JPH1192711A - Paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating film showing excellent adherence, bleeding stain resistance and impact resistance by making a paint composition contain a modified epoxy resin, a hardening agent for a modified epoxy resin and a petroleum solvent. SOLUTION: A paint composition comprises not less than one of 3 modified epoxy resins, a hardening agent for the modified epoxy resins having an active hydrogen equivalent of 150-300 such as an dimer acid-modified and/or a ketiminized dimer acid-modified polyamide resin, etc., and a petroleum solvent having an ignition point of not less than 40 deg.C such as naphtha, etc. Three modified epoxy resins are a reaction product from an epoxy resin having not less than 2 epoxy groups and an average epoxy equivalent of 150-1,000 and a carboxylic group-containing acrylic resin having a weight average molecular weight of 3,000-50,000 and an acid value of resin of 3-300 mgKOH/g, a reaction product from an epoxy resin and an acid anhydride group-containing acrylic resin having a weight average molecular weight of 3,000-50,000 and an acid value of resin of 3-300 mgKOH/g and a reaction product obtained by grafting or copolymerizing a polymerizable unsaturated monomer on an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful coating composition, and more particularly, to a coating composition which is soluble in a high flash point petroleum solvent such as mineral spirit and has good adhesion when applied to a surface of a sealing material. The present invention relates to a coating composition capable of obtaining a coating film having excellent bleed stain prevention properties and impact resistance.

[0002]

2. Description of the Related Art Epoxy resins have been widely used as anti-corrosion paint resins because of their excellent corrosion resistance, adhesion and chemical resistance. When such a conventional epoxy resin is used in an organic solvent-diluted paint, it is generally dissolved in a low flash point, low boiling point and highly toxic organic solvent represented by toluene, xylene, methyl ethyl ketone, and ethyl acetate. It has to be used as a paint, which is very problematic from the viewpoint of safety at the time of painting and environmental protection.

[0003] In addition, since a conventional coating material using an epoxy resin contains the above-mentioned solvent, when applied as a repair coating material to an old coating film, the old coating film is dissolved or swelled, and coating defects such as lifting are caused. And when applied on a sealing material, there is a problem that the adhesion is poor.

On the other hand, a high flash point as a diluting solvent,
It is conceivable to use a petroleum-based solvent such as mineral spirit having a high boiling point and low pollution, but the conventional epoxy resin hardly dissolves in a petroleum-based solvent such as mineral spirit.

[0005] In order to solve these problems, as a method of making an epoxy resin soluble in mineral spirits, it has been proposed to modify the epoxy resin by reacting it with an aliphatic monocarboxylic acid, a diisocyanate compound or an alkylphenol (for example, JP-A-3-115318, JP-A-4-115
-39320). According to this method, the epoxy resin can be dissolved in the mineral spirit, but there is a problem that the adhesion to the sealing material is poor.

[0006] Sealing materials are mainly used for waterproofing from rainwater and stress applied from outside to joints (joints) of various PC boards, ceramic building materials, metal building materials, etc., which are frequently used as constituents of buildings. Movement of building by /
Almost all of them are cast in the field to absorb the expansion and contraction of building materials. The construction method of applying a decorative coating material on the surface of the sealing material and building material to cover and hide the joints where the sealing material is cast, and finish it like a large wall with a sense of unity, has a seamless and beautiful impression It is done frequently to give.

However, such joints cannot follow the peeling due to poor adhesion between the decorative coating material and the sealing material, the stain contamination due to oozing out of the plasticizing component, and the high elasticity of the sealing material due to the composition of the sealing material. There are many cases of accidents such as cracks in decorative coating materials due to
Change the decorative coating material to one with high elasticity, apply a putty material after laminating a mesh sheet on the surface of the sealing material, or apply a decorative finish after applying a cement filler to the surface of the sealing material. I was Depending on the sealing material used, a primer specified by a sealing material maker is applied in advance, and then the decorative finish is applied in order to prevent bleeding stains and ensure interlayer adhesion with the decorative coating material.

However, in the above-mentioned conventional method, when a highly elastic decorative coating material is used, the stain resistance of the surface is inferior. When a mesh sheet or a cement filler is used, the finished appearance of the decorative coating finish is required. If the designated primer is used, it is necessary to have an assortment of products according to the type of sealing material, and when repainting after aging, the history is often unknown and the burden on the contractor is extremely large. There were many problems.

[0009]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have made intensive studies to develop an epoxy resin soluble in a petroleum solvent such as mineral spirits. Was found to be not only soluble in petroleum solvents such as mineral spirits, but also capable of realizing suitability as a sealing material primer, and completed the present invention. Thus, according to the present invention, (A) a modified epoxy resin (a-1) obtained by reacting an epoxy resin with a carboxyl group-containing acrylic resin, and a modified epoxy resin obtained by reacting an epoxy resin with an acid anhydride group-containing acrylic resin. (B) at least one modified epoxy resin selected from an epoxy resin (a-2) and a modified epoxy resin (a-3) obtained by graft-polymerizing or copolymerizing a polymerizable unsaturated monomer with the epoxy resin; A coating composition comprising a resin curing agent and (C) a petroleum-based solvent as essential components is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention will be described below.

The coating composition of the present invention comprises a specific modified epoxy resin (A) and a curing agent (B) for the modified epoxy resin.
And a petroleum-based solvent (C) as essential components.

Modified epoxy resin (A): The modified epoxy resin (A) used in the present invention includes the following (a-1) to (a-
At least one modified epoxy resin selected from 3).

(A-1) Epoxy resin and carboxyl group
Modified epoxy resin made by reacting with acrylic resin
Fat: Modified epoxy resin (a-1) is a modified epoxy resin obtained by reacting an epoxy resin with a carboxyl group-containing acrylic resin.

The above epoxy resin has two or more epoxy groups in one molecule, and has an average epoxy equivalent of about 150 to 150.
In the range of about 1,000, preferably about 150 to about 500
Epoxy resin within the range. When the epoxy equivalent of the epoxy resin exceeds about 1,000, the resulting modified epoxy resin has reduced solubility in mineral spirits,
In addition, the curability decreases, which is not preferable. Examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, epoxy ester resin obtained by modifying the above epoxy resin with dibasic acid, etc., alicyclic epoxy resin, poly Glycol type epoxy resin, epoxy group-containing acrylic resin and the like can be mentioned. Specifically, DER
-331J (manufactured by Dow Chemical Company), EPON # 828,
834, 806H (manufactured by Yuka Shell), GY # 260
(Made by Asahi Ciba), EPOMIC R # 140P (made by Mitsui Petrochemical Industries), Epototo YD128 (made by Toto Kasei), ERL-4221, 4229 (made by Union Carbide), Denacol EX-830 (Nagase Chemical) Commercially available products such as A. The epoxy resin preferably has an average epoxy equivalent in the range of about 150 to about 1,000.
Even if about 500 epoxy resins are used in combination, a mixture of epoxy resins having an average epoxy equivalent in the range of about 150 to about 1,000 can be used as a whole. The carboxyl group-containing acrylic resin generally has a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,
Within the range of 000 to 20,000, the resin acid value is 3 to 300.
mgKOH / g, preferably 10-100 mg
It is in the range of KOH / g. If the weight average molecular weight of the carboxyl group-containing acrylic resin is less than 3,000, the processability of the cured coating film becomes poor, and conversely 50,000
Exceeding both values is not preferred because the viscosity of the coating material increases. When the resin acid value of the carboxyl group-containing acrylic resin is less than 3 mgKOH / g, the solubility of the resulting modified epoxy resin in mineral spirit decreases, and when it exceeds 300 mgKOH / g, the viscosity of the paint increases. Neither is preferred.

The carboxyl group-containing acrylic resin can be easily obtained by copolymerizing a vinyl monomer having a carboxyl group and other vinyl monomers by a conventional method.

Examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate and the like can be mentioned.

Other vinyl monomers include, for example, vinyl monomers having a hydroxyl group; (meth) acrylates; vinyl ethers and aryl ethers;
Olefinic compounds and diene compounds; hydrocarbon ring-containing unsaturated monomers; nitrogen-containing unsaturated monomers; hydrolyzable alkoxysilyl group-containing monomers; epoxy group-containing monomers.

As the vinyl monomer having a hydroxyl group,
For example, 2-hydroxyethyl (meth) acrylate,
C2-C8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as 3-hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; and polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; A) Monoesters with unsaturated carboxylic acids such as acrylic acid; monoethers with polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol and hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; Monoesterified product of an unsaturated compound containing an acid anhydride group such as maleic acid or itaconic anhydride and a glycol such as ethylene glycol, 1,6-hexanediol, neopentyl glycol, etc. Is a diester product; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; allyl alcohol and the like; 2-hydroxypropyl (meth) acrylate; α, β-unsaturated carboxylic acid and Cardura E10 (manufactured by Shell Petrochemical Co., Ltd.) Adducts with monoepoxy compounds such as (name) and α-olefin epoxides; adducts of glycidyl (meth) acrylate with monobasic acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid and fatty acids; Adducts of the above hydroxyl group-containing monomer with lactones (eg, ε-caprolactone, γ-valerolactone) and the like can be mentioned.

Examples of (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, stearyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate,
C1-24 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as stearyl methacrylate and cyclohexyl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate,
Examples thereof include alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as ethoxybutyl acrylate and ethoxybutyl methacrylate.

Examples of the vinyl ethers and aryl ethers include chain alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, and octyl vinyl ether; cyclopentyl vinyl ether; Cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and trivinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether.

Examples of the olefinic compound and the diene compound include ethylene, propylene, butylene, vinyl chloride, butadiene, isoprene, chloroprene and the like.

Examples of the hydrocarbon ring-containing unsaturated monomer include styrene, α-methylstyrene, phenyl (meth) acrylate, phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-
Acryloyloxyethyl hydrogen phthalate, 2
-Acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, esterified product of p-tert-butyl-benzoic acid and hydroxyethyl (meth) acrylate, dicyclopentenyl (Meth) acrylate and the like.

Examples of the nitrogen-containing unsaturated monomer include:
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
Nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) Polymerizable amides such as acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 2-vinylpyridine, 1-vinyl-2-pyrrolidone, 4-vinylpyridine and the like Aromatic nitrogen-containing monomers; polymerizable nitriles such as acrylonitrile and methacrylonitrile; allylamine.

Examples of the hydrolyzable alkoxysilyl group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, and vinyltriacetoxy. Silane and γ- (meth) acryloyloxypropyltriethoxysilane.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.

As the copolymerization method, a general polymerization method of a vinyl monomer can be used, but a solution type radical polymerization method in an organic solvent is most suitable in consideration of versatility and cost. That is, by performing a copolymerization reaction in the range of about 60 to 150 ° C. in the presence of a polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide in a petroleum solvent such as mineral spirits, the objective is easily achieved. Can be obtained.

In the present invention, the epoxy resin and the carboxyl group-containing acrylic resin are reacted with each other to obtain the modified epoxy resin (a-1). The epoxy group and the carboxyl group of the carboxyl group-containing acrylic resin are mixed at an equivalent ratio of 1: 0.05 to 1: 0.5, for example, in the presence of an epoxy group / carboxyl group reaction catalyst. The heating reaction may be performed for about 1 to 10 hours. Examples of the epoxy group / carboxyl group reaction catalyst include quaternary salt catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, triphenylbenzylphosphonium chloride; triethylamine, tributylamine And the like. The reaction temperature is preferably about 120 to 150 ° C.

(A-2) Epoxy resin and acid anhydride group-containing resin
Modified epoxy resin obtained by reacting with a krill resin: Modified epoxy resin (a-2) is a modified epoxy resin obtained by reacting an epoxy resin with an acrylic resin having an acid anhydride group.

As the epoxy resin, the epoxy resin described in the modified epoxy resin (a-1) can be used as it is.

The acrylic resin containing an acid anhydride group is usually
Weight average molecular weight in the range of 3,000 to 50,000,
It is preferably in the range of 5,000 to 20,000, and the total acid value of the resin is in the range of 3 to 300 mgKOH / g, preferably in the range of 10 to 100 mgKOH / g. The acid anhydride group-containing acrylic resin has a weight average molecular weight of 3,000.
If it is less than 0, the processability of the cured coating film will be poor, and conversely 5
When it exceeds 000, the viscosity of the coating material becomes high, and neither is preferable. Further, when the acid value of the acid anhydride group-containing acrylic resin is less than 3 mgKOH / g, the solubility of the modified epoxy resin obtained in mineral spirit is reduced, and when it exceeds 300 mgKOH / g, the viscosity of the coating material is increased. Therefore, neither is preferable.

The acid anhydride group-containing acrylic resin can be easily prepared by copolymerizing a vinyl monomer having an acid anhydride group and another vinyl monomer in the same manner as in the case of the modified epoxy resin (a-1). Obtainable.

Examples of the vinyl monomer having an acid anhydride group include those having maleic anhydride, itaconic anhydride and the like.

Other vinyl monomers include, for example, a vinyl monomer having a carboxyl group as exemplified in the modified epoxy resin (a-1); a vinyl monomer having a hydroxyl group; (meth) acrylates; vinyl ether and aryl ether; Olefinic compounds and diene compounds; hydrocarbon ring-containing unsaturated monomers; nitrogen-containing unsaturated monomers; hydrolyzable alkoxysilyl group-containing monomers; epoxy group-containing monomers.

In the present invention, in order to obtain the modified epoxy resin (a-2) by reacting the epoxy resin and the acid anhydride group-containing acrylic resin, the epoxy resin and the acid anhydride group-containing acrylic resin are mixed with each other. Equivalent ratio of epoxy group of resin and acid anhydride group of acid anhydride group-containing acrylic resin is mixed at a ratio of 1: 0.02 to 1: 0.2, for example, tetraethylammonium bromide, tetrabutylammonium A quaternary salt catalyst such as bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, and triphenylbenzylphosphonium chloride; usually a heating reaction for about 1 to 10 hours in the presence of a catalyst such as amines such as triethylamine and tributylamine It should be done. The reaction temperature is 120
About 150 ° C. is appropriate.

(A-3) Polymerizable unsaturated monomer is added to the epoxy resin.
Modified epoxy obtained by graft polymerization or copolymerization of nomer
Resin: Modified epoxy resin (a-3) is a modified epoxy resin obtained by subjecting an epoxy resin to a graft reaction with a polymerizable unsaturated monomer.

As the epoxy resin, the epoxy resin described in the modified epoxy resin (a-1) can be used as it is.

In the present invention, the modified epoxy resin (a-
In order to obtain 3), a polymerizable unsaturated monomer is mixed with 100 parts by weight of the epoxy resin in a ratio within a range of 10 to 2,000 parts by weight, and azobisisobutyronitrile, benzoyl peroxide and the like are mixed. In the presence of a polymerization initiator, preferably a peroxide-based polymerization initiator such as benzoyl peroxide to promote the grafting efficiently, 60 to 1
The heating reaction may be carried out usually at about 50 ° C. for about 1 to 10 hours.

As the polymerizable unsaturated monomer, for example,
Vinyl monomers having an acid anhydride group exemplified in the modified epoxy resins (a-1) and (a-2); vinyl monomers having a carboxyl group; vinyl monomers having a hydroxyl group; (meth) acrylates; vinyl ethers and aryls Ether; olefinic compounds and diene compounds; hydrocarbon ring-containing unsaturated monomers; nitrogen-containing unsaturated monomers; hydrolyzable alkoxysilyl group-containing monomers; epoxy group-containing monomers. Curing agent for modified epoxy resin (B): The curing agent for modified epoxy resin used in the present invention has an active hydrogen equivalent of 150 to 30.
A curing agent that is in the range of 0.

As the above-mentioned curing agent, conventionally known curing agents for epoxy resins can be used. Specifically, for example, aliphatic curing agents such as metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, etc. Polyamines; epoxy resin adducts, ketiminated compounds, polyamidoamines, polyamide resins and the like of the aliphatic polyamines, and these can be used alone or in combination of two or more. Among them, in the present invention, as a curing agent for epoxy resin, for example, dimer acid-modified polyamide resin such as “S8022” (trade name, manufactured by Harima Corporation) and / or, for example, “G5B221” (Henkel Japan) It is preferable to use a ketiminated dimer acid-modified polyamide resin such as a product name of (trade name, manufactured by Corporation). In the ketiminated dimer acid-modified polyamide resin, the ketiminization rate is preferably 80% or more, and more preferably 90% or more, from the viewpoints of the elongation and adhesion of the coating film.

Petroleum-based solvent (C): As the petroleum-based solvent used in the present invention, for example, mineral spirit, naphtha,
Solvesso 100, 150, 200 (manufactured by Exxon Chemical Co., Ltd.) and Swazole 100, 200, 310 as commercial products
(Maruzen Petrochemical Co., Ltd.), A Solvent (Nippon Oil Co., Ltd.)
And the like, and a high flash point solvent having a flash point of 40 ° C. or more is suitably used. These may be used alone or in combination of two or more kinds, or may be used in combination with a small amount of another solvent containing these as a main component. Other solvents include hydrocarbon solvents such as toluene, xylene and solvent naphtha, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone,
Ester solvents such as ethyl acetate can be used.

The coating composition of the present invention may further contain, if necessary, pigments such as coloring pigments, extender pigments, anticorrosion pigments, etc .; additives for coatings such as modified resins, thickeners and dispersants. be able to.

[0042]

The coating composition of the present invention uses a modified epoxy resin which is soluble in petroleum solvents such as mineral spirit, which has a high flash point, a high boiling point and a low pollution property, It can be made into a paint, so the coating environment and workability are good. Furthermore, it does not dissolve or swell the old paint film even when it is applied for repairing old paint films, and has good adhesion even when applied to the sealing material surface. Thus, a coating film having excellent corrosion resistance, impact resistance, and the like can be obtained, and various excellent coating film performances that cannot be achieved by a conventional epoxy resin coating material can be exhibited.

[0043]

EXAMPLES Hereinafter, Production Examples, Examples and Comparative Examples will be given,
The present invention will be described more specifically. Note that “parts” and “%” in each example are based on weight.

Production Example 1 A four-necked flask equipped with a heating device, a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing device and a dropping funnel was charged with 704 parts of mineral spirit, and heated and stirred while introducing nitrogen gas. At 130 ° C., the following mixture was added
The mixture was dropped uniformly over time, and aged for 2 hours after dropping to obtain a carboxyl group-containing acrylic resin solution (a).

Acrylic acid 60 parts Styrene 60 parts Ethyl acrylate 60 parts Isobutyl methacrylate 720 parts 2-Ethylhexyl methacrylate 300 parts T-butyl peroxy-2-ethylhexanoate 96 parts The obtained carboxyl group-containing acrylic resin solution (a) Has a nonvolatile content of 61%, a carboxyl group-containing acrylic resin has a weight average molecular weight of about 10,000, and a resin acid value of 39.
mg KOH / g.

Production Example 2 A four-necked flask equipped with a heating device, a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing device and a dropping funnel was charged with 704 parts of mineral spirit, and heated and stirred while introducing nitrogen gas. At 130 ° C., the following mixture was added
The mixture was dropped uniformly over time, and aged for 2 hours after dropping to obtain a carboxyl group-containing acrylic resin solution (b).

Acrylic acid 60 parts Styrene 36 parts Ethyl acrylate 60 parts Isobutyl methacrylate 720 parts 2-ethylhexyl methacrylate 300 parts γ-methacryloxypropyl trimethoxysilane 24 parts t-butyl peroxy-2-ethylhexanoate 96 parts The carboxyl group-containing acrylic resin solution (b) had a nonvolatile content of 61%, a carboxyl group-containing acrylic resin having a weight average molecular weight of about 10,000 and a resin acid value of 39.
mg KOH / g.

Production Example 3 A four-necked flask equipped with a heating device, a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing device and a dropping funnel was charged with 704 parts of mineral spirit, and heated and stirred while introducing nitrogen gas. At 130 ° C., the following mixture was added
The mixture was dropped uniformly over time, and aged for 2 hours after dropping to obtain an acid anhydride group-containing acrylic resin solution (c).

Maleic anhydride 60 parts Styrene 30 parts Methyl methacrylate 60 parts T-butyl methacrylate 330 parts 2-ethylhexyl methacrylate 720 parts T-butyl peroxy-2-ethylhexanoate 96 parts The obtained acrylic resin containing an acid anhydride group Solution (c) has a nonvolatile content of 60%, a weight average molecular weight of the acid anhydride group-containing acrylic resin of about 10,000, and a total acid value of the resin of 57 mg KOH.
/ G.

Production Example 4 112.5 parts of "Epicoat 828EL" (product of Yuka Shell Epoxy Co., Ltd., trade name, bisphenol A type epoxy resin, epoxy equivalent 187) and "Versadim 216" (Henkel Hakusui 37.5 parts of a product, trade name, dimer acid, acid value 195 mg KOH / g) and 0.03 part of tetraethylammonium bromide, and heated to 130 ° C. under a nitrogen stream to carry out a reaction for about 3 hours to carry out an epoxy ester resin. I got The epoxy equivalent of the obtained epoxy ester resin was 323. Then
250 parts of the carboxyl group-containing acrylic resin solution (a) obtained in Production Example 1 and 0.06 parts of tetraethylammonium bromide were charged, and the mixture was heated to 120 ° C. and reacted for about 2 hours, and the acid value of the resin was 0.3 mg KOH / g or less, add 100 parts of mineral spirits,
An acryl-modified epoxy resin solution (d) was obtained. The obtained acrylic-modified epoxy resin solution (d) had a nonvolatile concentration of 61% and an epoxy equivalent of 803 (solid content).

Production Example 5 Production Example 4 was repeated except that the carboxyl group-containing acrylic resin solution (b) obtained in Production Example 2 was used instead of the carboxyl group-containing acrylic resin solution (a) obtained in Production Example 1. In the same manner as in Example 4, an acrylic-modified epoxy resin solution (e) having a nonvolatile content of 61% and an epoxy equivalent of 815 (solid content) was obtained.

Production Example 6 A reaction vessel was charged with 240 parts of “Epicoat 828EL”, 60 parts of nonylphenol (trade name, product of Mitsui Toatsu Co., Ltd., hydroxyl value 250 mg KOH / g), and 0.03 part of tetraethylammonium bromide. 1 under the airflow
The mixture was heated to 50 ° C. and reacted for about 2 hours to obtain a nonylphenol-modified epoxy resin. The epoxy equivalent of the obtained nonylphenol-modified epoxy resin was 281. Next, the acid anhydride group-containing acrylic resin solution (c) obtained in Production Example 3 was added to the obtained nonylphenol-modified epoxy resin.
333 parts and tetraethylammonium bromide 0.
One part was charged, and the mixture was heated to 120 ° C. and reacted for about 3 hours. When the resin acid value became 0.5 mg KOH / g or less, 200 parts of mineral spirit was added to obtain an acrylic-modified epoxy resin solution (f). Was. The obtained acrylic-modified epoxy resin solution (f) had a nonvolatile content of 60% and an epoxy equivalent of 511 (solid content).

Production Example 7 A reaction vessel was charged with 90 parts of “Epicoat 828EL” and 120 parts of mineral spirits, and charged under a nitrogen stream at 140 parts.
The mixture was heated to ℃, and the following mixture was dropped uniformly over 3 hours. After dropping, the mixture was aged for 2 hours, and then 107 parts of mineral spirit was added to obtain an acrylic-modified epoxy resin solution (g). The obtained acrylic-modified epoxy resin solution (g) had a nonvolatile concentration of 70% and an epoxy equivalent of 1,2.
70 (solid content).

Styrene 50 parts Methyl methacrylate 150 parts 2-ethylhexyl acrylate 120 parts 2-ethylhexyl methacrylate 190 parts t-butylperoxy-2-ethylhexanoate 30 parts Examples 1 to 12 and Comparative Examples 1 to 2 A main agent and a curing agent were prepared according to the formulation shown, and the main agent and the curing agent were mixed so that the ratio of active hydrogen equivalent of the curing agent / epoxy equivalent of the main agent was 0.8, to obtain a surface treatment agent for a sealing material.

A flexible plate having a joint groove of 10 mm × 8 mm square was prepared as a base plate, sealing materials having various compositions shown in the following (Note 1) were placed in the joint groove, and dried at room temperature for 3 days. The surface treating agent for a sealing material obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was
Coating was performed with a brush at a coating amount of 0 g / m ² . After drying it for 2 days, "Allethretan white" (trade name, acrylic urethane resin paint, manufactured by Kansai Paint Co., Ltd.) is applied to the entire surface of the test piece with a roller (coating amount: 150 g / m ² × 2 times).
The specimen was prepared.

(Note 1) to (Note 6) in Table 1 are as follows.

(Note 1) A: "Hamatite UH30" (manufactured by Yokohama Rubber Co., Ltd., trade name, two-pack type urethane sealing material) B: "Hamatite SC500" (manufactured by Yokohama Rubber Co., Ltd.)
Product name: two-component type polysulfide sealing material) C: "Hamatite Super II" (manufactured by Yokohama Rubber Co., Ltd., product name; two-component type modified silicone sealing material) D: "Hamatite Silicon 70" (Yokohama Rubber Co., Ltd.) (Trade name, two-pack type silicone sealing material) (Note 2) "A Solvent": Nippon Oil Co., Ltd., trade name, petroleum-based solvent (Note 3) "DMP-30": Shell Co., Ltd. Brand name, curing accelerator (Note 4) "BYK-053": Big Chemie Japan Co., Ltd., brand name, defoamer (Note 5) "80% S8022": Harima Co., Ltd. , Trade name, polyamide type curing agent, active hydrogen equivalent 190, resin solid content 80% (Note 6) "100% G5B221": manufactured by Henkel Japan Co., Ltd., trade name, ketiminated polyamide type curing agent,
Active hydrogen equivalent 220, resin solid content 100%, ketimine conversion rate 90% The specimens of Examples 1 to 12 and Comparative Examples 1 and 2 obtained as described above were subjected to a performance test and evaluated. The results are shown in Table 1.

The evaluation method of the performance test in Table 1 is as follows.

Stain resistance due to outdoor exposure: The test specimen was placed on the south side 3
It was exposed for 6 months at a 0 degree inclination, and the degree of contamination after the exposure was visually evaluated according to the following criteria.

◎: No stain is observed at all, ：: Slight stain is observed, X: Extremely stain is observed.

Adhesion: The adhesion was evaluated according to the following criteria in accordance with the test method of "cross cut tape method" of JIS K-5400.

◎: No peeling was observed at all, 一部: Peeling was observed in a part of the coating film of the scratch of the cutter, ×: 25% or more of the coating film was observed.

Initial Drying Property: The dryness to the touch after 24 hours was evaluated according to the following criteria according to the test method of “drying time / curing time” of JIS K-5400.

◎: No tackiness was observed at all, ：: Slight tackiness was observed, ×: Adhesion was remarkable.

Finishing property of top coat: JIS K-5400
Was visually evaluated according to the following criteria in accordance with the test method of “Overcoat compatibility”.

：: good, ×: shrinkage is observed.

Heating / cooling repetition test: JIS A-6909
"The coated surface after 10 cycles was visually evaluated according to the following criteria in accordance with the test method of resistance by repeated action of warming and cooling.

：: No abnormality at all, ×: Cracking and peeling were observed.

[0069]

[Table 1]

[0070]

[Table 2]

Claims (9)

[Claims] 1. A modified epoxy resin (a) obtained by reacting (A) an epoxy resin with a carboxyl group-containing acrylic resin.
-1), a modified epoxy resin (a-2) obtained by reacting an epoxy resin with an acid anhydride group-containing acrylic resin, and a modified epoxy resin (a) obtained by graft-polymerizing or copolymerizing a polymerizable unsaturated monomer with an epoxy resin. A coating composition comprising, as essential components, at least one modified epoxy resin selected from -3), (B) a curing agent for the modified epoxy resin, and (C) a petroleum-based solvent. 2. The modified epoxy resin (a-1) to (a)
The epoxy resin used in the production of -3) has two or more epoxy groups in one molecule and has an average epoxy equivalent of about 1
The composition of claim 1, wherein the composition is in the range of 50 to about 1,000. 3. A carboxyl group-containing acrylic resin used in the production of the modified epoxy resin (a-1) has a weight average molecular weight of 3,000 to 50,000, a resin acid value of 3 to 50,000.
The composition according to claim 1, wherein the composition is in the range of 300 mg KOH / g. 4. The modified epoxy resin (a-1) has an equivalent ratio of an epoxy group of the epoxy resin to a carboxyl group of the carboxyl group-containing acrylic resin of 1: 0.05 to 1:
The composition according to claim 1, which is a reaction product obtained by reacting at a ratio falling within the range of 0.5. 5. An acid anhydride group-containing acrylic resin used in the production of the modified epoxy resin (a-2) has a weight average molecular weight in the range of 3,000 to 50,000 and a total acid value of the resin of 3 to 3
A composition according to claim 1, which is in the range of 00 mg KOH / g. 6. The modified epoxy resin (a-2) has an equivalent ratio of an epoxy group of the epoxy resin to an acid anhydride group of the acrylic resin containing an acid anhydride group of 1: 0.02 to 1: 0.2. The composition according to claim 1, which is a reaction product obtained by reacting at a ratio within the above range. 7. A reaction obtained by reacting the modified epoxy resin (a-3) with a polymerizable unsaturated monomer in a proportion within the range of 10 to 2,000 parts by weight based on 100 parts by weight of the epoxy resin. The composition of claim 1 which is a product. 8. The composition according to claim 1, wherein the curing agent (B) for modified epoxy resin has an active hydrogen equivalent in the range of 150 to 300. 9. The curing agent for a modified epoxy resin (B),
The composition according to claim 1, which is a dimer acid-modified polyamide resin and / or a ketiminated dimer acid-modified polyamide resin.