WO2021200511A1 - Compound, method for producing compound, and curable composition - Google Patents

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

Compounds, methods for producing compounds, and curable compositions

The present invention relates to a compound and a method for producing the same, and more particularly to a curable compound having a reactive unsaturated bond and an epoxy group and a method for producing the same. Further, the present invention relates to at least one of the curable compounds, a curing agent and polymerization. The present invention relates to a curable composition comprising at least one selected from the initiators.

In recent years, as mobile devices such as smartphones have become thinner, camera modules mounted on mobile devices such as smartphones have become smaller. Due to the miniaturization of the camera module, the parts for joining the constituent members of the camera module are also becoming finer, so that the adhesive layer formed from the adhesive for joining these is required to have high adhesive strength.

In addition, the adhesive used for assembling camera modules and the like is required to have low-temperature curability in order to avoid thermal damage to the image sensor and the like due to high-temperature treatment, and also has short-time curability from the viewpoint of improving production efficiency. Required at the same time. From this point of view, ultraviolet curable adhesives and thermosetting epoxy resin adhesives are often used as low-temperature short-time curable adhesives. However, although the ultraviolet curable adhesive can be cured quickly, it has a demerit that it cannot be used for adhering a part that is not exposed to light. On the other hand, thermosetting epoxy resin-based adhesives, even low-temperature short-time curable adhesives, must be fixed with jigs or devices in order to maintain the bonding posture during bonding. In addition, the viscosity is lowered due to the temperature rise due to heating, causing problems such as sagging immediately before curing and flowing to a portion other than the desired portion, which is not always satisfactory.

In order to solve the above-mentioned problems, an adhesive of a type that is temporarily fixed by curing by light irradiation (pre-curing) and further cured (mainly cured) by heat to be bonded has been proposed. For example, Patent Document 1 proposes a light and heat-curable composition containing a curable component composed 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 a compound having a (meth) acryloyl group and an epoxy group. Is also described.
However, the epoxy (meth) acrylate described in Patent Documents 1 and 2 is a compound obtained by reacting the epoxy group of the epoxy resin with (meth) acrylic acid, and an unreacted epoxy resin remains at the time of production. As a result, it becomes a mixture of a plurality of kinds of compounds, which tends to increase the viscosity, and is not satisfactory for application to a curing system by light and heat.

Japanese Unexamined Patent Publication No. 2009-51954 WO2018 / 181421

Therefore, an object of the present invention is to provide a compound which can be produced by an industrially advantageous method with less labor for removing unreacted substances and can be cured by light and heat, and can be cured by light and heat. It is to provide a curable composition which can provide an excellent sealant or adhesive.

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

(In the formula, R ¹ and R ³ independently represent a hydrogen atom or a methyl group, respectively, and R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and a substituent. Represents a benzoyl group capable of having or a benzyl group capable of having a substituent, and A ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. The substituent represents 1 to 10 carbon atoms. It is a group selected from an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
However, when A ¹ is a single bond, the unsaturated ester group represented by the following formula (1α) becomes a glycidyloxy group represented by the following formula (1β) in the benzene ring in the formula (1). On the other hand, it is located in the meta position. n represents a number from 0 to 4. )

(The definition of the sign in the equation is the same as in equation (1). * Is a bond.)

Further, in the present invention, after the phenolic hydroxyl group of the compound represented by the following general formula (1-1-1) is glycidyl etherified, the alcoholic hydroxyl group bonded to ^{A 2 in the obtained compound is an acrylic acid ester or meta.} Provided is a method for producing a compound represented by the following general formula (1-1), which is esterified using an acrylic acid ester.

(In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a group selected from halogen atoms, and A ² is an alkylene group having 1 to 4 carbon atoms. Represents. M represents a number from 0 to 4.)

(In the formula, R ¹⁰¹ and R ¹⁰³ independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected, A ² represents an alkylene group having 1 to 4 carbon atoms, and m represents a number of 0 to 4).

Further, in the present invention, in a compound having two hydroxyl groups represented by the following general formula (1-2-1), the hydroxyl group located at the para position with respect to the benzoyl group which may be substituted with ^{R 5 is glycidyl ether.} Provided is a method for producing a compound represented by the following formula (1-2), in which the hydroxyl group located at the ortho position with respect to the benzoyl group is esterified or methacrylic acid esterified after the conversion.

(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. P represents a number from 0 to 5.)

(In the formula, R ²⁰¹ and R ²⁰³ independently represent a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected. P represents a number from 0 to 5.)

Further, the present invention has a curable composition containing (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. It provides things.

(In the formula, R ¹ and R ³ independently represent a hydrogen atom or a methyl group, respectively, and R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and a substituent. Represents a benzoyl group capable of having or a benzyl group capable of having a substituent, and A ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. The substituent represents 1 to 10 carbon atoms. It is a group selected from an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
However, when A ¹ is a single bond, the unsaturated ester group represented by the following formula (1α) becomes a glycidyloxy group represented by the following formula (1β) in the benzene ring in the formula (1). On the other hand, it is located in the meta position. n represents a number from 0 to 4. )

(The definition of the sign in the equation is the same as in equation (1). * Is a bond.)

Further, the present invention provides a method for producing a cured product obtained by curing the curable composition with light and then heat.

Furthermore, the present invention provides a cured product obtained by curing the curable composition with light and heat.

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 is excellent in photocurability and thermosetting. It is possible to carry out dual curing in which temporary curing is performed by heat and then main curing is performed by heat. Due to these characteristics, it can be used in applications such as liquid encapsulants, liquid adhesives, adhesives for camera modules, and liquid crystal sealants.
In addition, since it is not necessary to use an excess epoxy resin in the above-mentioned production method for producing the compound represented by the formula (1-1), it is not necessary to remove unreacted substances, and a simple purification method can be used for light and / /. Alternatively, it has the advantage that it can be used for thermosetting. Further, as a production method for producing a compound represented by the formula (1-1) using the formula (1-1-1) as a substrate, a method using a (meth) acrylic acid chloride such as acryloyl chloride, an acrylic acid ester or the like, etc. There is a method using the (meth) acrylic acid ester of the above, but in the former, there is a possibility that a side reaction may occur with the hydrochloric acid and the epoxy group generated by the reaction. Therefore, by using a (meth) acrylic acid ester, it is possible to suppress the above side reaction.
Further, in the above-mentioned production method for producing the compound represented by the formula (1-2), it is not necessary to use an excess epoxy resin, so that it takes less time to remove unreacted substances, and light and a simple purification method can be used. / Or has the advantage that it can be used for thermosetting.

^{FIG. 1 is a 1} H-NMR measurement result of the compound obtained in Example 1. ^{FIG. 2 shows the measurement results of 1} H-NMR of the compound obtained in Example 2.

Hereinafter, the compound of the present invention will be described in detail.

As shown above, the compound represented by the formula (1) of the present invention has a glycidyl ether group (sometimes called a "glycidyloxy group") and a reactive unsaturated bond. Therefore, it is possible to provide a cured product by light and / or heat by using it in combination with various curing agents and various polymerization initiators. The reactive unsaturated bond may also be referred to as an ethylenically unsaturated bond.

In the general formula (1) ^{, examples of the alkyl group having 1 to 10 carbon atoms represented by R 2} include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a second butyl group. , Tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group and the like.

In the general formula (1) ^{, examples of the alkoxy group having 1 to 10 carbon atoms represented by R 2} include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyroxy group, a hexyloxy group, a pentyroxy group and an octyloxy group. Examples include a group, a nonyloxy group, a decyloxy group and the like.

In the general formula (1) ^{, examples of the halogen atom represented by R 2} include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the general formula (1), the alkyl group having 1 to 10 carbon atoms as the substituent of the benzoyl group or the benzyl group represented by ^{R 2, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom are R. The} above-mentioned groups can be used 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 2.

In the general formula (1) ^{, examples of the alkylene group having 1 to 4 carbon atoms represented by A 1} include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and an ethylidene group. Examples thereof include a propyridene group, an isopropylidene group and a butylidene group.

Among the compounds represented by the general formula (1), when A ¹ is an alkylene group having 1 to 4 carbon atoms, n is 0 or R ² is an alkyl having 1 to 10 carbon atoms. A group, an alkoxy group having 1 to 10 carbon atoms, a halogen atom or a benzyl group capable of having a substituent, preferably ^{an alkyl group in which n is 0 or R 2} is 1 to 10 carbon atoms. It is more preferably an alkoxy group or a halogen atom having 1 to 10 carbon atoms. Further, when A ¹ is a single bond, n is 1, and R ² is a benzoyl group capable of having a substituent, and the benzoyl group is relative to the glycidyloxy group represented by the above formula (1β). It is preferable that it is located in the para position. In these cases, the compound represented by the general formula (1) can be produced more easily. In particular, the compound represented by the following general formula (1-1) or (1-2) can be easily produced, and by using various curing agents and / or various polymerization initiators in combination, light It is preferable because it has excellent curability by heat.

(In the formula, R ¹⁰¹ and R ¹⁰³ independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected, A ² represents an alkylene group having 1 to 4 carbon atoms, and m represents a number of 0 to 4).

(In the formula, R ²⁰¹ and R ²⁰³ independently represent a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected. P represents a number from 0 to 5.)

In the above formula (1-1), ^{the alkyl group having 1 to 10 carbon atoms represented by R 4} and the alkoxy group having 1 to 10 carbon atoms and the halogen atom have the number of carbon atoms represented by ^{R 2.} Examples of the alkyl group of 1 to 10, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom include the groups exemplified above.
In the above formula (1-1), as the alkylene group having 1 to 4 carbon atoms represented by ^{A 2} , the group exemplified above as the alkylene group having 1 to 4 carbon atoms exemplified as ^{A 1 is used.} Can be mentioned.
In the above formula (1-2), ^{the alkyl group having 1 to 10 carbon atoms represented by R 5} , the alkoxy group having 1 to 10 carbon atoms, and the halogen atom have 1 carbon atom represented by ^{R 2.} Examples of the alkyl group to 10, the alkoxy group having 1 to 10 carbon atoms, and the halogen atom include the groups exemplified above.

When the compound of the present invention is represented by the above formula (1-1), ^{it is most preferable that A 2} is an ethylene group in terms of availability of raw materials.

When the compound of the present invention is represented by the above formula (1-1), it is preferable that A ² is located at the para-position or the meta-position with respect to the glycidyloxy group in terms of ease of producing the compound, particularly at the para-position. It is preferably located at.

When the compound of the present invention is represented by the above formula (1-1), m is preferably 3 or less, more preferably 2 or less, and further preferably 1 or less, from the viewpoint of ease of raw materials. It is particularly preferable, that is, it is 0, that is, it is most preferable that only the unsaturated ester group having ^{a glycidyloxy group and A 2 and a hydrogen atom are bonded to the benzene ring of the formula (1-1).}
Further, in the compound represented by the formula (1-1), when m is 1 or more, R ⁴ is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. Is preferable from the viewpoint of availability of a raw material, 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. When m is 2 or more, a plurality of R ^4s may be the same or different.

When the compound of the present invention is represented by the above formula (1-1), it is particularly preferable that the compound is represented by the following formula (1-1A) from the viewpoint described above.

(In the formula, R ¹⁰¹ and R ¹⁰³ independently represent a hydrogen atom or a methyl group, respectively.)

When the compound of the present invention is represented by the above formula (1-1) or (1-1A), it is preferable that R ¹⁰¹ is a hydrogen atom because the reactivity of the reactive unsaturated bond is high.
Further ^{, it is preferable that R 103} is a hydrogen atom because the reaction with the latent curing agent is quick.
From these points, ^{it is preferable that both R 101} and R ¹⁰³ are hydrogen atoms from the viewpoint of quick curing reaction. Further, it tends to become a liquid at 25 ° C., which has an advantage of improving workability.

The fact that the compound of the present invention is represented by the above formula (1-2) has an advantage that the rate at the time of thermosetting is high because the reactivity of the epoxy group is structurally high. Further, there is an advantage that the heat resistance of the cured product by light curing and the cured product by light and heat curing is relatively high. When the compound of the present invention is represented by the above formula (1-2), p is preferably 4 or less, more preferably 3 or less, and 2 or less from the viewpoint of ease of raw materials. It is particularly preferable, it is more preferably 1 or less, and most preferably 0.
When p is 1 or more, it is preferable that R ⁵ is 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 R 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. When p is 2 or more, a plurality of R ^5s may be the same or different.

When the compound of the present invention is represented by the above formula (1-2), it is preferable that R ²⁰¹ is a hydrogen atom in that the reactivity of the reactive unsaturated bond is high. It is preferable ^{that R 201} is a methyl group because the storage stability of the curable composition is improved and the cured physical properties are excellent.
Further ^{, it is preferable that R 203} is a hydrogen atom because it reacts quickly with a latent curing agent.

Hereinafter, a suitable method for producing the compound of the present invention will be described.
In this production method, one hydroxyl group is glycidyl etherified by utilizing the difference between the two hydroxyl groups in a compound containing two hydroxyl groups, and then the other hydroxyl group is (meth) acrylic acid esterified. can. More specifically, for example, it can be produced by the production method as shown below.

^{The compound represented by the formula (1-1) is the alcoholic hydroxyl group (A 2} ) of the compound obtained after the phenolic hydroxyl group of the compound represented by the following formula (1-1-1) is glycidyl etherified. It can be produced by esterifying an acrylate or a methacrylic acid (a hydroxyl group bonded to an alkylene group represented by). Here, since the acidity of the phenolic hydroxyl group and the alcoholic hydroxyl group are different, it is considered that the glycidyl etherification of the phenolic hydroxyl group proceeds preferentially. Then, by esterifying the alcoholic hydroxyl group, the compound represented by the formula (1-1) can be obtained.

(In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a group selected from halogen atoms, and A ² is an alkylene group having 1 to 4 carbon atoms. Represents. M represents a number from 0 to 4.)

The compound represented by the formula (1-2) is, for example, a benzoyl group (formula ^{) which may be substituted with R 5} in the compound having two hydroxyl groups represented by the following formula (1-2-1). After glycidyl etherification of the hydroxyl group located at the para position with respect to the benzoyl group on the left side in (1-2-1), the hydroxyl group located at the ortho position with respect to the benzoyl group is acrylic acid esterified or methacrylic. It can be produced by acid esterification. Here, since the acidity of the hydroxyl group at the para position and the hydroxyl group at the ortho position are different with respect to the benzoyl group, it is considered that the glycidyl etherification of the hydroxyl group at the para position proceeds preferentially. Then, by esterifying the hydroxyl group at the ortho position, the compound represented by the formula (1-2) can be obtained.

(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. P represents a number from 0 to 5.)

Here, as a method for converting one hydroxyl group into glycidyl ether, the hydroxyl group of the compound represented by the general formula (1-1-1), the compound represented by the general formula (1-2-1), or the like is used. There is a method of adding an alkali to a mixture of a compound containing two of the above and epihalohydrin to cause a reaction. Examples of the method for adding the alkali include a method of dropping an aqueous alkali solution and a method of adding a solid alkali in a plurality of times.

Examples of epichlorohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like.
Examples of the alkali include metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide.
An interlayer transfer catalyst can also be used, and examples of the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, and N, N-dimethylpyrrolid. Nium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium Bromid, 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, etc. Can be mentioned.

Here, the amount of epihalohydrin used is 3 to 50 times, preferably 4 to 30 times, the molar ratio of the compound containing two hydroxyl groups.
The reaction is carried out under heating, pressurization or reduced pressure, if necessary.
From the viewpoint of shortening the production time and reaction efficiency, the reaction temperature is preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower. If the chlorhydrinization reaction and the ring closure reaction of the obtained chlorhydrinide occur stepwise, and the reaction temperature of the chlorhydrinization reaction and the reaction temperature of the ring closure reaction are different, the reaction temperature of either one is the above temperature. It is preferably within the range, and more preferably both are within the above range.

On the other hand, as a method for acrylic acid esterification or methacrylic acid esterification, a method performed using an acrylic acid ester and / or a methacrylic acid ester in the presence of a catalyst such as dialkyltin oxide or tetraalkyl titanate, chloride. Examples thereof include a method using acryloyl and / or methacryloyl chloride in the presence of a neutralizing agent such as triethylamine. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate and butyl methacrylate.
From the viewpoint of shortening the production time and reaction efficiency, the reaction temperature in the presence of the former (meth) acrylic acid ester and catalyst is preferably, for example, 50 to 100 ° C, more preferably 70 to 90 ° C. preferable. Further, from the viewpoint of shortening the production time and reaction efficiency, the reaction temperature in the presence of the latter (meth) acrylic acid chloride and the neutralizing agent is preferably 0 to 30 ° C., for example.

In particular, as for the method for producing the compound represented by the formula (1-1), it is preferable to adopt a method using an acrylic acid ester and / or a methacrylic acid ester from the viewpoint of easily preventing side reactions, and in particular, acrylic. It is preferable to use an acrylic acid ester such as methyl acrylate from the viewpoint of obtaining a compound having excellent reactivity.

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

The curable composition of the present invention includes (A) at least one of the compounds represented by the general formula (1) (hereinafter, may be referred to as "component (A)") and (B) a curing agent. Alternatively, it contains at least one selected from the polymerization initiators (hereinafter, may be referred to as "component (B)").

A compound having at least one reactive unsaturated bond and one or more epoxy groups other than the component (A) can be used in combination with the curable composition of the present invention, and these are, for example, glycidyl methacrylate and allyl phenol. Examples thereof include glycidyl ether, diglycidyl monoallyl ether, and epoxy acrylates.

Further, the curable composition of the present invention may be used in combination with a compound having only an epoxy group or a compound having only a reactive unsaturated bond among the reactive unsaturated bond and the epoxy group.

Examples of the compound having only the epoxy group include known epoxy resins. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluoroglusinol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, and thiodiglycol. , Polyglycidyl ethers of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, sveric acid, adipic acid. , Azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and other fats Glycidyl esters of group, aromatic or alicyclic polybasic acids; homopolymers or copolymers of glycidyl methacrylate; vinylcyclohexene diepoxides, dicyclopentane diene diepoxides, 3,4-epoxycyclohexylmethyl-3,4 -Epoxy cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, epoxides of cyclic olefin compounds such as bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxy Examples thereof include epoxidized conjugated diene polymers such as polybutadiene and epoxidized styrene-butadiene copolymers, and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins were internally crosslinked with a prepolymer of terminal isocyanate, or polyvalent active hydrogen compounds (polyvalent phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) were used to increase the molecular weight. It may be a thing.

Examples of commercially available products of the epoxy resin include Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, and 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); Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P (manufactured by Kyoei Kagaku 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 (manufactured by ADEKA); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical) YD series, YDF series, YDPN series, TDCN series (Nippon Steel & Sumitomo Metal Chemical); Selokiside 2021P, Selokiside 2081 (manufactured by Daicel); TECHMORE 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 Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); HP4032, HP4032D , HP4700 (manufactured by DIC Corporation) and the like.

Examples of the compound having only a reactive unsaturated bond include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide. , N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide and other N-alkyl group-containing (meth) acrylamide derivatives; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol- N-alkoxy group-containing (meth) acrylamide derivatives such as N-propane (meth) acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-acryloylmorpholine, N-acryloylpiperidin, N-methacryloylpiperidin, N-acryloyl (Meta) acrylamide derivatives such as pyrrolidine; unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid , Itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono-succinic acid [2- (meth) acrylicyloxyethyl ], Mono (meth) phthalic acid [2- (meth) acrylicyloxyethyl], ω-carboxypolycaprolactone Mono (meth) acrylate, etc. Polymer mono (meth) acrylate having carboxy groups and hydroxyl groups at both ends; hydroxyethyl ( Unsaturated polyusity such as meta) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups. Basic acid; -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic Acid-t-butyl, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, (Meta) methoxyethyl acrylate, (meth) dimethylaminomethyl acrylate, Dimethylaminoethyl (meth) acrylic acid, aminopropyl (meth) acrylic acid, dimethylaminopropyl (meth) acrylic acid, ethoxyethyl (meth) acrylic acid, poly (ethoxy) ethyl (meth) acrylic acid, (meth) acrylic acid Butoxyethoxyethyl, 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, trimethylol ethanetri (meth) acrylate, trimethylpropanthry (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomer, and the like. Esters of polyhydric alcohol or polyhydric phenol; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate, magnesium (meth) acrylate; maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, methyl Tetrahydro phthalic acid anhydride, tetrahydrophthalic acid anhydride, trialkyltetrahydrophthalic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydro Acid anhydrides of unsaturated polybasic acids such as phthalic acid anhydride-maleic acid anhydride adduct, succinic anhydride, methylhymic acid anhydride; unsaturated aldehydes such as achlorine; (meth) acrylic nitrile, α-chloroacrylic acid, cyanide Unsaturated nitriles such as vinylidene silicate and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl tolue , Vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether and other unsaturated aromatic compounds; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, Unsaturated amine compounds such as N-vinylpyrrolidone and vinylpiperidin; 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, Unsaturated imides such as N-phenylmaleimide and N-cyclohexylmaleimide; indens such as inden and 1-methylinden; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) Macromonomonics having a mono (meth) acryloyl group at the end of polymer molecular chains such as acrylate, poly-n-butyl (meth) acrylate, polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, Triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group-containing vinyl monomer and polyepoxy compound. Vinyl epoxy compound of.

The content of the component (A) in the curable composition of the present invention is, for example, preferably 15% by mass or more, and 30% by mass or more and 99% by mass in terms of curability and the like in the curable composition. It is preferably 50% by mass or more and 97% by mass, more preferably. Further, when the curable composition contains an epoxy group and / or another compound having a reactive unsaturated bond in addition to the component (A), the amount of the other compound is (in terms of curability and the like). A) It is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less with respect to 100 parts by mass of the component.

As the curing agent which is the component (B) used in the present invention, for example, an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, a polythiol compound, an amine-based latent curing agent and the like are mentioned as preferable ones. Be done.

Examples of the amine-based curing agent include alkylenediamines such as ethylene dihydric acid, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine; diethylenetriamine. , Triethylenetriamine, polyalkylpolyamines such as tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino -3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylpropane, bis ( 4-Adipic acid dihydric acid) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone dihydric acid, norbornene diamine and other adipic polyamines; m-xylylene dihydrium , Diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoludidiamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3 Fragrances such as 5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3', 5'-tetramethyl-4,4'-diaminodiphenylmethane Polyamines; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 2- Imidazoles such as phenyl-4-methylimidazole and 2-aminopropyl imidazole; dihydrazide oxalic acid, dihydrazide malonate, dihydrazide succinic acid, dihydrazide glutalide, dihydrazide adipic acid, dihydrazide dihydric acid, dihydrazide azelaide, dihydrazide sevacinic acid Dihydrazides such as acid dihydrazide; N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine, N, N-benzylmethi Luaminoethylamine, 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-diethylaminopropyl Amine, 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'-methylpiperidin, 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N-diisopropylamino) benzyl Amine, N, N, -dimethylisophoronediamine, N, N-dimethylbisaminocyclohexane, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethylethylenediamine, N, N, N'-trimethyl Ethylenediamine, N'-ethyl-N, N-dimethylpropanediamine, N'-ethyl-N, N-dibenzylaminopropylamine; N, N- (bisaminopropyl) -N-methylamine, N, N-bis Aminopropylethylamine, 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 can be mentioned.

Examples of the phenol-based curing agent include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and trisphenylol. Methan resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol cocondensation novolac resin, naphthol-cresol cocondensation novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl Modified naphthol resin (polyvalent naphthol compound in which a phenol nucleus is linked with 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 an alkoxy group-containing fragrance. Examples thereof include polyhydric phenol compounds such as ring-modified novolak resin (polyhydric phenol compound in which a phenol core and an alkoxy group-containing aromatic ring are linked with formaldehyde).

Examples of the acid anhydride-based curing agent include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl anhydride. Hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, hydride methylnadic acid anhydride and the like can be mentioned.

Examples of the polythiol compound include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate). Mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) -1,3,4,6-tetraazaocthydropentalene-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-trithiaundecane, 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluryl, 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-Trithiandecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecane, Tetrakiss (mercaptomethylthiomethyl) methane, Tetraquis (2-mercaptoethylthiomethyl) Methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercapto) Methylthio) -1,3-dithian, 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-dithiaheptan, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonan, 3-Mercaptomethylthio-1,6-dimercapto-2,5-dithiahexa , 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonan, tris (2,2-bis (mercaptomethylthio) Ethyl) methane, tris (4,5-bis (mercaptomethylthio) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2 -Thiabutyl) Methane, 3,5,9,11-Tetrakiss (Mercaptomethylthio) -1,13-Dimercapto-2,6,8,12-Tetrathiatridecane, 3,5,9,11,15,17- Hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13, 15-Tetrakiss (Mercaptomethylthio) -1,17-Dimercapto-2,6,8,10,12,16-Hexatiaheptadecane, 3,4,8,9-Tetrakis (Mercaptomethylthio) -1,11-Dimercapto -2,5,7,10-Tetrathiaundecane, 3,4,8,9,13,14-Hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexa Thiahexadecane, 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-dithiaheptilthio] -1,3-ditian, 4- [3,5-bis (mercaptomethylthio) -7 -Mercapto-2,6-dithiaheptilthio] -6-Mercaptomethylthio-1,3-dithian, 1,1-bis [4- (6-mercaptomethylthio) -1,3-dithianilthio] -1,3- Bis (mercaptomethylthio) propane, 1- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -3- [2,2-bis (mercaptomethylthio) ethyl] -7,9-bis (mercaptomethylthio) -2,4,5,6,10-Tetrathiaundecane, 1,5-bis [4- (6-mercaptomethylthio) -1,3-dithianylthio] -3- [2- (1,3-dithietanyl)] methyl- 2,4-Dithiapentane, 3- [2- (1,3-Dithietane)] Methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiandecan, 9- [2- (1,3) -Dithietane)] Methyl-3,5,13,15-Tetrax (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2- (1) , 3-Dithietane)] Methyl-7,9,13,15-Tetrax (mercaptomethylthio) -1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis [2- (1,3-Dithietane)] Methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4,6-bis {3- [2- (1,3-dithietane)] Methyl-5-mercapto-2,4-dithiapentylthio} -1,3-dithiolane, 4,6-bis [4- (6-mercaptomethylthio) -1,3-dithianilthio] -6- [4-( 6-Mercaptomethylthio) -1,3-dithianylthio] -1,3-dithiane, 4- [3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathia Undecyl] -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-tetrathiandesylthio] mercaptomethylthiomethyl-1 , 3-Dithietane, 2- [3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-me Lucapto-2,4,5-trithiaoctyl] mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis {1- [2- (1,3-dithietanyl)]-3-mercapto-2-thiapropyl Thio} -1,3-dithiolane, 4- {1- [2- (1,3-dithietane)]-3-mercapto-2-thiapropylthio} -5- [1,2-bis (mercaptomethylthio)- 4-Mercapto-3-thiabutylthio] -1,3-dithiolane, 2- {bis [4- (5-mercaptomethylthio-1,3-dithiolanyl) thio] methyl} -1,3-dithietane, 4- [4- [4- (5-Mercaptomethylthio-1,3-dithiolanyl) Thio] -5- {1- [2- (1,3-dithietanyl)]-3-Mercapto-2-thiapropylthio} -1,3-dithiolane, etc. Can be mentioned.
Examples of commercially available products of these polythiol compounds include TS-G manufactured by Shikoku Chemicals Corporation, DPMP and PEMP manufactured by SC Organic Chemistry Co., Ltd., and PETG manufactured by Yodo Chemical Co., Ltd.
In particular, it is preferable to use a polythiol compound having a valence of 4 or more because a compound having excellent curability can be obtained.

Examples of the amine-based latent curing agent include dihydrazide oxalate, dihydrazide malonic acid, dihydrazide succinate, dihydrazide glutarate, dihydrazide adipate, dihydrazide suberic acid, dihydrazide azelaine, dihydrazide sevacinate, and dihydrazide phthalate. Basic acid dihydrazide; guanamines such as benzoguanamine and acetoguanamine; dicyandiamide; melamine; dehydration condensates of amine compounds and carboxylic acids, additions of amine compounds and epoxy compounds, additions of amine compounds and isocyanate compounds, amine compounds Examples thereof include a Michael adduct, a Mannig reaction product of an amine compound, a condensate of an amine compound and urea, and a modified amine such as a condensate of an amine compound and a ketone.

Among the amine-based latent curing agents, those obtained by adducting an amine compound having one or more active hydrogens and a polyepoxy compound and / or a polyisocyanate compound, or a combination thereof with a phenol resin are preferable. Be done.

Examples of the amine compound having one or more active hydrogens include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine. Alkylenediamines; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diamino Adicyclic polyamines such as dicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorondiamine, norbornenediamine; m-xylylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoludidiamine, 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'-diamino Aromatic polyamines such as diphenylmethane; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- Imidazoles such as phenyl imidazole, 2-phenyl-4-methyl imidazole, 2-aminopropyl imidazole; dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide glutalic acid, dihydrazide adipic acid, dihydrazide siberic acid, dihydrazide azelaic acid Dihydrazides such as sebasic 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- (3-aminopropyl) 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-bisaminopropyl ethylamine, 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-dib) Tylaminopropyl)] Amine and the like can be mentioned.

Examples of the polyepoxy compound include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluoroglucolcinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), and methylenebis (orthocresol). , Echiliden bisphenol, isopropyridene bisphenol (bisphenol A), isopropyridene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumyl) Benzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolac, orthocresol novolac Polyglycidyl ether compounds of polynuclear polyvalent phenolic compounds such as ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinnovolac, terpenphenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, Polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid , Sevacinic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and other aliphatic and aromatic Glycidyl esters of group or alicyclic polybasic acids, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) Epoxy compounds having a glycidyl amino group such as methane, diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxyside, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy -6-Methylcyclohexylmethyl-6-methi Epoxides of cyclic olefin compounds such as lucyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, Examples thereof include heterocyclic compounds such as triglycidyl isocyanurate.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylenedi isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5. -Aromatic diisocyanates such as naphthylene diisocyanate, 1,5-tetrahydronaphthalenedisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4 , 4'-Diisocyanate, trans-1,4-cyclohexyldiisocyanate, norbornene diisocyanate and other alicyclic diisocyanates; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) )-Adicyclic diisocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate; isocyanurate trimersides, burette trimerates, trimethylolpropane adductates, etc. of the above-exemplified diisocyanates; triphenylmethane triisocyanates, 1-methylbenzol- Examples thereof include 2,4,6-triisocyanate and dimethyltriphenylmethanetetraisocyanate.
Further, these isocyanate compounds may be used in the form of carbodiimide modification, isocyanurate modification, biuret modification or the like, or may be used in the form of blocked isocyanate blocked by various blocking agents.

Examples of the phenol resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and 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 (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified Naftor resin (a polyvalent naphthol compound in which a phenol nucleus is linked with 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 an alkoxy group-containing aromatic ring. Examples thereof include polyhydric phenol compounds such as modified novolak resins (polyhydric phenol compounds in which a phenol core and an alkoxy group-containing aromatic ring are linked with formaldehyde).

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) and 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 (ADEKA Corporation) Made by Polyamine type latent curing agent), ADEKA Hardener EH-5057P (manufactured by ADEKA Corporation; Polyamine type latent curing agent), ADEKA Hardener EH-5057PK (made by ADEKA Corporation; Polyamine type latent curing agent), Amicure PN -23 (Ajinomoto Fine Techno Co., Ltd .; Amin Adduct-based latent curing agent), Amicure PN-40 (Ajinomoto Fine Techno Co., Ltd .; Amin Adduct-based latent curing agent), Amicure VDH (Ajinomoto Fine Techno Co., Ltd .; Hydrazide-based latent hardener), Fujicure FXR-1020 (manufactured by T & K TOKA Corporation; latent hardener) and the like.

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

Further, in the curable composition of the present invention, a curing catalyst can be used in combination with the curing agent as the component (B), and the curing catalyst includes, for example, a phosphine compound such as triphenylphosphine; tetraphenylphospho. Phosphonium salts such as nium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1- {3-[(3- Trimethoxysilyl) propylaminocarbonylamino] propyl} -2-methylimidazole, 1- [3-trimethoxysilylpropylaminomethyl] -4-methylimidazole, 1- [3- (trimethoxysilylpropyl)] imidazole, 1 -[3- (Trimethoxysilylpropyl)] imidazoles such as imidazole; imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6-tris Amines such as (dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1- Ureas such as dimethylurea, 3-phenyl-1,1-dimethylurea, isophoronediisocyanate-dimethylurea, tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines, ether compounds, etc. Can be exemplified. These curing accelerators may be used alone or in combination of two or more.

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

Examples of the polymerization initiator which is the component (B) used in the present invention include a thermal radical polymerization initiator, a photoradical polymerization initiator, and a cationic polymerization initiator.

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides, persulfates and the like are preferable. It can be exemplified as a thing.

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1, Examples thereof include 1'-azobis (1-acetoxy-1-phenylethane).

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate.

Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, etc. A thioxanthone-based compound, an oxime ester-based compound, and the like can be exemplified as preferable ones.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl. -2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tershalibutyldichloroacetophenone, p-tershaributyltrichloroacetophenone, p-azide Benzalacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -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- Examples thereof include 2-methyl-1-propane-1-one.

Examples of the benzyl compound include benzyl and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. Be done.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.

The oxime ester-based 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.

Among the oxime ester compounds, a compound having a carbazole skeleton, a diphenylsulfide skeleton, and a fluorene skeleton is more preferable than the curable composition of the present invention because of its particularly high sensitivity.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Il)] Titanosen-based compounds such as titanium can be mentioned.

Commercially available radical polymerization initiators include ADEKA PUTMER N-1414, N-1717, N-1919, ADEKA ARCLUS NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE. OXE 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by Trolly); and the like.

The cationic polymerization initiator may be any compound as long as it can release a substance that initiates cationic polymerization by irradiation with energy rays or heating, but is preferably Lewis acid by irradiation with energy rays. It is a double salt that is an onium salt that releases energy, or a derivative thereof. Typical examples of such compounds include the following general formulas.
[A] ^{r +} [B] ^r-
The salts of cations and anions represented by are given.

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example, the following general formula.
[(R ¹² ) _a Q] ^{r +}
Can be represented by.

Further, 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 from 1 to 5. The a R ^12s are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. 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, N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, it is necessary that the relationship r = aq is established (however, N = N is treated as having a valence of 0).

Further, the anion [B] ^r- is preferably a halide complex, and its structure is, for example, the following general formula.
It can be represented by [LY _b ] ^r-.

Further, here, L is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. Y is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] ^r- is p, it is necessary that the relationship r = bp is established.

Specific examples of the anion [LY _b ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, and tetrafluoroborate (BF ₄ ) ^-,. hexafluorophosphate (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloroantimonate (SbCl ₆₎ ^-, and the like.

The anion [B] ^r- is the following general formula,
[LY _b-1 (OH)] ^r
The structure represented by is also preferably used. L, Y, and b are the same as above.
Other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulphonate, nonafluorobutane sulphonate, hexadecafluorooctane sulphonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). From these, one of them can be used alone, or two or more of them can be mixed and used.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like.

(B) Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmil iodonium tetrakis (pentafluorophenyl) borate, etc. Iodonium salt

(C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimon ion, hexafluorophosphate ion, and tetrakis (pentafluorophenyl) borate ion.

The amount of the polymerization initiator used is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) and the epoxy group and / or other compound having a reactive unsaturated bond. By setting the content to 20 parts by mass or less, it is possible to suppress the influence on various physical properties such as the water absorption rate of the cured product and the strength of the cured product.

When the curable composition of the present invention is photocured with a polymerization initiator, a sensitizer and a sensitizing aid can be used. Examples of the sensitizer and the sensitizer aid include anthracene compounds and naphthalene compounds.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, and 9. , 10-Dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxy) Ethoxy) 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-dibutoxy Anthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like can be mentioned.

Examples of the naphthalene-based compound include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, and the like. Examples thereof include 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene and 1,4-dibutoxynaphthalene.

The curable composition of the present invention is, if necessary, 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 Aminosilanes such as-(2-aminoethyl) -8-aminooctyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine Compounds; Mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silane coupling agents such as epoxysilane compounds such as 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, monoglycidyl ethers, dioctylphthalate, dibutylphthalate, benzyl alcohol, coaltal and the like. Reactive or non-reactive diluent (plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black , Graphite, iron oxide, bituminous substance, etc. fillers or pigments; candelilla wax, carnauba wax, wood wax, ibotarou, mitsuro, lanolin, whale wax, montane wax, petroleum wax, fatty acid wax, fatty acid ester, fatty acid ether, Lubricants such as aromatic esters and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; antifoaming agents; rust preventives; colloidal silica, colloidal alumina, etc. Known additives may be contained, and adhesive resins such as xylene resin and petroleum resin can also be used in combination.

The curable composition of the present invention can be cured by light and heat by changing the types of the curing agent and the polymerization initiator as exemplified above or by using a plurality of them in combination.
Among them, a method can be adopted in which a photopolymerization initiator and a curing agent are used in combination, and after temporary curing by light irradiation, thermosetting is performed. In that case, if a large amount of the compound having only an epoxy group or the compound having only a reactive unsaturated bond among the epoxy group and the reactive unsaturated bond is contained, the curing may be insufficient or the cured product may be insufficiently cured. There is a risk that the physical properties of the Therefore, the total amount of the compound having only the epoxy group or the compound having only the reactive unsaturated bond among the epoxy group and the reactive unsaturated bond is 100 parts by mass or less with respect to 100 parts by mass of the compound of the present invention. It is preferably 70 parts by mass or less, and more preferably 70 parts by mass or less. Further, the photopolymerization initiator is preferably a photoradical polymerization initiator.

In photocuring, the light to be irradiated may include light having a wavelength of 300 nm to 450 nm. 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 halogen lamps, electron beam irradiators, X-ray irradiators, lasers (argon lasers, dye lasers, nitrogen lasers, etc.) LED, helium cadmium laser, etc.).

The heating temperature in the thermosetting may be any one as long as it can stably cure the composition, and is appropriately set according to the type of the curing agent and the like. For example, it is 10 ° C. or higher and 250 ° C. or lower. It is preferable that the temperature is 60 ° C. or higher and 200 ° C. or lower.

The cured product of the curable composition of the present invention is preferably a cured product obtained by heat-curing after photo-curing because of its excellent performance such as heat resistance. The Applicant believes that this statement represents a condition. Even if this description specifies a product by a production method, it takes a lot of experimental time to specify a structure / property other than that described in the present specification for a cured product obtained by curing a curable compound under predetermined conditions. There are impossible and impractical circumstances because it requires.

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 sizing agents, building materials, and electronic parts. In particular, since it has excellent curability by light and heat, it can be used in applications where dual curing is possible. That is, it can be suitably used for applications such as a liquid sealant, a liquid adhesive, a liquid crystal sealant, and an adhesive for a camera module.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

[Example 1] Production of compound 1-1a 386.9 g (2.8 mol) of p-hydroxyphenethyl alcohol and 1,295 g (14 mol) of epichlorohydrin are charged in a flask equipped with a reflux device, a stirrer, and a dropping device. , 221.7 g (0.95 mol) of a 48 mass% sodium hydroxide aqueous solution was placed in the dropping device. The aqueous sodium hydroxide solution was added dropwise over reflux at an internal temperature of 65 to 70 ° C. and a reduced pressure of 21 to 24 kPa over 2 hours, and at the same time, water was removed by an azeotropic upstream. Then, after further reacting for 1 hour, it was deepichlorohydrin, washed with water, desolvated and filtered to obtain the following compound 1-1a-1.
The epoxy equivalent of the compound 1-1a-1 is 216 g / eq. Met.
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 titanium tetra-n were placed. -Butoxide was charged in an amount of 21.8 g (0.06 mol), 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 mixture was cooled, 500 g of toluene and 30 g of water were added, and the mixture was stirred at 60 ° C. for 1 hour to hydrolyze the catalyst. The concentrated solution obtained by distilling and removing toluene and water was cooled, and then filtered to remove the precipitated catalytic decomposition product to obtain Compound 1-1a. Compound 1-1a was a liquid at 25 ° C.
^{The 1} H-NMR measurement result of the obtained compound 1-1a is shown in FIG.
NMR was measured using ECX-400 manufactured by JEOL Ltd. Deuterated chloroform was used as the measurement solvent.
The compound obtained by this production method can be suitably used for light and thermosetting as described later by the above-mentioned simple purification method, and it can be seen that this production method is advantageous.

[Example 2] Production of compound 1-2b 299.9 g (1.4 mol) of 2,4-dihydroxybenzophenone and 1,295 g (14 mol) of epichlorohydrin were placed in a flask equipped with a reflux device, a stirrer, and a dropping device. It was charged and heated at 50 ° C. After dropping 483.9 g of a 40 mass% potassium carbonate aqueous solution over 30 minutes, stirring was continued for 10 hours. After cooling, 490 g of water was added, the mixture was stirred for 30 minutes, and allowed to stand for 1 hour. The separated aqueous layer was extracted and deepichlorohydrin was performed. Then, 400 g of toluene was added and washed with water. After confirming that the aqueous layer became neutral, detoluene was performed to obtain 470 g of the following chlorohydrin compound 1-2b-1.
To 250 g of the obtained chlorohydrin compound 1-2b-1, 500 g of toluene was added, and the mixture was heated to 60 ° C. Then, 32.6 g of solid sodium hydroxide was added in 5 portions (1 division / 20 minutes). After adding the 5th division, the reaction was continued for 5 hours at 60 ° C. Then, it was washed with water, the organic layer was dried over magnesium sulfate, and detoluene was carried out to obtain 98.7 g of the following ring-closed body 1-2b-2. The epoxy equivalent of the ring closure 1-2b-2 is 290 g / eq. Met.
In a flask equipped with a reflux device, a stirrer, and a dropping device, 270 mg of the ring-closed body 1-2b-2 obtained above, 151 mg of triethylamine, and 2 mL of tetrahydrofuran (THF) were charged. Then, 150 mg of methacryloyl chloride was added dropwise 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 mixture was washed with water until the aqueous layer became neutral. Dechloroform was performed to obtain 268 mg of the following compound 1-2b. Compound 1-2b was liquid at 25 ° C.
^{The 1} H-NMR measurement result of the obtained compound is shown in FIG.
NMR was measured using ECX-400 manufactured by JEOL Ltd. Deuterated chloroform was used as the measurement solvent.
The compound obtained by this production method can be suitably used for light and thermosetting as described later by the above-mentioned simple purification method, and it can be seen that this production method is advantageous.

[Examples 3 to 6 and Comparative Example 1]
The curable compositions of Examples 3 to 6 and Comparative Example 1 were prepared by mixing each component in the amounts shown in Table 1 below.
The curable composition prepared above was applied on a glass plate with a bar coater to a thickness of 300 μm to obtain a coating film. For the obtained coating film, a test piece photo-cured under the following curing conditions and a test piece photo-cured under the following curing conditions and then thermosetting were prepared, and the glass transition point (Tg) was measured. bottom. At the time of photocuring, the photocurability was confirmed according to the following evaluation criteria.
These results are shown in Table 1 below.

[Curing conditions]
Photocuring: Using J-Cure 1500CV manufactured by JATEC, an exposure amount of 3,000 mJ / cm ^{2 was} irradiated and the curability was confirmed.
Thermosetting: Heated in a heat circulation type oven at 100 ° C. × 1 h and 150 ° C. × 2 h.

〔Evaluation criteria〕
Photocurability: After light irradiation, those in which the coating film was sufficiently cured to form a mold-releasable coating film were evaluated as 〇, and those in which the coating film could not be peeled off due to insufficient curing were evaluated as x.
Physical characteristics of cured product: The glass transition point (Tg) was measured using RSA manufactured by TA Instruments. As the test piece, a strip-shaped test piece having a width of 4 mm, a length of 60 mm, and a thickness of 300 μm was prepared.

Compound 1-1a: Compound 1-2b obtained in Example 1: Compound PTBPGE obtained in Example 2: p-Triary butylphenol glycidyl ether 2-PEA: 2-Phenylethanol acrylate Irg-184: Alkylphenone-based photopolymerization initiator manufactured by IGM Resins (omnirad184)
2E4MZ: Hardener manufactured by Shikoku Kasei Kogyo Co., Ltd. * 1: Not implemented * 2: Cannot be measured because the test piece could not be manufactured without curing.

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.

The compound of the present invention can be cured by light and / or heat, and the curable composition obtained by containing the compound can be cured by light and heat. It can be used for applications such as adhesives, adhesives for camera modules, and liquid crystal sealants.

Claims (9)

1. A compound represented by the following general formula (1).
   

   

   (In the formula, R ¹ and R ³ independently represent a hydrogen atom or a methyl group, respectively, and R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and a substituent. Represents a benzoyl group capable of having or a benzyl group capable of having a substituent, and A ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. The substituent represents 1 to 10 carbon atoms. It is a group selected from an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
   However, when A ¹ is a single bond, the unsaturated ester group represented by the following formula (1α) becomes a glycidyloxy group represented by the following formula (1β) in the benzene ring in the formula (1). On the other hand, it is located in the meta position. n represents a number from 0 to 4. )
   

   

   (The definition of the sign in the equation is the same as in equation (1). * Is a bond.)
2. The compound according to claim 1, wherein the general formula (1) is represented by the following general formula (1-1).
   

   

   (In the formula, R ¹⁰¹ and R ¹⁰³ independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected, A ² represents an alkylene group having 1 to 4 carbon atoms, and m represents a number of 0 to 4).
3. The compound according to claim 2, wherein the general formula (1-1) is represented by the following general formula (1-1A).
   

   

   (In the formula, R ¹⁰¹ and R ¹⁰³ independently represent a hydrogen atom or a methyl group, respectively.)
4. After the phenolic hydroxyl group of the compound represented by the following general formula (1-1-1) is glycidyl etherified, the alcoholic hydroxyl group of the obtained compound is esterified with an acrylic acid ester or a methacrylic acid ester. The method for producing a compound according to claim 2 or 3.
   

   

   (In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a group selected from halogen atoms, and A ² is an alkylene group having 1 to 4 carbon atoms. Represents. M represents a number from 0 to 4.)
5. The compound according to claim 1, wherein the general formula (1) is represented by the following general formula (1-2).
   

   

   (In the formula, R ²⁰¹ and R ²⁰³ independently represent a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Represents the group to be selected. P represents a number from 0 to 5.)
6. In a compound having two hydroxyl groups represented by the following general formula (1-2-1), the hydroxyl group located at the para position with respect to the benzoyl group capable of having a substituent represented by ^{R 5 is glycidyl etherified.} The method for producing a compound according to claim 5, wherein the hydroxyl group located at the ortho position with respect to the benzoyl group is subjected to acrylic acid esterification or methacrylic acid esterification.
   

   

   (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. P represents a number from 0 to 5.)
7. 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.
   

   

   (In the formula, R ¹ and R ³ independently represent a hydrogen atom or a methyl group, respectively, and R ² is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and a substituent. Represents a benzoyl group capable of having or a benzyl group capable of having a substituent, and A ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. The substituent represents 1 to 10 carbon atoms. It is a group selected from an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
   However, when A ¹ is a single bond, the unsaturated ester group represented by the following formula (1α) becomes a glycidyloxy group represented by the following formula (1β) in the benzene ring in the formula (1). On the other hand, it is located in the meta position. n represents a number from 0 to 4. )
   

   

   (The definition of the sign in the equation is the same as in equation (1). * Is a bond.)
8. A method for producing a cured product, wherein the curable composition according to claim 7 is cured by light and then cured by heat.
9. A cured product obtained by curing the curable composition according to claim 7 with light and heat.

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