JP7261580B2 - resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent and a specific solvent.

Epoxy resins are widely used industrially as paints, adhesives, various molding materials, and the like.

Furthermore, when sufficient properties cannot be obtained by using existing epoxy resins alone or in combination, cyanate-epoxy composite resin compositions obtained by mixing cyanate ester resins and epoxy resins have high heat resistance. Therefore, it is widely used as a useful material.

For example, a liquid epoxy resin composition for semiconductor encapsulation comprising a cyanate ester resin, an epoxy resin, an inorganic filler, a metal chelate, a dihydrazide compound, etc. has already been proposed (Patent Document 1). However, satisfactory performance has not been obtained because, for example, it is necessary to heat at a high temperature for a long period of time in order to harden it.

An example of using an amine-based curing agent in a composite composition containing a cyanate ester resin and an epoxy resin has also been proposed (Patent Document 2), but in this case sufficient storage stability is not obtained.

Furthermore, a thermosetting resin composition in which a latent curing agent containing an imidazole component is added to a cyanate ester resin and an epoxy resin has also been proposed (Patent Document 3). From the point of view, the amount of cyanate ester resin to be used is limited, and satisfactory results have not been obtained.

In addition, in the cyanate-epoxy composite resin composition, it is considered difficult to use a solvent for the purpose of lowering the viscosity, because the storage stability decreases.

Japanese Patent Application Laid-Open No. 2001-302767 JP-A-60-250026 Japanese Patent Publication No. 2001-506313

The problem to be solved by the present invention is to provide a cyanate-epoxy composite resin composition that has low viscosity, excellent storage stability, and can be cured quickly.

The present inventors have made intensive studies and found that the above problems can be solved by selecting a specific solvent in a cyanate-epoxy composite resin composition containing a cyanate ester resin, an epoxy resin and a latent curing agent. and arrived at the present invention.

That is, the present invention comprises (A) a cyanate ester resin, (B) an epoxy resin, (C) a latent curing agent, and (D) an SP value of 7.8 to 9.5 (cal/cm ³ ) ^{0.5 .} It is a resin composition containing an organic solvent.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used for applications such as printing coatings and adhesives, since it has low viscosity, excellent storage stability, and is capable of rapid curing.

The cyanate ester resin which is the component (A) used in the present invention may be any compound having two or more cyanate groups, and its molecular structure, molecular weight and the like are not particularly limited.

In the present invention, at least one selected from the group consisting of a compound represented by the following formula (1) as a cyanate ester resin, a compound represented by the following formula (2), and prepolymers thereof is used. This is preferable because a resin composition having excellent storage stability and capable of rapid curing can be obtained.

（式中、Ｙ^１は、２価の炭化水素基、２価の炭化水素基の水素原子がフッ素原子で置換された基、－Ｏ－、－Ｓ－、又は直接結合であり、Ａ^１及びＡ^２は、それぞれ独立してフェニレン基又は炭素数１～４のアルキル基を１～４個有するフェニレン基である。）

(Wherein, Y ¹ is a divalent hydrocarbon group, a group in which a hydrogen atom of the divalent hydrocarbon group is substituted with a fluorine atom, —O—, —S—, or a direct bond, and A ¹ and Each ^A2 is independently a phenylene group or a phenylene group having 1 to 4 alkyl groups of 1 to 4 carbon atoms.)

（式中、ｍは、１以上の整数であり、Ｙ^２は、２価の炭化水素基、又は２価の炭化水素基の水素原子がフッ素原子で置換された基であり、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又は炭素数１～４のアルキル基である。）

(Wherein, m is an integer of 1 or more, Y ² is a divalent hydrocarbon group or a group in which the hydrogen atoms of the divalent hydrocarbon group are substituted with fluorine atoms, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

Y ¹ in the above formula (1) and Y ² in the above formula (2) are preferably groups selected from the following formulas (Y-1) to (Y-9).

（式中、ｎは４～１２の整数であり、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、メチル基、又はメチル基の水素原子がフッ素原子で置換された基であり、＊は他の基との結合部位を表す。Ｙ^１及びＹ^２は同じであってもよく、異なっていてもよい。）

(In the formula, n is an integer of 4 to 12, R ³ and R ⁴ are each independently a hydrogen atom, a methyl group, or a group in which a hydrogen atom of a methyl group is substituted with a fluorine atom, * represents a bonding site with another group. ^{Y 1} and Y ² may be the same or different.)

Y ¹ in formula (1) and Y ² in formula (2) are particularly preferably groups selected from the following formulas (Y-1) and (Y-3).

The compound represented by the formula (1) and the prepolymer of the compound represented by the formula (2) are compounds in which a part of the cyanate groups of these compounds form a triazine ring. Examples include a compound obtained by trimerizing the compound of formula (1), and a compound obtained by trimerizing the compound of formula (1) and the compound of formula (2) at an arbitrary ratio.

The epoxy resin which is the component (B) used in the present invention may be a compound having at least two epoxy groups in the molecule, and its molecular structure, molecular weight and the like are not particularly limited.

Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol). , ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumyl benzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak , ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, Polyhydric alcohol compounds such as dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts Polyglycidyl ether compounds; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric 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, glycidyl ester compounds of aliphatic, aromatic or alicyclic polybasic acids such as endomethylenetetrahydrophthalic acid; homopolymers or copolymers of glycidyl methacrylate; -diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidylorthotoluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxy propoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, N,N,N',N'-tetra(2,3- Epoxy compounds having a glycidylamino group such as epoxypropyl)-4,4-diaminodiphenylmethane; vinylcyclohexene diepoxide, cyclopentane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, Epoxidized products of cyclic olefin compounds such as 4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized polybutadiene, epoxidized styrene-butadiene epoxidized conjugated diene polymers such as copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins are internally crosslinked with prepolymers having isocyanate groups at their ends, or polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.) with high molecular weights. It may be a modified one. These epoxy resins may be used alone or in combination of two or more.

In the present invention, the use of an epoxidized polyadduct of dicyclopentanediene and phenol or cresol as the epoxy resin provides a resin composition that is excellent in storage stability and capable of rapid curing. preferred from

The content of the epoxy resin in the resin composition of the present invention is not particularly limited. Containing up to 100 parts by mass is more preferable because a cured product having excellent heat resistance and the like can be obtained.

The latent curing agent that is the component (C) used in the present invention may be any curing agent that can initiate a curing reaction by heating. , adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dibasic acid dihydrazide such as phthalic acid dihydrazide; guanamines such as benzoguanamine and acetoguanamine; dicyandiamide; melamine; and epoxy adducts, amine and isocyanate adducts, Michael adducts of amines, Mannich reaction products of amines, condensates of amines and urea, modified amines such as condensates of amines and ketones. .

In the present invention, the latent curing agent includes (C-1) a modified amine obtained by reacting an amine compound having at least one active hydrogen with an epoxy compound, and (C-2) an amine compound having at least one active hydrogen. At least one selected from modified amines obtained by reacting with an isocyanate compound, and (C-3) modified amines obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound and an isocyanate compound, or modifications thereof A mixture of at least one selected from amines and a phenolic resin is preferred. Such a latent curing agent has low solubility in the specific solvent, which is the component (D) used in the present invention, and can initiate curing of the components (A) and (B) by heating. preferable.

Examples of the amine compound having one or more active hydrogens include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine, and the like. alkylenediamines; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diamino Alicyclic polyamines such as dicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, norbornenediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene , 1,3,5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3′,5′-tetramethyl-4,4′-diamino aromatic polyamines such as diphenylmethane; guanamines such as benzoguanamine and acetoguanamine; imidazoles such as phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, Dihydrazides such as dihydrazide sebacate and dihydrazide phthalate; N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-benzylmethylamino ethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N- (2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, 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-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-( 3-aminopropyl)-N'-methylpiperidine, 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-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine; N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropyl Ethylamine, 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.

Examples of the epoxy compound include the compounds exemplified as the epoxy resin, which is the component (B) used in the present invention.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5 - aromatic diisocyanates such as naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4 ,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4 )-aliphatic diisocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate; isocyanurate trimers, biuret trimers, trimethylolpropane adducts, etc. of these diisocyanates; triphenylmethane triisocyanate, 1-methylbenzol-2 ,4,6-triisocyanate, dimethyltriphenylmethanetetraisocyanate, and the like. Furthermore, these isocyanate compounds may be used in the form of carbodiimide modification, isocyanurate modification, biuret modification, etc., or may be used in the form of blocked isocyanate blocked with various blocking agents.

The amount of the amine compound having one or more active hydrogens and the epoxy compound used in the modified amine (C-1) is 0.1 to 0.1 to 1 equivalent of the NH group of the amine compound. It is preferably an amount that gives 1.1 equivalents, more preferably an amount that gives 0.2 to 1.0 equivalents. In addition, in the modified amine (C-2), the amount of the amine compound having one or more active hydrogens and the isocyanate compound used is such that the isocyanate group of the isocyanate compound is 0.00 with respect to 1 equivalent of the NH group of the amine compound. It is preferably in an amount of 1 to 1.1 equivalents, particularly preferably in an amount of 0.2 to 1.0 equivalents. Furthermore, in the modified amine (C-3), the amount of the amine compound having at least one active hydrogen, the epoxy compound and the isocyanate compound used is the epoxy group of the epoxy compound per equivalent of the NH group of the amine compound. is an amount of 0.1 to 1.0 equivalents, particularly an amount of 0.2 to 1.0 equivalents, and an amount of isocyanate groups of the isocyanate compound of 0.01 to 0.9 equivalents, particularly 0.05 It is preferable that the amount is ∼0.8 equivalents. If the amount of the epoxy compound and/or isocyanate compound relative to the amine compound having at least one active hydrogen is less than the lower limit, it is not preferable because the storage stability may decrease. It is not preferable because there is a possibility that the curability may be lowered.

The method for producing the modified amines (C-1), (C-2) and (C-3) is not particularly limited. A method of reacting for up to 10 hours may be mentioned. In the modified amine (C-3), it is preferable to react the amine compound with the epoxy compound and then further react with the isocyanate compound. When a solvent other than the solvent (D) used in the present invention is used, it is preferable to remove the solvent by heating under normal pressure or reduced pressure after the completion of the reaction.

Solvents used for producing the modified amine include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexane; tetrahydrofuran, 1,2-dimethoxyethane, 1, Ethers such as 2-diethoxyethane and propylene glycol monomethyl ether; Esters such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Carbon tetrachloride, chloroform, trichlorethylene, methylene chloride and the like and halogenated aromatic hydrocarbons such as chlorobenzene.

Examples of the phenol resin to be mixed with the modified amine include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), and naphthol aralkyl resin. , trisphenylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolac resin, biphenyl-modified phenol resin (polyhydric phenol in which phenol nuclei are linked by bismethylene groups compound), a biphenyl-modified naphthol resin (a polyvalent naphthol compound in which a phenol nucleus is linked by a bismethylene group), an aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring and a primary amino group in its molecular structure), and Examples include polyhydric phenol compounds such as alkoxy group-containing aromatic ring-modified novolac resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

In the present invention, it is preferable to use a phenolic resin having a number average molecular weight of 750 to 1,200 from the viewpoint of obtaining a resin composition having an excellent balance between storage stability and curability.

The amount of the phenol resin used is preferably 10 to 100 parts by mass, particularly preferably 20 to 60 parts by mass, per 100 parts by mass of the modified amine. If it is less than 10 parts by mass, sufficient curability cannot be obtained, and if it exceeds 100 parts by mass, the physical properties of the cured product, such as heat resistance, may deteriorate.

Among the latent curing agents, commercially available products include ADEKA HARDNER EH-3636S (manufactured by ADEKA Corporation; dicyandiamide type latent curing agent), ADEKA HARDNER EH-4351S (manufactured by ADEKA Corporation; dicyandiamide type latent curing agent ), ADEKA HARDNER EH-5011S (manufactured by ADEKA Corporation; imidazole type latent curing agent), ADEKA HARDNER EH-5046S (manufactured by ADEKA Corporation; imidazole type latent curing agent), ADEKA HARDNER EH-4357S (manufactured by ADEKA Corporation polyamine type latent curing agent), ADEKA HARDNER EH-5057P (manufactured by ADEKA Corporation; polyamine type latent curing agent), ADEKA HARDNER EH-5057PK (manufactured by ADEKA Corporation; polyamine type latent curing agent), Amicure PN- 23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-based latent curing agent), Amicure PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-based latent curing agent), Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazide system latent curing agent), Fujicure FXR-1020 (manufactured by T&K TOKA Co., Ltd.; latent curing agent), and the like.

The amount of the latent curing agent used in the resin composition of the present invention is not particularly limited. It is preferably contained in parts by mass, more preferably 3 to 60 parts by mass.

In the present invention, a curing accelerator may be used as necessary. As the curing accelerator, phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, imidazoles such as cyanoethyl-2-methylimidazole; imidazole salts which are salts of said imidazoles with trimellitic acid, isocyanuric acid, boron, etc.; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol amines such as; quaternary ammonium salts such as trimethylammonium chloride; 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl ureas such as -1,1-dimethylurea, isophoronediisocyanate-dimethylurea, and tolylenediisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines, ether compounds, and the like. These curing accelerators may be used alone or in combination of two or more. The content of the curing accelerator can be appropriately set according to the application.

The organic solvent, which is the component (D) used in the present invention, may have an SP value of 7.8 to 9.5 (cal/cm ³ ) ^0.5 and is not particularly limited, but has an SP value of 7.9 to 9. It is more preferably 0.0 (cal/cm ³ ) ^0.5 . In particular, at least one selected from dipropylene glycol methyl n-propyl ether (SP value: 8.0), diisobutyl ketone (SP value: 8.5) and butyl butyrate (SP value: 8.7) is used. is preferable because it shows a remarkable effect in improving the storage stability.

The SP value in the present invention is a value (δ) obtained by the following Fedors estimation formula, and specifically, a value estimated as the sum of each of the substituents and the main chain structure in the molecule. is.
The SP value is a physical property value defined by the square root of the cohesive energy density, and is a numerical value that indicates the dissolution behavior of a solvent. It is one of the useful parameters in a wide range of fields such as evaluation, solubility evaluation of pharmaceuticals, aggregation/degradability evaluation of microparticles in solvents.

（ｅｉ：原子団の蒸発エネルギー、ｖｉ：原子団のモル体積）

(ei: vaporization energy of atomic group, vi: molar volume of atomic group)

An organic solvent having an SP value of 7.8 to 9.5 (cal/cm ³ ) ^0.5 can dissolve the cyanate ester resin as component (A) and the epoxy resin as component (B). Since the latent curing agent, which is the component (C), cannot be completely dissolved, it is possible to provide a resin composition with low viscosity (1 Pa s or less), excellent storage stability, and capable of rapid curing. .

The amount of the organic solvent having an SP value of 7.8 to 9.5 (cal/cm ³ ) ^0.5 in the resin composition of the present invention is determined according to its application and is particularly limited. However, it is preferable to contain 10 to 100 parts by mass of the organic solvent with respect to 100 parts by mass of the total amount of components (A), (B) and (C). If the amount is less than 10 parts by mass, the viscosity-lowering effect may not be sufficiently exhibited, and if the amount exceeds 100 parts by mass, the drying property may deteriorate.

Various additives can be added to the resin composition of the present invention, if necessary. Examples of additives include reactive diluents such as monoalkyl glycidyl ether; non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol and coal tar; silica such as fused silica and crystalline silica; Powders of magnesium oxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, etc., or these beads, and fillers such as glass fiber, pulp fiber, synthetic fiber, ceramic fiber; reinforcing materials such as glass cloth, aramid cloth, carbon fiber; pigment; γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N′-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ - glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, Silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; , montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, lubricant such as aromatic ether; thickener; thixotropic agent; antioxidant; light stabilizer; ultraviolet absorber antifoaming agents; rust preventives; colloidal silica, colloidal alumina and other commonly used additives. In the present invention, tacky resins such as xylene resins and petroleum resins can also be added.

The resin composition of the present invention can be used as various paints, various adhesives, and various molding materials. In particular, it can be suitably used as an adhesive for electronic parts, an adhesive for electrical equipment such as copiers and printers, an adhesive for pad printing, and the like.

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

Production Example 1 [Production of latent curing agent (EH-1)]
A flask was charged with 352 g of isophorone diamine and heated to 60°C, and 580 g of ADEKA RESIN EP-4100E (manufactured by ADEKA; bisphenol A type epoxy resin, epoxy equivalent: 190) was kept at a temperature of 100 to 110°C. It was added little by little so that the After the addition was completed, the reaction was carried out at 140° C. for 1.5 hours to obtain a modified polyamine. Next, 20 g of phenolic resin H-4 (manufactured by Meiwa Kasei Co., Ltd.; novolak phenolic resin) is added to 100 g of the modified polyamine obtained, and the mixture is heated at 150 to 160° C. for 1 hour to melt and undergo latent curing. Agent (EH-1) was obtained.

Production Example 2 [Production of latent curing agent (EH-2)]
A flask was charged with 201 g of 1,2-diaminopropane and heated to 60.degree. After the addition was completed, the reaction was carried out at 140° C. for 1.5 hours to obtain a modified polyamine. Next, 20 g of phenolic resin was added to 100 g of the modified polyamine obtained, and the mixture was melted by heating at 150 to 160° C. for 1 hour to obtain a latent curing agent (EH-2).

Production Example 3 [Production of latent curing agent (EH-3)]
A flask was charged with 201 g of 1,3-diaminopropane and heated to 60°C. After the addition was completed, the reaction was carried out at 140° C. for 1.5 hours to obtain a modified polyamine. Next, 25 g of phenolic resin was added to 100 g of the modified polyamine obtained and melted at 150 to 160° C. for 1 hour to obtain a latent curing agent (EH-3).

Production Example 4 [Production of latent curing agent (EH-4)]
A flask was charged with 162.5 g of isobutanol, 162.5 g of xylene, 357 g of N,N-dimethylaminopropylamine, and 222 g of 1,2-propanediamine, and after mixing and stirring at 60 to 70° C. for 30 minutes, N,N- 540 g of diglycidyl toluidine was added dropwise, and refluxed for 2 hours. Then, 1166 g of a 67 mass % xylene solution of isophorone diisocyanate was added dropwise. After completion of dropping, reaction was carried out at 140 to 150° C. for 2 hours. It was confirmed by IR that the absorption at 2250 cm ^{-1 ,} which is the absorption of isocyanate, had disappeared, and the solvent was removed under normal pressure at 200°C for 2 hours. Further, the solvent was removed under reduced pressure at 190 to 200° C. and 50 to 60 mmHg for 1 hour to obtain a latent curing agent (EH-4).

[Examples 1 to 8]
Resin compositions were produced using the latent curing agents obtained in Production Examples 1 to 4 as component (C) and the following commercial products as components (A), (B) and (D). The resin composition was produced by mixing components (A) to (D) with a planetary mixer at room temperature. The obtained resin composition was evaluated for viscosity, storage stability and rapid curing under the following conditions. Table 1 shows the formulation of the resin composition and the evaluation results.

(A) Component Lecy: manufactured by Lonza; bisphenol-type cyanate ester resin DT-7000: manufactured by Lonza; dicyclopentadiene-type cyanate ester resin (B) Component XD-1000: manufactured by Nippon Kayaku Co., Ltd.; dicyclopentadiene novolak type epoxy resin EP-4088L: manufactured by ADEKA Corporation; dicyclopentadiene type epoxy resin (D) component DPMNP: dipropylene glycol methyl-n-propyl ether (SP value: 8.0)
DIBK: diisobutyl ketone (SP value: 8.5)
BAB: butyl butyrate (SP value: 8.7)

<Storage stability>
The resin compositions of Examples and Comparative Examples were placed in a 500 ml beaker, allowed to stand at room temperature for 24 hours after production, and then visually observed for gelation. A case where gelation was not observed was rated as ◯, and a case where gelation was observed was rated as x.

<Viscosity>
Using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., cone rotor: standard [1°34′×R24]), the viscosity at 25° C. was measured at 1 rpm. The case where the viscosity was less than 1 Pa·s was rated as ◯, and the case where the viscosity exceeded 1 Pa·s was rated as x.

<Fast curing>
0.5 g of the obtained resin composition was dropped on a hot plate maintained at 100° C. and stirred with a spatula to measure the time until fluidity disappeared. The case where the fluidity loss time was 3 seconds or less was evaluated as ◯, and the case where the time exceeded 3 seconds was evaluated as X.

[Comparative Example 1]
A resin composition was produced in the same manner as in Example 2, except that n-octane (nO, SP value: 7.6) was used instead of component (D). Component (C) was separated from n-octane, and viscosity, storage stability and rapid curing could not be evaluated.

[Comparative Example 2]
A resin composition was produced in the same manner as in Example 2, except that 3-methoxybutanol (MB, SP value: 10.9) was used instead of component (D). And it was not possible to evaluate the rapid curability.

As shown by the above examples, the resin composition of the present invention has low viscosity, excellent storage stability, and rapid curing. On the other hand, when a solvent other than the specific solvent used in the present invention is used, such performance as described above cannot be obtained.

Claims (6)

(A) cyanate ester resin, (B) epoxy resin, (C) latent curing agent, and (D) at least one organic solvent selected from dipropylene glycol methyl n-propyl ether, diisobutyl ketone and butyl butyrate. containing resin composition; The cyanate ester resin as component (A) is at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and prepolymers thereof. The resin composition of claim 1, wherein

(Wherein, Y ¹ is a divalent hydrocarbon group, a group in which a hydrogen atom of the divalent hydrocarbon group is substituted with a fluorine atom, —O—, —S—, or a direct bond, and A ¹ and Each ^A2 is independently a phenylene group or a phenylene group having 1 to 4 alkyl groups of 1 to 4 carbon atoms.)

(Wherein, m is an integer of 1 or more, Y ² is a divalent hydrocarbon group or a group in which the hydrogen atoms of the divalent hydrocarbon group are substituted with fluorine atoms, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The resin composition according to claim 2, wherein Y ¹ in the formula (1) and Y ² in the formula (2) are groups selected from the following formulas (Y-1) to (Y-9).

(In the formula, n is an integer of 4 to 12, R ³ and R ⁴ are each independently a hydrogen atom, a methyl group, or a group in which a hydrogen atom of a methyl group is substituted with a fluorine atom, * represents a bonding site with another group. ^{Y 1} and Y ² may be the same or different.) The latent curing agent, which is the component (C), includes (C-1) a modified amine obtained by reacting an amine compound having at least one active hydrogen with an epoxy compound, and (C-2) an amine having at least one active hydrogen. At least one selected from a modified amine obtained by reacting a compound with an isocyanate compound, and (C-3) a modified amine obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound and an isocyanate compound, or any of these The resin composition according to any one of claims 1 to 3, which is a mixture of at least one selected from modified amines and a phenolic resin. 5. The resin composition according to any one of claims 1 to 4 , containing 1 to 10,000 parts by mass of (B) epoxy resin per 100 parts by mass of (A) cyanate ester resin. An adhesive containing the resin composition according to any one of claims 1 to 5 .