Compound, method for producing compound, and curable composition

Abstract

A compound represented by formula (1). (In the formula, R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 represents a C1-10 alkyl group, a C1-10 alkoxy group, a halogen atom, a benzoyl group capable of having a substituent, or a benzyl group capable of having a substituent, and A1 represents a single bond or a C1-4 alkylene group. The substituent is a group selected from C1-10 alkyl groups, C1-10 alkoxy groups, or halogen atoms.　However, when A1 is a single bond, an unsaturated ester group is located at the meta position with respect to a glycidyloxy group. n represents an integer of 0-4.)

Description

[Technical field]

[0001] The present invention relates to a compound and a production method thereof, more particularly to a curable compound having a reactive unsaturated bond and an epoxy group and a production method thereof, and further to a curable composition containing at least one of the curable compounds and at least one selected from a curing agent and a polymerization initiator. [Background technology]

[0002] In recent years, as mobile devices such as smartphones become thinner, the camera modules mounted on such mobile devices are becoming smaller. As the camera modules become smaller, the areas where the components of the camera modules are bonded to each other are also becoming finer, so the adhesive layer formed from the adhesive that bonds them is required to have high adhesive strength.

[0003] In addition, adhesives used in assembling camera modules and the like are required to have low-temperature curing properties in order to avoid thermal damage to image sensors and the like caused by high-temperature processing, and are also required to have short-time curing properties in order to improve production efficiency. From this perspective, ultraviolet-curing adhesives and thermosetting epoxy resin adhesives are often used as low-temperature, short-time curing adhesives. However, while ultraviolet-curing adhesives can be cured quickly, they have the disadvantage that they cannot be used to bond parts that are not exposed to light. On the other hand, even though thermosetting epoxy resin adhesives are low-temperature, short-time curing adhesives, they are not necessarily satisfactory because they require the members (components) to be bonded to be fixed with a jig or device in order to maintain the bonding position during bonding, and the viscosity decreases due to the temperature increase caused by heating, causing problems such as dripping just before curing or flowing to parts other than the desired part.

[0004] In order to solve the above problems, an adhesive of the type that is temporarily fixed by curing (pre-curing) by light irradiation and further cured (main curing) by heat for adhesion has been proposed. For example, Patent Document 1 proposes a photo- and heat-curable composition that contains 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 that contains 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 group of an epoxy resin with (meth)acrylic acid, and become a mixture of multiple compounds due to residual unreacted epoxy resin during production, which tends to increase viscosity and is not satisfactory for application to light and heat curing systems. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2009-51954 A [Patent Document 2] WO2018 / 181421 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a compound that can be produced by an industrially advantageous method requiring less effort in removing unreacted substances and that can be cured by light and heat, and to provide a curable composition that can provide a sealant or adhesive that has excellent curing properties by light and heat. [Means for solving the problem]

[0007] That is, the present invention provides a compound represented by the following general formula (1).

[0008] [ka] (In the formula, R 1 and R 3 each independently represents a hydrogen atom or a methyl group; R 2 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a benzoyl group which may have a substituent, or a benzyl group which may have a substituent; A 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms. 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, or a halogen atom. However, A 1 When is a single bond, in the benzene ring in formula (1), the unsaturated ester group represented by the following formula (1α) is located at the meta position relative to the glycidyloxy group represented by the following formula (1β). n represents a number from 0 to 4. [ka] (The symbols in the formula are defined as in formula (1). * denotes a bond.)

[0009] The present invention also relates to a compound represented by the following general formula (1-1-1), which is obtained by glycidyl etherifying a phenolic hydroxyl group of the compound, 2 The present invention provides a method for producing a compound represented by the following general formula (1-1), in which an alcoholic hydroxyl group bonded to the following formula (1-2) is esterified with an acrylic acid ester or a methacrylic acid ester: [ka] (In the formula, R 4 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; A 2 represents an alkylene group having 1 to 4 carbon atoms. m represents a number from 0 to 4. [ka] (In the formula, R 101 and R 103 each independently represents a hydrogen atom or a methyl group; R 4 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; A 2 represents an alkylene group having 1 to 4 carbon atoms. m represents a number from 0 to 4.

[0010] The present invention also relates to a compound having two hydroxyl groups represented by the following general formula (1-2-1): 5 The present invention provides a method for producing a compound represented by the following formula (1-2), in which a hydroxyl group located at the para-position to a benzoyl group which may be substituted with [ka] (In the formula, R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5. [ka] (In the formula, R 201 and R 203 each independently represents a hydrogen atom or a methyl group; R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5.

[0011] The present invention also provides a curable composition comprising (A) at least one compound represented by the following general formula (1) and (B) at least one selected from a curing agent and a polymerization initiator:

[0012] [ka] (In the formula, R1 and R 3 each independently represents a hydrogen atom or a methyl group; R 2 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a benzoyl group which may have a substituent, or a benzyl group which may have a substituent; A 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms. 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, or a halogen atom. However, A 1 When is a single bond, in the benzene ring in formula (1), the unsaturated ester group represented by the following formula (1α) is located at the meta position relative to the glycidyloxy group represented by the following formula (1β). n represents a number from 0 to 4. [ka] (The symbols in the formula are defined as in formula (1). * denotes a bond.)

[0013] The present invention also provides a method for producing a cured product obtained by curing the curable composition by exposure to light and then by exposure to heat.

[0014] The present invention further provides a cured product obtained by curing the curable composition by exposure to light and heat. Effect of the Invention

[0015] The compound provided by the present invention is suitable as a material to be cured by light and heat, and the curable composition provided by the present invention has excellent photocurability and heat curability, and therefore can be used for dual curing in which the composition is provisionally cured by light and then fully cured by heat. Due to these properties, the composition can be used for applications such as liquid sealants, liquid adhesives, adhesives for camera modules, and liquid crystal sealants. In addition, the above-mentioned method for producing the compound represented by formula (1-1) has the advantage that it is not necessary to use an excess epoxy resin, so that the effort required for removing unreacted materials is reduced and the compound can be used for photo- and / or thermal curing with a simple purification method. In addition, the method for producing the compound represented by formula (1-1) using formula (1-1-1) as a substrate includes a method using a (meth)acrylic acid chloride such as acryloyl chloride and a method using a (meth)acrylic acid ester such as an acrylic acid ester, but the former may cause a side reaction between hydrochloric acid generated during the reaction and the epoxy group. Therefore, the above-mentioned side reaction can be suppressed by using a (meth)acrylic acid ester. In addition, the above-mentioned method for producing the compound represented by formula (1-2) has the advantage that it is not necessary to use an excess epoxy resin, so that the effort required for removing unreacted substances is reduced, and the compound can be used for photo- and / or thermal curing by a simple purification method. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 shows the results of 1H-NMR measurement of the compound obtained in Example 1. [Diagram 2] FIG. 2 shows the results of 1H-NMR measurement of the compound obtained in Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The compounds of the present invention will be described in detail below.

[0018] As described above, the compound of the present invention represented by the formula (1) has a glycidyl ether group (sometimes called a "glycidyloxy group") and a reactive unsaturated bond, and therefore can provide a cured product by applying light and / or heat when used in combination with various curing agents and various polymerization initiators. The reactive unsaturated bond is sometimes called an ethylenic unsaturated bond.

[0019] In the general formula (1), R 2Examples of the alkyl group having 1 to 10 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, and an isodecyl group.

[0020] In the general formula (1), R 2 Examples of the alkoxy group having 1 to 10 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, and a decyloxy group.

[0021] 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.

[0022] In the general formula (1), R 2 The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom as the substituent of the benzoyl group or the benzyl group represented by the formula: 2 As the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom used in the above, the groups mentioned above can be used.

[0023] In the general formula (1), A 1 Examples of the alkylene group having 1 to 4 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, and a butylidene group.

[0024] Among the compounds represented by the general formula (1), A 1 is an alkylene group having 1 to 4 carbon atoms, n is 0 or R 2is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a benzyl group which may have a substituent, and n is preferably 0 or R 2 More preferably, A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. 1 is a single bond, n is 1, and R 2 is a benzoyl group which may have a substituent, and the benzoyl group is preferably located at the para position relative to the glycidyloxy group represented by the above formula (1β). In these cases, the compound represented by the above general formula (1) can be produced more easily. In particular, the compound represented by the following general formula (1-1) or (1-2) is preferred because it can be produced easily and has excellent light and heat curing properties when used in combination with various curing agents and / or various polymerization initiators.

[0025] [ka] (In the formula, R 101 and R 103 each independently represents a hydrogen atom or a methyl group; R 4 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; A 2 represents an alkylene group having 1 to 4 carbon atoms. m represents a number from 0 to 4.

[0026] [ka] (In the formula, R 201 and R 203 each independently represents a hydrogen atom or a methyl group; R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5.

[0027] In the formula (1-1), R 4The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom represented by the above R 2 Examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom represented by the formula (I) include the groups exemplified above. In the formula (1-1), A 2 As the alkylene group having 1 to 4 carbon atoms represented by the formula 1 Examples of the alkylene group having 1 to 4 carbon atoms include the groups exemplified above. In the formula (1-2), R 5 The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom represented by the formula: 2 Examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom represented by the formula (I) include the groups exemplified above.

[0028] When the compound of the present invention is represented by the above formula (1-1), A 2 In terms of availability of raw materials, it is most preferable that the alkyl group is an ethylene group.

[0029] When the compound of the present invention is represented by the above formula (1-1), A 2 is preferably located at the para- or meta-position relative to the glycidyloxy group in terms of ease of production of the compound, and is particularly preferably located at the para-position.

[0030] When the compound of the present invention is represented by the above formula (1-1), in terms of the availability of raw materials, m is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less, and is 0. That is, in the case where the benzene ring of the formula (1-1) has a glycidyloxy group and A 2 It is most preferred that only hydrogen atoms are bonded to the unsaturated ester group having the formula: In addition, in the compound represented by formula (1-1), when m is 1 or more, R 4is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom from the viewpoint of availability of raw materials, and more preferably an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen atom. 4 may be the same or different.

[0031] When the compound of the present invention is represented by the above formula (1-1), it is particularly preferably a compound represented by the following formula (1-1A) from the above-mentioned viewpoints.

[0032] [ka] (In the formula, R 101 and R 103 each independently represents a hydrogen atom or a methyl group.

[0033] When the compound of the present invention is represented by the above formula (1-1) or (1-1A), R 101 is preferably a hydrogen atom in terms of increasing the reactivity of the reactive unsaturated bond. Also R 103 is preferably a hydrogen atom in view of rapid reaction with the latent curing agent. From these points, R 101 and R 103 It is preferable that all of the radicals are hydrogen atoms, since the curing reaction is rapid. In addition, the compound is easily liquid at 25°C, which improves workability.

[0034] The compound of the present invention represented by the formula (1-2) has the advantage that the epoxy group has a high reactivity due to its structure, so that the rate of thermal curing is fast. In addition, the cured product obtained by photocuring and the cured product obtained by photocuring and thermal curing have a relatively high heat resistance. When the compound of the present invention is represented by the formula (1-2), from the viewpoint of raw material ease, p is preferably 4 or less, more preferably 3 or less, particularly preferably 2 or less, more preferably 1 or less, and most preferably 0. If p is 1 or more, R5 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom in terms of availability of raw materials; 5 is more preferably an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen atom. 5 may be the same or different.

[0035] When the compound of the present invention is represented by the above formula (1-2), R 201 R is preferably a hydrogen atom in that the reactivity of the reactive unsaturated bond is high. 201 is preferably a methyl group in that the storage stability of the curable composition is improved and the cured product has excellent physical properties. Also R 203 is preferably a hydrogen atom in that it reacts quickly with the latent curing agent.

[0036] A preferred method for producing the compound of the present invention will now be described. In this production method, a compound containing two hydroxyl groups is used to convert one of the hydroxyl groups into a glycidyl ether, and then the other hydroxyl group into a (meth)acrylic acid ester, thereby producing the compound. More specifically, the compound can be produced, for example, by the production method shown below.

[0037] The compound represented by the formula (1-1) can be prepared by glycidyl etherifying a phenolic hydroxyl group of a compound represented by the following formula (1-1-1) and then glycidyl etherifying the alcoholic hydroxyl group (A 2 The compound represented by formula (1-1) can be produced by converting a phenolic hydroxyl group bonded to an alkylene group represented by formula (1-2) into an acrylic acid ester or a methacrylic acid ester. Since the acidity of the phenolic hydroxyl group is different from that of the alcoholic hydroxyl group, it is considered that the glycidyl etherification of the phenolic hydroxyl group proceeds preferentially. The alcoholic hydroxyl group is then esterified to obtain the compound represented by formula (1-1).

[0038] [ka] (In the formula, R 4 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; A 2 represents an alkylene group having 1 to 4 carbon atoms. m represents a number from 0 to 4.

[0039] The compound represented by the formula (1-2) is, for example, a compound having two hydroxyl groups represented by the following formula (1-2-1): 5 The compound can be produced by glycidyl etherifying the hydroxyl group at the para-position to the benzoyl group (the benzoyl group on the left side in formula (1-2-1)) which may be substituted with , and then acrylic esterifying or methacrylic esterifying the hydroxyl group at the ortho-position to the benzoyl group. Here, since the acidity of the hydroxyl group at the para-position and the hydroxyl group at the ortho-position to the benzoyl group differs, it is considered that the glycidyl etherification of the hydroxyl group at the para-position proceeds preferentially. Then, the hydroxyl group at the ortho-position is esterified to obtain the compound represented by formula (1-2).

[0040] [ka] (In the formula, R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5.

[0041] The above-mentioned method for converting one of the hydroxyl groups into a glycidyl ether may include a method of adding an alkali to a mixture of a compound containing two hydroxyl groups, such as the compound represented by the general formula (1-1-1) or the compound represented by the general formula (1-2-1), and epihalohydrin to cause a reaction. Methods for adding the alkali include a method of adding an aqueous alkali solution dropwise and a method of adding a solid alkali, preferably in multiple portions.

[0042] Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Examples of the alkali include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. A phase transfer catalyst can also be used. 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, and N-ethyl-N 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, and N-methyl-N-ethylpiperidinium iodide.

[0043] The amount of epihalohydrin used is 3 to 50 times, preferably 4 to 30 times, in molar ratio, the amount of the compound containing two hydroxyl groups. The reaction is carried out under heating and increased or reduced pressure as necessary. From the viewpoints of shortening the production time and reaction efficiency, the reaction temperature is preferably from 40° C. to 120° C., and more preferably from 60° C. to 80° C. When the chlorohydrination reaction and the cyclization reaction of the obtained chlorohydrinate occur stepwise and the reaction temperatures of the chlorohydrination reaction and the cyclization reaction are different, it is preferable that either one of the reaction temperatures is within the above-mentioned temperature range, and it is more preferable that both are within the above-mentioned range.

[0044] On the other hand, the method of converting to acrylic acid ester or methacrylic acid ester includes a method using acrylic acid ester and / or methacrylic acid ester in the presence of a catalyst such as dialkyltin oxide or tetraalkyl titanate, and a method using acryloyl chloride and / or methacryloyl chloride in the presence of a neutralizing agent such as triethylamine. Examples of acrylic acid ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. From the viewpoints of shortening the production time and reaction efficiency, the reaction temperature in the former case where the reaction is carried out in the presence of a (meth)acrylic acid ester and a catalyst is preferably, for example, 50 to 100° C., and more preferably 70 to 90° C. Also, from the viewpoints of shortening the production time and reaction efficiency, the reaction temperature in the latter case where the reaction is carried out in the presence of a (meth)acrylic acid chloride and a neutralizing agent is preferably, for example, 0 to 30° C.

[0045] In particular, for the production method of the compound represented by formula (1-1), it is preferable to adopt a method using an acrylic acid ester and / or a methacrylic acid ester since side reactions can be easily prevented, and it is particularly preferable to use an acrylic acid ester such as methyl acrylate since a compound having excellent reactivity can be obtained.

[0046] Next, the curable composition of the present invention will be described in detail.

[0047] The curable composition of the present invention contains (A) at least one compound represented by the general formula (1) (hereinafter may be referred to as "component (A)") and (B) at least one selected from a curing agent or a polymerization initiator (hereinafter may be referred to as "component (B)").

[0048] The curable composition of the present invention can be used in combination with a compound having one or more reactive unsaturated bonds and one or more epoxy groups other than the component (A). Examples of such a compound include glycidyl methacrylate, glycidyl ether of allylphenol, diglycidyl monoallyl ether, and epoxy acrylates.

[0049] In addition, in the curable composition of the present invention, a compound having only an epoxy group or a compound having only a reactive unsaturated bond, among those having a reactive unsaturated bond and an epoxy group, can also be used in combination.

[0050] Examples of the compound having only epoxy groups include known epoxy resins. Examples of the epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, 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; 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, hexaglycidyl 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; Examples of the epoxy resin 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, dicyclopentadiene 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 be internally crosslinked with a prepolymer of terminal isocyanate, or may be polymerized using a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.).

[0051] Commercially available products of the epoxy resin 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, Denacol EX-721 (manufactured by Nagase ChemteX Corporation); Epolite 200E, ... Polite 400E, Epolight 70P, Epolight 200P, Epolight 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); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (Osaka Gas Chemical Co., Ltd.); YD series, YDF series, YDPN series, TDCN series (Nippon Steel Sumikin Chemical Co., Ltd.); CELLOXIDE 2021P, CELLOXIDE 2081 (DAICEL); TECHMORE Examples of such polymers include VG-3101L (manufactured by Printec); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku); YX8800 (manufactured by Mitsubishi Chemical); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation).

[0052] Examples of the compound having only reactive unsaturated bonds 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; N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine; and N-acryloylpyrrolidine derivatives such as ethylene, propylene, butylene, and isobutyl. 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, hymic 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 ω-carboxypolycaprolactone mono(meth)acrylate 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, dimethylaminoethyl (meth)acrylate, 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, 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 esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol 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;Acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methyl hydric anhydride; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, cyanide unsaturated nitriles such as 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 ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, poly Macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as siloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, 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;

[0053] The content of the component (A) in the curable composition of the present invention is, for example, preferably 15% by mass or more, and preferably 30% by mass to 99% by mass in terms of the curability of the curable composition, and more preferably 50% by mass to 97% by mass. Furthermore, when the curable composition contains other compounds having an epoxy group and / or a reactive unsaturated bond in addition to the component (A), the amount of the other compounds is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less, relative to 100 parts by mass of the component (A), in terms of the curability, etc.

[0054] Preferred examples of the curing agent, which is the component (B) used in the present invention, include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, polythiol compounds, and amine-based latent curing agents.

[0055] Examples of the amine-based curing agent include alkylene diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine; polyalkyl polyamines 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-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-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.

[0056] 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 addition type resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trisphenylol methane resin, tetraphenylol ethane 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 a phenol nucleus is linked by a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which a phenol nucleus is linked by a bismethylene group), 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 a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde).

[0057] 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.

[0058] Examples of the polythiol compound 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(mercaptome 2-{bis[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]methyl}-1,3-dithietane, 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]-5-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, and the like. Examples of commercially available products of these polythiol compounds 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, the use of a polythiol compound having a valence of 4 or more is preferred because it provides excellent curability.

[0059] Examples of the amine-based latent curing agent 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.

[0060] Among the amine-based latent curing agents, preferred are adducts of an amine compound having one or more active hydrogens with a polyepoxy compound and / or a polyisocyanate compound, or those obtained by combining this with a phenol resin.

[0061] Examples of the amine compound having one or more active hydrogens include alkylene diamines 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, 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 ... aromatic polyamines such as diaminodiphenylmethane, diaminodiphenylsulfone, 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-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.

[0062] Examples of the polyepoxy compound include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; polynuclear polyhydric phenol compounds such as dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), tetrabromo bisphenol 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, sulfonyl bisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin 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 the epoxy compounds include cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, 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.

[0063] 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 the 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, trimethylolpropane adducts of the above-listed diisocyanates; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and the like. Furthermore, these isocyanate compounds may be used in a form modified by carbodiimide, isocyanurate, biuret, or the like, or may be used in a form of blocked isocyanate blocked with various blocking agents.

[0064] 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 addition type resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trisphenylol methane resin, tetraphenylol ethane 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 a phenol nucleus is linked by a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which a phenol nucleus is linked by a bismethylene group), 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 a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde).

[0065] Commercially available products of the amine-based latent curing agent include, for example, ADEKA HARDENER EH-3636S (manufactured by ADEKA CORPORATION; dicyandiamide type latent curing agent), ADEKA HARDENER EH-4351S (manufactured by ADEKA CORPORATION; dicyandiamide type latent curing agent), ADEKA HARDENER EH-5011S (manufactured by ADEKA CORPORATION; imidazole type latent curing agent), ADEKA HARDENER EH-5046S (manufactured by ADEKA CORPORATION; imidazole type latent curing agent), ADEKA HARDENER EH-4357S (manufactured by ADEKA CORPORATION; polyamine type latent curing agent), ADEKA HARDENER EH-5057P (manufactured by ADEKA CORPORATION; polyamine type latent curing agent), ADEKA HARDENER Examples of such hardeners include EH-5057PK (manufactured by ADEKA Corporation; polyamine-type latent hardener), Amicure PN-23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent hardener), Amicure PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent hardener), Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazide-type latent hardener), and Fujicure FXR-1020 (manufactured by T&K Toka Corporation; latent hardener).

[0066] The amount of the curing agent, which is the component (B) used in the present invention, is not particularly limited, but is 1 to 100 parts by mass, and preferably 2 to 50 parts by mass, per 100 parts by mass of the total of the component (A) and other compound having an epoxy group and / or a reactive unsaturated bond.

[0067] In the curable composition of the present invention, a curing catalyst can be used in combination with the curing agent (B), and 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, 1-[3-(trimethoxysilylpropyl)]imidazole, and the like. Examples of the curing accelerator include imidazoles such as imidazole (trimethoxysilylpropyl) imidazole; imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron, etc.; 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 complexes of boron trifluoride with amines, ether compounds, etc. These curing accelerators may be used alone or in combination of two or more.

[0068] The amount of the curing catalyst used is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of the component (A) and other compound having an epoxy group and / or a reactive unsaturated bond.

[0069] The polymerization initiator, which is the component (B) used in the present invention, includes a thermal radical polymerization initiator, a photoradical polymerization initiator, and a cationic polymerization initiator.

[0070] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and any conventionally known compound can be used. For example, preferred examples include azo compounds, peroxides, and persulfates.

[0071] Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0072] Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate.

[0073] Examples of the persulfate include ammonium persulfate, sodium persulfate, and potassium persulfate.

[0074] 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.

[0075] Examples of the acetophenone-based 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 of such aryl ethers 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.

[0076] The benzyl compounds include, for example, benzyl.

[0077] Examples of the benzophenone-based compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0078] Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0079] The oxime ester compound means a compound having an oxime ester group, and since it has good sensitivity among the photoradical polymerization initiators, it can be preferably used in the curable composition of the present invention.

[0080] Among the oxime ester compounds, those having a carbazole skeleton, a diphenyl sulfide skeleton, or a fluorene skeleton are particularly preferred for the curable composition of the present invention because of their high sensitivity.

[0081] 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.

[0082] Examples of commercially available radical polymerization initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARCLES NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (all manufactured by Tronly); and the like.

[0083] The cationic polymerization initiator may be any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays or heating, but is preferably a double salt, which is an onium salt that releases a Lewis acid by 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 salts of cations and anions represented by the following formula:

[0084] Here, cation [A] r+ is preferably an onium, the structure of which is, for example, the following general formula: [(R 12 ) a Q] r+ It can be expressed as:

[0085] 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 independent 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).

[0086] In addition, the anion [B] r- is preferably a halide complex, the structure of which is, for example, represented by the following general formula: [LY b ] r- in It can be represented.

[0087] Furthermore, here, L is a metal or metalloid which 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, Co, etc. Y is a halogen atom. b is an integer of 3 to 7. In addition, the anion [B] r- When the valence of L in is p, the relationship r=bp must hold.

[0088] The anion of the above general formula [LY b ] r- Specific examples of the above include tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, and tetrafluoroborate (BF4). - , Hexafluorophosphate (PF6) - , Hexafluoroantimonate (SbF6) - , Hexafluoroarsenate (AsF6)- , Hexachloroantimonate (SbCl6) - etc. can be mentioned.

[0089] In addition, the anion [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). - , trifluoromethylsulfite ion (CF3SO3) - , fluorosulfonate ion (FSO3) - , toluenesulfonate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like.

[0090] In the present invention, among such onium salts, the following aromatic onium salts (A) to (C) are particularly effective for use. Among these, one of them may be used alone, or two or more of them may be used in combination.

[0091] (a) Aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate.

[0092] (b) Diaryl iodonium salts such as diphenyl iodonium hexafluoroantimonate, di(4-methylphenyl) iodonium hexafluorophosphate, di(4-tert-butylphenyl) iodonium hexafluorophosphate, and triaryl iodonium tetrakis(pentafluorophenyl)borate.

[0093] (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.

[0094] [ka]

[0095] [ka]

[0096] The amount of the polymerization initiator used is preferably 0.001 to 20 parts by mass per 100 parts by mass of the total of component (A) and other compounds having an epoxy group and / or a reactive unsaturated bond. By keeping it at 20 parts by mass or less, the influence on various physical properties such as the water absorption rate and strength of the cured product can be suppressed.

[0097] When the curable composition of the present invention is photocured using a polymerization initiator, a sensitizer and a sensitization assistant can be used. Examples of the sensitizer and the sensitization assistant include anthracene-based compounds and naphthalene-based compounds.

[0098] 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 of the anthracene 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.

[0099] 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.

[0100] 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 3-mercaptopropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy ... 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; defoamers; 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.

[0101] The curable composition of the present invention can be cured by light and heat by using different types of curing agents and polymerization initiators as exemplified above, or by using a combination of a plurality of them. Among them, a method of using a photopolymerization initiator and a curing agent in combination, temporarily curing by light irradiation, and then thermal curing can be adopted. In that case, if the amount of the compound having only an epoxy group among the epoxy group and the reactive unsaturated bond or the compound having only a reactive unsaturated bond is large, the curing may be insufficient or the physical properties of the cured product may be deteriorated. For this reason, the amount of the compound having only an epoxy group among the epoxy group and the reactive unsaturated bond or the compound having only a reactive unsaturated bond is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, relative to 100 parts by mass of the compound of the present invention. In addition, the photopolymerization initiator is preferably a photoradical polymerization initiator.

[0102] In photocuring, the light to be irradiated may include light having a wavelength of 300 nm to 450 nm. Examples of light sources used in photocuring include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers, etc.).

[0103] The heating temperature for thermal curing may be any temperature that can stably cure the composition and is set appropriately depending on the type of curing agent, etc., but is preferably, for example, from 10°C to 250°C, and more preferably from 60°C to 200°C.

[0104] The cured product of the curable composition of the present invention is preferably a cured product obtained by photocuring followed by thermal curing, in that it has excellent performance such as heat resistance. The applicant considers that this description represents a state. Even if this description specifies a product by a manufacturing method, there are circumstances in which it is impossible or impractical to specify a structure or properties other than those described in this specification for a cured product obtained by curing a curable compound under specified conditions, because it requires a significant amount of experimental time.

[0105] The curable composition of the present invention can be used in a wide range of applications, such as paints, adhesives, sealants, pressure sensitive adhesives, coating agents, fiber bundling agents, building materials, electronic components, etc. In particular, since it has excellent curing properties due to light and heat, 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. EXAMPLES

[0106] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0107] [Example 1] Preparation of compound 1-1a In a flask equipped with a reflux device, a stirrer, and a dropping device, 386.9 g (2.8 mol) of p-hydroxyphenethyl alcohol and 1,295 g (14 mol) of epichlorohydrin were charged, and 221.7 g (0.95 mol) of 48% by mass aqueous sodium hydroxide solution was placed in the dropping device. The aqueous sodium hydroxide solution was dropped over 2 hours under reflux at an internal temperature of 65 to 70°C and a reduced pressure of 21 to 24 kPa, and water was simultaneously removed by azeotropic distillation. After that, the reaction was continued for another hour, and then the following compound 1-1a-1 was obtained by removing epichlorohydrin, washing with water, removing the solvent, and filtering. The epoxy equivalent of the compound 1-1a-1 was 216 g / eq. In a flask equipped with a reflux device and a stirrer, 498.2 g (2.6 mol) of the compound 1-1a-1 obtained above, 1.102 g (12.8 mol) of methyl acrylate, and 21.8 g (0.06 mol) of titanium tetra-n-butoxide were charged, and the reaction was carried out while distilling off the methanol produced under reflux. The reaction was carried out at a reaction temperature of 78°C to 87°C for 10 hours, and the reaction was terminated when the conversion rate to compound 1-1a reached 95% or more. The reaction liquid was cooled, and 500 g of toluene and 30 g of water were added and stirred at 60°C for 1 hour to hydrolyze the catalyst. The concentrated liquid obtained by distilling off toluene and water was cooled, filtered to remove the precipitated catalyst decomposition product, and compound 1-1a was obtained. Compound 1-1a was liquid at 25°C. The obtained compound 1-1a 1 The H-NMR measurement results are shown in Figure 1. NMR was measured using a JEOL ECX-400. Deuterated chloroform was used as the measurement solvent. The compound obtained by the present production method can be suitably used for photo- and heat-curing by the above-mentioned simple purification method, as described below, and it is therefore clear that the present production method is advantageous.

[0108] [ka]

[0109] [Example 2] Preparation of compound 1-2b In a flask equipped with a reflux device, a stirrer, and a dropping device, 299.9 g (1.4 mol) of 2,4-dihydroxybenzophenone and 1,295 g (14 mol) of epichlorohydrin were charged and heated to 50°C. 483.9 g of 40% by mass potassium carbonate aqueous solution was dropped over 30 minutes, and then stirring was continued for 10 hours. The mixture was cooled, 490 g of water was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. The separated aqueous layer was extracted and subjected to epichlorohydrin removal. Then, 400 g of toluene was added and washed with water. After confirming that the aqueous layer was neutral, toluene was removed to obtain 470 g of the following chlorohydrin body 1-2b-1. 500 g of toluene was added to 250 g of the obtained chlorohydrin 1-2b-1, and the mixture was heated to 60°C. Then, 32.6 g of solid sodium hydroxide was added in 5 portions (1 portion / 20 minutes). After the 5th portion was added, the reaction was continued for 5 hours at 60°C. Then, the mixture was washed with water, the organic layer was dried over magnesium sulfate, and the toluene was removed to obtain 98.7 g of the ring-closed product 1-2b-2 shown below. The epoxy equivalent of the ring-closed product 1-2b-2 was 290 g / eq. In a flask equipped with a reflux device, a stirrer, and a dropping device, 270 mg of the ring-closed product 1-2b-2 obtained above, 151 mg of triethylamine, and 2 mL of tetrahydrofuran (THF) were charged. Then, 150 mg of methacryloyl chloride was dropped over 3 minutes, and the mixture was stirred at room temperature for 6 hours. Then, 10 mL of chloroform was added to the reaction solution, and the aqueous layer was washed with water until it became neutral. The chloroform was removed, and 268 mg of the following compound 1-2b was obtained. Compound 1-2b was a liquid at 25°C. The obtained compound 1 The H-NMR measurement results are shown in Figure 2. NMR was measured using a JEOL ECX-400. Deuterated chloroform was used as the measurement solvent. The compound obtained by the present production method can be suitably used for photo- and heat-curing by the above-mentioned simple purification method, as described below, and it is therefore clear that the present production method is advantageous.

[0110] [ka]

[0111] [Examples 3 to 6 and Comparative Example 1] The components were mixed in the amounts shown in Table 1 below to prepare the curable compositions of Examples 3 to 6 and Comparative Example 1. The curable composition prepared above was applied to a glass plate with a thickness of 300 μm using a bar coater to obtain a coating film. The obtained coating film was photocured under the following curing conditions to prepare a test piece, and photocured under the following curing conditions and then heat-cured to prepare a test piece, and the glass transition point (Tg) was measured. During photocuring, the photocurability was confirmed according to the following evaluation criteria. The results are shown in Table 1 below.

[0112] [Curing conditions] Photocuring: JATEC J-Cure1500CV, exposure dose 3,000mJ / cm 2 The curing property was confirmed by irradiation. Heat curing: Heated in a heat circulation oven at 100℃ for 1 hour and 150℃ for 2 hours.

[0113] [Evaluation Criteria] Photocurability: After irradiation with light, if the coating film was sufficiently cured and could be peeled off, it was marked as ◯, and if the coating film was not sufficiently cured and could not be peeled off, it was marked as x. Physical properties of the cured product: The glass transition temperature (Tg) was measured using an RSA manufactured by TA Instruments Co., Ltd. A rectangular test piece measuring 4 mm wide x 60 mm long x 300 μm thick was prepared.

[0114] [Table 1]

[0115] Compound 1-1a: the compound obtained in Example 1 Compound 1-2b: the compound obtained in Example 2 PTBPGE: p-tert-butylphenol glycidyl ether 2-PEA: 2-phenylethanol acrylate Irg-184: IGM Resins alkylphenone photoinitiator (omnirad184) 2E4MZ: Hardener manufactured by Shikoku Chemical Industries Co., Ltd. *1: Not implemented *2: Measurements were not possible because the material did not harden and test pieces could not be produced.

[0116] As is clear from the results shown in Table 1, the compound provided by the present invention can provide a curable composition that can be cured by light or heat. [Industrial Applicability]

[0117] 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 (1-2): 【Chemistry 1】 (In the formula, R 201 and R 203 each independently represents a hydrogen atom or a methyl group; R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5.

2. In the compound having two hydroxyl groups represented by the following general formula (1-2-1), R 5 The method for producing the compound according to claim 1, further comprising the steps of: converting a hydroxyl group located at the para-position to a benzoyl group, which may have a substituent represented by the following formula: 【Chemistry 2】 (In the formula, R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; and p represents a number from 0 to 5.

3. A curable composition comprising (A) at least one compound represented by the following general formula (1-2) and (B) at least one selected from a curing agent and a polymerization initiator: 【Chemistry 3】 (In the formula, R 201 and R 203 each independently represent a hydrogen atom or a methyl group, R 5 represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and p represents a number from 0 to 5.)

4. A method for producing a cured product, comprising curing the curable composition according to claim 3 with light and then curing the composition with heat.

5. A cured product obtained by curing the curable composition according to claim 3 with light and heat.

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