Amine derivatives

Abstract

The purpose of the present invention is to provide a novel amine derivative. The present invention provides an amine derivative having a phthalimide backbone, wherein according to differential scanning calorimetry (DSC), the value of (melting start temperature at a temperature increase speed of 50°C / min) / (melting start temperature at a temperature increase speed of 10°C / min) is 1.00 to 1.10.

Description

[Technical Field]

[0001] This invention relates to amine derivatives. [Background technology]

[0002] One-component adhesives contain either a main component and a curing catalyst, or a main component, a curing agent, and a curing catalyst. The curing catalyst is considered to have the greatest influence on the adhesive's pot life and curing conditions.

[0003] Currently, various types of curing catalysts used in one-component adhesives are commercially available, but the mainstream types are those in which functional groups such as amines are modified on thermosetting resins or thermoplastic resins (Japanese Patent Publication No. 59-053526; Japanese Patent Publication No. 3-177418), shell types in which amine-based curing catalysts are covered with a polymer shell (Japanese Patent Publication No. 2000-080146), and types that are simply epoxy resins adducted with imidazole (Japanese Patent Publication No. 60-004524). [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to provide novel amine derivatives. [Means for solving the problem]

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

[0006] Other embodiments of the present invention include a curing catalyst for epoxy resins containing any of the above-mentioned amine derivatives, a resin composition containing the curing catalyst, a encapsulant or adhesive containing the resin composition, or a cured product of the resin composition. A further embodiment of the present invention is a method for producing any of the above-mentioned amine derivatives, comprising the step of adducting a compound having a phthalimide skeleton and one epoxy group to an amine.

[0007] ==Cross-reference with related literature== This application claims priority based on Japanese Patent Application No. 2021-058236, filed on 30 March 2021, which is incorporated herein by reference. [Brief explanation of the drawing]

[0008] [Figure 1] These are the structural formulas of the compounds used in the examples and comparative examples. [Modes for carrying out the invention]

[0009] The object, features, advantages, and ideas of the present invention will be apparent to those skilled in the art from the description herein, and will be easily reproducible to those skilled in the art from the description herein. The embodiments and specific examples of the invention described below are examples of preferred embodiments of the present invention and are provided for illustrative or explanatory purposes only, and do not limit the present invention thereto. It will be apparent to those skilled in the art that various modifications and modifications can be made based on the description herein, within the intent and scope of the present invention as disclosed herein.

[0010] ==Amine Derivatives== The amine derivatives disclosed herein have a phthalimide skeleton and, in differential scanning calorimetry (DSC), the value of (temperature at which melting occurs at a heating rate of 50°C / min) / (temperature at which melting occurs at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less. The amine derivative is preferably an epoxyamine adduct.

[0011] Amine derivatives exhibiting such a structure and properties are useful as curing catalysts for thermosetting resins such as epoxy resins and compounds having polymerizable double bond groups (e.g., (meth)acrylic compounds and maleimide compounds). The curing catalysts and resin compositions using the amine derivatives according to the present invention will be described below. In this specification, acrylic and methacrylic will be collectively referred to as (meth)acrylic.

[0012] ==Characteristics of Amine Derivatives== An amine derivative according to one embodiment of the present invention exhibits a long pot life and sufficient curability when used as a curing catalyst for epoxy resins and compounds having polymerizable double bond groups ((meth)acrylic compounds and maleimide compounds).

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

[0014] As described above, when calculating the melting point, the heat flow at the melting point (i.e., the maximum heat flow) and the area of ​​the peak at the melting point (i.e., the heat of fusion) are analyzed using the device's analysis software. Then, the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) can be calculated. Next, the heat flow (mW / mg) is measured in the range of 25 to 250°C under heating rates of 10°C / min and 50°C / min, and the melting onset temperature (°C) under each condition is analyzed. As a degree of dependence on the heating rate, (melting onset temperature at a heating rate of 50°C / min) / (melting onset temperature at a heating rate of 10°C / min) can be calculated.

[0015] The larger the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]), the less likely the curing catalyst is to dissolve into the resin at unintended temperature ranges, thus allowing for a longer pot life. Furthermore, the smaller the dependence on the heating rate, the more instantaneously the curing catalyst dissolves into the resin at the intended temperature range, allowing for sufficient curing performance while maintaining a sufficient pot life.

[0016] The heating rate dependence of this amine derivative is preferably such that the ratio of (onset melting temperature at a heating rate of 50°C / min) / (onset melting temperature at a heating rate of 10°C / min) is 1.00 or more and 1.10 or less, more preferably 1.00 or more and 1.08 or less, even more preferably 1.00 or more and 1.05 or less, even more preferably 1.00 or more and 1.02 or less, and even more preferably 1.00 or more and 1.01 or less. Furthermore, when the heat flow (mW / mg) is measured under a heating rate of 10°C / min, the absolute value of 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 containing an amine derivative having a phthalimide skeleton disclosed in this specification is a curing catalyst containing a compound having the following structural formula (I). In this specification, the curing catalyst means a catalyst having a function of promoting the initiation and / or progress of polymerization when the main agent self-polymerizes or when the main agent and the curing agent polymerize. Note that the curing catalyst may be incorporated only at the ends of the polymer. [Chemical formula] (In the formula, R 1 is a group selected from hydrogen, phenyl, and C1-C17, preferably C1-C11 alkyl, R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl, R 4 is a group selected from hydrogen, OH, and OAc (Ac: abbreviation for acetyl group), and n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, more preferably 3 or less. ) Preferably, when R 4 is hydrogen, the sum of n and m is 1, and when R 4 is OH, both n and m are 1.

[0018] These compounds can be easily produced using the methods described in the examples and known methods. When the compound is an epoxyamine adduct, the synthesis method includes a step of adducting a compound having a phthalimide skeleton and having one epoxy group to an amine.

[0019] Since this curing catalyst has a phthalimide skeleton and satisfies the above specific parameters, in the resin composition, the dissolution of the curing catalyst into the resin in an unintended temperature range is unlikely to occur, the pot life is prolonged, and it is useful as a curing catalyst for thermosetting resins.

[0020] The curing catalysts disclosed herein may contain one or more compounds having structural formula (I). They may also contain one or more other curing catalysts other than compounds having structural formula (I).

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

[0022] The resin is not particularly limited, but thermosetting resins are preferred. Specifically, epoxy resins and compounds having polymerizable double bond groups (e.g., (meth)acrylic compounds and maleimide compounds) are examples.

[0023] (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 conventionally 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, monofunctional epoxy resins are preferably those with an epoxy equivalent of 180 to 400 g / eq.

[0024] Examples of aromatic monofunctional epoxy resins include, but are not limited to, phenylglycidyl ether, cresyl glycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, p-tert-butylphenylglycidyl ether, o-phenylphenol glycidyl ether, m-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, and N-glycidylphthalimide. Of these, p-tert-butylphenylglycidyl ether and phenylglycidyl ether are preferred, with p-tert-butylphenylglycidyl ether being particularly preferred.

[0025] 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-methyloxyranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and glycidyl neodecanoate.

[0026] A polyfunctional epoxy resin refers to an epoxy resin having two or more epoxy groups. Therefore, the resin composition of this disclosure may include a difunctional epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, and the like. Polyfunctional epoxy resins are broadly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.

[0027] 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, dicyclopentadiene-type diglycidyl ether; trimethylolpropane triglycidyl ether, Examples 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 backbone such as -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0028] In the above examples, "cyclohexane-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are each bonded via ether bonds to a divalent saturated hydrocarbon group having a cyclohexane ring as its parent structure. "Dicyclopentadiene-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are each bonded via ether bonds to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as its parent structure. Furthermore, cyclohexanedimethanol diglycidyl ether is particularly preferred as the cyclohexane-type diglycidyl ether.

[0029] Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins that have a structure containing aromatic rings such as benzene rings. Many conventionally used epoxy resins, such as bisphenol A type epoxy resins, belong to this category. 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.

[0030] As aromatic polyfunctional epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins, and glycidylamine type epoxy resins are preferred, and among these, those with an epoxy equivalent of 90 to 200 g / eq are preferred.

[0031] (2) Compounds having polymerizable double bond groups Polymeric polymer compounds having polymerizable double bond groups are not particularly limited, but polymeric polymer compounds having vinyl groups, especially (meth)acrylic groups or maleimide groups, as reactive double bond groups are preferred.

[0032] Among (meth)acrylic compounds, for example, compounds having alkyl groups 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, n-heptyl acrylate, n-heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, etc.; compounds having alicyclic hydrocarbon groups include cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc.; vinyl monomers having aromatic groups include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc.; 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, cyclohexanedimethanol monomethacrylate, etc. 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, N-butoxymethylmethacrylamide, etc.Furthermore, as compounds having three or more vinyl groups, polyfunctional (meth)acrylates of polyol derivatives such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; pentaerythritol triarylate, pentaerythritol triacrylate, pentaerythritol triacrylate, etc. Polyfunctional arylates such as thritol tetraarylate and trimethylolpropane triarylate; polyester (meth)acrylates such as Aronics M-7100, Aronics M-8030, and Aronics 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 ( All manufactured by Daicel-Scytech Co., Ltd., Arronix M-305, Arronix M-309, Arronix M-310, M-315, M-320, Arronix M-350, Arronix M-360, Arronix M-370, Arronix M-400, Arronix M-402, Arronix M-408, Arronix M-450 (all manufactured by Toagosei Co., Ltd.), Neomar TA-401, TA-505, EA-301, DA-600 (all manufactured by Sanyo Chemical Industries, Ltd.) Examples of polyether (meth)acrylates include 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 Industry Co., Ltd.).

[0033] For example, compounds containing a maleimide group include N,N'-(4,4'-diphenylmethane)bismaleimide and bisphenol A Examples 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-bismaleimide hexane, 1,2-bismaleimide ethane (N,N'-ethylene dimaleimide), N,N'-(1,2-phenylene) bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyl di-p-phenylene) dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide. It is also possible to use dimer acid-modified bismaleimides. For example, dimer acid-modified bismaleimides include the liquid bismaleimides BMI-689, BMI-1500, and BMI-1700, or the solid bismaleimide BMI-3000 (all manufactured by Designer Molecules).

[0034] <Hardening agent> The resin compositions disclosed herein may contain one or more curing agents. The curing agents that may be contained in the resin composition of this disclosure are not particularly limited, but include, for example, nitrogen-containing compounds such as amines and their derivatives; oxygen-containing compounds such as carboxylic acid-terminated polyesters, acid anhydride-based compounds, phenol-based compounds, bisphenol A and cresol novolacs, and phenol-terminated epoxy resins; and sulfur-containing compounds such as thiol compounds.

[0035] Nitrogen-containing compounds such as amines and their derivatives are not particularly limited, but include aliphatic polyamines such as triethylenetetraamine, 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; and 1,4-bis(2-aminomethylpiperazine). Examples of aromatic polyamines include piperazine-type polyamines such as (no-2-methylpropyl)piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethylene oxide-di-p-aminobenzoate. Commercially available products include Epicure-W, Epicure-Z (product name from Yoka Shell Epoxy Co., Ltd.), jER Cure®-W, jER Cure®-Z (product name from Mitsubishi Chemical Corporation), Kaya Hard AA, Kaya Hard AB, Kaya Hard AS (product name from Nippon Kayaku Co., Ltd.), Totamine HM-205 (product name from Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Adeka Hardner EH-101 (product name from ADEKA Corporation), Epomic Q-640, Epomic Q-643 (product name from Mitsui Chemicals, Inc.), DETDA80 (product name from Lonza), Totamine HM-205 (product name from Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), and others.

[0036] The acid anhydride-based curing agent is not particularly limited, but examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhymic anhydride, succinic anhydride substituted with an alkenyl group, glutaric anhydride, etc. In particular, 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo[2.2.2]octo-5-ene-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, hydrogenated methylnadic anhydride, succinic anhydride substituted with an alkenyl group, and diethylglutaric anhydride are preferred.

[0037] Phenolic curing agents refer to monomers, oligomers, and polymers in general that have phenolic hydroxyl groups, and examples include phenol novolac resins and their alkylated or allylated derivatives, cresol novolac resins, phenol aralkyl (including phenylene and biphenylene skeletons) resins, naphthol aralkyl resins, triphenolmethane resins, and dicyclopentadiene-type phenolic resins. Among these, allylphenol novolac resins are preferred.

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

[0039] Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals: PEMP). Examples include dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko Corporation: Karenz MT® PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Corporation: Karenz MT® NR1).

[0040] Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl (trade name: TS-G, manufactured by Shikoku Chemicals Co., Ltd.), 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl (trade name: C3 TS-G, manufactured by Shikoku Chemicals Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl) glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluryl, and 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethyl glycoluryl. Examples include lyl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluryl, pentaerythritol trippropanthol (trade name: PEPT, manufactured by SC Organic Chemicals), pentaerythritol tetrapropanthol, etc.

[0041] As non-hydrolyzable polyfunctional thiol compounds, three- or more polythiol compounds 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, and 4,8-dimercaptomethyl Tyl-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-dithiaundecane, tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiaundecane, tetrakis(mercaptomethylthio) Ahexane, 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) (Tylthio)ethyl)methane, Tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, Tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, Tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-Tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-Hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-Hexatianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexatiaheptadecane, 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-hexatiahexadecane, 8-[bis(mercaptomethylthio)ethyl) [(Tylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexatiapentadecane, 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) Tomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithiethanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithiethanyl)]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-dithiethanyl)]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, 4,4,8,9-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-dithiethane, 2-[3,4-bis(mercaptomethylthio) Examples of polythiol compounds having a cyclic structure include -6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, and 4-{1-[2-(1,3-dithiethanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane.

[0042] <Percentage of composition 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.

[0043] The time it takes for the viscosity of the resin composition to double is defined as the pot life. In epoxy-thiol curing systems, the pot life is preferably 8 hours or more, more preferably 12 hours or more, and even more preferably 24 hours or more. In other curing systems as well, a longer pot life is preferable from the viewpoint of stability.

[0044] <Other components of the resin composition> In addition to the main component, curing catalyst, and curing agent, the curable composition of this disclosure may optionally contain, for example, the following:

[0045] (1) Stabilizer The resin compositions of this disclosure may contain stabilizers to improve their storage stability and extend their pot life. Various known stabilizers can be used as stabilizers for one-component adhesives mainly composed of epoxy resin, but at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates, and organic acids is preferred.

[0046] Examples of liquid borate 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-tetraoxowndecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxowndecyl)borane, trimenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like.

[0047] 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.

[0048] (2) Filler Fillers may be added to the resin composition of this 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 may be hollow, spherical, or amorphous. Furthermore, the fillers may be surface-treated.

[0049] (3) Coupling agent A coupling agent may be added to the resin composition of this disclosure. A silane coupling agent is preferred, and various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto-based agents can be used. These silane coupling agents may be used alone or in combination of two or more.

[0050] Examples of silane coupling agents include alkenyl group-containing silane coupling agents such as vinyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-1003, Momentive Performance Materials Japan; A-171, Toray Dow Corning; Z-6300, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL XL10, Nichibi Shoji Co., Ltd.; Sylace S210, etc.), vinyltriethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBE-1003, Momentive Performance Materials Japan; A-151, Toray Dow Corning; Z-6519, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF56, Nichibi Shoji Co., Ltd.; Sylace S220, etc.), and vinyltriacetoxysilane (commercial products include Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL Examples include GF62, vinyltris(2-methoxyethoxy)silane (commercial products include A-172 from Momentive Performance Materials Japan), vinylmethyldimethoxysilane (commercial products include A-2171 from Momentive Performance Materials Japan, GENIOSIL XL12 from Asahi Kasei Wacker Silicone, etc.), octenyltrimethoxysilane (commercial products include KBM-1083 from Shin-Etsu Chemical Co., Ltd.), allyltrimethoxysilane (commercial products include Z-6825 from Toray Dow Corning Co., Ltd.), and p-styryltrimethoxysilane (commercial products include KBM-1403 from Shin-Etsu Chemical Co., Ltd.). For example, silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-5103, etc.), and silane coupling agents having a methacrylic group include 3-methacryloxypropylmethyldimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-502, Toray Dow Corning Co., Ltd.; Z-6033, etc.), and 3-methacryloxypropyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-503, Momentive Performance Materials Japan;Examples include A-174 (manufactured by Toray Dow Corning; Z-6030 (manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF31 (manufactured by Nichibi Shoji Co., Ltd.; Sylace S710, etc.)), 3-methacryloxypropylmethyldiethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBE-502), 3-methacryloxypropyltriethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBE-503, and Momentive Performance Materials Japan; Y-9936), methacryloxyoctyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-5803), etc., and as silane coupling agents having an epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-303 Examples include Momentive Performance Materials Japan's A-186, Toray Dow Corning's Z-6043, and Nichibi Shoji's Sylace S530), 3-Glycidoxypropylmethyldimethoxysilane (commercial products include Shin-Etsu Chemical's KBM-402, Toray Dow Corning's Z-6044, and Nichibi Shoji's Sylace S520), 3-Glycidoxypropyltrimethoxysilane (commercial products include Shin-Etsu Chemical's KBM-403, Momentive Performance Materials Japan's A-187, Toray Dow Corning's Z-6040, and Asahi Kasei Wacker Silicone's GENIOSIL) Examples include GF80, Cyra Ace S510 manufactured by Nichibi Shoji Co., Ltd., etc., 3-glycidoxypropylmethyldiethoxysilane (commercial products include KBE-402 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (commercial products include KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd., A-1871 manufactured by Momentive Performance Materials Japan, GENIOSIL GF82 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), glycidoxyoctyltrimethoxysilane (commercial products include KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.), etc., and as a silane coupling agent having an amino group, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.;Examples include KBM-602 (manufactured by Momentive Performance Materials Japan), A-2120 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), GENIOSIL GF-95 (manufactured by Nichibi Shoji Co., Ltd.), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-603, Momentive Performance Materials Japan; A-1120, Momentive Performance Materials Japan; A-1122, Toray Dow Corning; Z-6020, Toray Dow Corning; Z-6094, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-91, manufactured by Nichibi Shoji Co., Ltd.; Cyra Ace S320, etc.), 3-aminopropyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBM-903, Momentive Performance Materials Japan; A-1110, Toray Dow Corning Co., Ltd.; Z-6610, Nichibi Shoji Co., Ltd.; Cyra Ace S360, etc.), 3-aminopropyltriethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.; KBE-903, Momentive Performance Materials Japan; A-1100, Toray Dow Corning Co., Ltd.; Z-6011, Nichibi Shoji Co., Ltd.; Cyra Ace S330, etc.), 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine (commercial products Examples include Shin-Etsu Chemical Co., Ltd.'s KBE-9103 and Nichibi Shoji Co., Ltd.'s Sylace S340), N-phenyl-3-aminopropyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.'s KBM-573, Momentive Performance Materials Japan's Y-9669, and Toray Dow Corning's Z-6883), N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (commercial products include Nichibi Shoji's Sylace XS1003), and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane (commercial products include Shin-Etsu Chemical Co., Ltd.'s KBM-575, Toray Dow Corning's Z-6032, and Nichibi Shoji Co., Ltd.Examples include Cyra Ace S350, etc., and as a silane coupling agent having an isocyanurate group, tris-(trimethoxysilylpropyl)isocyanurate (a commercially available product is KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.), and as a silane coupling agent having a mercapto group, 3-mercaptopropylmethyldimethoxysilane (commercial products include KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6852 manufactured by Toray Dow Corning Co., Ltd., etc.), 3-mercaptopropyltrimethoxysilane (commercial products are Examples include Shin-Etsu Chemical Co., Ltd. (KBM-803), Momentive Performance Materials Japan (A-189), Toray Dow Corning (Z-6062), and Nichibi Shoji Co., Ltd. (Syla Ace S810, etc.), 3-mercaptopropyltriethoxysilane (commercial products include Momentive Performance Materials Japan (A-1891) and Toray Dow Corning (Z-6911), and 3-ureidopropyltrialkoxysilane (commercial products) as silane coupling agents having a ureido group. Examples include KBE-585 (manufactured by Shin-Etsu Chemical Co., Ltd.), 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane (A commercially available example is A-1160 (manufactured by Momentive Performance Materials Japan)), bis(triethoxysilylpropyl)tetrasulfide as a silane coupling agent having a sulfide group, and 3-octanoylthio-1-propyltriethoxysilane (a commercially available example is Momentive... Examples include Performance Materials Japan's A-LINK599, and silane coupling agents having an isocyanate group, such as 3-isocyanate-propyltriethoxysilane (commercial products include Shin-Etsu Chemical's KBE-9007 and Momentive Performance Materials Japan's A-1310), and 3-isocyanate-propyltrimethoxysilane (commercial products include Momentive Performance Materials Japan's Y-5187 and Asahi Kasei Wacker Silicone's Y-5187).Examples include GENIOSIL GF40, etc.

[0051] (4) Other additives The resin compositions disclosed herein may contain other additives, such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, defoaming agents, thixotropes, viscosity modifiers, flame retardants, colorants, solvents, etc., to the extent that they do not impair the objectives of the present invention. The type and amount of each additive are in accordance with conventional methods.

[0052] ==Methods of using the resin composition== The resin compositions disclosed herein can be used, for example, as encapsulants and fillers for electronic components, dam materials, conductive or insulating adhesives, die attach materials, films, coatings, and shielding materials. They can also be used in paints, composite materials such as pipe materials and tank materials, flooring materials, civil engineering and construction materials such as membranes, and adhesives, but the methods of use are not limited to these. [Examples]

[0053] ==Method of compound synthesis== Synthesis of (Compound 1) 2-[2-hydroxy-3-(2-methyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [ka] In a reaction vessel containing DMA (dimethylacetamide) (200 g) and a magnetic stirrer, Curesol 2MZ-H (Shikoku Chemicals, 39.9 g, 0.486 mol) was added while stirring, and the mixture was heated to 60°C to dissolve. Denacol EX-731 (Nagase ChemteX, 100 g, 0.363 mmol) was gradually 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 precipitate crystals. The resulting solid was filtered by suction, washed twice with water and twice with IPA, and then dried to obtain compound 1 (85.7 g) (recovery rate 61%). The measured physical properties of the product are as follows.

[0054] 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)

[0055] Synthesis of (Compound 2) 2-[2-hydroxy-3-(1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione (CAS Registry Number: 112086-61-0) [ka] Into a reaction vessel containing DMA (10 mL), Curezol SIZ (manufactured by Shikoku Chemicals Corporation, 1.65 g, 24.3 mmol) was added while stirring with a stirrer, and the mixture was heated to 60 °C to dissolve it. To the resulting solution, Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 5.00 g, 23.1 mmol) was added little by little 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 (about 15 mL) was added and 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 physical property measurement values of the product are as follows.

[0056] 1 H NMR (400 MHz DMSO-d6): 7.93 - 7.77 ppm (m, 4H), 7.58 ppm (s, 1H), 7.16 ppm (s, 1H), 6.84 ppm (s, 1H), 5.41 ppm (d, 5.6 Hz), 4.11 ppm (dd, 3.2 Hz, 13.6 Hz, 1H), 4.04 - 3.94 ppm (m, 1H), 3.89 ppm (dd, 7.2 Hz, 14 Hz, 1H), 3.60 - 3.47 ppm (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 Structure

[0058] 3.00 g of crude crystals were mixed with 1.7 mL of 0.5 N hydrochloric acid and ground in a mortar. Water was added to the resulting powder and suspended it. The suspension was filtered by suction, and the solid was dissolved in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed in the following order: water, saturated sodium bicarbonate solution, and saline solution. The chloroform layer was dehydrated with sodium sulfate, filtered through liquid-phase separation filter paper, and 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 by suction 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.

[0059] 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)

[0060] (Compound 4) Synthesis of 2-[2-hydroxy-3-(2-undecyl-1H-imidazol-1-yl)propyl]-1H-isoindole-1,3(2H)-dione [ka] In a reaction vessel containing DMA (15 mL), Curesol C11Z (Shikoku Chemicals, 5.14 g, 24.3 mmol) was added while stirring with a stirrer, and the mixture was heated to 60°C to dissolve. Denacol EX-731 (Nagase ChemteX, 5.00 g, 23.1 mmol) was gradually 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 the mixture was stirred at 15°C to precipitate crystals. The obtained crystals were filtered by suction, washed with water, and dried to obtain 5.70 g of crude crystals.

[0061] 3.00 g of crude crystals were mixed with 1.8 mL of 1N hydrochloric acid and ground in a mortar. Water was added to the resulting powder and suspended. The suspension was filtered by suction, and the solid was dissolved in chloroform (approximately 50 mL) and transferred to a separatory funnel. The resulting solution was washed in the following order: water, saturated sodium bicarbonate solution, and saline solution. The chloroform layer was dehydrated with magnesium sulfate, filtered through liquid-phase separation filter paper, and the organic layer was concentrated using a rotary evaporator. Ethyl acetate and hexane were added to the resulting white solid and suspended. The suspension was filtered by suction, and 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.

[0062] 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)

[0063] (Compound 5)2-[2-(2-methyl-1H-imidazol-1-yl)ethyl]-1H-isoindole-1,3(2H)-dione Compound 5 (CAS Registry Number: 858512-76-2) was 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 Registry Number: 72459-53-1) was a commercially available product (purchased from Enamine).

[0065] (Compound 7) Synthesis of 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol [ka]

[0066] 2-Methyl-1H-imidazole (Shikoku Chemicals, 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, 22.0 g, 147 mmol) in toluene (38.1 mL) was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. The resulting solution was cooled to room temperature, and the solvent was removed 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 The result was confirmed by 1H NMR.

[0067] (Compound 8) Synthesis of 1-[([1,1'-biphenyl]-2-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol [ka]

[0068] 2-methyl-1-H-imidazole (Shikoku Chemicals, 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. To the resulting solution, a solution of 2-{[([1,1'-biphenyl]-2-yl)oxy]methyl}oxirane (Sanko Co., Ltd., 210 g, 0.913 mol, epoxy equivalent 230 g / eq) dissolved in toluene (363 mL) at room temperature was added at a dropping rate of 3.75 mL / min. After the entire volume was added, the resulting mixture was stirred at 80°C for 75 minutes. Subsequently, the solvent was removed from the resulting reaction product using an evaporator at 50°C to obtain compound 8 (392 g). The identification of the product was... 1 The result was confirmed by 1H NMR.

[0069] ==Evaluation of Compounds== <Measuring the melting point> The melting point was measured using a differential scanning calorimetry system (DSC 204 F1 Phoenix®) (manufactured by NETZSCH). First, 5 mg of the synthesized compound was weighed into an aluminum pan, sealed with an aluminum lid, and then a hole was made in the center of the lid with a needle to prepare the sample for measurement. Next, the heat flow (mW / mg) of this sample was measured while increasing the temperature in the range of 25 to 250°C at a rate of 10°C / min under a nitrogen atmosphere (100 mL / min). The temperature corresponding to the melting point, at which a peak was obtained on the graph, was calculated using analysis 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 flow at the melting point (i.e., maximum heat flow) and the peak area (i.e., heat of fusion) were analyzed using the instrument's analysis software, and the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) was calculated. Furthermore, heat flow (mW / mg) was measured in the range of 25-250°C under heating rates of 10°C / min and 50°C / min. The melting onset temperature (°C) under each condition was analyzed, and the degree of dependence on the heating rate was calculated as (melting onset temperature at a heating rate of 50°C / min) / (melting onset temperature at a heating rate of 10°C / min). The melting onset temperature is defined as the temperature at the intersection of the tangent line with the maximum slope among the tangent lines of the melting peak curve and the baseline of the DSC, at temperatures lower than the melting point.

[0070] The evaluation results for the compound (curing catalyst) are shown in Table 1. [Table 1]

[0071] ==Method for preparing resin composition==

[0072] <Examples 1-4, 6, Comparative Examples 1, 2: Epoxy-thiol curing systems> Compounds 1-4, 6, 7, and 8, used as curing catalysts, were added to the epoxy resin EXA835LV (manufactured by DIC Corporation) and mixed. The mixture was then ground in a mortar until no agglomeration occurred, and stirring and defoaming were performed under vacuum using a planetary stirring and defoaming apparatus. EXA835LV, or a mixture of EXA835LV and CDMDG (manufactured by Showa Denko Corporation), was then added and mixed. Stirring and defoaming were then performed under vacuum using a planetary stirring and defoaming apparatus. Furthermore, PEMP (manufactured by SC Organic Chemicals Co., Ltd.), a thiol resin, was added and mixed. Finally, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming apparatus to obtain the resin composition.

[0073] <Example 5: Epoxy-thiol curing system> Compound 1, used as 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 agglomeration occurred, and stirring and defoaming were performed under vacuum using a planetary stirring and defoaming apparatus. C3TSG (manufactured by Shikoku Chemicals Co., Ltd.), a thiol resin, was then added and mixed. Finally, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming apparatus to obtain the resin composition.

[0074] <Examples 7, 11, 12: Epoxy homopolymerization curing system> Compounds 1, 5, and 6, used as curing catalysts, were added to EXA835LV and mixed. The mixture was then ground in a mortar until no more aggregates formed, and the mixture was stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain the resin composition.

[0075] <Example 8: Epoxy-acid anhydride curing system> Compound 1, used as a curing catalyst, was added to the epoxy resin EXA835LV and mixed. The mixture was then ground in a mortar until no more aggregates formed, and then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. YDF8170 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) was added and mixed. The mixture was then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. Finally, YH306 (manufactured by Mitsubishi Chemical Corporation), an acid anhydride resin, was added and mixed. The mixture was then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain the resin composition.

[0076] <Example 9: Epoxy-phenol curing system> Compound 1, used as a curing catalyst, was added to EXA835LV and mixed. The mixture was then ground in a mortar until no more aggregates formed, and then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. EXA835LV was then added and mixed. The mixture was then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. Finally, MEH8005 (manufactured by Meiwa Kasei Co., Ltd.), a phenolic resin, was added and mixed. The mixture was then stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain the resin composition.

[0077] <Example 10: Acrylic-thiol curing system> Acrylic resin M7100 (manufactured by Toagosei Co., Ltd.), photoradical generator OMNIRAD184 (manufactured by IGM resins BV Co., Ltd.), polymerization inhibitor Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and vibration modifier TS720 were dispersed in a three-roll mill. Compound 1, as a curing catalyst, was added to the resulting mixture and dispersed again in a three-roll mill. PEMP was then added and mixed, and the mixture was stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain a resin composition.

[0078] ==Method for evaluating resin compositions== <Measuring Pot Life> 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 preset appropriate range (H, R, or U). Next, the resin composition was left in a sealed container at 25°C and 50% humidity, and its viscosity 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 and 25°C. The viscosity was measured within a pre-set appropriate range (H, R, or U). The viscosity after standing at each time point was calculated as (viscosity after standing at each time point) / (initial viscosity) to determine the viscosity increase ratio after standing at each time point. For the pot life, samples that did not harden within 8 hours were marked with ○, and those that hardened were marked with ×.

[0079] <Measuring gel time> The time before gelation (referred to as gel time) was measured using a gelation tester (GT-D-15A: manufactured by Eucalyptus Giken Co., Ltd.). The 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 time it took for the resin composition to become stringy when touched with the test rod was defined as the gel time.

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

[0081] [Table 2] [Table 3]

[0082] As shown in Tables 1 to 3, in the resin compositions using compounds 1 to 6, which had a large absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) and low dependence on the heating rate, the viscosity remained almost unchanged even after 8 hours after the resin composition was prepared. On the other hand, compound 7, for which a clear melting peak could not be obtained and the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) could not be calculated, readily dissolved in epoxy resins and cured within 4 hours. Compound 8, which had a small absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) and high dependence on the heating rate, also cured within 8 hours. Thus, the resin compositions in the examples had a longer pot life.

[0083] The resin compositions in the examples gelled within 10 minutes and exhibited sufficient reactivity and curability.

[0084] Furthermore, as shown in Table 3, the curing catalyst of this disclosure can be used not only in epoxy-thiol curing systems, but also in epoxy homopolymerization systems, epoxy-acid anhydride systems, epoxy-phenol systems, and acrylate-thiol systems. It is particularly preferred as a curing catalyst for epoxy-thiol curing systems.

[0085] Thus, the curing catalyst of this disclosure, having a phthalimide skeleton, exhibits high crystallinity and a higher melting point than conventional adducts to which epoxy resin and imidazole derivatives are added. Furthermore, the curing catalyst of this disclosure provides a stable resin composition that is less prone to dissolution of the curing catalyst into the resin at unintended temperatures and has a long pot life. [Industrial applicability]

[0086] This invention makes it possible to provide novel amine derivatives.

Claims

1. In differential scanning calorimetry (DSC), The following structural formula (I) has a value of (initiation temperature at a heating rate of 50°C / min) / (initiation temperature at a heating rate of 10°C / min) of 1.00 or more and 1.10 or less. (In the formula, R １ R is a group selected from phenyl and C1-C17 alkyl groups, ２ , R ３ , R ５ Each of these is independently a hydrogen and a group selected from C1-C6 alkyl groups, and R ４ (where n and m are integers and their sum is 1 or greater) Amine derivatives containing the following characteristics.

2. The amine derivative according to claim 1, wherein the value of (melting onset temperature at a heating rate of 50°C / min) / (melting onset temperature at a heating rate of 10°C / min) is 1.00 or more and 1.02 or less.

3. In differential scanning calorimetry (DSC) with a heating rate of 10°C / min, The amine derivative according to claim 1 or 2, wherein the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) in melting is 0.01 or more and 0.10 or less.

4. The amine derivative according to claim 3, wherein the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is 0.023 or more and 0.045 or less.

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

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

7. A sealing material containing the resin composition described in claim 6.

8. An adhesive containing the resin composition described in claim 6.

9. A cured product of the resin composition according to claim 6.

10. A method for producing an amine derivative according to any one of claims 1 to 4, comprising the step of adducting a compound having a phthalimide skeleton and one epoxy group to an amine.

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