WO2012020572A1

WO2012020572A1 - Latent curing agent composition and one-part curable epoxy resin composition

Info

Publication number: WO2012020572A1
Application number: PCT/JP2011/004551
Authority: WO
Inventors: 小川　亮; 謙介横田; 葉子正宗
Original assignee: 株式会社Adeka
Priority date: 2010-08-12
Filing date: 2011-08-11
Publication date: 2012-02-16
Also published as: KR20130108280A; CN103068877B; KR101803123B1; JP5876414B2; TW201213380A; TWI555771B; JPWO2012020572A1; CN103068877A

Abstract

The present invention is a latent curing agent composition comprising (A) an adduct obtained by reacting (a) an amine compound having an active hydrogen group and (b) a polyglycidyl compound, and (B) a curing agent composition for epoxy resin containing phenol resin, characterized in that the phenol resin comprises 10 to 40 mass% of a dikaryon, and the number average molecular weight (Mn) is 900 to 2,000, the weight average molecular weight (Mw) is 2,500 to 5,000, and the molecular weight distribution (Mw/Mn) is 2.0 to 4.0.

Description

Latent curing agent composition and one-part curable epoxy resin composition

The present invention relates to a latent curing agent composition suitable for use with a polyepoxy compound and / or a cyanate ester, in particular, an addition reaction product obtained by reacting an amine compound with a polyglycidyl compound, and a molecular weight A latent curing agent composition containing an optimized phenol resin, which is stable at normal temperature and functions as a curing agent when heated, and a one-part curable epoxy resin containing the latent curing agent composition Relates to the composition.

Epoxy resins have excellent adhesion to various substrates, and cured products obtained by curing epoxy resins with curing agents have relatively excellent heat resistance, chemical resistance, electrical properties, mechanical properties, etc. Therefore, it is applied in a wide range of industrial fields, and in particular, it is used in the fields of paints and adhesives.

Conventional epoxy resin compositions are mainly two-component systems in which a curing agent or a curing accelerator is added immediately before use. This two-component epoxy resin composition has a feature that it can be cured at room temperature or low temperature, but on the other hand, it must be weighed and mixed immediately before use and has a short usable time. For this reason, it has a drawback that its use conditions are limited, such as difficulty in application to automatic machines. In order to eliminate such drawbacks, a one-part curable epoxy resin composition is desired.

In order to obtain such a one-component curable epoxy resin composition, a so-called latent curing agent is required which is a curing agent that does not react at room temperature but has a property of starting a curing reaction when heated. As such a latent curing agent, for example, dicyandiamide, dibasic acid dihydrazide, boron trifluoride amine complex salt, guanamines, melamine, imidazoles and the like have been proposed.

However, for example, a mixture of dicyandiamide, melamine, or guanamines with an epoxy resin is excellent in storage stability, but must be cured at a high temperature of 150 ° C. or higher for a long time. It has the disadvantage of requiring unsuitable curing conditions. In addition, it has been widely practiced to shorten the curing time by using these and a curing accelerator in combination, but in this case, there is a disadvantage that storage stability is significantly impaired.

On the other hand, when dibasic acid dihydrazide or imidazoles are used, they are cured at a relatively low temperature but have poor storage stability. When boron trifluoride amine complex salt is used, it has advantages such as excellent storage stability and a short curing time, but has disadvantages such as poor water resistance and corrosion of metals.

Furthermore, it has also been proposed to use an epoxy adduct of isophoronediamine, which is an adduct-modified amine obtained by reacting an epoxy compound with a polyamine compound, as a latent curing agent (Patent Document 1). Has poor storage stability. Therefore, it has been proposed to use a reaction product of an imidazole compound, a polyepoxy compound, and a phenol novolak as a latent curing agent (Patent Document 2), but in this case, only a poor adhesive property can be obtained. There is a drawback.

Furthermore, in applications such as semiconductor sealing and molding, when existing epoxy resin alone or in combination is not sufficient, it is a highly heat-resistant cyanide that is a mixture of epoxy resin and cyanate ester. An acid ester-epoxy composite resin composition is frequently used. The use of an amine-based curing agent as a curing agent for such a composite resin has also been proposed (Patent Document 3), but in this case as well, there is a drawback that sufficient storage stability cannot be obtained.

In particular, high adhesiveness is required in applications related to electronic components such as small motors and actuators, but one-part curable resin compositions using epoxy resins and epoxy-cyanate ester composite resins that satisfy these requirements. No suitable latent curing agent has yet been found.

JP 58-147417 A U.S. Pat. No. 4,066,625 Japanese Patent Laid-Open No. 60-250026

Accordingly, a first object of the present invention is to provide a latent curing agent composition suitable for a one-component curable resin composition having excellent storage stability and excellent curability and adhesiveness. is there.
The second object of the present invention is to provide a one-part curable resin composition having excellent storage stability and excellent curability and adhesiveness.

As a result of intensive studies to achieve the above objects, the present inventors have used a mixture of an adduct-modified polyamine compound and a phenol resin having an optimized molecular weight as a latent curing agent, and a polyepoxy compound and The inventors have found that a one-part curable resin composition containing a cyanate ester has good storage stability, curability and adhesiveness, and reached the present invention.

That is, the present invention relates to (A) (a) an addition compound obtained by reacting an amine compound having an active hydrogen group and (b) a polyglycidyl compound, and (B) an epoxy resin containing a phenol resin. Curing agent composition, wherein the phenol resin contains 10 to 40% by mass of a binuclear substance, the number average molecular weight (Mn) is 900 to 2000, and the weight average molecular weight (Mw) is 2500 to 5000. A latent curing agent composition having a molecular weight distribution (Mw / Mn) of 2.0 to 4.0, and a one-component curability comprising the latent curing agent composition It is a resin composition.

By using the latent curing agent composition of the present invention in combination with a polyepoxy compound and, if necessary, a cyanate ester, a one-part curable resin composition excellent in storage stability, curability and adhesiveness. Things are obtained.

The latent curing agent composition of the present invention comprises (A) component, (a) an addition reaction product obtained by reacting an amine compound having an active hydrogen group and (b) a polyglycidyl compound, and (B) It is the hardening | curing agent composition for epoxy resins which uses the phenol resin which is a component as an essential component.

Examples of the amine compound having an active hydrogen group used as the component (a) include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane. Alkylenediamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine, etc .; 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane Alicyclic polyamines such as isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; guanamines such as benzoguanamine and acetoguanamine; Imidazoles such as ru-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole; Dihydrazides such as dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide; N, N-dimethylaminoethylamine Diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine, N, N-benzylmethylaminoethylamine, N, N-diben Laminoethylamine, N, N-cyclohexylmethylaminoethylamine, N, N-dicyclohexylaminoethylamine; N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N-diisopropylaminopropylamine, N, N -Diallylaminopropylamine, N, N-benzylmethylaminopropylamine, N, N-dibenzylaminopropylamine, N, N-cyclohexylmethylaminopropylamine, N, N-dicyclohexylaminopropylamine; N- (2- Aminoethyl) pyrrolidine, N- (3-aminopropyl) pyrrolidine; N- (2-aminoethyl) piperidine, N- (3-aminopropyl) piperidine; N- (2-aminoethyl) morpholine, N- (3- Aminopropyl) mol Holin; N- (2-aminoethyl) -N′-methylpiperazine, N- (2-aminoethyl) piperazine, N- (3-aminopropyl) piperazine; N- (3-aminopropyl) -N′-methyl Piperidine; 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N-diisopropylamino) benzylamine; N, N, -dimethylisophoronediamine, N , N-dimethylbisaminocyclohexane, N, N, N′-trimethylethylenediamine, N′-ethyl-N, N-dimethylethylenediamine, N, N, N′-trimethylethylenediamine, N′-ethyl-N, N-dimethyl Propanediamine, N′-ethyl-N, N-dibenzylaminopropylamine; N, N- (bisaminopro ) -N-methylamine, N, N-bisaminopropylethylamine, N, N-bisaminopropylpropylamine, N, N-bisaminopropylbutylamine, N, N-bisaminopropylpentylamine, N, N- Bisaminopropylhexylamine, N, N-bisaminopropyl-2-ethylhexylamine, N, N-bisaminopropylcyclohexylamine, N, N-bisaminopropylbenzylamine, N, N-bisaminopropylallylamine, bis [ 3- (N, N-dimethylaminopropyl)] amine, bis [3- (N, N-diethylaminopropyl)] amine, bis [3- (N, N-diisopropylaminopropyl)] amine, bis [3- ( N, N-dibutylaminopropyl)] amine and the like.

In the present invention, from the viewpoint of improving low-temperature curability, it is preferable to use an amine compound having at least one tertiary amino group among the above amine compounds, from the viewpoint of heat resistance of the cured product. In particular, it is preferable to use a dialkylaminoalkylamine represented by the following general formula (I) or an imidazole compound represented by the following general formula (II).

Formula (I)

However, R ₁ and R ₂ in the general formula (I) are each independently an alkyl group having 1 to 8 carbon atoms, or R ₁ and R ₂ are bonded to each other to contain an oxygen atom or a nitrogen atom. And n represents an integer of 1 to 6.

Formula (II)

However, R ₃ to R ₅ in the general formula (II) represent a hydrogen atom, an alkyl group or an aryl group which can have a substituent.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ₁ and R ₂ in the general formula (I) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl , Amyl, isoamyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl and the like.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ₃ , R ₄ and R ₅ in the general formula (II) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Examples include octadecyl, vinyl, allyl, hydroxymethyl, hydroxyethyl, aminomethyl, aminopropyl and the like.

In addition, examples of the aryl group represented by R ₃ , R _4, and R ₅ include groups such as phenyl and naphthyl. One to four of these aryl groups may be substituted with the alkyl group described above.

Among the amine compounds represented by the general formula (I) as the component (a), for example, N, N-dialkylaminoalkylamines include, for example, N, N-dimethylaminopropylamine, N, N— Diethylaminopropylamine, N, N-dipropylaminopropylamine, N, N-dibutylaminopropylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminobutylamine, aminopropylmorpholine Aminoethylpiperidine, 1- (2-aminoethyl) -4-methylpiperazine, and the like.

Examples of the imidazole compound represented by the general formula (II) as the component (a) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2 -Heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole and the like.

Examples of the polyglycidyl compound as the component (b) used in the component (A) in the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; Dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4- Hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) Nyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol, phenolic dicyclopentadiene Polyglycidyl of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Ether; maleic acid, fumaric acid, itaconic acid, succinic acid, Taric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N- Epoxy compounds having a glycidylamino group such as methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3 , 4-epoki Epoxidized products of cyclic olefin compounds such as cis-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer And heterocyclic compounds such as epoxidized conjugated diene polymers such as triglycidyl isocyanurate.

In the present invention, the reaction between the polyamine compound of component (a) and the polyglycidyl compound of component (b) is based on the amount of active hydrogen of the polyamine compound of component (a) equivalent to 1 equivalent of the component (b). The ratio is such that the epoxy equivalent is 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents. When the epoxy equivalent of the component (b) to be used is less than 0.5 equivalent, the storage stability of the one-part curable resin composition of the present invention may be insufficient, and the use exceeds 2 equivalents. In such a case, the curability of the one-part curable resin composition of the present invention may decrease, which is not preferable.

The phenol resin which is the component (B) used in the present invention is a phenol resin synthesized from phenols and aldehydes. Examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone. 2,2-bis (4-hydroxyphenyl) propane, 4,4′-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpenephenol, phenolized dicyclopentadiene, etc., and the aldehydes include formaldehyde .

The phenol resin which is the component (B) used in the present invention needs to contain 10 to 40% by mass of a binuclear substance, and its number average molecular weight (Mn) is 900 to 2000, preferably 950 to 1500, It is necessary that the weight average molecular weight (Mw) is 2500 to 5000, preferably 3000 to 4000, and the molecular weight distribution (Mw / Mn) is 2.0 to 4.0. The number average molecular weight (Mn) is preferably 950 to 1500, the weight average molecular weight (Mw) is preferably 3000 to 4000, and the molecular weight distribution (Mw / Mn) is 2.5 to 3.5. It is preferable. When using a latent curing agent composition obtained by using a phenol resin exceeding the above range, the stability of the one-part curable epoxy resin composition obtained in combination with the polyepoxy compound is reduced, Since adhesiveness falls, it is unpreferable.

The use amount of the phenol resin as the component (B) is preferably 150 parts by mass or less, particularly preferably 10 to 100 parts by mass with respect to 100 parts by mass of the addition reaction product as the component (A). . Even if it exceeds 150 parts by mass, it is not preferable because it is not only useless but also may adversely affect curability.

The phenol resin as the component (B) can be simply blended, but can also be used by reacting as a blocking agent for the active hydrogen compound as the component (a).

The latent curing agent composition of the present invention includes, for example, adipic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic A polycarboxylic acid such as an acid can also be contained.

The latent curing agent composition of the present invention can be used by dissolving in various solvents in order to facilitate handling. Examples of such solvents include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane; iso- or n-butanol, iso- or n-propanol, amyl alcohol, benzyl alcohol, Examples include alcohols such as furfuryl 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 0 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the total solid content. If the amount of the organic solvent used exceeds 200 parts by mass, it is not preferable because it volatilizes and is harmful, and there is a risk of ignition.

The latent curing agent composition of the present invention is used in combination with a main agent mainly composed of a polyepoxy compound and / or a cyanate ester.

Examples of the polyepoxy compound include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol) ), Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxyc) Milbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as alcohol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol , Hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycidyl ethers of polyhydric alcohols such as bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid , Glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, Aliphatic, aromatic or alicyclic polybasic acid glycidyl such as taric acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Homopolymers or copolymers of esters and glycidyl methacrylate; epoxy compounds having a glycidylamino group such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinyl Cyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis ( Epoxidized products of cyclic olefin compounds such as 3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and complex such as triglycidyl isocyanurate And ring compounds. In addition, these epoxy resins may be internally crosslinked by a prepolymer of a terminal isocyanate, or may have a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, polyphosphate ester, etc.).

In addition, the polyepoxy compound used in the present invention preferably has an epoxy equivalent of 100 to 2000, and particularly preferably 150 to 1500. When an epoxy equivalent of less than 100 is used, the curability may be lowered, and when an epoxy equivalent of more than 2000 is used, there is a possibility that sufficient physical properties of the coating film may not be obtained.

The above-mentioned polyepoxy compound can be used by dissolving in various solvents for easy handling. As the solvent used in this case, in addition to the solvents described above, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone; ethyl acetate, n-acetate Esters such as butyl; Terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Examples include boiling-point paraffinic solvents.

The amount of the organic solvent used is 0 to 200 parts by mass with respect to 100 parts by mass of the polyepoxy compound, but 30 to 150 parts by mass is particularly preferable. If the amount of the organic solvent used exceeds 200 parts by mass, it is not preferable because it volatilizes and is harmful, and there is a risk of ignition and the like.

Also, a reactive or non-reactive diluent can be used as the main agent mainly composed of the polyepoxy compound used in the present invention. Examples of reactive diluents include phenol, cresol, ethylphenol, propylphenol, p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol, and terpenephenol. These monoglycidyl ether compounds are listed. On the other hand, examples of the non-reactive diluent include dioctyl phthalate, dibutyl phthalate, and benzyl alcohol.

The amount of the polyepoxy compound and the latent curing agent composition of the present invention used in the one-component curable resin composition of the present invention may be used so that the former epoxy equivalent and the latter active hydrogen equivalent are equal. Although preferable, the amount can be changed in any range as required.

The latent curing agent composition of the present invention is combined with a main component mainly composed of a polyepoxy compound, for example, a paint for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, or the like. Adhesives: adhesive tapes for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, adhesive flooring, etc .; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbon Processing paper such as paperless copying machines and impregnated paper; fiber treatment agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fraying prevention agents, processing agents, etc .; sealing materials, cement admixtures, waterproofing It can be used for a wide range of applications such as building materials such as materials; electrical and electronic materials such as laminates and semiconductor encapsulants.

In addition, the latent curing agent composition of the present invention is particularly preferably used in combination with the above-mentioned polyepoxy compound in combination with a main agent mainly composed of a cyanate ester.

The cyanate ester that can be used in the present invention is not particularly limited. For example, the following general formula (1)

Or a compound represented by
The following general formula (2)

The compound represented by these is mentioned.
However, R ¹ in the general formula (1) represents an unsubstituted or fluorine-substituted divalent hydrocarbon group, or —O—, —S—, or a single bond, and R ² and R ³ are: Each independently represents a phenylene group which is unsubstituted or substituted with 1 to 4 alkyl groups, n in the general formula (2) is an integer of 1 or more, and R ⁴ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Represents a group.

In addition, a prepolymer in which a part of the cyanate group in the compound of the general formula (1) or (2) forms a triazine ring can also be used as a main agent mainly composed of a cyanate ester. Examples of the prepolymer include those in which all or part of the compound represented by the general formula (1) is trimerized.

More preferable as the main component mainly composed of cyanate ester used in the present invention is the following general formula (3):

In the present invention, 4,4′-ethylidenebisphenylene cyanate, 2,2-bis (4-cyanatophenyl) propane, and bis (4-cyanato- Preferably, 3,5-dimethylphenyl) methane is the main agent.
In the general formula (3), R ⁵ represents the following group.

Or the group:

N in the above group is an integer of 4 to 12, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or an unsubstituted or fluorine-substituted methyl group, R ¹⁰ and R ¹¹ are Each independently represents a hydrogen atom or an unsubstituted or fluorine-substituted methyl group.

In the present invention, the cyanate ester may be used alone or in combination of two or more.

In the one-part curable resin composition of the present invention, glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, Fillers or pigments such as titanium, carbon black, graphite, iron oxide, bituminous substances, metal particles, metal-coated resin particles; thickeners; thixotropic agents; flame retardants; antifoaming agents; Conventional additives such as silica and colloidal alumina may be contained, and adhesive resins such as xylene resin and petroleum resin may be used in combination.

The one-component curable resin composition of the present invention can also be used in a solvent-free one-component type as described above. In the case of using no solvent in this way, for example, the occurrence of VOC can be suppressed, so that not only can a highly safe material with reduced environmental load be provided, but also the material can penetrate into the space and cure. For example, there is an advantage that it can be used for applications where a solvent cannot be used.

The one-component curable resin composition of the present invention is used in a wide range of applications such as paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. be able to. In particular, since it has high heat resistance and excellent adhesiveness, it is suitably used for electronic material applications and automotive material applications such as semiconductor protective sealing and electronic component adhesion.

Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto.

[Production Examples 1 to 6]
Production of phenolic resins (PR1 to PR6) A 4-neck separable flask equipped with a thermometer, a stirrer, a dropping device and a condenser tube was charged with phenol, 50% formalin aqueous solution and oxalic acid and heated at reflux temperature. The reaction was performed for 4 hours. After the reflux reaction, the temperature was raised to 160 ° C. at normal pressure, followed by concentration over 3 hours. Further, while maintaining the temperature at 160 ° C., the pressure was reduced to 20 to 30 Torr, and the solution was concentrated under reduced pressure until no distillate was produced. Thus, yellowish brown phenol resins (PR1 to PR6) having the molecular weight distribution shown in [Table 1] below were obtained.
After 0.01 g of each obtained sample was dissolved in 10 g of THF, gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) was used, and Shodex manufactured by Showa Denko KK was used as a sample column for measurement. KF-802, Shodex KF-800RH manufactured by Showa Denko Co., Ltd. as the reference column, THF as the developing solvent, and the polystyrene-equivalent number average molecular weight, weight average molecular weight and molecular weight of each sample from the values measured by the RI detector Distribution was calculated.

A flask equipped with a thermometer, a cooling device, a stirring device, a dropping device, and a dehydrating device was charged with 300 g of propylene glycol monomethyl ether and 100 g of N, N-diethylaminopropylamine, and the reaction system was heated to 70 to 75 ° C., 213 g of Adeka Resin EP-4100E (trade name of ADEKA Corporation; bisphenol A type epoxy resin, epoxy equivalent 190) was added dropwise. After completion of the dropping, the mixture was aged at 110 to 130 ° C. for 1 hour, and the solvent was removed at 110 to 130 ° C. at normal pressure for 1 hour, and at 175 to 185 ° C. and 20 to 30 torr for 1 hour. Next, 210 g of phenol resin PR1 was dividedly charged at 175 to 185 ° C., and the phenol resin was dissolved. Furthermore, vacuum degassing was performed at 180 to 190 ° C. and 20 to 30 torr for 1 hour to obtain a curing agent composition (HC-1). The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device (MP-S3, the same shall apply hereinafter) manufactured by Yanaco. The melting point was 85 ° C.

A curing agent composition (HCH-1) was obtained by reacting and treating in the same manner as in Example 1 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 91 ° C.

A curing agent composition (HC-2) was obtained by reacting and treating in the same manner as in Example 1 except that the phenol resin PR2 was used instead of the phenol resin PR1. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 85 ° C.

A curing agent composition (HCH-2) was obtained by reacting and treating in the same manner as in Example 3 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 90 ° C.

A curing agent composition (HC-3) was obtained by reacting and treating in the same manner as in Example 1 except that the phenol resin PR3 was used instead of the phenol resin PR1. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 82 ° C.

A curing agent composition (HCH-3) was obtained by reacting and treating in the same manner as in Production Example 5 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained hardening | curing agent composition was ground with a mortar, and when it measured using the melting | fusing point measuring device made from Yanaco, melting | fusing point was 88 degreeC.

[Comparative Example 1]
A curing agent composition (HC-4) was obtained by reacting and treating in the same manner as in Example 1 except that the phenol resin PR4 was used instead of the phenol resin PR1. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 86 ° C.

[Comparative Example 2]
A curing agent composition (HCH-4) was obtained by reacting and treating in the same manner as in Comparative Example 1 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 89 ° C.

[Comparative Example 3]
A curing agent composition (HC-5) was obtained by reacting and treating in the same manner as in Example 1 except that the phenol resin PR5 was used instead of the phenol resin PR1. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 95 ° C.

[Comparative Example 4]
A curing agent composition (HCH-5) was obtained by reacting and treating in the same manner as in Comparative Example 3 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 91 ° C.

[Comparative Example 5]
A curing agent composition (HC-6) was obtained by reacting and treating in the same manner as in Example 1 except that the phenol resin PR6 was used instead of the phenol resin PR1. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 82 ° C.

[Comparative Example 6]
A curing agent composition (HCH-6) was obtained by reacting and treating in the same manner as in Comparative Example 3 except that 74 g of 1,2-diaminopropane was used instead of 100 g of N, N-diethylaminopropylamine. The obtained curing agent composition was ground in a mortar and measured using a melting point measuring device manufactured by Yanaco. The melting point was 87 ° C.

[Examples 7 to 9 and Comparative Examples 7 to 9]
The hardening | curing agent composition manufactured in the said Example and comparative example was mix | blended with the composition shown in [Table 2], the one-pack curable epoxy resin composition was manufactured, and the following performance evaluation was performed. The results are shown in [Table 3].

(Curable)
The curability of the one-part curable epoxy resin composition obtained in accordance with Table 2 was measured immediately after production using a gelation tester (hot plate type gelation tester GT-DS-SF: product name manufactured by Yukari Giken Co., Ltd.). ). At this time, the time when the yarn was not pulled was defined as the gel time.

(Reaction start temperature)
Using a differential scanning calorimeter DSC 6220 manufactured by SII Nano Technologies, the heating rate was 10 ° C./min and the scanning temperature range was 25 to 300 ° C., and the exothermic starting temperature read from the DSC chart was taken as the reaction starting temperature.

(viscosity)
The one-part curable epoxy resin composition obtained according to Table 2 was allowed to stand at 25 ° C., and the viscosity at 25 ° C. was measured at 5 rpm using a Brookfield E-type rotational viscometer.

(Adhesiveness)
About the one-pack curable epoxy resin composition obtained according to Table 2, the shear adhesive strength of the steel plate / steel plate after curing for 60 minutes at 80 ° C. was determined by a method based on JIS K 6850.

As is clear from the results of the examples, an addition reaction product obtained by reacting an amine compound having an active hydrogen group with a polyglycidyl compound, and a curing agent composition for an epoxy resin containing a phenol resin, The phenol resin used in the production contains 10 to 40% by mass of the binuclear body, the number average molecular weight (Mn) is 900 to 2000, the weight average molecular weight (Mw) is 2500 to 5000, and the molecular weight distribution (Mw / Mn ) Is 2.0 to 4.0, the curable, stable, and adhesive properties of the one-part curable epoxy resin composition containing the obtained latent curing agent composition are extremely excellent. It was confirmed that

On the other hand, when a phenol resin having a binuclear content of less than 10% by mass is used (Comparative Example 1), even if the binuclear content is 10% by mass to 40% by mass, the weight average When the molecular weight is larger than 5000 and the molecular weight distribution is larger than 4.0 (Comparative Example 2), only a one-part curable epoxy resin composition having poor adhesion can be obtained, and the content of the binuclear substance as a phenol resin is obtained. Is greater than 40% by mass and the number average molecular weight is less than 900 (Comparative Example 3), it was confirmed that only a one-component curable epoxy resin composition having poor stability can be obtained.

By using the latent curing agent composition of the present invention in combination with a polyepoxy compound and, if necessary, a cyanate ester, one-component curability excellent in storage stability, curability and adhesiveness. Since the resin composition is obtained, this is used with an automatic machine, for example, a paint or adhesive for concrete, various metals, leather, glass, rubber, plastic, etc .; adhesive tape for packaging, adhesive label, frozen food label Adhesives such as adhesive wallpaper and adhesive flooring; Processing paper such as impregnated paper; Converging agent such as natural fiber, synthetic fiber and glass fiber; Fiber treatment agent such as fraying preventive and processing agent; Sealing material and cement admixture , Building materials such as waterproofing materials; electrical and electronic materials such as laminates and semiconductor encapsulants can be used efficiently in a wide range of applications, thereby contributing to industrial development

Claims

(A) (a) an addition reaction product obtained by reacting an amine compound having an active hydrogen group and (b) a polyglycidyl compound, and (B) a curing agent composition for an epoxy resin containing a phenol resin. The phenol resin contains 10 to 40% by mass of the binuclear body, the number average molecular weight (Mn) is 900 to 2000, the weight average molecular weight (Mw) is 2500 to 5000, and the molecular weight distribution ( A latent curing agent composition having a Mw / Mn) of 2.0 to 4.0.
The latent curing agent composition according to claim 1, wherein the amine compound (a) having an active hydrogen group includes an amine compound having at least one tertiary amino group.
The amine compound having at least one tertiary amino group is a dialkylaminoalkylamine represented by the following general formula (I) or an imidazole compound represented by the following general formula (II). The latent curing agent composition described;
Formula (I):

However, R 1 and R 2 in the above general formula (I) each independently represent an alkyl group having 1 to 8 carbon atoms, or R 1 and R 2 are bonded to form an oxygen atom or a nitrogen atom. Represents an alkylene group which can be contained, and n represents an integer of 1 to 6.
General formula (II):

However, R 3 to R 5 in the general formula (II) represent a hydrogen atom, an alkyl group or an aryl group which can have a substituent.
The latent curing agent composition according to claim 2, wherein the amine compound having at least one tertiary amino group is at least one selected from diethylaminopropylamine, diethylaminoethylamine, and N-aminoethylpiperazine. object.
The latent curing agent composition according to any one of claims 1 to 4, wherein the (B) phenol resin is a phenol resin obtained from phenol and formaldehyde.
A one-part curable resin composition comprising a polyepoxy compound and at least one latent curing agent composition according to any one of claims 1 to 5.
A one-part curable resin composition comprising a polyepoxy compound, a cyanate ester and at least one latent curing agent composition according to any one of claims 1 to 5.