WO2021112091A1

WO2021112091A1 - Resin composition

Info

Publication number: WO2021112091A1
Application number: PCT/JP2020/044718
Authority: WO
Inventors: 真吾出口; 木村　朋子; 啓介太田; 慎介山田; 小川　亮
Original assignee: 株式会社Adeka
Priority date: 2019-12-03
Filing date: 2020-12-01
Publication date: 2021-06-10
Also published as: TW202128811A

Abstract

The present invention addresses the problem of providing a rapidly curable resin composition that produces a low-modulus cured article.　A resin composition according to the present invention includes: (A) a cyanate ester resin; (B) a cardanol compound or glycidyl ether thereof; (C) a potential amine curing agent; and (D) an epoxy resin (excluding polyglycidyl ether of a cardanol compound). The resin composition preferably contains 50 to 5,000 parts by mass of a cardanol compound and glycidyl ether thereof with respect to 100 parts by mass of component (A). Component (C) is preferably a potential amine curing agent having an active hydrogen.

Description

Resin composition

The present invention relates to a resin composition.

Epoxy resin compositions are widely used industrially in paints, adhesives, various molding materials, etc.

When it is not enough to use the existing epoxy resin alone or in combination, the cyanate-epoxy composite resin composition obtained by mixing the epoxy resin and the cyanate ester resin has high heat resistance. Therefore, it has come to be widely used as a useful material.

For example, Patent Document 1 proposes a liquid epoxy resin composition for semiconductor encapsulation, which comprises a cyanate ester resin, an epoxy resin, an inorganic filler, a metal chelate, a dihydrazide compound, and the like. Patent Document 2 proposes a composite composition containing a cyanate ester resin, an epoxy resin, and an amine-based curing agent. Patent Document 3 proposes a thermosetting resin composition containing a cyanate ester resin, an epoxy resin, and a latent curing agent containing an imidazole component. Patent Document 4 proposes a composite resin containing a cyanate ester resin, an epoxy resin, and a latent curing agent containing a dialkylaminoalkylamine. However, only a hard cured product was obtained from the cyanate-epoxy composite resin composition proposed in these patent documents.

On the other hand, it is known that cardanol or its glycidyl ether is used in the epoxy resin composition (see Patent Documents 5 to 8). However, these patent documents do not describe a combination of cardanol or its glycidyl ether and a cyanate-epoxy composite resin composition, and the combination reduces the elasticity of the cured product obtained from the resin composition. I don't suggest anything about that.

US6469074B1 Japanese Unexamined Patent Publication No. 60-250026 US6342577B1 Japanese Unexamined Patent Publication No. 2009-13205 US2003 / 62911A1 WO03 / 075338A1 WO2004 / 078870A1 US2009 / 203813A1

Therefore, the problem to be solved by the present invention is to provide a resin composition which can obtain a cured product having low elasticity and can be cured quickly.

As a result of diligent studies to solve the above problems, the present inventors have solved the above problems with a resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent and a cardanol compound or a glycidyl ether thereof. We found that we could do it, and arrived at the present invention.

That is, the present invention includes (A) cyanate ester resin, (B) cardanol compound or glycidyl ether thereof, (C) amine-based latent curing agent and (D) epoxy resin (excluding polyglycidyl ether of cardanol compound). It is a resin composition containing.

According to the present invention, there is provided a resin composition that can be cured quickly and a cured product having low elasticity can be obtained. The resin composition of the present invention can be suitably used for applications such as adhesives.

The resin composition of the present invention will be described below.
The resin composition of the present invention comprises (A) cyanate ester resin, (B) cardanol compound or glycidyl ether thereof, (C) amine-based latent curing agent and (D) epoxy resin (provided that polyglycidyl ether of cardanol compound is used. Excludes).

First, the component (A) contained in the resin composition of the present invention will be described. In the present invention, as the cyanate ester resin as the component (A), a compound having two or more cyanate groups can be used without particular limitation, and the molecular structure, molecular weight and the like thereof are not particularly limited.

As the cyanate ester resin, it is preferable to use at least one selected from the group consisting of the compound represented by the following formula (1), the compound represented by the following formula (2), and these prepolymers. In the present invention, the prepolymer means a compound self-polymerized or slightly polymerized by an arbitrary trace component.

NC-O-A ^1- Y ^1- A ^2- O-CN (1)

In the formula, Y ¹ represents an unsubstituted or fluorine-substituted divalent hydrocarbon group, —O—, —S—, or a single bond.
A ¹ and A ² each independently represent a phenylene group which is unsubstituted or substituted with 1 to 4 alkyl groups.

Examples of the divalent hydrocarbon group represented by Y ¹ in the formula (1), for example, an alkylene group, a cycloalkylene group, a cycloalkylene group, an arylene group and arylenealkylene group, and the like. In the present invention, Y ¹ is preferably an alkylene group because it is easily available and has excellent physical properties.

The alkylene group may be linear or branched. Examples of the linear alkylene group include those having 1 to 20 carbon atoms. Specific examples thereof include carbon atoms at the ends of linear alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl. A divalent group obtained by removing one hydrogen atom from the group can be mentioned. On the other hand, examples of the branched alkylene group include those having 1 to 20 carbon atoms. Specific examples thereof include one hydrogen atom from a branched alkylene group such as isopropyl, isobutyl, s-butyl, t-butyl, isoamyl, t-amyl, isooctyl, 2-ethylhexyl, t-octyl, isononyl and isodecyl. The removed divalent group can be mentioned. In the present invention, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and 1 to 4 carbon atoms, because it is easily available and has excellent physical properties. Is more preferable.

The cycloalkylene group may be monocyclic or polycyclic. Examples of the monocyclic cycloalkylene group include those having 3 to 20 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundesyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, and cyclohepta. Examples thereof include a divalent group obtained by removing one hydrogen atom from a monocyclic cycloalkyl group such as decyl, cyclooctadecyl, cyclononadecil and cycloicosyl. Examples of the polycyclic alkyl group include those having 8 to 14 carbon atoms. Specific examples thereof include divalentity obtained by removing one hydrogen atom from a polycyclic alkyl group such as adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthrasenyl. The basis of.

In the present invention, the cycloalkylene alkylene group is a divalent group in which one or more alkylene groups and one or more cycloalkylene groups are combined. The cycloalkylene group in the cycloalkylene alkylene group may be a monocyclic group or a polycyclic group. The monocyclic cycloalkylene alkylene group is a divalent group in which one or more hydrogen atoms of the alkyl group are substituted with the monocyclic cycloalkyl group and one hydrogen atom is removed from the group, or the monocyclic group. Examples thereof include a divalent group in which two or more hydrogen atoms of the formula cycloalkyl group are substituted with the alkyl group and one hydrogen atom is removed from the group. The polycyclic cycloalkylene alkylene group is a divalent group in which one or more hydrogen atoms of the alkyl group are substituted with the polycyclic cycloalkyl group and one hydrogen atom is removed from the group, or the polycyclic group. Examples thereof include a divalent group in which two or more hydrogen atoms of the formula cycloalkyl group are substituted with the alkyl group and one hydrogen atom is removed from the group.

The arylene group may be of a monocyclic type or a condensed ring type. Examples of the monocyclic arylene group include those having 6 to 20 carbon atoms. Specific examples thereof include a divalent group obtained by removing one hydrogen atom from a monocyclic aryl group such as phenyl and biphenylyl. Examples of the fused cyclic arylene alkylene group include those having 10 to 18 carbon atoms. Specific examples thereof include a divalent group obtained by removing one hydrogen atom from a fused cyclic aryl group such as naphthyl, anthryl, phenanthrenyl, and fluorene.

In the present invention, the arylene alkylene group is a divalent group in which one or more alkylene groups and one or more arylene groups are combined. The arylene group in the arylene alkylene group may be of a monocyclic type or a condensed ring type. The monocyclic arylene alkylene group is a divalent group in which one or more hydrogen atoms of the alkyl group are substituted with the monocyclic aryl group and one hydrogen atom is removed from the group, or the monocyclic aryl group. Examples thereof include a divalent group in which two or more hydrogen atoms of the group are substituted with the alkyl group and one hydrogen atom is removed from the group. The fused ring-type arylene alkylene group is a divalent group in which one or more hydrogen atoms of the alkyl group are substituted with the fused ring-type aryl group and one hydrogen atom is removed from the group, or the fused ring-type aryl. Examples thereof include a divalent group in which two or more hydrogen atoms of the group are substituted with the alkyl group and one hydrogen atom is removed from the group.

Divalent hydrocarbon group represented by Y ¹ in Formula (1) are readily available, and because it becomes the physical properties were excellent, the following formula (Y-1) ~ (Y -10) It preferably contains a group selected from the group consisting of. "Including a group selected from the group consisting of formulas (Y-1) to (Y-10)" means that Y ^{1 is one of the} groups selected from the group consisting of (Y-1) to (Y-10). It means that it consists of only two or more of the groups selected from the group consisting of (Y-1) to (Y-10).

In the formula, n represents an integer of 4 to 12 and represents
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an unsubstituted or fluorine-substituted methyl group.
* Represents a bond.

The alkyl group substituting the phenylene group represented by ^{A 1} and A ² in the formula (1) may be linear or branched. Examples of the linear alkyl group include those having 1 to 20 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl. Examples of the branched alkyl group include those having 1 to 20 carbon atoms. Specific examples thereof include isopropyl, isobutyl, s-butyl, t-butyl, isoamyl, t-amyl, isooctyl, 2-ethylhexyl, t-octyl, isononyl and isodecyl.

In the formula, m represents an integer of 1 or more.
Y ² is a sulfur atom, a divalent hydrocarbon group unsubstituted or fluorine-substituted, a plurality of Y ² may be the same or different,
R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

^{Examples of the alkyl group having 1 to 4 carbon atoms represented by R 1} and R ² in the formula (2) include linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, second butyl and third butyl. And branched alkyl groups such as isobutylmethyl groups.

Examples of the divalent hydrocarbon group represented by Y ² in the formula (2) include the same divalent hydrocarbon group represented by ^{Y 1 in the formula (2).}

^{Y 2} in the formula (2) includes a group selected from the group consisting of the formulas (Y-1) to (Y-10) because it is easily available and has excellent physical properties. Is preferable.

M in the above equation (2) represents an integer of 1 or more. In the present invention, the upper limit of m can be 10 or less.

Next, the cardanol compound of the component (B) contained in the resin composition of the present invention and its glycidyl ether will be described. In the present invention, the cardanol compound is one of the phenols obtained from cashew nuts or the like and substituted with a chain hydrocarbon group having an unsaturated bond. The number of unsaturated bonds in the chain hydrocarbon group contained in the cardanol compound may be 1, 2, or 3. Specific examples of the chain hydrocarbon group having one unsaturated bond include an 8-pentadecaneyl group. Specific examples of the chain hydrocarbon group having two unsaturated bonds include a 7,10-pentadecadienyl group and an 8,11-pentadecadienyl group. Specific examples of the chain hydrocarbon group having two unsaturated bonds include an 8,11,14-pentadecatorienyl group. In the present invention, the chain hydrocarbon group in the cardanol compound preferably has two unsaturated bonds. A specific example thereof is preferably represented by the following formula (a-1). As described above, since the cardanol compound is extracted from a natural product such as cashew nuts, it is difficult to obtain a highly pure compound. Therefore, those containing 10% by mass or less of impurities are also included in the cardanol compounds used in the present invention. The glycidyl ether of the cardanol compound may be a monoglycidyl ether or a polyglycidyl ether. In the present invention, since the elasticity of the obtained cured product is further lowered, it is preferable to use a cardanol compound or a monoglycidyl ether thereof, and it is more preferable to use a cardanol compound monoglycidyl ether.

The glycidyl ether of the cardanol compound can be produced by a known method used when producing the glycidyl ether from the phenol compound. The glycidyl ether of the cardanol compound may be a polyfunctional compound as represented by the following formula.

In the formula, G represents a hydroxyl group or the following group (i), and p represents a number from 0 to 10.

Commercially available products may be used as the cardanol compound and its glycidyl ether. Commercially available products include, for example, Cardolite NX-2021 (manufactured by Cardorite; Cardanol), Cardolite NX-2022 (manufactured by Cardorite; high-purity cardanol), Cardolite NX-2023D (manufactured by Cardorite; dark color, color stable). Cardolite), Cardolite NX-2023 (Caldorite; bright hue, color stable Cardanol), Cardolite NX-2024 (Caldorite; regular cycle, standard purity Cardanol), Cardolite NX-2025 (Caldorite; high) Purity Cardanol), Cardolite Ultra LITE NX-2023 (bright hue, color stable cardanol), Cardolite NC-513 (Caldorite; Cardanol monoglycidyl ether), Ultra LITE 513 (Bright hue, low viscosity) Cardanol Monoglycidyl Ether), NC-514 (Cardolite; Polycardanol Polyglycidyl Ether), NC-514S (Cardolite; Low Viscosity Polycardanol Polyglycidyl Ether), NC-547 (Cardlite) Manufactured by; polycardanol polyglycidyl ether) and the like.

The content of the cardanol compound and its glycidyl ether in the resin composition of the present invention is not particularly limited, but is the total amount of the cyanate ester resin of the component (A) and the epoxy compound of the component (D) described later. It is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the cardanol compound and its glycidyl ether is 5% by mass or more, the elasticity of the obtained cured product is low, and when it is 50% by mass or less, the adhesiveness is further high, which is preferable.

In the present invention, since the elasticity of the obtained cured product is further lowered, the content of the cardanol compound and its glycidyl ether is contained in an amount of 10 to 1000 parts by mass with respect to 100 parts by mass of the cyanate ester resin as the component (A). It is preferable, and it is more preferable to contain 20 to 500 parts by mass.

Next, the component (C) contained in the resin composition of the present invention will be described. Examples of the amine-based latent curing agent include dihydrazide oxalate, dihydrazide malonate, dihydrazide succinate, dihydrazide glutarate, dihydrazide adipic acid, dihydrazide suberic acid, dihydrazide azelaine, dihydrazide sebacate, and dihydrazide phthalate. Acid dihydrazide; guanamines such as benzoguanamine and acetoguanamine; dicyandiamide; melamine; and dehydration condensates of amine compounds and carboxylic acids, additions of amine compounds and epoxy compounds, additions of amine compounds and isocyanate compounds, amine compounds Examples thereof include a Michael adduct, a Mannig reaction product of an amine compound, a condensate of an amine compound and urea, and a modified amine such as a condensate of an amine compound and a ketone. These amine-based latent curing agents may be used alone or in combination of two or more. In the present invention, since the reactivity of the resin composition is good, it is preferable to use a component (C) having active hydrogen. Examples of the amine-based latent curing agent having active hydrogen include dihydrazide dibasic acid, guanamine, and a modified amine described later.

In the present invention, it is also preferable to use a modified amine because the physical properties can be easily adjusted. As the modified amine, it is preferable to use at least one selected from the group consisting of the following (C-1) to (C-2).
(C-1) A modified amine obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound.
(C-2) A modified amine formed by reacting an amine compound having one or more active hydrogens with an isocyanate compound.
(C-3) A modified amine obtained by reacting an amine compound having one or more active hydrogens, an epoxy compound, and an isocyanate compound.

Examples of the amine compound having one or more active hydrogens include polyether polyamines such as polyether triamine, polyether dihydric acid, polyoxypropylene dihydric acid, polytetradiamine, and polyoxypropylene triamine; ethylenediamine and 1,2-diaminopropane. , 1,3-Diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, alkylenediamines such as hexamethylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, 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'-diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2, Adipic polyamines such as 2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, norbornenediamine; m-xylylene diamine, 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- Aromatic polyamines such as 4,4'-diaminodiphenylmethane, 3,5,3', 5'-tetramethyl-4,4'-diaminodiphenylmethane; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2 -Idazoles such as ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undesyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 2-aminopropyl imidazole; Shu Acid dihydrazide, malonic acid dihydrazide, succinate dihydrazide, glutarate dihydrazide, adipic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalate dihydrazide Dihydrazides such as N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine, N, N-benzylmethylaminoethylamine, N, N-di Benzylaminoethylamine, N, N-cyclohexylmethylaminoethylamine, N, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) morpholin , N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N'-methylpiperazine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N-diisopropylaminopropyl Amine, 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 '-Methylpiperidin, 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N-diisopropylamino) benzylamine, N, N, -dimethylisophorone Diamine, N, N-dimethylbisaminocyclohexane, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethylethylenediamine, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-Dimethylpropandiamine, N'-ethyl-N, N-dibenzylaminopropylamine; N, N- (bisaminopropyl) -N-methylamine, N, N-bisaminopropylethylamine, N, N-bis Aminopropylpropylamine, 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-dime) Tylaminopropyl)] amine, bis [3- (N, N-diethylaminopropyl)] amine, bis [3- (N, N-diisopropylaminopropyl)] amine, bis [3- (N, N-dibutylaminopropyl)] )] Amine and the like can be mentioned.

Examples of the epoxy compound include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluoroglusinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), and the like. Echilidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropyridene 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) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, orthocresol novolak, Polyglycyl ether compounds of polynuclear polyvalent phenolic compounds such as ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpenphenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, Polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid , Sebasic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and other aliphatic and aromatic Glycidyl esters of group or alicyclic polybasic acids, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) Epoxy compounds having a glycidyl amino group such as methane, diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentane diene diepoxyside, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy -6-methylcyclohexylmethyl-6-methyl Epoxides of cyclic olefin compounds such as cyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, tri. Examples thereof include a heterocyclic compound such as glycidyl isocyanurate.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylenedi isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5. -Aromatic diisocyanates such as naphthylene diisocyanate, 1,5-tetrahydronaphthalenedisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4 , 4'-Diisocyanate, trans-1,4-cyclohexyldiisocyanate, norbornene diisocyanate and other alicyclic diisocyanates; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) )-Adicyclic diisocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate; isocyanurate trimersides, burette trimerates, trimethylolpropane adductates, etc. of the above-exemplified diisocyanates; triphenylmethane triisocyanates, 1-methylbenzol Examples thereof include 2,4,6-triisocyanate and dimethyltriphenylmethanetetraisocyanate. Further, these isocyanate compounds may be used in the form of carbodiimide modification, isocyanurate modification, biuret modification or the like, or may be used in the form of blocked isocyanate blocked by various blocking agents.

The modified amine (C-1) has an amine compound having one or more active hydrogens and an epoxy compound, and the epoxy group of the epoxy compound is 0.1 to 1. An amount of 1 equivalent, particularly an amount of 0.2 to 1.0 equivalent, is preferably reacted. It is preferable to use the modified amine because a resin composition having good storage stability and curability can be obtained.

The modified amine (C-2) is an amine compound having one or more active hydrogens and an isocyanate compound, and the isocyanate group of the isocyanate compound is 0.1 to 1. An amount of 1 equivalent, particularly an amount of 0.2 to 1.0 equivalent, is preferably reacted. It is preferable to use the modified amine because a resin composition having good storage stability and curability can be obtained.

The modified amine (C-3) is an amine compound having one or more active hydrogens, an epoxy compound (C-2), and an isocyanate compound (C-3). The amount of the epoxy group of the epoxy compound is 0.1 to 1.0 equivalent to 1 equivalent of H group, particularly the amount of 0.2 to 1.0 equivalent, and the isocyanate group of the polyisocyanate compound is 0.01 to 0. An amount of 9.9 equivalents, particularly an amount of 0.05 to 0.8 equivalents, is preferable. It is preferable to use the modified amine because a resin composition having good storage stability and curability can be obtained.

The method for producing the modified amines (C-1), (C-2) and (C-3) is not particularly limited, but heating at room temperature to 140 ° C. using a solvent, if necessary. It can be produced by reacting underneath for 1 to 10 hours.
In the (C-3) modified amine, it is usually preferable to react the amine compound with the epoxy compound and then react with the polyisocyanate compound.
When a solvent is used, the solvent can be removed under normal pressure or reduced pressure under heating after the reaction is completed.
Further, these solid ones can also be crushed by using a crusher such as a jet mill.

Examples of the solvent 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, , 2-Diethoxyethane, ethers such as propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Such as halogenated aliphatic hydrocarbons; examples thereof include halogenated aromatic hydrocarbons such as chlorobenzene.

In the resin composition of the present invention, when at least one modified amine selected from the group consisting of the above (C-1) to (C-3) is used as the amine-based latent curing agent as the component (C). From the viewpoint that the reactivity can be adjusted, it is also preferable to use at least one modified amine selected from the group consisting of (C-1) to (C-3) in combination with the (E) phenol resin.

Examples of the phenol resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and trisphenylol methane. Resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyvalent phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified Naftor resin (a polyvalent naphthol compound in which a phenol nucleus is linked by a bismethylene group), aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring and a primary amino group in its molecular structure), and an alkoxy group-containing aromatic ring. Examples thereof include polyhydric phenol compounds such as modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

In the present invention, from the viewpoint of obtaining a resin composition having an excellent balance between storage stability and curability, it is preferable to use a phenol resin having a number average molecular weight of 750 to 1200.

The amount of the phenol resin used as the component (C-1), the component (C-2) or the component (C-3) as opposed to the component (C-1), the component (C-2) and the component (C-2) is as follows. 3) The amount is preferably 10 to 150 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass of the total of the modified amine as a component. When the content of the phenol resin is 10 parts by mass or more, the curability of the resin composition is further improved, and when it is 150 parts by mass or less, the physical properties of the obtained cured product are further improved, which is preferable.

A commercially available product may be used as the amine-based latent curing agent. Commercially available amine-based latent curing agents include Adeca Hardener EH-3636S (manufactured by ADEKA Co., Ltd .; dicyandiamide type latent curing agent), Adeca Hardener EH-4351S (manufactured by ADEKA Co., Ltd .; dicyandiamide type latent curing agent), Adeca Hardener EH-5011S (manufactured by ADEKA Co., Ltd .; imidazole type latent curing agent), Adeca Hardener EH-5046S (manufactured by ADEKA Co., Ltd .; imidazole type latent curing agent), Adeca Hardener EH-4357S (manufactured by ADEKA Co., Ltd .; polyamine) Type Latent Curing Agent), Adeca Hardener EH-5057P (manufactured by ADEKA Co., Ltd .; Polyamine Type Latent Curing Agent), Adeca Hardener EH-5057PK (manufactured by ADEKA Co., Ltd .; Polyamine Type Latent Curing Agent), Amicure PN-23 (Made by Polyamine Type Latent Curing Agent) Ajinomoto Fine Techno Co., Ltd .; Amine Adduct-based latent curing agent), Amicure PN-40 (Ajinomoto Fine Techno Co., Ltd .; Amine Adduct-based latent curing agent), Amicure VDH (Ajinomoto Fine Techno Co., Ltd .; Hydrazide-based latent curing agent) (Sex hardener), Fujicure FXR-1020 (manufactured by T & K TOKA Co., Ltd .; latent hardener) and the like.

The content of the (C) amine-based latent curing agent in the resin composition of the present invention is not particularly limited, but the total amount of the (A) cyanate ester resin and the (D) epoxy compound described later is 100 parts by mass. It is preferably 2 to 200 parts by mass, and more preferably 5 to 100 parts by mass. It is preferable that the content of the amine-based latent curing agent (C) is in the above range because the viscosity of the obtained resin composition is in an appropriate range.

Next, the component (D) contained in the resin composition of the present invention will be described. The epoxy resin (D) as a component (excluding the polyglycidyl ether of the cardanol compound) can be used without particular limitation as long as it has at least two epoxy groups in the molecule, and its molecular structure and its molecular structure There is no particular limitation on the molecular weight and the like.

Examples of the epoxy resin include a polyglycidyl ether compound of a mononuclear polyvalent phenol compound, a polyglycidyl ether compound of a polynuclear polyvalent phenol compound, a polyglycidyl ether compound of a polyhydric alcohol compound, and a glycidyl ester compound of an aliphatic polybasic acid. , Aromatic polybasic acid glycidyl ester compound, alicyclic polybasic acid glycidyl ester compound, glycidyl methacrylate homopolymer or copolymer, epoxy compound having glycidyl amino group, epoxidized cyclic olefin compound, epoxidation Examples thereof include conjugated diene polymers, heterocyclic compounds and fluorene type epoxy resins. These epoxy resins may be internally crosslinked with a prepolymer of terminal isocyanate, or have a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). You may. In the resin composition of the present invention, one type of epoxy resin may be used alone, or two or more types may be used in combination.

Examples of the mononuclear polyhydric phenol compound include hydroquinone, resorcinol, pyrocatechol, fluoroglucosinol and the like.

Examples of the polynuclear polyphenol compound include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidenebisphenol, isopropyridenebisphenol (bisphenol A), isopropyridenebis (orthocresol), and tetrabromobisphenol A. , 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2, Examples thereof include 2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.

Examples of the polyhydric alcohol compound include ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, and 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenation). Bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct and the like can be mentioned.

Examples of the alicyclic polybasic acid include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid and trimer acid.

Examples of the aromatic polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid and pyromellitic acid.

Examples of the alicyclic polybasic acid include tetrahydrophthalic acid and endomethylene tetrahydrophthalic acid.

Examples of the epoxy compound having a glycidylamino group include N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, and N, N-bis ( 2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline and Examples thereof include N, N, N', N'-tetra (2,3-epoxypropyl) -4,4-diaminodiphenylmethane and the like.

Examples of the cyclic olefin compound include vinylcyclohexene diepoxide, cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-6-methylcyclohexylmethyl-6. -Methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and the like can be mentioned.

Examples of the epoxidized conjugated diene polymer include epoxidized polybutadiene and epoxidized styrene-butadiene copolymer.

Examples of the heterocyclic epoxy compound include triglycidyl isocyanurate.

Examples of the fluorene type epoxy resin include an epoxy compound represented by the following formula (3). In the resin composition of the present invention, since the elastic modulus of the obtained cured product can be further reduced, it is preferable to use a fluorene type epoxy resin as the epoxy resin, and the epoxy represented by the following formula (3) is preferable. It is more preferable to use a compound. Examples of commercially available products of the fluorene type epoxy resin represented by the formula (3) include OGSOL EG-280 (manufactured by Osaka Gas Chemical Co., Ltd.).

In the formula, n ¹ and n ² each independently represent a number from 1 to 50.
X ₁ and X ₂ each independently represent an alkylene group having 1 to 4 carbon atoms.
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the halogen atom represented by ^{R 7} , R ⁸ , R ⁹ and R ¹⁰ in the formula (3) include chlorine, bromine and iodine.
As the alkyl group having 1 to 4 carbon atoms represented by ^{R 7} , R ⁸ , R ⁹ and R ¹⁰ in the formula (3), the ^{number of carbon atoms represented by R 1} and R ² in the formula (2) The same as 1 to 4 alkyl groups can be mentioned.

The alkylene groups having 1 to 4 carbon atoms represented by _{X 1} and X ₂ in the formula (3) may be linear or branched. Examples of the linear alkylene group include a divalent group obtained by removing one hydrogen atom from the carbon atom at the end of the linear alkyl group such as methyl, ethyl, n-propyl and n-butyl. Examples of the branched alkylene group include a divalent group obtained by removing one hydrogen atom from a branched alkylene group such as isopropyl, isobutyl, s-butyl, and t-butyl.

The content of the epoxy resin as the component (D) in the resin composition of the present invention is not particularly limited, but is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the cyanate ester resin. , 200 to 800 parts by mass is more preferable because excellent cured physical properties can be obtained.

In the present invention, a known curing accelerator can be used in combination with the latent curing agent, if necessary. Specific examples of these curing accelerators include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-un. Imidazoles such as decylimidazole and 1-cyanoethyl-2-methylimidazole; imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6-tris ( Amines such as dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethyl Ureas such as urea, 3-phenyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines and ether compounds. It can be exemplified. These curing accelerators may be used alone or in combination of two or more. The content of the epoxy resin curing accelerator in the one-component cyanate-epoxy composite resin composition of the present invention is not particularly limited, and can be appropriately set according to the application of the one-component cyanate-epoxy composite resin composition.

The resin composition of the present invention may contain various additives, if necessary. Examples of the additive include reactive diluents such as monoalkylglycidyl ether; non-reactive diluents (plasticizers) such as dioctylphthalate, dibutylphthalate, benzyl alcohol and coaltal; silica such as molten silica and crystalline silica; Powders of magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, berilia, zirconia, zircon, fosterite, steatite, spinel, mulite, titania, etc., or Spherical beads and fillers such as glass fiber, pulp fiber, synthetic fiber, ceramic fiber; reinforcing material 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-epylcyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane , Γ-Methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and other silane coupling agents; candelilla wax, carnauba wax, wood wax, ibotarou, mitsuro, lanolin, whale Lubricants such as wax, monttan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, aromatic ether; thickener; thixotropic agent; antioxidant; light stabilizer; ultraviolet absorption Agents; antifoaming agents; rust preventives; commonly used additives such as colloidal silica and colloidal alumina. In the present invention, adhesive resins such as xylene resin and petroleum resin can also be used in combination.

The resin composition of the present invention can be used for various paints, various adhesives, and various molding materials. Since the obtained cured product has low elasticity, it can be suitably used as a material or an adhesive that requires impact resistance.

The present invention will be described in detail below based on examples. However, the present invention is not limited to these examples.

Production Example 1 (Synthesis of amine-based latent curing agent)
230 g of Jeffamine D230 (polyetherpolyamine, manufactured by Huntsman) was placed in a flask and heated to 60 ° C. Next, 190 g of ADEKA REGIN EP-4901E (bisphenol F type epoxy resin having an epoxy equivalent of 170, manufactured by ADEKA Corporation) was added little by little to the flask so that the temperature inside the system was maintained at 100 to 110 ° C. After adding Adecaledin EP-4901E, the reaction system was heated to 140 ° C. and reacted for 1.5 hours to obtain a modified amine.
To 100 g of the obtained modified amine, 50 g of MP-800K (phenol resin having a softening point of 100 ° C., manufactured by Asahi Organic Materials Co., Ltd.) was charged, and the solvent was removed at 180 to 190 ° C. and 30 to 40 Torr for 1 hour. This was carried out to obtain a mixture CE of a modified amine and a phenol resin.

[Example 1-3 and Comparative Example 1-3]
The raw materials shown in [Table 1] below were mixed at room temperature to produce a resin composition. A planetary mixer was used for mixing. The following test was carried out on the cured product of the obtained resin composition. The evaluation results are shown in [Table 1] below. The reference numerals in Table 1 represent the following components. The content of the raw material in Table 1 is by mass. When the obtained resin compositions of Examples 1 to 3 were heated at 100 ° C., they were rapidly cured.

A: Bisphenol type cyanate ester resin (manufactured by Lonza, trade name: Lecy)
B-1: Cardanol monoglycidyl ether (manufactured by Cardlite, trade name: NC-513)
B-2: C12-13 alkyl monoglycidyl ether (manufactured by ADEKA Corporation, trade name: ED-502)
B-3: pt-Butylphenylmonoglycidyl ether (manufactured by ADEKA Corporation, trade name: ED-509E)
CE: Mixture of modified amine and phenol resin obtained in Production Example 1 D-1: Fluorene type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: OGSOL EG-280)
D-2: Dicyclopentadiene type epoxy resin (manufactured by ADEKA Corporation, trade name: EP-4088L)
F: 3-glycidoxypropyltriethoxysilane (silane coupling agent; trade name KBM-403, manufactured by Shinetsu Silicone)

<RSA test>
The loss elastic modulus (E'') and the storage elastic modulus (E') were measured using a dynamic viscoelasticity measuring device RSA G2 (TA Instruments Japan Co., Ltd.). The measurement range was −50 ° C. to 200 ° C., and the measurement conditions were a frequency of 1 Hz, a heating rate of 10 ° C./min, a sample width of 4 mm, and a distance between chucks of 20 mm. Table 1 shows the storage elastic modulus (E') at 25 ° C. Further, from the measured loss elastic modulus (E ″) and storage elastic modulus (E ′), the glass transition temperature (Tg) is determined by tan δ (tan δ = loss elastic modulus (E ″) / storage elastic modulus (E ′). ) Was obtained from the peak temperature. The results are shown in Table 1.

As is clear from Table 1, the resin compositions of Examples 1 to 3 had a lower glass transition temperature and storage elastic modulus (E') than the resin compositions of Comparative Examples 1 to 3. From this result, it is clear that the resin composition of the present invention can be cured quickly and a cured product having low elasticity can be obtained.

Claims

A resin containing (A) cyanate ester resin, (B) cardanol compound or glycidyl ether thereof, (C) amine-based latent curing agent and (D) epoxy resin (excluding polyglycidyl ether of cardanol compound). Composition.
Claimed that the cyanate ester resin 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 a prepolymer of these compounds. Item 2. The resin composition according to Item 1.

NC-O-A 1- Y 1- A 2- O-CN (1)

In the formula, Y 1 represents an unsubstituted or fluorine-substituted divalent hydrocarbon group, —O—, —S—, or a single bond.
A 1 and A 2 each independently represent a phenylene group which is unsubstituted or substituted with 1 to 4 alkyl groups.

In the formula, m represents an integer of 1 or more.
Y 2 is a sulfur atom, a divalent hydrocarbon group unsubstituted or fluorine-substituted, a plurality of Y 2 may be the same or different,
R 1 and R 2 independently represent 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) contain a group selected from the group consisting of the following formulas (Y-1) to (Y-10). ..

In the formula, n represents an integer of 4 to 12 and represents
R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or an unsubstituted or fluorine-substituted methyl group.
* Represents a bond.
The resin composition according to any one of claims 1 to 3, wherein the component (B) is a cardanol compound or a monoglycidyl ether thereof.
The resin composition according to any one of claims 1 to 4, wherein the component (C) is an amine-based latent curing agent having active hydrogen.
The resin composition according to claim 5, wherein the amine-based latent curing agent having active hydrogen is a modified amine.
The resin composition according to any one of claims 1 to 6, wherein the component (C) is at least one selected from the group consisting of the following (C-1) to (C-3).
(C-1): A modified amine obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound.
(C-2): A modified amine obtained by reacting an amine compound having one or more active hydrogens with an isocyanate compound.
(C-3): A modified amine obtained by reacting an amine compound having one or more active hydrogens, an epoxy compound, and an isocyanate compound.
The amine-based latent curing agent which is the component (C) is (C-1).
The amine compound having one or more active hydrogens is a polyether polyamine.
The resin composition according to claim 7, wherein the epoxy compound is a polyglycyl ether compound of a polynuclear polyhydric phenol compound.
The resin composition according to claim 7 or 8, further containing a phenol resin.
The resin composition according to claim 9, which contains 10 to 150 parts by mass of phenol resin with respect to a total of 100 parts by mass of (C-1), (C-2) and (C-3).
The resin composition according to any one of claims 1 to 10, wherein the content of the component (B) is 10 to 1000 parts by mass with respect to 100 parts by mass of the component (A).
Claimed that the content of the amine-based latent curing agent as the component (C) is 2 to 200 parts by mass with respect to 100 parts by mass of the total amount of the (A) cyanate ester resin and the (D) epoxy resin. Item 2. The resin composition according to any one of Items 1 to 11.
The resin composition according to any one of claims 1 to 12, wherein the content of the component (D) is 10 to 10000 parts by mass with respect to 100 parts by mass of the component (A).
An adhesive comprising the resin composition according to any one of claims 1 to 13.
Use of the resin composition according to any one of claims 1 to 13 as an adhesive.