CN115003709A

CN115003709A - Compound, method for producing compound, and curable composition

Info

Publication number: CN115003709A
Application number: CN202180011205.8A
Authority: CN
Inventors: 小林将太; 玉祖健一; 小川亮; 永松保
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2020-03-31
Filing date: 2021-03-24
Publication date: 2022-09-02
Anticipated expiration: 2041-03-24
Also published as: CN115003709B; KR20220162687A; WO2021200511A1; JPWO2021200511A1

Abstract

A compound represented by the following formula (1). (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, an optionally substituted benzoyl group or an optionally substituted benzyl group, A ¹ Represents a single bond or an alkylene group having 1 to 4 carbon atoms. The substituent is selected from alkyl with 1-10 carbon atoms and carbon atom1 to 10 alkoxy groups or halogen atoms. Wherein, in A ¹ In the case of a single bond, the unsaturated ester group is a group located at a meta position with respect to the glycidyloxy group. n represents a number of 0 to 4. )

Description

Compound, method for producing compound, and curable composition

Technical Field

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, 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

In recent years, with the thinning of portable devices such as smartphones, camera modules mounted on portable devices such as smartphones have been reduced in size. Since the camera module is miniaturized and the portions where the components of the camera module are joined to each other are also minute, a high adhesive strength is required for the adhesive layer formed of the adhesive joining them.

In addition, an adhesive used for assembling a camera module or the like is required to be curable at a low temperature in order to avoid thermal damage to an image sensor or the like due to high-temperature treatment, and is also required to be curable for a short time in order to improve production efficiency. From such a viewpoint, many ultraviolet-curable adhesives and thermosetting epoxy resin adhesives are used as the low-temperature short-time curable adhesive. However, the ultraviolet-curable adhesive can be cured quickly, but has a disadvantage that it cannot be used for bonding a part which cannot be irradiated with light. On the other hand, the thermosetting epoxy resin adhesive is not necessarily satisfactory because it is necessary to fix the members (components) to be bonded with a jig or a device in order to maintain the bonding posture during the bonding, and it has a problem that the viscosity decreases due to the temperature increase caused by heating, and the adhesive sags immediately before curing or flows to other than desired portions.

In order to solve the above-described problems, an adhesive of a type that temporarily fixes by curing (precuring) by light irradiation and further cures (main curing) by heat has been proposed. For example, patent document 1 proposes a photo-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, a latent curing agent, and 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 the reaction between an epoxy group of an epoxy resin and (meth) acrylic acid, and the epoxy resin that has not reacted during production remains, and the like, and a mixture of a plurality of compounds is obtained, and the viscosity tends to be high, or the epoxy (meth) acrylates are not satisfactory for application to a curing system using light and heat.

Documents of the prior art

Patent literature

Patent document 1: japanese laid-open patent publication No. 2009-51954

Patent document 2: WO2018/181421

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a compound which can be produced by an industrially advantageous method with less trouble of removing unreacted materials and can be cured by light and heat, and a curable composition which can provide a sealant or an adhesive having excellent light and heat curability.

Means for solving the problems

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

[ chemical formula 1]

(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.

Wherein, in A ¹ In the case of a single bond, the unsaturated ester group represented by the following formula (1 α) is a group located at a meta position with respect to the glycidyloxy group represented by the following formula (1 β) in the benzene ring in the formula (1). n represents a number of 0 to 4. )

[ chemical formula 2]

(wherein the symbols are as defined in the formula (1). ANGSTROM.. the bonding points.)

The present invention also provides a method for producing a compound represented by the following general formula (1-1), wherein a phenolic hydroxyl group of a compound represented by the following general formula (1-1-1) is glycidyl-etherified, and then the compound obtained is reacted with A ² The bonded alcoholic hydroxyl groups are esterified using an acrylate or methacrylate.

[ chemical formula 3]

(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 of 0 to 4. )

[ chemical formula 4]

(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 of 0 to 4. )

The present invention also provides a method for producing a compound represented by the following formula (1-2), wherein in the compound having 2 hydroxyl groups represented by the following general formula (1-2-1), the compound is represented by R ⁵ After glycidyl etherification of the hydroxyl group at the para-position of the substituted benzoyl group, the hydroxyl group at the ortho-position with respect to the aforementioned benzoyl group is acrylated or methacrylated.

[ chemical formula 5]

(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 of 0 to 5. )

[ chemical formula 6]

(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. p represents a number of 0 to 5. )

The present invention also provides 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.

[ chemical formula 7]

(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, an optionally substituted benzoyl group or an optionally substituted benzyl group, 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.

[ chemical formula 8]

The present invention also provides a method for producing a cured product, which comprises curing the curable composition with light and then curing the cured composition with heat.

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

Effects of the invention

The compound provided by the present invention is suitable as a material that is cured by light and heat, and the curable composition provided by the present invention has excellent photocurability and excellent thermosetting properties, and therefore can be subjected to dual curing in which temporary curing is performed by light and then main curing is performed by heat. Due to these characteristics, the liquid sealing agent can be used for applications such as a liquid sealing agent, a liquid adhesive, an adhesive for camera modules, and a liquid crystal sealing agent.

Further, the above-mentioned production method for producing the compound represented by the formula (1-1) does not require the use of an excess amount of epoxy resin, and therefore has the advantages that the trouble of removing unreacted materials is small and the method can be used for light and/or heat curing by a simple purification method. Further, as a method for producing the compound represented by the formula (1-1) using the formula (1-1-1) as a substrate, there can be mentioned a method using (meth) acryloyl chloride such as acryloyl chloride and a method using (meth) acrylic acid ester such as acrylic acid ester, and in the former case, there is a possibility that side reaction occurs with hydrochloric acid and epoxy group which are generated along with the reaction. Therefore, the use of the (meth) acrylate can suppress the side reaction.

Further, the above-mentioned production method for producing the compound represented by the formula (1-2) does not require the use of an excess amount of epoxy resin, and therefore has advantages that the method is less troublesome for removing unreacted materials and can be used for photo-and/or thermal curing by a simple purification method.

Drawings

FIG. 1 shows the compound obtained in example 1 ¹ H-NMR measurement results.

FIG. 2 is a photograph of the compound obtained in example 2 ¹ H-NMR measurement results.

Detailed Description

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

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

In the above general formula (1), R is ² The alkyl group having 1 to 10 carbon atoms includes, for example, a methyl groupAnd (b) a group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, or the like.

In the above general formula (1), R is ² Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy (amyl oxy), hexyloxy, pentyloxy (amyl oxy), octyloxy, nonyloxy, decyloxy, and the like.

In the above general formula (1), R is ² Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the above general formula (1), R is ² The substituent of benzoyl or benzyl group represented by (A) can be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom ² 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-mentioned groups.

In the above general formula (1), A is ¹ Examples of the alkylene group having 1 to 4 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, ethylidene, propylidene, isopropylidene and butylidene.

In the compound represented by the above general formula (1), A is ¹ When the alkylene group has 1 to 4 carbon atoms, n is preferably 0 or R ² Is 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 more preferably n is 0 or R ² Is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom. In addition, A ¹ When the bond is a single bond, n is preferably 1, R ² Is an optionally substituted benzoyl group which is located at the para-position relative to the glycidyloxy group represented by the above formula (1 β). In these cases, the compound represented by the above general formula (1) can be produced more easily. In particular, a compound represented by the following general formula (1-1) or (1-2)Can be easily produced, and is preferably used in combination with various curing agents and/or various polymerization initiators because of excellent curability with light and heat.

[ chemical formula 9]

(wherein R is 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 of 0 to 4. )

[ chemical formula 10]

In the above formula (1-1), as R ⁴ The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom are represented by the above R ² The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom are each the groups exemplified above.

In the above formula (1-1), as A ² The alkylene group having 1 to 4 carbon atoms includes the above-mentioned A ¹ The alkylene group having 1 to 4 carbon atoms is exemplified as the group exemplified above.

In the above formula (1-2), as R ⁵ The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom are represented by R ² The alkyl group having 1 to 10 carbon atoms and the alkane having 1 to 10 carbon atomsOxy and halogen atoms are each the groups exemplified above.

In the case where the compound of the present invention is represented by the above formula (1-1), A is used in view of easy availability of raw materials ² Particularly, ethylene is most preferable.

When the compound of the present invention is represented by the above formula (1-1), A is preferably used from the viewpoint of ease of production of the compound ² It is preferably located at the para-position or meta-position relative to the glycidyloxy group, and particularly preferably located at the para-position.

In the case where 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, particularly preferably 1 or less, most preferably 0, that is, m is a group having a structure in which only glycidyloxy group is bonded to benzene ring of the formula (1-1), from the viewpoint of easiness of raw material ² And a hydrogen atom.

In addition, when m of the compound represented by the formula (1-1) is 1 or more, R is preferably R from the viewpoint of easy availability of raw materials ⁴ Is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, 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's are present ⁴ May be the same or different.

When the compound of the present invention is represented by the above formula (1-1), the compound represented by the following formula (1-1A) is particularly preferable from the above-mentioned viewpoints.

[ chemical formula 11]

(in the formula, R ¹⁰¹ And R ¹⁰³ Each independently represents a hydrogen atom or a methyl group. )

In the case where the compound of the present invention is represented by the above formula (1-1) or (1-1A), R is a reactive unsaturated bond because the reactivity of the reactive unsaturated bond is high ¹⁰¹ Preferably a hydrogen atom.

In addition, R is preferably R from the viewpoint of fast reaction with a latent curing agent ¹⁰³ Is a hydrogen atom.

From these viewpoints, R is preferably R from the viewpoint of fast curing reaction ¹⁰¹ And R ¹⁰³ Are all hydrogen atoms. In addition, the resin composition is easily changed into liquid at 25 ℃ and has the advantage of improved workability.

The compound of the present invention represented by the above formula (1-2) has an advantage of high speed at the time of thermal curing because the reactivity of the epoxy group is structurally high. Further, there is an advantage that the heat resistance of a cured product cured by light curing and a cured product cured by light and heat curing is relatively high. In the case where 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, particularly preferably 2 or less, more preferably 1 or less, and most preferably 0, from the viewpoint of easiness of raw materials.

When p is 1 or more, R is preferably R in view of easy availability of raw materials ⁵ Is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, more preferably R ⁵ Is 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's are present ⁵ May be the same or different.

In the case where the compound of the present invention is represented by the above formula (1-2), R is a reactive unsaturated bond because the reactivity of the reactive unsaturated bond is high ²⁰¹ Preferably a hydrogen atom. R is preferably R in view of improvement in storage stability of the curable composition and excellent physical properties of the cured product ²⁰¹ Is methyl.

In addition, R is preferably R from the viewpoint of fast reaction with a latent curing agent ²⁰³ Is a hydrogen atom.

Hereinafter, a preferred method for producing the compound of the present invention will be described.

The present production method can be produced by glycidyl etherification of one hydroxyl group and (meth) acrylation of the other hydroxyl group using the difference in 2 hydroxyl groups in a compound having 2 hydroxyl groups. More specifically, the present invention can be manufactured by a manufacturing method described below, for example.

The compound represented by the above formula (1-1) can be prepared by glycidyletherifying a phenolic hydroxyl group of a compound represented by the following formula (1-1-1), and then reacting the alcoholic hydroxyl group (with A) of the resulting compound ² The alkylene-bonded hydroxyl group represented by the above) is subjected to acrylation or methacrylation. Here, it is considered that glycidyl etherification of the phenolic hydroxyl group proceeds preferentially because the phenolic hydroxyl group and the alcoholic hydroxyl group have different degrees of acidity. Then, the alcoholic hydroxyl group is esterified to obtain a compound represented by the formula (1-1).

[ chemical formula 12]

The compound represented by the above formula (1-2) can be produced, for example, by subjecting a compound having 2 hydroxyl groups represented by the following formula (1-2-1) to R substitution ⁵ A substituted benzoyl group (left benzoyl group in the formula (1-2-1)) is produced by glycidylethylating a hydroxyl group at the para-position, and then acrylating or methacrylating a hydroxyl group at the ortho-position with respect to the benzoyl group. Here, it is considered that glycidyl etherification of the hydroxyl group at the para-position is preferentially performed because the hydroxyl group at the para-position and the hydroxyl group at the ortho-position have different degrees of acidity from each other with respect to the benzoyl group. Then, the compound represented by the formula (1-2) can be obtained by esterifying the hydroxyl group at the ortho position.

[ chemical formula 13]

Here, as the above-mentioned method for glycidyletherifying one hydroxyl group, there can be mentioned a method in which a base is added to a mixture of a compound having 2 hydroxyl groups such as the compound represented by the above-mentioned general formula (1-1-1) or the compound represented by the above-mentioned general formula (1-2-1) and epihalohydrin, and the mixture is reacted. Examples of the method of adding the base include a method of dropwise adding an aqueous base solution and a method of adding a solid base preferably in multiple portions.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and β -methylepichlorohydrin.

Examples of the base include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.

Further, an interlayer transfer catalyst may be used, and examples of the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecanylammonium chloride, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium bromide, and N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide and the like.

The amount of epihalohydrin used is 3 to 50 times, preferably 4 to 30 times, in terms of a molar ratio to the compound having 2 hydroxyl groups.

The reaction is carried out under heating, under increased pressure or under reduced pressure as required.

The reaction temperature is preferably 40 ℃ to 120 ℃ inclusive, and more preferably 60 ℃ to 80 ℃ inclusive, from the viewpoint of shortening the production time and improving the reaction efficiency. When the chlorohydrination reaction and the ring-closure reaction of the resulting chlorohydrate compound occur stepwise and the reaction temperature of the chlorohydrination reaction and the reaction temperature of the ring-closure reaction are different from each other, it is preferable that either one of the reaction temperatures is within the above-mentioned temperature range, and it is more preferable that both the reaction temperatures are within the above-mentioned range.

On the other hand, as a method for acrylation or methacrylation, a method using an acrylate and/or a methacrylate in the presence of a catalyst such as dialkyltin oxide or tetraalkyltitanate, and a method using acryloyl chloride and/or methacryloyl chloride in the presence of a neutralizing agent such as triethylamine can be mentioned. Examples of the acrylic ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

The reaction temperature in the case of the former being carried out in the presence of a (meth) acrylic ester and a catalyst is, for example, preferably 50 to 100 ℃, more preferably 70 to 90 ℃ from the viewpoints of shortening the production time and improving the reaction efficiency. In addition, from the viewpoint of shortening the production time and improving the reaction efficiency, the reaction temperature in the case of conducting the latter in the presence of (meth) acryloyl chloride and a neutralizing agent is preferably 0 to 30 ℃.

In particular, as for the method for producing the compound represented by the formula (1-1), the method using an acrylic acid ester and/or a methacrylic acid ester is preferable in terms of easy prevention of side reactions, and particularly, the method using an acrylic acid ester such as methyl acrylate is preferable in terms 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 contains (a) at least one compound represented by the above general formula (1) (hereinafter, sometimes referred to as "component a") and (B) at least one compound selected from a curing agent and a polymerization initiator (hereinafter, sometimes referred to as "component B").

The curable composition of the present invention may be used in combination with a compound having 1 or more reactive unsaturated bonds and epoxy groups, respectively, other than the component (a), and examples thereof include glycidyl methacrylate, glycidyl ether of allyl phenol, diglycidyl monoallyl ether, epoxy acrylates, and the like.

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

Examples of the compound having only an epoxy group include known epoxy resins. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol a-alkylene oxide adducts; glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as 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, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, etc.; a homopolymer or copolymer of glycidyl methacrylate; epoxides of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate and the like; 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 those obtained by internally crosslinking a prepolymer of a terminal isocyanate or those obtained by using a polyvalent active hydrogen compound (e.g., a polyphenol, a polyamine, a carbonyl group-containing compound, and a polyphosphate) to increase the molecular weight.

Examples of commercially available products of the above epoxy resins include 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 NagaChemteX Co.); epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P (manufactured by Kyoho 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 (manufactured by ADEKA Co., Ltd.); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250(Osaka Gas Chemicals, Inc.); YD series, YDF series, YDPN series, TDCN series (new day iron-gold chemical); CELLOXIDE 2021P, CELLOXIDE 2081 (manufactured by Daicel Corporation); TECHNORE VG-3101L (manufactured by Printec corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon chemical Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical); HP4032, HP4032D, HP4700(DIC products) and the like.

Examples of the compound having only a reactive unsaturated bond include (meth) acrylamide derivatives having an N-alkyl group such as N-methyl (meth) acrylamide, N-dimethyl (meth) acrylamide, 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-methoxymethacrylamide and N-ethoxymethacrylamide, and (meth) acrylamide derivatives such as N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine and N-acryloylpyrrolidine; unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene fluoride, and tetrafluoroethylene; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, norbornenedioic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ester ], phthalic acid mono [2- (meth) acryloyloxyethyl ester ], and ω -carboxy polycaprolactone mono (meth) acrylates; unsaturated polybasic acids such as hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate, and polyfunctional (meth) acrylates having 1 carboxyl group and 2 or more (meth) acryloyl groups; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-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, n-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and mixtures thereof, Ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (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, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol tri (meth) acrylate, propylene glycol (meth) acrylate, ethylene glycol (meth) acrylate, ethylene glycol tri (acrylate, ethylene glycol (meth) acrylate, ethylene glycol (acrylate, ethylene glycol tri (meth) acrylate, ethylene glycol (meth) acrylate, ethylene glycol (meth) acrylate, and pentaerythritol tri (meth) acrylate, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as tricyclodecane dimethylol di (meth) acrylate, tris [ (meth) acryloylethyl ] isocyanurate, and polyester (meth) acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; 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, dodecenylsuccinic anhydride, and methylnadic anhydride; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth) acrylonitrile, α -chloroacrylonitrile, vinylidene cyanide, and allylnitrile; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxides.

The content of the component (a) in the curable composition of the present invention is, for example, preferably 15% by mass or more, and from the viewpoint of curability and the like in the curable composition, preferably 30% by mass or more and 99% by mass, and more preferably 50% by mass or more and 97% by mass. When the curable composition further contains another compound having an epoxy group and/or a reactive unsaturated bond in addition to the component (a), the amount of the other compound is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, based on 100 parts by mass of the component (a), from the viewpoint of curability and the like.

As the curing agent which is the component (B) used in the present invention, preferred examples include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, polythiol compounds, amine-based latent curing agents, and the like.

Examples of the amine-based curing agent include alkylenediamines such as ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminobutane, 1, 4-diaminobutane and hexamethylenediamine; polyalkyl polyamines such as diethylene triamine, triethylene triamine and tetraethylene pentamine; alicyclic polyamines such as 1, 4-diaminocyclohexane, 1, 3-diaminomethylcyclohexane, 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, 4 ' -diaminodicyclohexylmethane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 4 ' -diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4 ' -diaminodicyclohexylether, 2 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, isophoronediamine, and norbornendiamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3, 5-diethyl-2, 4-diaminobenzene, 1-methyl-3, 5-diethyl-2, 6-diaminobenzene, 1,3, 5-triethyl-2, 6-diaminobenzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, and 3,5,3 ', 5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane; guanamines such as benzoguanamine and acetoguanamine; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; dihydrazides such as oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, and phthalic dihydrazide; n, N-dimethylaminoethylamine, N-diethylaminoethylamine, N-diisopropylaminoethylamine, N-diallylaminoethylamine, N-benzylmethylaminoethylamine, N-dibenzylaminoethylamine, N-cyclohexylmethylaminoethylamine, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N' -methylpiperazine, N-dimethylaminopropylamine, N-diethylaminopropylamine, N-diisopropylaminopropylamine, N-diisopropylaminopropylamine, N, N-diallylaminopropylamine, N-benzylmethylaminopropylamine, N-dibenzylaminopropylamine, N-cyclohexylmethylaminopropylamine, 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, -dimethylisophoronediamine, N-dimethylisopropylaminopyrrolidine, N-diisopropylamino-N, N-diisopropylamino-4-methyl-2-methyl-piperidine, N-dimethylisophoronediamine, N-diisopropylamino-methyl-2-methyl-4-methyl-propyl-piperidine, N-diethylamino-propyl-piperidine, N-3-methyl-piperidine, N-propyl-piperidine, N-morpholine-methyl-amide, N-propyl-methyl-piperidine, N-methyl-propyl-piperidine, N-methyl-amino-4-methyl-propyl-amino-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl, N, N-dimethylbisaminocyclohexane, N ' -trimethylethylenediamine, N ' -ethyl-N, N-dimethylethylenediamine, N ' -trimethylethylenediamine, N ' -ethyl-N, N-dimethylpropanediamine, N ' -ethyl-N, N-dibenzylaminopropylamine; n, N- (bisaminopropyl) -N-methylamine, N-bisaminopropylethylamine, N-bisaminopropylpropylamine, N-bisaminopropylbutylamine, N-bisaminopropylpentylamine, N-bisaminopropylhexylamine, N-bisaminopropyl-2-ethylhexylamine, N-bisaminopropylcyclohexylamine, 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.

Examples of the phenol-based curing agent include a phenol-novolak resin, a cresol-novolak resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin, a dicyclopentadiene phenol addition-type resin, a phenol aralkyl resin (Xyloc resins), a naphthol aralkyl resin, a triphenolmethane resin, a tetraphenolethane resin, a naphthol-phenol novolak resin, a naphthol-phenol cocondensed phenol novolak resin, a naphthol-cresol cocondensed phenol novolak resin, a biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are connected by a dimethylene group), a biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are connected by a dimethylene group), an aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring and a primary amino group in a molecular structure), and an alkoxy-containing aromatic ring-modified phenol novolak resin (a phenol nucleus and an alkoxy-containing aromatic ring are connected by formaldehyde group) to each other Cyclic polyphenol compounds) and the like.

Examples of the acid anhydride curing agent include nadic anhydride, phthalic anhydride, maleic anhydride, methylnadic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrogenated nadic methyl anhydride.

Examples of the polythiol compound include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexa (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptobutyrate), 1,3,4, 6-tetrakis (2-mercaptoethyl) -1,3,4, 6-tetraazaoctahydropentalene-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-trithioundecane, 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-dimercapto-methyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 7-dimercapto-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 8-dimercapto-1, 11-dimercapto-3, 6, 9-trithioundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,3, 3-tetrakis (mercaptomethylthio) propane, 1,2, 2-tetrakis (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, 1,5, 5-tetrakis (mercaptomethylthio) -3-thiapentane, 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, 1,9, 9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thiopropyl) 3, 7-dithianonane, tris (2, 2-bis (mercaptomethylthio) ethyl) methane, tris (4, 4-bis (mercaptomethylthio) -2-thietanyl) methane, tetrakis (2, 2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4, 4-bis (mercaptomethylthio) -2-thietanyl) methane, 3,5,9, 11-tetrakis (mercaptomethylthio) -1, 13-dimercapto-2, 6,8, 12-tetrathiatridecane, 3,5,9,11,15, 17-hexakis (mercaptomethylthio) -1, 19-dimercapto-2, 6,8,12,14, 18-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-dithiaheptylthio ] -6-mercaptomethylthio-1, 3-dithiane, 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-dithianobutylkynyl) ] methyl-2, 4-dithiapentane, 3- [2- (1, 3-dithianobutylky-lmethyl) ] methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- [2- (1, 3-dithiacyclobutyloxy) ] methyl-3, 5,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathiaheptadecane, 3- [2- (1, 3-dithiacyclobutyloxy) ] methyl-7, 9,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 4,6,10,12, 16-hexathiaheptadecane, 3, 7-bis [2- (1, 3-dithiacyclobutyloxy) ] methyl-1, 9-dimercapto-2, 4,6, 8-tetrathianonane, 4, 6-bis {3- [2- (1, 3-dithiacyclobutylalkyl) ] 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-tetrathiaundecanyl ] -5-mercaptomethylthio-1, 3-dithiane, 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-trithiooctyl ] -5-mercaptomethylthio-1, 3-dithiolane, 2- { bis [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiahexylthio ] methyl } -1, 3-dithiacyclobutane, 2- [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiahexylthio ] mercaptomethylthiomethyl-1, 3-dithiacyclobutane, 2- [3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio ] mercaptomethylthiomethyl-1, 3-dithiacyclobutane, 2- [ 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithio-ctyl ] mercaptomethylthiomethyl-1, 3-dithiolane, 4, 5-bis {1- [2- (1, 3-dithiocyclobutylalkyl) ] -3-mercapto-2-thiolpropylthio } -1, 3-dithiolane, 4- {1- [2- (1, 3-dithiocyclobutylalkyl) ] -3-mercapto-2-thiolpropylthio } -5- [1, 2-bis (mercaptomethylthio) -4-mercapto-3-thiolbutylthio ] -1, 3-dithiolane, 2- { bis [4- (5-mercaptomethylthio-1, 3-dithiolane) thio ] methyl } -1, 3-dithiolane, 2-bis- (3-mercaptomethylthio-1, 3-dithiolane, and, 4- [4- (5-mercaptomethylthio-1, 3-dithiolane) thio ] -5- {1- [2- (1, 3-dithiocyclobutylalkyl) ] -3-mercapto-2-thiolpropylthio } -1, 3-dithiolane and the like.

Examples of commercially available products of these polythiol compounds include DPMP, PEMP, PETG, and the like, which are manufactured by TS-G, SC organic chemical Co., Ltd.

In particular, the use of a 4-membered or higher polythiol compound is preferable because a composition having excellent curability can be obtained.

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; modified amines such as dehydration condensates 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, and the like.

Among the amine-based latent curing agents, preferred examples include adducts of amine compounds having 1 or more active hydrogen atoms and polyepoxide compounds and/or polyisocyanate compounds, and those obtained by combining a phenolic resin with the above-mentioned adducts.

Examples of the amine compound having 1 or more active hydrogen include alkylenediamines such as ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminobutane, 1, 4-diaminobutane and hexamethylenediamine; polyalkyl polyamines such as diethylene triamine, triethylene triamine and tetraethylene pentamine; alicyclic polyamines such as 1, 4-diaminocyclohexane, 1, 3-diaminomethylcyclohexane, 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, 4 ' -diaminodicyclohexylmethane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 4 ' -diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4 ' -diaminodicyclohexylether, 2 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, isophoronediamine, and norbornendiamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3, 5-diethyl-2, 4-diaminobenzene, 1-methyl-3, 5-diethyl-2, 6-diaminobenzene, 1,3, 5-triethyl-2, 6-diaminobenzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, and 3,5,3 ', 5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane; guanamines such as benzoguanamine and acetoguanamine; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-aminopropylimidazole; dihydrazides such as oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, and phthalic dihydrazide; n, N-dimethylaminoethylamine, N-diethylaminoethylamine, N-diisopropylaminoethylamine, N-diallylaminoethylamine, N-benzylmethylaminoethylamine, N-dibenzylaminoethylamine, N-cyclohexylmethylaminoethylamine, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N' -methylpiperazine, N-dimethylaminopropylamine, N-diethylaminopropylamine, N-diisopropylaminopropylamine, N-diisopropylaminopropylamine, N, N-diallylaminopropylamine, N-benzylmethylaminopropylamine, N-dibenzylaminopropylamine, N-cyclohexylmethylaminopropylamine, 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, -dimethylisophoronediamine, N-dimethylisopropylaminopyrrolidine, N-diisopropylamino-N, N-diisopropylamino-4-methyl-2-methyl-piperidine, N-dimethylisophoronediamine, N-diisopropylamino-methyl-2-methyl-4-methyl-propyl-piperidine, N-diethylamino-propyl-piperidine, N-3-methyl-piperidine, N-propyl-piperidine, N-morpholine-methyl-amide, N-propyl-methyl-piperidine, N-methyl-propyl-piperidine, N-methyl-amino-4-methyl-propyl-amino-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl, N, N-dimethylbisaminocyclohexane, N ' -trimethylethylenediamine, N ' -ethyl-N, N-dimethylethylenediamine, N ' -trimethylethylenediamine, N ' -ethyl-N, N-dimethylpropanediamine, N ' -ethyl-N, N-dibenzylaminopropylamine; n, N- (bisaminopropyl) -N-methylamine, N-bisaminopropylethylamine, N-bisaminopropylpropylamine, N-bisaminopropylbutylamine, N-bisaminopropylpentylamine, N-bisaminopropylhexylamine, N-bisaminopropyl-2-ethylhexylamine, N-bisaminopropylcyclohexylamine, 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.

Examples of the above-mentioned polyepoxide compounds include polyglycidyl ether compounds of mononuclear polyphenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; polyglycidyl ether compounds of polynuclear polyphenol compounds such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (o-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol a), isopropylidenebis (o-cresol), tetrabromobisphenol a, 1, 3-bis (4-hydroxycumylbenzene), 1, 4-bis (4-hydroxycumylbenzene), 1, 3-tris (4-hydroxyphenyl) butane, 1,2, 2-tetrakis (4-hydroxyphenyl) ethane, thiobisphenol, sulfonylbisphenol, oxobisphenol, novolak, o-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, terpene phenol and the like; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol a-alkylene oxide adducts; glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as 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, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and the like, and a homopolymer or copolymer of glycidyl methacrylate; epoxy compounds having a glycidylamino group such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidylanthro-toluidine and the like; epoxides of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate and the like; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers, and heterocyclic compounds such as triglycidyl isocyanurate.

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-naphthalene diisocyanate, 1, 5-tetrahydronaphthalene diisocyanate, 3 ' -dimethyldiphenyl-4, 4 ' -diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, and the like; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, trans-1, 4-cyclohexyl diisocyanate, and norbornene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2,4 and/or (2,4,4) -trimethylhexamethylene diisocyanate, lysine diisocyanate and the like; isocyanurate trimer, biuret trimer, trimethylolpropane adduct of the above exemplified diisocyanates, etc.; triphenylmethane triisocyanate, 1-methylbenzene-2, 4, 6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and the like.

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 isocyanates blocked with various blocking agents.

Examples of the phenol resin include a novolak resin, a cresol novolak resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin, a dicyclopentadiene phenol addition-type resin, a phenol aralkyl resin (Xyloc resins), a naphthol aralkyl resin, a triphenolmethane resin, a tetraphenolethane resin, a naphthol novolak resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, a biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by a dimethylene group), a biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by a dimethylene group), an aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring, and a primary amino group in a molecular structure), and an alkoxy-containing aromatic ring-modified novolak resin (a phenol nucleus and an alkoxy-containing aromatic nucleus are linked by formaldehyde group), for example Polycyclic polyphenol compounds) and the like.

Examples of commercially available products of the above-mentioned amine-based latent curing agent include Adeka Harden EH-3636S (manufactured by ADEKA, Inc.; dicyandiamide type latent curing agent), Adeka Harden EH-4351S (manufactured by ADEKA, Inc.; dicyandiamide type latent curing agent), Adeka Harden EH-5011S (manufactured by ADEKA, Inc.; imidazole type latent curing agent), Adeka Harden EH-5046S (manufactured by ADEKA, Inc.; imidazole type latent curing agent), Adeka Harden EH-4357S (manufactured by ADEKA, Inc.; polyamine type latent curing agent), Adeka Harden EH-5057P (manufactured by ADEKA, Inc.; polyamine type latent curing agent), Adeka Harden-7P (manufactured by ADEKA, Inc.; Amjjn polyamine type latent curing agent), and Adeka Harden type latent curing agent (manufactured by ADeka, Inc.; polyamine type latent curing agent), Adeka Harden type latent curing agent, Adeka Harden-50523, and Adeka polyamine type latent curing agent, Amicure PN-40 (available from Ajinomoto Finetechno K.K.; amine adduct type latent curing agent), Amicure VDH (available from Ajinomoto Finetechno K.K.; hydrazide type latent curing agent), Fujicure FXR-1020 (available from T & K TOKA; latent curing agent), and the like.

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

In the curable composition of the present invention, a curing catalyst may be used in combination with the curing agent as the component (B), and examples of the curing catalyst include phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1- {3- [ (3-trimethoxysilyl) propylaminocarbonylamino ] propyl } -2-methylimidazole, 1- [ 3-trimethoxysilylpropylaminomethyl ] -4-methylimidazole, 1- [3- (trimethoxysilylpropyl) ] imidazole and 1- [3- (trimethoxysilylpropyl) ] imidazole; salts of the above imidazoles with trimellitic acid, isocyanuric acid, boron and the like, i.e., imidazole salts; 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, tolylene diisocyanate-dimethylurea and the like; and complexes of boron trifluoride with amines, ether compounds, and the like. These curing accelerators may be used alone or in combination of 2 or more.

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

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

The thermal radical polymerization initiator is not particularly limited as long as it is a substance that generates radicals by heating, and conventionally known compounds can be used, and examples thereof include azo compounds, peroxides, persulfates, and the like.

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

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

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

The photo radical polymerization initiator is not particularly limited as long as it is a substance that generates radicals by light irradiation, and conventionally known compounds can be used, and preferable examples thereof include acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, and oxime ester compounds.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4' -isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylidene acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and, 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.

Examples of the benzil-based compound include benzil and the like.

Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, michler's ketone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, and 4-benzoyl-4' -methyldiphenyl sulfide.

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

The oxime ester compound is a compound having an oxime ester group, and among the photo radical polymerization initiators, the one having a good sensitivity can be preferably used in the curable composition of the present invention.

Among the oxime ester compounds, compounds having a carbazole skeleton, a diphenyl sulfide skeleton, and a fluorene skeleton are particularly preferable for the curable composition of the present invention because of their particularly high sensitivity.

Examples of the other 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- (pyrrol-1-yl) ] titanium.

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

The cationic polymerization initiator may be any compound as long as it is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with an energy ray or heating, and is preferably an onium salt or double salt that releases a lewis acid by irradiation with an energy ray, or a derivative thereof. Representative examples of the compound include salts of cations and anions represented by the following general formula,

[A] ^r+ [B] ^r-

wherein the cation [ A ]] ^r+ Preferably an onium whose structure can be represented by the following general formula,

[(R ¹² ) _a Q] ^r+ 。

further, wherein R ¹² Has 1 to 60 carbon atoms and may contain several decarbonogenAn organic group of an atom other than a molecule. a is an integer of 1 to 5. a number of R ¹² Are independent of each other, and may be the same or different. At least 1 of the organic groups is preferably an organic group having an aromatic ring as described above. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N ═ N. In addition, in the reaction of a cation [ A ]] ^r+ In (2), when the valence of Q is Q, a relationship of r ═ a to Q must be established (where N ═ N is treated as valence 0).

Furthermore, an anion [ B ]] ^r- Preferably a halide complex, the structure of which can be represented by, for example,

[LY _b ] ^r- 。

here, L is a metal or semimetal (metaloid) which is a 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. Furthermore, in the reaction of anions [ B ]] ^r- When the valence of L in (b) is p, a relationship of r ═ b-p must be established.

As anions of the above formula [ LY _b ] ^r- Specific examples of the salt include tetrakis (pentafluorophenyl) borate, tetrakis (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.

Furthermore, an anion [ B ]] ^r- Anions of the structure represented by the following general formula may also be preferably used:

[LY _b-1 (OH)] ^r

l, Y, b are the same as described above.

Examples of other anions that can be used include perchlorate ion (ClO) ₄ ) ^- Trifluoromethyl sulfite ion (CF) ₃ SO ₃ ) ^- Fluorosulfonate ion (FSO) ₃ ) ^- Tosylate anionTrinitrobenzene sulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.

In the present invention, among such onium salts, the aromatic onium salts described in the following (1) to (3) are particularly effective. One kind of them may be used alone or 2 or more kinds may be mixed and used.

(1) Aryldiazonium salts such as benzenediazonium hexafluorophosphate, 4-methoxybenzdiazonium hexafluoroantimonate and 4-methylbenzdiazonium hexafluorophosphate

(2) Diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate and tolylcumyliodione tetrakis (pentafluorophenyl) borate

(3) Sulfonium salts of sulfonium cations represented by the following group I or group II with hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, or the like

[ chemical formula 14]

< group I >

[ chemical formula 15]

< group II >

The amount of the polymerization initiator used is preferably 0.001 to 20 parts by mass based on 100 parts by mass of the total of the component (a) and the other compound having an epoxy group and/or a reactive unsaturated bond. By setting to 20 parts by mass or less, the influence on various physical properties such as water absorption of the cured product and strength of the cured product can be suppressed.

When the curable composition of the present invention is photocured using a polymerization initiator, a sensitizer and a sensitization aid can be used. Examples of the sensitizer and the sensitization 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-diisopropoxylanthracene, 9, 10-dibutoxyanthracene, 9, 10-dipentyloxylanthracene, 9, 10-dihexyloxyanthracene, 9, 10-bis (2-methoxyethoxy) anthracene, 9, 10-bis (2-ethoxyethoxy) anthracene, 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-diisopropoxylanthracene, 2-methyl-or 2-ethyl-9, 10-dibutoxyanthracene, 2-methyl-or 2-ethyl-9, 10-dipentyloxylanthracene, 2-methyl-or 2-ethyl-9, 10-dihexyloxyanthracene, and the like.

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, 1, 4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-dipropoxynaphthalene, and 1, 4-dibutoxynaphthalene.

The curable composition of the present invention may contain, 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- (2-aminoethyl) -8-aminooctyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, aminosilane compounds such as 3-dimethylbutylidene) propylamine; mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane; silane coupling agents such as epoxy silane compounds such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, 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 fibers, carbon fibers, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely powdered silica, titanium dioxide, carbon black, graphite, iron oxide, and pitch; lubricants such as candelilla wax, carnauba wax, wood wax, white wax, beeswax, lanolin, spermaceti wax, montan wax, petroleum wax, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; a thickener; a thixotropic agent; an antioxidant; a light stabilizer; an ultraviolet absorber; a flame retardant; defoaming agents; a rust inhibitor; known additives such as colloidal silica and colloidal alumina, and further, adhesive resins such as xylene resin and petroleum resin may 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 combination of a plurality of curing agents and polymerization initiators.

Among them, a method of using a photopolymerization initiator and a curing agent in combination, temporarily curing by light irradiation, and then thermally curing may be employed. In this case, if the amount of the compound having only an epoxy group and an epoxy group of the reactive unsaturated bonds or the compound having only a reactive unsaturated bond is large, curing may be insufficient or the physical properties of the cured product may be deteriorated. Therefore, the total amount of the compound having only an epoxy group and an epoxy group of the reactive unsaturated bond or the compound having only a reactive unsaturated bond is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less, based on 100 parts by mass of the compound of the present invention. Further, the photopolymerization initiator is preferably a photo radical polymerization initiator.

The light irradiated during photocuring may be set to include light having a wavelength of 300nm to 450 nm. Examples of the light source used for photocuring include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electron beam irradiation device, an X-ray irradiation device, and a laser (e.g., an argon laser, a dye laser, a nitrogen laser, an LED, and a helium-cadmium laser).

The heating temperature in the thermal curing may be appropriately set according to the kind of the curing agent and the like as long as the composition can be stably cured, and is preferably set to, for example, 10 ℃ or more and 250 ℃ or less, and more preferably 60 ℃ or more and 200 ℃ or less.

The cured product of the curable composition of the present invention is preferably a cured product obtained by heat curing after photocuring, from the viewpoint of excellent properties such as heat resistance. The applicant believes that the present description is a description of the state. Even if the present description is a description of specifying a substance by a production method, it is impossible and impractical to specify a structure and characteristics other than those described in the present specification because a large amount of experimental time is required for a cured product obtained by curing a curable compound under predetermined conditions.

The curable composition of the present invention can be used in a wide range of applications such as paints, adhesives, sealants, adhesives, coating agents, fiber bundling agents, building materials, and electronic components. In particular, since the curable composition is excellent in curability by light and heat, it can be used for applications capable of dual curing. That is, the adhesive composition can be suitably used for applications such as a liquid sealant, a liquid adhesive, a liquid crystal sealant, and an adhesive for camera modules.

Examples

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

Example 1 production of Compound 1-1a

386.9g (2.8mol) of p-hydroxyphenylethanol and 1,295g (14mol) of epichlorohydrin were put into a flask equipped with a reflux apparatus, a stirring apparatus, and a dropping apparatus, and 221.7g (0.95mol) of a 48 mass% aqueous solution of sodium hydroxide was added to the dropping apparatus. Removing water by azeotropic distillation while dropping an aqueous sodium hydroxide solution over 2 hours under reflux at an internal temperature of 65 to 70 ℃ and a reduced pressure of 21 to 24 kPa. After the reaction was further carried out for 1 hour, epichlorohydrin was removed, washing with water, desolvation and filtration were carried out to obtain the following compound 1-1 a-1.

The epoxy equivalent of the above compound 1-1a-1 was 216g/eq.

498.2g (2.6mol) of Compound 1-1a-1 obtained as described above, 1.102g (12.8 mol) of methyl acrylate, and 21.8g (0.06mol) of titanium tetra-n-butoxide were put into a flask equipped with a reflux apparatus and a stirring apparatus, and the reaction was carried out while distilling off methanol produced under reflux. The reaction is carried out at a reaction temperature of 78 to 87 ℃ for 10 hours, and the reaction is terminated when the conversion rate to the compound 1-1a reaches 95% or more. The reaction solution was cooled, 500g of toluene and 30g of water were added thereto, and the mixture was stirred at 60 ℃ for 1 hour to hydrolyze the catalyst. Toluene and water were distilled off, and the obtained concentrated solution was cooled and then filtered to remove the precipitated catalyst decomposition product, thereby obtaining compound 1-1 a. Compound 1-1a is a liquid at 25 ℃.

Subjecting the obtained Compound 1-1a to ¹ The results of H-NMR measurement are shown in FIG. 1.

NMR was measured using ECX-400 (manufactured by Japan Electron Ltd.). As a measurement solvent, deuterated chloroform was used.

The compound obtained by the present production method can be suitably used for light and heat curing as described below by the above-mentioned simple purification method, and it is judged that the present production method is advantageous.

[ chemical formula 16]

Example 2 production of Compounds 1-2b

A flask equipped with a reflux apparatus, a stirring apparatus and a dropping apparatus was charged with 299.9g (1.4mol) of 2, 4-dihydroxybenzophenone and 1,295g (14mol) of epichlorohydrin, and the mixture was heated at 50 ℃. 483.9g of a 40 mass% potassium carbonate aqueous solution was added dropwise over 30 minutes, followed by stirring for 10 hours. Then, the mixture was cooled, and 490g of water was added thereto, stirred for 30 minutes, and allowed to stand for 1 hour. The separated aqueous layer was taken out and epichlorohydrin was removed. Thereafter, 400g of toluene was added thereto, and the mixture was washed with water. After confirming that the aqueous layer became neutral, toluene was removed to obtain 470g of the following chlorohydrin 1-2 b-1.

To 250g of the chlorohydrin 1-2b-1 thus obtained was added 500g of toluene, and the mixture was heated to 60 ℃. Thereafter, 32.6g of sodium hydroxide as a solid was added in 5 portions (1 portion/20 minutes). After the addition of the 5 th part, the reaction was continued at 60 ℃ for 5 hours. Thereafter, the organic layer was washed with water, dried over magnesium sulfate and subjected to toluene removal to obtain 98.7g of the following closed ring system 1-2 b-2. The epoxy equivalent of the closed ring body 1-2b-2 is 290g/eq.

Into a flask equipped with a reflux apparatus, a stirring apparatus and a dropping apparatus, 270mg of the ring-closed product 1-2b-2 obtained above, 151mg of triethylamine and 2mL of Tetrahydrofuran (THF) were placed. Thereafter, 150mg of methacryloyl chloride was added dropwise over 3 minutes, and the mixture was stirred at room temperature for 6 hours. Then, 10mL of chloroform was added to the reaction solution, and washing was performed with water until the aqueous layer became neutral. Chloroform was removed to obtain 268mg of the following compounds 1 to 2 b. Compounds 1-2b are liquids at 25 ℃.

Of the resulting compound ¹ The results of H-NMR measurement are shown in FIG. 2.

NMR was measured using ECX-400 (manufactured by Japan Electron microscope). As a measurement solvent, deuterated chloroform was used.

[ chemical formula 17]

[ examples 3 to 6 and comparative example 1]

The curable compositions of examples 3 to 6 and comparative example 1 were prepared by mixing the respective components in the amounts shown in table 1 below.

The curable composition prepared above was applied to a glass plate in a thickness of 300 μm by means of a bar coater to obtain a coating film. For the obtained coating film, a test piece obtained by photocuring the coating film under the following curing conditions and then thermally curing the coating film were prepared, and the glass transition temperature (Tg) was measured. In the case of photocuring, photocurability was confirmed according to the following evaluation criteria.

These results are shown in table 1 below.

[ curing conditions ]

And (3) photocuring: J-Cure1500CV manufactured by JATEC with exposure of 3,000mJ/cm ² Irradiation was performed to confirm curability.

Thermal curing: heating at 100 ℃ for 1h and at 150 ℃ for 2h by using a thermal circulation type oven.

[ evaluation criteria ]

Photocuring: the case where curing sufficiently proceeded after light irradiation to form a coating film capable of releasing was evaluated as good, and the case where curing was insufficient to peel off the coating film was evaluated as x.

Physical properties of the cured product: the glass transition temperature (Tg) was measured using RSA from TA Instruments. As the test piece, a long test piece having a width of 4mm, a length of 60mm and a thickness of 300 μm was prepared.

TABLE 1

Compound 1-1 a: the compound obtained in example 1 above

Compounds 1-2 b: the compound obtained in example 2 above

PTBPGE: p-tert-butylphenol glycidyl ether

2-PEA: 2-Phenylethanolacrylate

Irg-184: alkylbenzene photopolymerization initiator (omnirad184) manufactured by IGM Resins Co., Ltd

2E4 MZ: curing agent prepared by four-country chemical industry

*1: is not implemented

*2: the test piece could not be produced because it was not cured, and thus the measurement was impossible.

As shown by the results shown in table 1, the compound provided by the present invention can provide a curable composition curable by light and heat.

Industrial applicability

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

Claims

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

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, an optionally substituted benzoyl group or an optionally substituted benzyl group, A ¹ Represents a single bond or an alkylene group having 1 to 4 carbon atoms, wherein 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,

wherein, in A ¹ In the case of a single bond, in the benzene ring in the formula (1), the unsaturated ester group represented by the following formula (1 alpha) is a group located at a meta position relative to the glycidyloxy group represented by the following formula (1 beta), n represents a number of 0 to 4,

wherein the symbols are as defined in the formula (1) and represent bonding sites.

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 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, 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 Each independently represents a hydrogen atom or a methyl group.

4. The method for producing a compound according to claim 2 or 3, wherein a phenolic hydroxyl group of a compound represented by the following general formula (1-1-1) is glycidyletherified, and then an alcoholic hydroxyl group of the obtained compound is esterified with an acrylate or a methacrylate,

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, and m represents a number of 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 (I), the compound is shown in the specification,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 of 0 to 5.

6. A process for producing a compound according to claim 5, wherein R is allowed to exist in a compound having 2 hydroxyl groups represented by the following general formula (1-2-1) ⁵ The hydroxyl group at the para-position of the benzoyl group of the substituent is glycidyletherified, and then the hydroxyl group at the ortho-position relative to the benzoyl group is acrylated or methacrylated,

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 of 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 member selected from the group consisting of a curing agent and a polymerization initiator,

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, wherein 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,

wherein, in A ¹ In the case of a single bond, the benzene ring in the formula (1)Wherein the unsaturated ester group represented by the following formula (1 alpha) is a group positioned at a meta position with respect to the glycidyloxy group represented by the following formula (1 beta), n represents a number of 0 to 4,

wherein the symbols are as defined in formula (1) and represent bonding sites.

8. A method for producing a cured product, which comprises curing the curable composition according to claim 7 with light and then curing the cured product with heat.

9. A cured product obtained by curing the curable composition according to claim 7 with light and heat.