Compound, method for producing compound, epoxy resin composition, and curable composition

Abstract

To provide a compound for providing a curable composition excellent in workability and curability.SOLUTION: The present invention provides: a compound represented by the following general formula (1); a method for producing the compound; and an epoxy resin composition and a curable composition containing the compound. (In formula (1), A represents an alkylene group or an alkylidene group; R1 represents a hydrogen atom or a C1-10 optionally substituted hydrocarbon group; and X1 and X2 each represent a hydrogen atom or a group represented by the following general formula (11), provided that at least one of X1 and X2 is a group represented by general formula (11).) (In formula (11), R2 represents a hydrogen atom or a methyl group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, and more particularly to a glycidyl ether compound having a 1,3-dioxane skeleton. [Background technology]

[0002] Epoxy resins are widely used industrially as components or raw materials for coating materials, adhesives, and various molding materials.

[0003] Epoxy resins include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, and are used for various purposes depending on their properties. For example, Patent Document 1 reports an epoxy resin obtained by curing and crosslinking an epoxy monomer having an acetal skeleton. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Chinese Patent No. 111704711 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the curable compositions containing epoxy compounds known so far have high viscosity, which makes them insufficient in workability, and they do not have excellent curability. Therefore, an object of the present invention is to provide an epoxy compound for obtaining a curable composition having excellent workability and curability. [Means for solving the problem]

[0006] That is, the present invention provides a compound represented by the following general formula (1).

[0007] [ka]

[0008] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 represents a hydrogen atom or a group represented by the following general formula (11), where X 1 or X 2 At least one of the above is a group represented by the following general formula (11).

[0009] [ka]

[0010] In the formula, R 2 is a hydrogen atom or a methyl group.

[0011] The present invention also provides a method for producing a compound represented by the following general formula (1): The present invention provides a method for producing a compound, which comprises an epoxidation step of reacting a compound represented by the following general formula (2) with epihalohydrin:

[0012] [ka]

[0013] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 represents a hydrogen atom or a group represented by the following general formula (11), where X 1 or X 2 At least one of the above is a group represented by the following general formula (11).

[0014] [ka]

[0015] In the formula, R 2 is a hydrogen atom or a methyl group.

[0016] [ka]

[0017] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.

[0018] The present invention also provides an epoxy resin composition containing the compound represented by the above general formula (1). In this specification, the term "epoxy resin composition" refers to a composition containing one or more glycidyl ether compounds, which are epoxy compounds.

[0019] Furthermore, the present invention provides a curable composition containing the compound represented by the above general formula (1) and a curing agent. [Effects of the Invention]

[0020] According to the present invention, a compound for obtaining a curable composition having excellent workability and curability can be provided. [Brief explanation of the drawings]

[0021] [Figure 1] 1 is a GC chart of epoxy resin composition 1. [Figure 2] This is the MS spectrum of peak 1 in Figure 1. [Figure 3] This is the MS spectrum of peak 2 in Figure 1. [Figure 4] This is the MS spectrum of peak 3 in Figure 1. [Figure 5] 1 is a GC chart of epoxy resin composition 2. [Figure 6] 1 is a GC chart of epoxy resin composition 3. DETAILED DESCRIPTION OF THE INVENTION

[0022] The compound of the present invention, its production method, epoxy resin composition, and curable composition will be described in detail below.

[0023] A. Compound First, the compounds of the present disclosure will be described. The compound of the present disclosure (hereinafter, sometimes referred to as compound (1)) is characterized by being represented by the following general formula (1).

[0024] [ka]

[0025] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 represents a hydrogen atom or a group represented by the following general formula (11), where X 1 or X 2 At least one of the above is a group represented by the general formula (11).

[0026] [ka]

[0027] In the formula, R 2 is a hydrogen atom or a methyl group.

[0028] In the above general formula (1), the alkylene group or alkylidene group represented by A is preferably an alkylene group or alkylidene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and a cyclohexylene group. In the present disclosure, the alkylene group or alkylidene group represented by A is more preferably an alkylene group or alkylidene group having 1 to 4 carbon atoms, and examples of such alkylene groups or alkylidene groups include a methylene group, an ethylene group, an ethylidene group, a propylene group, an isopropylene group, a propylidene group, an isopropylidene group, a butylene group, an isobutylene group, a butylidene group, and an isobutylidene group. In particular, an ethylidene group, an isopropylidene group, or an isobutylidene group is preferred, and an isopropylidene group is most preferred. When the alkylene group or alkylidene group represented by A is the above alkylene group or alkylidene group, a composition having excellent workability and curability can be provided.

[0029] R 1 Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group. In the present disclosure, examples of the "substituent" in the phrase "may have a substituent" include halogen atoms such as fluorine, chlorine, bromine, and iodine. In this disclosure, R 1 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms, even more preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group, and most preferably an ethyl group. 1This is because a composition having excellent workability and curability can be obtained when the amount of the hydroxyl group falls within the above range. R 2 is a hydrogen atom or a methyl group, but is preferably a hydrogen atom, since this makes it possible to provide a composition that is excellent in workability and curability.

[0030] Specific examples of compounds represented by the above general formula (1) are given below.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] Among the compounds exemplified by the above general formulas (1-1) to (1-9), the compounds represented by formula (1-1) and formula (1-2) are preferred because they can be easily produced due to the easy availability of raw materials.

[0041] The compound (1) can be used alone or in combination with other epoxy compounds to form an epoxy resin composition.

[0042] B. Methods for producing compounds Next, a method for producing the compound of the present disclosure will be described. The method for producing a compound of the present disclosure is a method for producing a compound represented by the following general formula (1), and is characterized by having an epoxidation step of reacting a compound represented by the following general formula (2) with epihalohydrin.

[0043] [ka]

[0044] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 represents a hydrogen atom or a group represented by the following general formula (11), where X 1 or X 2 At least one of the above is a group represented by the general formula (11).

[0045] [ka]

[0046] In the formula, R 2 is a hydrogen atom or a methyl group.

[0047] [ka]

[0048] In the formula, A represents an alkylene group or an alkylidene group, and R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. The compound represented by the general formula (2) above can be used as a raw material for the compound represented by the general formula (1) above.

[0049] The production method of the present disclosure includes an epoxidation step.

[0050] B-1. Epoxidation process This step is a step of reacting the compound represented by the above general formula (2) (hereinafter sometimes referred to as compound (2)) with epihalohydrin. A and R in compound (2) 1 represents A and R in the above compound (1). 1 It can be similar to:

[0051] The reaction method in this step may be any method that can react the compound represented by the general formula (2) above with epihalohydrin to form the compound represented by the general formula (1) above. Such a reaction method may be a method in which the reaction is carried out in the presence of a phase transfer catalyst. By carrying out the reaction in the presence of a phase transfer catalyst, the reaction between the compound represented by general formula (2) and epihalohydrin can be made to proceed quickly.

[0052] Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin.

[0053] Examples of the phase transfer catalyst include cetyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium chloride, N-methyl ... Examples of suitable ammonium salts include ethylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N,N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, and N-methyl-N-ethylpiperidinium iodide. From the viewpoint of high reactivity, cetyltrimethylammonium chloride is preferred.

[0054] The content of the phase transfer catalyst is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 3.0 parts by mass or less, relative to 100 parts by mass of the compound represented by general formula (2). By setting the content of the phase transfer catalyst within the above range, the reaction can be promoted quickly without producing by-products.

[0055] The reaction method is preferably a method in which the reaction is carried out in the presence of an alkali. This is because the reaction rate can be increased.

[0056] Examples of alkalis include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0057] The content of the alkali is preferably 0.1 mol or more and 10 mol or less, more preferably 0.2 mol or more and 5.0 mol or less, and even more preferably 0.8 mol or more and 1.5 mol or less, relative to 1 mol of the compound represented by general formula (2). By ensuring that the alkali content is within the above range, it is possible to prevent the ring-opening of epoxy groups in the product and the generation of by-products, thereby increasing the reaction rate. The alkali is preferably added dropwise as an aqueous solution under reflux at an internal temperature of 50 to 70°C and a pressure of 110 to 210 hPa, and water is preferably removed simultaneously by azeotropic distillation.

[0058] The reaction method is preferably a method in which the reaction is carried out under heating conditions. The reaction is preferably carried out under atmospheric or reduced pressure, and excess epichlorohydrin is preferably removed by distillation.

[0059] The heating temperature is preferably 25°C or higher and 200°C or lower, more preferably 40°C or higher and 180°C or lower, and even more preferably 60°C or higher and 150°C or lower. By keeping the heating temperature within the above range, it is possible to prevent the ring-opening of epoxy groups in the product and the generation of by-products, thereby increasing the reaction rate.

[0060] B-2.Other The production method of the present disclosure includes the above-described epoxidation step, but may include other steps as necessary. Such other steps may include separation and purification means such as oil-water separation using water or an organic solvent, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, and column chromatography, or a combination of these means.

[0061] C. Epoxy Resin Composition Next, the epoxy resin composition of the present disclosure will be described. The epoxy resin composition of the present disclosure is characterized by containing the above-mentioned compound (1).

[0062] The compound (1) can be the same as described in the section "A. Compounds" above. In the present disclosure, only one of the compounds (1) may be contained, but it is preferable to contain two or more of them. In the present disclosure, the compound represented by the above general formula (1), X 1 and X 2 is a group represented by the above general formula (11) (hereinafter, may be referred to as compound (1x)), and 1 is a group represented by the general formula (11), and X 2 is a hydrogen atom (hereinafter, may be referred to as compound (1y)), and 1 is a hydrogen atom, and X 2 is a group represented by the above general formula (11) (hereinafter, may be referred to as compound (1z)), and it is particularly preferable to contain compound (1x), compound (1y), and compound (1z). This is because the curable composition containing these compounds has excellent workability and curability. The epoxy resin composition containing the compound (1x), the compound (1y), and the compound (1z) may be one obtained by mixing the respective compounds, or may be one produced in a state containing the compound (1x), the compound (1y), and the compound (1z) during the production of the compound (1).

[0063] In the present disclosure, the content of the compound (1x) is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 75 parts by mass or less, based on a total of 100 parts by mass of the compound (1). This is because the curable compositions containing these compounds have low viscosity and high glass transition points (Tg).

[0064] In the present disclosure, the content of the compound (1y) is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 5 parts by mass or more and 70 parts by mass or less, and even more preferably 15 parts by mass or more and 60 parts by mass or less, per 100 parts by mass of the compound (1). This is because the epoxy resin composition has excellent workability and curability.

[0065] In the present disclosure, the content of the compound (1z) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, even more preferably 3 parts by mass or more and 15 parts by mass or less, and particularly preferably 4 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the compound (1). This is because the epoxy resin composition containing the compound has excellent workability and curability.

[0066] In the present disclosure, the total content of the compounds (1y) and (1z) is preferably 10 to 90 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the compound (1). Note that, per 100 parts by mass of the compound (1), the content of each of the compounds (1y) and (1z) is preferably 1 part by mass or more. At or below the upper limit, the epoxy resin composition containing the compound does not gel and has excellent storage stability, while at or above the lower limit, a curable composition having excellent workability and curability can be prepared.

[0067] From the viewpoint of excellent curability and workability, the epoxy equivalent of the epoxy resin composition of the present invention is preferably 150 to 300 g / eq, more preferably 160 to 260 g / eq, and particularly preferably 170 to 210 g / eq.

[0068] The total chlorine content of the epoxy resin composition of the present invention is preferably 20,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 5,000 ppm or less. Use of an epoxy resin composition having a total chlorine content within the above range is preferred because it results in excellent reliability and eliminates or minimizes poor contact due to metal corrosion under high temperature and high humidity conditions.

[0069] The viscosity of the epoxy resin composition of the present invention is preferably 5 to 5000 mPa·s, more preferably 10 to 2000 mPa·s, and even more preferably 50 to 300 mPa·s, because this provides excellent workability when preparing a curable composition. Furthermore, as long as the viscosity of the epoxy resin composition is within the above range, no significant increase in viscosity is observed due to the addition of a curing agent or the like, and therefore the workability of the epoxy resin composition and the curable composition containing a curing agent or the like can be said to be excellent.

[0070] D. Curable composition Next, the curable composition of the present invention will be described in detail. The curable composition of the present invention is characterized by containing the above-mentioned compound (1) and a curing agent.

[0071] D-1. Compound (1) The compound (1) can be the same as described in the section "A. Compounds" above.

[0072] In the present disclosure, only one of the compounds (1) may be contained, but it is preferable to contain two or more of them. This is because the curable composition containing the compound (1) has an excellent balance between the curability and the modulus of elasticity of the cured product. In the present disclosure, when two or more types of compound (1) are contained, the details of the two or more types of compound (1) may be the same as those described in the section "C. Epoxy resin composition" above.

[0073] The content of the compound (1) is preferably 50 parts by mass or more and 99.9 parts by mass or less, more preferably 60 parts by mass or more and 99.5 parts by mass or less, and particularly preferably 70 parts by mass or more and 99 parts by mass or less, per 100 parts by mass of the curable composition. This is because it is possible to provide a curable composition that is excellent in workability and curability.

[0074] D-2. Other epoxy compounds The curable composition may contain an epoxy compound other than the compound (1) (hereinafter, sometimes referred to as an "other epoxy compound"). Examples of the other epoxy compounds include known epoxy compounds. Examples of the epoxy compounds include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; polyglycidyl ethers of maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydroxybenzo ... Examples of suitable epoxy resins include glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids such as tetrahydrophthalic acid and endomethylenetetrahydrophthalic acid; homopolymers or copolymers of glycidyl methacrylate; epoxidized products of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may also be internally crosslinked with a prepolymer of terminal isocyanate or polymerized using a polyvalent active hydrogen compound (such as a polyphenol, polyamine, carbonyl group-containing compound, or polyphosphate ester).

[0075] Commercially available epoxy compounds include, for example, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-920, Denacol EX-931, Denacol EX-201, Denacol EX-711, and Denacol EX-721 (manufactured by Nagase ChemteX Corporation); Epolite 200E, ... Polite 400E, Epolite 70P, Epolite 200P, Epolite 400P (Kyoeisha Chemical Co., Ltd.), Adeka Resin EP-4088S, EP-4088L, EP-4080E, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (ADEKA Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (Osaka Gas Chemicals Co., Ltd.); YD series, YDF series, YDPN series, TDCN series (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Celloxide 2021P, Celloxide 2081 (Daicel Corporation); TECHMORE Examples include VG-3101L (manufactured by Printec Co., Ltd.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation).

[0076] From the viewpoint of achieving an excellent balance between curability and the elastic modulus of the cured product, the content of the other epoxy compounds is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the epoxy resin.

[0077] The total content of the compound (1) and other epoxy compounds is preferably 50 parts by mass or more and 99.9 parts by mass or less, more preferably 60 parts by mass or more and 99.5 parts by mass or less, and even more preferably 70 parts by mass or more and 99 parts by mass or less, per 100 parts by mass of the curable composition, from the viewpoint of achieving an excellent balance between curability and the elastic modulus of the cured product.

[0078] D-3. Hardener Preferred examples of the curing agent include phenol-based curing agents, acid anhydride-based curing agents, thiol-based curing agents, amine-based curing agents, cationic polymerization initiators, and active ester-based curing agents.

[0079] Examples of phenol-based curing agents include polyhydric phenol compounds such as phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol adduct resin, phenol aralkyl resin (Xyloc resin), naphthol aralkyl resin, trisphenylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring, and a primary amino group in its molecular structure), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0080] Examples of acid anhydride curing agents include himic anhydride, phthalic anhydride, maleic anhydride, methyl himic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrogenated methylnadic anhydride.

[0081] Examples of the thiol-based curing agent include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), 1,3,4,6-tetrakis(2-mercaptoethyl)-1,3,4,6-tetraazaochydropentalene-2,5-dione, 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoctane, Undecane, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11 -Dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 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, 4,6-bis(mercaptomethyl thio)-1,3-dithiane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-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)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 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8 ,9,13,14-Hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithia heptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2-(1,3-dithietanyl)]methyl-2,4-Dithiapentane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16 -Hexathiaheptadecane, 3,7-bis[2-(1,3-dithietanyl)]methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4,6-bis{3-[2-(1,3-dithietanyl)]methyl-5-mercapto-2,4-dithiapentylthio}-1,3-dithiane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5 ,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1 ,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)methyl] Examples of suitable mercaptothiolane include 4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2-{bis[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]methyl}-1,3-dithietane, and 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]-5-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane. Examples of commercially available thiol-based curing agents include TS-G manufactured by Shikoku Chemical Industry Co., Ltd., DPMP and PEMP manufactured by SC Organic Chemical Co., Ltd., and PETG manufactured by Yodo Chemical Co., Ltd. In particular, it is preferable to use a thiol-based curing agent that is a polythiol compound having 4 or more valences, since this will provide excellent curability.

[0082] Examples of the amine-based curing agent include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, and 1,4-diamino-3 Alicyclic polyamines such as 6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine; m-xylylenediamine, diaminodiphenyl Aromatic polyamines such as methane, diaminodiphenyl sulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, etc.; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2-ethyl imidazoles such as 2-methyl-4-imidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide;N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine N,N-Cyclohexylmethylaminopropylamine, N,N-Dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N,N,-dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine;N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropylcyclohexylamine, N,N-bisaminopropylbenzylamine, N,N-bisaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diaminopropyl)]amine Examples of imidazoles include bis[3-(N,N-dibutylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-{3-[(3-trimethoxysilyl)propylaminocarbonylamino]propyl}-2-methylimidazole, 1-[3-trimethoxysilylpropylaminomethyl]-4-methylimidazole, 1-[3-(trimethoxysilylpropyl)]imidazole, and 1-[3-(trimethoxysilylpropyl)]imidazole;

[0083] Among the amine-based curing agents, amine-based latent curing agents that do not react with the epoxy compound when mixed but react and cure by heating can also be used. Examples of the amine-based latent curing agents include dibasic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; guanamines such as benzoguanamine and acetoguanamine; dicyandiamide; melamine; and modified amines such as dehydration condensation products of amine compounds and carboxylic acids, adducts of amine compounds and epoxy compounds, adducts of amine compounds and isocyanate compounds, Michael adducts of amine compounds, Mannich reaction products of amine compounds, condensates of amine compounds and urea, and condensates of amine compounds and ketones.

[0084] Among the above-mentioned amine-based latent curing agents, preferred are adducts of amine compounds having one or more active hydrogens with polyepoxy compounds and / or polyisocyanate compounds, or those obtained by combining these with phenolic resins.

[0085] Examples of the amine compound having one or more active hydrogens include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, and 1, Alicyclic polyamines such as 4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine; m-xylylenediamine, diaminodicyclohexylmethane, and diaminodicyclohexylmethane; Aromatic polyamines such as diaminodiphenylmethane, diaminodiphenyl sulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2 Imidazoles such as 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide;N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine N,N-Cyclohexylmethylaminopropylamine, N,N-Dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N,N,-dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine;N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropylcyclohexylamine, N,N-bisaminopropylbenzylamine, N,N-bisaminopropyl imidazoles such as allylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole;

[0086] Examples of the polyepoxy compounds include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; and polynuclear polyhydric phenols such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenol. Polyglycidyl ether compounds of alcohol compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, Glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having a glycidylamino group, such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine;Examples of epoxy compounds include epoxidized cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate.

[0087] Examples of the polyisocyanate compound include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; Examples of suitable diisocyanates include alicyclic diisocyanates such as trans-1,4-cyclohexyl diisocyanate and norbornene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4)-trimethylhexamethylene diisocyanate and lysine diisocyanate; isocyanurate trimer, biuret trimer, and trimethylolpropane adducts of the above-exemplified diisocyanates; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate. Furthermore, these isocyanate compounds may be used in a carbodiimide-modified, isocyanurate-modified, biuret-modified or other form, or may be used in the form of a blocked isocyanate blocked with various blocking agents.

[0088] Examples of the phenolic resin include polyhydric phenol compounds such as phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, dicyclopentadiene phenol adduct resin, phenol aralkyl resin (Xyloc resin), naphthol aralkyl resin, trisphenylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenolic resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenolic resin (a compound having a phenol skeleton, a triazine ring, and a primary amino group in its molecular structure), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0089] Commercially available products of the amine-based latent curing agent include, for example, ADEKA HARDNER EH-3636S (manufactured by ADEKA CORPORATION; dicyandiamide-type latent curing agent), ADEKA HARDNER EH-4351S (manufactured by ADEKA CORPORATION; dicyandiamide-type latent curing agent), ADEKA HARDNER EH-5011S (manufactured by ADEKA CORPORATION; imidazole-type latent curing agent), ADEKA HARDNER EH-5046S (manufactured by ADEKA CORPORATION; imidazole-type latent curing agent), ADEKA HARDNER EH-4357S (manufactured by ADEKA CORPORATION; polyamine-type latent curing agent), ADEKA HARDNER EH-5057P (manufactured by ADEKA CORPORATION; polyamine-type latent curing agent), ADEKA HARDNER Examples of such curing agents include EH-5057PK (manufactured by ADEKA Corporation; polyamine-type latent curing agent), Amicure PN-23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent curing agent), Amicure PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent curing agent), Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazide-type latent curing agent), and Fujicure FXR-1020 (manufactured by T&K TOKA Corporation; latent curing agent).

[0090] The cationic polymerization initiator is a compound capable of releasing a substance that initiates cationic polymerization upon exposure to heat or energy rays. Particularly preferred cationic polymerization initiators are double salts or derivatives thereof, which are onium salts that release a Lewis acid upon exposure to heat or light. Representative examples of such compounds include salts of cations and anions represented by the following general formula: [A] m+ [B] m-

[0091] Cation [A] m+ is preferably an onium, and its structure is, for example, represented by the general formula [(R 5 )pQ] m+ It can be expressed as: where R 5 is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms, and p is an integer of 1 to 5. 5are each independently selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. The cation [A] m+ When the valence of Q in the formula is q, the relationship m=pq must hold (however, N=N is treated as having a valence of 0).

[0092] Also, anions [B] m- is preferably a halide complex, and its structure is, for example, represented by the general formula [LX r ] m- It can be expressed as: Here, L is a metal or metalloid that is the central atom of the halide complex, such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, or Co, and X is a halogen atom. r is an integer from 3 to 7, and the anion [B] m- When the valence of L in the formula is s, the relationship m=rs must hold.

[0093] The anion [LX r ] m- A specific example is tetrafluoroborate (BF4) - , hexafluorophosphate (PF6) - , hexafluoroantimonate (SbF6) - , hexafluoroarsenate (AsF6) - , hexachloroantimonate (SbCl6) - etc.

[0094] Also, anions [B] m- As for LX r -1 (OH)] m- The structure represented by the following formula can also be preferably used. Here, L, X, and r are the same as those described above. Other anions that can be used in the present invention include perchlorate ion (ClO4)- , trifluoromethyl sulfite ion (CF3SO3) - , fluorosulfonate ion (FSO3) - , toluenesulfonate anion, trinitrobenzenesulfonate anion, etc.

[0095] As the onium salt, for example, the following aromatic onium salts A) to C) can be used. Among these, one type can be used alone, or two or more types can be used in combination. a) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate b) Diaryl iodonium salts such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, and di(4-tert-butylphenyl)iodonium hexafluorophosphate c) Triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bis-hexafluoroantimonate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bis-hexafluorophosphate, 4,4'-bis[ Triarylsulfonium salts such as di(β-hydroxyethoxy)phenylsulfonio]phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenyl sulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl)phenylthio]phenyl-di-(4-fluorophenyl)sulfonium hexafluoroantimonate, and 4-[4'-(benzoyl)phenylthio]phenyl-di-(4-fluorophenyl)sulfonium hexafluorophosphate

[0096] In addition, examples of cationic polymerization initiators other than those mentioned above include (η 5 and mixtures of aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, and tris(salicylaldehydato)aluminum with silanols such as triphenylsilanol.

[0097] Furthermore, for example, cationic polymerization initiators described in JP-A-6-41215, JP-A-6-65310, JP-A-6-206862, JP-A-6-247925, Japanese Patent No. 2699188, Japanese Patent No. 2706833, Japanese Patent No. 2709625, Japanese Patent No. 2782093, Japanese Patent No. 2782104, Japanese Patent No. 2782106, JP-A-2006-282633, JP-A-2007-91702, etc. can also be used.

[0098] Commercially available cationic polymerization initiators include, for example, Kayarad PCI-220 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad PCI-620 (manufactured by Nippon Kayaku Co., Ltd.), UVI-6990 (manufactured by Union Carbide Corporation), Adeka Optomer SP-150 (manufactured by ADEKA Corporation), Adeka Optomer SP-170 (manufactured by ADEKA Corporation), CI-5102 (manufactured by Nippon Soda Co., Ltd.), CIT-1370 (manufactured by Nippon Soda Co., Ltd.), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), CIP-1866S (manufactured by Nippon Soda Co., Ltd.), CIP-2048S (manufactured by Nippon Soda Co., Ltd.), CIP-2064S (manufactured by Nippon Soda Co., Ltd.), DPI-101 (manufactured by Midori Chemical Co., Ltd.), DPI-102 (manufactured by Nippon Soda Co., Ltd.), and the like. ), DPI-103 (same manufacturer), DPI-105 (same manufacturer), MPI-103 (same manufacturer), MPI-105 (same manufacturer), BBI-101 (same manufacturer), BBI-102 (same manufacturer), BBI-103 (same manufacturer), BBI-105 (same manufacturer), TPS-101 (same manufacturer), TPS-102 (same manufacturer), TOS-103 (same manufacturer), TPS-105 (same manufacturer), MDS-103 (same manufacturer), MDS-105 (same manufacturer), DTS-102 (same manufacturer), DTS-103 (same manufacturer), PI-2074 (manufactured by Rhodia), SI-60L (manufactured by Sanshin Chemical Co., Ltd.), SI-80L (same manufacturer), SI-100L (same manufacturer), and the like.

[0099] The active ester curing agent is not particularly limited, and known active ester curing agents can be used. Compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance in particular, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., and halides thereof. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins. Specific examples of preferred active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins which are acetylated phenol novolac, and active ester resins which are benzoylated phenol novolac. Of these, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in terms of their excellent ability to improve peel strength. Commercially available active ester curing agents include HPC-8000-65T (an active ester curing agent containing a dicyclopentadiene structure) and HPC-8150-60T (an active ester curing agent containing a naphthalene structure in the main skeleton) (both manufactured by DIC Corporation), and V-575 and V-577 (polyarylates having a bisphenol skeleton, both manufactured by Unitika Ltd.). The active ester curing agent may be used alone or as a mixture of two or more kinds in any combination and ratio.

[0100] In the present disclosure, among the above curing agents, amine-based curing agents are preferred, and imidazole-based curing agents are particularly preferred. This is because a curable resin composition having excellent workability and curability can be obtained.

[0101] The preferred amount of the curing agent varies depending on the type of curing agent. Phenol-based curing agent: When a phenol-based curing agent is used as the curing agent, the amount used is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass, and particularly preferably 40 to 100 parts by mass, per 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Acid anhydride curing agent: When an acid anhydride curing agent is used as the curing agent, the amount used is preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, and particularly preferably 40 to 100 parts by mass, per 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Thiol-based curing agent: When a thiol-based curing agent is used as the curing agent, the amount used is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and particularly preferably 10 to 70 parts by mass, per 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Amine-based curing agent: When an amine-based curing agent is used as the curing agent, the amount used is preferably 0.01 to 80 parts by mass, more preferably 0.05 to 60 parts by mass, and particularly preferably 0.1 to 40 parts by mass, per 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Cationic polymerization initiator: When a cationic polymerization initiator is used in the curing agent, the amount used is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 20 parts by mass, and particularly preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Active ester curing agent: When an active ester curing agent is used as the curing agent, the amount used is preferably 0.2 to 2.0 parts by mass, more preferably 0.5 to 1.5 parts by mass, and particularly preferably 0.7 to 1.3 parts by mass, per 100 parts by mass of the total mass of the compound represented by formula (1) and other epoxy compounds. Within the above range, a composition with excellent workability and curability can be obtained.

[0102] D-4. Other ingredients The curable composition may contain other components in addition to the compound (1), other epoxy compounds, and curing agents. Examples of such other components include commonly used additives such as curing catalysts, anionic or cationic polymerization initiators, inorganic fillers, diluents, reinforcing materials, silane coupling agents, lubricants, pigments, thickeners, thixotropic agents such as hydrophobic fumed silica, antioxidants, light stabilizers, ultraviolet absorbers, antifoaming agents, rust inhibitors, colloidal silica, colloidal alumina, etc. In the present invention, adhesive resins such as xylene resins and petroleum resins can also be used in combination.

[0103] Examples of the curing catalyst include phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-{3-[(3-trimethoxysilyl)propylaminocarbonylamino]propyl}-2-methylimidazole, 1-[3-trimethoxysilylpropylaminomethyl]-4-methylimidazole, 1-[3-(trimethoxysilylpropyl)]imidazole, and 1-[3-(trimethoxysilylpropyl)]imidazole. Examples of the curing accelerator include imidazoles; imidazole salts obtained by combining the above imidazoles with trimellitic acid, isocyanuric acid, boron, or the like; amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts such as trimethylammonium chloride; ureas such as 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, and tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines, ether compounds, or the like. These curing accelerators may be used alone or in combination of two or more.

[0104] The use of the curing catalyst is optional, but when used, the amount used is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the compound represented by formula (1) and the other epoxy compounds.

[0105] Examples of the inorganic filler include silica such as fused silica and crystalline silica; powders such as magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllium, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or beads obtained by spheronizing these, and inorganic fillers such as glass fiber.

[0106] Examples of the diluent include non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar.

[0107] Examples of the reinforcing material include fibrous fillers such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber; and reinforcing materials such as glass cloth, aramid cloth, and carbon fiber.

[0108] Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

[0109] Examples of the lubricant include candelilla wax, carnauba wax, Japan wax, Ibota wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic wax, aliphatic esters, aliphatic ethers, aromatic esters, and aromatic ethers.

[0110] The curable composition of the present invention preferably has a glass transition temperature (Tg) of 10°C or higher, more preferably from 20 to 300°C, and particularly preferably from 30 to 200°C, from the viewpoint of heat resistance.

[0111] The curable resin composition of the present invention can be used for applications such as adhesives, paints, civil engineering and building materials, and insulating materials for electronic components. It is particularly useful as insulating casting materials, laminating materials, and sealing materials in the electronics field. Furthermore, the epoxy resin of the present invention and a curable composition containing the same can be used for multilayer printed wiring boards, laminates for electric and electronic circuits, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, insulating sheets, prepregs, heat dissipation substrates, and the like. [Example]

[0112] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0113] [Example 1] [Preparation of Epoxy Resin Composition 1] A 1-L flask equipped with a reflux apparatus, stirrer, pressure reducer, and dropping apparatus was charged with 109.67 g (0.50 mol) of 5-ethyl-5-(hydroxymethyl)-β,β-dimethyl-1,3-dioxane-2-ethanol, 371.29 g (4.01 mol) of epichlorohydrin, and 1.65 g (5.16 mmol) of cetyltrimethylammonium chloride. The pressure was reduced to reflux, and 108.77 g (1.31 mol) of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After an additional hour of reaction, the mixture was cooled to below 40°C and unreacted solids were removed by filtration. The epichlorohydrin was removed under reduced pressure, yielding 139.45 g of a pale yellow liquid, Epoxy Resin Composition 1. The GC chart of the obtained product is shown in Figure 1, and the MS spectrum of the product is shown in Figures 2, 3, and 4. The MS spectrum confirmed the formation of compounds 1 to 3, and the GC chart showed that the respective ratios were 40:7:53 (wt%). The epoxy equivalent of epoxy resin composition 1 was 200 g / eq, the total chlorine was 10,300 ppm, and the viscosity was 230 mPa s. The viscosity was measured using a rotational viscometer TV-35 type viscometer rotor No. 2 manufactured by Toki Sangyo Co., Ltd., at a rotation speed of 60 rpm and a temperature of 25°C. The above compounds 1 to 3 correspond to the compound (1y), compound (1z), and compound (1x), respectively, explained in the section "C. Epoxy resin composition."

[0114] [ka]

[0115] [Examples 2 and 3] [Preparation of Epoxy Resin Compositions 2 and 3] 20.22 g of epoxy resin composition 1 was placed in a round-bottom flask equipped with a distillation apparatus, rotor, and thermometer, and distilled under 1 hPa. 10.14 g of epoxy resin composition 2, a pale yellow liquid with a boiling point of 125-130°C, and 6.12 g of epoxy resin composition 3, a colorless, transparent liquid with a boiling point of 131-137°C, were obtained. GC charts of epoxy resin composition 2 and epoxy resin composition 3 are shown in Figures 5 and 6, respectively. The ratio of compounds 1 to 3 in epoxy resin composition 2 was 52:8:40, and the ratio of compounds 1 to 3 in epoxy resin composition 3 was 21:7:72. The epoxy equivalent of epoxy resin composition 2 was 209 g / eq, the total chlorine was 2980 ppm, and the viscosity was 200 mPa·s. The epoxy equivalent of epoxy resin composition 3 was 172 g / eq, the total chlorine was 1030 ppm, and the viscosity was 180 mPa·s. The viscosity was measured under the same conditions as in Example 1.

[0116] [Comparative Examples 1 and 2] As Comparative Examples 1 and 2, the following B-1 and B-2 were used, respectively, and the viscosity was measured under the same conditions as in Example 1. B-1: ADEKA Resin EP-4100E, bisphenol A epoxy resin (manufactured by ADEKA Corporation) B-2: ADEKA Glycirol ED-509S, t-butylphenyl glycidyl ether (manufactured by ADEKA Corporation)

[0117] [Evaluation example 1] <Workability> Epoxy resin compositions with a viscosity of less than 5000 mPa·s were deemed to pass, and those with a viscosity of 5000 mPa·s or more were deemed to fail.

[0118] [Table 1]

[0119] Example 4 A 100 mL disposable cup was charged with 10 g of epoxy resin composition 1, 0.5 g of 2-ethyl-4-methylimidazole (2E4MZ) as a curing agent, and 0.4 g of hydrophobic fumed silica as a thixotropic agent, and the mixture was stirred with a spatula at 25°C for 5 minutes to prepare a curable composition. The curable composition was then heated in a thermostatic chamber at 80°C for 2 hours and then at 150°C for 2 hours to obtain a cured product. The glass transition temperature (Tg) of the resulting cured product was 36°C.

[0120] [Examples 5 and 6] Curable compositions were prepared by changing the formulation as shown in Table 2, and the same procedures as in Example 4 were carried out to obtain cured products. The glass transition temperatures (Tg) and curability of the obtained cured products are shown in Table 2. [Comparative Examples 3 and 4] Cured products were obtained in the same manner as in Example 4, except that the formulations were changed as shown in Table 2. The glass transition points (Tg) and curability of the obtained cured products are shown in Table 2.

[0121] [Evaluation example 2] <Glass transition temperature (Tg)> To measure the glass transition temperature (Tg), strip-shaped test pieces measuring 5 mm wide x 60 mm long x 300 μm thick were cut out from the cured sample, and a dynamic viscoelasticity test was performed using a TA Instruments RSA. The temperature at Tan δ was taken as the Tg value.

[0122] [Evaluation example 3] <Curability> 2 g of each of the obtained curable compositions was placed in a thermostatic bath at 120° C. and left to stand for 2 hours. When the resin composition after heating was touched with a spatula, those that had no fluidity were rated as passed, and those that had fluidity were rated as failed.

[0123] [Table 2] C-1: 2-ethyl-4-methyl-imidazole (2E4MZ, manufactured by Shikoku Kasei Holdings Co., Ltd.) D-1: RY-200S, hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd.)

[0124] As is clear from the results shown in Table 1, the compound represented by general formula (1) provided by the present invention can provide a curable composition that can be cured by heat. Furthermore, it was confirmed that the viscosity of the composition was 500 mPa s or less, which provided excellent workability. [Industrial Applicability]

[0125] The compound of the present invention is useful as an epoxy resin material, and the curable composition containing it has excellent workability and good curing properties, and therefore can be used in applications such as adhesives, paints, civil engineering and building materials, and insulating materials for electronic components. It is particularly useful as insulating casting, laminating materials, and sealing materials in the electronics field. Furthermore, the epoxy resin of the present invention and the curable composition containing it can be used in multilayer printed wiring boards, laminates for electric and electronic circuits, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, insulating sheets, prepregs, heat dissipation substrates, and the like.

Claims

1. A compound represented by the following general formula (1): 【Chemical 1】 (In the formula, A represents an alkylene group or an alkylidene group, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent; X １ and X ２ represents a hydrogen atom or a group represented by the following general formula (11): １ or X ２ At least one of the groups is a group represented by the general formula (11). 【Chemistry 2】 (In the formula, R ２ is a hydrogen atom or a methyl group.

2. A method for producing a compound represented by the following general formula (1): A method for producing a compound, comprising an epoxidation step of reacting a compound represented by the following general formula (2) with epihalohydrin: 【Chemistry 3】 (In the formula, A represents an alkylene group or an alkylidene group, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, X １ and X ２ represents a hydrogen atom or a group represented by the following general formula (11): １ or X ２ At least one of the groups is a group represented by the general formula (11). 【Chemistry 4】 (In the formula, R ２ is a hydrogen atom or a methyl group. 【Chemistry 5】 (In the formula, A represents an alkylene group or an alkylidene group, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.

3. The method for producing the compound according to claim 2, wherein the epoxidation step is a step of reacting in the presence of a phase transfer catalyst.

4. An epoxy resin composition containing the compound according to claim 1.

5. Represented by the general formula (1), X １ and X ２ is a group represented by the general formula (11), Represented by the general formula (1), X １ is a group represented by the general formula (11), and X ２ is a hydrogen atom, and a compound represented by the general formula (1), １ is a hydrogen atom, and X ２ is a group represented by the general formula (11), and The epoxy resin composition according to claim 4, comprising:

6. Represented by the general formula (1), X １ and X ２ is a group represented by general formula (11), is 20 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the compounds represented by general formula (1).

7. Represented by the general formula (1), X １ is a group represented by the general formula (11), and X ２ is a hydrogen atom is 1 part by mass or more and 80 parts by mass or less per 100 parts by mass of the compound represented by general formula (1).

8. A curable composition comprising the compound according to claim 1 and a curing agent.

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