JP2002114835A - Curing agent composition for epoxy resin and coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curing agent composition for epoxy resins capable of providing a nontar and low-solvent type anticorrosive coating composition excellent in adhesion to a substrate or a top coat by combination with a polyepoxy compound. SOLUTION: This curing agent composition for the epoxy resins is characterized in that the curing agent composition is obtained by adding (c) a glycidyl ether compound to a polyamidoamine compound obtained from (a) a polyamine compound containing >=50 mol% of m-xylylenediamine with (b) a dimer acid, a trimer acid or a hydrogenatad substance thereof or a mixture of aliphatic carboxylic acid compounds in which the dimer acid, trimer acid or the hydrogenated substance thereof accounts for >=0.5 equivalent in one equivalent of the total carboxy groups, the content of the carboxy groups in the component (b) is 0.1-0.35 equivalent based on 1 equivalent of primary amino groups in the component (a), the total content of the carboxy groups in the component (b) and the epoxy groups in the component (c) is 0.4-0.6 equivalent and the chlorine content is <=0.05 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curing agent composition for an epoxy resin, and more particularly to a polyamine compound mainly composed of metaxylenediamine, a carboxylic acid compound mainly composed of dimer acid or a hydrogenated product thereof, and a glycidyl ether compound. The present invention relates to a curing agent composition for an epoxy resin which can provide a coating composition having excellent adhesion to a base material such as a steel plate or a top coating by combining this with a main agent comprising a polyepoxy compound. .

[0002]

2. Description of the Related Art Epoxy resins have good adhesiveness to various substrates, heat resistance, chemical resistance, and the like.
Because of their excellent electrical and mechanical properties, they are widely used as paints, adhesives and the like.

[0003] Solvent type tar-containing paints and paints containing heavy metals and the like have hitherto been used for heavy anticorrosion applications such as steel structures on land and bridges or ships. However, particularly in the case of an outdoor structure, the paint is often applied in an erection environment, and most of the solvent in the paint is released into the atmosphere, so that there is a concern about the influence on the environment and the human body. In particular, the carcinogenicity of tar has become a problem, and since it is difficult to discriminate corrosion or the like after painting due to its black color, the movement of tar removal has become active. In addition, in recent years VOCs in Europe
(Volatile organic compounds) The development of low solvent type paints has been desired, for example, as emission regulations become stricter.

Many studies have been made on non-tar anticorrosive paints, for example, as disclosed in Japanese Patent Application Laid-Open No. 9-30227.
No. 6 proposes an anticorrosion paint composition comprising an epoxy resin, an amine-based curing agent, and a residual oil having a softening point of 50 to 150 ° C. JP-A-10-259351 proposes a non-tar epoxy resin coating composition comprising a curing agent composed of a bisphenol epoxy resin, a vinyl chloride copolymer and a polyamide or a modified product thereof. JP-A-11-171977 proposes an amine-based curing agent obtained by reacting an epoxy resin with a mixture of xylylenediamine and an aliphatic amine, bisphenol A, bisphenol F or a condensate of carbonic acid and formaldehyde. It is described that this is suitably used for an anticorrosion paint. Further, Japanese Unexamined Patent Application Publication No. 11-1
JP-A-72195 discloses an anticorrosion paint comprising an epoxy resin, a mixture of xylylenediamine and an aliphatic amine, bisphenol A, bisphenol F or an amine-based curing agent obtained by reacting a condensate of phenol and formaldehyde with an epoxy resin and a petroleum resin. Compositions have been proposed.

However, with known amine curing agents, when the solvent is reduced, only those having insufficient adhesion to a base material such as a steel sheet or adhesion to a top coat are obtained. There is no current situation.

Accordingly, an object of the present invention is to provide a non-tar, low-solvent type anticorrosion coating composition having excellent adhesion to a base material or a top coating composition by combining with a polyepoxy compound. It is to provide a curing agent composition.

[0007]

The present inventors have conducted intensive studies and as a result, have found that polyamine compounds mainly composed of meta-xylene diamine, carboxylic acid compounds mainly composed of dimer acid, trimer acid or hydrogenated products thereof. And a specific epoxy resin curing agent composition obtained from a polyglycidyl ether compound, a non-tar, low solvent type anticorrosion paint having excellent adhesion to a base material or a topcoat paint by using in combination with a polyepoxy compound. Finding what we can offer,
The present invention has been reached.

That is, the present invention relates to (a) a polyamine compound containing at least 50 mol% of metaxylenediamine and (b) a dimer acid, trimer acid or a hydrogenated product thereof, or a mixture thereof in an amount of 0 equivalents per 1 equivalent of total carboxyl groups. (C) a curing agent composition for epoxy resin obtained by adding a glycidyl ether compound to a polyamidoamine compound obtained from a mixture of an aliphatic carboxylic acid compound occupying at least 5 equivalents; The carboxyl group of the component (b) is 0.1 equivalent to 1 equivalent of the primary amino group of the component.
And the carboxyl group of the component (b) and the epoxy group of the component (c) together are 0.4 to 0.65 equivalents.
An object of the present invention is to provide a curing agent composition for an epoxy resin, which has an equivalent weight and a chlorine content of 0.05% by weight or less.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the curing agent composition for an epoxy resin of the present invention will be described in detail.

The curing agent composition for an epoxy resin of the present invention comprises:
(A) a polyamine compound containing at least 50 mol% of meta-xylene diamine and (b) dimer acid or a hydrogenated product thereof or 0.5% or less of them in one equivalent of total carboxyl groups.
An epoxy resin curing agent composition comprising a polyamine-based curing agent obtained by adding (c) a glycidyl ether compound to a polyamideamine compound obtained from a mixture of an aliphatic carboxylic acid compound occupying an equivalent amount or more.

The carboxyl group of the component (b) is used in an amount of 0.1 to 1 equivalent of the primary amino group of the component (a).
0.35 equivalents, especially 0.15 to 0.3 equivalents. Here, when the carboxyl group of the component (b) is used in less than 0.1 equivalent, there is a possibility that the adhesion to the base material and the top coating material may be reduced. Is not preferable because the curability may decrease. Further, the total of the carboxyl group of the component (b) and the epoxy group of the component (c) is 0.4 to 0.6 equivalent, particularly 0.45 to 0.6.
0.55. If it is less than 0.4 equivalent, there is a possibility that the adhesion to the base material or the top coat may decrease, and if it exceeds 0.6 equivalent, the viscosity increases and the curability may decrease, which is not preferable. .

A chlorine content of 0.05% by weight or less;
In particular, it is at most 0.03% by weight. If the content exceeds 0.05% by weight, turbidity, phase separation or precipitation occurs, which is not preferred because storage stability may decrease or water resistance of the coating film may decrease.

The polyamine compound (a) used in the present invention is a polyamine compound comprising 50 mol%, particularly 55 mol% or more of meta-xylene diamine. When the content of meta-xylene diamine is less than 50 mol%, It is not preferable because the cured film has poor curability, solvent resistance, and corrosion resistance.

The polyamine compound other than metaxylenediamine is, for example, a compound having two or more primary or secondary amino groups in the molecule, for example, an alkylenediamine such as ethylenediamine and hexamethylenediamine; diethylenetriamine , Triethylenetetramine, tetraethylenepentamine and other polyalkylenepolyamines; 1,2-diaminocyclohexane, 1,4-
Diamino-3,6-diethylcyclohexane, isophoronediamine, mensendiamine, bis (4-amino-3
Alicyclic polyamines such as -methyldicyclohexyl) methane and diaminodicyclohexylmethane; heterocyclic polyamines such as 1,4-bis (3-aminopropyl) piperazine; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone. .

The carboxylic acid compound (b) used in the present invention may be a dimer acid, a trimer acid or a hydrogenated product thereof, or 0.5 equivalent or more, especially 0.6 equivalent or more in 1 equivalent of all carboxyl groups. Is a mixture of aliphatic carboxylic acid compounds occupying If the amount of dimer acid, trimer acid or a hydrogenated product thereof is less than 0.5 equivalent, the curability, solvent resistance, and corrosion resistance of the cured coating film are not preferable. Here, the dimer acid is a dibasic acid obtained by polymerizing two molecules of unsaturated fatty acids obtained from a drying oil, a semi-drying oil and the like. The trimer acid is a tribasic acid obtained by polymerizing three molecules of unsaturated fatty acids obtained from a drying oil, a semi-drying oil, and the like. Representative unsaturated fatty acids that serve as raw materials for dimer acid and trimer acid include, for example, oleic acid and linoleic acid. The hydrogenated products of dimer acid and trimer acid are those obtained by adding hydrogen to unsaturated double bonds in a molecule to form saturated bonds.

The aliphatic carboxylic acid compounds other than dimer acid and trimer acid include, for example, saturated or unsaturated long-chain fatty acids. The saturated or unsaturated long-chain fatty acids include, for example, caproic acid. , Caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, isostearic acid, 12
-Hydroxystearic acid, chlorostearic acid, 12
-Ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soy oil fatty acids and Mixtures of the above naturally occurring acids, such as cottonseed oil fatty acids, and the like.

The glycidyl ether compound (c) used in the present invention includes, for example, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A),
Isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4 Polyglycidyl ethers of bisphenol compounds such as -hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol and terpene diphenol; butyl glycidyl ether; Alkyl glycidyl ethers; polyglycidyl ethers of phenol novolak compounds such as phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, and resorcinol novolak Compounds; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerol, trimethylolpropane, pentaerythritol,
And polyglycidyl ethers of polyhydric alcohols such as sorbitol and bisphenol A-ethylene oxide adduct.

The component (c) preferably contains at least 10% by weight of a polyglycidyl ether of a bisphenol compound, more preferably 10 to 90% by weight of a diglycidyl ether of a bisphenol compound and 90 to 10% by weight of an alkyl glycidyl ether compound. % Of the mixture is preferable because the compatibility with the polyepoxy compound is excellent without increasing the viscosity.

The glycidyl ether compound usually contains chlorine due to its production method, and this chlorine remains in the obtained epoxy resin curing agent composition and exerts an adverse effect. Therefore, it is preferable to use the glycidyl ether compound (c) having a chlorine content of 0.2% by weight or less as the glycidyl ether compound used in the present invention. The content can be suppressed to 0.05% by weight or less.

The curing agent composition for an epoxy resin of the present invention comprises:
The active hydrogen equivalent is preferably from 100 to 300.

The method for producing the epoxy resin curing agent composition of the present invention is not particularly limited. For example, (a) a polyamine compound and (b) a carboxylic acid compound are subjected to normal pressure at 100 to 250 ° C. After dehydration reaction for 1 to 10 hours, a dehydration reaction is further performed at 100 to 250 ° C. for 1 to 10 hours to produce a polyamide polyamine compound, which is cooled to 100 ° C. or lower, and (c) glycidyl. The compound can be easily produced by gradually adding an ether compound and performing an addition reaction at 80 to 150 ° C. for 1 to 10 hours.

The curing agent composition for an epoxy resin of the present invention comprises:
It can be used by dissolving in various solvents for easy handling. Examples of these solvents include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and the like; iso- or n-butanol, iso- or n-propanol, amyl alcohol, benzyl alcohol, furfuryl Alcohols such as alcohol and tetrahydrofurfuryl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; aniline, triethylamine, pyridine, dioxane, acetonitrile and the like.

The amount of the organic solvent used is from 0 to 200 parts by weight, based on 100 parts by weight of the curing agent composition for epoxy resin.
Preferably it is 30 to 150 parts by weight. The usage amount is 20
If it exceeds 0 parts by weight, it is not preferable because it volatilizes and generates danger and harmfulness.

The curing agent composition for an epoxy resin of the present invention comprises:
It is used in combination with a main component mainly composed of a polyepoxy compound.

Examples of the polyepoxy compounds include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (Orthocresol), ethylidene bisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,
3-bis (4-hydroxycumylbenzene), 1,4-
Bis (4-hydroxycumylbenzene), 1,1,3-
Tris (4-hydroxyphenyl) butane, 1,1,
Polynuclear polyphenols such as 2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, terpene phenol, etc. Polyglycidyl ether compounds of compounds; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-
Polyglycidyl ethers of polyhydric alcohols such as ethylene oxide adducts; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid,
Azelaic acid, sebacic acid, dimer acid, trimer acid,
Glycidyl, an aliphatic, aromatic or alicyclic polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endmethylenetetrahydrophthalic acid Homopolymer or copolymer of esters and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino)
Epoxy compounds having a glycidylamino group such as phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanedienediepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-6-carboxylate Epoxy products of cyclic olefin compounds such as methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxy such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer And heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be those internally crosslinked with a prepolymer of terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, polyphosphate ester, etc.).

Here, the terpene phenol is obtained by adding an alkylphenol compound such as phenol or orthocresol to a cyclic terpene compound, and includes, for example, compounds represented by the following (1) to (6). And the like.

[0027]

Embedded image

The polyepoxy compound preferably has an epoxy equivalent of 100 to 2,000, more preferably 150 to 1500. If the epoxy equivalent is less than 100, the curability may be reduced.
It is not preferable because sufficient coating film physical properties may not be obtained.

These polyepoxy compounds can be used by dissolving them in various solvents for easy handling. Examples of these solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; and esters such as ethyl acetate and n-butyl acetate. Terpene-based hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Sekiyu KK), solvesso # 10
0 (Exxon Chemical Co., Ltd.) and the like.

The amount of the organic solvent to be used is 0 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the polyepoxy compound. If the used amount exceeds 200 parts by weight, it is not preferable because it volatilizes and generates danger and harm.

Further, a reactive or non-reactive diluent can be used as a main component mainly composed of a polyepoxy compound. As the reactive diluent, for example, phenol,
Cresol, ethyl phenol, propyl phenol,
Monoglycidyl ether compounds such as monoglycidyl ether such as p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol or terpenephenol,
Non-reactive diluents include, for example, dioctyl phthalate, dibutyl phthalate, benzyl alcohol and the like.

A thermoplastic resin may be used in combination with the polyepoxy compound. Examples of the thermoplastic resin include a vinyl chloride resin, a chlorinated polyolefin, a (meth) acrylic resin, a styrene resin, and a xylene resin. Resins and petroleum resins.

If necessary, glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black,
Fillers or pigments such as graphite, iron oxide, bituminous substances, etc .; thickeners; thixotropic agents; flame retardants; defoamers; rust inhibitors; and may contain conventional additives such as colloidal silica and colloidal alumina. .

The curing agent composition for an epoxy resin of the present invention comprises:
In combination with the main agent mainly composed of polyepoxy compound,
For example, concrete, cement mortar, various metals,
Paint or adhesive for leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for floor material; art paper , Lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, processed paper such as impregnated paper; sizing agent such as natural fiber, synthetic fiber, glass fiber, carbon fiber, metal fiber, anti-fraying agent, processing agent Fiber treatment agents such as; sealing materials, cement admixtures,
Although it can be used for a wide range of applications such as building materials such as waterproofing materials, in particular, among these applications, it can be suitably used as a heavy-duty anticorrosive paint for steel structures such as lands and bridges or ships. .

[0035]

EXAMPLES Hereinafter, the curing agent composition for epoxy resin of the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited thereto.

[Preparation Example 1] (Preparation of curing agent composition for epoxy resin) In a flask equipped with a heating and cooling device, a stirring device, a dropping device, and a dehydrating device, 136.0 g of metaxylenediamine (1.
0 mol: 2 equivalents of primary amino group) and Primol 101
7 (manufactured by Unichema; dimer acid) in an amount of 88.5 g (0.3
(Equivalent to a carboxyl group), dehydrated under normal pressure at 180 ° C. for 3 hours, and further dehydrated under reduced pressure at 180 ° C. and 3000 Pa. After confirming that the theoretical amount of dehydration (5.4 g) was obtained, the mixture was cooled to 80 ° C. and ADEKARESIN EP-410 was obtained.
0E (manufactured by Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190, total chlorine 0.1% by weight) 66.5 g (0.35 epoxy equivalent) and butyl glycidyl ether (total chlorine 0.02% by weight) 4
5.5 g (0.35 epoxy equivalent) was added dropwise and aged for 4 hours. Further add 142 g of isobutanol,
A curing agent composition for an epoxy resin having a solid content of 70% by weight, an active hydrogen equivalent of 175, and a chlorine content of 0.02% by weight was obtained.
The storage stability of the epoxy resin curing agent composition was measured by the following method, and the results are shown in Table 3.

[Production Examples 2 to 17] (Production of epoxy resin curing agent composition) According to Production Example 1, epoxy resin curing agent compositions were produced with the compositions shown in Tables 1 and 2. In Tables 1 and 2, (a) the polyamine compound is expressed in molar,
(B) Carboxylic acid compounds and (c) glycidyl compounds are expressed in equivalent amounts. The storage stability of these curing agents for epoxy resins was measured by the following method, and the results are shown in Tables 3 and 4.

[0038]

[Table 1]

[0039]

[Table 2]

(Storage stability) After the obtained curing agent composition was allowed to stand at room temperature for one week, it was evaluated as "O" when there was no change, and as "X" when it became cloudy.

[Examples 1 to 8 and Comparative Examples 1 to 8] (Preparation of paint composition) The following ingredients were kneaded with a ball mill to prepare a paint base material. This was mixed with the curing agent (curing agent composition for epoxy resin) obtained by the above production example, and the following test (drying property,
Metal adhesion and secondary coating adhesion) were performed, and the results are shown in Tables 3 and 4.

(Blending) Parts by weight Adeka Resin EP-4100 25 Talc 20 Barium sulfate 15 Titanium dioxide 5 Petiole 5 Benton 1 Xylene 5 Methyl isobutyl ketone 5 Nicanol Y-1001 20

(Dryability) A coating composition having a predetermined composition was applied to a mild steel plate SPCC-SD so as to have a dry film thickness of 50 μm, and the dry state after 24 hours was observed. Evaluation,
：: no stickiness, Δ: slight stickiness, ×: large stickiness.

(Metal Adhesion)
It was applied to a mild steel plate SPCC-SD so as to have a dry film thickness of 50 μm, dried at 23 ° C. for 7 days, and then subjected to a grid adhesion test. The same test was performed after immersing this in hot water at 50 ° C. for 7 days. The evaluation results were shown as the remaining amount for 100 grids.

(Overcoat Secondary Adhesion) A coating composition having a predetermined composition was applied to a mild steel plate SPCC-SD so as to have a dry film thickness of 50 μm, dried at 23 ° C. for 7 days, and then sunshine carbon weatherometer. -Exposure to (WOM) for 200 hours, further applying the same coating composition (top coat-1) to a dry film thickness of 50 microns, drying at 23 ° C for 7 days, and immersing in 50 ° C warm water for 7 days Later, the adhesion between the layers was observed. The adhesiveness was evaluated by cross-cutting the coating film surface, and when the tape was peeled along the surface, the film was not peeled off, and the film was peeled off.

On the coated steel sheet exposed to WOM, Hypon 50 (top coat-2; urethane resin paint manufactured by Nippon Paint) was applied.
And dried at 23 ° C. for 7 days.
After immersion for days, the adhesion between the layers was evaluated.

[0047]

[Table 3]

[0048]

[Table 4]

As is clear from the results in Tables 3 and 4, in the coating composition comprising a polyepoxy compound and a curing agent (curing agent composition for epoxy resin), a polyamide curing agent comprising meta-xylene diamine and dimer acid was used. Is used (Comparative Example 1), the drying property is deteriorated, the adhesion to the top coat is inferior, and an adduct-type polyamine-based curing agent composed of meta-xylene diamine and a glycidyl ether compound is used. In the case (Comparative Example 2), although the drying property was excellent, the adhesion to the base material or the top coat was poor.

Even when a curing agent composed of meta-xylene diamine, dimer acid and glycidyl ether compound is used, if the amount of dimer acid and glycidyl ether compound is less than a specified amount (Comparative Example 3) or if dimer acid is specified When the amount is less than the amount (Comparative Example 4), the adhesion to the base material or the top coat is poor, and when the amount of dimer acid is more than the specified amount (Comparative Example 5), the adhesion to the top coat is poor, and the dimer When the amount of the acid and the glycidyl ether compound are larger than the specified amounts (Comparative Example 6), the drying property is reduced, and the adhesion to the base material or the top coat is poor.

Furthermore, even when the specific amount of the curing agent comprising the polyamine compound, dimer acid and glycidyl ether compound of the present invention was used, the total amount of meta-xylene diamine was changed to tetraethylenepentamine (Comparative Example). In 7), the water resistance is reduced, the adhesion to the top coat is inferior, and when the chlorine content exceeds 0.05% by weight in the solid content (Comparative Example 8), as a curing agent, It is inferior in storage stability and has a disadvantage that the water resistance of the coating film is reduced.

On the other hand, by using the epoxy resin curing agent composition of the present invention, which comprises meta-xylene diamine, dimer acid, and glycidyl ether compound and satisfies specific conditions, in combination with a polyepoxy compound, excellent drying properties can be obtained. Thus, a coating composition having excellent adhesion to the base material and adhesion to the top coating can be obtained.

[0053]

EFFECTS OF THE INVENTION The curing agent composition for epoxy resin of the present invention provides a non-tar low-solvent type coating composition having excellent drying properties, excellent adhesion to a substrate, and excellent adhesion to a top coating. can do.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Tomohito Ishiguro F-term (reference) 4J036 AA01 DA09 JA01 KA01 4J038 DB031 DB032 DB051 DB052 DB061 DB062 DB071 DB072 in Asahi Denka Kogyo Co., Ltd. DB081 DB082 DB091 DB092 DB111 DB112 DB151 DB152 DB201 DB202 DB221 DB222 DB261 DB262 DB281 DB282 DB491 DB492 JB08 JB12 KA06 NA12 NA24 NA26 NA27 PB05 PC02 PC04 PC06 PC07 PC08 PC09 PC10

Claims (6)

[Claims] (1) a polyamine compound containing at least 50 mol% of metaxylenediamine and (b) a dimer acid,
(C) a glycidyl ether compound with respect to a polyamidoamine compound obtained from a trimer acid or a hydrogenated product thereof or a mixture of an aliphatic carboxylic acid compound occupying 0.5 equivalent or more in 1 equivalent of total carboxyl groups; A curing agent composition for an epoxy resin obtained by addition, wherein the carboxyl group of the component (b) is 0.1 to 0.35 equivalent based on 1 equivalent of the primary amino group of the component (a),
Furthermore, the carboxyl group of the component (b) and the epoxy group of the component (c) together are 0.4 to 0.6 equivalents, and the chlorine content is 0.05% by weight or less. Curing agent composition for epoxy resin. 2. The epoxy resin curing agent composition according to claim 1, wherein the active hydrogen equivalent is from 100 to 300. 3. The curing agent composition for an epoxy resin according to claim 1, wherein the chlorine content of the glycidyl ether compound (c) is 0.2% by weight or less. 4. The glycidyl ether compound (c) is a polyglycidyl ether 1 of a bisphenol compound.
The curing agent composition for an epoxy resin according to any one of claims 1 to 3, which contains 0% by weight or more. 5. The glycidyl ether compound as the component (c) contains 10 to 90% by weight of polyglycidyl ether of bisphenol compound and 90 to 10% by weight of alkyl monoglycidyl ether. A curing agent composition for an epoxy resin. 6. A coating composition comprising a polyepoxy compound and the curing agent composition for an epoxy resin according to claim 1.