidyl ether having an epoxy equivalent of 340 and bisphenol A
Charge 456 parts, gradually heat while mixing and stirring, 1
After reacting at 20 ° C and confirming that the epoxy equivalent is 980, ethylene glycol monobutyl ether 492
Parts, and 158 parts of diethanolamine and 43 parts of the amine compound (B-2) were added while maintaining the temperature at 100 ° C. and reacted until the increase in viscosity stopped, solid content 80%, amine value 57, primary hydroxyl group equivalent. 532 comparative resin (1) was obtained. (No component A) Comparative Example 2 680 parts of Denacol EX-611 (epoxy equivalent 170 manufactured by Nagase Kasei Kogyo Co., Ltd.) and 275 parts of ethylene glycol monobutyl ether were placed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Then, 420 parts of diethanolamine was charged, the mixture was gradually heated with mixing and stirring, and reacted at 150 ° C., and it was confirmed that the residual amount of epoxy groups was zero.

Thereafter, 189 parts of diethanolamine, 1710 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 798 parts of bisphenol A, and 674 parts of ethylene glycol monobutyl ether were added, and the mixture was reacted at 150 ° C. for 5 hours to give a residual epoxy group of 0. It was confirmed that they were present, and a comparative resin (2) having a solid content of 80%, an amine value of 86, a primary hydroxyl group equivalent of 327, and an A component of 18% was obtained. Example 8: Pigment Paste (VI-1) 10 parts of the above cationic resin (I-2), 20 parts of titanium white (Typepec CR93 manufactured by Ishihara Sangyo Co., Ltd.), carbon (Mitsubishi Kasei Co., Ltd.) MA-7) 2 parts, aluminum tripolyphosphate (K White 84 manufactured by Teikoku Kako Co., Ltd.) 4 parts, clay (Dikelite manufactured by Sikhlite Chemical Co., Ltd.) 24 parts, acetic acid 0.4 parts After adding 39.6 parts of deionized water and kneading, add 200 parts of glass beads and disperse with a paint shaker. Coarse particles with a particle gauge of 10 μ or less, solid content 5
8% of pigment paste (VI-1) was obtained.

Examples 9 to 16 and Comparative Examples 3 to 4 A curing agent and a neutralizing agent were added to the above-mentioned cationic resin as shown in Table 2, and deionized water was added while sufficiently stirring and mixing the mixture to obtain a solid content. A 30% emulsion was obtained. Then, a mixture of the catalyst amount shown in Table 2 and 75 parts of the pigment paste (VI-1) was added to 333 parts of the emulsion, and deionized water was further added to the mixture to prepare a cationic electrodeposition coating having a solid content of 20%. (III) was obtained.

[0140]

[Table 2]

In Table 2, the lead content of lead octenoate is 38%, and the zinc content of zinc octenoate is 38%.

The cationic electrodeposition coating composition (III) obtained in Examples 9 to 16 and Comparative Examples 3 to 4 was applied to a zinc phosphate-treated steel sheet and an untreated steel sheet at a bath temperature of 25 ° C. to 100 V to 250 V.
The film was electrodeposited at a voltage of V for 3 minutes, washed with water, and then heated at 150 ° C. for 30 minutes to cure the coating film. The cured coating film thickness was 20μ. The performance test results of the above cationic electrodeposition coating (III) and the cured coating film are shown in Table 3.

[0143]

[Table 3]

(Test method) Stability: An emulsion having a solid content of 30% was used for 30 times.
It was stored tightly at 15 ° C. for 15 days, and the change in the particle size of the emulsion before and after storage was measured by using Coulter Nanonizer N-4. When the particle size is 0.3 μm or less, it is said that the dispersibility in water is excellent.

PH: JIS K-0802-83
JIS PH-8802-78
The measurement method is used.

Coating surface smoothness: The surface of the coating film which had been baked and cured under the above-mentioned conditions was visually judged.

SST: Salt spray resistance Under the above-mentioned coating conditions, the test paint was applied at a voltage to obtain 20μ and baked at 160 ° C. for 20 minutes.
Tested according to the method of Z2871, and within 2.0 mm on one side of the clique width from the cut (linear cut) portion of the coating film, and when the blisters of the coating film other than the cut portion are 8 F (ASTM) or less,
I passed. The test time was 1000 hours.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-2-265975 (JP, A) JP-A-60-79072 (JP, A) JP-A-3-170567 (JP, A) JP-A-4- 226172 (JP, A) JP 5-171108 (JP, A) JP 55-5932 (JP, A) JP 4-348171 (JP, A) JP 2-73876 (JP, A) JP-A-5-222157 (JP, A) JP-A-3-294499 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 163/00 C08G 59/50 C08G 59/62 C09D 5/44

Claims (7)

(57) [Claims] 1. (I) (A) A compound having at least 2.5 glycidyl ether groups on average derived from a polyol having at least 3 alcoholic hydroxyl groups bonded to an aliphatic carbon atom in one molecule, (B) a primary or secondary amine compound containing a primary hydroxyl group, and (C) the following general formula (1): [Wherein R ₁ and R ₂ represent the same or different groups selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, R _{3 to} R ₆ are hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, And a primary hydroxyl group-containing cationic resin obtained by reacting a phenol compound having a phenolic hydroxyl group-containing functional group represented by the same or different groups selected from an aromatic group, an allyl group and a halogen atom. (II) A cationic electrodeposition coating composition containing a curing agent as a coating film forming component. 2. The component (A) has an epoxy equivalent of 100 to 100.
The cationic electrodeposition coating composition according to claim 1, wherein the cationic electrodeposition coating composition is 1000 and has an average of 3 to 10 glycidyl ether groups in one molecule. 3. The cationic electrodeposition coating composition according to claim 1 or 2, wherein the component (C) is subjected to an addition reaction in a ratio of 0.05 to 1.4 mol per mol of the component (A). 4. The curing agent (II) is at least one selected from a blocked isocyanate compound, a polyepoxide compound, and a compound having two or more carbon-carbon unsaturated groups in one molecule. The cationic electrodeposition coating composition according to any one of 1 to 3. 5. A self-curable coating resin (IV) obtained by partially reacting the primary hydroxyl group-containing cationic resin (I) according to claim 1 with a curing agent (II).
A cationic electrodeposition coating composition containing as a coating film forming component. 6. A pigment paste comprising the primary hydroxyl group-containing cationic resin (I) according to claim 1 or the self-curable coating resin (IV) according to claim 5 and a pigment. . 7. An article coated with the cationic electrodeposition coating composition according to claim 1.