Amine derivatives, curing catalysts for epoxy resins, resin compositions, sealing materials, adhesives, cured products, manufacturing methods of amine derivatives, and applications of amine derivatives as curing catalysts for epoxy resins.

Abstract

The object of this invention is to provide novel amine derivatives having an o-phthalimide skeleton, wherein, in differential scanning calorimetry (DSC), the value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less.

Description

[Technical Field]

[0001] This invention relates to an amine derivative. [Previous Technology]

[0002] Single-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 considered to have the greatest impact on the usable time and curing conditions of the adhesive.

[0003] Currently, there are various curing catalysts available on the market for single-component adhesives. The mainstream types are those modified with functional groups such as amines from thermosetting or thermoplastic resins (Japanese Patent Application Publication No. 59-053526; Japanese Patent Application Publication No. 3-177418), those that encapsulate amine-based curing catalysts with a polymer shell (Japanese Patent Application Publication No. 2000-080146), and those that combine epoxy resin with imidazole (Japanese Patent Application Publication No. 60-004524). [Summary of the Invention]

[0004] The purpose of this invention is to provide a novel amine derivative.

[0005] One embodiment of the present invention is an amine derivative having a phthalimide skeleton. In differential scanning calorimetry (DSC), the value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less. This value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) can be 1.00 or more and 1.01 or less. In differential scanning calorimetry (DSC) at a heating rate of 10°C / min, the absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) can be 0.01 or more and 0.10 or less. The absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) can be 0.023 or more and 0.045 or less.

[0006] Other embodiments of the present invention include a curing catalyst for an epoxy resin containing any of the above-mentioned amine derivatives, a resin composition containing the curing catalyst, a sealing material containing the resin composition, an adhesive, or a cured product of the resin composition. Yet another embodiment of the present invention is a method for manufacturing any of the above-mentioned amine derivatives, comprising the step of adding a compound having a phthalimide backbone and an epoxy group to an amine.

[0007] Cross-reference with related documents: This application claims priority based on Japanese Patent Application No. 2021-058236 filed on March 30, 2021, and is included in this specification by reference to that basic application.

Implementation Method

[0009] Based on the description in this specification, those skilled in the art will understand the purpose, features, advantages, and concept of this invention, and can easily reproduce it based on the description in this specification. The embodiments and specific examples described below are preferred embodiments of the invention and are used for illustration and explanation, not to limit the invention. Those skilled in the art will understand that various changes and modifications can be made based on the description in this specification within the intent and scope of the invention disclosed herein.

[0010] ==Amine Derivatives== The amine derivatives of this specification have a phthalimide skeleton, and in differential scanning calorimetry (DSC), the value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less. The amine derivatives are preferably epoxyamine adducts.

[0011] Amine derivatives exhibiting this framework and properties can be used as curing catalysts for thermosetting resins such as epoxy resins or compounds having polymerizable double bonds (e.g., (meth)acrylate compounds or maleimide compounds). The following describes curing catalysts and resin compositions using the amine derivatives of the present invention. Furthermore, in this specification, acrylic groups and methacrylate groups are collectively referred to as (meth)acrylate groups.

[0012] ==Characteristics of Amine Derivatives== When the amine derivatives of one embodiment of the present invention are used as curing catalysts for epoxy resins or compounds having polymerizable double bond groups ((meth)acrylate compounds or maleimide compounds), they can be used for a long time and exhibit sufficient curing properties.

[0013] The melting point of this amine derivative can be determined using, for example, a differential scanning calorimetry apparatus (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH) using the following steps. First, 5 mg of each resin component is measured on an aluminum pan, sealed with an aluminum cap, and a needle hole is made in the center of the cap to prepare the sample for testing. Next, the sample is heated under a nitrogen atmosphere (100 mL / min) at a temperature range of 25°C to 250°C and a heating rate of 10°C / min, while the heat flux (mW / mg) is measured. The temperature at which the peak is obtained on the graph is calculated using analytical software (NETZSCH Proteus-Thermal Analysis version 8.0.2), and this temperature is taken as the melting point.

[0014] When calculating the melting point as described above, the heat flux (i.e., maximum heat flux) and the area of ​​the melting point peak (i.e., heat of fusion) are analyzed using the analysis software of the apparatus. Then, the absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) can be calculated. Next, the heat flux (mW / mg) is measured under the conditions of a temperature range of 25°C to 250°C, a heating rate of 10°C / min, and a heating rate of 50°C / min. The melting start temperature (°C) under each condition is analyzed, and the ratio of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is calculated as the heating rate dependence.

[0015] The larger the absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]), the less likely the catalyst will dissolve in the resin and harden in unexpected temperature ranges, thus extending the usable time. Furthermore, the smaller the dependence on the heating rate, the longer the usable time and the better the curing properties can be maintained.

[0016] The heating rate dependence of this amine derivative is the heating rate dependence when the heat flux (mW / mg) is measured under the conditions of heating rate of 10℃ / min and heating rate of 50℃ / min, that is, (melting start temperature at heating rate of 50℃ / min) / (melting start temperature at heating rate of 10℃ / min), preferably 1.00 to 1.10 and more preferably 1.00 to 1.08 and more preferably 1.00 to 1.05 and more preferably 1.00 to 1.02 and even more preferably 1.00 to 1.01 and less. Furthermore, when measuring heat flow (mW / mg) at a heating rate of 10°C / min, the absolute value of the maximum heat flow / heat of fusion is preferably 0.007 or more, more preferably 0.01 or more, even more preferably 0.023 or more, and preferably 0.1 or less, even more preferably 0.07 or less, and even more preferably 0.045 or less.

[0017] ==Curing Catalyst== One embodiment of the curing catalyst comprising an amine derivative having a phthalimide skeleton in this specification is a curing catalyst containing a compound having the following structural formula (I). Furthermore, in this specification, curing catalyst means a catalyst that promotes the initiation and / or progress of polymerization during the self-polymerization of the main agent or the polymerization of the main agent and the curing agent. In addition, the curing catalyst may only be attached to the end of the polymer. [Chemical Formula 1](I) (wherein, R1 is a group selected from hydrogen, phenyl, and C1-C17 alkyl groups, preferably a group selected from C1-C11 alkyl groups; R2, R3, and R5 are each independently a group selected from hydrogen and C1-C6 alkyl groups; R4 is a group selected from hydrogen, OH, and OAc (Ac is an abbreviation for acetyl); n and m are integers, and the sum of n and m is 1 or more and 12 or less, preferably 6 or less, and more preferably 3 or less). Even better, when R4 is hydrogen, the sum of n and m is 1, and when R4 is OH, the sum of n and m is also 1.

[0018] These compounds can be readily manufactured using the methods described in the examples and conventional methods. In the case of compounds having an epoxyamine adduct, the method of synthesis includes the step of adding a compound having a phthalimide skeleton and an epoxy group to an amine.

[0019] This curing catalyst, by having an orthophthalimide skeleton, satisfies the above-mentioned specific parameters. Therefore, in the resin composition, the curing catalyst is less likely to dissolve in the resin within an unexpected temperature range, and the usable time is extended. It can be used as a curing catalyst for thermosetting resins.

[0020] The curing catalyst disclosed in this specification may contain one or more compounds having structural formula (I). It may also contain one or more other curing catalysts besides compounds having structural formula (I).

[0021] ==Resin Composition== One embodiment of the resin composition disclosed in this specification, comprising an amine derivative having a phthalimide skeleton, is a resin composition containing a curing catalyst having structural formula (I) and a resin. This resin composition is more stable than resin compositions using conventional curing catalysts and has the characteristic of a longer service life.

[0022] The resin is not particularly limited, but is preferably a thermosetting resin. Specifically, examples include epoxy resins or compounds having polymerizable double bonds (e.g., (meth)acrylate compounds or maleimide compounds).

[0023] (1) Epoxy Resin Epoxy resin is not particularly limited and can be a monofunctional epoxy resin or a polyfunctional epoxy resin. A monofunctional epoxy resin is an epoxy resin having one epoxy group, and it is known to be used as a reactive diluent for viscosity adjustment of epoxy resin compositions. Monofunctional epoxy resins are broadly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From a volatility point of view, the epoxy equivalent of a monofunctional epoxy resin is preferably 180–400 g / eq.

[0024] Aromatic monofunctional epoxy resins include, for example, phenyl epoxy propylene ether, cresol epoxy propylene ether, ps-butylphenyl epoxy propylene ether, phenyl ethylene oxide, p-tert-butylphenyl epoxy propylene ether, o-phenylphenol epoxy propylene ether, m-phenylphenol epoxy propylene ether, p-phenylphenol epoxy propylene ether, N-epoxypropylphthalimide, etc., but are not limited to these. Among these, p-tert-butylphenyl epoxy propylene ether and phenyl epoxy propylene ether are preferred, and p-tert-butylphenyl epoxy propylene ether is particularly preferred.

[0025] Examples of aliphatic monofunctional epoxy resins include, but are not limited to, n-butyl epoxypropyl ether, 2-ethylhexyl epoxypropyl ether, α-epoxypine, allyl epoxypropyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methylepoxyethylene)-1-methylcyclohexane, 1,3-bis(3-epoxypropoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecanoic acid epoxypropyl ether, etc.

[0026] Multifunctional epoxy resin refers to epoxy resin having two or more epoxy groups. Therefore, the resin composition of the present invention may include difunctional epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, etc. Multifunctional epoxy resins are broadly classified into aliphatic multifunctional epoxy resins and aromatic multifunctional epoxy resins.

[0027] Aliphatic multifunctional epoxy resins include, for example, (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, polytetrahydrofuran diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; and triglycidyl ether, trimethylolpropane triglycidyl ether, and glycerol 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; epoxypropylamine epoxy resins such as tetracyclooxypropylbis(aminomethyl)cyclohexane; hydantoin epoxy resins such as 1,3-diepoxypropyl-5-methyl-5-ethylhydantoin; and epoxy resins having a silica backbone such as 1,3-bis(3-epoxypropoxypropyl)-1,1,3,3-tetramethyldisiloxane, etc., but not limited to these.

[0028] In the above examples, "cyclohexane-type diglycidyl ether" is a compound having the following structure: two glycidyl groups are respectively bonded via ether bonds to a divalent saturated hydrocarbon group having a cyclohexane ring as the parent structure. "Dicyclopentadiene-type diglycidyl ether" is a compound having the following structure: two glycidyl groups are respectively bonded via ether bonds to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as the parent structure. Furthermore, cyclohexane-type diglycidyl ether is particularly preferably cyclohexanediethanol diglycidyl ether.

[0029] Aromatic multifunctional epoxy resins are multifunctional epoxy resins containing aromatic ring structures such as benzene rings. Commonly used epoxy resins, such as bisphenol A type epoxy resins, contain many of these types. Examples of aromatic multifunctional epoxy resins include, but are not limited to, bisphenol A type epoxy resins; branched multifunctional bisphenol A type epoxy resins such as p-epoxypropyloxyphenyl dimethyl bisphenol A diepoxypropyl ether; bisphenol F type epoxy resins; bisphenol E type epoxy resins; bisphenol S type epoxy resins; phenolic (novolac) type epoxy resins; tetrabromo-bisphenol A type epoxy resins; fluorene type epoxy resins; biphenyl aralkyl epoxy resins; diepoxypropyl ether such as 1,4-phenyldiethanol diepoxypropyl ether; biphenyl type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diepoxypropyloxybiphenyl; epoxypropylamine type epoxy resins such as diepoxypropylaniline, diepoxypropyltoluidine, triepoxypropyl-p-aminophenol, and tetraepoxypropyl-m-m-phenylenediamine; and naphthalene ring-containing epoxy resins, etc.

[0030] Aromatic polyfunctional epoxy resins are preferably bisphenol F type epoxy resins, bisphenol A type epoxy resins and epoxypropylamine type epoxy resins, among which those with an epoxy equivalent of 90 to 200 g / eq are preferred.

[0031] (2)A compound having a polymerizable double bond group The compound having a polymerizable double bond group is not particularly limited, but it is preferred to be a polymer having a vinyl group, especially a (meth)acrylic acid group or a maleic anhydride group as a reactive double bond group.

[0032] Among (meth)acrylic acid compounds, examples of compounds having an acrylic group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-dodecyl acrylate, dodecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, etc.; examples of compounds having an alicyclic hydrocarbon group include cyclohexyl acrylate, cyclohexyl methacrylate, isoborneol acrylate, isoborneol methacrylate, etc.; examples of vinyl monomers having an aromatic group include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc.; examples of compounds having a hydroxyl group include 2-hydroxyethyl acrylate. Esters, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, cyclohexanediethanol monoacrylate, cyclohexanediethanol monomethacrylate, etc.; (meth)acrylamides include acrylamide, N-hydroxymethyl... Acrylamide, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, methacrylamide, N-hydroxymethylmethacrylamide, N-(methoxymethyl)methacrylamide, N-(ethoxymethyl)methacrylamide, N-(isobutoxymethyl)methacrylamide, N-(butoxymethyl)methacrylamide, etc.Furthermore, compounds having three or more vinyl groups include, for example, polyfunctional (meth)acrylates derived from polyols such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; polyfunctional allyl esters such as pentaerythritol triallyl, pentaerythritol tetraallyl, and trimethylolpropane triallyl; polyester (meth)acrylates such as ARONIX M-7100, ARONIX M-8030, and ARONIX M-8060 (all manufactured by Toa Synthetic); EO-modified polyfunctional acrylates, PO-modified polyfunctional acrylates, PETIA, PETRA, TMPTA, TMPEOTA, OTA480, EBECRYL12, EBECRYL40, EBECRYL140, and DPHA (all manufactured by DAICEL). Cytec (stock), 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 Toa Synthetic (stock), NEOMER TA-401, TA-505, EA-301, DA-600 (all manufactured by Sanyo Chemical Industry (stock), 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 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and other polyether (meth) acrylates, etc.

[0033] Examples of compounds containing a maleimide group include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-epoxyphenyl bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane, m-epoxyphenyl Phenylated bismaleimide (N,N'-1,3-epenylated bismaleimide), 1,6-bismaleimide hexane, 1,2-bismaleimide ethane (N,N'-epenylated ethyl bismaleimide), N,N'-(1,2-epenylated phenyl)bismaleimide, N,N'-1,4-epenylated bismaleimide, N,N'-(sulfonylated di-p-epenylated)bismaleimide, N,N'-[3,3'-(1,3-epenylated dioxy)diphenyl]bismaleimide, etc. Alternatively, bismaleimide can be modified with a dimer acid. Dimeric acid-modified bismaleimides include, for example, liquid bismaleimides BMI-689, BMI-1500, and BMI-1700, or solid bismaleimides BMI-3000 (all manufactured by Designer Molecules).

[0034] <Curing Agent> The resin composition of the present invention may contain one or more curing agents. The curing agents contained in the resin composition of the present invention are not particularly limited, and may include nitrogen-containing compounds such as amines and their derivatives; oxygen-containing compounds such as carboxylic acid-terminated polyesters, acid anhydride-based and phenolic curing agents, bisphenol A and cresol phenolic resins, and phenolic-terminated epoxy resins; and sulfur-containing compounds such as thiols.

[0035] Nitrogen-containing compounds such as amines and their derivatives are not particularly limited, but may include, for example, aliphatic polyamines such as triethyltetramine, tetraethylpentamine, m-m-phenylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine; isophorone diamine; 1,3-diaminomethylcyclohexane; bis(4-aminocyclohexyl)methane; norbornene diamine; 1,2-diaminocyclohexane; N-aminoethylpiperazine; 1,4- Aromatic polyamines include piperazine-type polyamines such as bis(2-amino-2-methylpropyl)piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylamine, diethyltoluenediamine, trimethylbis(4-aminobenzoate), and polytetramethyloxy-di-p-aminobenzoate. Commercially available products include, for example, Epikure-W, Epikure-Z (trade name of Yuka Shell Epoxy Co., Ltd.), jERCURE (registered trademark)-W, jERCURE (registered trademark)-Z (trade name of Mitsubishi Chemical Co., Ltd.), Kayahard AA, Kayahard AB, Kayahard AS (trade name of Nippon Kayaku Co., Ltd.), Totoamine HM-205 (trade name of Nippon Steel & Sumitomo Chemical Co., Ltd.), ADEKA HARDENER EH-101 (trade name of ADEKA Co., Ltd.), EPOMIK Q-640, EPOMIK Q-643 (trade name of Mitsui Chemicals Co., Ltd.), DETDA80 (trade name of Lonza Co., Ltd.), and Totoamine HM-205 (trade name of Nippon Steel & Sumitomo Chemical Co., Ltd.).

[0036] The anhydride-based curing agent is not particularly limited, and examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methyl bridged methylenetetrahydrophthalic 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, methyl norbornane-2,3-dicarboxylic anhydride, hydrogenated methyl bridged methylenetetrahydrophthalic anhydride, alkenyl-substituted succinic anhydride, and diethylglutaric anhydride.

[0037] Phenolic curing agents generally refer to monomers, oligomers, and polymers with phenolic hydroxyl groups, such as phenolic resins and their alkyl or allyl derivatives, cresol phenolic resins, phenolic aralkyl (including phenyl and biphenyl skeletons) resins, naphthol aralkyl resins, triphenol methane resins, dicyclopentadiene type phenolic resins, etc. Among them, allyl phenolic resins are preferred.

[0038] Thiol compounds include hydrolyzable polyfunctional thiool compounds and non-hydrolyzable polyfunctional thiool compounds.

[0039] Examples of hydrolyzable polyfunctional thiols include trimethylolpropane-3-mercaptopropionate (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tris-[(3-mercaptopropionic acid)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetra(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), triethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP-4), dipentaerythritol thallium(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetra(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) PE1), 1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Co., Ltd.: Karenz). MT (registered trademark) NR1, etc.

[0040] Examples of non-hydrolyzable polyfunctional thiols include 1,3,4,6-tetra(2-mercaptoethyl)ethynurea (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetra(3-mercaptopropyl)ethynurea (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd.), 1,3,4,6-tetra(mercaptomethyl)ethynurea, 1,3,4,6-tetra(mercaptomethyl)-3a-methylethynurea, 1,3,4,6-tetra(2-mercaptoethyl)-3a-methylethynurea, 1,3,4,6-tetra(3-mercaptopropyl)-3a-methylethynurea, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-dimethylethynurea, 1,3,4,6-tetra(2-mercaptoethyl)-3a,6a- Dimethylacetylenurea, 1,3,4,6-tetra(3-mercaptopropyl)-3a,6a-dimethylacetylenurea, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-diphenylacetylenurea, 1,3,4,6-tetra(2-mercaptoethyl)-3a,6a-diphenylacetylenurea, 1,3,4,6-tetra(3-mercaptopropyl)-3a,6a-diphenylacetylenurea, pentaerythritol tripropanethiol (trade name: PEPT, manufactured by SC Organic Chemistry), pentaerythritol tetrapropanethiol, etc.

[0041] Non-hydrolyzable polyfunctional thiols can also be polythiols with more than two thioether bonds in the molecule. Examples of such thiols 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-dithiooctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, 1,1, 3,3-Tetra(mercaptomethylthio)propane, 1,1,2,2-Tetra(mercaptomethylthio)ethane, 1,1,5,5-Tetra(mercaptomethylthio)-3-thiopentane, 1,1,6,6-Tetra(mercaptomethylthio)-3,4-dithiohexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithioheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithiononane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiohexane, 1,1,9,9-Tetra(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiopropyl)3,7-dithiononane, San(2,2-bis(mercaptomethylthio)ethyl)methane, San(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane, Tetra(2,2-bis(mercaptomethylthio)ethyl)methane, Tetra(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane, 3,5,9,11-tetra(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiotridecane, 3,5,9,11,15,17-tert-(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathiononadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetra(mercaptomethylthio)-1,17-dimercapto 2,6,8,10,12,16-hexathachitagane, 3,4,8,9-tetra(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathioundecane, 3,4,8,9,13,14-tert-(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathachitagane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetra(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiopentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-1,3-dithionecyclohexane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-6-mercaptomethylthio-1,3-dithiohexacyclohexane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithiohexacyclohexylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithiohexacyclohexylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathioundecane, 3-[2-(1,3-dithiohexacyclobutane)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathioundecane, 9-[2-(1,3-dithiohexacyclobutane)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathioundecane, 9-[2-(1,3-dithiohexacyclobutane)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathioundecane, Aliphatic polythiols such as alkyl[methyl-3,5,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathioheptadecane, 3-[2-(1,3-dithioheptadecane)]methyl-7,9,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane; 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithioheptadecane]-6-[4-(6-mercaptomethylthio)-1,3-dithioheptadecane, 4-[3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,1] [0-Tetrathioundecyl]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]-1,3-dithiocyclopentane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]-5-mercaptomethylthio-1,3-dithiocyclopentane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]methyl}-1,3-dithiocyclobutane, 2- [3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]mercaptomethylthiomethyl-1,3-dithiohexacyclic butane, 2-[3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathioundecylthio]mercaptomethylthiomethyl-1,3-dithiohexacyclic butane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]mercaptomethylthiomethyl-1,3-dithiohexacyclic butane, 4-{1-[2-(1,3-dithiohexacyclic butane)]-3-mercapto-2-thiopropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiobutylthio]-1,Polythiol compounds with cyclic structures, such as 3-dithionecyclopentane.

[0042] <Composition ratio of resin composition> The proportion of curing catalyst in resin composition is not particularly limited. The proportion of curing catalyst relative to thermosetting resin in resin composition is preferably 0.01 to 50 wt%, more preferably 0.01 to 30 wt%, and even more preferably 0.01 to 20 wt%.

[0043] The time it takes for the viscosity ratio of the resin composition to reach twice the initial value is defined as the usable time. For epoxy-thiol curing systems, the usable time is preferably 8 hours or more, more preferably 12 hours or more, and even more preferably 24 hours or more. For other curing systems, from a stability point of view, a longer usable time is also preferred.

[0044] <Other components of the resin composition> In addition to the main agent, the curing catalyst and the curing agent, the curing composition of the present invention may contain, as needed, the following.

[0045] (1) Stabilizer In order to improve storage stability and extend usability, a stabilizer may be added to the resin composition of the present invention. Various known stabilizers may be used as stabilizers for single-component adhesives with epoxy resin as the main component, preferably at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates and organic acids.

[0046] Examples of liquid borate esters include 2,2'-oxobis(5,5'-dimethyl-1,3,2-oxoborane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tri(undecyl)borate, tri(hexadecyl)borate, tri(octadecyl)borate, tri(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundeyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundeyl)borane, triphenylmethylborate, triphenylborate, tri-o-tolylborate, tri-m-tolylborate, triethanolamine borate, etc.

[0047] Aluminum chelates may be, for example, aluminum chelate A (manufactured by Sichuan Fine Chemical Co., Ltd.). Organic acids may be, for example, barbituric acid.

[0048] (2) Filler The resin composition of the present invention may contain fillers. Specific examples of fillers include silicon oxide 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, or nickel, etc. The shape of the filler is not particularly limited and may be hollow, spherical, or non-fixed. Furthermore, the filler may be surface-treated.

[0049] (3) Coupling agent The resin composition of the present invention may be supplemented with a coupling agent. The coupling agent is preferably a silane coupling agent, and various silane coupling agents such as epoxy, amino, vinyl, methacrylate, acrylic, and mercapto can be used. Such silane coupling agents may be used alone or in combination of two or more.

[0050] Silane coupling agents, for example, are silane coupling agents containing an alkenyl group, such as vinyltrimethoxysilane (commercially available products include KBM-1003 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-171 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6300 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL XL10 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S210 manufactured by Nichimi Shoji Co., Ltd.), vinyltriethoxysilane (commercially available products include KBE-1003 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-151 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6519 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL GF56 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S220 manufactured by Nichimi Shoji Co., Ltd.), vinyltriethoxysilane (commercially available products include Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S220 manufactured by Nichimi Shoji Co., Ltd.), and vinyltriethoxysilane (commercially available products include Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S220 manufactured by Nichimi Shoji Co., Ltd.), and vinyltriethoxysilane (commercially available products include Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S220). GENIOSIL GF62 (manufactured by Silicone), vinyltrimethoxysilane (commercially available products include A-172 manufactured by Momentive Performance Materials Japan), vinylmethyldimethoxysilane (commercially available products include A-2171 manufactured by Momentive Performance Materials Japan and GENIOSIL XL12 manufactured by Asahi Kasei Wacker Silicone), octenyltrimethoxysilane (commercially available products include KBM-1083 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), allyltrimethoxysilane (commercially available products include Z-6825 manufactured by Toray Dow Corning), and p-styryltrimethoxysilane (commercially available products include KBM-1403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Examples of acrylic-based silane coupling agents include 3-propenylated propyltrimethoxysilane and 3-propenylated propyltriethoxysilane (commercially available products include KBM-5103 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), while examples of methacrylic-based silane coupling agents include 3-methacrylated propylmethyldimethoxysilane (commercially available products include KBM-502 manufactured by Shin-Etsu Chemical Industry Co., Ltd. and Z-6033 manufactured by Toray Dow Corning Co., Ltd.), and 3-methacrylated propyltrimethoxysilane (commercially available products include KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-174 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6030 manufactured by Toray Dow Corning Co., Ltd., and Wacker manufactured by Asahi Kasei Co., Ltd.).Silicone's GENIOSIL GF31 and Nichimi Shoji's Sila-Ace S710 are examples of silicone coupling agents. Examples of commercially available silicone coupling agents include 3-methacryloxypropylmethyldiethoxysilane (such as Shin-Etsu Chemical's KBE-502), 3-methacryloxypropyltriethoxysilane (such as Shin-Etsu Chemical's KBE-503 and Momentive Performance Materials Japan's Y-9936), and methacryloxyoctyltrimethoxysilane (such as Shin-Etsu Chemical's KBM-5803). Examples of epoxy-based silicone coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (such as Shin-Etsu Chemical's KBM-303, Momentive Performance Materials Japan's A-186, Toray Dow Corning's Z-6043, and Nichimi Shoji's Sila-Ace). S530, etc.), 3-epoxypropoxypropylmethyldimethoxysilane (commercially available products include KBM-402 manufactured by Shin-Etsu Chemical Industry Co., Ltd., Z-6044 manufactured by Toray Dow Corning Co., Ltd., and Sila-Ace S520 manufactured by Nichimi Shoji Co., Ltd.), 3-epoxypropoxypropyltrimethoxysilane (commercially available products include KBM-403 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-187 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6040 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL GF80 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace manufactured by Nichimi Shoji Co., Ltd. Examples of silicone coupling agents containing amino groups include S510, 3-epoxypropoxypropylmethyldiethoxysilane (commercially available products include KBE-402 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-epoxypropoxypropyltriethoxysilane (commercially available products include KBE-403 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-1871 manufactured by Momentive Performance Materials Japan Co., Ltd., and GENIOSIL GF82 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and epoxypropoxyoctyltrimethoxysilane (commercially available products include KBM-4803 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc. Examples of silicone coupling agents containing amino groups include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (KBM-602 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-2120 manufactured by Momentive Performance Materials Japan Co., Ltd., GENIOSIL GF-95 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace manufactured by Nichimi Shoji Co., Ltd.S310, etc.), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (commercially available products include KBM-603 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-1120 and A-1122 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6020 and Z-6094 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL GF-91 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and Sila-Ace S320 manufactured by Nichimi Shoji Co., Ltd.), 3-aminopropyltrimethoxysilane (commercially available products include KBM-903 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-1110 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6610 manufactured by Toray Dow Corning Co., Ltd., and Sila-Ace manufactured by Nichimi Shoji Co., Ltd.) S360, etc.), 3-aminopropyltriethoxysilane (commercially available products include KBE-903 manufactured by Shin-Etsu Chemical Industry Co., Ltd., A-1100 manufactured by Momentive Performance Materials Japan Co., Ltd., Z-6011 manufactured by Toray Dow Corning Co., Ltd., and Sila-Ace S330 manufactured by Nichimi Shoji Co., Ltd.), 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine (commercially available products include KBE-9103 manufactured by Shin-Etsu Chemical Industry Co., Ltd., and Sila-Ace S340 manufactured by Nichimi Shoji Co., Ltd.), N-phenyl-3-aminopropyltrimethoxysilane (commercially available products include KBM-573 manufactured by Shin-Etsu Chemical Industry Co., Ltd., Y-9669 manufactured by Momentive Performance Materials Japan Co., Ltd., and Toray Dow Corning Co., Ltd., etc.). Corning Corporation's Z-6883, etc.), N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (commercially available products include Sila-Ace XS1003 manufactured by Nichimi Shoji Co., Ltd.), and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (commercially available products include KBM-575 manufactured by Shin-Etsu Chemical Industry Co., Ltd., Z-6032 manufactured by Toray Dow Corning Corporation, and Sila-Ace manufactured by Nichimi Shoji Co., Ltd.)Examples of silane coupling agents containing isocyanurate groups include tris(trimethoxysilylpropyl)isocyanurate (commercially available example: Shin-Etsu Chemical Co., Ltd.'s KBM-9659), and examples of silane coupling agents containing mercapto groups include 3-mercaptopropylmethyldimethoxysilane (commercially available examples: Shin-Etsu Chemical Co., Ltd.'s KBM-802, Toray Dow Corning Co., Ltd.'s Z-6852, etc.), 3-mercaptopropyltrimethoxysilane (commercially available examples: Shin-Etsu Chemical Co., Ltd.'s KBM-803, Momentive Performance Materials Japan Co., Ltd.'s A-189, Toray Dow Corning Co., Ltd.'s Z-6062, Nichimi Shoji Co., Ltd.'s Sila-Ace S810, etc.), and 3-mercaptopropyltriethoxysilane (commercially available examples: Momentive Performance Materials Japan Co., Ltd.'s A-1891, Toray Dow Corning ... Examples of urea-containing silane coupling agents include 3-ureopropyltrialkoxysilane (commercially available examples include KBE-585 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-ureopropyltrimethoxysilane, and 3-ureopropyltriethoxysilane (commercially available examples include A-1160 manufactured by Momentive Performance Materials Japan Co., Ltd.). Examples of thioether-containing silane coupling agents include bis(triethoxysilylpropyl)tetrasulfide. Examples of thioester-containing silane coupling agents include 3-octylthio-1-propyltriethoxysilane (commercially available examples include Momentive Performance Materials). Examples of isocyanate-containing silane coupling agents include 3-isocyanopropyltriethoxysilane (commercially available products include KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., and A-1310 manufactured by Momentive Performance Materials Japan Co., Ltd.), and 3-isocyanopropyltrimethoxysilane (commercially available products include Y-5187 manufactured by Momentive Performance Materials Japan Co., Ltd., and GENIOSIL GF40 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.).

[0051] (4) Other additives: Other additives may be added to the resin composition of the present invention without prejudice to the purpose of the present invention, such as carbon black, titanium black, ion scavengers, leveling agents, antioxidants, defoamers, volatile modifiers, viscosity modifiers, flame retardants, colorants, solvents, etc. The types and amounts of each additive are the same as in general methods.

[0052] =Application Methods of the Resin Composition= The resin composition disclosed in this specification is a single-component epoxy resin, and can be used, for example, as a sealing or filling material for electronic components, a damping material, a conductive or insulating adhesive, a wafer bonding material, a film, a coating agent, a masking material, etc. It can also be used in other composite materials such as coatings, pipeline materials, and storage tank materials, flooring materials, civil engineering materials such as films, adhesives, etc., but the application methods are not limited to these.

[0053] Example: ==Synthetic Method of Compounds== Synthesis of 2-[2-hydroxy-3-(2-methyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [Chemical Formula 2] In a reaction vessel containing DMA (dimethylacetamide) (200 g) and a magnetic stir bar, CUREZOL 2MZ-H (manufactured by Shikoku Chemical Industry Co., Ltd., 39.9 g, 0.486 mol) was added while stirring, and the mixture was heated to 60°C to dissolve it. DENACOL EX-731 (manufactured by Nagase ChemteX Co., Ltd., 100 g, 0.363 mmol) was slowly added to the resulting solution over approximately 10 minutes. After complete dissolution, 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 allow crystals to precipitate. The resulting solid was filtered under vacuum, washed twice with water and twice with IPA, and then dried to obtain compound 1 (85.7 g) (recovery rate 61%). The physical properties of the product are as follows.

[0054] 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)

[0055] Synthesis of (Compound 2) 2-[2-hydroxy-3-(1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione (CAS No.: 112086-61-0) [Chemical Formula 3] CUREZOL SIZ (manufactured by Shikoku Chemical Industry Co., Ltd., 1.65 g, 24.3 mmol) was added to a reaction vessel containing DMA (10 mL) while stirring with a stir bar, and the mixture was heated to 60°C to dissolve. DENACOL EX-731 (manufactured by Nagase ChemteX Co., Ltd., 5.00 g, 23.1 mmol) was slowly added to the resulting solution over 5 minutes. After complete dissolution, 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 stirred at 15°C to allow crystallization. The resulting solid was filtered under vacuum, washed with water, and dried to obtain solid Compound 2 (3.69 g). The physical properties of the product are as follows.

[0056] 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)

[0057] (Compound 3) Synthesis of 2-[2-hydroxy-3-(2-phenyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [Chemical Formula 4] In a reaction vessel containing DMA (10 mL), CUREZOL 2PZ-PW (manufactured by Shikoku Chemical Industry Co., Ltd., 3.50 g, 24.3 mmol) was added while stirring with a stir bar, and the mixture was heated to 60°C to dissolve. DENACOL EX-731 (manufactured by Nagase ChemteX Co., Ltd., 5.00 g, 23.1 mmol) was slowly added to the resulting solution over 5 minutes. After complete dissolution, 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 stirred at 15°C to allow crystallization. The resulting solid was filtered under vacuum, washed with water, and dried to obtain 4.04 g of crude crystals.

[0058] 3.00 g of crude crystals were added to 1.7 mL of 0.5 N hydrochloric acid and ground in a mortar. Water was added to the resulting powder to form a suspension. The suspension was filtered under vacuum to dissolve the solid in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed sequentially with water, saturated sodium bicarbonate solution, and saline solution. The chloroform layer was dehydrated with sodium sulfate and filtered through phase separator paper. The organic layer was concentrated using a rotary evaporator. Ethyl acetate and hexane were added to the resulting orange oily substance to crystallize it. The crystals were filtered under vacuum and dried under reduced pressure to obtain solid compound 3 (1.33 g). The physical properties of the product are as follows.

[0059] 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)

[0060] (Compound 4) Synthesis of 2-[2-hydroxy-3-(2-undecyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [Chemical Formula 5] CUREZOL C11Z (manufactured by Shikoku Chemical Industry Co., Ltd., 5.14 g, 24.3 mmol) was added to a reaction vessel containing DMA (15 mL) while stirring with a stir bar, and the mixture was heated to 60°C to dissolve. DENACOL EX-731 (manufactured by Nagase ChemteX Co., Ltd., 5.00 g, 23.1 mmol) was slowly added to the resulting solution over 5 minutes. After complete dissolution, the mixture 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 stirred at 15°C to allow crystallization. The resulting solid was filtered under vacuum, washed with water, and dried to obtain 5.70 g of crude crystals.

[0061] 3.00 g of crude crystals were added to 1.8 mL of 1N hydrochloric acid and ground in a mortar. Water was added to the resulting powder to form a suspension. The suspension was filtered under vacuum to dissolve the solid in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed sequentially with water, saturated sodium bicarbonate solution, and saline solution. The chloroform layer was dehydrated with magnesium sulfate and filtered through phase separator 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. The suspension was filtered under vacuum, and the resulting crystals were dried under reduced pressure to obtain compound 4 (1.97 g). The physical properties of the product are as follows.

[0062] 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)

[0063] (Compound 5) 2-[2-(2-methyl-1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione Compound 5 (CAS No.: 858512-76-2) is a commercially available product (purchased from FCH Group).

[0064] (Compound 6) 2-[2-(1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione Compound 6 (CAS No.: 72459-53-1) is a commercially available product (purchased from Enamine).

[0065] (Compound 7) Synthesis of 1-(2-methyl-1H-imidazol-1-yl)-3-phenoxyprop-2-ol [Chemical Formula 6]

[0066] 2-Methyl-1H-imidazolium (manufactured by Shikoku Chemical Industry Co., Ltd., 21.8 g, 266 mmol) was dissolved in a mixed solvent of toluene (78.7 mL) and methanol (17.7 mL). The solution was heated to 80°C, and a solution of DENACOL EX-141 (manufactured by Nagase ChemteX, 22.0 g, 147 mmol) in toluene (38.1 mL) was added dropwise over 1 hour. The mixture was then stirred at the same temperature for 1 hour. The resulting solution was cooled to room temperature, and the solvent was removed by distillation under reduced pressure to obtain a yellow solid of 1-(2-methyl-1H-imidazol-1-yl)-3-phenoxyprop-2-ol (47.85 g). The product was identified by 1H NMR, confirming the presence of the target compound.

[0067] (Compound 8) Synthesis of 1-[([1,1'-biphenyl]-2-yl)oxy]-3-(2-methyl-1H-imidazol-1-yl)prop-2-ol [Chemical Formula 7]

[0068] 2-Methyl-1-H-imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., 150 g, 1.83 mol) was dissolved in a mixed solvent of toluene (443 mL) and methanol (121 mL) at room temperature. The resulting solution was heated to 80°C and refluxed with stirring. A solution of 2-{[([1,1'-biphenyl]-2-yl)oxy]methyl}ethylene oxide (manufactured by Sankosha Co., Ltd., 210 g, 0.913 mol, epoxy equivalent 230 g / eq) dissolved in toluene (363 mL) at room temperature was added to the resulting solution at a dropping rate of 3.75 mL / min. After the total amount was added, the resulting mixture was stirred at 80°C for 75 minutes. The solvent was then removed by distillation at 50°C using an evaporator to obtain a crude product (392 g). The product was identified by 1H NMR, confirming the presence of the target compound.

[0069] ==Compound Evaluation== <Melting Point Determination> The melting point was determined using a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH). First, 5 mg of each resin component was measured on an aluminum pan, sealed with an aluminum cap, and a needle hole was made in the center of the cap to prepare the sample for testing. Next, the sample was heated under a nitrogen atmosphere (100 mL / min) at a temperature range of 25°C to 250°C and a heating rate of 10°C / min, while simultaneously measuring the heat flux (mW / mg). The temperatures at which peaks were obtained on the graph were calculated using analytical software (NETZSCH Proteus-Thermal Analysis version 8.0.2). Clear peaks were obtained for compounds 1–6 and 8, but no clear peak was obtained for compound 7. Next, the heat flux at the melting point (i.e., maximum heat flux) and the area of ​​the melting point peak (i.e., heat of fusion) are analyzed using the device's analysis software, and the absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) is calculated. Furthermore, the heat flux (mW / mg) is measured within a temperature range of 25℃ to 250℃, at heating rates of 10℃ / min and 50℃ / min, and the melting onset temperature (℃) under each condition is analyzed. The ratio of (melting onset temperature at 50℃ / min) / (melting onset temperature at 10℃ / min) is calculated as the dependence on the heating rate. The melting onset temperature is defined as the temperature at the intersection of the tangent with the steepest slope of the tangent line to the melting peak curve on the side lower than the melting point and the baseline of the DSC. The evaluation results of the compound (hardening catalyst) are shown in Table 1. compound 1 2 structure Melting point (°C) 198 198 Maximum heat flux (mW / mg) -6.85 -3.76 Heat of fusion (J / g) 159 127 Maximum heat flux / heat of fusion (absolute value) 0.043 0.03 Dependence on heating rate 1.01 1.00 compound 3 4 structure Melting point (°C) 171 112 Maximum heat flux (mW / mg) -4.31 -4.22 Heat of fusion (J / g) 174 186 Maximum heat flux / heat of fusion (absolute value) 0.025 0.023 Dependence on heating rate 1.00 1.00 compound 5 6 structure Melting point (°C) 181 165 Maximum heat flux (mW / mg) -5.38 -7.02 Heat of fusion (J / g) 157 162 Maximum heat flux / heat of fusion (absolute value) 0.034 0.043 Dependence on heating rate 1.00 1.00 compound 7 8 structure Melting point (°C) ND 150 Maximum heat flux (mW / mg) ND -0.59 Heat of fusion (J / g) ND 107 Maximum heat flux / heat of fusion (absolute value) ND 0.006 Dependence on heating rate ND 1.11 ND: Undetectable

[0071] ==Preparation method of resin composition==

[0072] <Examples 1-4, 6, Comparative Examples 1, 2: Epoxy-Mercaprol Curing System> Compounds 1-4, 6, 7, and 8, which served as curing catalysts, were added to epoxy resin EXA835LV (manufactured by DIC Corporation) and mixed. Then, the mixture was ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Next, EXA835LV or a mixture of EXA835LV and CDMDG (manufactured by Showa Denko Corporation) was added and mixed. Then, stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Furthermore, thiol resin PEMP (manufactured by SC Organic Chemicals Corporation) was added and mixed. Then, stirred and degassed under vacuum using a planetary stirring and degassing apparatus to obtain the resin composition.

[0073] <Example 5: Epoxy-Mercaprol Curing System> Compound 1, serving as a curing catalyst, was added to a mixture of EXA835LV and TS720 (manufactured by Cabot Specialty Chemicals) dispersed using three rollers and mixed. The mixture was then ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Here, thiol resin C3TSG (manufactured by Shikoku Chemical Industry Co., Ltd.) was added and mixed. Then, stirred and degassed under vacuum using a planetary stirring and degassing apparatus to obtain the resin composition.

[0074] <Examples 7, 11, 12: Epoxy Homopolymer Curing System> Compounds 1, 5, and 6, which serve as curing catalysts, were added to epoxy resin EXA835LV and mixed. The mixture was then ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus to obtain the resin composition.

[0075] <Example 8: Epoxy-Anhydride Curing System> Compound 1, serving as a curing catalyst, was added to epoxy resin EXA835LV and mixed. Then, it was ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Next, YDF8170 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was added and mixed. Then, it was stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Furthermore, anhydride resin YH306 (manufactured by Mitsubishi Chemical Co., Ltd.) was added and mixed. Then, it was ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus to obtain the resin composition.

[0076] <Example 9: Epoxy-Phenolic Curing System> Compound 1, serving as a curing catalyst, was added to epoxy resin EXA835LV and mixed. Then, it was ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Next, EXA835LV was added and mixed. Then, it was stirred and degassed under vacuum using a planetary stirring and degassing apparatus. Furthermore, phenolic resin MEH8005 (manufactured by Meiwa Chemical Co., Ltd.) was added and mixed. Then, it was ground in a mortar until no agglomeration occurred, and stirred and degassed under vacuum using a planetary stirring and degassing apparatus to obtain the resin composition.

[0077] <Example 10: Acrylic-based-thiol curing system> Acrylic resin M7100 (manufactured by Toa Synthetic Co., Ltd.), photoradical generator OMNIRAD184 (manufactured by IGM Resins BV Co., Ltd.), polymerization inhibitor Q-1301 (manufactured by Fujifilm and Koichi Chemical Co., Ltd.), and volatile modifier TS720 were dispersed using a three-roller. Compound 1, which serves as a curing catalyst, was added to the resulting mixture, and the mixture was then dispersed again using a three-roller. Here, PEMP was added and mixed, and the mixture was stirred and degassed under vacuum using a planetary stirring and degassing device to obtain the resin composition.

[0078] ==Evaluation Method of Resin Composition== <Determination of Usable Time> 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 and 25°C within a pre-set appropriate range (H, R, or U). Next, the resin composition stored in a sealed container was left to stand for 4 hours at 25°C and 50% humidity. 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 within a pre-set appropriate range (H, R, or U). Then, the ratio of (viscosity after each standing time) to (initial viscosity) was calculated as the viscosity increase ratio after each standing time, which was taken as the usable time. Those not cured within 8 hours were considered ○, and those cured were considered ╳.

[0079] <Determination of gelation time> The gelation time (hereinafter referred to as gelation time) is determined using a gelation testing machine (GT-D-15A: manufactured by Yu-kari Corporation). The heating plate is set to 100°C, 120°C, or 150°C, and the resin composition is transferred onto the heating plate using a test rod. The gelation time is defined as the time from when the test rod contacts the resin composition until it reaches a stringy state.

[0080] ==Results== The composition and evaluation results of each component of the above resin composition are summarized in Tables 2 and 3.

[0081] Table 2 Example Example and Comparative Example Numbers 1 2 3 4 Material hardened catalyst Compound 1 (wt%) 1 Compound 2 (wt%) 1 Compound 3 (wt%) 1 Compound 4 (wt%) 1 Compound 5 (wt%) Compound 6 (wt%) Compound 7 (wt%) Compound 8 (wt%) Epoxy resin EXA835LV(wt%) 57 57 57 57 YDF8170 (wt%) CDMDG (wt%) Thiol resins PEMP (wt%) 42 42 42 42 C3TSG (wt%) acid anhydride resin YH306 (wt%) Phenolic resin MEH8005 (wt%) acrylic resin M7100 (wt%) Free radical generators OMNIRAD-184 (wt%) Polymerization inhibitor Q-1301 (wt%) Viscosity modifier TS720 (wt%) Evaluation results Viscosity increase ratio (times) 4 hours later 1.01 1.03 1.02 8 hours later 1.03 1.09 1.04 12 hours later 1.11 1.51 1.12 16 hours later 1.55 23.49 1.24 20 hours later 42.49 UM 2.16 24 hours later 1.9 UM UM UM Usable time ○ ○ ○ ○ Gelation time at 100℃ (seconds) 125 174 200 205 Melting point (°C) of hardened catalyst 198 198 171 113 Example Comparative example Example and Comparative Example Numbers 5 6 1 2 Material hardened catalyst Compound 1 (wt%) 1 1 Compound 2 (wt%) Compound 3 (wt%) Compound 4 (wt%) Compound 5 (wt%) Compound 6 (wt%) Compound 7 (wt%) 1 Compound 8 (wt%) 1 Epoxy resin EXA835LV(wt%) 57 27 57 57 YDF8170 (wt%) CDMDG (wt%) 27 Thiol resins PEMP (wt%) 45 42 42 C3TSG (wt%) 39 acid anhydride resin YH306 (wt%) Phenolic resin MEH8005 (wt%) acrylic resin M7100 (wt%) Free radical generators OMNIRAD-184 (wt%) Polymerization inhibitor Q-1301 (wt%) Viscosity modifier TS720 (wt%) 3 Evaluation results Viscosity increase ratio (times) 4 hours later hardening 1.47 8 hours later UM hardening 12 hours later UM UM 16 hours later UM UM 20 hours later UM UM 24 hours later 1.0 1.15 UM UM Usable time ○ ○ ╳ ╳ Gelation time at 100℃ (seconds) 198 198 twenty four 105 Melting point (°C) of hardened catalyst 198 198 ND 150 UM: Unable to measure (slash indicates not measured) Table 3 Example Example and Comparative Example Numbers 7 8 9 10 11 12 Material hardened catalyst Compound 1 (wt%) 12 1 1 1.4 Compound 2 (wt%) Compound 3 (wt%) Compound 4 (wt%) Compound 5 (wt%) 12 Compound 6 (wt%) 12 Compound 7 (wt%) Compound 8 (wt%) Epoxy resin EXA835LV(wt%) 88 6 57 88 88 YDF8170 (wt%) 53 CDMDG (wt%) Thiol resins PEMP (wt%) 38.0 C3TSG (wt%) acid anhydride resin YH306 (wt%) 40 Phenolic resin MEH8005 (wt%) 42 acrylic resin M7100 (wt%) 57.0 Free radical generators OMNIRAD-184 (wt%) 1.0 Polymerization inhibitor Q-1301 (wt%) 0.2 Viscosity modifier TS720 (wt%) 2.4 Evaluation results Viscosity increase ratio (times) 4 hours later 0.63 1.23 8 hours later 1.36 1.66 12 hours later 1.56 2.70 16 hours later 1.78 UM 20 hours later 1.99 UM 24 hours later 1.0 1.84 2.46 UM 1.24 1.55 Usable time ○ ○ ○ ○ ○ ○ gelation time (seconds) 100℃ 170 120℃ 286 467 150℃ 28 80 259 UM: Unable to measure (slash indicates not measured)

[0082] As shown in Tables 1-3, the resin compositions using compounds 1-6, which have a large absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) and a small dependence on the heating rate, showed almost no change in viscosity after 8 hours of preparation. On the other hand, compound 7, which did not produce a clear melting peak and whose absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) could not be calculated, was easily soluble in epoxy resins and the like, and hardened within 4 hours. Compound 8, which had a small absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) and a large dependence on the heating rate, also hardened within 8 hours. Thus, the resin compositions of the examples have a longer usable time.

[0083] The resin composition of the embodiment gels within 10 minutes and has sufficient reactivity and hardening properties.

[0084] As shown in Table 3, the curing catalyst of the present invention can utilize not only epoxy-thiol curing systems, but also epoxy homopolymer curing systems, epoxy-anhydride curing systems, epoxy-phenol curing systems, and acrylic-thiol curing systems. In particular, epoxy-thiol curing catalysts are preferred.

[0085] In this way, the curing catalyst of the present invention has a phthalimide skeleton, which has high crystallinity and a high melting point compared with conventional epoxy resin and imidazole derivative adducts. Furthermore, with the curing catalyst of the present invention, the resin composition system can be stable and the curing catalyst is not prone to dissolving in the resin in unexpected temperature ranges.

[0086] Industrial applicability: According to the present invention, novel amine derivatives can be provided. [Simplified Explanation of the Diagram]

[0008] [Figure 1]Structural formulas of the compounds used in the examples and comparative examples.

Claims

1. An amine derivative, in differential scanning calorimetry, having a melting start temperature (heating rate of 50°C / min) / (heating rate of 10°C / min) value of 1.00 or more and 1.10 or less, wherein the amine derivative has the following structural formula (I): (I) (wherein, R1 is a group selected from phenyl and C1 to C17 alkyl groups, R2, R3, and R5 are each independently a group selected from hydrogen and C1 to C6 alkyl groups, R4 is a group selected from OH and OAc, n and m are integers, and the sum of n and m is 1 or more).

2. As in claim 1, the amine derivative, wherein, The value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is greater than or equal to 1.00 and less than or equal to 1.

02.

3. An amine derivative such as claimed in claim 1 or 2, wherein, In differential scanning calorimetry (DSC) with a heating rate of 10°C / min, the absolute value of the ratio of (maximum heat flux [mW / mg]) to (heat of fusion [J / g]) is greater than 0.01 and less than 0.

10.

4. As in claim 3, the amine derivative, wherein, The absolute value of (maximum heat flux [mW / mg]) / (heat of fusion [J / g]) is greater than or equal to 0.023 and less than or equal to 0.

045.

5. A curing catalyst for epoxy resin, comprising an amine derivative having a phthalimide skeleton, wherein, in differential scanning calorimetry, the value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less, and the amine derivative is a compound having the following structural formula (I): (I) (wherein, R1 is a group selected from hydrogen, phenyl and C1 to C17 alkyl groups, R2, R3 and R5 are each independently selected from hydrogen and C1 to C6 alkyl groups, R4 is a group selected from hydrogen, OH and OAc, n and m are integers, and the sum of n and m is 1 or more).

6. A resin composition containing the curing catalyst as claimed in claim 5.

7. A sealing material comprising the resin composition as claimed in claim 6.

8. An adhesive comprising the resin composition of claim 6.

9. A cured material, which is a cured material of the resin composition as claimed in claim 6.

10. A method for manufacturing an amine derivative, comprising the method for manufacturing an amine derivative as claimed in any one of claims 1 to 4, including the step of adding a compound having a phthalimide skeleton and an epoxy group to an amine.

11. Use of an amine derivative as a curing catalyst for epoxy resin, wherein the value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) in differential scanning calorimetry is 1.00 or more and 1.10 or less, and the amine derivative is a compound having the following structural formula (I): (I) (wherein, R1 is a group selected from hydrogen, phenyl and C1 to C17 alkyl groups, R2, R3 and R5 are each independently selected from hydrogen and C1 to C6 alkyl groups, R4 is a group selected from hydrogen, OH and OAc, n and m are integers, and the sum of n and m is 1 or more).

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