Compound, method for producing said compound, and curable composition containing said compound

Abstract

To provide a compound which can be used for a curable composition capable of being cured by light and heat.SOLUTION: A compound is represented by the following general formula (1) (where A1 represents a C1-10 alkylene group; R1 represents a hydrogen atom or a methyl group; each R2 independently represents a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group which may have a substituent, or a halogen atom; R3 represents a hydrogen atom or a methyl group; the substituent is a C1-10 alkyl group, a C1-10 alkoxy group, or a halogen atom; and n represents a number of 0-4).SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a compound, and more particularly to a specific compound having a reactive unsaturated bond and an epoxy group. The present invention also relates to a method for producing the compound, and a curable composition containing the compound and a curing agent. [Background technology]

[0002] In recent years, as mobile devices such as smartphones have become thinner, the camera modules mounted on such devices have become smaller. As camera modules become smaller, the areas where the components of the camera modules are joined together have also become finer, so the adhesive layers formed from the adhesive that join these components are required to have high adhesive strength.

[0003] Adhesives used in the assembly of camera modules and the like must be able to cure at low temperatures to avoid thermal damage to image sensors and other components caused by high-temperature processing. They must also be able to cure quickly to improve production efficiency. From this perspective, ultraviolet-curing adhesives and thermosetting epoxy resin adhesives are widely used as low-temperature, short-curing adhesives. However, while ultraviolet-curing adhesives can cure quickly, they have the disadvantage of being unable to be used to bond areas that are not exposed to light. On the other hand, even thermosetting epoxy resin adhesives, even though they are low-temperature, short-curing adhesives, require the components to be fixed with a jig or device to maintain their bonding position during bonding. Furthermore, their viscosity decreases due to temperature increases caused by heating, resulting in problems such as sagging just before curing or flowing to areas other than the desired area, making them less than satisfactory.

[0004] To solve the above problems, adhesives have been proposed that are temporarily fixed by curing (pre-curing) with light irradiation and then further cured (mainly cured) with heat to form an adhesive bond. For example, Patent Document 1 proposes a photo- and heat-curable composition containing a curable component consisting of a compound having a glycidyl group and a (meth)acryloyl group, a polythiol compound, and an epoxy curing accelerator. Patent Document 2 proposes a curable composition containing a compound having a (meth)acryloyl group, a polythiol compound, a photoradical generator, and a latent curing agent, and also describes a compound having a (meth)acryloyl group and an epoxy group. However, the epoxy (meth)acrylates described in Patent Documents 1 and 2 are compounds obtained by reacting an epoxy resin with (meth)acrylic acid, and are not satisfactory for application to light and heat curing systems, since they tend to become a mixture of multiple compounds due to unreacted epoxy resin remaining during production, and tend to have high viscosity.

[0005] Furthermore, Patent Document 3 proposes a compound having a (meth)acryloyl group and a glycidyl group, but the compound does not have sufficient curability to be used as a material in a curing system using light and heat. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-51954 [Patent Document 2] WO2018 / 181421 [Patent Document 3] US Patent Application Publication No. 2020 / 0048301 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a compound that can be used in a curable composition that can be cured by light and heat, and to provide a curable composition that has excellent curability by light and heat. [Means for solving the problem]

[0008] That is, the present invention provides a compound represented by the following general formula (1).

[0009] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R 3 represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0010] The present invention also provides a compound represented by the following general formula (2):

[0011] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0012] The present invention also provides a method for producing a compound represented by the general formula (1), which comprises reacting a compound represented by the following general formula (3) with epihalohydrin to produce a compound represented by the general formula (2), and then esterifying the compound represented by the general formula (2) with an acrylic acid derivative and / or a methacrylic acid derivative:

[0013] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0014] The present invention also provides a curable composition comprising component (A): at least one compound represented by the following general formula (1) and component (B): a curing agent.

[0015] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R 3 represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4. [Effects of the Invention]

[0016] The compound provided by the present invention is suitable as a material to be cured by light and heat. Furthermore, the curable composition provided by the present invention has excellent photocuring properties and excellent thermosetting properties, and therefore can be used for dual curing, in which pre-curing is performed by light and then full curing is performed by heat. Due to these properties, the curable composition provided by the present invention can be used for applications such as liquid sealants, liquid adhesives, adhesives for camera modules, and liquid crystal sealants. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 shows the results of 1H-NMR measurement of the compound obtained in Production Example 1. [Figure 2] FIG. 2 shows the results of 1H-NMR measurement of the compound obtained in Example 1. [Figure 3] FIG. 3 shows the results of 1H-NMR measurement of the compound obtained in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below. The present invention provides a compound represented by the following general formula (1):

[0019] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R 3 represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0020] The compound of the present invention represented by the general formula (1) has a glycidyl ether group and a reactive unsaturated bond, and therefore can be cured by light and / or heat using various curing agents and / or various polymerization initiators. The reactive unsaturated bond is also sometimes called an ethylenically unsaturated bond.

[0021] In the general formula (1), R 2 Examples of the alkyl group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a benzyl group, a phenethyl group, a vinyl group, an allyl group, and an ethynyl group.

[0022] In the general formula (1), R 2 Examples of the alkoxy group having 1 to 20 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a pentyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, and an eicosyloxy group.

[0023] In the general formula (1), R 2 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0024] In the general formula (1), R 2Examples of the aryl group represented by the formula (I) include a phenyl group and a naphthyl group. These may also be substituted with an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, or a decyl group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a pentyloxy group, an octyloxy group, a nonyloxy group, or a decyloxy group; or a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0025] In the general formula (1), A 1 Examples of the alkylene group having 1 to 10 carbon atoms represented by the formula (I) 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, and a decylene group.

[0026] Among the compounds represented by the general formula (1), the compounds represented by the following general formula (1a) are preferred because they can be easily produced due to the easy availability of raw materials, and because they have excellent photo- and heat-curing properties when used in combination with various curing agents and various polymerization initiators.

[0027] [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 3 represents a hydrogen atom or a methyl group, and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom; and m represents a number from 0 to 4.

[0028] In the general formula (1a), R 4Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; and examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

[0029] The present invention also provides a compound represented by the following general formula (2):

[0030] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0031] A in the general formula (2) 1 and R 2 Specific examples of the above are, for example, A 1 and R 2 Examples of specific examples include the following:

[0032] The compound represented by the general formula (2) has both an alcoholic hydroxyl group and a glycidyl ether group, and therefore can be used in a variety of applications. In addition, the compound represented by the general formula (2) is useful as a raw material for the compound represented by the general formula (1) of the present invention.

[0033] The method for producing the compound of the present invention represented by the general formula (1) is not particularly limited, but it can be produced by utilizing the difference between one phenolic hydroxyl group and two alcoholic hydroxyl groups in a compound containing three hydroxyl groups represented by the following general formula (3). Specifically, the compound can be produced by glycidyl etherifying only the phenolic hydroxyl groups to produce a compound represented by the general formula (2), and then converting the alcoholic hydroxyl groups into acrylate or methacrylate esters. More specifically, it can be produced, for example, by the production method described below.

[0034] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, and R 2 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

[0035] The compound of the present invention represented by the general formula (2) can be produced by glycidyl etherifying only the phenolic hydroxyl group in the compound represented by the general formula (3).

[0036] A method for glycidyl etherifying the phenolic hydroxyl group in the compound represented by the general formula (3) includes a method in which an alkali is added to a mixture of the compound represented by the general formula (3) and epihalohydrin to cause a reaction. Examples of the method for adding the alkali include a method in which an aqueous alkali solution is added dropwise, and a method in which a solid alkali is added, preferably in multiple portions.

[0037] Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Examples of the alkali include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0038] The amount of epihalohydrin used in the reaction of the compound represented by the general formula (3) with epihalohydrin is 3 to 50 times, preferably 4 to 30 times, in molar ratio, the amount of the compound represented by the general formula (3). The amount of alkali used is in the range of 0.8 to 1.5 equivalents, preferably 0.9 to 1.2 equivalents, relative to the compound represented by the general formula (3).

[0039] The reaction can also be carried out using a phase transfer catalyst. Examples of the phase transfer catalyst include 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-butyl-N-methylpyrrolidinium 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, N-methyl-N-ethylpiperidinium iodide, and the like. In order to selectively produce the compound represented by the general formula (2), it is preferable not to use a phase transfer catalyst.

[0040] The reaction of the compound represented by the general formula (3) with epihalohydrin is carried out under heating and increased or reduced pressure as required. The reaction temperature is not particularly limited, but is preferably 40°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower, from the viewpoint of shortening the production time and improving the reaction efficiency.

[0041] Examples of a method for producing a compound represented by general formula (1) by converting a compound represented by general formula (2) into an acrylic acid ester or a methacrylic acid ester include a method of esterification using an acrylic acid derivative and / or a methacrylic acid derivative. Examples of the acrylic acid derivatives include acrylic acid esters and acryloyl chloride, and examples of the methacrylic acid derivatives include methacrylic acid esters and methacryloyl chloride. Specifically, examples of such methods include a method of esterifying an acrylic acid ester such as methyl acrylate and / or a methacrylic acid ester such as methyl methacrylate in the presence of a catalyst such as dialkyltin oxide or tetraalkyl titanate, and a method of esterifying an acrylic acid ester such as methyl acrylate in the presence of a neutralizing agent such as triethylamine using acryloyl chloride and / or methacryloyl chloride. From the viewpoints of shortening the production time and reaction efficiency, when the former (meth)acrylic acid ester is used for esterification in the presence of a catalyst, the reaction temperature is preferably, for example, 50 to 100° C., and more preferably 70 to 90° C. Furthermore, from the viewpoints of shortening the production time and reaction efficiency, when the latter (meth)acrylic acid chloride is used for esterification in the presence of a neutralizing agent, the reaction temperature is preferably, for example, 0 to 30° C.

[0042] Next, the curable composition of the present invention will be described in detail.

[0043] The curable composition of the present invention contains (A) at least one compound represented by the general formula (1) (hereinafter sometimes referred to as "component (A)") and (B) a curing agent (hereinafter sometimes referred to as "component (B)").

[0044] The curable composition of the present invention may contain a compound other than the component (A) that has one or more reactive unsaturated bonds and one or more epoxy groups. Examples of such compounds include glycidyl methacrylate, glycidyl ether of allylphenol, diglycidyl monoallyl ether, and epoxy acrylates.

[0045] Furthermore, the curable composition of the present invention may contain, among reactive unsaturated bonds and epoxy groups, a compound having only an epoxy group or a compound having only a reactive unsaturated bond.

[0046] Examples of the compound having only epoxy groups include known epoxy resins. Examples of the epoxy resin 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, hexahydroxybenzoic acid, and the like. Examples of epoxy resins include glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids such as hydrophthalic 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 copolymer; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may also be internally crosslinked with a prepolymer of terminal isocyanates or polymerized using polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.).

[0047] Commercially available epoxy resins 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).

[0048] Examples of the compound having only a reactive unsaturated bond include N-alkyl group-containing (meth)acrylamide derivatives such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, and N-hexyl(meth)acrylamide; N-alkoxy group-containing (meth)acrylamide derivatives such as N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methylol-N-propane(meth)acrylamide, N-methoxymethylacrylamide, and N-ethoxymethylacrylamide; (meth)acrylamide derivatives such as N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine; and copolymers of ethylene, propylene, butylene, and isobutylene. Unsaturated aliphatic hydrocarbons such as ethylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, himic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, and mono(meth)acrylates of polymers having carboxy groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasic acids such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, and polyfunctional (meth)acrylates having one carboxy group and two or more (meth)acryloyl groups;2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, di(meth)acrylate Methylaminoethyl, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as pentaerythritol tri(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester(meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; unsaturated aldehydes, such as acrolein; unsaturated nitriles, such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide;Unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide unsaturated imides such as indenes, indene, 1-methylindene, etc.; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, etc.; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyloxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds.

[0049] The content of component (A) in the curable composition of the present invention is preferably 30% by mass or more and 99% by mass or less, and more preferably 50% by mass or more and 97% by mass or less, from the viewpoint of curability, etc. Furthermore, when the curable composition contains, in addition to component (A), another compound having an epoxy group and / or a reactive unsaturated bond, from the viewpoint of curability, etc., the content of the compound is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less, per 100 parts by mass of component (A).

[0050] Preferred examples of the curing agent, which is the component (B), used in the curable resin composition of the present invention include curing agents for epoxy resins, such as amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polythiol-based curing agents; polymerization initiators, and the like.

[0051] 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, and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane; 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-Dibenzyl Aminopropylamine, 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'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine;Examples include 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-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, and the like;

[0052] The amine-based curing agent may also be an amine-based latent curing agent obtained by various modifications. Examples of modified amines include dehydration condensation products of the amine compounds and carboxylic acids, adducts of the amine compounds and epoxy compounds (compounds exemplified as the epoxy resins), adducts of the amine compounds and isocyanate compounds (isocyanate compounds exemplified below), Michael adducts of amine compounds, Mannich reaction products of amine compounds, condensates of amine compounds and urea, and condensates of amine compounds and ketones. Further, for example, 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 the like can also be used as the amine-based latent curing agent.

[0053] Examples of the isocyanate 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.

[0054] Examples of the phenol-based curing agent 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).

[0055] 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.

[0056] Examples of the polythiol 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-tri ... 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 include 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]-5-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-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. In particular, the use of a tetravalent or higher polythiol compound is preferred because it allows for a curable composition with excellent curability.

[0057] Commercially available products of the epoxy resin 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 suitable 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), Fujicure FXR-1020 (manufactured by T&K TOKA Corporation; latent curing agent), 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.).

[0058] The amount of the epoxy resin curing agent used in the curable composition of the present invention is not particularly limited, but is preferably 100 parts by mass or less, and more preferably 2 to 50 parts by mass, per 100 parts by mass of component (A). When component (A) and another compound having an epoxy group and / or a reactive unsaturated bond are contained, the amount is preferably 100 parts by mass or less, and more preferably 2 to 50 parts by mass, per 100 parts by mass of the total of the compound and component (A).

[0059] In addition, in the curable composition of the present invention, the epoxy resin curing agent can be used in combination with a curing catalyst. Examples of the curing catalyst include phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; tertiary 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 catalysts can be used alone or in combination of two or more.

[0060] The amount of the curing catalyst used in the curable composition of the present invention is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A). When component (A) and another compound having an epoxy group and / or a reactive unsaturated bond are contained, the amount is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the compound and component (A).

[0061] Examples of the polymerization initiator include a thermal radical polymerization initiator, a photoradical polymerization initiator, and a cationic polymerization initiator.

[0062] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals upon heating, and any conventionally known compound can be used. Preferred examples of the thermal radical polymerization initiator include azo compounds, peroxides, and persulfates.

[0063] Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0064] Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate.

[0065] Examples of the persulfate include ammonium persulfate, sodium persulfate, and potassium persulfate.

[0066] The photoradical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and any conventionally known compound can be used. Preferred examples of the photoradical polymerization initiator include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime ester-based compounds.

[0067] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxy ... Examples include cyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

[0068] Examples of the benzyl compounds include benzyl.

[0069] Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0070] Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0071] The oxime ester compound means a compound having an oxime ester group, and can be preferably used in the curable composition of the present invention because it has good sensitivity among the photoradical polymerization initiators.

[0072] Among the oxime ester compounds, compounds having a carbazole skeleton, a diphenyl sulfide skeleton, or a fluorene skeleton have particularly high sensitivity, and therefore can be more preferably used in the curable composition of the present invention.

[0073] Other examples of the radical polymerization initiator include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1-yl)]titanium.

[0074] Commercially available radical polymerization initiators include ADEKA Optomer N-1414, N-1717, N-1919, ADEKA Arcles NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly); and the like.

[0075] The cationic polymerization initiator may be any compound capable of releasing a substance that initiates cationic polymerization upon irradiation with energy rays or heating, but is preferably a double salt, which is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include those represented by the following general formula: [A] r+ [B] r- Examples of the salt include cations and anions represented by the following formula:

[0076] Here, cation [A] r+ is preferably an onium, and its structure is, for example, represented by the following general formula: [(R 12 ) a Q] r+ It can be expressed as:

[0077] Furthermore, here, R 12 is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. a R 12 are each independently and may be the same or different. At least one of them is preferably an organic group having an aromatic ring as described above. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Also, the cation [A] r+When the valence of Q in the formula is q, the relationship r=aq must hold (however, N=N is treated as having a valence of 0).

[0078] Also, anions [B] r- is preferably a halide complex, and its structure is, for example, represented by the following general formula: [LY b ] r- in It can be expressed as:

[0079] Furthermore, 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. Y is a halogen atom. b is an integer from 3 to 7. In addition, the anion [B] r- When the valence of L in the formula is p, the relationship r=bp must hold.

[0080] The anion [LY b ] r- Specific examples include tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, and tetrafluoroborate (BF4). - , hexafluorophosphate (PF6) - , hexafluoroantimonate (SbF6) - , hexafluoroarsenate (AsF6) - , hexachloroantimonate (SbCl6) - The following can be mentioned:

[0081] Also, anions [B] r- is represented by the following general formula: [LY b-1 (OH)] r The structure represented by the following formula can also be preferably used. L, Y, and b are the same as above. Other anions that can be used include perchlorate ion (ClO4) -, trifluoromethyl sulfite ion (CF3SO3) - , fluorosulfonate ion (FSO3) - toluenesulfonate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like.

[0082] Among these onium salts, the following aromatic onium salts (A) to (C) are particularly effective in the present invention. One of these may be used alone, or two or more may be used in combination.

[0083] (a) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate

[0084] (b) Diaryl iodonium salts such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, and tolylcumyliodonium tetrakis(pentafluorophenyl)borate.

[0085] (c) Sulfonium cations represented by the following Group I or Group II and sulfonium salts such as hexafluoroantimony ion, hexafluorophosphate ion, and tetrakis(pentafluorophenyl)borate ion.

[0086] [ka]

[0087] [ka]

[0088] The amount of the polymerization initiator used in the curable composition of the present invention is preferably 0.001 to 20 parts by mass per 100 parts by mass of component (A). When component (A) and another compound having an epoxy group and / or a reactive unsaturated bond are contained, the amount is preferably 0.001 to 20 parts by mass per 100 parts by mass of the total of component (A) and the compound. By using an amount of the polymerization initiator that is 0.001 part by mass or more, sufficient curability can be obtained, and by using an amount that is 20 parts by mass or less, the influence on various physical properties such as the water absorption and strength of the cured product can be suppressed.

[0089] When the curable composition of the present invention is photocured using a polymerization initiator, a sensitizer and a sensitization aid may be used. Examples of the sensitizer and the sensitization aid include an anthracene-based compound and a naphthalene-based compound.

[0090] Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethoxyethoxy)anthracene, Examples thereof include 9,10-bis(2-butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, and 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

[0091] Examples of the naphthalene compounds include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, and 1,4-dibutoxynaphthalene.

[0092] The curable composition of the present invention may optionally contain 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxysilane, aminosilane compounds such as silane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine; mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. The composition may contain known additives such as silane coupling agents, such as epoxy silane compounds such as dipropyltriethoxysilane; reactive or non-reactive diluents (plasticizers), such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments, such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely powdered silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous substances; lubricants, such as candelilla wax, carnauba wax, Japan wax, Ibota wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, fatty acid wax, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; antifoaming agents; rust inhibitors; colloidal silica, colloidal alumina, and the like. Furthermore, adhesive resins, such as xylene resins and petroleum resins, may also be used in combination.

[0093] The curable composition of the present invention can be cured by light and / or heat by changing the type of curing agent (epoxy resin curing agent and polymerization initiator) as component (B) or by using multiple curing agents in combination. Among these, the curable composition of the present invention is preferably used in a method in which a photopolymerization initiator and an epoxy resin curing agent are used in combination as component (B), and the composition is pre-cured by light irradiation followed by thermal curing. In this case, if the composition contains a large amount of a compound having only epoxy groups and / or a compound having only reactive unsaturated bonds, curing may be insufficient or the physical properties of the cured product may be reduced. For this reason, the total amount of the compound having only epoxy groups and the compound having only reactive unsaturated bonds is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, per 100 parts by mass of component (A). Furthermore, the photopolymerization initiator is preferably a photoradical polymerization initiator.

[0094] The light irradiated during photocuring may include light with a wavelength of 300 nm to 450 nm. Examples of light sources used for photocuring include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium-cadmium lasers, etc.).

[0095] The heating temperature for thermal curing may be any temperature that can stably cure the curable composition and is set appropriately depending on the type of curing agent, etc., but is preferably, for example, 10°C or higher and 250°C or lower, and more preferably 60°C or higher and 200°C or lower.

[0096] The cured product of the curable composition of the present invention is preferably a cured product obtained by photocuring followed by thermal curing, as this provides excellent performance such as heat resistance. The applicant believes that this description describes the state of the cured product. Even if this description were to specify a product based on the manufacturing method, it would be impossible or impractical to specify the structure or properties other than those described in this specification for a cured product obtained by curing the curable composition under specified conditions, as this would require a significant amount of experimental time.

[0097] The curable composition of the present invention can be used in a wide range of applications, such as paints, adhesives, pressure-sensitive adhesives, coating agents, fiber sizing agents, building materials, and electronic components. In particular, because it has excellent photo- and heat-curing properties, it can be used in applications where dual curing is possible. That is, it can be suitably used in applications such as liquid sealants, liquid adhesives, liquid crystal sealants, and adhesives for camera modules. [Example]

[0098] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0099] [Production Example 1] Production of Compound 3-1 [Compound of Formula (3)] In a flask equipped with a reflux device, a stirrer, and a dropping device, 15.26 g (0.14 mol) of p-aminophenol, 27.37 g (0.34 mol) of chloroethanol, and 20 g of xylene were charged. Meanwhile, 11.2 g (0.28 mol) of 48% aqueous sodium hydroxide solution was placed in the dropping device, and this aqueous sodium hydroxide solution was added dropwise over 1 hour at an internal temperature of 120°C. After further reaction for 1 hour, the solvent was removed and purification was carried out to obtain the following compound 3-1. The obtained compound 3-1 1 The results of H-NMR measurement are shown in Figure 1. NMR was measured using a JEOL ECX-400. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

[0100] [ka]

[0101] Example 1: Preparation of Compound 2-1 (Compound of Formula (2)) In a flask equipped with a reflux apparatus and a stirrer, 10.0 g (50 mmol) of compound 3-1 obtained in Production Example 1 and 69.4 g (750 mmol) of epichlorohydrin were charged. Meanwhile, 4.0 g (50 mmol) of 48% aqueous sodium hydroxide solution was placed in a dropping apparatus, and 0.4 g (5 mmol) of this aqueous sodium hydroxide solution was added dropwise over 1 hour at an internal temperature of 90°C, and then further added dropwise over 3 hours while refluxing under conditions of an internal temperature of 86°C and a reduced pressure of 44.4 kPa, while simultaneously removing water. After further reaction for 1 hour, the mixture was subjected to removal of epichlorohydrin, washed with water, solvent removal, and filtration to obtain the following compound 2-1. The obtained compound 2-1 1 The results of H-NMR measurement are shown in Figure 2. NMR was measured using a JEOL ECX-400. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

[0102] [ka]

[0103] Example 2: Preparation of Compound 1-1 (Compound of Formula (1)) In a flask equipped with a reflux device and a stirrer, 5.0 g (20 mmol) of compound 2-1 obtained in Example 1, 34.4 g (400 mmol) of methyl acrylate, and 0.4 g (1.2 mmol) of titanium tetra-n-butoxide were charged, and the reaction was carried out while distilling off the methanol produced under reflux. After the reaction was carried out at a reaction temperature of 78°C for 9 hours, the solvent was removed and the mixture was purified to obtain the following compound 1-1. 1 The results of H-NMR measurement are shown in Figure 3. NMR was measured using a JEOL ECX-400. Deuterated dimethyl sulfoxide (deuterated DMSO) was used as the measurement solvent.

[0104] [ka]

[0105] [Examples 3 and 4 and Comparative Example 1] The components were mixed in the amounts shown in Table 1 below to prepare the curable compositions of Examples 3 and 4 and Comparative Example 1. The curable composition prepared above was applied to a glass plate using a bar coater to a thickness of 300 μm, and the curable composition was cured under the following curing conditions to confirm its photocurability and thermosetting properties. The results are shown in Table 1 below.

[0106] [Curing conditions] Photocuring: JATEC J-Cure 1500CV, exposure dose 3,000 mJ / cm 2 The curing property was confirmed by irradiating the composition with 365 nm ultraviolet light. Heat curing: After heating in a heat circulation oven at 100°C for 1 hour, the resin was further heated at 150°C for 2 hours.

[0107] [Photocurable] After light irradiation, the coating film was sufficiently cured to form a releasable film, which was marked with a circle, and the coating film was not sufficiently cured to be peeled off, which was marked with an X.

[0108] [Thermosetting] The coating film obtained by the photo-curing was further heat-cured, and the IR of the cured product was measured before and after the heat-curing. -1 If the peak derived from the nearby epoxy group disappeared, it was judged that thermal curing had progressed and was marked with a circle, and if it did not disappear, it was judged that thermal curing had not progressed and was marked with an x.

[0109] [Table 1]

[0110] The components in Table 1 are as follows: Compound 1-1: Component (A) of Compound 1-1 obtained in Example 2 PTBPGE: p-tert-butylphenol glycidyl ether 2-PEA: 2-phenoxyethyl acrylate Irg-184: Omnirad184 (Acetophenone-based photopolymerization initiator) manufactured by IGM Resins (Component B) 2E4MZ: 2-ethyl-4-methylimidazole (amine-based curing agent) manufactured by Shikoku Chemicals Corporation (Component B)

[0111] As is clear from the results shown in Table 1, the compound represented by the general formula (1) provided by the present invention can provide a curable composition that can be cured by light and / or heat. Furthermore, from Example 1, the compound represented by the general formula (2) is useful as a raw material for the compound represented by the general formula (1). [Industrial Applicability]

[0112] The compound of the present invention can be cured by light and / or heat, and a curable composition containing the compound can be cured by light and heat. Therefore, the compound can be used for applications such as a liquid sealant, a liquid adhesive, an adhesive for camera modules, and a liquid crystal sealant.

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R １ represents a hydrogen atom or a methyl group, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R ３ represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

2. A compound represented by the following general formula (1a): 【Chemistry 2】 (In the formula, R １ represents a hydrogen atom or a methyl group, R ３ represents a hydrogen atom or a methyl group, R ４ each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom; and m represents a number from 0 to 4.

3. A compound represented by the following general formula (2): 【Transformation 3】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R １ represents a hydrogen atom or a methyl group, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

4. A method for producing a compound represented by the following general formula (1), comprising reacting a compound represented by the following general formula (3) with epihalohydrin to produce a compound represented by the following general formula (2), and then esterifying the compound represented by the following general formula (2) using an acrylic acid derivative and / or a methacrylic acid derivative: 【Chemistry 4】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4. 【Transformation 5】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R １ represents a hydrogen atom or a methyl group, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4. 【Transformation 6】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R １ represents a hydrogen atom or a methyl group, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R ３ represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

5. A curable composition comprising component (A): at least one compound represented by the following general formula (1) and component (B): a curing agent. 【Transformation 7】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, R １ represents a hydrogen atom or a methyl group, R ２ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or a halogen atom; R ３ represents a hydrogen atom or a methyl group. The substituent is a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. n represents a number from 0 to 4.

6. The curable composition according to claim 5 , wherein the curing agent (B) comprises at least one selected from photopolymerization initiators and at least one selected from amine-based latent curing agents.

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