WO2022210189A1 - Curing catalyst, resin composition, sealing material, adhesive, and cured product - Google Patents

Curing catalyst, resin composition, sealing material, adhesive, and cured product Download PDF

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WO2022210189A1
WO2022210189A1 PCT/JP2022/013646 JP2022013646W WO2022210189A1 WO 2022210189 A1 WO2022210189 A1 WO 2022210189A1 JP 2022013646 W JP2022013646 W JP 2022013646W WO 2022210189 A1 WO2022210189 A1 WO 2022210189A1
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manufactured
resin composition
compound
mercaptomethylthio
resin
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PCT/JP2022/013646
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French (fr)
Japanese (ja)
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友也 中井
理恵子 永田
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ナミックス株式会社
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Priority to CN202280009235.XA priority Critical patent/CN116745281A/en
Priority to KR1020237020573A priority patent/KR20230161929A/en
Priority to JP2023511074A priority patent/JPWO2022210189A1/ja
Publication of WO2022210189A1 publication Critical patent/WO2022210189A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F34/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
  • a one-component adhesive contains a main agent and a curing catalyst, or a main agent, a curing agent, and a curing catalyst. Cure catalysts are believed to have the greatest impact on the pot life and cure conditions of adhesives.
  • the purpose of the present invention is to provide novel curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
  • One embodiment of the present invention is a curing catalyst comprising a compound of structural formula (I) below.
  • R 1 is a group selected from hydrogen, phenyl and C1-C17 alkyl
  • R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl
  • R4 is a group selected from hydrogen, OH and OAc (Ac: abbreviation for acetyl group)
  • n and m are integers, the sum of which is 1 or more and 12 or less or 1 or more and 3 or less.
  • thermosetting resin may be an epoxy resin.
  • the thermosetting resin may be a compound having a polymerizable double bond.
  • a curing agent for the thermosetting resin may be further included.
  • the curing agent may be one selected from the group consisting of oxygen-containing compounds, nitrogen-containing compounds, and thiol compounds.
  • a further embodiment of the present invention is a sealing material, adhesive, or cured product containing any of the above resin compositions.
  • a further embodiment of the present invention is a compound of structural formula (I) below.
  • R 1 is a group selected from phenyl and C1-C17 alkyl
  • R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl
  • R4 is a group selected from OH and OAc
  • n and m are integers, the sum of which is 1 or more and 12 or less.
  • R 1 is a group selected from phenyl and C1-C10 alkyl
  • R 2 , R 3 , R 5 are hydrogen, R4 is OH
  • n and m may be one.
  • the present invention has made it possible to provide novel curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
  • R 1 is a group selected from phenyl and C1-C17 alkyl
  • R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl
  • R4 is a group selected from OH and OAc
  • n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, more preferably 3 or less.
  • R 1 is preferably selected from phenyl and C1-C11 alkyl.
  • R 2 , R 3 and R 5 are preferably hydrogen.
  • R4 is preferably OH.
  • n and m are each 1.
  • the term "curing catalyst” means a catalyst having a function of promoting the initiation and/or progress of polymerization when the main agent is self-polymerized or when the main agent and the curing agent are polymerized. do.
  • the curing catalyst may be incorporated only at the terminal of the polymer.
  • R 1 is a group selected from hydrogen, phenyl and C1-C17, preferably C1-C11 alkyl
  • R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl
  • R4 is a group selected from hydrogen, OH and OAc
  • n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, more preferably 3 or less.
  • More preferably, the sum of n and m is 1 when R4 is hydrogen, and both n and m are 1 when R4 is OH.
  • this curing catalyst has a phthalimide skeleton, it is difficult for the curing catalyst to dissolve in the resin in an unintended temperature range in the resin composition, the pot life becomes longer, and it is useful as a curing catalyst for thermosetting resins. is.
  • the curing catalyst disclosed herein may contain one or more compounds having the structural formula (I). It may also contain one or more curing catalysts other than the compound having structural formula (I).
  • the resin is not particularly limited, but a thermosetting resin is preferred.
  • epoxy resins and compounds having a polymerizable double bond group for example, (meth)acrylic compounds and maleimide compounds
  • (meth)acrylic compounds and maleimide compounds can be exemplified.
  • acryl and methacryl are collectively referred to as (meth)acryl.
  • Epoxy resin The epoxy resin is not particularly limited, and may be a monofunctional epoxy resin or a multifunctional epoxy resin.
  • a monofunctional epoxy resin is an epoxy resin having one epoxy group, and has been conventionally used as a reactive diluent to adjust the viscosity of an epoxy resin composition.
  • Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the monofunctional epoxy resin preferably has an epoxy equivalent of 180 to 400 g/eq.
  • aromatic monofunctional epoxy resins include phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, m- Examples include, but are not limited to, phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, and the like.
  • p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred.
  • aliphatic monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, ⁇ -pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4 -(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecanoic acid glycidyl ester, etc. can be, but are not limited to:
  • a polyfunctional epoxy resin is an epoxy resin having two or more epoxy groups. Accordingly, the resin composition of the present disclosure may include difunctional epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins, and the like. Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.
  • aliphatic polyfunctional epoxy resins examples include (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether.
  • diepoxy resins such as ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether; Triepoxy resins such as methylolpropane triglycidyl ether, glycerin triglycidyl ether; vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxy Cycloaliphatic epoxy resins such as cyclohexyl)-m-dioxane; glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; h
  • cyclohexane-type diglycidyl ether means that two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as a base structure.
  • a compound having a structure is meant.
  • dicyclopentadiene-type diglycidyl ether refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a base structure. means.
  • cyclohexane-type diglycidyl ether cyclohexanedimethanol diglycidyl ether is particularly preferred.
  • Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins having a structure containing aromatic rings such as benzene rings. Many conventional epoxy resins, such as bisphenol A type epoxy resin, are of this type. Examples of aromatic polyfunctional epoxy resins include bisphenol A type epoxy resins; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resins; type epoxy resin; bisphenol S type epoxy resin; novolac type epoxy resin; tetrabromobisphenol A type epoxy resin; fluorene type epoxy resin; biphenyl aralkyl epoxy resin; ,3′,5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl; diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m- glycidylamine-type epoxy resins
  • aromatic polyfunctional epoxy resins bisphenol F-type epoxy resins, bisphenol A-type epoxy resins and glycidylamine-type epoxy resins are preferable, and among them, those having an epoxy equivalent of 90 to 200 g/eq are preferable.
  • the polymer compound having a polymerizable double bond group is not particularly limited.
  • compounds having an alkyl group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal Butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, etc.; compounds having cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isobornyl methacryl
  • trimethylolpropane triacrylate pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
  • Multifunctional (meth)acrylates of polyol derivatives such as; Pentaerythritol triarylate, pentaerythritol tetraarylate, trimethylolpropane triarylate and other polyfunctional arylates; Aronix M-7100, Aronix M-8030, Aronix M-8060 polyester (meth)acrylates such as Toagosei Co., Ltd.; Co., Ltd.), Aronix M-305, Aronix M-309, Aronix M-310, M-315, M-320, Aronix M-350, Aronix M-360, Aronix M-370, Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, (all manufactured by Toagosei Co., Ltd.), Neomer TA-401, TA-505, EA-301, DA-600 (both Sanyo Chemical Industries Co., Ltd.) ), NK Ester A-TMPT, NK Ester
  • compounds having a maleimide group include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl) ) methane, m-phenylenebismaleimide (N,N′-1,3-phenylenebismaleimide), 1,6-bismaleimidohexane, 1,2-bismaleimidoethane (N,N′-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyl
  • dimer acid-modified bismaleimide It is also possible to use dimer acid-modified bismaleimide.
  • dimer acid-modified bismaleimides include liquid bismaleimides BMI-689, BMI-1500 and BMI-1700, and solid bismaleimides BMI-3000 (all manufactured by Designer Molecules).
  • the resin composition of the present disclosure may contain one or more curing agents.
  • Curing agents that may be contained in the resin composition of the present disclosure are not particularly limited, but include, for example, nitrogen-containing compounds such as amines and their derivatives; , oxygen-containing compounds such as phenol-terminated epoxy resins; sulfur-containing compounds such as thiol compounds.
  • Nitrogen-containing compounds such as amines and derivatives thereof are not particularly limited, but aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine, isophorone diamine.
  • Epomic Q-640 Epomic Q-643 (Mitsui Chemicals, trade name), DETDA80 (Lonza, trade name), Thothamine HM-205 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), etc. is mentioned.
  • the acid anhydride-based curing agent is not particularly limited, but for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhimic acid anhydride, alkenyl-substituted Succinic anhydride, glutaric anhydride and the like can be mentioned.
  • Phenolic curing agents refer to monomers, oligomers, and polymers generally having phenolic hydroxyl groups, such as phenol novolac resins and their alkylated or allylated products, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeleton) resins, and naphthol aralkyls. Resins, triphenol methane resins, dicyclopentadiene type phenol resins, and the like. Among them, allylphenol novolac resin is preferable.
  • Thiol compounds include hydrolyzable polyfunctional thiol compounds and non-hydrolyzable polyfunctional thiol compounds.
  • hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate Nurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.) : EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manu
  • non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Shikoku Kasei Co., Ltd.), (1,3, 4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Kasei Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4 ,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercapto Propyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril,
  • non-hydrolyzable polyfunctional thiol compound it is also possible to use a trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule.
  • thiol compounds include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercapto propylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7- dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, tetrakis(mercaptomethylthiomethyl) Methane
  • the ratio of the curing catalyst in the resin composition is not particularly limited, it is preferably 0.01 to 50 wt%, more preferably 0.01 to 30 wt%, relative to the thermosetting resin in the resin composition. More preferably, it is 0.01 to 20 wt%.
  • the pot life is defined as the time until the thickening ratio of the resin composition doubles from the initial value, and the pot life in the epoxy-thiol curing system is preferably 8 hours or longer, more preferably 12 hours or longer. , more preferably 16 hours or longer. Also in other curing systems, a longer pot life is preferable from the viewpoint of stability.
  • the curable composition of the present disclosure may optionally contain, for example, the following in addition to the main agent, curing catalyst, and curing agent.
  • Stabilizer A stabilizer can be added to the resin composition of the present disclosure in order to improve its storage stability and prolong its pot life.
  • Various known stabilizers can be used as stabilizers for one-component adhesives based on epoxy resins. preferable.
  • liquid borate compounds examples include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri - n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris(2 -ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentoxatetradecyl)(1,4,7-trioxaundecyl) Borane, tribenzylborate, triphenylborate,
  • aluminum chelate for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used.
  • organic acid for example, barbituric acid can be used.
  • filler A filler can be added to the resin composition of the present disclosure.
  • fillers include silica fillers, glass fillers, alumina fillers, titanium oxide fillers, boron nitride fillers, aluminum nitride fillers, talc fillers, calcium carbonate fillers, resin fillers (e.g., polytetrafluoroethylene (PTFE) fillers, silicone rubber fillers, etc.), conductive fillers such as silver, copper and nickel.
  • the shape is not particularly limited, and may be hollow, spherical, or amorphous.
  • the filler may be surface-treated.
  • Coupling agent A coupling agent can be added to the resin composition of the present disclosure.
  • the coupling agent is preferably a silane coupling agent, and various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto can be used. These silane coupling agents may be used alone or in combination of two or more.
  • Silane coupling agents include, for example, vinyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-1003, Momentive Performance Materials Japan Co., Ltd.; A -171, Dow Corning Toray Co., Ltd.; Z-6300, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL XL10, Himi Shoji Co., Ltd.; KBE-1003, Momentive Performance Materials Japan; A-151, Dow Corning Toray; Z-6519, Asahi Kasei Wacker Silicone; GENIOSIL GF56, Himi Shoji; Sila Ace S220, etc.
  • vinyltriacetoxysilane commercially available from Asahi Kasei Wacker Silicone; GENIOSIL GF62
  • vinyltris(2-methoxyethoxy)silane commercially available from Momentive Performance Materials Japan
  • A-172 vinylmethyldimethoxysilane
  • commercially available products include Momentive Performance Materials Japan; A-2171, Asahi Kasei Wacker Silicone; GENIOSIL XL12, etc.
  • octenyltri Methoxysilane commercially available from Shin-Etsu Chemical Co., Ltd.; includes KBM-1083
  • allyltrimethoxysilane commercially available from Dow Corning Toray; includes Z-6825
  • p-styryltrimethoxysilane Commercially available products include KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-5103, etc.), and the like.
  • silane coupling agents having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-502, Toray Dow Corning Co., Ltd.; Z-6033, etc.).
  • 3-methacryloxypropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-503, Momentive Performance Materials Japan Co., Ltd.; A-174, Dow Corning Toray Co., Ltd.; Z-6030 , Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF31, Himi Shoji Co., Ltd.; Sila Ace S710, etc.), 3-methacryloxypropylmethyldiethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBE-502.
  • N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-602; Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-95, Himi Shoji Co.; Sila Ace S310, etc.
  • N-2-(aminoethyl)-3-aminopropyltrimethoxysilane commercially available from Shin-Etsu Chemical KBM-603, Momentive Performance Materials Japan; A-1120, Momentive Performance Materials Japan; A-1122, Dow Corning Toray; Z-6020, Dow Toray Z-6094 manufactured by Corning Corporation; Z-6094 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-91 manufactured by Himi Shoji Co.; KBM-903, manufactured by Momentive Performance Materials Japan; A-1110, manufactured by Dow Corning Toray Co.,
  • KBM-802 manufactured by Dow Corning Toray; Z-6852, etc.
  • 3-mercaptopropyltrimethoxysilane commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-803, Momentive Performance Materials Co., Ltd.; A-189 manufactured by Japan Co., Ltd.; Z-6062 manufactured by Dow Corning Toray; Sila Ace S810 manufactured by Himi Shoji Co., Ltd.; A-1891 manufactured by Dow Corning Toray Co., Ltd.; Z-6911 manufactured by Toray Dow Corning Co., Ltd.; Shin-Etsu Chemical Co., Ltd.; includes KBE-585), 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane (commercially available from Momentive Performance Materials Japan; A-1160).
  • examples of the silane coupling agent having a sulfide group include bis(triethoxysilylpropyl) tetrasulfide
  • examples of the silane coupling agent having a thioester group include 3-octanoylthio-1-propyltriethoxysilane (Commercially available products include A-LINK599 manufactured by Momentive Performance Materials Japan), and have an isocyanate group.
  • 3-isocyanatopropyltriethoxysilane (commercially available products include KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., A-1310 manufactured by Momentive Performance Materials Japan, etc.), 3 -Isocyanatopropyltrimethoxysilane (commercially available products include Y-5187 manufactured by Momentive Performance Materials Japan, GENIOSIL GF40 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like.
  • the resin composition of the present disclosure may contain other additives such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, digestive agents, etc., within a range that does not impair the object of the present invention.
  • Foaming agents, thixotropic agents, viscosity modifiers, flame retardants, coloring agents, solvents and the like can be added.
  • the type and amount of each additive are as per conventional methods.
  • the resin composition disclosed herein can be used, for example, as sealing materials and fillers for electronic components, dam materials, conductive or insulating adhesives, die attach materials, films, coating agents, shielding materials, and the like. can. In addition, it can be used for paints, composite materials such as pipe materials and tank materials, floor materials, civil engineering and construction materials such as membranes, adhesives, and the like, but the usage is not limited to these.
  • Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 100 g, 0.363 mmol) was gradually added to the resulting solution over about 10 minutes. After dissolving everything, the mixture was heated to 70° C. and stirred at the same temperature for 6 hours. After cooling to room temperature, water (about 200 mL) was added and stirred to precipitate crystals. The resulting solid was suction filtered, washed twice with water and twice with IPA, and then dried to obtain compound 1 (85.7 g) (61% recovery).
  • the measured physical properties of the product are as follows.
  • 2-Methyl-1H-imidazole (manufactured by Shikoku Kasei Co., Ltd., 21.8 g, 266 mmol) was dissolved in a mixed solvent of toluene (78.7 mL) and methanol (17.7 mL), heated to 80° C., and Denacol EX was prepared.
  • a toluene (38.1 mL) solution of -141 (manufactured by Nagase ChemteX Corporation, 22.0 g, 147 mmol) was added dropwise over 1 hour, followed by stirring at the same temperature for 1 hour.
  • Table 1 shows the evaluation results of the compounds.
  • PEMP manufactured by SC Organic Chemical Co., Ltd.
  • SC Organic Chemical Co., Ltd. which is a thiol resin
  • stirring and defoaming were performed under vacuum to obtain a resin composition.
  • Epoxy-thiol curing system Compound 1 as a curing catalyst was added to a mixture obtained by dispersing EXA835LV and TS720 (manufactured by Cabot Specialty Chemicals) using a three-roll mill and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. C3TSG (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a thiol resin, was added thereto and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
  • EXA835LV and TS720 manufactured by Cabot Specialty Chemicals
  • Examples 7, 11, 12 Epoxy homopolymerization curing system> Compound 1, compound 5, and compound 6 as curing catalysts were put into EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain a resin composition.
  • Epoxy-acid anhydride curing system Compound 1 as a curing catalyst was put into EXA835LV, which is an epoxy resin, and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. Then, YDF8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device.
  • EXA835LV an epoxy resin
  • Epoxy-phenol curing system > Compound 1 as a curing catalyst was added to EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. EXA835LV was put in there and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device. Furthermore, MEH8005 (manufactured by Meiwa Kasei Co., Ltd.), which is a phenolic resin, was added and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
  • MEH8005 manufactured by Meiwa Kasei Co., Ltd.
  • Acrylic-thiol curing system > M7100 (manufactured by Toagosei Co., Ltd.) as an acrylic resin, OMNIRAD184 (manufactured by IGM resins B.V.) as a photoradical generator, Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, and a stabilizing agent.
  • TS720 was dispersed with a three-roll mill as a component, and compound 1 as a curing catalyst was added to the resulting mixture and further dispersed with a three-roll mill. After PEMP was added thereto and mixed, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device to obtain a resin composition.
  • the time before gelation (referred to as gel time) was measured using a gelation tester (GT-D-15A: manufactured by Eucalyptus Giken Co., Ltd.).
  • a hot plate was set to 100° C., 120° C., or 150° C., and the resin composition was transferred onto the hot plate using a test rod.
  • the gel time was defined as the time from touching the resin composition with a test rod until it became stringy.
  • Comparative Example 2 has a high melting point, it has a low molecular weight, so it is easily dissolved in epoxy resins and the like, and lacks stability.
  • a comparison of the pot life of the resin composition revealed that the comparative examples were already cured in 4 hours, whereas the viscosity increase rate doubled in all the examples in 8 hours or longer.
  • the resin composition in the example gelled within 10 minutes and had sufficient reactivity and curability.
  • the curing catalyst of the present disclosure has a phthalimide skeleton, so it has high crystallinity and a higher melting point than the conventional adducts obtained by adding an epoxy resin and an imidazole derivative. , a stable resin composition is obtained in which the curing catalyst is less likely to dissolve in the resin at unintended temperatures.

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Abstract

The purpose of the present invention is to provide a novel curing catalyst, resin composition, sealing material, adhesive, and cured product. A curing catalyst having a compound according to structural formula (I) is used. (In the formula, R1 is a group selected from hydrogen, phenyl, and C1-C17 alkyls, R2, R3, and R5 each independently are groups selected from hydrogen and C1-C6 alkyls, R4 is a group selected from hydrogen, OH, and OAc, n and m are integers, and the sum of n and m is 1-12.)

Description

硬化触媒、樹脂組成物、封止材、接着剤、及び硬化物Curing catalyst, resin composition, encapsulant, adhesive, and cured product
　本発明は、硬化触媒、樹脂組成物、封止材、接着剤、及び硬化物に関する。 The present invention relates to curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
　一液性の接着剤には主剤と硬化触媒、または主剤と硬化剤と硬化触媒が含まれる。硬化触媒は接着剤の可使時間と硬化条件に最も影響を与えると考えられている。 A one-component adhesive contains a main agent and a curing catalyst, or a main agent, a curing agent, and a curing catalyst. Cure catalysts are believed to have the greatest impact on the pot life and cure conditions of adhesives.
　現在、一液性の接着剤に用いられる硬化触媒は多種市販されているが、熱硬化性樹脂や熱可塑性樹脂にアミン等の官能基が修飾しているタイプ（特開昭５９－０５３５２６号公報；特開平３－１７７４１８号公報）、アミン系硬化触媒を高分子体のシェルで覆ったシェルタイプ（特開２０００－０８０１４６号公報）、エポキシ樹脂とイミダゾールをアダクトしただけのタイプ（特開昭６０－００４５２４号公報）が主流である。 At present, various types of curing catalysts used for one-component adhesives are commercially available. ; JP-A-3-177418), a shell type in which an amine-based curing catalyst is covered with a polymer shell (JP-A-2000-080146), a type in which an epoxy resin and imidazole are just adducted (JP-A-60 -004524) is the mainstream.
　本発明は、新規な硬化触媒、樹脂組成物、封止材、接着剤、及び硬化物を提供することを目的とする。 The purpose of the present invention is to provide novel curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
　本発明の一実施態様は、下記構造式（Ｉ）の化合物を有する、硬化触媒である。
Figure JPOXMLDOC01-appb-C000003
 （式中、
　Ｒ１は、水素、フェニルおよびＣ１～Ｃ１７のアルキルから選択される基であり、
　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
　Ｒ４は、水素、ＯＨおよびＯＡｃから選択される基であり（Ａｃ：アセチル基の略号）、　ｎとｍは整数であり、その和が１以上１２以下または１以上３以下である。） One embodiment of the present invention is a curing catalyst comprising a compound of structural formula (I) below.
Figure JPOXMLDOC01-appb-C000003
 (In the formula,
R 1 is a group selected from hydrogen, phenyl and C1-C17 alkyl;
R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
R4 is a group selected from hydrogen, OH and OAc (Ac: abbreviation for acetyl group), n and m are integers, the sum of which is 1 or more and 12 or less or 1 or more and 3 or less. )
　本発明の他の実施態様は、上記いずれかの硬化触媒と熱硬化性樹脂とを含有する樹脂組成物である。前記熱硬化性樹脂がエポキシ樹脂であってもよい。前記熱硬化性樹脂が重合性二重結合を有する化合物であってもよい。前記熱硬化性樹脂の硬化剤をさらに含んでもよい。前記硬化剤が、酸素含有化合物、窒素含有化合物、およびチオール化合物からなる群から選択される１つであってもよい。 Another embodiment of the present invention is a resin composition containing any of the above curing catalysts and a thermosetting resin. The thermosetting resin may be an epoxy resin. The thermosetting resin may be a compound having a polymerizable double bond. A curing agent for the thermosetting resin may be further included. The curing agent may be one selected from the group consisting of oxygen-containing compounds, nitrogen-containing compounds, and thiol compounds.
　本発明のさらなる実施態様は上記いずれかの樹脂組成物を含有する封止材、接着剤、または硬化物である。 A further embodiment of the present invention is a sealing material, adhesive, or cured product containing any of the above resin compositions.
　本発明のさらなる実施態様は下記構造式（Ｉ）の化合物である。
Figure JPOXMLDOC01-appb-C000004
 （式中、
　Ｒ１は、フェニルおよびＣ１～Ｃ１７のアルキルから選択される基であり、
　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
　Ｒ４は、ＯＨおよびＯＡｃから選択される基であり、
　ｎとｍは整数であり、その和が１以上１２以下である。）
上記式中、
　Ｒ１は、フェニルおよびＣ１～Ｃ１０のアルキルから選択される基であり、
　Ｒ２、Ｒ３、Ｒ５は、水素であり、
　Ｒ４は、ＯＨであり、
　ｎとｍは１であってもよい。 A further embodiment of the present invention is a compound of structural formula (I) below.
Figure JPOXMLDOC01-appb-C000004
 (In the formula,
R 1 is a group selected from phenyl and C1-C17 alkyl;
R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
R4 is a group selected from OH and OAc;
n and m are integers, the sum of which is 1 or more and 12 or less. )
In the above formula,
R 1 is a group selected from phenyl and C1-C10 alkyl;
R 2 , R 3 , R 5 are hydrogen,
R4 is OH;
n and m may be one.
＝＝関連文献とのクロスリファレンス＝＝
　本出願は、２０２１年３月３０日付で出願した日本国特許出願特願２０２１－０５８８４９に基づく優先権を主張するものであり、当該基礎出願を引用することにより、本明細書に含めるものとする。 == Cross-reference with related literature ==
This application claims priority based on Japanese Patent Application No. 2021-058849 filed on March 30, 2021, and is incorporated herein by reference to the basic application. .
　本発明によって、新規な硬化触媒、樹脂組成物、封止材、接着剤、及び硬化物を提供することができるようになった。 The present invention has made it possible to provide novel curing catalysts, resin compositions, sealing materials, adhesives, and cured products.
実施例及び比較例で用いられた化合物の構造式である。1 is a structural formula of a compound used in Examples and Comparative Examples;
　本発明の目的、特徴、利点、及びそのアイデアは、本明細書の記載により、当業者には明らかであり、本明細書の記載から、当業者であれば、容易に本発明を再現できる。以下に記載された発明の実施の形態及び具体的な実施例などは、本発明の好ましい実施態様を示すものであり、例示又は説明のために示されているのであって、本発明をそれらに限定するものではない。本明細書で開示されている本発明の意図並びに範囲内で、本明細書の記載に基づき、様々な改変並びに修飾ができることは、当業者にとって明らかである。 The purpose, features, advantages, and ideas of the present invention are clear to those skilled in the art from the description of the present specification, and those skilled in the art can easily reproduce the present invention from the description of the present specification. DETAILED DESCRIPTION OF THE INVENTION The embodiments, specific examples, and the like set forth below are indicative of preferred embodiments of the invention, and are presented by way of illustration or description, without regard to the invention. It is not limited. Based on the description herein, it will be apparent to those skilled in the art that various alterations and modifications can be made within the spirit and scope of the invention disclosed herein.
＝＝化合物＝＝
　本実施形態にかかる化合物は、
下記構造式（Ｉ）の化合物である。
Figure JPOXMLDOC01-appb-C000005
 （式中、
　Ｒ１は、フェニルおよびＣ１～Ｃ１７のアルキルから選択される基であり、
　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
　Ｒ４は、ＯＨおよびＯＡｃから選択される基であり、
　ｎとｍは整数であり、その和が１以上であって、１２以下、好ましくは６以下、より好ましくは３以下である。）
　Ｒ１は、フェニルおよびＣ１～Ｃ１１のアルキルから選択されることが好ましい。Ｒ２、Ｒ３、Ｒ５は水素であることが好ましい。Ｒ４は、ＯＨであることが好ましい。ｎとｍは、それぞれ１であることが好ましい。 == compound ==
The compound according to this embodiment is
It is a compound of the following structural formula (I).
Figure JPOXMLDOC01-appb-C000005
 (In the formula,
R 1 is a group selected from phenyl and C1-C17 alkyl;
R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
R4 is a group selected from OH and OAc;
n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, more preferably 3 or less. )
R 1 is preferably selected from phenyl and C1-C11 alkyl. R 2 , R 3 and R 5 are preferably hydrogen. R4 is preferably OH. Preferably, n and m are each 1.
＝＝硬化触媒＝＝
　本実施形態にかかる硬化触媒は、下記の構造式（Ｉ）を有する化合物を含有する。なお、本明細書において、硬化触媒（ｃｕｒｉｎｇ　ｃａｔａｌｙｓｔ）とは、主剤が自己重合するか、または主剤と硬化剤が重合する時に、その重合の開始及び／又は進行を促進する機能を有する触媒を意味する。なお、硬化触媒は、重合体の末端のみに取り込まれることがある。
Figure JPOXMLDOC01-appb-C000006
 （式中、
　Ｒ１は、水素、フェニルおよびＣ１～Ｃ１７、好ましくはＣ１～Ｃ１１のアルキルから選択される基であり、
　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
　Ｒ４は、水素、ＯＨおよびＯＡｃから選択される基であり、
　ｎとｍは整数であり、その和が１以上であって、１２以下、好ましくは６以下、より好ましくは３以下である。）
　より好ましくは、Ｒ４が水素のときｎとｍの和が１で、Ｒ４がＯＨのときｎもｍも１である。 == Curing catalyst ==
The curing catalyst according to this embodiment contains a compound having the following structural formula (I). In the present specification, the term "curing catalyst" means a catalyst having a function of promoting the initiation and/or progress of polymerization when the main agent is self-polymerized or when the main agent and the curing agent are polymerized. do. In addition, the curing catalyst may be incorporated only at the terminal of the polymer.
Figure JPOXMLDOC01-appb-C000006
 (In the formula,
R 1 is a group selected from hydrogen, phenyl and C1-C17, preferably C1-C11 alkyl,
R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
R4 is a group selected from hydrogen, OH and OAc;
n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, more preferably 3 or less. )
More preferably, the sum of n and m is 1 when R4 is hydrogen, and both n and m are 1 when R4 is OH.
　これらの化合物は、実施例に記載の方法および公知の方法を用いて、容易に製造可能である。 These compounds can be easily produced using the methods described in the Examples and known methods.
　この硬化触媒は、フタルイミド骨格を有することにより、樹脂組成物中で、意図しない温度域での硬化触媒の樹脂への溶解が起こりにくく、ポットライフが長くなり、熱硬化性樹脂の硬化触媒として有用である。 Since this curing catalyst has a phthalimide skeleton, it is difficult for the curing catalyst to dissolve in the resin in an unintended temperature range in the resin composition, the pot life becomes longer, and it is useful as a curing catalyst for thermosetting resins. is.
　本明細書に開示の硬化触媒は、構造式（Ｉ）を有する化合物の１種または複数種を含有してもよい。また、構造式（Ｉ）を有する化合物以外の１種または複数種の他の硬化触媒を含有してもよい。 The curing catalyst disclosed herein may contain one or more compounds having the structural formula (I). It may also contain one or more curing catalysts other than the compound having structural formula (I).
＝＝樹脂組成物＝＝
　本明細書に開示の樹脂組成物は、構造式（Ｉ）を有する硬化触媒と、樹脂とを含有する。この樹脂組成物は、従来の硬化触媒を含有する樹脂組成物より安定であり、可使時間が長いという特徴を有する。 == resin composition ==
The resin composition disclosed herein contains a curing catalyst having structural formula (I) and a resin. This resin composition is more stable than resin compositions containing conventional curing catalysts, and has a longer pot life.
　樹脂は特に限定されないが、熱硬化性樹脂が好ましい。具体的には、エポキシ樹脂や重合性二重結合基を有する化合物（例えば、（メタ）アクリル化合物やマレイミド化合物）が例示できる。なお、本明細書では、アクリルとメタクリルを総称して、（メタ）アクリルと記載するものとする。 The resin is not particularly limited, but a thermosetting resin is preferred. Specifically, epoxy resins and compounds having a polymerizable double bond group (for example, (meth)acrylic compounds and maleimide compounds) can be exemplified. In this specification, acryl and methacryl are collectively referred to as (meth)acryl.
（１）エポキシ樹脂
　エポキシ樹脂は特に限定されず、単官能エポキシ樹脂であっても、多官能エポキシ樹脂であってもよい。
　単官能エポキシ樹脂は、エポキシ基を１個有するエポキシ樹脂であり、従来から反応性希釈剤としてエポキシ樹脂組成物の粘度調整に用いられている。単官能エポキシ樹脂は、脂肪族単官能エポキシ樹脂と芳香族単官能エポキシ樹脂に大別される。揮発性の観点から、単官能エポキシ樹脂は、エポキシ当量が１８０～４００ｇ／ｅｑであることが好ましい。 (1) Epoxy resin The epoxy resin is not particularly limited, and may be a monofunctional epoxy resin or a multifunctional epoxy resin.
A monofunctional epoxy resin is an epoxy resin having one epoxy group, and has been conventionally used as a reactive diluent to adjust the viscosity of an epoxy resin composition. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the monofunctional epoxy resin preferably has an epoxy equivalent of 180 to 400 g/eq.
　芳香族単官能エポキシ樹脂の例としては、フェニルグリシジルエーテル、クレジルグリシジルエーテル、ｐ－ｓ－ブチルフェニルグリシジルエーテル、スチレンオキシド、ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテル、ｏ－フェニルフェノールグリシジルエーテル、ｍ－フェニルフェノールグリシジルエーテル、ｐ－フェニルフェノールグリシジルエーテル、Ｎ－グリシジルフタルイミド等を挙げることができるが、これらに限定されない。これらのうち、ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテル及びフェニルグリシジルエーテルが好ましく、ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテルが特に好ましい。 Examples of aromatic monofunctional epoxy resins include phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, m- Examples include, but are not limited to, phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, and the like. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred.
　脂肪族単官能エポキシ樹脂の例としては、ｎ－ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、α－ピネンオキシド、アリルグリシジルエーテル、１－ビニル－３，４－エポキシシクロヘキサン、１，２－エポキシ－４－（２－メチルオキシラニル)－１－メチルシクロヘキサン、１，３－ビス（３－グリシドキシプロピル）－１，１，３，３－テトラメチルジシロキサン、ネオデカン酸グリシジルエステル等を挙げることができるが、これらに限定されない。 Examples of aliphatic monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4 -(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecanoic acid glycidyl ester, etc. can be, but are not limited to:
　多官能エポキシ樹脂とは、２個以上のエポキシ基を有するエポキシ樹脂をいう。従って、本開示の樹脂組成物は、２官能エポキシ樹脂、３官能エポキシ樹脂、４官能エポキシ樹脂、などを含んでもよい。多官能エポキシ樹脂は、脂肪族多官能エポキシ樹脂と芳香族多官能エポキシ樹脂に大別される。 A polyfunctional epoxy resin is an epoxy resin having two or more epoxy groups. Accordingly, the resin composition of the present disclosure may include difunctional epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins, and the like. Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.
　脂肪族多官能エポキシ樹脂の例としては、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ポリテトラメチレンエーテルグリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、シクロヘキサン型ジグリシジルエーテル、ジシクロペンタジエン型ジグリシジルエーテルのようなジエポキシ樹脂；トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシ樹脂；ビニル（３，４－シクロヘキセン）ジオキシド、２－（３，４－エポキシシクロヘキシル）－５，１－スピロ－（３，４－エポキシシクロヘキシル）－ｍ－ジオキサンのような脂環式エポキシ樹脂；テトラグリシジルビス（アミノメチル）シクロヘキサンのようなグリシジルアミン型エポキシ樹脂；１，３－ジグリシジル－５－メチル－５－エチルヒダントインのようなヒダントイン型エポキシ樹脂；及び－１，３－ビス（３－グリシドキシプロピル）－１，１，３，３－テトラメチルジシロキサンのようなシリコーン骨格を有するエポキシ樹脂などが挙げられるが、これらに限定されない。 Examples of aliphatic polyfunctional epoxy resins include (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether. diepoxy resins such as ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether; Triepoxy resins such as methylolpropane triglycidyl ether, glycerin triglycidyl ether; vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxy Cycloaliphatic epoxy resins such as cyclohexyl)-m-dioxane; glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; hydantoins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin. type epoxy resin; and epoxy resins having a silicone skeleton such as -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, but are limited to these not.
　前記の例のうち、「シクロヘキサン型ジグリシジルエーテル」とは、２個のグリシジル基が、各々エーテル結合を介して、１個のシクロヘキサン環を母体構造として有する２価の飽和炭化水素基に結合した構造を有する化合物を意味する。「ジシクロペンタジエン型ジグリシジルエーテル」とは、２個のグリシジル基が、各々エーテル結合を介して、ジシクロペンタジエン骨格を母体構造として有する２価の飽和炭化水素基に結合した構造を有する化合物を意味する。また、シクロヘキサン型ジグリシジルエーテルとしては、シクロヘキサンジメタノールジグリシジルエーテルが特に好ましい。 Among the above examples, "cyclohexane-type diglycidyl ether" means that two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as a base structure. A compound having a structure is meant. The term "dicyclopentadiene-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a base structure. means. As the cyclohexane-type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferred.
　芳香族多官能エポキシ樹脂は、ベンゼン環等の芳香環を含む構造を有する多官能エポキシ樹脂である。ビスフェノールＡ型エポキシ樹脂など、従来頻用されているエポキシ樹脂にはこの種のものが多い。芳香族多官能エポキシ樹脂の例としては、ビスフェノールＡ型エポキシ樹脂；ｐ－グリシジルオキシフェニルジメチルトリスビスフェノールＡジグリシジルエーテルのような分岐状多官能ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；ビスフェノールＥ型エポキシ樹脂；ビスフェノールＳ型エポキシ樹脂；ノボラック型エポキシ樹脂；テトラブロモビスフェノールＡ型エポキシ樹脂；フルオレン型エポキシ樹脂；ビフェニルアラルキルエポキシ樹脂；１，４－フェニルジメタノールジグリシジルエーテルのようなジエポキシ樹脂；３，３'，５，５'－テトラメチル－４，４'－ジグリシジルオキシビフェニルのようなビフェニル型エポキシ樹脂；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジル－ｐ－アミノフェノール、テトラグリシジル－ｍ－キシリレンジアミンのようなグリシジルアミン型エポキシ樹脂；及びナフタレン環含有エポキシ樹脂などが挙げられるが、これらに限定されない。 Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins having a structure containing aromatic rings such as benzene rings. Many conventional epoxy resins, such as bisphenol A type epoxy resin, are of this type. Examples of aromatic polyfunctional epoxy resins include bisphenol A type epoxy resins; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resins; type epoxy resin; bisphenol S type epoxy resin; novolac type epoxy resin; tetrabromobisphenol A type epoxy resin; fluorene type epoxy resin; biphenyl aralkyl epoxy resin; ,3′,5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl; diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m- glycidylamine-type epoxy resins such as xylylenediamine; and naphthalene ring-containing epoxy resins, but are not limited thereto.
　芳香族多官能エポキシ樹脂としては、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂及びグリシジルアミン型エポキシ樹脂が好ましく、中でもそのエポキシ当量が９０～２００ｇ／ｅｑであるものが好ましい。 As aromatic polyfunctional epoxy resins, bisphenol F-type epoxy resins, bisphenol A-type epoxy resins and glycidylamine-type epoxy resins are preferable, and among them, those having an epoxy equivalent of 90 to 200 g/eq are preferable.
（２）重合性二重結合基を有する化合物
　重合性二重結合基を有する高分子化合物は特に限定されないが、ビニル基、特に（メタ）アクリル基やマレイミド基を、反応性二重結合基として有する高分子化合物が好ましい。 (2) Compound having a polymerizable double bond group The polymer compound having a polymerizable double bond group is not particularly limited. A polymer compound having
　（メタ）アクリル化合物のうち、例えば、アルキル基を持つ化合物として、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ－プロピルアクリレート、ｎ－プロピルメタクリレート、イソプロピルアクリレート、イソプロピルメタクリレート、ノルマルブチルアクリレート、ノルマルブチルメタクリレート、ノルマルヘキシルアクリレート、ノルマルヘキシルメタクリレート、ノルマルヘプチルアクリレート、ノルマルヘプチルメタクリレート、２－エチルヘキシルアクリレート、２－エチルヘキシルメタクリレート、ノルマルラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート等；脂環式炭化水素基を有する化合物として、シクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート等；芳香族基を有するビニル系単量体として、スチレン、α－メチルスチレン、α－クロロスチレン、ビニルトルエン等；水酸基を有する化合物として、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、ジエチレングリコールモノアクリレート、シクロヘキサンジメタノールモノアクリレート、シクロヘキサンジメタノールモノメタクリレート等；（メタ）アクリルアミド類として、アクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－ブトキシメチルアクリルアミド、メタクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルメタクリルアミド、Ｎ－イソブトキシメチルメタクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等が例示できる。また、ビニル基を３個以上有する化合物として、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等のポリオール誘導体の多官能（メタ）アクリレート；ペンタエリスリトールトリアリレート、ペンタエリスリトールテトラアリレート、トリメチロールプロパントリアリレート等の多官能アリレート；アロニックスＭ－７１００、アロニックスＭ－８０３０、アロニックスＭ－８０６０（いずれも東亞合成（株）製）等のポリエステル（メタ）アクリレート；ＥＯ変性多官能アクリレート、ＰＯ変性多官能アクリレート、ＰＥＴＩＡ、ＰＥＴＲＡ、ＴＭＰＴＡ、ＴＭＰＥＯＴＡ、ＯＴＡ４８０、ＥＢＥＣＲＹＬ１２、ＥＢＥＣＲＹＬ４０、ＥＢＥＣＲＹＬ１４０、ＤＰＨＡ（いずれもダイセル・サイテック（株）製）、アロニックスＭ－３０５、アロニックスＭ－３０９、アロニックスＭ－３１０、Ｍ－３１５、Ｍ－３２０、アロニックスＭ－３５０、アロニックスＭ－３６０、アロニックスＭ－３７０、アロニックスＭ－４００、アロニックスＭ－４０２、アロニックスＭ－４０８、アロニックスＭ－４５０、（いずれも東亞合成（株）製）、ネオマーＴＡ－４０１、ＴＡ－５０５、ＥＡ－３０１、ＤＡ－６００（いずれも三洋化成工業（株）製）、ＮＫエステルＡ－ＴＭＰＴ、ＮＫエステルＡＤ－ＴＭＰ、ＮＫエステルＡ－ＴＭＰＴ－３ＥＯ、ＮＫエステルＡ－ＴＭＰＴ－９ＥＯ、ＮＫエステルＡ－ＴＭ－４Ｅ、ＮＫエステルＡ－ＴＭ－４Ｐ、ＮＫエステルＴＭＰＴ－９ＥＯ、ＮＫエステルＡ－ＤＰＨ、ＮＫエステルＡ－ＴＭＭＴ、ＮＫエステルＡ－９５５０、ＮＫエステルＡＴＭ－３５Ｅ、ＮＫエステルＴＭＰＴ（いずれも新中村化学工業（株）製）などのポリエーテル（メタ）アクリレート等が例示できる。 Among (meth)acrylic compounds, for example, compounds having an alkyl group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal Butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, etc.; compounds having cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc.; vinyl monomers having an aromatic group, styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc.; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Butyl methacrylate, diethylene glycol monoacrylate, cyclohexanedimethanol monoacrylate, cyclohexanedimethanol monomethacrylate, etc.; Examples include methylacrylamide, N-butoxymethylacrylamide, methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, and N-butoxymethylmethacrylamide. . Further, as compounds having 3 or more vinyl groups, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. Multifunctional (meth)acrylates of polyol derivatives such as; Pentaerythritol triarylate, pentaerythritol tetraarylate, trimethylolpropane triarylate and other polyfunctional arylates; Aronix M-7100, Aronix M-8030, Aronix M-8060 polyester (meth)acrylates such as Toagosei Co., Ltd.; Co., Ltd.), Aronix M-305, Aronix M-309, Aronix M-310, M-315, M-320, Aronix M-350, Aronix M-360, Aronix M-370, Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, (all manufactured by Toagosei Co., Ltd.), Neomer TA-401, TA-505, EA-301, DA-600 (both Sanyo Chemical Industries Co., Ltd.) ), NK Ester A-TMPT, NK Ester AD-TMP, NK Ester A-TMPT-3EO, NK Ester A-TMPT-9EO, NK Ester A-TM-4E, NK Ester A-TM-4P, NK Ester TMPT -9EO, NK Ester A-DPH, NK Ester A-TMMT, NK Ester A-9550, NK Ester ATM-35E, NK Ester TMPT (both manufactured by Shin-Nakamura Chemical Co., Ltd.) and other polyether (meth)acrylates etc. can be exemplified.
　例えば、マレイミド基を持つ化合物として、Ｎ，Ｎ’－（４，４’－ジフェニルメタン）ビスマレイミド、ビスフェノール Ａ ジフェニルエーテルビスマレイミド、３,３'－ジメチル－５,５'－ジエチル－４,４'－ジフェニルメタンビスマレイミド、４－メチル－１,３－フェニレンビスマレイミド、１，６’－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、ビス－（３－エチル－５－メチル－４－マレイミドフェニル）メタン、ｍ－フェニレンビスマレイミド（Ｎ，Ｎ’－１，３－フェニレンビスマレイミド）、１，６－ビスマレイミドヘキサン、１，２－ビスマレイミドエタン（Ｎ，Ｎ'－エチレンジマェイミド）、Ｎ，Ｎ'－（１，２－フェニレン）ビスマレイミド、Ｎ，Ｎ'－１，４－フェニレンジマレイミド、Ｎ，Ｎ'－（スルホニルジ－ｐ－フェニレン）ジマレイミド、Ｎ，Ｎ'－［３，３'－（１，３－フェニレンジオキシ）ジフェニル］ビスマレイミド等が挙げられる。また、ダイマー酸変性ビスマレイミドを用いることも可能である。例えば、ダイマー酸変性ビスマレイミドとして、液状のビスマレイミドであるＢＭＩ－６８９、ＢＭＩ－１５００、ＢＭＩ－１７００、または固形のビスマレイミドであるＢＭＩ－３０００（いずれもＤｅｓｉｇｎｅｒ　ｍｏｌｅｃｕｌｅｓ社製）が挙げられる。 For example, compounds having a maleimide group include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl) ) methane, m-phenylenebismaleimide (N,N′-1,3-phenylenebismaleimide), 1,6-bismaleimidohexane, 1,2-bismaleimidoethane (N,N′-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3 , 3′-(1,3-phenylenedioxy)diphenyl]bismaleimide and the like. It is also possible to use dimer acid-modified bismaleimide. Examples of dimer acid-modified bismaleimides include liquid bismaleimides BMI-689, BMI-1500 and BMI-1700, and solid bismaleimides BMI-3000 (all manufactured by Designer Molecules).
＜硬化剤＞
　本開示の樹脂組成物は、１種または複数種の硬化剤を含有してもよい。
　本開示の樹脂組成物が含有してもよい硬化剤は特に限定されないが、例えば、アミンとその誘導体などの窒素含有化合物；カルボン酸末端ポリエステル、酸無水物系、フェノール系、ビスフェノールＡ及びクレゾールノボラック、フェノール末端エポキシ樹脂などの酸素含有化合物；チオール化合物などの含硫黄化合物が挙げられる。 <Curing agent>
The resin composition of the present disclosure may contain one or more curing agents.
Curing agents that may be contained in the resin composition of the present disclosure are not particularly limited, but include, for example, nitrogen-containing compounds such as amines and their derivatives; , oxygen-containing compounds such as phenol-terminated epoxy resins; sulfur-containing compounds such as thiol compounds.
　アミンとその誘導体などの窒素含有化合物は特に限定されないが、トリエチレンテトラアミン、テトラエチレンペンタミン、ｍ－キシレンジアミン、トリメチルヘキサメチレンジアミン、２－メチルペンタメチレンジアミンなどの脂肪族ポリアミン、イソフォロンジアミン、１，３－ビスアミノメチルシクロヘキサン、ビス（４－アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２－ジアミノシクロヘキサンなどの脂環式ポリアミン、Ｎ－アミノエチルピペラジン、１，４－ビス（２－アミノ－２－メチルプロピル）ピペラジンなどのピペラジン型のポリアミン、ジエチルトルエンジアミン、ジメチルチオトルエンジアミン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、ビス（メチルチオ）トルエンジアミン、ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン、トリメチレンビス（４－アミノベンゾエート）、ポリテトラメチレンオキシド－ジ－ｐ－アミノベンゾエートなどの芳香族ポリアミン類が例示できる。市販品としては、エピキュア－Ｗ、エピキュア－Ｚ（油化シェルエポキシ株式会社、商品名）、ｊＥＲキュア（登録商標）－Ｗ、ｊＥＲキュア（登録商標）－Ｚ（三菱ケミカル株式会社、商品名）、カヤハードＡ－Ａ、カヤハードＡ－Ｂ、カヤハードＡ－Ｓ（日本化薬株式会社、商品名）、トートアミンＨＭ－２０５（新日鉄住金化学株式会社、商品名）、アデカハードナーＥＨ－１０１（株式会社ＡＤＥＫＡ、商品名）、エポミックＱ－６４０、エポミックＱ－６４３（三井化学株式会社、商品名）、ＤＥＴＤＡ８０（Ｌｏｎｚａ社、商品名）、トートアミンＨＭ－２０５（新日鉄住金化学株式会社、商品名）等が挙げられる。 Nitrogen-containing compounds such as amines and derivatives thereof are not particularly limited, but aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine, isophorone diamine. , 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, alicyclic polyamines such as 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis(2-amino -piperazine-type polyamines such as 2-methylpropyl)piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m- Aromatic polyamines such as phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethyleneoxide-di-p-aminobenzoate can be exemplified. Commercially available products include Epicure-W, Epicure-Z (Yuka Shell Epoxy Co., Ltd., trade name), jER Cure (registered trademark)-W, jER Cure (registered trademark)-Z (Mitsubishi Chemical Co., Ltd., trade name). , Kayahard AA, Kayahard AB, Kayahard AS (Nippon Kayaku Co., Ltd., trade name), Thothamine HM-205 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Adeka Hardner EH-101 (Co., Ltd. ADEKA, trade name), Epomic Q-640, Epomic Q-643 (Mitsui Chemicals, trade name), DETDA80 (Lonza, trade name), Thothamine HM-205 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), etc. is mentioned.
　酸無水物系硬化剤は特に限定されないが、例えば、メチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、アルキル化テトラヒドロフタル酸無水物、メチルハイミック酸無水物、アルケニル基で置換されたコハク酸無水物、グルタル酸無水物等が挙げられる。特に、３，４－ジメチル－６－（２－メチル－１－プロペニル）－１，２，３，６－テトラヒドロフタル酸無水物、１－イソプロピル－４－メチル－ビシクロ［２．２．２］オクト－５－エン－２，３－ジカルボン酸無水物、ノルボルナン－２，３－ジカルボン酸無水物、メチルノルボルナン－２，３－ジカルボン酸無水物、水素化メチルナジック酸無水物、アルケニル基で置換されたコハク酸無水物、ジエチルグルタル酸無水物が好ましい。　 The acid anhydride-based curing agent is not particularly limited, but for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhimic acid anhydride, alkenyl-substituted Succinic anhydride, glutaric anhydride and the like can be mentioned. especially 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, hydrogenated methylnadic anhydride, substituted with alkenyl groups succinic anhydride and diethylglutaric anhydride are preferred.　
　フェノール系硬化剤はフェノール性水酸基を有するモノマー、オリゴマー、ポリマー全般をいい、例えば、フェノールノボラック樹脂およびそのアルキル化物またはアリル化物、クレゾールノボラック樹脂、フェノールアラルキル（フェニレン、ビフェニレン骨格を含む）樹脂、ナフトールアラルキル樹脂、トリフェノールメタン樹脂、ジシクロペンタジエン型フェノール樹脂等が挙げられる。中でも、アリルフェノールノボラック樹脂が好ましい。 Phenolic curing agents refer to monomers, oligomers, and polymers generally having phenolic hydroxyl groups, such as phenol novolac resins and their alkylated or allylated products, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeleton) resins, and naphthol aralkyls. Resins, triphenol methane resins, dicyclopentadiene type phenol resins, and the like. Among them, allylphenol novolac resin is preferable.
　チオール化合物には、加水分解性の多官能チオール化合物、非加水分解性の多官能チオール化合物が含まれる。 Thiol compounds include hydrolyzable polyfunctional thiol compounds and non-hydrolyzable polyfunctional thiol compounds.
　加水分解性の多官能チオール化合物の例としては、トリメチロールプロパントリス（３－メルカプトプロピオネート）（ＳＣ有機化学社製：ＴＭＭＰ）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート（ＳＣ有機化学社製：ＴＥＭＰＩＣ）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）（ＳＣ有機化学社製：ＰＥＭＰ）、テトラエチレングリコールビス（３－メルカプトプロピオネート）（ＳＣ有機化学社製：ＥＧＭＰ－４）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）（ＳＣ有機化学社製：ＤＰＭＰ）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）（昭和電工社製：カレンズＭＴ（登録商標）ＰＥ１）、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（昭和電工社製：カレンズＭＴ（登録商標）ＮＲ１）等を挙げることができる。 Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate Nurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.) : EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) ) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) NR1) and the like can be mentioned.
　非加水分解性多官能チオール化合物の例としては、１，３，４，６－テトラキス（２－メルカプトエチル）グリコールウリル（商品名：ＴＳ－Ｇ、四国化成工業社製）、（１，３，４，６－テトラキス（３－メルカプトプロピル）グリコールウリル（商品名：Ｃ３　ＴＳ－Ｇ、四国化成工業社製）、１，３，４，６－テトラキス（メルカプトメチル）グリコールウリル、１，３，４，６－テトラキス（メルカプトメチル）－３ａ－メチルグリコールウリル、１，３，４，６－テトラキス（２－メルカプトエチル）－３ａ－メチルグリコールウリル、１，３，４，６－テトラキス（３－メルカプトプロピル）－３ａ－メチルグリコールウリル、１，３，４，６－テトラキス（メルカプトメチル）－３ａ，６ａ－ジメチルグリコールウリル、１，３，４，６－テトラキス（２－メルカプトエチル）－３ａ，６ａ－ジメチルグリコールウリル、１，３，４，６－テトラキス（３－メルカプトプロピル）－３ａ，６ａ－ジメチルグリコールウリル、１，３，４，６－テトラキス（メルカプトメチル）－３ａ，６ａ－ジフェニルグリコールウリル、１，３，４，６－テトラキス（２－メルカプトエチル）－３ａ，６ａ－ジフェニルグリコールウリル、１，３，４，６－テトラキス（３－メルカプトプロピル）－３ａ，６ａ－ジフェニルグリコールウリル、ペンタエリスリトールトリプロパンチオール（商品名：ＰＥＰＴ、ＳＣ有機化学社製）、ペンタエリスリトールテトラプロパンチオール等が挙げられる。 Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Shikoku Kasei Co., Ltd.), (1,3, 4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Kasei Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4 ,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercapto Propyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a - dimethyl glycol uril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycol uril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycol uril , 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, penta Erythritol trippropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd.), pentaerythritol tetrapropanethiol, and the like can be mentioned.
　非加水分解性多官能チオール化合物としては、分子内にスルフィド結合を２つ以上有する３官能以上のポリチオール化合物を使用することもできる。このようなチオール化合物としては、例えば、１，２，３－トリス（メルカプトメチルチオ）プロパン、１，２，３－トリス（２－メルカプトエチルチオ）プロパン、１，２，３－トリス（３－メルカプトプロピルチオ）プロパン、４－メルカプトメチル－１，８－ジメルカプト－３，６－ジチアオクタン、５，７－ジメルカプトメチル－１，１１－ジメルカプト－３，６，９－トリチアウンデカン、４，７－ジメルカプトメチル－１，１１－ジメルカプト－３，６，９－トリチアウンデカン、４，８－ジメルカプトメチル－１，１１－ジメルカプト－３，６，９－トリチアウンデカン、テトラキス（メルカプトメチルチオメチル）メタン、テトラキス（２－メルカプトエチルチオメチル）メタン、テトラキス（３－メルカプトプロピルチメチル）メタン、１，１，３，３－テトラキス（メルカプトメチルチオ）プロパン、１，１，２，２－テトラキス（メルカプトメチルチオ）エタン、１，１，５，５－テトラキス（メルカプトメチルチオ）－３－チアペンタン、１，１，６，６－テトラキス（メルカプトメチルチオ）－３，４－ジチアヘキサン、２，２－ビス（メルカプトメチルチオ）エタンチオール、３－メルカプトメチルチオ－１，７－ジメルカプト－２，６－ジチアヘプタン、３，６－ビス（メルカプトメチルチオ）－１，９－ジメルカプト－２，５，８－トリチアノナン、３－メルカプトメチルチオ－１，６－ジメルカプト－２，５－ジチアヘキサン、１，１，９，９－テトラキス（メルカプトメチルチオ）－５－（３，３－ビス（メルカプトメチルチオ）－１－チアプロピル）３，７－ジチアノナン、トリス（２，２－ビス（メルカプトメチルチオ）エチル）メタン、トリス（４，４－ビス（メルカプトメチルチオ）－２－チアブチル）メタン、テトラキス（２，２－ビス（メルカプトメチルチオ）エチル）メタン、テトラキス（４，４－ビス（メルカプトメチルチオ）－２－チアブチル）メタン、３，５，９，１１－テトラキス（メルカプトメチルチオ）－１，１３－ジメルカプト－２，６，８，１２－テトラチアトリデカン、３，５，９，１１，１５，１７－ヘキサキス（メルカプトメチルチオ）－１，１９－ジメルカプト－２，６，８，１２，１４，１８－ヘキサチアノナデカン、９－（２，２－ビス（メルカプトメチルチオ）エチル）－３，５，１３，１５－テトラキス（メルカプトメチルチオ）－１，１７－ジメルカプト－２，６，８，１０，１２，１６－ヘキサチアヘプタデカン、３，４，８，９－テトラキス（メルカプトメチルチオ）－１，１１－ジメルカプト－２，５，７，１０－テトラチアウンデカン、３，４，８，９，１３，１４－ヘキサキス（メルカプトメチルチオ）－１，１６－ジメルカプト－２，５，７，１０，１２，１５－ヘキサチアヘキサデカン、８－［ビス（メルカプトメチルチオ）メチル］－３，４，１２，１３－テトラキス（メルカプトメチルチオ）－１，１５－ジメルカプト－２，５，７，９，１１，１４－ヘキサチアペンタデカン、４，６－ビス［３，５－ビス（メルカプトメチルチオ）－７－メルカプト－２，６－ジチアヘプチルチオ］－１，３－ジチアン、４－［３，５－ビス（メルカプトメチルチオ）－７‐メルカプト－２，６－ジチアヘプチルチオ］－６－メルカプトメチルチオ－１，３－ジチアン、１，１－ビス［４－（６－メルカプトメチルチオ）－１，３－ジチアニルチオ］－１，３－ビス（メルカプトメチルチオ）プロパン、１－［４－（６－メルカプトメチルチオ）－１，３－ジチアニルチオ］－３－［２，２－ビス（メルカプトメチルチオ）エチル］－７，９－ビス（メルカプトメチルチオ）－２，４，６，１０－テトラチアウンデカン、３－［２－（１，３－ジチエタニル）］メチル－７，９－ビス（メルカプトメチルチオ）－１，１１－ジメルカプト－２，４，６，１０－テトラチアウンデカン、９－［２－（１，３－ジチエタニル）］メチル－３，５，１３，１５－テトラキス（メルカプトメチルチオ）－１，１７－ジメルカプト－２，６，８，１０，１２，１６－ヘキサチアヘプタデカン、３－［２－（１，３－ジチエタニル）］メチル－７，９，１３，１５－テトラキス（メルカプトメチルチオ）－１，１７－ジメルカプト－２，４，６，１０，１２，１６－ヘキサチアヘプタデカン等の脂肪族ポリチオール化合物；４，６－ビス［４－（６－メルカプトメチルチオ）－１，３－ジチアニルチオ］－６－［４－（６‐メルカプトメチルチオ）－１，３－ジチアニルチオ］－１，３－ジチアン、４－［３，４，８，９‐テトラキス（メルカプトメチルチオ）－１１－メルカプト－２，５，７，１０－テトラチアウンデシル］－５－メルカプトメチルチオ－１，３－ジチオラン、４，５－ビス［３，４－ビス（メルカプトメチルチオ）－６－メルカプト－２，５－ジチアヘキシルチオ］－１，３－ジチオラン、４－［３，４－ビス（メルカプトメチルチオ）－６－メルカプト－２，５－ジチアヘキシルチオ］－５－メルカプトメチルチオ－１，３－ジチオラン、４－［３－ビス（メルカプトメチルチオ）メチル－５，６－ビス（メルカプトメチルチオ）－８－メルカプト－２，４，７－トリチアオクチル］－５－メルカプトメチルチオ－１，３－ジチオラン、２－｛ビス［３，４－ビス（メルカプトメチルチオ）－６－メルカプト－２，５－ジチアヘキシルチオ］メチル｝－１，３－ジチエタン、２－［３，４－ビス（メルカプトメチルチオ）－６－メルカプト－２，５－ジチアヘキシルチオ］メルカプトメチルチオメチル－１，３－ジチエタン、２－［３，４，８，９－テトラキス（メルカプトメチルチオ）－１１－メルカプト－２，５，７，１０－テトラチアウンデシルチオ］メルカプトメチルチオメチル－１，３－ジチエタン、２－［３－ビス（メルカプトメチルチオ）メチル－５，６－ビス（メルカプトメチルチオ）－８－メルカプト－２，４，７－トリチアオクチル］メルカプトメチルチオメチル－１，３－ジチエタン、４－｛１－［２－（１，３－ジチエタニル）］－３－メルカプト－２－チアプロピルチオ｝－５－［１，２－ビス（メルカプトメチルチオ）－４－メルカプト－３－チアブチルチオ］－１，３－ジチオラン等の環式構造を有するポリチオール化合物が挙げられる。 As the non-hydrolyzable polyfunctional thiol compound, it is also possible to use a trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule. Examples of such thiol compounds include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercapto propylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7- dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, tetrakis(mercaptomethylthiomethyl) Methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthymethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercapto methylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio) ) ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianone, 3-mercaptomethylthio- 1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianone, tris (2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4) , 4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3, 5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio) ) ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)- 1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10 -tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis( mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3, 5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-di Thiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1 -[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10 -tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9- [2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiahepta Aliphatic polythiol compounds such as decane; 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1 ,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane , 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2 ,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3 -dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]-5-mercaptomethylthio-1,3-dithiolane , 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiethane, 2-[3,4-bis(mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7 , 10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7 -trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2- Examples include polythiol compounds having a cyclic structure such as bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane.
＜樹脂組成物の構成割合＞
　樹脂組成物中の硬化触媒の割合は特に限定されないが、樹脂組成物中の熱硬化性樹脂に対して、０．０１～５０ｗｔ％であることが好ましく、０．０１～３０ｗｔ％であることがより好ましく、０．０１～２０ｗｔ％であることがさらに好ましい。 <Composition ratio of resin composition>
Although the ratio of the curing catalyst in the resin composition is not particularly limited, it is preferably 0.01 to 50 wt%, more preferably 0.01 to 30 wt%, relative to the thermosetting resin in the resin composition. More preferably, it is 0.01 to 20 wt%.
　樹脂組成物の増粘倍率が初期の２倍になるまでの時間をポットライフとし、エポキシ－チオール硬化系におけるポットライフは、８時間以上であることが好ましく、１２時間以上であることがより好ましく、１６時間以上であることがさらに好ましい。その他の硬化系においても、ポットライフは長い方が安定性の観点から好ましい。 The pot life is defined as the time until the thickening ratio of the resin composition doubles from the initial value, and the pot life in the epoxy-thiol curing system is preferably 8 hours or longer, more preferably 12 hours or longer. , more preferably 16 hours or longer. Also in other curing systems, a longer pot life is preferable from the viewpoint of stability.
＜樹脂組成物のそのほかの成分＞
　本開示の硬化性組成物は、主剤、硬化触媒、硬化剤以外に、例えば以下に述べるものを必要に応じて含有してもよい。 <Other components of the resin composition>
The curable composition of the present disclosure may optionally contain, for example, the following in addition to the main agent, curing catalyst, and curing agent.
（１）安定剤
　本開示の樹脂組成物には、その貯蔵安定性を向上させ、ポットライフを長くするために、安定剤を添加することができる。エポキシ樹脂を主剤とする一液型接着剤の安定剤として公知の種々の安定剤を使用することができるが、液状ホウ酸エステル化合物、アルミキレート及び有機酸からなる群から選択される少なくとも１つが好ましい。 (1) Stabilizer A stabilizer can be added to the resin composition of the present disclosure in order to improve its storage stability and prolong its pot life. Various known stabilizers can be used as stabilizers for one-component adhesives based on epoxy resins. preferable.
　液状ホウ酸エステル化合物の例としては、２，２'－オキシビス（５，５'－ジメチル－１，３，２－オキサボリナン）、トリメチルボレート、トリエチルボレート、トリ－ｎプロピルボレート、トリイソプロピルボレート、トリ－ｎ－ブチルボレート、トリペンチルボレート、トリアリルボレート、トリヘキシルボレート、トリシクロヘキシルボレート、トリオクチルボレート、トリノニルボレート、トリデシルボレート、トリドデシルボレート、トリヘキサデシルボレート、トリオクタデシルボレート、トリス（２－エチルヘキシロキシ）ボラン、ビス（１，４，７，１０－テトラオキサウンデシル）（１，４，７，１０，１３－ペンタオキサテトラデシル）（１，４，７－トリオキサウンデシル）ボラン、トリベンジルボレート、トリフェニルボレート、トリ－ｏ－トリルボレート、トリ－ｍ－トリルボレート、トリエタノールアミンボレート等が挙げられる。 Examples of liquid borate compounds include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri - n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris(2 -ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentoxatetradecyl)(1,4,7-trioxaundecyl) Borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m-tolylborate, triethanolamineborate and the like.
　アルミキレートとしては、例えばアルミキレートＡ（川研ファインケミカル株式会社製）を用いることができる。有機酸としては、例えばバルビツール酸を用いることができる。 As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As an organic acid, for example, barbituric acid can be used.
（２）充填剤
　本開示の樹脂組成物には、充填剤を添加することができる。
　充填剤の具体的な例としては、シリカフィラー、ガラスフィラー、アルミナフィラー、酸化チタンフィラー、窒化ホウ素フィラー、窒化アルミフィラー、タルクフィラー、炭酸カルシウムフィラー、樹脂フィラー（例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）フィラー、シリコーンゴムフィラーなど）、銀や銅やニッケルなどの導電性フィラー等が挙げられる。形状は特に限られず、中空状であっても、球状であっても、不定形であってもよい。また、充填剤は、表面処理されたものであってもよい。 (2) Filler A filler can be added to the resin composition of the present disclosure.
Specific examples of fillers include silica fillers, glass fillers, alumina fillers, titanium oxide fillers, boron nitride fillers, aluminum nitride fillers, talc fillers, calcium carbonate fillers, resin fillers (e.g., polytetrafluoroethylene (PTFE) fillers, silicone rubber fillers, etc.), conductive fillers such as silver, copper and nickel. The shape is not particularly limited, and may be hollow, spherical, or amorphous. Moreover, the filler may be surface-treated.
（３）カップリング剤
　本開示の樹脂組成物には、カップリング剤を添加することができる。カップリング剤は、シランカップリング剤が好ましく、エポキシ系、アミノ系、ビニル系、メタクリル系、アクリル系、メルカプト系等の各種シランカップリング剤を用いることができる。これらのシランカップリング剤は、単独で用いても、２種以上を併用してもよい。 (3) Coupling agent A coupling agent can be added to the resin composition of the present disclosure. The coupling agent is preferably a silane coupling agent, and various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto can be used. These silane coupling agents may be used alone or in combination of two or more.
　シランカップリング剤としては、例えば、アルケニル基を有するシランカップリング剤として、ビニルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－１００３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１７１、東レ・ダウコーニング社製；Ｚ－６３００、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＸＬ１０、日美商事社製；サイラエースＳ２１０等が挙げられる）、ビニルトリエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－１００３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１５１、東レ・ダウコーニング社製；Ｚ－６５１９、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ５６、日美商事社製；サイラエースＳ２２０等が挙げられる）、ビニルトリアセトキシシラン（市販品としては旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ６２が挙げられる）、ビニルトリス（２－メトキシエトキシ）シラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１７２が挙げられる）、ビニルメチルジメトキシシラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－２１７１、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＸＬ１２等が挙げられる）、オクテニルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－１０８３が挙げられる）、アリルトリメトキシシラン（市販品として東レ・ダウコーニング社製；Ｚ－６８２５が挙げられる）、ｐ－スチリルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－１４０３等が挙げられる）。例えば、アクリル基を有するシランカップリング剤として、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－５１０３等が挙げられる）等が挙げられ、メタクリル基を有するシランカップリング剤として、３－メタクリロキシプロピルメチルジメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－５０２、東レ・ダウコーニング社製；Ｚ－６０３３等が挙げられる）、３－メタクリロキシプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－５０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１７４、東レ・ダウコーニング社製；Ｚ－６０３０、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ３１、日美商事社製；サイラエースＳ７１０等が挙げられる）、３－メタクリロキシプロピルメチルジエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－５０２が挙げられる）、３－メタクリロキシプロピルトリエトキシシラン（信越化学工業社製；ＫＢＥ－５０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ｙ－９９３６が挙げられる）、メタクリロキシオクチルトリメトキシシラン（信越化学工業社製；ＫＢＭ－５８０３が挙げられる）等が挙げられ、エポキシ基を有するシランカップリング剤として、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－３０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１８６、東レ・ダウコーニング社製；Ｚ－６０４３、日美商事社製；サイラエースＳ５３０等が挙げられる）、３－グリシドキシプロピルメチルジメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－４０２、東レ・ダウコーニング社製；Ｚ－６０４４、日美商事社製；サイラエースＳ５２０等が挙げられる）、３－グリシドキシプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－４０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１８７、東レ・ダウコーニング社製；Ｚ－６０４０、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ８０、日美商事社製サイラエースＳ５１０等が挙げられる）、３－グリシドキシプロピルメチルジエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－４０２が挙げられる）、３－グリシドキシプロピルトリエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－４０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１８７１、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ８２等が挙げられる）、グリシドキシオクチルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－４８０３が挙げられる）等が挙げられ、アミノ基を有するシランカップリング剤として、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン（信越化学工業社製；ＫＢＭ－６０２、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－２１２０、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ－９５、日美商事社製；サイラエースＳ３１０等が挙げられる）、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－６０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１１２０、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１１２２、東レ・ダウコーニング社製；Ｚ－６０２０、東レ・ダウコーニング社製；Ｚ－６０９４、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ－９１、日美商事社製；サイラエースＳ３２０等が挙げられる）、３－アミノプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－９０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン製；Ａ－１１１０、東レ・ダウコーニング株式会社製；Ｚ－６６１０、日美商事社製；サイラエースＳ３６０等が挙げられる）、３－アミノプロピルトリエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－９０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１１００、東レ・ダウコーニング社製；Ｚ－６０１１、日美商事社製；サイラエースＳ３３０等が挙げられる）、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン（・BR>S販品としては信越化学工業社製；ＫＢＥ－９１０３、日美商事社製のサイラエースＳ３４０等が挙げられる）、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－５７３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ｙ－９６６９、東レ・ダウコーニング社製；Ｚ－６８８３等が挙げられる）、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミン（市販品としては日美商事社製；サイラエースＸＳ１００３が挙げられる）、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩（市販品としては信越化学工業社製；ＫＢＭ－５７５、東レ・ダウコーニング社製；Ｚ－６０３２、日美商事社製；サイラエースＳ３５０等が挙げられる）等が挙げられ、イソシアヌレート基を有するシランカップリング剤として、トリス－（トリメトキシシリルプロピル）イソシアヌレート（市販品としては信越化学工業社製のＫＢＭ－９６５９が挙げられる）が挙げられ、メルカプト基を有するシランカップリング剤として、３－メルカプトプロピルメチルジメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－８０２、東レ・ダウコーニング社製；Ｚ－６８５２等が挙げられる）、３－メルカプトプロピルトリメトキシシラン（市販品としては信越化学工業社製；ＫＢＭ－８０３、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１８９、東レ・ダウコーニング社製；Ｚ－６０６２、日美商事社製；サイラエースＳ８１０等が挙げられる）、３－メルカプトプロピルトリエトキシシラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１８９１、東レ・ダウコーニング社製；Ｚ－６９１１が挙げられる）等が挙げられ、ウレイド基を有するシランカップリング剤として、３－ウレイドプロピルトリアルコキシシラン（市販品として信越化学工業社製；ＫＢＥ－５８５が挙げられ）、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１１６０が挙げられる）等が挙げられ、スルフィド基を有するシランカップリング剤として、ビス（トリエトキシシリルプロピル）テトラスルフィドが挙げられ、チオエステル基を有するシランカップリング剤として、３－オクタノイルチオ－１－プロピルトリエトキシシラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－ＬＩＮＫ５９９が挙げられる）が挙げられ、イソシアネート基を有するシランカップリング剤として、３－イソシアネートプロピルトリエトキシシラン（市販品としては信越化学工業社製；ＫＢＥ－９００７、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ａ－１３１０等が挙げられる）、３－イソシアネートプロピルトリメトキシシラン（市販品としてはモメンティブ・パフォーマンス・マテリアルズ・ジャパン社製；Ｙ－５１８７、旭化成ワッカーシリコーン社製；ＧＥＮＩＯＳＩＬ  ＧＦ４０等が挙げられる）等が挙げられる。 Silane coupling agents include, for example, vinyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-1003, Momentive Performance Materials Japan Co., Ltd.; A -171, Dow Corning Toray Co., Ltd.; Z-6300, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL XL10, Himi Shoji Co., Ltd.; KBE-1003, Momentive Performance Materials Japan; A-151, Dow Corning Toray; Z-6519, Asahi Kasei Wacker Silicone; GENIOSIL GF56, Himi Shoji; Sila Ace S220, etc. ), vinyltriacetoxysilane (commercially available from Asahi Kasei Wacker Silicone; GENIOSIL GF62), vinyltris(2-methoxyethoxy)silane (commercially available from Momentive Performance Materials Japan) A-172), vinylmethyldimethoxysilane (commercially available products include Momentive Performance Materials Japan; A-2171, Asahi Kasei Wacker Silicone; GENIOSIL XL12, etc.), octenyltri Methoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; includes KBM-1083), allyltrimethoxysilane (commercially available from Dow Corning Toray; includes Z-6825), p-styryltrimethoxysilane (Commercially available products include KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.). For example, silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-5103, etc.), and the like. and silane coupling agents having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-502, Toray Dow Corning Co., Ltd.; Z-6033, etc.). ), 3-methacryloxypropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-503, Momentive Performance Materials Japan Co., Ltd.; A-174, Dow Corning Toray Co., Ltd.; Z-6030 , Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF31, Himi Shoji Co., Ltd.; Sila Ace S710, etc.), 3-methacryloxypropylmethyldiethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBE-502. ), 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-503, Momentive Performance Materials Japan; Y-9936), methacryloxyoctyltrimethoxysilane (Shin-Etsu Chemical manufactured by KBM-5803) and the like, and as a silane coupling agent having an epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-303, manufactured by Momentive Performance Materials Japan; A-186, manufactured by Dow Corning Toray; Z-6043, manufactured by Himi Shoji; Sila Ace S530, etc.), 3-glycidoxypropyl Methyldimethoxysilane (commercially available products include KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd.; Z-6044 manufactured by Dow Corning Toray; Methoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-403, Momentive Performance Materials Japan Co., Ltd.; A-187, Dow Corning Toray Co., Ltd.; Z-6040, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF80, Sila Ace S510 manufactured by Himi Shoji Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane (commercially available is manufactured by Shin-Etsu Chemical Co., Ltd.; includes KBE-402), 3-glycidoxypropyltriethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBE-403, manufactured by Momentive Performance Materials Japan; A-1871, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF82, etc.), glycidoxyoctyltrimethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-4803 is included), etc., and amino groups. as a silane coupling agent having N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-602; Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-95, Himi Shoji Co.; Sila Ace S310, etc.), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (commercially available from Shin-Etsu Chemical KBM-603, Momentive Performance Materials Japan; A-1120, Momentive Performance Materials Japan; A-1122, Dow Corning Toray; Z-6020, Dow Toray Z-6094 manufactured by Corning Corporation; Z-6094 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-91 manufactured by Himi Shoji Co.; KBM-903, manufactured by Momentive Performance Materials Japan; A-1110, manufactured by Dow Corning Toray Co., Ltd.; Z-6610, manufactured by Himi Shoji Co., Ltd.; Ethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBE-903, Momentive Performance Materials Japan Co., Ltd.; A-1100, Dow Corning Toray Co., Ltd.; Z-6011, Himi Shoji Co., Ltd.; Sila Ace S330, etc.), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (・BR> S products manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-9103, manufactured by Himi Shoji Co., Ltd. Sila Ace S340, etc.), N-phenyl-3-aminopropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-573, Momentive Performance Y-9669 manufactured by Mance Materials Japan, Z-6883 manufactured by Dow Corning Toray Co., Ltd.), N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (commercially available is manufactured by Himi Shoji Co., Ltd.; includes Sila Ace XS1003), N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-575 , manufactured by Dow Corning Toray Co.; Z-6032, manufactured by Himi Shoji Co., Ltd.; Sila Ace S350, etc.), and as a silane coupling agent having an isocyanurate group, tris-(trimethoxysilylpropyl) isocyanate Nurate (commercially available products include KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.), and as a silane coupling agent having a mercapto group, 3-mercaptopropylmethyldimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd. KBM-802, manufactured by Dow Corning Toray; Z-6852, etc.), 3-mercaptopropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-803, Momentive Performance Materials Co., Ltd.; A-189 manufactured by Japan Co., Ltd.; Z-6062 manufactured by Dow Corning Toray; Sila Ace S810 manufactured by Himi Shoji Co., Ltd.; A-1891 manufactured by Dow Corning Toray Co., Ltd.; Z-6911 manufactured by Toray Dow Corning Co., Ltd.; Shin-Etsu Chemical Co., Ltd.; includes KBE-585), 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane (commercially available from Momentive Performance Materials Japan; A-1160). ) and the like, examples of the silane coupling agent having a sulfide group include bis(triethoxysilylpropyl) tetrasulfide, and examples of the silane coupling agent having a thioester group include 3-octanoylthio-1-propyltriethoxysilane (Commercially available products include A-LINK599 manufactured by Momentive Performance Materials Japan), and have an isocyanate group. As a silane coupling agent, 3-isocyanatopropyltriethoxysilane (commercially available products include KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., A-1310 manufactured by Momentive Performance Materials Japan, etc.), 3 -Isocyanatopropyltrimethoxysilane (commercially available products include Y-5187 manufactured by Momentive Performance Materials Japan, GENIOSIL GF40 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like.
（４）その他の添加剤
　本開示の樹脂組成物には、本発明の目的を損なわない範囲で、その他の添加剤、例えばカーボンブラック、チタンブラック、イオントラップ剤、レベリング剤、酸化防止剤、消泡剤、揺変剤、粘度調整剤、難燃剤、着色剤、溶剤等を添加することができる。各添加剤の種類、添加量は常法通りである。 (4) Other Additives The resin composition of the present disclosure may contain other additives such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, digestive agents, etc., within a range that does not impair the object of the present invention. Foaming agents, thixotropic agents, viscosity modifiers, flame retardants, coloring agents, solvents and the like can be added. The type and amount of each additive are as per conventional methods.
＝＝樹脂組成物の利用方法＝＝
　本明細書に開示の樹脂組成物は、例えば、電子部品用の封止材や充填材、ダム材、導電性あるいは絶縁性の接着剤、ダイアタッチ材、フィルム、コート剤、シールド材などに利用できる。他にも塗料、パイプ用材、タンク用材などの複合材料、床材、メンブレンなどの土木建築材料、接着剤、などに用いることができるが、利用方法はこれらに限定されない。 == How to use the resin composition ==
The resin composition disclosed herein can be used, for example, as sealing materials and fillers for electronic components, dam materials, conductive or insulating adhesives, die attach materials, films, coating agents, shielding materials, and the like. can. In addition, it can be used for paints, composite materials such as pipe materials and tank materials, floor materials, civil engineering and construction materials such as membranes, adhesives, and the like, but the usage is not limited to these.
＝＝化合物の合成方法＝＝
（化合物１）2-[2-hydroxy-3-(2-methyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dioneの合成
Figure JPOXMLDOC01-appb-C000007
 　ＤＭＡ（ジメチルアセトアミド）（２００ｇ）とマグネチックスターラーの入っている反応容器に、キュアゾール２ＭＺ－Ｈ（四国化成工業社製、３９．９ｇ、０．４８６ｍｏｌ）を撹拌しながら加え、６０℃に加熱して溶解させた。得られた溶液にデナコールＥＸ－７３１（ナガセケムテックス社製、１００ｇ、０．３６３ｍｍｏｌ）を約１０分間かけて少しずつ加えた。全て溶解後、７０℃まで加熱し、同じ温度で６時間撹拌した。常温まで冷却後、水（約２００ｍＬ）を加えて撹拌し、結晶を析出させた。生じた固体を吸引ろ過し、水で２回、ＩＰＡで２回、洗浄した後、乾燥させ、化合物１（８５．７ｇ）（回収率６１％）を得た。生成物の物性測定値は以下の通りである。 ==Method for Synthesizing Compounds==
(Compound 1) Synthesis of 2-[2-hydroxy-3-(2-methyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione
Figure JPOXMLDOC01-appb-C000007
 Curesol 2MZ-H (manufactured by Shikoku Kasei Kogyo Co., Ltd., 39.9 g, 0.486 mol) was added with stirring to a reaction vessel containing DMA (dimethylacetamide) (200 g) and a magnetic stirrer, and heated to 60°C. to dissolve. Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 100 g, 0.363 mmol) was gradually added to the resulting solution over about 10 minutes. After dissolving everything, the mixture was heated to 70° C. and stirred at the same temperature for 6 hours. After cooling to room temperature, water (about 200 mL) was added and stirred to precipitate crystals. The resulting solid was suction filtered, washed twice with water and twice with IPA, and then dried to obtain compound 1 (85.7 g) (61% recovery). The measured physical properties of the product are as follows.
1H NMR(DMSO-d6): 7.89-7.78ppm (m, 4H), 7.05ppm (s, 1H), 6.67ppm (s, 1), 5.37ppm (d, 4.8Hz, 1H), 4.08-3.95ppm (m, 2H), 3.83 (dd, 8.6Hz, 15Hz, 1H), 3.62ppm (dd, 7.6Hz, 13.6Hz, 1H),  3.57ppm (dd, 4.8Hz, 13.6Hz, 1H), 2.26ppm (s, 3H) 1 H NMR(DMSO-d6): 7.89-7.78ppm (m, 4H), 7.05ppm (s, 1H), 6.67ppm (s, 1), 5.37ppm (d, 4.8Hz, 1H), 4.08-3.95ppm (m, 2H), 3.83 (dd, 8.6Hz, 15Hz, 1H), 3.62ppm (dd, 7.6Hz, 13.6Hz, 1H), 3.57ppm (dd, 4.8Hz, 13.6Hz, 1H), 2.26ppm (s , 3H)
（化合物２）2-[2-hydroxy-3-(1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione（ＣＡＳ登録番号：１１２０８６－６１－０）の合成
Figure JPOXMLDOC01-appb-C000008
 　ＤＭＡ（１０ｍＬ）の入っている反応容器に、キュアゾールＳＩＺ（四国化成工業社製、１．６５ｇ、２４．３ｍｍｏｌ）をスターラーで撹拌しながら加え、６０℃に加熱して溶解させた。得られた溶液にデナコールＥＸ－７３１（ナガセケムテックス社製、５．００ｇ、２３．１ｍｍｏｌ）を５分間かけて少しずつ加えた。全て溶解後、７０℃まで加熱し、同じ温度で６時間撹拌した。常温まで冷却後、水（約１５ｍＬ）を加え１５℃にて撹拌し、結晶を析出させた。生じた固体を吸引ろ過して水で洗浄した後、乾燥させ、固体として化合物２（３．６９ｇ）を得た。生成物の物性測定値は以下の通りである。 (Compound 2) Synthesis of 2-[2-hydroxy-3-(1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione (CAS Registry Number: 112086-61-0)
Figure JPOXMLDOC01-appb-C000008
 Curesol SIZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., 1.65 g, 24.3 mmol) was added to a reaction vessel containing DMA (10 mL) while stirring with a stirrer, and dissolved by heating to 60°C. Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was gradually added to the obtained solution over 5 minutes. After dissolving everything, the mixture was heated to 70° C. and stirred at the same temperature for 6 hours. After cooling to room temperature, water (about 15 mL) was added and the mixture was stirred at 15°C to precipitate crystals. The resulting solid was filtered by suction, washed with water, and dried to obtain compound 2 (3.69 g) as a solid. The measured physical properties of the product are as follows.
1H NMR (400 MHz DMSO-d6): 7.93-7.77ppm (m, 4H), 7.58ppm (s, 1H), 7.16ppm (s, 1H), 6.84ppm (s, 1H), 5.41ppm (d, 5.6 Hz), 4.11ppm (dd, 3.2Hz, 13.6Hz, 1H), 4.04-3.94ppm (m, 1H), 3.89ppm (dd, 7.2Hz, 14Hz, 1H), 3.60-3.47ppm (m, 2H) 1 H NMR (400 MHz DMSO-d6): 7.93-7.77ppm (m, 4H), 7.58ppm (s, 1H), 7.16ppm (s, 1H), 6.84ppm (s, 1H), 5.41ppm (d, 5.6Hz), 4.11ppm (dd, 3.2Hz, 13.6Hz, 1H), 4.04-3.94ppm (m, 1H), 3.89ppm (dd, 7.2Hz, 14Hz, 1H), 3.60-3.47ppm (m, 2H)
（化合物３）2-[2-hydroxy-3-(2-phenyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dioneの合成
Figure JPOXMLDOC01-appb-C000009
 　ＤＭＡ（１０ｍＬ）の入っている反応容器に、キュアゾール２ＰＺ－ＰＷ（四国化成工業社製、３．５０ｇ、２４．３ｍｍｏｌ）をスターラーで撹拌しながら加え、６０℃に加熱して溶解させた。得られた溶液にデナコールＥＸ－７３１（ナガセケムテックス社製、５．００ｇ、２３．１ｍｍｏｌ）を５分間かけて少しずつ加えた。全て溶解後、７０℃まで加熱し、同じ温度で２３時間撹拌した。常温まで冷却した後、水（約１５ｍＬ）を加えて１５℃で撹拌し、結晶を析出させた。生じた固体を吸引ろ過して水で洗浄後、乾燥させ、粗結晶４．０４ｇを得た。 (Compound 3) Synthesis of 2-[2-hydroxy-3-(2-phenyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione
Figure JPOXMLDOC01-appb-C000009
 Curesol 2PZ-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 3.50 g, 24.3 mmol) was added to a reaction vessel containing DMA (10 mL) while stirring with a stirrer, and heated to 60° C. to dissolve. Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was gradually added to the obtained solution over 5 minutes. After all was dissolved, the mixture was heated to 70° C. and stirred at the same temperature for 23 hours. After cooling to room temperature, water (about 15 mL) was added and the mixture was stirred at 15°C to precipitate crystals. The resulting solid was filtered by suction, washed with water, and dried to obtain 4.04 g of crude crystals.
　粗結晶３．００ｇに０．５Ｎ塩酸１．７ｍＬを加え、乳鉢ですり潰し、得られた粉体に水を加えて懸濁させた。得られた懸濁液を吸引ろ過し、固体をクロロホルム（約５０ｍＬ）に溶解させて分液ロートに移し、得られた溶液を、水－飽和重曹水－食塩水で、この順に洗浄した。クロロホルム層を硫酸ナトリウムで脱水したのち、液相分離ろ紙でろ過し、有機層をロータリーエバポレーターで濃縮した。得られたオレンジ色の油状物に酢酸エチルおよびヘキサンを加えて結晶化させ、結晶を吸引ろ過した後、減圧乾燥することで、固体として化合物３（１．３３ｇ）を得た。生成物の物性測定値は以下の通りである。 1.7 mL of 0.5N hydrochloric acid was added to 3.00 g of the crude crystals and ground in a mortar, and water was added to the resulting powder to suspend it. The resulting suspension was suction filtered, the solid was dissolved in chloroform (about 50 mL) and transferred to a separating funnel, and the resulting solution was washed with water-saturated sodium bicarbonate solution-brine in this order. After the chloroform layer was dehydrated with sodium sulfate, it was filtered through liquid phase separation filter paper, and the organic layer was concentrated with a rotary evaporator. Ethyl acetate and hexane were added to the resulting orange oil to crystallize, and the crystals were suction-filtered and dried under reduced pressure to obtain compound 3 (1.33 g) as a solid. The measured physical properties of the product are as follows.
1H NMR (400 MHz DMSO-d6) : 7.90-7.79ppm (m, 4H), 7.63-7.54ppm (m, 2H), 7.39-7.26 (m, 4H), 6.97ppm (s, 1H), 5.54ppm (d, 5.6Hz, 1H), 4.17-3.92ppm (m, 3H), 3.57ppm (dd, 6.8Hz, 13.6Hz, 1H), 3.45ppm (dd, 5.6Hz, 13.6Hz, 1H) 1 H NMR (400 MHz DMSO-d6) : 7.90-7.79ppm (m, 4H), 7.63-7.54ppm (m, 2H), 7.39-7.26 (m, 4H), 6.97ppm (s, 1H), 5.54ppm (d, 5.6Hz, 1H), 4.17-3.92ppm (m, 3H), 3.57ppm (dd, 6.8Hz, 13.6Hz, 1H), 3.45ppm (dd, 5.6Hz, 13.6Hz, 1H)
（化合物４）2-[2-hydroxy-3-(2-undecyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dioneの合成
Figure JPOXMLDOC01-appb-C000010
 　ＤＭＡ（１５ｍＬ）の入っている反応容器に、キュアゾールＣ１１Ｚ（四国化成工業社製、５．１４ｇ、２４．３ｍｍｏｌ）をスターラーで撹拌しながら加え、６０℃に加熱して溶解させた。得られた溶解液にデナコールＥＸ－７３１（ナガセケムテックス社製、５．００ｇ、２３．１ｍｍｏｌ）を５分間かけて少しずつ加えた。全てが溶解した後、７０℃まで加熱し、同じ温度で２３時間撹拌した。常温まで冷却後、水（約２０ｍＬ）を加えて１５℃で撹拌し、結晶を析出させた。得られた結晶を吸引ろ過し、水で洗浄後、乾燥させ粗結晶５．７０ｇを得た。 (Compound 4) Synthesis of 2-[2-hydroxy-3-(2-undecyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione
Figure JPOXMLDOC01-appb-C000010
 Curesol C11Z (manufactured by Shikoku Kasei Kogyo Co., Ltd., 5.14 g, 24.3 mmol) was added to a reaction vessel containing DMA (15 mL) while stirring with a stirrer, and heated to 60° C. to dissolve. Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was added little by little to the resulting solution over 5 minutes. After everything was dissolved, it was heated to 70° C. and stirred at the same temperature for 23 hours. After cooling to room temperature, water (approximately 20 mL) was added and the mixture was stirred at 15°C to precipitate crystals. The obtained crystals were suction-filtered, washed with water, and dried to obtain 5.70 g of crude crystals.
　粗結晶３．００ｇに１Ｎ塩酸１．８ｍＬを加え、乳鉢ですり潰し、得られた粉体に水を加えて懸濁させた。得られた懸濁液を吸引ろ過し、固体をクロロホルム（約５０ｍＬ）に溶解させて分液ロートに移し、得られた溶液を、水－飽和重曹水－食塩水で、この順に洗浄した。クロロホルム層を硫酸マグネシウムで脱水したのち、液相分離ろ紙でろ過し、有機層をロータリーエバポレーターで濃縮した。得られた白色固体に酢酸エチルおよびヘキサンを加えて懸濁させたのち、懸濁液を吸引ろ過し、得られた結晶減圧乾燥することで、化合物４（１．９７ｇ）を得た。生成物の物性測定値は以下の通りである。 1.8 mL of 1N hydrochloric acid was added to 3.00 g of crude crystals and ground in a mortar, and water was added to the resulting powder to suspend it. The resulting suspension was suction filtered, the solid was dissolved in chloroform (about 50 mL) and transferred to a separating funnel, and the resulting solution was washed with water-saturated sodium bicarbonate solution-brine in this order. After the chloroform layer was dehydrated with magnesium sulfate, it was filtered through liquid phase separation filter paper, and the organic layer was concentrated with a rotary evaporator. Ethyl acetate and hexane were added to the resulting white solid to suspend it, and the suspension was suction-filtered, and the obtained crystals were dried under reduced pressure to obtain Compound 4 (1.97 g). The measured physical properties of the product are as follows.
1H NMR (400 MHz DMSO-d6): 7.91-7.81ppm (m, 4H), 7.04ppm (s, 1H), 6.70ppm (s, 1H), 5.37ppm (d, 5.6Hz, 1H), 4.05-3.93ppm (m, 2H),  3.82ppm (dd, 8.8Hz, 15.2Hz, 1H), 3.63ppm (dd, 7.8Hz, 14Hz, 1H), 3.53ppm (dd, 4.8Hz, 14Hz) 1 H NMR (400 MHz DMSO-d6): 7.91-7.81ppm (m, 4H), 7.04ppm (s, 1H), 6.70ppm (s, 1H), 5.37ppm (d, 5.6Hz, 1H), 4.05- 3.93ppm (m, 2H), 3.82ppm (dd, 8.8Hz, 15.2Hz, 1H), 3.63ppm (dd, 7.8Hz, 14Hz, 1H), 3.53ppm (dd, 4.8Hz, 14Hz)
（化合物５）2-[2-(2-methyl-1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione
　化合物５（ＣＡＳ登録番号：８５８５１２－７６－２）は市販品（FCH Group社より購入）を用いた。 (Compound 5) 2-[2-(2-methyl-1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione
Compound 5 (CAS registration number: 858512-76-2) was a commercially available product (purchased from FCH Group).
（化合物６）2-[2-(1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione
　化合物６（ＣＡＳ登録番号：７２４５９－５３－１）は市販品（Enamine社より購入）を用いた。 (Compound 6) 2-[2-(1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione
Compound 6 (CAS registration number: 72459-53-1) was a commercially available product (purchased from Enamine).
（化合物７）1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-olの合成
Figure JPOXMLDOC01-appb-C000011
 (Compound 7) Synthesis of 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol
Figure JPOXMLDOC01-appb-C000011
　２－Ｍｅｔｈｙｌ－１Ｈ－ｉｍｉｄａｚｏｌｅ（四国化成工業社製、２１．８ｇ、２６６ｍｍｏｌ）をトルエン（７８．７ｍL）とメタノール（１７．７ｍL）の混合溶媒に溶解させ、８０℃に昇温し、デナコールＥＸ－１４１（ナガセケムテックス社製、２２．０ｇ、１４７ｍｍｏｌ）のトルエン（３８．１ｍL）溶液を１時間かけて滴下し、その後、同温度で１時間攪拌した。得られた溶液を室温まで冷却し、減圧下で溶媒を留去し、１－（２－ｍｅｔｈｙｌ－１Ｈ－ｉｍｉｄａｚｏｌｅ－１－ｙｌ）－３－ｐｈｅｎｏｘｙｐｒｏｐａｎ－２－ｏｌ（４７．８５ｇ）を黄色固体として得た。生成物の同定は1HNMRより行い、目的物が得られていることを確認した。 2-Methyl-1H-imidazole (manufactured by Shikoku Kasei Co., Ltd., 21.8 g, 266 mmol) was dissolved in a mixed solvent of toluene (78.7 mL) and methanol (17.7 mL), heated to 80° C., and Denacol EX was prepared. A toluene (38.1 mL) solution of -141 (manufactured by Nagase ChemteX Corporation, 22.0 g, 147 mmol) was added dropwise over 1 hour, followed by stirring at the same temperature for 1 hour. The resulting solution was cooled to room temperature, the solvent was removed under reduced pressure, and 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol (47.85 g) was obtained as a yellow solid. obtained as The product was identified by 1 HNMR, and it was confirmed that the desired product was obtained.
（化合物８）２ＭＺ－Ｈ
　化合物８は市販品（四国化成工業社より購入）を用いた。 (Compound 8) 2MZ-H
A commercially available product (purchased from Shikoku Kasei Co., Ltd.) was used as compound 8.
＝＝化合物の評価方法＝＝
＜融点の測定＞
　示差走査熱量測定装置（ＤＳＣ　２０４　Ｆ１　Ｐｈｏｅｎｉｘ（登録商標））（ＮＥＴＺＳＣＨ社製）を用いて融点を測定した。まず、アルミパンに合成した化合物５ｍｇを計量し、アルミ製の蓋でシーリングした後、その蓋の中心に針で穴を開けて測定サンプルを準備した。次に、この測定サンプルを窒素雰囲気下（１００ｍＬ／分）、２５～２５０℃の範囲で、速度１０℃／分の条件で昇温しながら熱流（ｍＷ／ｍｇ）を測定した。融点に相当し、グラフ上でピークが得られる温度を解析ソフト（ＮＥＴＺＳＣＨ　Ｐｒｏｔｅｕｓ－Ｔｈｅｒｍａｌ　Ａｎａｌｙｓｉｓ　バージョン８．０．２）で算出した。 == Method for evaluating compounds ==
<Measurement of melting point>
The melting point was measured using a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH). First, 5 mg of the synthesized compound was weighed in an aluminum pan, sealed with an aluminum lid, and a hole was made in the center of the lid with a needle to prepare a measurement sample. Next, the heat flow (mW/mg) was measured while raising the temperature of this measurement sample in a nitrogen atmosphere (100 mL/min) in the range of 25 to 250° C. at a rate of 10° C./min. The temperature corresponding to the melting point and at which a peak is obtained on the graph was calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 8.0.2).
　化合物の評価結果を表１に示す。
Figure JPOXMLDOC01-appb-T000012
 Table 1 shows the evaluation results of the compounds.
Figure JPOXMLDOC01-appb-T000012
＝＝樹脂組成物の作製方法＝＝ == Method for preparing resin composition ==
＜実施例１～４、６、比較例１、２：エポキシ－チオール硬化系＞
　硬化触媒としての化合物１～４、７、８をエポキシ樹脂であるＥＸＡ８３５ＬＶ（ＤＩＣ社製）に投入して混合した。その後、乳鉢で凝集が無くなるまですり潰し、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。そこへ、ＥＸＡ８３５ＬＶ、またはＥＸＡ８３５ＬＶとＣＤＭＤＧ（昭和電工社製）の混合物を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。さらに、チオール樹脂であるＰＥＭＰ（ＳＣ有機化学社製）を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行い、樹脂組成物を得た。 <Examples 1 to 4, 6, Comparative Examples 1, 2: Epoxy-thiol curing system>
Compounds 1 to 4, 7, and 8 as curing catalysts were put into EXA835LV (manufactured by DIC), which is an epoxy resin, and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. Then, EXA835LV or a mixture of EXA835LV and CDMDG (manufactured by Showa Denko KK) was added and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device. Furthermore, PEMP (manufactured by SC Organic Chemical Co., Ltd.), which is a thiol resin, was added and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
＜実施例５：エポキシ－チオール硬化系＞
　ＥＸＡ８３５ＬＶとＴＳ７２０（キャボット・スペシャルティー・ケミカルズ社製）を３本ロールミルで分散した混合物へ硬化触媒としての化合物１を投入して混合した。その後、乳鉢で凝集が無くなるまですり潰し、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。そこへ、チオール樹脂であるＣ３ＴＳＧ（四国化成工業社製）を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行い、樹脂組成物を得た。 <Example 5: Epoxy-thiol curing system>
Compound 1 as a curing catalyst was added to a mixture obtained by dispersing EXA835LV and TS720 (manufactured by Cabot Specialty Chemicals) using a three-roll mill and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. C3TSG (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a thiol resin, was added thereto and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
＜実施例７、１１、１２：エポキシホモ重合硬化系＞
　硬化触媒としての化合物１、化合物５、および化合物６をＥＸＡ８３５ＬＶに投入して混合した。その後、乳鉢で凝集が無くなるまですり潰し、遊星式撹拌脱泡装置を用いて、真空下にて撹拌及び脱泡を行い、樹脂組成物を得た。 <Examples 7, 11, 12: Epoxy homopolymerization curing system>
Compound 1, compound 5, and compound 6 as curing catalysts were put into EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain a resin composition.
＜実施例８：エポキシ－酸無水物硬化系＞
　硬化触媒としての化合物１をエポキシ樹脂であるＥＸＡ８３５ＬＶに投入して混合した。その後、乳鉢で凝集が無くなるまですり潰し、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。そこへ、ＹＤＦ８１７０（新日鐵住金化学社製）を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。さらにそこへ酸無水物樹脂であるＹＨ３０６（三菱ケミカル社製）を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行い、樹脂組成物を得た。 <Example 8: Epoxy-acid anhydride curing system>
Compound 1 as a curing catalyst was put into EXA835LV, which is an epoxy resin, and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. Then, YDF8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device. Furthermore, YH306 (manufactured by Mitsubishi Chemical Co., Ltd.), which is an acid anhydride resin, was added thereto and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
＜実施例９：エポキシ－フェノール硬化系＞
　硬化触媒としての化合物１をＥＸＡ８３５ＬＶに投入して混合した。その後、乳鉢で凝集が無くなるまですり潰し、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。そこへ、ＥＸＡ８３５ＬＶを投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行った。さらにそこへフェノール樹脂であるＭＥＨ８００５（明和化成社製）を投入して混合した。その後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行い、樹脂組成物を得た。 <Example 9: Epoxy-phenol curing system>
Compound 1 as a curing catalyst was added to EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. EXA835LV was put in there and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device. Furthermore, MEH8005 (manufactured by Meiwa Kasei Co., Ltd.), which is a phenolic resin, was added and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
＜実施例１０：アクリル－チオール硬化系＞
　アクリル樹脂であるＭ７１００（東亞合成社製）、光ラジカル発生剤であるＯＭＮＩＲＡＤ１８４（ＩＧＭ　ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、重合禁止剤としてＱ－１３０１（富士フィルム和光純薬社製）、搖変剤としてＴＳ７２０を３本ロールミルで分散させ、得られた混合物に、硬化触媒としての化合物１を投入し、さらに３本ロールミルで分散させた。そこへ、ＰＥＭＰを投入して混合した後、遊星式攪拌脱泡装置を用いて、真空下にて攪拌及び脱泡を行い、樹脂組成物を得た。 <Example 10: Acrylic-thiol curing system>
M7100 (manufactured by Toagosei Co., Ltd.) as an acrylic resin, OMNIRAD184 (manufactured by IGM resins B.V.) as a photoradical generator, Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, and a stabilizing agent. TS720 was dispersed with a three-roll mill as a component, and compound 1 as a curing catalyst was added to the resulting mixture and further dispersed with a three-roll mill. After PEMP was added thereto and mixed, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device to obtain a resin composition.
＝＝樹脂組成物の評価方法＝＝
＜ポットライフの測定＞
　樹脂組成物の初期粘度を、Ｅ型粘度計（ＴＶＥ‐２５Ｈ：東機産業社製、ロータ名称：３°×Ｒ９．７）を用いて、５０ｒｐｍ、２５℃で、予め設定された適切なレンジ（Ｈ、Ｒ、またはＵ）で測定した。次に、２５℃、湿度５０％の環境下にて、密閉容器に保存した樹脂組成物を４時間放置し、ポットライフとして４時間以内に硬化しなかったものを○、硬化したものを×とした。その後、４時間ごとに、その樹脂組成物の粘度を、Ｅ型粘度計（ＴＶＥ‐２５Ｈ：東機産業社製、ロータ名称：３°×Ｒ９．７）を用いて、５０ｒｐｍ、２５℃で、予め設定された適切なレンジ（Ｈ、Ｒ、またはＵ）で測定した。そして、（各時間における放置した後の粘度）／（初期粘度）を算出して各時間における放置後の増粘倍率とした。 == Evaluation method of resin composition ==
<Measurement of pot life>
The initial viscosity of the resin composition is measured using an E-type viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3 ° × R9.7) at 50 rpm, 25 ° C., an appropriate range set in advance Measured in (H, R, or U). Next, the resin composition stored in a sealed container was left for 4 hours in an environment of 25 ° C. and 50% humidity. did. After that, every 4 hours, the viscosity of the resin composition was measured using an E-type viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3 ° × R9.7) at 50 rpm and 25 ° C. Measurements were taken in the appropriate preset range (H, R, or U). Then, (viscosity after standing for each time)/(initial viscosity) was calculated as the thickening ratio after standing for each time.
＜ゲルタイムの測定＞
　ゲル化する前の時間（ゲルタイムを称する）を、ゲル化試験機（ＧＴ－Ｄ－１５Ａ：ユーカリ技研社製）を用いて測定した。ホットプレートを１００℃、１２０℃、または１５０℃に設定し、試験棒にて樹脂組成物をホットプレート上に転写した。試験棒で樹脂組成物に触れて、糸引きする状態になるまでの時間をゲルタイムとした。 <Measurement of gel time>
The time before gelation (referred to as gel time) was measured using a gelation tester (GT-D-15A: manufactured by Eucalyptus Giken Co., Ltd.). A hot plate was set to 100° C., 120° C., or 150° C., and the resin composition was transferred onto the hot plate using a test rod. The gel time was defined as the time from touching the resin composition with a test rod until it became stringy.
＝＝結果＝＝
　以上の樹脂組成物の各構成成分の分量と評価結果を表２～３にまとめた。 == Results ==
Tables 2 and 3 summarize the amount of each constituent component of the above resin composition and the evaluation results.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　実施例で用いた硬化触媒の融点は、比較例１の硬化触媒より高かった。比較例２は高融点ではあるが、分子量が小さいため、エポキシ樹脂などに溶解しやすく安定性に欠ける。
　樹脂組成物のポットライフの比較より、比較例では４時間ですでに硬化していたのに対し、実施例では、増粘率が２倍になるのがすべて８時間以上であった。 The melting point of the curing catalyst used in Examples was higher than that of Comparative Example 1. Although Comparative Example 2 has a high melting point, it has a low molecular weight, so it is easily dissolved in epoxy resins and the like, and lacks stability.
A comparison of the pot life of the resin composition revealed that the comparative examples were already cured in 4 hours, whereas the viscosity increase rate doubled in all the examples in 8 hours or longer.
　実施例における樹脂組成物は、１０分以内にゲル化し、十分な反応性および硬化性があった。 The resin composition in the example gelled within 10 minutes and had sufficient reactivity and curability.
　このように、本開示の硬化触媒は、フタルイミド骨格を有することにより、結晶性が高く、従来のエポキシ樹脂とイミダゾール誘導体を付加させたアダクト体よりも高融点であり、また本開示の硬化触媒によって、安定で、意図しない温度における硬化触媒の樹脂への溶解が起こりにくい樹脂組成物が得られる。  Thus, the curing catalyst of the present disclosure has a phthalimide skeleton, so it has high crystallinity and a higher melting point than the conventional adducts obtained by adding an epoxy resin and an imidazole derivative. , a stable resin composition is obtained in which the curing catalyst is less likely to dissolve in the resin at unintended temperatures. 

Claims (12)

  1. 　下記構造式（Ｉ）の化合物を有する、硬化触媒。
    Figure JPOXMLDOC01-appb-C000001
     （式中、
    　Ｒ１は、水素、フェニルおよびＣ１～Ｃ１７のアルキルから選択される基であり、
    　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
    　Ｒ４は、水素、ＯＨおよびＯＡｃから選択される基であり、
    　ｎとｍは整数であり、その和が１以上１２以下である。）     A curing catalyst having a compound of the following structural formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula,
    R 1 is a group selected from hydrogen, phenyl and C1-C17 alkyl;
    R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
    R4 is a group selected from hydrogen, OH and OAc;
    n and m are integers, the sum of which is 1 or more and 12 or less. )
  2. 　ｎとｍの和が３以下である、請求項１に記載の硬化触媒。 The curing catalyst according to claim 1, wherein the sum of n and m is 3 or less.
  3. 　請求項１または２に記載の硬化触媒と熱硬化性樹脂とを含有する樹脂組成物。 A resin composition containing the curing catalyst according to claim 1 or 2 and a thermosetting resin.
  4. 　前記熱硬化性樹脂がエポキシ樹脂である、請求項３記載の樹脂組成物。 The resin composition according to claim 3, wherein the thermosetting resin is an epoxy resin.
  5. 　前記熱硬化性樹脂が重合性二重結合を有する化合物である、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the thermosetting resin is a compound having a polymerizable double bond.
  6. 　前記熱硬化性樹脂の硬化剤をさらに含む、請求項４または５に記載の樹脂組成物。 The resin composition according to claim 4 or 5, further comprising a curing agent for said thermosetting resin.
  7. 　前記硬化剤が、酸素含有化合物、窒素含有化合物、およびチオール化合物からなる群から選択される１つである請求項４～６のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 4 to 6, wherein the curing agent is one selected from the group consisting of oxygen-containing compounds, nitrogen-containing compounds and thiol compounds.
  8. 　請求項３～７のいずれか１項に記載の樹脂組成物を含有する封止材。 A sealing material containing the resin composition according to any one of claims 3 to 7.
  9. 　請求項３～７のいずれか１項に記載の樹脂組成物を含有する接着剤。 An adhesive containing the resin composition according to any one of claims 3 to 7.
  10. 　請求項３～７のいずれか１項に記載の樹脂組成物の硬化物。 A cured product of the resin composition according to any one of claims 3 to 7.
  11. 　下記構造式（Ｉ）の化合物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、
    　Ｒ１は、フェニルおよびＣ１～Ｃ１７のアルキルから選択される基であり、
    　Ｒ２、Ｒ３、Ｒ５は、それぞれ独立して、水素およびＣ１～Ｃ６のアルキルから選択される基であり、
    　Ｒ４は、ＯＨおよびＯＡｃから選択される基であり、
    　ｎとｍは整数であり、その和が１以上１２以下である。）     A compound of the following structural formula (I).
    Figure JPOXMLDOC01-appb-C000002
     (In the formula,
    R 1 is a group selected from phenyl and C1-C17 alkyl;
    R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl;
    R4 is a group selected from OH and OAc;
    n and m are integers, the sum of which is 1 or more and 12 or less. )
  12. 　請求項１１に記載の化合物であって、式中、
    　Ｒ１は、フェニルおよびＣ１～Ｃ１０のアルキルから選択される基であり、
    　Ｒ２、Ｒ３、Ｒ５は、水素であり、
    　Ｒ４は、ＯＨであり、
    　ｎとｍは１である化合物。      12. A compound of claim 11, wherein
    R 1 is a group selected from phenyl and C1-C10 alkyl;
    R 2 , R 3 , R 5 are hydrogen,
    R4 is OH;
    a compound in which n and m are 1;
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58172392A (en) * 1982-04-02 1983-10-11 Hidetoshi Tsuchida Imidazole-coordinated hem complex included in cyclodextrin and gas-absorbing and desorbing agent
WO1988008840A1 (en) * 1987-05-04 1988-11-17 Centre National De La Recherche Scientifique (Cnrs Anti-tumoral targetting agents, preparation thereof and applications
WO2007071028A1 (en) * 2005-12-23 2007-06-28 St. Mary's University Compounds, complexes and uses thereof
JP2010524895A (en) * 2007-04-18 2010-07-22 プロビオドルグ エージー Cyanoguanidine derivatives as glutaminyl cyclase inhibitors
CN104876936A (en) * 2015-05-25 2015-09-02 中国人民解放军第二军医大学 Preparation of 2-hydroxy-1, 2-di-2-pyridylethanone and pyrazole class compound and application as medicine
CN106749407A (en) * 2017-01-06 2017-05-31 中国工程物理研究院核物理与化学研究所 A kind of phosphoramidic acid base functionalized ion liquid and its production and use
WO2019238786A1 (en) * 2018-06-12 2019-12-19 Ryvu Therapeutics S.A. Modulators of stimulator of interferon genes (sting)

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58172392A (en) * 1982-04-02 1983-10-11 Hidetoshi Tsuchida Imidazole-coordinated hem complex included in cyclodextrin and gas-absorbing and desorbing agent
WO1988008840A1 (en) * 1987-05-04 1988-11-17 Centre National De La Recherche Scientifique (Cnrs Anti-tumoral targetting agents, preparation thereof and applications
WO2007071028A1 (en) * 2005-12-23 2007-06-28 St. Mary's University Compounds, complexes and uses thereof
JP2010524895A (en) * 2007-04-18 2010-07-22 プロビオドルグ エージー Cyanoguanidine derivatives as glutaminyl cyclase inhibitors
CN104876936A (en) * 2015-05-25 2015-09-02 中国人民解放军第二军医大学 Preparation of 2-hydroxy-1, 2-di-2-pyridylethanone and pyrazole class compound and application as medicine
CN106749407A (en) * 2017-01-06 2017-05-31 中国工程物理研究院核物理与化学研究所 A kind of phosphoramidic acid base functionalized ion liquid and its production and use
WO2019238786A1 (en) * 2018-06-12 2019-12-19 Ryvu Therapeutics S.A. Modulators of stimulator of interferon genes (sting)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VINCENT GAUCHOT; MATHIEU BRANCA; ANDREEA SCHMITZER: "Encapsulation of a Catalytic Imidazolium Salt into Avidin: Towards the Development of a Biohybrid Catalyst Active in Ionic Liquids", CHEMISTRY - A EUROPEAN JOURNAL, JOHN WILEY & SONS, INC, DE, vol. 20, no. 6, 2 January 2014 (2014-01-02), DE, pages 1530 - 1538, XP071840907, ISSN: 0947-6539, DOI: 10.1002/chem.201303865 *

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