Curing catalysts, resin compositions, sealing materials, adhesives, and cured products

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

[Technical Field]

[0001] The present invention relates to a curing catalyst, a resin composition, a sealant, an adhesive, and a cured product. [Background technology]

[0002] One-component adhesives contain a base agent and a curing catalyst, or a base agent, a curing agent, and a curing catalyst. The curing catalyst is thought to have the greatest impact on the adhesive's usable life and curing conditions.

[0003] Currently, there are many types of curing catalysts commercially available for use in one-component adhesives, but the most common are types in which thermosetting resins or thermoplastic resins are modified with functional groups such as amines (Japanese Patent Laid-Open Nos. 59-053526 and 3-177418), shell types in which an amine-based curing catalyst is covered with a polymer shell (Japanese Patent Laid-Open No. 2000-080146), and types that are simply adducts of epoxy resin and imidazole (Japanese Patent Laid-Open No. 60-004524). Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a novel curing catalyst, a resin composition, a sealant, an adhesive, and a cured product. [Means for solving the problem]

[0005] One embodiment of the present invention is a curing catalyst having a compound of the following structural formula (I): [ka] (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, R 4is a group selected from hydrogen, OH, and OAc (Ac: an abbreviation for acetyl group), and n and m are integers, the sum of which is 1 to 12 or 1 to 3.

[0006] Another embodiment of the present invention is a resin composition containing any one of the curing catalysts described above and a thermosetting resin. The thermosetting resin may be an epoxy resin. The thermosetting resin may be a compound having a polymerizable double bond. The composition may further contain a curing agent for the thermosetting resin. The curing agent may be one selected from the group consisting of an oxygen-containing compound, a nitrogen-containing compound, and a thiol compound.

[0007] A further embodiment of the present invention is a sealant, adhesive, or cured product containing any of the above resin compositions.

[0008] A further embodiment of the present invention is a compound of structural formula (I): [ka] (In the formula, R 1 is a group selected from phenyl and C1 to C17 alkyl, R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl, R 4 is a group selected from OH and OAc, n and m are integers whose sum is between 1 and 12.) In the above formula, R 1 is a group selected from phenyl and C1-C10 alkyl, R 2 , R 3 , R 5 is hydrogen, R 4 is OH, n and m may be 1.

[0009] ==Cross-reference to related literature== This application claims priority based on Japanese Patent Application No. 2021-058849, filed on March 30, 2021, and the basic application is incorporated herein by reference. [Effects of the Invention]

[0010] The present invention makes it possible to provide a novel curing catalyst, a resin composition, a sealant, an adhesive, and a cured product. [Brief explanation of the drawings]

[0011] [Figure 1] 1 shows the structural formulas of compounds used in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0012] The objectives, features, advantages, and ideas of the present invention will be apparent to those skilled in the art from the description in this specification, and those skilled in the art can easily reproduce the present invention from the description in this specification. The embodiments and specific examples of the invention described below show preferred embodiments of the present invention and are shown for the purpose of illustration and explanation, and are not intended to limit the present invention thereto. It will be apparent to those skilled in the art that various changes and modifications can be made based on the description in this specification within the spirit and scope of the present invention disclosed in this specification.

[0013] ==Compound== The compound according to this embodiment is It is a compound of the following structural formula (I): [ka] (In the formula, R 1 is a group selected from phenyl and C1 to C17 alkyl, R 2 , R 3 , R 5are each independently a group selected from hydrogen and C1-C6 alkyl, R 4 is a group selected from OH and OAc, n and m are integers, and the sum thereof is 1 or more and 12 or less, preferably 6 or less, and more preferably 3 or less. R 1 is preferably selected from phenyl and C1 to C11 alkyl. 2 , R 3 , R 5 is preferably hydrogen. 4 is preferably OH. n and m are each preferably 1.

[0014] ==Curing catalyst== The curing catalyst according to this embodiment contains a compound having the following structural formula (I): In this specification, the term "curing catalyst" refers to a catalyst that has the function of promoting the initiation and / or progress of polymerization when the base resin self-polymerizes or when the base resin and the curing agent polymerize. The curing catalyst may be incorporated only into the terminal of the polymer. [ka] (In the formula, R 1 is a group selected from hydrogen, phenyl and C1 to C17, preferably C1 to C11 alkyl, R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl, R 4 is a group selected from hydrogen, OH and OAc, n and m are integers, and the sum thereof is 1 or more and 12 or less, preferably 6 or less, and more preferably 3 or less. More preferably, R 4 When is hydrogen, the sum of n and m is 1, and R 4 When is OH, both n and m are 1.

[0015] These compounds can be easily prepared using the methods described in the examples and known methods.

[0016] Because this curing catalyst has a phthalimide skeleton, it is less likely to dissolve in the resin in an unintended temperature range in the resin composition, and the pot life is extended, making it useful as a curing catalyst for thermosetting resins.

[0017] The curing catalyst disclosed herein may contain one or more compounds having structural formula (I), and may also contain one or more other curing catalysts other than the compound having structural formula (I).

[0018] ==Resin composition== The resin composition disclosed herein contains a resin and a curing catalyst having structural formula (I). This resin composition is characterized by being more stable and having a longer usable life than resin compositions containing conventional curing catalysts.

[0019] The resin is not particularly limited, but a thermosetting resin is preferred. Specific examples include epoxy resins and compounds having a polymerizable double bond group (for example, (meth)acrylic compounds and maleimide compounds). In this specification, acrylic and methacrylic are collectively referred to as (meth)acrylic.

[0020] (1) Epoxy resin The epoxy resin is not particularly limited, and may be a monofunctional epoxy resin or a polyfunctional epoxy resin. Monofunctional epoxy resins are epoxy resins having one epoxy group and have been used as reactive diluents to adjust the viscosity of epoxy resin compositions. Monofunctional epoxy resins are broadly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, it is preferable that the monofunctional epoxy resin has an epoxy equivalent of 180 to 400 g / eq.

[0021] Examples of aromatic monofunctional epoxy resins include, but are not limited to, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, m-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidylphthalimide, etc. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred.

[0022] Examples of aliphatic monofunctional epoxy resins include, but are not limited to, 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, and neodecanoic acid glycidyl ester.

[0023] A multifunctional epoxy resin is an epoxy resin having two or more epoxy groups. Therefore, the resin composition of the present disclosure may contain a difunctional epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, etc. Multifunctional epoxy resins are broadly classified into aliphatic multifunctional epoxy resins and aromatic multifunctional epoxy resins.

[0024] Examples of aliphatic polyfunctional epoxy resins include diepoxy resins such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether; trimethylolpropane triglycidyl ether; Examples of epoxy resins include, but are not limited to, triepoxy resins such as glycerin triglycidyl ether; alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; glycidylamine-type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; hydantoin-type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy resins having a silicone skeleton such as -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0025] Among the above examples, "cyclohexane-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 one cyclohexane ring as the parent structure. "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 the parent structure. Furthermore, cyclohexanedimethanol diglycidyl ether is particularly preferred as the cyclohexane-type diglycidyl ether.

[0026] Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins that contain aromatic rings such as benzene rings. Many of the epoxy resins that have been commonly used in the past, such as bisphenol A epoxy resins, are of this type. Examples of aromatic polyfunctional epoxy resins include, but are not limited to, bisphenol A type epoxy resins; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resins; bisphenol E type epoxy resins; bisphenol S type epoxy resins; novolac type epoxy resins; tetrabromobisphenol A type epoxy resins; fluorene type epoxy resins; biphenyl aralkyl epoxy resins; diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy resins.

[0027] As the aromatic polyfunctional epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin and glycidylamine type epoxy resin are preferred, and among them, those having an epoxy equivalent of 90 to 200 g / eq are preferred.

[0028] (2) Compounds having a polymerizable double bond group The polymer compound having a polymerizable double bond group is not particularly limited, but a polymer compound having a vinyl group, particularly a (meth)acrylic group or a maleimide group, as the reactive double bond group is preferred.

[0029] 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 an alicyclic hydrocarbon group include cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc.; vinyl monomers having an aromatic group include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc.; and water. Examples of compounds having an acid group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, cyclohexanedimethanol monoacrylate, and cyclohexanedimethanol monomethacrylate; and examples of (meth)acrylamides include acrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-isobutoxymethylacrylamide, N-butoxymethylacrylamide, methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, and N-butoxymethylmethacrylamide.Further, examples of compounds having three or more vinyl groups include polyfunctional (meth)acrylates of polyol derivatives such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; Polyfunctional arylates such as thritol tetraarylate and trimethylolpropane triallylate; polyester (meth)acrylates such as Aronix M-7100, Aronix M-8030, and Aronix M-8060 (all manufactured by Toagosei Co., Ltd.); EO-modified polyfunctional acrylates, PO-modified polyfunctional acrylates, PETIA, PETRA, TMPTA, TMPEOTA, OTA480, EBECRYL12, EBECRYL40, EBECRYL140, DPHA (and (All manufactured by Daicel-Cytec 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 (All manufactured by Sanyo Chemical Industries, Ltd.) Examples include polyether (meth)acrylates such as 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, and NK Ester TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0030] For example, compounds with maleimide groups include N,N'-(4,4'-diphenylmethane)bismaleimide and bisphenol A. Examples of the bismaleimide include diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide. Dimer acid-modified bismaleimides can also be used, such as liquid bismaleimides BMI-689, BMI-1500, and BMI-1700, or solid bismaleimide BMI-3000 (all manufactured by Designer Molecules).

[0031] <Curing agent> The resin composition of the present disclosure may contain one or more curing agents. The curing agent that may be contained in the resin composition of the present disclosure is not particularly limited, and examples thereof include nitrogen-containing compounds such as amines and their derivatives; oxygen-containing compounds such as carboxylic acid-terminated polyesters, acid anhydrides, phenols, bisphenol A, cresol novolac, and phenol-terminated epoxy resins; and sulfur-containing compounds such as thiol compounds.

[0032] Nitrogen-containing compounds such as amines and their derivatives are not particularly limited, and examples thereof include aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; N-aminoethylpiperazine; 1,4-bis(2-aminomethyl)cyclohexane; Examples of suitable aromatic polyamines include piperazine-type polyamines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethyleneoxide-di-p-aminobenzoate. Commercially available products include Epicure-W, Epicure-Z (Yuka Shell Epoxy Co., Ltd., trade names), jER Cure (registered trademark)-W, jER Cure (registered trademark)-Z (Mitsubishi Chemical Corporation, trade names), Kayahard AA, Kayahard AB, Kayahard AS (Nippon Kayaku Co., Ltd., trade names), Tautoamine HM-205 (Nippon Steel Sumikin Chemical Co., Ltd., trade names), Adeka Hardener EH-101 (ADEKA Corporation, trade names), Epomic Q-640, Epomic Q-643 (Mitsui Chemicals, Inc., trade names), DETDA80 (Lonza, trade names), and Tautoamine HM-205 (Nippon Steel Sumikin Chemical Co., Ltd., trade names).

[0033] The acid anhydride curing agent is not particularly limited, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhimic anhydride, alkenyl-substituted succinic anhydride, glutaric anhydride, etc. Particularly preferred are 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, alkenyl-substituted succinic anhydride, and diethylglutaric anhydride.

[0034] The phenolic curing agent refers to a monomer, oligomer, or polymer in general having a phenolic hydroxyl group, and examples thereof include phenol novolac resin and its alkylated or allylated products, cresol novolac resin, phenol aralkyl (including phenylene or biphenylene skeleton) resin, naphthol aralkyl resin, triphenolmethane resin, dicyclopentadiene type phenol resin, etc. Among these, allylphenol novolac resin is preferred.

[0035] The thiol compound includes a hydrolyzable polyfunctional thiol compound and a non-hydrolyzable polyfunctional thiol compound.

[0036] Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP). Examples of suitable mercaptobutyrates include EGMP-4, dipentaerythritol hexakis(3-mercaptopropionate) (DPMP, manufactured by SC Organic Chemicals), pentaerythritol tetrakis(3-mercaptobutyrate) (KarenzMT (registered trademark) PE1, manufactured by Showa Denko KK), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (KarenzMT (registered trademark) NR1, manufactured by Showa Denko KK).

[0037] Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry 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-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, and 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril. uril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, pentaerythritol trippropanethiol (trade name: PEPT, manufactured by SC Organic Chemicals), pentaerythritol tetrapropanethiol, and the like.

[0038] As the non-hydrolyzable polyfunctional thiol compound, a polythiol compound having three or more functional groups and having two or more sulfide bonds in the molecule can also be used. Examples of such thiol compounds include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the like. 1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiapentane hexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio) 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)] 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio) 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, Aliphatic polythiol compounds such as 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-hexathiaheptadecane; 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-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio) Examples of polythiol compounds having a cyclic structure include 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, and 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane.

[0039] <Constituent ratio of resin composition> The proportion of the curing catalyst in the resin composition is not particularly limited, but is preferably 0.01 to 50 wt %, more preferably 0.01 to 30 wt %, and even more preferably 0.01 to 20 wt %, relative to the thermosetting resin in the resin composition.

[0040] The pot life is the time it takes for the viscosity increase ratio of the resin composition to double its initial value, and the pot life for an epoxy-thiol curing system is preferably 8 hours or more, more preferably 12 hours or more, and even more preferably 16 hours or more. In other curing systems, a longer pot life is also preferable from the viewpoint of stability.

[0041] <Other components of the resin composition> The curable composition of the present disclosure may contain, as necessary, the following components in addition to the base resin, curing catalyst, and curing agent.

[0042] (1) Stabilizer A stabilizer can be added to the resin composition of the present disclosure to improve its storage stability and extend its pot life. Various stabilizers known as stabilizers for one-component adhesives based on epoxy resins can be used, but at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates, and organic acids is preferred.

[0043] Examples of liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0044] As the aluminum chelate, for example, Aluminum Chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

[0045] (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.), and conductive fillers such as silver, copper, and nickel. The shape is not particularly limited, and the filler may be hollow, spherical, or amorphous. The filler may also be surface-treated.

[0046] (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-based, amino-based, vinyl-based, methacrylic-based, acrylic-based, and mercapto-based silane coupling agents can be used. These silane coupling agents can be used alone or in combination of two or more.

[0047] Examples of the silane coupling agent include silane coupling agents having an alkenyl group, such as vinyltrimethoxysilane (commercially available products include KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd., A-171 manufactured by Momentive Performance Materials Japan, Z-6300 manufactured by Toray Dow Corning, GENIOSIL XL10 manufactured by Asahi Kasei Silicones, and Sila-Ace S210 manufactured by Nichibi Shoji Co., Ltd.), vinyltriethoxysilane (commercially available products include KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., A-151 manufactured by Momentive Performance Materials Japan, Z-6519 manufactured by Toray Dow Corning, GENIOSIL GF56 manufactured by Asahi Kasei Silicones, and Sila-Ace S220 manufactured by Nichibi Shoji Co., Ltd.), and vinyltriacetoxysilane (commercially available products include GENIOSIL GF56 manufactured by Asahi Kasei Silicones, and Sila-Ace S220 manufactured by Nichibi Shoji Co., Ltd.). GF62), vinyltris(2-methoxyethoxy)silane (a commercially available product is A-172 manufactured by Momentive Performance Materials Japan), vinylmethyldimethoxysilane (a commercially available product is A-2171 manufactured by Momentive Performance Materials Japan, and GENIOSIL XL12 manufactured by Wacker Asahi Kasei Silicones), octenyltrimethoxysilane (a commercially available product is KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd.), allyltrimethoxysilane (a commercially available product is Z-6825 manufactured by Dow Corning Toray Co., Ltd.), and p-styryltrimethoxysilane (a commercially available product is KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.). For example, silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane (commercially available products include KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), and silane coupling agents having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane (commercially available products include KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd. and Z-6033 manufactured by Dow Corning Toray Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (commercially available products include KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. and Z-6033 manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like.Examples of suitable silane coupling agents include A-174 (manufactured by Dow Corning Toray Co., Ltd.); Z-6030 (manufactured by Wacker Asahi Kasei Silicone Co., Ltd.); GENIOSIL GF31 (manufactured by Nitto Shoji Co., Ltd.); Sila-Ace S710 (manufactured by Nitto Shoji Co., Ltd.); 3-methacryloxypropylmethyldiethoxysilane (commercially available products include KBE-502 (manufactured by Shin-Etsu Chemical Co., Ltd.)); 3-methacryloxypropyltriethoxysilane (KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Y-9936 (manufactured by Momentive Performance Materials Japan Co., Ltd.); and methacryloxyoctyltrimethoxysilane (KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.)). Examples of suitable silane coupling agents having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (commercially available products include KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.)). , Momentive Performance Materials Japan; A-186, Toray Dow Corning; Z-6043, Nitto Shoji; Sila Ace S530, etc.), 3-glycidoxypropylmethyldimethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBM-402, Toray Dow Corning; Z-6044, Nitto Shoji; Sila Ace S520, etc.), 3-glycidoxypropyltrimethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBM-403, Momentive Performance Materials Japan; A-187, Toray Dow Corning; Z-6040, Wacker Asahi Kasei Silicone; GENIOSIL Examples of the silane coupling agent include N-2-(aminoethyl)-3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-4803), and examples of the silane coupling agent having an amino group include N-2-(aminoethyl)-3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-4803). Examples ...KBM-602, manufactured by Momentive Performance Materials Japan; A-2120, manufactured by Wacker Asahi Kasei Silicone; GENIOSIL GF-95, manufactured by Nitto Shoji Co., Ltd.; Sila-Ace S310, etc.), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBM-603, manufactured by Momentive Performance Materials Japan; A-1120, manufactured by Momentive Performance Materials Japan; A-1122, manufactured by Dow Corning Toray; Z-6020, manufactured by Dow Corning Toray; Z-6094, manufactured by Wacker Asahi Kasei Silicone; GENIOSIL GF-91, manufactured by Nichibi Shoji Co., Ltd.; Sila-Ace S320, etc.), 3-aminopropyltrimethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBM-903, manufactured by Momentive Performance Materials Japan; A-1110, manufactured by Toray Dow Corning Co., Ltd.; Z-6610, manufactured by Nichibi Shoji Co., Ltd.; Sila-Ace S360, etc.), 3-aminopropyltriethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBE-903, manufactured by Momentive Performance Materials Japan; A-1100, manufactured by Toray Dow Corning Co., Ltd.; Z-6011, manufactured by Nichibi Shoji Co., Ltd.; Sila-Ace S330, etc.), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (·BR>S Examples of commercially available products include KBE-9103 manufactured by Shin-Etsu Chemical Co., Ltd. and Sila-Ace S340 manufactured by Nitto Shoji Co., Ltd.), N-phenyl-3-aminopropyltrimethoxysilane (commercially available products include KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd., Y-9669 manufactured by Momentive Performance Materials Japan, Inc., and Z-6883 manufactured by Dow Corning Toray Co., Ltd.), N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (commercially available products include Sila-Ace XS1003 manufactured by Nitto Shoji Co., Ltd.), N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (commercially available products include KBM-575 manufactured by Shin-Etsu Chemical Co., Ltd. and Z-6032 manufactured by Dow Corning Toray Co., Ltd. and Nitto Shoji Co., Ltd.),Examples of silane coupling agents having an isocyanurate group include tris-(trimethoxysilylpropyl)isocyanurate (commercially available product: KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane (commercially available products: KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd., and Z-6852 manufactured by Dow Corning Toray Co., Ltd.), 3-mercaptopropyltrimethoxysilane (commercially available products: Examples of silane coupling agents having a ureido group include KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd., A-189 manufactured by Momentive Performance Materials Japan, Z-6062 manufactured by Dow Corning Toray Co., Ltd., and Sila-Ace S810 manufactured by Nitto Shoji Co., Ltd.), 3-mercaptopropyltriethoxysilane (commercially available products include A-1891 manufactured by Momentive Performance Materials Japan, and Z-6911 manufactured by Dow Corning Toray Co., Ltd.), and the like. Examples of silane coupling agents having a ureido group include 3-ureidopropyltrialkoxysilane (commercially available products include A-1891 manufactured by Momentive Performance Materials Japan, and Z-6911 manufactured by Dow Corning Toray Co., Ltd.). Examples of silane coupling agents having a sulfide group include bis(triethoxysilylpropyl)tetrasulfide, and examples of silane coupling agents having a thioester group include 3-octanoylthio-1-propyltriethoxysilane (commercially available products include Momentive Performance Materials Japan; A-1160). Examples of silane coupling agents having an isocyanate group include 3-isocyanatepropyltriethoxysilane (commercially available products include KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd. and A-1310 manufactured by Momentive Performance Materials Japan Co., Ltd.), 3-isocyanatepropyltrimethoxysilane (commercially available products include Y-5187 manufactured by Momentive Performance Materials Japan Co., Ltd. and Wacker Asahi Kasei Silicones Co., Ltd.), andGENIOSIL GF40, etc.);

[0048] (4) Other additives To the resin composition of the present disclosure, other additives such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, etc. may be added within the scope of not impairing the object of the present invention. The type and amount of each additive are as per usual.

[0049] ==How to use the resin composition== The resin composition disclosed herein can be used, for example, as a sealant or filler for electronic components, a dam material, a conductive or insulating adhesive, a die attach material, a film, a coating agent, a shielding material, etc. It can also be used in paints, composite materials such as pipe materials and tank materials, civil engineering and construction materials such as flooring materials and membranes, adhesives, etc., but the usage is not limited to these. [Example]

[0050] ==Compound synthesis method== (Compound 1) Synthesis of 2-[2-hydroxy-3-(2-methyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [ka] To a reaction vessel containing DMA (dimethylacetamide) (200 g) and a magnetic stirrer, Curesol 2MZ-H (Shikoku Chemicals Corporation, 39.9 g, 0.486 mol) was added with stirring and heated to 60 °C to dissolve. Denacol EX-731 (Nagase ChemteX Corporation, 100 g, 0.363 mmol) was added portionwise over approximately 10 minutes. After dissolving, the mixture was heated to 70 °C and stirred at the same temperature for 6 hours. After cooling to room temperature, water (approximately 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 physical properties of the product were as follows:

[0051] 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)

[0052] (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) [ka] To a reaction vessel containing DMA (10 mL), Curesol SIZ (Shikoku Chemicals Corporation, 1.65 g, 24.3 mmol) was added while stirring with a stirrer and heated to 60 °C to dissolve. Denacol EX-731 (Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was added portionwise over 5 minutes to the resulting solution. After dissolving, the mixture was heated to 70 °C and stirred at the same temperature for 6 hours. After cooling to room temperature, water (approximately 15 mL) was added and the mixture was stirred at 15 °C to precipitate crystals. The resulting solid was suction filtered, washed with water, and then dried to obtain compound 2 (3.69 g) as a solid. The measured physical properties of the product are as follows.

[0053] 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, 5.6 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)

[0054] (Compound 3) Synthesis of 2-[2-hydroxy-3-(2-phenyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [ka] To a reaction vessel containing DMA (10 mL), Curesol 2PZ-PW (Shikoku Chemicals Corporation, 3.50 g, 24.3 mmol) was added while stirring with a stirrer and heated to 60 °C to dissolve. Denacol EX-731 (Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was added portionwise over 5 minutes to the resulting solution. After dissolving, the mixture was heated to 70 °C and stirred at the same temperature for 23 hours. After cooling to room temperature, water (approximately 15 mL) was added and the mixture was stirred at 15 °C to precipitate crystals. The resulting solid was suction filtered, washed with water, and dried to obtain 4.04 g of crude crystals.

[0055] 1.7 mL of 0.5 N hydrochloric acid was added to 3.00 g of crude crystals and ground in a mortar. Water was added to the resulting powder to form a suspension. The resulting suspension was suction filtered, and the solid was dissolved in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed with water, saturated sodium bicarbonate solution, and brine, in that order. The chloroform layer was dehydrated over sodium sulfate and then filtered through a liquid phase separation filter paper. The organic layer was concentrated using a rotary evaporator. Ethyl acetate and hexane were added to the resulting orange oil to crystallize it. The crystals were suction filtered and then dried under reduced pressure to obtain compound 3 (1.33 g) as a solid. The measured physical properties of the product are as follows:

[0056] 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)

[0057] (Compound 4) Synthesis of 2-[2-hydroxy-3-(2-undecyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [ka] To a reaction vessel containing DMA (15 mL), Curesol C11Z (Shikoku Chemicals Corporation, 5.14 g, 24.3 mmol) was added while stirring with a stirrer and heated to 60 °C to dissolve. Denacol EX-731 (Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was added portionwise over 5 minutes to the resulting solution. After dissolving completely, the solution 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 resulting crystals were suction filtered, washed with water, and dried to obtain 5.70 g of crude crystals.

[0058] 1.8 mL of 1N hydrochloric acid was added to 3.00 g of crude crystals and ground in a mortar. Water was added to the resulting powder to form a suspension. The resulting suspension was filtered under suction, and the solid was dissolved in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed with water, saturated sodium bicarbonate solution, and brine, in that order. The chloroform layer was dehydrated over magnesium sulfate and then filtered through a liquid phase separation filter paper. The organic layer was concentrated using a rotary evaporator. Ethyl acetate and hexane were added to the resulting white solid to form a suspension, and the suspension was filtered under suction. The resulting crystals were dried under reduced pressure to obtain compound 4 (1.97 g). The measured physical properties of the product are as follows:

[0059] 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)

[0060] (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).

[0061] (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).

[0062] (Compound 7) Synthesis of 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol [ka]

[0063] 2-Methyl-1H-imidazole (Shikoku Chemicals Corporation, 21.8 g, 266 mmol) was dissolved in a mixed solvent of toluene (78.7 mL) and methanol (17.7 mL), and the temperature was raised to 80°C. A solution of Denacol EX-141 (Nagase ChemteX Corporation, 22.0 g, 147 mmol) in toluene (38.1 mL) was added dropwise over 1 hour, and the mixture was then stirred at the same temperature for 1 hour. The resulting solution was cooled to room temperature, and the solvent was distilled off under reduced pressure to obtain 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol (47.85 g) as a yellow solid. The product was identified as follows: 1 HNMR confirmed that the target product was obtained.

[0064] (Compound 8)2MZ-H Compound 8 was a commercially available product (purchased from Shikoku Chemicals Corporation).

[0065] ==Compound evaluation method== <Melt point measurement> The melting point was measured using a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (NETZSCH). First, 5 mg of the synthesized compound was weighed into an aluminum pan, sealed with an aluminum lid, and then a measurement sample was prepared by piercing the center of the lid with a needle. Next, the heat flow (mW / mg) was measured while heating the measurement sample under a nitrogen atmosphere (100 mL / min) in the range of 25 to 250 °C at a rate of 10 °C / min. The temperature at which a peak appears on the graph, corresponding to the melting point, was calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 8.0.2).

[0066] The evaluation results of the compounds are shown in Table 1. [Table 1]

[0067] ==Method for producing resin composition==

[0068] <Examples 1 to 4, 6, Comparative Examples 1 and 2: Epoxy-thiol curing system> Compounds 1 to 4, 7, and 8 serving as curing catalysts were added to and mixed with EXA835LV (manufactured by DIC Corporation), an epoxy resin. The mixture was then ground in a mortar until no agglomerates remained, and stirred and degassed under vacuum using a planetary stirring and degassing device. EXA835LV or a mixture of EXA835LV and CDMDG (manufactured by Showa Denko K.K.) was then added and mixed. This was then stirred and degassed under vacuum using a planetary stirring and degassing device. Furthermore, PEMP (manufactured by SC Organic Chemical Industry), a thiol resin, was added and mixed. This was then stirred and degassed under vacuum using a planetary stirring and degassing device, yielding a resin composition.

[0069] Example 5: Epoxy-thiol curing system Compound 1, a curing catalyst, was added to a mixture of EXA835LV and TS720 (manufactured by Cabot Specialty Chemicals) dispersed in a three-roll mill and mixed. The mixture was then ground in a mortar until no agglomerates remained, and then stirred and degassed under vacuum using a planetary mixer / degasser. C3TSG (manufactured by Shikoku Chemicals Corporation), a thiol resin, was then added and mixed. The mixture was then stirred and degassed under vacuum using a planetary mixer / degasser to obtain a resin composition.

[0070] <Examples 7, 11, and 12: Epoxy homopolymerization curing system> Compound 1, compound 5, and compound 6 were added as curing catalysts to EXA835LV and mixed. The mixture was then ground in a mortar until no agglomerates remained, and stirred and degassed under vacuum using a planetary stirring and degassing device to obtain a resin composition.

[0071] Example 8: Epoxy-acid anhydride curing system Compound 1, which serves as a curing catalyst, was added to and mixed with EXA835LV, an epoxy resin. The mixture was then ground in a mortar until no agglomerates remained, and stirred and degassed under vacuum using a planetary stirring and degassing device. YDF8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was then added and mixed. This mixture was then stirred and degassed under vacuum using a planetary stirring and degassing device. Furthermore, YH306 (manufactured by Mitsubishi Chemical Corporation), an acid anhydride resin, was added and mixed. This mixture was then stirred and degassed under vacuum using a planetary stirring and degassing device, yielding a resin composition.

[0072] Example 9: Epoxy-phenol curing system Compound 1 as a curing catalyst was added to EXA835LV and mixed. The mixture was then ground in a mortar until no agglomerates remained, and stirred and degassed under vacuum using a planetary stirring and degassing device. EXA835LV was then added and mixed. This was then stirred and degassed under vacuum using a planetary stirring and degassing device. MEH8005 (manufactured by Meiwa Kasei Co., Ltd.), a phenolic resin, was then added and mixed. This was then stirred and degassed under vacuum using a planetary stirring and degassing device to obtain a resin composition.

[0073] Example 10: Acrylic-thiol curing system An acrylic resin, M7100 (manufactured by Toagosei Co., Ltd.), a photoradical generator, OMNIRAD184 (manufactured by IGM resins BV), a polymerization inhibitor, Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and a thixotropic agent, TS720, were dispersed using a three-roll mill, and the resulting mixture was charged with Compound 1 as a curing catalyst and further dispersed using a three-roll mill. PEMP was then charged and mixed, and the mixture was stirred and defoamed under vacuum using a planetary stirring and defoaming device to obtain a resin composition.

[0074] ==Evaluation method for resin composition== <Pot life measurement> The initial 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, 25°C, and a preset appropriate range (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. Pot life was measured by assigning a rating of O if the composition did not cure within 4 hours and an X if it cured. Thereafter, the viscosity of the resin composition was measured every 4 hours using an E-type viscometer (TVE-25H, manufactured by Toki Sangyo Co., Ltd., rotor name: 3° × R9.7) at 50 rpm, 25°C, and a preset appropriate range (H, R, or U). The viscosity increase ratio after each time of standing was calculated by dividing the viscosity by the initial viscosity.

[0075] <Gel time measurement> 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 the time from when the resin composition was touched with the test rod until it became stringy.

[0076] ==Result== The amounts of the components of the resin compositions and the evaluation results are summarized in Tables 2 and 3.

[0077] [Table 2] [Table 3]

[0078] The melting point of the curing catalyst used in the examples was higher than that of the curing catalyst of Comparative Example 1. Although Comparative Example 2 has a high melting point, its molecular weight is small, so it is easily dissolved in epoxy resins and the like, and is therefore lacking in stability. A comparison of the pot life of the resin compositions showed that the comparative examples were already cured in 4 hours, whereas in the examples, the viscosity increase rate doubled in all cases after 8 hours or more.

[0079] The resin compositions in the examples gelled within 10 minutes and had sufficient reactivity and curability.

[0080] As described above, the curing catalyst of the present disclosure has a phthalimide skeleton, and therefore has high crystallinity and a higher melting point than conventional adducts obtained by adding an epoxy resin to an imidazole derivative. Furthermore, the curing catalyst of the present disclosure makes it possible to obtain a stable resin composition in which the curing catalyst is less likely to dissolve in the resin at unintended temperatures.

Claims

1. A curing catalyst having a compound of the following structural formula (I): 【Chemical 1】 (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, R ４ is a group selected from hydrogen, OH and OAc, n and m are integers, and either n and m are each 1 or the sum of n and m is 1.) 2. The curing catalyst according to claim 1, wherein R 1 is a group selected from hydrogen, phenyl, and C1 to C11 alkyl.

3. The curing catalyst according to claim 1, wherein R 2 , R 3 and R 5 are hydrogen.

4. A resin composition containing the curing catalyst described in any one of claims 1 to 3 and a thermosetting resin.

5. 5. The resin composition according to claim 4, wherein the thermosetting resin is an epoxy resin.

6. The resin composition according to claim 5 , wherein the thermosetting resin is a compound having a polymerizable double bond.

7. The resin composition according to claim 5 or 6, further comprising a curing agent for the thermosetting resin.

8. 8. The resin composition according to claim 7, wherein the curing agent is one selected from the group consisting of an oxygen-containing compound, a nitrogen-containing compound, and a thiol compound.

9. A sealing material containing the resin composition described in any one of claims 4 to 8.

10. An adhesive containing the resin composition described in any one of claims 4 to 8.

11. A cured product of the resin composition described in any one of claims 4 to 8.

12. A compound of the following structural formula (I): 【Chemistry 2】 (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, R ４ is a group selected from OH and OAc, n and m are integers, and either n and m are each 1 or the sum of n and m is 1.) 13. The compound according to claim 12, wherein R 1 is a group selected from phenyl and C1-C11 alkyl.

14. The compound according to claim 12 or 13, wherein R 2 , R 3 and R 5 are hydrogen.

15. R １ is a group selected from phenyl and C1-C10 alkyl, R ２ , R ３ , R ５ is hydrogen, R ４ is OH, The compound according to any one of claims 12 to 14, wherein n and m are each 1.

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