TW202128811A - Resin composition - Google Patents

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 for paints, adhesives, various molding materials, and the like.

When the existing epoxy resin is not sufficient when used alone or in combination, the cyanate ester-epoxy composite resin composition formed by mixing epoxy resin and cyanate ester resin has high heat resistance, so it is often used Make useful materials.

For example, Patent Document 1 proposes a liquid epoxy resin composition for semiconductor sealing, which contains a cyanate ester resin, an epoxy resin, an inorganic filler, a metal chelate compound, a dihydrazine compound, and the like. Patent Document 2 proposes a composite composition containing a cyanate ester resin, an epoxy resin, and an amine-based hardener. 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, using the cyanate ester-epoxy composite resin composition proposed in these patent documents can only obtain a harder cured product.

On the other hand, it is known in the industry to use cardanol or its glycidyl ether for epoxy resin compositions (see Patent Documents 5 to 8). However, these patent documents do not describe the combination of cardanol or its glycidyl ether and cyanate ester-epoxy composite resin composition, and do not even suggest that the elasticity of the cured product obtained from the resin composition will be reduced by this combination. [Prior Technical Literature] [Patent Literature]

Patent Document 1: US6469074B1 Patent Document 2: Japanese Patent Laid-Open No. 60-250026 Patent Document 3: US6342577B1 Patent Document 4: Japanese Patent Laid-Open No. 2009-13205 Patent Document 5: US2003/62911A1 Patent Document 6: WO03/075338A1 Patent Document 7: WO2004/078870A1 Patent Document 8: US2009/203813A1

[The problem to be solved by the invention]

Therefore, the problem to be solved by the present invention is to provide a resin composition that can obtain a cured product with low elasticity and can be cured quickly. [Technical means to solve the problem]

The inventors of the present invention have made diligent studies to solve the above-mentioned problems. As a result, they have found that a resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent, and a cardanol compound or its glycidyl ether can be used The above-mentioned problems are solved, thereby completing the present invention.

That is, the present invention is a resin composition containing (A) a cyanate ester resin, (B) a cardanol compound or its glycidyl ether, (C) an amine-based latent curing agent, and (D) an epoxy resin (but , Except for the polyglycidyl ether of cardanol compounds). [Effects of Invention]

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

Hereinafter, the resin composition of the present invention will be described. The resin composition of the present invention contains (A) a cyanate ester resin, (B) a cardanol compound or its glycidyl ether, (C) an amine-based latent hardener, and (D) an epoxy resin (but, one of the cardanol compounds Except for polyglycidyl ether).

First, the component (A) contained in the resin composition of the present invention will be described. In the present invention, as the cyanate 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 are not particularly limited.

As the cyanate resin, it is preferable to use 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 these prepolymers . In the present invention, the term “prepolymer” refers to a compound obtained by self-polymerization, or one obtained by slightly polymerizing an arbitrary trace component.

NC-OA 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, and A ¹ and A ² each independently represent unsubstituted or 1-4 alkyl groups Substituted phenylene.

^{As the divalent hydrocarbon group represented by Y 1} in the above formula (1), for example, alkylene, cycloalkylene, cycloalkylene, arylene, and arylalkylene are mentioned. ^{In the present invention, Y 1 is} preferably an alkylene group in terms of easy availability and excellent physical properties.

The above-mentioned alkylene group may be linear or branched. Examples of the linear alkylene group include those having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tetradecyl. A divalent group obtained by removing one hydrogen atom from the terminal carbon atom of a linear alkyl group such as a hexadecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group. On the other hand, examples of the branched alkylene group include those having 1 to 20 carbon atoms. Specific examples thereof include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, tertiary pentyl, isooctyl, 2-ethylhexyl, tertiary octyl, A divalent group obtained by removing one hydrogen atom from branched alkylene such as isononyl and isodecyl. In the present invention, in terms of easy availability and excellent physical properties, the carbon number of the alkylene group is preferably 1-10, more preferably 1-8, and still more preferably 1-4.

The above-mentioned cycloalkylene group may be monocyclic or polycyclic. Examples of the monocyclic cycloalkylene group include those having 3 to 20 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl , Cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecanyl, cyclooctadecyl, cyclononadecyl and cycloeicosyl, etc. Cyclic cycloalkyl is a divalent group obtained by removing one hydrogen atom. Examples of the polycyclic alkyl group include those having 8 to 14 carbon atoms. Specific examples include the removal of one hydrogen atom from polycyclic alkyl groups such as adamantyl, decahydronaphthyl, octahydrocyclopentadiene, bicyclo[1.1.1]pentyl, and tetradecahydroanthryl. The resulting divalent base.

In the present invention, the so-called cycloalkylene is a divalent group formed by combining one or more alkylene groups and one or more cycloalkylene groups. The cycloalkylene in the above-mentioned cycloalkylene may be monocyclic or polycyclic. As the monocyclic cycloalkylene alkylene group, one or more hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned monocyclic cycloalkyl group and the divalent group obtained by removing one hydrogen atom A group or a divalent group obtained by removing one hydrogen atom from a group formed by substituting two or more hydrogen atoms of the monocyclic cycloalkyl group with the above-mentioned alkyl group. As the polycyclic cycloalkylene alkylene group, one or more hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned polycyclic cycloalkyl group and the divalent group obtained by removing one hydrogen atom. A group or a divalent group obtained by removing one hydrogen atom from a group formed by substituting two or more hydrogen atoms of the polycyclic cycloalkyl group with the above-mentioned alkyl group.

The above-mentioned aryl extension group may be a monocyclic type or a condensed ring type. Examples of the monocyclic arylene group include those having 6 to 20 carbon atoms. As a specific example, a divalent group obtained by removing one hydrogen atom from a monocyclic aryl group such as a phenyl group and a biphenyl group can be cited. Examples of the condensed cyclic arylene alkylene group include those having 10 to 18 carbon atoms. Specific examples thereof include divalent groups obtained by removing one hydrogen atom from condensed cyclic aryl groups such as naphthyl, anthracenyl, phenanthryl, and stilbene.

In the present invention, the so-called arylene alkylene group is a divalent group formed by combining one or more alkylene groups and one or more aryl alkylene groups. The arylene group in the above arylene alkylene group may be a monocyclic type or a condensed ring type. Examples of the monocyclic arylalkylene group include a divalent group obtained by removing one hydrogen atom from a group formed by substituting one or more hydrogen atoms of the above-mentioned alkyl group with the above-mentioned monocyclic aryl group, Or a divalent group obtained by removing one hydrogen atom from a group in which two or more hydrogen atoms of the monocyclic aryl group are substituted with the above-mentioned alkyl group. Examples of the condensed cyclic arylalkylene group include a divalent group obtained by substituting one or more hydrogen atoms of the above-mentioned alkyl group with the above-mentioned condensed cyclic aryl group by removing one hydrogen atom, Or a divalent group obtained by removing one hydrogen atom from a group in which two or more hydrogen atoms of the condensed cyclic aryl group are substituted with the above-mentioned alkyl group.

In terms of easy availability and excellent physical properties, the ^{divalent hydrocarbon group represented by Y 1} in the above formula (1) preferably includes one selected from the group consisting of the following formulas (Y-1) to (Y-10) The base of the group. The so-called "including the base selected from the group consisting of free formulas (Y-1) ~ (Y-10)" means that Y ¹ only includes the group selected from the group consisting of (Y-1) ~ (Y-10) One group, or a group consisting of two or more groups selected from the group consisting of (Y-1) to (Y-10).

[化1]

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

The alkyl group of the phenylene group represented ^{by A 1} and A ² in the substituted formula (1) may be linear or branched. Examples of the linear alkyl group include those having 1 to 20 carbon atoms. Specific examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl Group, hexadecyl, octadecyl and eicosyl, etc. Examples of the branched alkyl group include those having 1 to 20 carbon atoms. Specific examples thereof include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, tertiary pentyl, isooctyl, 2-ethylhexyl, tertiary octyl, Isononyl and isodecyl, etc.

[化2]

In the formula, m represents an integer of 1 or more, Y ² represents a sulfur atom, an unsubstituted or fluorine-substituted divalent hydrocarbon group, a plurality of Y ² may be the same or different, and R ¹ and R ² each 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, as well as isopropyl, and Branched alkyl groups such as dibutyl, tertiary butyl and isobutyl methyl.

^{As the divalent hydrocarbon group represented by Y 2} in the above formula (2), the same divalent hydrocarbon group represented by ^{Y 1} in the formula (2) can be cited.

^{As Y 2} in the above formula (2), it is preferable to include a group selected from the group consisting of the above formulas (Y-1) to (Y-10) in terms of easy availability and excellent physical properties.

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

Next, the cardanol compound and its glycidyl ether of the component (B) contained in the resin composition of the present invention will be described. In the present invention, the cardanol compound is a kind of phenol obtained from cashew nuts and the like 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 one, two, or three. As a specific example of the chain hydrocarbon group which has 1 unsaturated bond, 8-pentadecenyl group is mentioned. Specific examples of the chain hydrocarbon group having two unsaturated bonds include 7,10-pentadienyl and 8,11-pentadienyl. As a specific example of the chain hydrocarbon group which has 2 unsaturated bonds, 8,11,14-pentadecatrienyl group is mentioned. In the present invention, the chain hydrocarbon group in the cardanol compound preferably has 2 unsaturated bonds. The specific example is preferably represented by the following formula (a-1). As mentioned above, the cardanol compound is extracted from natural products such as cashew nuts, so it is not easy to obtain those with higher purity. Therefore, those containing 10% by mass or less of impurities are also included in the cardanol compound used in the present invention. The glycidyl ether of the cardanol compound may be monoglycidyl ether or polyglycidyl ether. In the present invention, it is preferable to use a cardanol compound or its monoglycidyl ether, and it is more preferable to use a cardanol compound's monoglycidyl ether in terms of further reducing the elasticity of the obtained cured product.

[化3]

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

[化4]

[化5]

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

[化6]

As the cardanol compound and its glycidyl ether, commercially available products can be used. As commercially available products, for example, Cardolite NX-2021 (manufactured by Cardolite; cardanol), Cardolite NX-2022 (manufactured by Cardolite; high-purity cardanol), Cardolite NX-2023D (manufactured by Cardolite; dark color, color Stable cardanol), Cardolite NX-2023 (manufactured by Cardolite; bright hue and color stable cardanol), Cardolite NX-2024 (manufactured by Cardolite; fixed cycle, standard purity cardanol), Cardolite NX-2025 (Cardolite) Manufactured by the company; high-purity cardanol), Cardolite Ultra LITE NX-2023 (bright hue, stable color cardanol), Cardolite NC-513 (manufactured by Cardolite; cardanol monoglycidyl ether), Ultra LITE 513 (Cardolite) Manufacturing; bright hue, low viscosity cardanol monoglycidyl ether), NC-514 (manufactured by Cardolite; polycardanol polyglycidyl ether), NC-514S (manufactured by Cardolite; low-viscosity polycardanol polyglycidyl ether) ), NC-547 (manufactured by Cardolite; 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 it is preferably the total amount of the cyanate resin of component (A) and the epoxy compound of component (D) below 5-50% by mass, more preferably 10-30% by mass. If the content of the cardanol compound and its glycidyl ether is 5% by mass or more, the elasticity of the obtained cured product will decrease, and if it is 50% by mass or less, the adhesiveness will further increase, which is preferable.

In the present invention, it is preferable that the content of the cardanol compound and its glycidyl ether is contained relative to 100 parts by mass of the cyanate ester resin of the component (A) in terms of further lowering the elasticity of the obtained cured product. ~1000 parts by mass, more preferably 20-500 parts by mass.

Next, the component (C) contained in the resin composition of the present invention will be described. Examples of amine-based latent hardeners include ethylenedihydrazine, malondihydrazine, succinonadiazine, glutaric hydrazine, hexadihydrazine, suberylhydrazine, azeladiahydrazine, and sebacic Dibasic acid dihydrazine such as hydrazine and phthalic acid hydrazine; guanamines such as benzoguanamine and betaguanidine; dicyandiamide; melamine; and dehydration condensate of amine compound and carboxylic acid, amine compound and ring The adduct of oxygen compound, the adduct of amine compound and isocyanate compound, the Michael adduct of amine compound, the Mannich reactant of amine compound, the condensate of amine compound and urea, the condensate of amine compound and ketone And other modified amines. These amine-based latent curing agents may be used singly, or two or more of them may be used in combination. In the present invention, in terms of improving the reactivity of the resin composition, it is preferable to use one having active hydrogen as the component (C). Examples of the amine-based latent curing agent having active hydrogen include dibasic acid dihydrazine, guanamine, and the following modified amines.

In the present invention, it is also preferable to use a modified amine in terms of easy adjustment of physical properties. 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 formed by reacting an amine compound having at least one active hydrogen with an epoxy compound. (C-2) A modified amine obtained by reacting an amine compound having at least one active hydrogen with an isocyanate compound. (C-3) A modified amine obtained by reacting an amine compound having at least one active hydrogen, an epoxy compound, and an isocyanate compound.

As the amine compound having one or more active hydrogens, for example, polyether polyamines such as polyether triamine, polyether diamine, polyoxypropylene diamine, polytetrahydrofuran diamine, and polyoxypropylene triamine; Amine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine, etc. Diamines; Diethylenetriamine, Triethylenetriamine, Tetraethylenepentamine and other polyalkyl polyamines; 1,4-Diaminocyclohexane, 1,3-diamino Cyclohexane, 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'-diaminobicyclic Hexylpropane, bis(4-aminocyclohexyl) sulfide, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, iso Alicyclic polyamines such as phorone diamine and norbornene diamine; meta-xylylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, diethyltoluenediamine, 1-methyl -3,5-diethyl-2,4-diaminobenzene, 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'- Aromatic polyamines such as diaminodiphenylmethane; guanamines such as benzoguanamine and betaguanidine; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, Imidazoles such as 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole, etc.; ethylenedihydrazine, propane Dihydrazine, succinyl hydrazine, glutaric hydrazine, hexadihydrazine, suberyl hydrazine, azeladia hydrazine, sebacic hydrazine, phthalic hydrazine and other dihydrazides; N,N -Dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine , N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylamine Ethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-amine Ethyl) piper, N-(2-aminoethyl)-N'-methyl piper, N,N-dimethylaminopropylamine, N,N-diethylaminopropyl Amine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzyl Aminopropylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-( 3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piper, N-(3-aminopropyl)-N'- Methyl piperidine , 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzyl Amine, N,N-dimethylisophoronediamine, N,N-dimethyldiaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl -N,N-Dimethylethylenediamine, N,N,N'-Trimethylethylenediamine, N'-Ethyl-N,N-Dimethylpropylenediamine, N'-Ethyl-N ,N-dibenzylaminopropylamine; N,N-(diaminopropyl)-N-methylamine, N,N-diaminopropylethylamine, N,N-diamino Propylpropylamine, N,N-diaminopropylbutylamine, N,N-diaminopropylpentylamine, N,N-diaminopropylhexylamine, N,N-diamine Propyl-2-ethylhexylamine, N,N-diaminopropylcyclohexylamine, N,N-diaminopropylbenzylamine, N,N-diaminopropylallylamine , 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: polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, catechol, and phloroglucinol; dihydroxynaphthalene, biphenol, and methylene Bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (o-cresol), tetrabromo Bisphenol 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, sulfonyl bisphenol, oxybisphenol, phenol novolac, o-cresol novolac, ethyl Polyglycidyl ether compounds of polynuclear polyphenol compounds such as phenol novolac, butyl phenol novolac, octylphenol novolac, resorcinol novolac, terpene phenol, etc.; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol , Polyglycol, thiodiethanol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adducts and other polyglycidyl ethers of polyols; 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, 1,3,5-trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids, and homopolymers or copolymers of glycidyl methacrylate; N,N-diglycidylaniline, bis(4-(N- Methyl-N-glycidylamino) phenyl) methane, diglycidyl o-toluidine and other epoxy compounds with glycidyl amino groups; vinyl cyclohexene diepoxide, dicyclopentadiene Diepoxide, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl, 6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexylmethyl Epoxides of cyclic olefin compounds such as esters, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, etc.; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer Heterocyclic compounds such as epoxidized conjugated diene polymers and triglycidyl isocyanurate.

As said polyisocyanate compound, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetra Methylxylylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, fennel Amine diisocyanate, tetramethylxylylene diisocyanate and other aromatic diisocyanates; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, Alicyclic diisocyanates such as norbornene diisocyanate; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexa Aliphatic diisocyanates such as methylene diisocyanate and lysine diisocyanate; isocyanurate trimers, biuret trimers, trimethylolpropane adducts, etc. of the diisocyanates exemplified above; Triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc. Furthermore, these isocyanate compounds can be used in the form of carbodiimide modification, isocyanurate modification, biuret modification, etc., and can also be used in the form of blocked isocyanate after blocking with various blocking agents use.

As the modified amine of (C-1), it is preferable that the amine compound and epoxy compound having at least one active hydrogen have 1 equivalent relative to the NH group of the amine compound, and the epoxy group of the epoxy compound becomes 0.1 to 1.1 equivalent In particular, it is a reaction that becomes 0.2 to 1.0 equivalent. By using the modified amine, a resin composition with good storage stability and curability can be obtained, which is preferable.

As the modified amine of (C-2), it is preferable that the amine compound and isocyanate compound having at least one active hydrogen have 1 equivalent relative to the NH group of the amine compound, and the isocyanate group of the isocyanate compound becomes 0.1 to 1.1 equivalent. The amount, in particular, is a reaction that becomes 0.2 to 1.0 equivalent. By using the modified amine, a resin composition with good storage stability and curability can be obtained, which is preferable.

The modified amine as (C-3) is preferably an amine compound having one or more active hydrogens, an epoxy compound as (C-2), and an isocyanate compound as (C-3) relative to the amine compound 1 equivalent of the NH group, the epoxy group of the epoxy compound becomes 0.1 to 1.0 equivalent, especially 0.2 to 1.0 equivalent, and the isocyanate group of the polyisocyanate compound becomes 0.01 to 0.9 equivalent, especially It is made by reacting the amount of 0.05 to 0.8 equivalent. By using the modified amine, a resin composition with good storage stability and curability can be obtained, which is preferable.

The above-mentioned method for producing modified amines as (C-1), (C-2) and (C-3) is not particularly limited. If necessary, it can be carried out under heating at room temperature to 140°C by using a solvent. It is produced by reacting for 10 hours. In the (C-3) modified amine, it is generally preferable to react with the polyisocyanate compound after the amine compound and the epoxy compound are reacted. In the case of using a solvent, the solvent can be removed under normal pressure or reduced pressure under heating after the completion of the reaction. In addition, among these, solid ones can also be pulverized using a pulverizer such as a jet mill.

Examples of the solvent used in the production of the modified amine include: methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, and propylene glycol monomethyl ether acetate , Cyclohexane and other ketones; tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether and other ethers; ethyl acetate, n-butyl acetate and other esters Classes; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene.

In the resin composition of the present invention, as the amine-based latent curing agent as the component (C), at least one modified amine selected from the group consisting of (C-1) to (C-3) is used In this case, it is also preferable to use at least one modified amine selected from the group consisting of (C-1) to (C-3) and (E) phenol resin in combination from the viewpoint of adjusting the reactivity .

Examples of the phenol resin include: phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition molding resin, phenol aralkyl resin (ZYLOCK resin), Naphthol aralkyl resin, trisphenol methane resin, tetraphenol ethane resin, naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolak resin, biphenyl modification Phenolic resin (polyphenol compound connected to phenol core with bismethylene group), biphenyl modified naphthol resin (polynaphthol compound connected to phenol core with bismethylene group), amino three-modified phenol resin ( A compound with a phenol skeleton, three rings and a primary amine group in the molecular structure), and an alkoxy-containing aromatic ring-modified novolac resin (a polyphenol compound that links the phenol nucleus and the alkoxy-containing aromatic ring with formaldehyde) And other polyphenol compounds.

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 one having a number average molecular weight of 750 to 1200 as the phenol resin.

Regarding the usage amount of the (E) component relative to the (C-1) component, (C-2) component or (C-3) component phenol resin, relative to the (C-1) component and (C-2) component The total amount of the modified amine of the component (C-3) is 100 parts by mass, preferably 10 to 150 parts by mass, and more preferably 20 to 60 parts by mass. If the content of the phenol resin is 10 parts by mass or more, the curability of the resin composition becomes better, so it is preferred. If it is 150 parts by mass or less, the physical properties of the cured product obtained become better, so it is preferred. .

As the above-mentioned amine-based latent curing agent, commercially available products can be used. Commercial products of the amine-based latent hardener include: Adeka Hardener EH-3636S (made by ADEKA Co., Ltd.; dicyandiamide type latent hardener), Adeka Hardener EH-4351S (made by ADEKA Co., Ltd.; double Cyanamide type latent hardener), Adeka Hardener EH-5011S (made by ADEKA Co., Ltd.; imidazole type latent hardener), Adeka Hardener EH-5046S (made by ADEKA Co., Ltd.; imidazole type latent hardener), Adeka Hardener EH-4357S (made by ADEKA Co., Ltd.; polyamine-type latent hardener), Adeka Hardener EH-5057P (made by ADEKA Co., Ltd.; polyamine-type latent hardener), Adeka Hardener EH-5057PK (ADEKA Co., Ltd.) Company-made; polyamine-type latent hardener), Amicure PN-23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-based latent hardener), Amicure PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) ; Amine adduct series latent hardener), Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazine series latent hardener), FUJICURE FXR-1020 (manufactured by T&K TOKA Co., Ltd.; latent hardener) Wait.

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

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

Examples of the aforementioned epoxy resins include: polyglycidyl ether compounds of mononuclear polyphenol compounds, polyglycidyl ether compounds of polynuclear polyphenol compounds, polyglycidyl ether compounds of polyol compounds, and glycidol of aliphatic polybasic acids Ester compound, glycidyl ester compound of aromatic polybasic acid, glycidyl ester compound of alicyclic polybasic acid, homopolymer or copolymer of glycidyl methacrylate, epoxy compound with glycidyl amino group, ring Epoxides of olefinic compounds, epoxidized conjugated diene polymers, heterocyclic compounds and sulphur-type epoxy resins. These epoxy resins can be internally cross-linked by prepolymers of terminal isocyanates, or can be polymerized by multivalent active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.). 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.

As said mononuclear polyphenol compound, hydroquinone, resorcinol, catechol, phloroglucinol, etc. are mentioned.

Examples of the polynuclear polyphenol compound include dihydroxy naphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, and isopropylidene bisphenol. (Bisphenol A), isopropylidene bis (o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxyisopropyl) Phenylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol , Oxybisphenol, phenol novolac, o-cresol novolac, ethyl phenol novolac, butyl phenol novolac, octylphenol novolak, resorcinol novolac and terpene phenol, etc.

Examples of the polyol compound include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, thioethylene glycol, dicyclopentadiene dimethanol, 2,2-bis(4 -Hydroxycyclohexyl) propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts, etc.

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

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

As said alicyclic polybasic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, etc. are mentioned, for example.

Examples of the epoxy compound having a glycidylamino group include N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, Diglycidyl o-toluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis( 2,3-epoxypropyl)-4-(2,3-epoxypropyloxy)aniline and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4 -Diaminodiphenylmethane, etc.

Examples of the cyclic olefin compound include: vinyl cyclohexene diepoxide, cyclopentadiene diepoxide, 3,4-epoxycyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl Ester, 6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl methyl ester and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, etc. .

As said epoxidized conjugated diene polymer, an epoxidized polybutadiene, an epoxidized styrene-butadiene copolymer, etc. are mentioned, for example.

As said heterocyclic epoxy compound, triglycidyl isocyanurate etc. are mentioned, for example.

As said sulphur-type epoxy resin, the epoxy compound represented by following formula (3) is mentioned, for example. In the resin composition of the present invention, in terms of further reducing the modulus of elasticity of the cured product obtained, as the epoxy resin, it is preferable to use a sulphur-type epoxy resin, and it is more preferable to use the following formula (3) The epoxy compound represented. As a commercially available product of the tea-type epoxy resin represented by the formula (3), for example, OGSOL EG-280 (manufactured by Osaka Gas Chemicals) can be cited.

[化7]

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, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently Ground represents 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 above formula (3) include chlorine, bromine, and iodine. Examples of the alkyl group having 1 to 4 carbons represented ^{by R 7} , R ⁸ , R ⁹ and R ¹⁰ in the above formula (3) ^{include those represented by R 1} and R ^{2 in the formula (2)} The alkyl groups of 1 to 4 are the same.

The alkylene group having 1 to 4 carbon atoms represented _{by X 1} and X ₂ in the above formula (3) may be linear or branched. Examples of the linear alkylene group include a divalent group obtained by removing one hydrogen atom from a carbon atom at the terminal of a 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, second butyl, and tertiary butyl.

The content of the epoxy resin of the component (D) in the resin composition of the present invention is not particularly limited. It is preferably 10 to 1000 parts by mass relative to 100 parts by mass of the cyanate ester resin, since excellent curing can be obtained The physical properties are more preferably 200 to 800 parts by mass.

In the present invention, a known hardening accelerator can be used in combination with the above-mentioned latent hardening agent as necessary. Specific examples of these hardening accelerators include: phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4- Imidazoles such as methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole; imidazole salt as the salt of the above-mentioned imidazoles with trimellitic acid, isocyanuric acid, boron, etc. Classes; amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts such as trimethylammonium chloride; 3-(p-chlorophenyl )-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, isophor Urea such as ketone diisocyanate-dimethylurea and toluene diisocyanate-dimethylurea; and complexes of boron trifluoride with amines or ether compounds, etc. These hardening accelerators may be used alone, or two or more of them may be used in combination. The content of the epoxy resin hardening accelerator in the one-liquid cyanate ester-epoxy composite resin composition of the present invention is not particularly limited, and may be appropriate according to the use of the one-liquid cyanate ester-epoxy composite resin composition set up.

The resin composition of the present invention may contain various additives as necessary. Examples of the above additives include: reactive diluents such as monoalkyl glycidyl ether; non-reactive diluents such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar (plasticizing Agent); fused silica, crystalline silica and other silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllium oxide, zirconium oxide, zirconium Quartzite, forsterite, talc, spinel, mullite, titanium oxide and other powders, or spheroidized particles, and filled with glass fiber, pulp fiber, synthetic fiber, ceramic fiber, etc. Agent; glass cloth, aromatic polyamide cloth, carbon fiber and other reinforcing materials; pigments; γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethyl Oxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane , Γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyl triethoxysilane, N-β-(N- Vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercapto Silane coupling agents such as propyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, insect wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic Lubricants such as ethers, aromatic esters, and aromatic ethers; tackifiers; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; defoamers; rust inhibitors; colloidal silica, colloidal alumina, etc. The additives. In the present invention, adhesive resins such as xylene resin and petroleum resin may be further used in combination.

The resin composition of the present invention can be used for various coatings, various adhesives, and various molding materials. Since the obtained hardened product has low elasticity, it can be suitably used as a material or adhesive requiring impact resistance. Example

Hereinafter, the present invention will be explained in detail based on examples. However, the present invention is not limited in any way by these embodiments.

Production Example 1 (Synthesis of amine-based latent hardener) 230 g of JEFFAMINE D230 (polyether polyamine, manufactured by Huntsman) was put in the flask and heated to 60°C. Next, 190 g of Adeka Resin EP-4901E (bisphenol F type epoxy resin with epoxy equivalent of 170, manufactured by ADEKA Co., Ltd.) was added to the flask in small amounts, with the temperature in the system maintained at 100-110°C. After adding Adeka Resin EP-4901E, the reaction system was heated to 140°C, and the reaction was performed for 1.5 hours to obtain a modified amine. Add 50 g of MP-800K (phenol resin with a softening point of 100°C, manufactured by Asahi Organic Materials Co., Ltd.) to 100 g of the obtained modified amine, and remove it at 180 to 190°C and 30 to 40 Torr for 1 hour. Solvent to obtain a mixture of modified amine and phenol resin CE.

[Example 1-3 and Comparative Example 1-3] The raw materials shown in the following [Table 1] were mixed at normal temperature to produce a resin composition. For mixing, use a planetary mixer. The following test was performed on the cured product of the obtained resin composition. The evaluation results are shown in the following [Table 1]. The symbols in Table 1 indicate the following components. In addition, the content of the raw materials in Table 1 is parts by mass. The obtained resin compositions of Examples 1 to 3 were heated at 100°C, and as a result, they hardened quickly.

A: Bisphenol type cyanate resin (manufactured by Lonza, trade name: Lecy) B-1: Cardanol monoglycidyl ether (manufactured by Cardolite, trade name: NC-513) B-2: C12-13 alkyl monoglycidyl ether (manufactured by ADEKA Co., Ltd., trade name: ED-502) B-3: p-tert-butylphenyl monoglycidyl ether (manufactured by ADEKA Co., Ltd., trade name: ED-509E) CE: The mixture of modified amine and phenol resin obtained in Manufacturing Example 1 D-1: Chrysanthemum type epoxy resin (manufactured by Osaka Gas Chemicals, trade name: OGSOL EG-280) D-2: Dicyclopentadiene epoxy resin (manufactured by ADEKA Co., Ltd., trade name: EP-4088L) F: 3-glycidoxypropyltriethoxysilane (silane coupling agent; trade name KBM-403, manufactured by Shin-Etsu Silicones)

＜RSA test＞ A dynamic viscoelasticity measuring device RSA G2 (TA Instruments Japan Co., Ltd.) was used to measure the loss elastic modulus (E") and the storage modulus (E'). The measurement range is set to -50°C to 200°C, and the measurement conditions are set to frequency 1 Hz, heating rate 10°C/min, sample width 4 mm, and distance between chucks 20 mm. Table 1 shows the storage modulus (E') at 25°C. In addition, according to the measured loss elastic modulus (E'') and storage modulus (E'), according to the peak temperature of tanδ (tanδ=loss elastic modulus (E'')/storage modulus (E')) Determine the glass transition temperature (Tg). The results are shown in Table 1.

[Table 1] Example Comparative example 1 2 3 1 2 3 Element A 40 40 20 40 40 40 B-1 20 30 10 B-2 10 20 B-3 20 CE 100 100 100 100 100 100 D-1 80 60 90 100 D-2 80 80 F 2 2 2 2 2 2 Evaluation results Glass transition temperature Tg(℃) 49 47 43 112 98 61 Storage modulus (GPa) 0.9 0.7 0.4 2.1 2.0 1.7

Table 1 shows that the resin compositions of Examples 1 to 3 are those having lower glass transition temperature and storage modulus (E') than the resin compositions of Comparative Examples 1 to 3. The results indicate that the resin composition of the present invention can be cured quickly, and a cured product with lower elasticity can be obtained.

Claims (15)

A resin composition containing (A) a cyanate ester resin, (B) a cardanol compound or its glycidyl ether, (C) an amine-based latent hardener, and (D) an epoxy resin (but, one of the cardanol compounds Except for polyglycidyl ether). The resin composition of claim 1, wherein the cyanate ester resin is selected from the group consisting of compounds represented by the following formula (1), compounds represented by the following formula (2), and prepolymers of these compounds At least one of the group consisting of NC-OA 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 an unsubstituted or substituted phenylene group with 1 to 4 alkyl groups;

In the formula, m represents an integer of 1 or more, Y ² represents a sulfur atom, an unsubstituted or fluorine-substituted divalent hydrocarbon group, a plurality of Y ² may be the same or different, and R ¹ and R ² each independently represent a hydrogen atom or An alkyl group having 1 to 4 carbon atoms. The requested item composed of the resin composition of 2, wherein the sum of the above-described formula ⁽¹⁾ Y 1 and the formula (2) comprising the Y ² is selected from the formula (Y-1) ~ (Y -10) group In the base,

In the formula, n represents an integer of 4-12, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an unsubstituted or fluorine-substituted methyl group, and * represents a bonding bond. The resin composition of claim 1, wherein the above-mentioned component (B) is a cardanol compound or its monoglycidyl ether. The resin composition of claim 1, wherein the above-mentioned component (C) is an amine-based latent curing agent having active hydrogen. The resin composition according to claim 5, wherein the above-mentioned amine-based latent hardener having active hydrogen is a modified amine. The resin composition of claim 1, wherein the above-mentioned component (C) is at least one selected from the group consisting of the following (C-1) to (C-3), (C-1): A modified amine formed by reacting an amine compound with more than one active hydrogen and an epoxy compound; (C-2): A modified amine formed by reacting an amine compound with more than one active hydrogen and an isocyanate compound; (C-3): A modified amine formed by reacting an amine compound having at least one active hydrogen, an epoxy compound, and an isocyanate compound. The resin composition of claim 7, wherein the amine-based latent curing agent as the component (C) is (C-1), The above-mentioned amine compound with more than one active hydrogen is a polyether polyamine, The above-mentioned epoxy compound is a polyglycidyl ether compound of a polynuclear polyphenol compound. The resin composition according to claim 7, which further contains a phenol resin. The resin composition of claim 9 contains 10 to 150 parts by mass of a phenol resin with respect to 100 parts by mass of the total of (C-1), (C-2), and (C-3). The resin composition according to claim 1, wherein the content of the above-mentioned (B) component is 10 to 1000 parts by mass relative to 100 parts by mass of the above-mentioned (A) component. The resin composition of claim 1, wherein the content of the amine-based latent hardener as the component (C) is 100 parts by mass of the total amount of the (A) cyanate resin and the (D) epoxy resin 2 to 200 parts by mass. The resin composition of claim 1, wherein the content of the above-mentioned (D) component is 10 to 10,000 parts by mass relative to 100 parts by mass of the (A) component. An adhesive comprising the resin composition of claim 1. A use of the resin composition according to claim 1, which is used as an adhesive.