TW201302833A - Polyfunctional epoxy compound - Google Patents

Abstract

To provide an epoxy resin composition which has low viscosity and which exhibits not only high heat curability but also high cationic curability. An epoxy compound represented by formula (1), and a curable composition which comprises the epoxy compound and an acid generator or a curing agent. In formula (1), A is an (n4)-valent C2-10 unsaturated hydrocarbon group, an (n4)-valent C4-20 cyclic hydrocarbon group, an (n4)-valent nitrogen-containing ring group, an (n4)-valent linear c3-10 hydrocarbon group, or an (n4)-valent group consisting of a combination of two or more of such groups, R1 and R2 are each independently a hydrogen atom or C1-10 alkyl, R3 is an (n3+1)-valent hydrocarbon group, n1 is an integer of 2, n2 is an integer of 1, n3 is an integer of 2 to 5, n4 is an integer of 2 to 8, n5 is an integer of 0 or 1, and n6 is an integer of 0 or 1. The acid generator is a photoacid generator or a thermal acid generator, while the curing agent is an acid anhydride or an amine.

Description

Polyfunctional epoxy compound

This invention relates to a light or thermosetting epoxy resin composition. More specifically, it relates to a light or heat which can be used to obtain a cured product having excellent properties such as high adhesion to a substrate, high transparency (transparency to visible light), hard coating property, high heat resistance and the like. A curable epoxy resin composition (a resin composition for an electronic material and an optical material) and a cured product (composite cured product).

Conventionally, epoxy resins have been widely used in the field of electronic materials for epoxy resin compositions combined with hardeners. In the field of electronic materials, for example, a high refractive index layer such as an antireflection film (antireflection film for liquid crystal display), an optical film (such as a reflector), an electronic component package, a printed wiring substrate, and an interlayer insulating film material ( In applications such as an interlayer insulating film material for a build-up printed circuit board, etc., the molding material is required to have high adhesion to the substrate, hard coatability, heat resistance, and high transparency to visible light.

Further, an epoxy resin composition in which an epoxy compound and a photo-and thermal acid generator are combined does not use a solvent, and the epoxy compound can be hardened alone, and has been studied in recent years. In particular, the photocationic curing by ultraviolet light does not require a large-sized curing oven, and is excellent in that the amount of energy input is small.

An alicyclic epoxy compound having only an epoxy group in an alicyclic structure The cation hardening system using light is widely used, but its structure is hard, so that the cured product tends to be hard and brittle.

A method of producing an epoxy resin composition using a polyfunctional alicyclic epoxy compound modified with a lactone and an epoxy compound thereof, and the like has been proposed (see Patent Document 1).

Further, the glycidyl ester type epoxy compound is low in reactivity with an acid generator and takes a long time to react, and is generally considered to be unsuitable for cationic hardening.

A polyfunctional epoxy compound having a glycidyl ester has been proposed to use a cyclobutane tetracarboxylic acid tetraglycidyl ester or a cyclopentane tetracarboxylic acid tetraglycidyl ester or a cyclohexane tricarboxylic acid triglycidyl group. Epoxy resin composition (see Patent Documents 2 and 3).

Further, a carboxyl group-containing resin having an epoxy group-containing cyclohexanedicarboxylic acid as the crosslinkable compound has been proposed (see Patent Document 4).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-4-069360

[Patent Document 2] JP-A-50-010893

[Patent Document 3] JP-A-2006-274190

[Patent Document 4] US Patent No. 3659922

[Summary of the Invention]

As a result of intensive research, the present inventors have found that the mother nucleus has various skeletons, and the organic group of the skeleton has a complex side chain, and the side chain system has a structure of a plurality of epoxy groups via a hydrocarbon group. A polyfunctional epoxy compound having a plurality of such epoxy groups in one molecule is not only thermosetting, but also imparts cationic hardenability.

Accordingly, the present invention is to provide a curable composition having the above epoxy composition and a liquid form using the epoxy compound, which is not only thermosetting but also highly cationically curable. The cured product obtained from the curable composition has high transparency and high heat resistance.

The present invention is an epoxy compound which is represented by the following formula (1); [In the formula (1), A represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 at (n4), a cyclic hydrocarbon group having a carbon number of 4 to 20 at (n4), and a nitrogen-containing ring having a (n4) valence. a chain hydrocarbon group having a (n4) valence of 3 to 10 carbon atoms, or a group having a (n4) valence thereof, wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, n4 represents an integer of 2 to 8, and n5 represents an integer of 0 or 1, n6 Indicates an integer of 0 or 1.].

The second aspect is the epoxy compound according to the first aspect, wherein the formula (1) is represented by the formula (1-1), the formula (1-2), or the formula (1-3); [In the formula (1-1) and the formula (1-3), the A system represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 (n4) and a ring having a carbon number of 4 to 20 at a (n4) value. a hydrocarbon group, a (n4)-valent nitrogen-containing cyclic group, a (n4)-valent chain hydrocarbon group having a carbon number of 3 to 10, or a (n4)-valent group thereof, in the formula (1-2), A' The nitrogen-containing cyclic group of (n4) valence, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ represents a (n3+1)-valent hydrocarbon group, and n1 represents an integer of 2 , n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8.

According to a third aspect, the epoxy compound according to the first aspect or the second aspect, wherein the A is removed from ethylene, propylene, or norbornene (n4) An (n4)-valent unsaturated hydrocarbon group of a hydrogen atom.

The epoxy compound according to the first aspect or the second aspect, wherein the A is a cyclobutane, a cyclopentane, a cyclohexane, an epoxycyclohexane, or an alkyl group. The (n4)-valent cyclic hydrocarbon group of (n4) hydrogen atoms is removed by epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane.

According to a fifth aspect, the epoxy compound according to the first aspect or the second aspect, wherein the A is a (n4)-valent nitrogen-containing cyclic group from which a (n4) hydrogen atom is removed from the trialkyl trimer isocyanate, A' is a (n4)-valent nitrogen-containing cyclic group which removes (n4) hydrogen atoms from trimeric isocyanic acid, cyanuric acid, or caprolactone or barbiturate.

The sixth aspect is the epoxy compound according to the first aspect or the second aspect, wherein the A is a chain of (n4) valences of (n4) hydrogen atoms removed from propane, butane, pentane or hexane. Hydrocarbyl group.

In a seventh aspect, the curable composition contains the epoxy compound and the curing agent according to any one of the first to sixth aspects.

The eighth aspect is the seventh aspect of the curable composition, wherein the curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polythiol.

According to a ninth aspect, the curable composition of the seventh aspect or the eighth aspect contains the curing agent in a ratio of 0.5 to 1.5 equivalents per equivalent of the epoxy group of the epoxy compound.

In a tenth aspect, the curable composition is an epoxy compound or an acid generator according to any one of the first to sixth aspects.

The eleventh aspect is the curable composition of the tenth aspect, wherein the acid generator is a photoacid generator or a thermal acid generator.

According to a twelfth aspect, the curable composition of the eleventh aspect, wherein the acid generator is an onium salt.

According to a thirteenth aspect, the curable composition according to the eleventh aspect, wherein the acid generator is an onium salt compound or an iodonium salt compound.

The curable composition according to any one of the tenth aspect to the thirteenth aspect, wherein the acid generator is contained in a ratio of 0.1 to 20% by mass based on the mass of the epoxy compound.

An epoxy compound having a plurality of epoxy groups bonded to an organic group serving as a skeleton via a hydrocarbon group increases the hydrocarbon group, and the higher the degree of freedom of the epoxy ring, the higher the reactivity, and the epoxy group All participate in the reaction, and have a plurality of epoxy groups, and the cation hardenability becomes high.

Further, when the epoxy compound and the curable composition containing at least the photoacid generator are photocured, it is expected that a cured product or a cured coating film which can provide excellent mechanical properties and excellent optical properties can be formed. In particular, it is expected that the more the hydrocarbon group is grown, the higher the toughness of the cured product and the cured coating film.

The epoxy compound of the present invention proposed from such a viewpoint exerts the following effects: the mother nucleus has various skeletons, and the organic group which becomes the skeleton has a plurality of side chains, and the side chain is via a hydrocarbon group. On the other hand, a structure having a plurality of epoxy groups has a plurality of such epoxy groups in one molecule, and the ruthenium is not only thermosetting but also cationically curable.

The curable composition of the present invention may contain an epoxy compound represented by the above formula (1) and a curing agent (for example, an amine or an acid anhydride), and may further contain a curing aid as the case may be.

In the present invention, an epoxy compound represented by the above formula (1), a photoacid generator or a thermal acid generator is used to photoharden or thermally harden it. Therefore, by using a photoacid generator or a thermal acid generator, since the hardener (for example, an amine or an acid anhydride) which does not generally use an epoxy group is used, or the content thereof is extremely small even if it is used, the present invention The storage stability of the curable composition is good.

Since the curable composition of the present invention is cured by photohardening by UV irradiation, it can be suitably used for a material (substrate) which is not heat resistant.

Further, since the epoxy compound used in the present invention can be used in a liquid form, the curable composition of the present invention using the same is excellent in filling property.

Further, the curable composition containing the epoxy compound of the present invention has characteristics such as low viscosity and quick-drying property, and can be used for coating or adhesion of electronic parts, optical parts, and precision mechanism parts.

[Formation for implementing the invention]

The present invention is an epoxy compound represented by the above formula (1). In the above formula (1), A represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 (n4), a cyclic hydrocarbon group having a carbon number of 4 to 20 (n4), and a nitrogen-containing ring having a (n4) value. a chain hydrocarbon group having a (n4) valence of 3 to 10 carbon atoms, or a group having a (n4) valence thereof, wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, n4 represents an integer of 2 to 8, and n5 represents an integer of 0 or 1, n6 An integer representing 0 or 1.

The above formula (1) includes an epoxy compound represented by the above formula (1-1), formula (1-2) or formula (1-3). In the formula (1-1) and the formula (1-3), the system A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms (n4), and a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence. (n4) a nitrogen-containing cyclic group, a (n4)-valent chain hydrocarbon group having 3 to 10 carbon atoms, or a group having a (n4) valence thereof, and in the formula (1-2), A' represents (n4) a nitrogen-containing cyclic group, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ represents a (n3+1)-valent hydrocarbon group, and n1 represents an integer of 2, n2 An integer representing 1 is used, n3 is an integer from 2 to 5, and n4 is an integer from 2 to 8.

In the formula (1), the formula (1-1) and the formula (1-3), when A is an (n4)-valent unsaturated hydrocarbon group, the A system may be, for example, removed from ethylene, propylene or norbornene (n4). An (n4)-valent unsaturated hydrocarbon group of a hydrogen atom.

In the formula (1), the formula (1-1) and the formula (1-3), when A is a (n4)-valent cyclic hydrocarbon group, the A system may, for example, be cyclobutane, cyclopentane or cyclohexane. a (n4)-valent cyclic hydrocarbon group having an epoxy group, an alkyl group-substituted epoxycyclohexane, a bicycloheptene, a bicyclooctene, or an adamantane to remove (n4) hydrogen atoms .

In the formula (1), the formula (1-1), the formula (1-2), and the formula (1-3), when A and A' are nitrogen-containing cyclic groups of (n4) valence, in the case of A, For example, the (n4)-valent nitrogen-containing cyclic group of (n4) hydrogen atoms is removed from the trialkyl trimer isocyanate, and in the case of A', for example, from isocyanuric acid or melamine The (n4) valence nitrogen-containing cyclic group of (n4) hydrogen atoms is removed by acid, or caprolactam or barbiturate.

In the formula (1), the formula (1-1) and the formula (1-3), when A is a (n4)-valent chain hydrocarbon group, the A may be, for example, propane, butane or pentane. Or a hexane-removed (n4)-valent chain hydrocarbon group of (n4) hydrogen atoms.

R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group or a ring. Butyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl 1,1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2-methyl-2-ethyl-n-propyl, 2-methyl-2-methyl- N-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl -cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl , 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1 ,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3 - dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl - n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl - n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclo Butyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl 2,2-Dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1 - n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-ring Propyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl- 1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl.

R ³ represents a (n3+1)-valent hydrocarbon group, and the hydrocarbon group may, for example, be a (n3+1)-valent hydrocarbon group in which a (n3+1)-valent hydrogen atom is removed from the above alkyl group.

The B group substituted with the above-mentioned mother nucleus may, for example, be an alkyl ester group having an epoxy group exemplified below, an alkyl group, and an alkyloxy group. In the following A, the mother nucleus is indicated.

[In the formula (2-1) to the formula (2-4), n5 represents an integer of 0 or 1, and n6 represents an integer of 0 or 1]

Further, the A and A' which are the mother cores are exemplified below. In the following, B represents the above polyfunctional epoxy group.

When A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms in the (n4) valence, the case of A is exemplified below.

When A represents a cyclic hydrocarbon group having a carbon number of 4 to 20 (n4), the case of A is exemplified below.

When A and A' represent a nitrogen-containing cyclic group of (n4) valence, the following are exemplified for A and A'.

[(In the formula (5-1), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]

When A represents a chain hydrocarbon group having 3 to 10 carbon atoms in the (n4) valence, the case of A is exemplified below.

The compound represented by the formula (1) of the present invention is composed of the above-mentioned parent core A and the above-mentioned substituent B.

The epoxy compound represented by the above formula (1-1) is, for example, a carboxylic acid having a structure of the above A or a carboxylic acid derivative such as a carboxylic anhydride, which is reacted with an enol, and then has the obtained unsaturated bond. The compound (intermediate) is produced by reacting with a peroxide. Also, the intermediate system does not depend on carboxylic acid, or carboxylic acid The reaction of the anhydride with the enol can also be carried out by any method, and an intermediate having an unsaturated bond thereof is reacted with a peroxide to produce an epoxy compound represented by the above formula (1-1).

The enol type corresponding to the above-mentioned parent core A substituted B (alkyl ester having a polyfunctional epoxy group) can be exemplified below.

The carboxylic acid or the carboxylic anhydride having the structure of the parent core A can be exemplified below.

A is a carboxylic acid or a carboxylic anhydride which shows an unsaturated hydrocarbon group of 2-10 of carbon atoms of (n4), and can be exemplified below.

A is a carboxy group of a cyclic hydrocarbon group having a carbon number of 4 to 20 which is (n4) valence The acid or the carboxylic anhydride system can be exemplified below.

A represents a carboxylic acid group having a (n4)-valent nitrogen-containing cyclic group, and examples thereof include a tricarboxyalkyl trimer isocyanate (however, the alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms). Can be exemplified below.

[(In the formula (5-1-1), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]

A carboxylic acid or a carboxylic acid anhydride having a chain hydrocarbon group having 3 to 10 carbon atoms in the (n4) valence can be exemplified below.

A compound (intermediate) which has a carboxylic acid having a structure of the above A, or a carboxylic acid anhydride, and an unsaturated bond obtained by reacting with an enol can be exemplified in the formula (1-1-1).

[In the formula (1-1-1), A represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 (n4), a cyclic hydrocarbon group having a carbon number of 4 to 20 (n4), and (n4) a nitrogen-containing cyclic group having a valence, a chain hydrocarbon group having a carbon atom number of 3 to 10 at a (n4) valence, or a group having a (n4) valence thereof, wherein R ¹ and R ² each independently represent a hydrogen atom or a carbon atom number of 1 An alkyl group of ~10, R ³ represents a hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2-8.

That is, the epoxy compound represented by the formula (1-1) used in the present invention may be a formula (1) composed of a combination of the formula (4-3) and the formula (2-1). 1) The epoxy compound shown is taken as an example and can be obtained as follows To.

The intermediate (olefin) is synthesized by reacting a carboxylic anhydride with an enol. This reaction is carried out in a solvent such as toluene or the like using a catalyst such as p-toluenesulfonic acid or sulfuric acid at a temperature of room temperature (for example, 20 ° C) to 110 ° C for 0 to 100 hours. Then, this unsaturated compound is oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid or the like can be used. This reaction is carried out in a solvent such as chloroform at 0 to 60 ° C for 1 to 200 hours. The above reaction system can also be carried out by using a dicarboxylic acid compound as a raw material instead of an acid anhydride. Further, when it is difficult to dissolve a carboxylic acid in a solvent such as toluene, it is esterified with an alcohol such as methanol, followed by a method of transesterification with an enol or a condensing agent such as carbodiimide to form a carboxylic acid. The above intermediate (olefin) can also be synthesized by a method of reacting with an enol or by converting a carboxylic acid into acid chloride with sulfinium chloride or the like and reacting with an enol.

The epoxy compound represented by the above formula (1-2) has a structure of A' a nitrogen-containing cyclic compound (having an NH group), reacting with an enol or allyl halogen having a leaving group, and then reacting a compound (intermediate) having the obtained unsaturated bond with a peroxide To modulate.

Further, the epoxy compound represented by the above formula (1-2) is a nitrogen-containing compound having a structure of A' (the compound has an NH group), and reacts with an epoxy compound having an unsaturated bond, and then The obtained alcohol compound is reacted with an enol or allyl halogen having a leaving group, and then a compound (intermediate) having the obtained unsaturated bond is reacted with a peroxide to prepare.

The enol or allyl halogen having a leaving group corresponding to B of the parent A' substitution may be, for example, the above formula (2-1-1), formula (2-2-1), and formula (2- The compounds shown in 3-1) and (2-4-1) are methanesulfonium halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, and anhydride. , a reaction of trifluoroacetic anhydride, phosphorus oxychloride, phosphorus oxybromide, sulfinyl halide, sulfur dihalide, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc., obtained by the following formula (2-1-2) A compound represented by the formula (2-2-2), the formula (2-3-2), and the formula (2-4-2).

[Formula (2-1-2), Formula (2-2-2), Formula (2-3-2), and Formula (2-4-2), X represents methanesulfonyloxy, trifluoromethane Sulfomethoxy, toluenesulfonyloxy, nitrobenzenesulfonyloxy, ethoxycarbonyl, trifluoroethaneoxy, chlorine, bromine, iodine].

The nitrogen-containing cyclic compound having a structure of the parent core A' (the compound having an NH group) is exemplified below.

A nitrogen-containing cyclic compound having a structure of A' (the compound has an NH group), and a compound (intermediate) having an unsaturated bond obtained by reacting an enol or an allyl halide having a leaving group can be exemplified in the formula. (1-2-1).

[In the formula (1-2-1), A' represents a nitrogen-containing cyclic group of (n4) valence, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ³ represents The hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2-8.

That is, the epoxy compound represented by the formula (1-2) used in the present invention may be a formula (1) composed of a combination of the formula (5-6) and the formula (2-1). 2) The epoxy compound shown is exemplified and can be obtained by the following method.

An intermediate (olefin) is synthesized by reacting a nitrogen-containing cyclic compound which has an NH group with an enol having a leaving group. This reaction is in DMF The solvent such as sodium hydroxide, potassium carbonate, tert-butyl potassium or triethylamine is used in a solvent such as room temperature (for example, 20 ° C) to the boiling point of the solvent, and it is carried out for 0 to 100 hours. Then, this unsaturated compound is oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid or the like can be used. This reaction is carried out in a solvent such as chloroform at 0 to 60 ° C for 1 to 200 hours.

Further, the epoxy compound represented by the above formula (1-3) is a compound having an unsaturated bond (an intermediate) obtained by reacting an alcohol having the structure of the above A with an enol or an allyl halogen having a leaving group. ) is produced by reacting with peroxide.

The enol or allyl halogen having a leaving group corresponding to the B substituted by the parent core A can be, for example, the above formula (2-1-1), formula (2-2-1), and formula (2-3). -1) and (2-4-1) compounds such as methanesulfonium halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acid anhydride, a reaction of trifluoroacetic anhydride, phosphorus oxychloride, phosphorus oxybromide, sulfinyl halide, dihalogenated sulfur, hydrogen chloride, hydrogen bromide or hydrogen iodide obtained by the above formula (2-1-2), A compound represented by the formula (2-2-2), the formula (2-3-2), and the formula (2-4-2).

The alcohol having the structure of the parent core A can be exemplified below.

A's alcohol which is an unsaturated hydrocarbon group which shows the (n4) valence of 2-10 of carbon atoms can be illustrated below.

A is an alcohol of the cyclic hydrocarbon group which has a carbon number of 4 to 20 of (n4), and can be exemplified below.

The alcohol represented by A in the (n4)-valent nitrogen-containing cyclic group can be exemplified below.

[(In the formula (5-1-3), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]

An alcohol system in which a chain hydrocarbon group having 3 to 10 carbon atoms of (n4) is exemplified is exemplified below.

The compound (intermediate) having an unsaturated bond obtained by reacting an alcohol having the structure of the above A with an enol or an allyl halogen having a leaving group can be exemplified in the formula (1-3-1).

[In the formula (1-3-1), A represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 (n4), a cyclic hydrocarbon group having a carbon number of 4 to 20 (n4), (n4) a nitrogen-containing cyclic group having a valence, a chain hydrocarbon group having a carbon atom number of 3 to 10 at a (n4) valence, or a group having a (n4) valence thereof, wherein R ¹ and R ² each independently represent a hydrogen atom or a carbon atom number of 1 An alkyl group of ~10, R ³ represents a hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2-8.

That is, the epoxy compound represented by the formula (1-3) used in the present invention may be a formula (1) composed of a combination of the formula (4-4) and the formula (2-1). 3) The epoxy compound shown is exemplified and can be obtained by the following method.

The intermediate (olefin) is synthesized by reacting an alcohol with an enol having a leaving group. This reaction is carried out using a base such as sodium hydroxide, potassium carbonate, t-butyl potassium or triethylamine in a solvent such as ether or decylamine at room temperature (for example, 20 ° C) to the boiling point of the solvent, 0 to 100. Hour. Then, this unsaturated compound is oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, m-chlorobenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, or the like can be used. . This reaction is carried out in a solvent such as chloroform at 0 to 60 ° C for 1 to 200 hours.

The epoxy compound represented by the above formula (1-3) is, for example, chlorinated cyanuric acid, and the formula (2-1-1), the formula (2-2-1), and the formula (2-3-). 1) A compound (intermediate) having an unsaturated bond obtained by the reaction of allyl alcohol represented by the formula (2-4-1) and the like is reacted with a peroxide as described above.

Moreover, the present invention contains a curable composition of the epoxy compound represented by the above formula (1) and a curing agent.

Further, the present invention relates to a curable composition containing the epoxy compound represented by the above formula (1) and an acid generator.

The curable composition of the present invention may further contain a solvent, another epoxy compound, a curing agent, a surfactant, an adhesion promoter, and the like as needed.

The ratio of the solid content in the curable composition of the present invention may be 1 to 100% by mass, or 5 to 100% by mass, or 80 to 100% by mass.

The solid fraction removes the ratio of the remaining components of the solvent from the curable composition. In the present invention, a liquid epoxy compound is used, and a hardener or an acid generator is mixed therein, so that it is basically unnecessary to use a solvent, but a solvent may be added as needed. For example, the acid generator is a solid, and the acid generator is dissolved in a solvent such as propylene carbonate, and mixed with a liquid epoxy compound to produce a curable composition. Further, when the acid generator is dissolved in the liquid epoxy compound, a general solvent can be added to adjust the viscosity of the obtained curable composition.

The content of the epoxy compound represented by the above formula (1) in the curable composition of the present invention is from 8 to 99.9% by mass, preferably from 40 to 99% by mass, based on the solid content of the curable composition. , the most suitable is 70~99% by mass.

Further, the content of the acid generator in the curable composition of the present invention is 0.1 to 20% by mass or 0.1 to 10% by mass based on the content of the solid content of the curable composition.

The curable composition of the present invention may contain an acid generator in a ratio of 0.1 to 20% by mass or 0.1 to 10% by mass based on the mass of the epoxy compound represented by the above formula (1).

In the present invention, the epoxy compound represented by the above formula (1) can be used in combination with an epoxy compound other than the epoxy compound. The epoxy compound represented by the above formula (1) and the epoxy compound other than the epoxy compound may have a molar ratio of epoxy groups in the range of 1:0.1 to 1:10.

The epoxy compound other than the epoxy compound represented by the above formula (1) can be exemplified below.

Solid epoxy compound, gin-(2,3-epoxypropyl)-trimeric isocyanide Acid ester (formula (7-1), trade name TEPIC, manufactured by Nissan Chemical Industries Co., Ltd.).

A liquid epoxy compound, trade name Epikote 828 (formula (7-2), manufactured by Japan Epoxy Resin Co., Ltd.).

A liquid epoxy compound, trade name YX 8000 (formula (7-2), manufactured by Japan Epoxy Resin Co., Ltd.).

Liquid epoxy compound, trade name DME100 (formula (7-4), manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.).

Liquid epoxy compound, trade name CE-2021P (formula (7-5), manufactured by Daicel Co., Ltd.).

Further, in the present invention, as the liquid epoxy compound, the following ginseng-(3,4-epoxypropyl)-trimeric isocyanate (formula (7-6)) and gins-(4, 5-epoxy pentyl)-trimeric isocyanate (formula (7-7)), gins-(5,6-epoxyhexyl)-trimeric isocyanate (formula (7-8)), ginseng (glycidol) Alkyloxyethyl)trimeric isocyanate (formula (7-9)).

A liquid epoxy compound modified by adding 0.8 mol of propionic anhydride to ginseng-(2,3-epoxypropyl)-trimeric isocyanate 1 mol (Formula (7-10), Nissan Chemical Industry Co., Ltd. ), product name: TEPIC-PAS B22). Formula (7-10) is contained in a ratio of about 35%:45%:17%:3% in terms of molar ratio (7-10-1):(7-10-2):(7-10-3 ): (7-10-4).

Adding a liquid epoxy compound modified with propanhydride 0.4 mol to ginseng-(2,3-epoxypropyl)-trimeric isocyanate 1 mol (Formula (7-11), Nissan Chemical Industry Co., Ltd. ), product name: TEPIC-PAS B26). Formula (7-11) is contained in a ratio of about 60%:32%:8% in terms of molar ratio (7-11-1): (7-11-2): (7-11-3).

In the present invention, as the cationically curable monomer, a vinyl ether compound, an oxetane compound or the like can be used in addition to the epoxy compound.

The vinyl group-containing compound (such as a vinyl ether compound) is not particularly limited as long as it is a compound having a vinyl group, and examples thereof include 2-hydroxyethyl vinyl ether (HEVE) and diethylene glycol monovinyl ether. (DEGV), 2-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether. Further, a vinyl compound having a substituent such as an alkyl group or an allyl group at the α and/or β position may be used. Further, a vinyl ether compound containing a cyclic ether group such as an epoxy group and/or an oxetanyl group can be used, and examples thereof include an oxygen norbornene divinyl ether and a 3,3-dimethanol oxygen heterocyclic ring. Butane divinyl ether. Further, a mixed compound having a vinyl group and a (meth)acrylic group can be used, and examples thereof include 2-(2-vinyloxyethoxy)ethyl (VEEA, VEEM) (meth)acrylate. These systems can be used alone or in combination of two or more. .

The oxetane group-containing compound (oxetane compound) is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3-(phenoxy group) is exemplified. Methyl)oxetane (POX), bis[1-ethyl(3-oxetanyl)methyl ether (DOX), 3-ethyl-3-(2-ethylhexyloxy) Methyl)oxetane (EHOX), 3-ethyl-3{[3-(triethoxymethoxy)propoxy]methyl}oxetane (TESOX), oxalate Cyclobutane ratio semi-oxime (OX-SQ), phenol novolac oxetane (PNOX-1009), and the like. Further, a mixed compound (1-ethyl-3-oxetanylmethyl (meth) acrylate) having an oxetane group and a (meth)acrylic group can be used. These oxetane-based compounds may be used singly or in combination of two or more.

In the present invention, a curable composition containing the epoxy compound represented by the above formula (1) and a curing agent can be obtained.

As the hardener, an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polyhydrogen sulfide can be used. Among these, an acid anhydride and an amine are particularly preferred. These hardeners may be solid or may be used by dissolving in a solvent. However, the evaporation of the solvent causes a decrease in the density of the curing agent or a decrease in strength and a decrease in water resistance by the formation of pores, so that the curing agent itself should be liquid at normal temperature and normal pressure.

The curing agent is contained in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group of the epoxy compound, and is preferably contained in a ratio of from 0.8 to 1.2 equivalents. The equivalent weight of the hardener to the epoxy compound is shown by the equivalent ratio of the hardener to the hardening group of the epoxy group.

Examples of the phenol resin include a phenol novolak resin and a cresol novolak resin.

The amine system may, for example, be hexahydropyridine, N,N-dimethylhexahydropyrazine, triethylenediamine, 2,4,6-cis (dimethylaminomethyl)phenol or benzyldimethyl Amine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethyl Pyridine, bis(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, diaminodicyclohexylmethane, 1,3-diamine Cyclohexane, xylene diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, and the like. Among these, it is preferred to use liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylhexahydropyrazine , bis(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, and diaminodicyclohexylmethane.

The polyamine resin is formed by condensation of a divalent acid with a polyamine, and is a polyamine amine having a primary amine and a secondary amine in the molecule.

Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolinium trimellitate, and epoxy imidazole. Adults and so on.

The polythiol is, for example, a thiol group present at the terminal of the polypropylene glycol chain or a thiol group at the terminal of the polyethylene glycol chain, and is preferably liquid.

The acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. Examples of such acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol trimellitate, and glycerin. Para-p-benzoic acid ester, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrogen Phthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexenyldicarboxylic anhydride, hexachloro-m-alkenyl-tetrahydrophthalic acid ( Chlorendic acid).

Among these, it is preferably methyl tetrahydrophthalic anhydride or methyl-5-norbornene-2,3-dicarboxylic anhydride (methyl nadic anhydride, methyl Himic anhydride) which is liquid at normal temperature and pressure. And a mixture of hydrogenated methyl nadic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, methyl hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride. The viscosity of these liquid anhydrides was determined to be 10 mPas to 1000 mPas at 25 °C. In the acid anhydride group, one anhydride group is calculated as one equivalent.

Further, when a cured product is obtained from the curable composition of the present invention, a curing aid may be used in combination as appropriate.

Examples of the curing aid include an organophosphorus compound such as triphenylphosphine or tributylphosphine, a fourth-order phosphonium salt such as ethyltriphenylphosphonium bromide or diethyltetrabutylphosphonium disulfide, and the like. , 8-diazocyclo[5.4.0]undec-7-ene, 1,8-diazocyclo[5.4.0]undec-7-ene and caprylic acid, zinc octoate, A fourth-grade ammonium salt of tetrabutylammonium bromide or the like. These hardening aids can be used in a ratio of 0.001 to 0.1 parts by mass based on 1 part by mass of the curing agent.

In the present invention, a curable composition can be obtained by mixing the epoxy compound represented by the above formula (1) with the above-mentioned curing agent and, if necessary, a curing aid. These mixing systems are not particularly limited as long as they can be uniformly mixed, but can be carried out, for example, by using a reaction flask, a stirring blade, a mixer, or the like. .

The mixing system measures the viscosity and is carried out under heating as needed, and is carried out at a temperature of 10 ° C to 100 ° C for 0.5 to 1 hour.

The resulting hardenable composition has an appropriate viscosity for use as a liquid sealing material. The curable composition of the present invention can be used as a transparent encapsulant for LEDs by a casting method, a dispensing method, a seasoning method, a printing method, or the like, and can be partially packaged at any position. The curable composition is directly encapsulated in a liquid state in an LED or the like by the above-described method, dried, and cured to obtain a cured epoxy resin.

The cured product obtained from the curable composition is applied to the substrate by the curable composition, or injected into the casting template to which the release agent has been applied, and is pre-hardened at a temperature of 100 to 120 ° C, and then It is obtained by post-hardening at a temperature of 120 to 200 °C.

The heating time is preferably about 1 to 12 hours and about 2 to 5 hours.

The thickness of the coating film obtained from the curable composition of the present invention is selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product.

The above-mentioned curable composition may contain a solvent as needed.

The solvent may, for example, be an ether such as tetrahydrofuran, a glycol ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, methyl cellosolve acetate or ethyl cellosolve acetate. Ethylene glycol alkyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl a propylene glycol monoalkyl ether such as diethylene glycol such as diol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether or propylene glycol butyl ether, or propylene glycol methyl ether acetate Propylene glycol B Propylene glycol alkyl ether acetates such as phenyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl Propylene glycol alkyl ether acetates such as ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2- Ketones such as pentanone, and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -ethyl methacrylate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxyl Ethyl propionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxy vinegar Ethyl ester, propyl propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxyl Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxy Methyl propionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

In the present invention, a curable composition containing the epoxy compound represented by the above formula (1) and an acid generator can be obtained. As the acid generator, a photoacid generator or a thermal acid generator can be used.

The photoacid generator or the thermal acid generator is not particularly limited as long as it can directly or indirectly generate an acid by light irradiation or heating.

Specific examples of the photoacid generator include a triazine compound, an acetophenone derivative compound, a dioxon compound, a diazomethane compound, a sulfonic acid derivative compound, an iodonium salt, a phosphonium salt, and a phosphonium salt. A phosphonium salt such as selenium sulfonium salt, a ferrocene complex, an iron propadiene complex, or the like.

The onium salt to be used as the photoacid generator may, for example, be iodonium salt, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate or diphenyliodonium methanesulfonate. Diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluoroarsenate, Bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate , bis(p-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-butylphenyl)iodonium tetrafluoroborate, bis(p-butylphenyl) iodine chloride Bismuth, bis(p-chlorophenyl) iodonium chloride, bis(p-chlorophenyl) iodonium tetrafluoroborate. Further, for example, bis(alkylphenyl)iodonium salt or alkoxycarbonylalkoxy-trialkylaryl iodide salt such as bis(4-t-butylphenyl)iodonium hexafluorophosphate may be mentioned. (eg 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl) a bis(alkoxybenzene) such as iodonium hexafluorophosphate or the like, or a bis(alkoxyaryl)iodonium salt (for example, (4-methoxyphenyl)phenyliodonium hexafluoroantimonate) Base) iodonium salt).

The above sulfonium salt may, for example, be triphenylsulfonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate or tris(p-methoxyphenyl)phosphonium hexafluorophosphonate. , tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylsulfonium trifluorosulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, etc. Salt, or (4-phenylthiophenyl)diphenylphosphonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylphosphonium hexafluorophosphate, bis[4-(diphenylsulfonate) Phenyl] thioether-bis-hexafluoroantimonate, bis[4-(diphenylsulfonyl)phenyl] sulfide-bis-hexafluorophosphate, (4-methoxyphenyl) Bismuth salt of diphenylphosphonium hexafluoroantimonate).

The above sulfonium salt may, for example, be triphenylsulfonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate or tris(p-methoxyphenyl)phosphonium hexafluorophosphonate. An antimony salt such as tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorophenyldiazepine hexafluorophosphate or benzyltriphenylphosphonium hexafluoroantimonate.

The selenium sulfonium salt may, for example, be a selenium sulfonium salt such as triphenylselenium sulphate or hexafluorophosphate. Further, the ferrocene complex may be, for example, (η5 or η6-isopropylbenzene) (η5-ring). A ferrocene complex such as pentadienyl) iron (II) hexafluorophosphate.

Further, as the photoacid generator, the following compounds can also be used.

The photoacid generator is preferably an onium salt compound and an iodonium salt compound. Examples of the anionic species thereof include CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , C ₈ F ₁₇ SO ₃ ^- , camphorsulfonate anion, toluenesulfonic acid anion, BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , and SbF ₆ ^- and so on. In particular, it is preferably an anionic species such as phosphorus hexafluoride or ruthenium hexafluoride which is strongly acidic.

Then, the photoacid generator is preferably the above formulas (8-1), (8-2), (8-3), (8-8), (8-9), and (8-10), and particularly preferably (8-1) and (8-2).

These photoacid generators can be used singly or in combination of two or more.

The thermal acid generator may, for example, be a phosphonium salt or a phosphonium salt, and a phosphonium salt is preferably used.

Further, the thermal acid generator may be exemplified by the following compounds.

R' each independently represents an alkyl group having 1 to 12 carbon atoms and a carbon number of 6 to 20 aryl groups, and particularly preferably an alkyl group having 1 to 12 carbon atoms.

These thermal acid generators can be used singly or in combination of two or more.

The above-mentioned composition may contain a conventional additive as needed. Examples of such additives include pigments, colorants, tackifiers, sensitizers, antifoaming agents, leveling agents, coating improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.). ), a plasticizer, a surfactant, a dissolution promoter, a filler, an antistatic agent, a hardener, and the like. These additives may be used alone or in combination of two or more.

In the present invention, a curable composition containing the epoxy compound represented by the above formula (1) and a photoacid generator can be applied onto a substrate and cured by irradiation with light. Further, it is also possible to heat it before and after the light irradiation.

In the present invention, a curable composition containing the epoxy compound represented by the above formula (1) and a thermal acid generator can be applied onto a substrate and cured by heating.

Further, a curable composition containing the epoxy compound, the thermal acid generator, and the photoacid generator represented by the above formula (1) may be applied onto a substrate, and after heating, it may be cured by light irradiation.

The curable composition may contain a solvent. As the solvent, the above solvents can be used.

The method of applying the curable composition of the present invention to a substrate may, for example, be a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a rod coating method, a curtain coating method, a roll coating method, or the like. Gravure coating method, dipping method, slit method, and the like.

The thickness of the coating film formed of the curable composition of the present invention can be selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product, and can be, for example, 0.05 to 10 μm (especially 0.1 to 5 μm) when used for photoresist. When used in a printed circuit board, it can be about 10 μm to 5 mm (especially 100 μm to 1 mm), and when used in an optical film, it can be about 0.1 to 100 μm (especially 0.3 to 50 μm).

The light which is irradiated or exposed when the photoacid generator is used may, for example, be a gamma ray, an X ray, an ultraviolet ray, a visible ray or the like. Generally, visible light or ultraviolet ray, in particular, ultraviolet ray is often used.

The wavelength of light is, for example, 150 to 800 nm, preferably 150 to 600 nm, more preferably 200 to 400 nm, and particularly preferably 300 to 400 nm.

The amount of irradiation light varies depending on the thickness of the coating film, but may be, for example, 2 to 20,000 mJ/cm ² , preferably about 5 to 5,000 mJ/cm ² .

The light source can be selected according to the type of light to be exposed, and for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a deuterium lamp, a halogen lamp, a laser beam, a xenon-cadmium laser, an excimer laser, etc. can be used. )Wait. The hardening reaction of the above composition is carried out by irradiation with such light.

When a thermal acid generator is used, or a photoacid generator is used, the heating of the coating film as needed after light irradiation is performed, for example, at room temperature to about 250 °C. The heating time can be selected from the range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.

Further, when a pattern or an image is formed (for example, when a printed circuit board or the like is manufactured), the coating film formed on the substrate may be subjected to pattern exposure. This pattern exposure can also be performed by scanning the laser light or by irradiating the light through the mask. The non-irradiated area (unexposed portion) generated by such pattern exposure can be developed (or dissolved) with a developing liquid to form a pattern or an image.

As the developing liquid, an aqueous alkali solution or an organic solvent can be used.

The aqueous alkali solution may, for example, be an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, or a tetrahydrogen hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or caustic. An aqueous solution of an ammonium chloride solution, an amine amine such as ethanolamine, propylamine or ethylenediamine.

The alkali developing solution is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass or the like can be used. Further, an alcohol or a surfactant may be added to the above-mentioned developing solution, and the amount thereof is preferably 0.05 to 10 parts by mass per 100 parts by mass of the developing solution. its Among them, 0.1 to 2.38 mass% of an aqueous solution of tetramethylammonium hydroxide can be used.

Further, as the organic solvent of the developing liquid, a general organic solvent can be used, and examples thereof include acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, and propylene glycol ethyl ether. , propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone Wait. These may be used alone or in combination of two or more. It is particularly preferable to use propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate or the like.

In the curable composition of the present invention, a surfactant may be added for the purpose of improving coatability. Examples of such a surfactant include, for example, a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant, but are not particularly limited thereto. The surfactant system may be used singly or in combination of two or more.

Among these surfactants, a fluorine-based surfactant is preferred from the viewpoint of improving the coating property. Specific examples of the fluorine-based surfactant include, for example, EFTOP [registered trademark] EF 301, EF 303, EF 352 (Mitsubishi Material Chemical Co., Ltd.), and trade name: Megafac [registered trademark] F 171, F173, R-30, R-08, R-90, BL-20, F-482 (DIC (share) (Daily In Chemical Industry Co., Ltd.), trade name: Fluorad FC 430, FC 431 (Sumitomo 3M Co., Ltd.), trade name: Asahiguard [registered trademark] AG 710, Surflon [registered trademark] S-382, SC 101, SC 102, SC 103, SC 104, SC 105, SC 106 (Asahi Glass Co., Ltd.), etc. However, it is not limited to this.

The amount of the surfactant added to the curable composition of the present invention is 0.0008 to 4.5% by mass, preferably 0.0008 to 2.7% by mass, particularly preferably 0.0008 to 1.8, based on the solid content of the curable composition. quality%.

In the curable composition of the present invention, an adhesion promoter may be added for the purpose of improving the adhesion of the substrate after development. Examples of such adhesion promoters include chlorodecanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorodecane, and chloromethyldimethylchloromethane, and trimethylol. Methoxy decane, dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, diphenyl dimethoxy decane, phenyl triethoxy decane, etc. Alkoxy decanes, hexamethyldioxane, N,N'-bis(trimethyldecyloxy)urea, dimethyltrimethyldecyloxyamine, trimethyldecyloxyimidazole, etc. Indoloxanes, vinyl trichlorodecane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-ring a decane such as oxypropoxypropyltrimethoxydecane or γ-(N-hexahydropyridyl)propyltrimethoxydecane, benzotrimene, benzimidazole, anthracene, imidazole or 2-hydrogen sulfide a heterocyclic compound such as a benzimidazole, a 2-hydrothiobenzothiazole, a 2-hydrothiobenzoxazole, a carbazole, a thiourea, a hydrothioimidazole or a thiopyrimidine; or 1-dimethylurea, 1,3-dimethylurea Of urea, urea or a sulfur compound. These adhesion promoters can be used individually or in combination of 2 or more types.

The amount of the adhesion promoter added to the curable composition of the present invention is generally 18% by mass or less, preferably 0.0008 to 9% by mass, more preferably 0.04 to 9%, based on the solid content of the curable composition. quality%.

The curable composition of the present invention may further contain a sensitizer. Examples of the sensitizer which can be used include onion, phenothiazine, anthraquinone, thioglycone, and benzophenone thioglycone. Further, the sensitizing dye system may be exemplified by a thiopyranium salt-based dye, a merocyanine-based dye, a quinoline-based dye, a styrylquinoline-based dye, a coumarin-based dye, a thioindene-based dye, or an oxa compound. An anthraquinone dye, an Oxonol dye, a cyanine dye, a rhodamine dye, a pyrylium salt dye, or the like. Particularly preferred is an onion-based sensitizer which, when used in combination with a cationic hardening catalyst (sensitized radioactive cationic polymerization initiator), has a rapid increase in sensitivity and also has a radical polymerization initiation function, as in the present invention, in combination with a cation In the mixed molding of the hardening system and the radical hardening system, the catalyst species can be simplified. The compound of the onion is preferably a dibutoxy onion, a dipropoxy onion or the like.

The amount of the sensitizer added to the curable composition of the present invention is usually 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the curable composition.

[Examples]

The following machines were used for each measurement.

NMR: FT-NMR (ECX 300) manufactured by Nippon Electronics Co., Ltd.

LC-MS: Liquid chromatography analysis quality analyzer (Alliance-ZQ-LC-MS) manufactured by the company Waters.

GC-MS: Gas chromatographic analysis mass spectrometer (GC-MS QP5050A) manufactured by Shimadzu Corporation

TOF-MS (MALDI): manufactured by Bruker Daltonics AG MALDI-TOF mass spectrometer (auto flex III)

Viscosity measurement: E-type viscometer made by the stock company Tokimec (VISCONIC ED type)

Determination of penetration rate: UV, visible, near-infrared spectrophotometer (UV-3600) manufactured by Shimadzu Corporation

Bending test: Precision universal testing machine (AGS-X series) manufactured by Shimadzu Corporation

Linear expansion rate, glass transition temperature measurement, TA Instruments thermomechanical measuring device (TMA Q400)

Prepare the following epoxy compounds.

[Preparation of epoxy compound] Synthesis Example 1

Synthesis of bis(2,2-bis(2,3-epoxypropyloxymethyl)butyl)-4,5-epoxycyclohexane-1,2-dicarboxylate

Add cis-4-cyclohexene-1,2-dicarboxylic anhydride 10 g, p-toluenesulfonic acid monohydrate and 1.2 g, toluene 100 ml, trimethylolpropane to a reactor equipped with a Dean Stark apparatus and a cooler. 34 g of diallyl ether (90%) was reacted at reflux temperature for 15 hours. After the completion of the reaction, the mixture was washed with sodium hydrogencarbonate water, washed with water, concentrated, and purified by silica gel chromatography (hexane: ethyl acetate = 80:20) to give a pale yellow liquid (2, 2-bis(allyloxymethyl)butyl)-4,5-epoxycyclohexane-1,2-dicarboxylate 38 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.92~5.80 (m, 4H), 5.66 (s, 2H), 5.27~5.11 (m, 8H), 4.12~3.98 (m, 4H), 3.93~3.91 ( m, 8H), 3.30 (s, 8H), 3.03 (m, 2H), 2.56~2.35 (m, 4H), 1.46~1.39 (q, 4H), 0.87~0.82 (t, 6H)

GC-MS (CI): m/z = 564 (M + 1).

Add bis (2,2-bis(allyloxymethyl)butyl)-4,5-epoxycyclohexane-1,2-dicarboxylate 35g, chloroform 300ml, m-chlorochloride to the reactor After benzoic acid 86g, the reaction was carried out for 2 days. After the completion of the reaction, it was inhibited with an aqueous sodium thiosulfate solution, and sodium hydrogencarbonate water was added thereto to extract. The organic layer was distilled off from a solvent to obtain a crude product. It was purified by silica gel color layer chromatography (hexane: ethyl acetate = 50:50 → 10:90) to obtain 32 g of pale yellow liquid.

The obtained compound corresponds to a bis (2,2-bis(2,3-epoxypropyl group) corresponding to the combination of the formula (4-3) of the mother nucleus and the formula (2-1) corresponding to the substituent. Oxymethyl)butyl)-4,5-epoxycyclohexane-1,2-dicarboxylate.

The viscosity is 2867 mPa ‧ at 25 ° C. This epoxy compound is used as (i-1).

H-NMR (300MHz, CDCl ₃ ): δ = 4.11~3.98 (m, 4H), 3.74~3.68 (m, 4H), 3.42~3.30 (m, 12H), 3.23 (s, 2H), 3.13~3.08 ( m, 4H), 2.92~2.89 (m, 2H), 2.79~2.76 (m, 4H), 2.59~2.56 (m, 4H), 2.35~2.22 (m, 4H), 1.46~1.39 (q, 4H), 0.88~0.83 (t, 6H)

GC-MS (CI): m/z = 643 (M + 1).

Synthesis Example 2

Bis(3-(2,3-epoxypropyloxy)-2,2-bis(2,3-epoxypropyloxymethyl)propyl)-4,5-epoxycyclohexane Synthesis of -1,2-dicarboxylate

Add 8.0 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, 2.0 g of p-toluenesulfonic acid monohydrate, 150 ml of toluene, pentaerythritol triene to a reactor equipped with a Dean Stark apparatus and a cooler. 39 g of ethyl ether (70%) was reacted at reflux temperature for 35 hours. After the completion of the reaction, the mixture was washed with sodium hydrogencarbonate, washed with water, concentrated, and purified by silica gel chromatography (hexane: ethyl acetate = 90:10) to give a colorless liquid (3-( Allyloxy) 2,2-bis(allyloxymethyl)propyl)-4,5-epoxycyclohexane-1,2-dicarboxylate 17 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.92~5.79 (m, 6H), 5.66 (s, 2H), 5.26~5.11 (m, 12H), 4.25~4.10 (q, 4H), 3.94~3.91 ( m, 12H), 3.49 (s, 12H), 3.03 (m, 2H), 2.61 to 2.54 (m, 2H), 2.39 to 2.31 (m, 2H)

GC-MS (CI): m/z = 647 (M + 1).

Add bis(3-(allyloxy) 2,2-bis(allyloxymethyl)propyl)-4,5-epoxycyclohexane-1,2-dicarboxylate to the reactor. 16 g of an acid ester, 500 ml of chloroform, and 60 g of m-chloroperbenzoic acid were reacted for 5 days. After the reaction is completed, it is inhibited by an aqueous solution of sodium thiosulfate, and sodium hydrogencarbonate water is added thereto for extraction. The organic layer was distilled off from a solvent to obtain a crude product. It was purified by cerium oxide gel chromatography (ethyl acetate = 100) to obtain 22 g of a colorless liquid.

The obtained compound corresponds to a bis(3-(2,3-epoxypropyloxy)- group corresponding to the formula (4-3) of the mother nucleus and the combination of the formula (2-2) corresponding to the substituent. 2,2-bis(2,3-epoxypropyloxymethyl)propyl)-4,5-epoxycyclohexane-1,2-dicarboxylate.

The viscosity is 15808 mPa ‧ at 25 ° C. This epoxy compound is used as (i-2).

H-NMR (300MHz, CDCl ₃ ): δ = 4.22~4.10 (q, 4H), 3.74~3.69 (m, 6H), 3.53~3.44 (m, 12H), 3.36~3.31 (m, 6H), 3.24 ( s, 2H), 3.13~3.08 (m, 6H), 2.93~2.89 (m, 2H), 2.78~2.75 (t, 6H), 2.59~2.56 (m, 6H), 2.32~2.24 (m, 4H)

LC-MS (ESI): m.

Synthesis Example 3

Synthesis of bis(2,2-bis(2,3-epoxypropyloxymethyl)butyl)-1,2,3-propane tricarboxylate

Add 12 g of propane-1,2,3-tricarboxylic acid, p-toluenesulfonic acid monohydrate and 2.6 g, toluene 200 ml, trimethylolpropane allyl ether to a reactor equipped with a Dean Stark apparatus and a cooler. 90%) 49 g, reacted at reflux temperature for 24 hours. After the completion of the reaction, the mixture was washed with sodium hydrogencarbonate, washed with water, concentrated, and purified by silica gel chromatography (hexane: ethyl acetate = 80:20) to obtain a yellow liquid (2, 2) - bis(allyloxymethyl)butyl)-1,2,3-propane tricarboxylate 46 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.92~5.79 (m, 6H), 5.27~5.12 (m, 12H), 4.06~4.05 (m, 6H), 3.93~3.91 (m, 12H), 3.30~ 3.23 (m, 13H), 2.82~2.74 (m, 4H), 1.47~1.39 (q, 6H), 0.87~0.82 (t, 9H)

GC-MS (CI): m/z = 766 (M + 1).

Adding 45 g of ginseng (2,2-bis(allyloxymethyl)butyl)-1,2,3-propane tricarboxylate, 600 ml of chloroform and 87 g of m-chloroperbenzoic acid to the reactor, the reaction was carried out for 4 days. . After the completion of the reaction, it was inhibited with an aqueous sodium thiosulfate solution, and sodium hydrogencarbonate water was added thereto to extract. The organic layer was distilled off from a solvent to obtain a crude product. The oil was chromatographed (hexane: ethyl acetate = 70:30) to afford 22 g of colorless liquid.

The obtained compound corresponds to a reference (2,2-bis(2,3-epoxypropyl) corresponding to the formula (6-1) of the mother nucleus and the combination of the formula (2-1) corresponding to the substituent. Oxymethyl)butyl)-1,2,3-propane tricarboxylate. Viscosity is 25 ° C Under 5421mPa. s. This epoxy compound is used as (i-3).

H-NMR (300MHz, CDCl ₃ ): δ = 4.05~4.04 (m, 6H), 3.73~3.68 (m, 6H), 3.42~3.24 (m, 19H), 3.12~3.10 (m, 6H), 2.83~ 2.80 (d, 2H), 2.78~2.75 (m, 6H), 2.65~2.63 (d, 2H), 2.59~2.56 (m, 6H), 1.46~1.39 (q, 6H), 0.88~0.83 (t, 9H) )

LC-MS (ESI): m.

Synthesis Example 4

Synthesis of tetrakis(2,2-bis(2,3-epoxypropyloxymethyl)butyl)-1,2,3,4-butane tetracarboxylate

Add 7g of butane-1,2,3,4-tetracarboxylic dianhydride, p-toluenesulfonic acid monohydrate and 0.7g, toluene 150ml, trimethylolpropane to the reactor equipped with Dean Stark apparatus and cooler. 35 g of diallyl ether (90%) was reacted at reflux temperature for 51 hours. After the reaction was completed, it was washed with sodium hydrogencarbonate water, washed with water, concentrated, and analyzed by cerium oxide gel chromatography (hexane: ethyl acetate) =90:10) Purification gave 20 g of (2,2-bis(allyloxymethyl)butyl)-1,2,3,4-butanetetracarboxylate as a yellow liquid.

H-NMR (300MHz, CDCl ₃ ): δ = 5.92~5.79 (m, 8H), 5.27~5.12 (m, 16H), 4.13~4.00 (m, 8H), 3.95~3.91 (m, 16H), 3.32~ 3.30 (m, 18H), 2.85~2.76 (m, 2H), 2.40~2.35 (m, 2H), 1.45~1.41 (m, 8H), 0.87~0.81 (m, 12H)

TOF-MS (MALDI): m/z = 1042 (M+Na).

19 g of tetrakis(2,2-bis(allyloxymethyl)butyl)-1,2,3,4-butanetetracarboxylate, 500 ml of chloroform and 42 g of m-chloroperbenzoic acid were added to the reactor. The reaction was 9 days. After the completion of the reaction, it was inhibited with an aqueous sodium thiosulfate solution, and sodium hydrogencarbonate water was added thereto to extract. The organic layer was distilled off from a solvent to obtain a crude product. The mixture was purified by silica gel chromatography (hexane: ethyl acetate = 20: 80). After concentration, 170 g of toluene and 3.4 g of activated carbon were added, and the mixture was stirred for 3 hours. The activated carbon was filtered, and the solvent was evaporated to give a pale yellow liquid (16 g).

The obtained compound corresponds to a combination of the formula (6-2) corresponding to the mother nucleus and the combination of the formula (2-1) corresponding to the substituent (2,2-bis(2,3-epoxypropyl) Oxymethyl)butyl)-1,2,3,4-butane tetracarboxylate.

The viscosity is 12186 mPa ‧ at 25 ° C. This epoxy compound is used as (i-4).

H-NMR (300MHz, CDCl ₃ ): δ = 4.15~3.97 (m, 8H), 3.72~3.68 (d, 8H), 3.42~3.32 (m, 26H), 3.13~3.09 (m, 8H), 2.85~ 2.82 (m, 2H), 2.78~2.75 (m, 8H), 2.59~2.56 (m, 8H), 2.45~2.39 (m, 2H), 1.45~1.41 (m, 8H), 0.88~0.82 (m, 12H) )

TOF-MS (MALDI): m/z = 1170 (M+Na).

Synthesis Example 5

Synthesis of 1,3,5-gin[2-[2,2-bis(2,3-epoxypropyloxymethyl)butyloxy]carbonylethyl]trimeric isocyanate

45 g of trimethylolpropane diallyl ether, 360 ml of dichloromethane, 23 g of 4-dimethylaminopyridine, and 1-ethyl-3-(3-dimethylaminopropyl) were added to the reactor. Carboquinone imine hydrochloride 36g, trimeric isocyanate (2- Carboxyethyl) 18 g, reacted at room temperature for 3 days. After the completion of the reaction, the organic layer was washed with hydrochloric acid and sodium hydrogencarbonate, concentrated, and purified by silica gel chromatography (hexane: ethyl acetate=80:20→50:50) to obtain a colorless liquid. 3,5-Shen[2-[2,2-bis(2,3-propenyloxymethyl)butyloxy]carbonylethyl]trimeric isocyanate 27 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.93~5.80 (m, 6H), 5.28~5.12 (m, 12H), 4.21~4.11 (m, 6H), 4.01 (s, 6H), 3.95~3.92 ( m, 12H), 3.31 (s, 12H), 2.70~2.65 (m, 6H), 1.47~1.40 (m, 6H), 0.88~0.83 (m, 9H)

LC-MS (ESI): m.

To the reactor was added 27 g of 1,3,5-gin[2-[2,2-bis(2,3-propenyloxymethyl)butyloxy]carbonylethyl]trimeric isocyanate, chloroform 530 ml, and m-chlorochloride. 50 g of benzoic acid was passed and reacted at room temperature for 3 days. After the completion of the reaction, the mixture was neutralized with an aqueous sodium thiosulfate solution, and washed with sodium hydrogencarbonate water and water. The organic layer was distilled off from a solvent to obtain a crude product. The mixture was purified by silica gel chromatography (hexane: ethyl acetate = 40:60 to 0:100). After concentration, 250 ml of toluene and 5 g of activated carbon were added and stirred. The activated carbon was filtered, and the solvent was evaporated to give 23 g of a colorless liquid.

The obtained compound corresponds to a combination of the formula (5-2) corresponding to the mother nucleus and the combination of the formula (2-1) corresponding to the substituent, and the 1,3,5-para [2-[2,2-dual ( 2,3-Ethoxypropyloxymethyl)butyloxy]carbonylethyl]trimeric isocyanate.

The viscosity is 14464 mPa ‧ at 30 ° C. This epoxy compound is used as (i-5).

H-NMR (300MHz, CDCl ₃ ): δ = 4.20~4.16 (m, 6H), 4.06 (s, 6H), 3.73~3.67 (m, 6H), 3.44~3.31 (m, 18H), 3.14~3.08 ( m, 6H), 2.79~2.76 (m, 6H), 2.71~2.66 (m, 6H), 2.59~2.57 (m, 6H), 1.47~1.40 (m, 6H), 0.89~0.84 (m, 6H)

MALDI-TOFMS: m/z = 1052.82 (M+Na).

Synthesis Example 6

1,3,5-gin[2-[2,2-bis(2,3-epoxypropyloxymethyl)-3-(2,3-epoxypropyloxy)propyloxy]carbonyl Synthesis of ethyl]trimeric isocyanate

56 g of pentaerythritol, 400 ml of dichloromethane, 29 g of 4-dimethylaminopyridine, and 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride 46 g were added to the reactor. 25 g of trimeric isocyanate (2-carboxyethyl) was reacted overnight at room temperature. After the completion of the reaction, the organic layer was washed with hydrochloric acid and sodium hydrogen carbonate and concentrated. Analysis by cerium oxide gel chromatography (hexane: ethyl acetate) =90:10→80:20→60:40) Refining to obtain 1,3,5-para [2-[2,2-bis(2,3-propenyloxymethyl)-3-) as a colorless liquid 2,3-Propyloxy)propyloxy]carbonylethyl]trimeric isocyanate 24 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.92~5.79 (m, 9H), 5.27~5.12 (m, 18H), 4.18 (m, 12H), 3.95~3.92 (m, 18H), 3.43 (s, 18H), 2.70~2.65 (m, 6H)

TOF-MS (MALDI): m/z = 10.82.43 (M+Na).

Add 1,3,5-gin[2-[2,2-bis(2,3-propenyloxymethyl)-3-(2,3-propenyloxy)propyloxy]carbonyl B to the reactor. 23 g of trimeric isocyanate, 1 L of chloroform and 63 g of m-chloroperbenzoic acid were reacted at room temperature for 6 days. After the completion of the reaction, the mixture was neutralized with an aqueous sodium thiosulfate solution, and washed with sodium hydrogencarbonate water and water. The organic layer was distilled off from a solvent to obtain a crude product. The mixture was purified by silica gel chromatography (hexane: ethyl acetate = 20: 80 to 0: 100). After concentration, 500 ml of toluene and 4 g of activated carbon were added and stirred. The activated carbon was filtered, and the solvent was distilled off to obtain 33 g of a colorless liquid.

The obtained compound corresponds to a combination of the formula (5-2) corresponding to the mother nucleus and the combination of the formula (2-2) corresponding to the substituent, 1,3,5-para [2-[2,2-dual ( 2,3-Epoxypropyloxymethyl)-3-(2,3-epoxypropyloxy)propyloxy]carbonylethyl]trimeric isocyanate.

The viscosity is 15462 mPa ‧ at 30 ° C. This epoxy compound is used as (i-6).

H-NMR (300MHz, CDCl ₃ ): δ = 4.20~4.15 (m, 12H), 3.74~3.31 (m, 36H), 3.12~3.08 (m, 9H), 2.79~2.57 (m, 24H)

TOF-MS (MALDI): m/z = 1226.52 (M+Na).

Synthesis Example 7

1,3,5-gin[2-[1-(2,3-epoxypropyloxymethyl)-2-(2,3-epoxypropyloxy)ethyloxy]carbonylethyl] Synthesis of trimeric isocyanate

To the reactor, 55 g of tris-isocyanatoic acid (2-carboxyethyl) and 170 ml of N,N-dimethylformamide were added, and after confirming dissolution, 63 g of sulfoxide chloride was added dropwise. After stirring at room temperature for 1 hour, the precipitated solid was filtered, washed with chloroform, and dried to give a white solid, 54 g of 1,3,5- s (2-chloromethylethyl) tris.

After adding 100 ml of chloroform, 37 g of glycerol-α,α'-diallyl ether and 17 g of pyridine to the reactor, stirring was carried out, and 1,3,5-gino(2-chloromethylhydrazineethyl) trimer was added little by little. Isocyanate 20g. The reaction was carried out at 65 ° C for 3 hours. Distillate After the solvent, the precipitated salt was removed by filtration, and chloroform was added to the filtrate, which was washed with water. After concentrating the organic layer, it was purified by ruthenium dioxide gel chromatography (hexane: ethyl acetate = 70:30 → 50:50) to obtain 1,3,5-para [2-[1-( 2,3-Propyloxymethyl)-2-(2,3-propenyloxy)ethyloxy]carbonylethyl]trimeric isocyanate 27 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.94~5.80 (m, 6H), 5.29~5.12 (m, 15H), 4.20~4.16 (m, 6H), 4.04~3.98 (m, 12H), 3.60~ 3.58 (d, 12H), 2.74 to 2.69 (t, 6H)

Add 1,3,5-gin[2-[1-(2,3-propenyloxymethyl)-2-(2,3-propenyloxy)ethyloxy]carbonylethyl]three to the reactor 27 g of polyisocyanate, 1 L of chloroform, and 59 g of m-chloroperbenzoic acid were reacted at room temperature for 4 days. After the completion of the reaction, the mixture was neutralized with an aqueous sodium thiosulfate solution, and washed with sodium hydrogencarbonate water and water. The organic layer was distilled off from a solvent to obtain a crude product. It is refined by ruthenium dioxide gel chromatography (hexane: ethyl acetate = 70:30 → 50:50 → 30: 70 → 10: 90 → 0: 100), and after concentration, 120 ml of toluene and 2 g of activated carbon are added. Stir. The activated carbon was filtered, and the solvent was distilled off to obtain 12 g of a colorless liquid.

The obtained compound corresponds to 1,3,5-para [2-[1-(2,3) corresponding to the combination of the formula (5-2) of the mother nucleus and the formula (2-3) corresponding to the substituent. -Epoxypropyloxymethyl)-2-(2,3-epoxypropyloxy)ethyloxy]carbonylethyl]trimeric isocyanate.

The viscosity is 18061 mPa‧s at 30 °C. This epoxy compound is used as (i-7).

H-NMR (300MHz, CDCl ₃ ): δ = 5.15~5.12 (m, 3H), 4.21~4.16 (m, 6H), 3.83~3.35 (m, 24H), 3.14~3.13 (m, 6H), 2.80~ 2.58 (m, 18H)

LC-MS (ESI): m.

Synthesis Example 8

Synthesis of 1,3,5-gin[2,3-bis(2,3-epoxypropyloxy)propyl)trimeric isocyanate

30 g of trimeric isocyanic acid, 5 g of tetramethylammonium chloride, 300 ml of 1,3-dimethyl-2-imidazolidinone, and 95 g of allyl glycidyl ether were added to the reactor, and stirred at 100 ° C. 5 hours. After the reaction was completed, the mixture was extracted with ethyl acetate. Purification by ceria gel chromatography (hexane: ethyl acetate = 30:70) to give 1,3,5-non-[2-hydroxy-3-(2,3-propenyloxy) as a colorless liquid. Propyl]trimeric isocyanate 37g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.94~5.85 (m, 3H), 5.31~5.18 (m, 6H), 4.27~3.93 (m, 15H), 3.57~3.45 (m, 6H), 2.67~ 2.65 (m, 3H)

GC-MS (CI): m/z = 471 (M).

11 g of sodium hydroxide and 700 ml of dimethylformamide were added to the reactor, and 1,3,5-gin[2-hydroxy-3-(2,3-propenyloxy)propane was added dropwise while stirring at 0 °C. 35 g of trimeric isocyanate and 54 g of bromopropene were reacted at room temperature for 1 day. After completion of the reaction, the mixture was quenched with water, extracted with toluene, and the organic layer was washed with brine and concentrated. Purification by ceria gel chromatography (hexane: ethyl acetate = 80:20 → 50:50) to obtain 1,3,5-para [2,3-bis(2,3-propene) as a colorless liquid. Alkoxy)propyl]trimeric isocyanate 13 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.94~5.79 (m, 6H), 5.27~5.11 (m, 12H), 4.19~3.94 (m, 18H), 3.86~3.83 (m, 3H), 3.52~ 3.51 (m, 6H)

GC-MS (CI): m/z = 592 (M+2).

21 g of 1,3,5-gin[2,3-bis(2,3-propenyloxy)propyl]trimeric isocyanate, 630 ml of chloroform and 59 g of m-chloroperbenzoic acid were added to the reactor, and the reaction was carried out at room temperature. 4th. After the completion of the reaction, the mixture was neutralized with an aqueous sodium thiosulfate solution, and washed with sodium hydrogencarbonate water and water. The organic layer was distilled off from a solvent to obtain a crude product. The mixture was purified by silica gel chromatography (hexane: ethyl acetate = 20: 80). After concentration, 320 ml of toluene and 7 g of activated carbon were added and stirred. The activated carbon was filtered, and the solvent was evaporated to give 30 g of a colorless liquid.

The obtained compound corresponds to a combination of the formula (5-6) corresponding to the mother nucleus and the combination of the formula (2-4) corresponding to the substituent, 1,3,5-para [2,3-dual ( 2,3-Propyloxy)propyl]trimeric isocyanate.

The viscosity is 17011 mPa ‧ at 25 ° C. This epoxy compound is used as (i-8).

H-NMR (300MHz, CDCl ₃ ): δ=4.09~3.76 (m, 15H), 3.66~3.32 (m, 12H), 3.16~3.08 (m, 6H), 2.79~2.71 (m, 6H), 2.62~ 2.57 (m, 6H)

LC-MS (ESI): m.

Synthesis Example 9

Synthesis of bis(2,2-bis(2,3-epoxypropyloxymethyl)butyl)-adamantane-1,3-dicarboxylate

20 g of 1,3-adamantane dicarboxylic acid, 200 g of methanol, and 0.8 g of concentrated sulfuric acid were placed in the reactor, and the mixture was reacted at reflux temperature for 2 hours. The reaction solution was concentrated, and 200 ml of toluene was added thereto, followed by washing with sodium hydrogen carbonate and water. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 3:1) to afford 21 g of 1,3- adamantane dicarboxylate as a white solid.

H-NMR (300MHz, CDCl ₃ ): δ=3.66 (s, 6H), 2.15~1.68 (m, 14H)

GC-MS (CI): m/z = 253 (M+H).

20 g of methyl 1,3-adamantane dicarboxylate, 12 g of p-toluenesulfonic acid water and 12 g of toluene, 200 ml of toluene, and 70 g of trimethylolpropane diallyl ether (90%) were added to the reactor to react at reflux temperature. 26th. The reaction solution was concentrated and washed with sodium bicarbonate water and aqueous sodium hydroxide. The organic layer was concentrated and purified by ruthenium dioxide gel chromatography (hexane: ethyl acetate=100:0→95:5→80:20) to give a brown liquid double (2,2-bis(propenyloxy) Methyl)butyl)-adamantane-1,3-dicarboxylate 14g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.91~5.82 (m, 4H), 5.27~5.13 (m, 8H), 3.97 (s, 4H), 3.94~3.92 (m, 8H), 3.32 (s, 8H), 2.16~1.69 (m, 14H), 1.46~1.43 (q, 4H), 0.88~0.83 (t, 6H)

GC-MS (ESI): m/z = </RTI> (M+H).

Adding 13 g of bis(2,2-bis(propenyloxymethyl)butyl)-adamantane-1,3-dicarboxylate, 500 ml of chloroform and 47 g of m-chloroperbenzoic acid to the reactor at room temperature The reaction was 3 days. After the completion of the reaction, the mixture was neutralized with an aqueous sodium thiosulfate solution, and washed with sodium hydrogencarbonate water and water. The organic layer was distilled off from a solvent to obtain a crude product. The oil was chromatographed (hexane: ethyl acetate = 70:30 -> 50:50 -> 30:70 -> 10:90). After concentration, 130 ml of toluene and 3 g of activated carbon were added and stirred. The activated carbon was filtered, and the solvent was evaporated to give 9 g of pale yellow liquid.

The obtained compound corresponds to a bis (2,2-bis(2,3-epoxypropyl group) corresponding to the combination of the formula (4-1) of the mother nucleus and the formula (2-1) corresponding to the substituent. Oxymethyl)butyl)-adamantane-1,3-dicarboxylate.

The viscosity is 2609 mPa ‧ at 25 ° C. This epoxy compound is used as (i-9).

H-NMR (300MHz, CDCl ₃ ): δ=4.00 (s, 4H), 3.72~3.67 (m, 4H), 3.44~3.32 (m, 12H), 3.10 (s, 4H), 2.79~2.76 (m, 4H), 2.59~2.57 (m, 4H), 2.02~1.69 (m, 14H), 1.46~1.43 (q, 6H), 0.89~0.83 (t, 4H)

LC-MS (ESI): m.

Comparative Synthesis Example 1

Synthesis of bis(2,3-epoxypropyl)-4,5-epoxycyclohexane-1,2-dicarboxylate

15 g of cis-4-cyclohexene-1,2-dicarboxylic acid, 37 g of potassium carbonate, 255 ml of dimethylformamide and 32 g of bromopropene were added to the reactor, and the mixture was reacted at room temperature for 15 hours. After the reaction was completed, it was filtered, and toluene and water were added, and the mixture was extracted. After washing with water and concentrating, it was purified by ruthenium dioxide gel chromatography (hexane: ethyl acetate = 75:25) to give bis(2-propenyl)-4-cyclohexene as a pale yellow liquid. 1,2-dicarboxylate 21 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.96~5.82 (m, 2H), 5.68~5.67 (m, 2H), 5.33~5.19 (m, 4H), 4.60~4.58 (m, 4H), 3.11~ 3.07 (m, 2H), 2.62~2.55 (m, 2H), 2.41~2.33 (m, 2H)

GC-MS (CI): m/z = 250 (M).

21 g of bis(2-propenyl)-4-cyclohexene-1,2-dicarboxylate and 300 ml of chloroform were added to the reactor, and after cooling to 0 to 10 ° C, 87 g of m-chloroperbenzoic acid was added thereto, and the temperature was raised to The reaction was carried out for 5 days at room temperature. After the reaction was completed, it was inhibited with an aqueous sodium thiosulfate solution, and extracted with sodium hydrogencarbonate. The organic layer was washed with sodium bicarbonate water, washed with water, and dried. The solvent was distilled off to obtain a crude product. It was purified by cerium oxide gel chromatography (hexane: ethyl acetate = 50:50 → 10:90) to obtain 20 g of a colorless liquid.

The compound obtained was bis(2,3-epoxypropyl)-4,5-epoxycyclohexane-1,2-dicarboxylate.

The viscosity is 1992 mPa ‧ at 25 ° C. This epoxy compound is used as (i10).

H-NMR (300MHz, CDCl ₃ ): δ = 4.51~4.41 (m, 2H), 3.96~3.84 (m, 2H), 3.25~3.19 (m, 4H), 3.01~2.98 (m, 2H), 2.84~ 2.81 (m, 2H), 2.66~2.61 (m, 2H), 2.27~2.20 (m, 4H)

GC-MS (ESI): m/z = 298 (M).

Comparative Synthesis Example 2

Synthesis of tetrakis(2,3-epoxypropyl)-1,2,3,4-butane tetracarboxylate into a reactor, adding 53 g of 1,2,3,4-butanetetracarboxylic acid, carbonic acid 155 g of potassium, 892 ml of N,N-dimethylformamide, and 177 g of bromopropene were reacted at 68 °C for 11 hours. After the completion of the reaction, the toluene and water were washed, concentrated, and purified by ruthenium dioxide gel chromatography (hexane: ethyl acetate = 80:20) to obtain a pale yellow liquid of tetrakis(2-propenyl)-1. 2,3,4-butane tetracarboxylate 71 g.

H-NMR (300MHz, CDCl ₃ ): δ = 5.94~5.82 (m, 4H), 5.35~5.22 (m, 8H), 4.61~4.58 (m, 8H), 3.41~3.37 (m, 2H), 2.90~ 2.81 (m, 2H), 2.50~2.43 (m, 2H),

GC-MS (CI): m/z = 495 (M+H).

40 g of tetrakis(2-propenyl)-1,2,3,4-butanetetracarboxylate and 800 ml of chloroform were added to the reactor, and after cooling to 0 to 10 ° C, 112 g of m-chlorobenzoic acid was added thereto, and the temperature was raised to The reaction was carried out for 96 hours at room temperature. After the completion of the reaction, it was inhibited with an aqueous sodium thiosulfate solution, and extracted with sodium hydrogencarbonate. The organic layer was washed with water, and the solvent was evaporated to give a crude product. It was purified by silica gel color chromatography (hexane: ethyl acetate = 20:80) to obtain 22 g of a colorless liquid. After standing at room temperature, it was crystallized and washed with ethanol to give a white solid. After determining the melting point of the crystal by DSC, it was 49.6 °C. The compound obtained was tetrakis(3,4-epoxypropyl)-1,2,3,4-butanetetracarboxylate.

This epoxy compound is used as (i-11).

H-NMR (300MHz, CDCl ₃ ): δ=4.52~4.42 (m, 4H), 4.00~3.90 (m, 4H), 3.44~3.41 (m, 2H), 3.25~3.18 (m, 4H), 2.93~ 2.83 (m, 6H), 2.67~2.63 (m, 4H), 2.55~2.49 (m, 2H)

LC-MS (ESI): m.

Comparative Synthesis Example 3

Synthesis of bis(2,3-epoxypropyl)-adamantane-1,3-dicarboxylate

20 g of 1,3-adamantane dicarboxylic acid, 32 g of potassium carbonate, 500 ml of N,N-dimethylformamide, and 32 g of bromopropene were placed in the reactor, and the mixture was reacted at 65 ° C for 4 hours. The reaction solution was filtered, toluene was added to the filtrate, and washed with water. The obtained organic layer was concentrated to give 28 g of bis(2,3-propenyl)-adamantane-1,3-dicarboxylate as a yellow liquid.

H-NMR (300MHz, CDCl ₃ ): δ = 5.97~5.84 (m, 2H), 5.33~5.20 (m, 4H), 4.58~4.55 (m, 4H), 2.17~1.69 (m, 14H)

GC-MS (ESI): m/z = 304 (M).

Adding bis(2,3-propenyl)-adamantane-1,3-dicarboxylic acid to the reactor 27 g of ester, 62 g of m-chloroperbenzoic acid, and 500 ml of chloroform were reacted at room temperature for 5 days. After the completion of the reaction, it was inhibited with an aqueous sodium thiosulfate solution, and extracted with sodium hydrogencarbonate. The organic layer was washed with water, and the solvent was evaporated to give a crude product. The mixture was purified by ruthenium dioxide gel chromatography (hexane: ethyl acetate = 70:30 to 50:50). After concentration, 250 ml of toluene and 5 g of activated carbon were added and stirred. The activated carbon was filtered, and the solvent was evaporated to give 20 g of a colorless liquid.

The compound obtained was bis(2,3-epoxypropyl)-adamantane-1,3-dicarboxylate.

The viscosity is 207 mPa ‧ at 25 ° C. This epoxy compound is used as (i-12).

H-NMR (300MHz, CDCl ₃ ): δ = 4.43~4.38 (m, 2H), 3.96~3.90 (m, 2H), 3.23~3.17 (m, 2H), 2.86~2.83 (m, 2H), 2.66~ 2.63 (m, 2H), 2.18~1.70 (m, 14H)

GC-MS (ESI): m/z = 356 (M).

For the liquid epoxy compound, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate of the formula (7-5) is prepared. This epoxy compound is used as (i-13).

The liquid epoxy compound is a hydrogenated bisphenol A type diglycidyl ether of the formula (7-3). This epoxy compound is used as (i-14).

[Preparation of photoacid generator]

A propylene carbonate solution of the cerium salt (formula (8-2), active ingredient 50%, trade name CPI-101A, manufactured by San-Apro Co., Ltd.) was prepared. This was used as the photoacid generator (ii-1). A propylene carbonate solution of the cerium salt (formula (8-1), active ingredient 50%, trade name CPI-100P, manufactured by San-Apro Co., Ltd.) was prepared. This was used as the photoacid generator (ii-2).

[Preparation of Curable Composition and Photocurability Test] Example 1

The epoxy compound and the photoacid generator were blended at a ratio shown in Table 1, and a device for stirring and defoaming (trade name: defoaming chain Taro, manufactured by Thinky Co., Ltd.) was mixed, and defoaming was carried out to prepare a curable composition. . The blending amounts are all described in parts by mass, and the epoxy compound and the photoacid generator are described as parts by mass of the active ingredient. The photoacid generators (ii-1) and (ii-2) of the propylene carbonate solution are used as they are.

The curable composition prepared was subjected to UV (ultraviolet) irradiation from a distance of 9.5 cm, and the photohardening behavior was observed by a rheometer (viscometer) so that the storage elastic modulus was 10 ⁴ Pa (1 × 10 ⁴ Pa). (seconds) is defined as the hardening time (seconds). UV irradiation was carried out for 600 seconds.

The rheometer was manufactured by Reologica Co., Ltd. (trade name: VAR-50 type), and the lamp system was an Hg-Xe lamp. The UV wavelength of the irradiation was 365 nm, and the irradiation amount was 20 mW/cm ² . The irradiation window for UV irradiation used 3 mm thick hard glass, and the film thickness of the coating film formed from the curable composition was 50 μm. The photohardening time of the curable composition was measured and described in Table 1.

Example 2 to Example 8 and Comparative Example 1 to Comparative Example 5

In the same manner as in the above-mentioned Example 1, the curable composition was prepared at the blending ratios shown in Tables 1 to 4, and the photocuring time of the curable composition was measured, and it is described in Tables 1 to 4.

Example 9

In the same manner as in the above-mentioned Example 1, the curable composition prepared at the blending ratio shown in Table 5 was applied to a PET film (Toyobo A4100 125 μm) by a 75 μm thin coater, and UV was carried out from the distance of 26.5 cm with the integrated light amount described below. (UV) irradiation, and a non-stick test (finger dry time test) was performed immediately after the irradiation.

The UV irradiation machine used a batch type furnace type ultraviolet curing device (manufactured by Eyegraphics Co., Ltd.) of 2 kW × 1 lamp, and the lamp system used Hg lamps (H02-L41 2.0 kW Eyegraphics Co., Ltd.), and the illuminance was 20 mW/cm ² (365 nm). The illumination window for UV irradiation uses quartz glass. The tack free time of the curable composition was evaluated and is shown in Table 5.

Example 10, Comparative Example 6 to Comparative Example 9

In the same manner as in the above-mentioned Example 9, the curable composition prepared by the blending ratio shown in Table 5 was used to evaluate the tack-free time of the curable composition, and the results are shown in Table 5.

Further, the evaluation criteria in Table 5 were evaluated in five stages of hardening (?), slightly tacky (?), residual fingerprint (?), surface hardening but internal hardening (?x), and unhardened (x).

[Production of thermosetting material] Example 11

24.6 g of the epoxy compound (i-1) and 31.3 g of the acid anhydride hardener Rikacid MH-700 (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd., and the composition is mixed with a molar ratio of 70:30 in the reactor 4) Methylhexahydrophthalic anhydride and hexahydrofurfuric anhydride were degassed under reduced pressure at room temperature for 30 minutes. 0.25 g of Hishicolin PX-4ET (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd., component tetrabutylphosphonium diethylsulfonate) was added as a curing accelerator, and the mixture was further degassed for 5 minutes. This mixture was poured into a release-treated glass plate (manufactured by Toray Dow Corning Co., Ltd., manufactured by Toray Dow Corning Co., Ltd., using a release agent SR-2410 (trade name) at 150 ° C for 1 hour). The hardening was carried out at 100 ° C for 2 hours, and the hardening was performed at 150 ° C for 5 hours.

Example 12

In the same manner as in the above Example 1, 9.4 g of the epoxy compound (i-2), 14.3 g of Rikacid MH-700, and 0.10 g of Hishicolin PX-4ET were fed to obtain a cured product.

Example 13

In the same manner as in the above Example 1, 16.5 g of the epoxy compound (i-3), 18.7 g of Rikacid MH-700, and 0.17 g of Hishicolin PX-4ET were fed to obtain a cured product.

Example 14

10.2 g of an epoxy compound (i-4) was fed in the same manner as in the above Example 1. 11.7 g of Rikacid MH-700 and 0.11 g of Hishicolin PX-4ET gave a cured product.

Example 15

In the same manner as in the above Example 1, 5.02 g of the epoxy compound (i-5), 4.66 g of Rikacid MH-700, and 0.063 g of Hishicolin PX-4ET were fed to obtain a cured product.

Example 16

In the same manner as in the above Example 1, 13.5 g of the epoxy compound (i-6), 16.6 g of Rikacid MH-700, and 0.13 g of Hishicolin PX-4ET were fed to obtain a cured product.

Example 17

In the same manner as in the above Example 1, 7.66 g of the epoxy compound (i-7), 8.38 g of Rikacid MH-700, and 0.078 g of Hishicolin PX-4ET were fed to obtain a cured product.

Example 18

In the same manner as in the above Example 1, 14.2 g of the epoxy compound (i-8), 20.0 g of Rikacid MH-700, and 0.15 g of Hishicolin PX-4ET were fed to obtain a cured product.

Comparative Example 10

In the same manner as in the above Example 1, 14.7 g of the epoxy compound (i-5), 24.1 g of Rikacid MH-700, and 0.15 g of Hishicolin PX-4ET were fed to obtain a cured product.

Comparative Example 11

In the same manner as in the above Example 1, 14.6 g of the epoxy compound (i-6), 20.9 g of Rikacid MH-700, and 0.15 g of Hishicolin PX-4ET were fed to obtain a cured product.

With respect to the obtained cured product, a three-point bending test (bending strength, bending elastic modulus), a transmittance, a linear expansion ratio, and a glass transition temperature were measured.

(Measurement of bending characteristics)

It was measured by a universal testing machine in accordance with JIS K6911.

The height and width of the test piece were measured, and the test piece was supported, and the center was pressed to apply a load to the wedge body, and the load at the time of bending the test piece was measured to calculate the bending strength (σ).

Bending strength σ: (MPa) {kgf/mm ² }, P: load when the test piece is bent (N) {kgf}

L: distance between fulcrums (mm)

W: width of test piece (mm)

h: height of test piece (mm)

σ=(3PL)/(2 Wh ² )

Bending modulus (E): (MPa) {kgf/mm ² } is F/Y: if it is the gradient of the load-bending curve (N/mm) {kgf/mm}

E=[L ³ /(4Wh ³ )]×[F/Y]

(Measurement of penetration rate)

The transmittance at 400 nm was measured using a spectrophotometer.

(Measurement of linear expansion rate)

The measurement of the coefficient of linear expansion was measured in accordance with JIS K-6911.

The thickness of the test piece was accurately measured and measured by TMA (thermo-mechanical analysis) expansion and compression at a load of 0.05 N and a temperature increase rate of 5 ° C/min.

The linear expansion coefficient α 1 was determined by the amount of change (ΔL1) of the length of 30 to 80 ° C / the initial length (L) of the test piece × 50 = α 1 .

(Measurement of glass transition temperature (Tg))

The thickness of the test piece was accurately measured and measured by TMA expansion and compression at a load of 0.05 N and a temperature increase rate of 5 ° C/min. The curve is drawn after the curve of the glass transition point, and the Tg is obtained from the intersection of the tangent lines.

[Industrial use possibility]

The curable composition containing an epoxy compound of the present invention has light and thermosetting properties, and has excellent adhesion to a substrate, high transparency (transparency to visible light), hard coatability, and high heat resistance. Features can be used for covering or adhering electronic parts, optical parts, and precision mechanical parts. It can be used for, for example, a lens of a mobile phone or a camera, an optical element such as a light emitting diode (LED), a semiconductor laser (LD), a liquid crystal panel, a biochip, a lens of a camera lens or the like, a personal computer, or the like. Magnetic parts for hard discs, pickups for CDs and DVD players (portions for obtaining light information reflected from optical discs), cones and coils for horns, magnets for motors, circuit boards, electronic parts, automobiles, etc. The parts inside the engine are stuck.

For hard coating materials for surface protection of automobile bodies, lamps or galvanized products, building materials, plastics, etc., for example, for automobile bodies, motorcycle bodies, lenses or lenses for headlights, plastic lenses for glasses, mobile phones, game Machine, optical film, ID card, etc.

Examples of the ink materials printed on metals such as aluminum and plastics, such as credit cards and membership cards, switches for electrochemical products or OA devices, inks for printing on keyboards, and inkjet printing for CDs and DVDs. Table machine ink.

Moreover, the curable composition of the present invention may be, for example, a technique in which a resin is cured in combination with a three-dimensional CAD to produce a complicated three-dimensional object, or a light-shaping, optical fiber coating, or adhesion which is suitable for model production of industrial products. , optical waveguide, film thickness resist (for MEMS).

Claims (14)

An epoxy compound represented by the following formula (1); [In the formula (1), A represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 at (n4), a cyclic hydrocarbon group having a carbon number of 4 to 20 at (n4), and a nitrogen-containing ring having a (n4) valence. a chain hydrocarbon group having a (n4) valence of 3 to 10 carbon atoms, or a group having a (n4) valence thereof, wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrocarbon group of (n3+1) valence, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2 to 5, n4 represents an integer of 2 to 8, and n5 represents an integer of 0 or 1, n6 Indicates an integer of 0 or 1.]. The epoxy compound according to claim 1, wherein the above formula (1) is represented by formula (1-1), formula (1-2), or formula (1-3); [In the formula (1-1) and the formula (1-3), the A system represents an unsaturated hydrocarbon group having a carbon atom number of 2 to 10 (n4) and a ring having a carbon number of 4 to 20 at a (n4) value. a hydrocarbon group, a (n4)-valent nitrogen-containing cyclic group, a (n4)-valent chain hydrocarbon group having a carbon number of 3 to 10, or a (n4)-valent group thereof, in the formula (1-2), A' The nitrogen-containing cyclic group of (n4) valence, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ represents a (n3+1)-valent hydrocarbon group, and n1 represents an integer of 2 , n2 represents an integer of 1, n3 represents an integer of 2 to 5, and n4 represents an integer of 2 to 8. The epoxy compound according to claim 1 or 2, wherein the A is an (n4)-valent unsaturated hydrocarbon group which removes (n4) hydrogen atoms from ethylene, propylene or norbornene. The epoxy compound according to claim 1 or 2, wherein the A is from cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl-substituted epoxycyclohexane, The (n4)-valent cyclic hydrocarbon group of (n4) hydrogen atoms is removed by cycloheptene, bicyclooctene, or adamantane. The epoxy compound according to claim 1 or 2, wherein the aforementioned A is a (n4)-valent nitrogen-containing cyclic group which removes (n4) hydrogen atoms from the trialkyl trimer isocyanate, and the aforementioned A' is a trimeric polymer. The (n4)-valent nitrogen-containing cyclic group of (n4) hydrogen atoms is removed by isocyanic acid, cyanuric acid, or caprolactone or barbiturate. Such as the epoxy compound of claim 1 or 2, wherein The above A is a (n4)-valent chain hydrocarbon group which removes (n4) hydrogen atoms from propane, butane, pentane or hexane. A curable composition comprising the epoxy compound and the curing agent according to any one of claims 1 to 6. The hardenable composition of claim 7, wherein the hardener is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polythiol. The curable composition according to claim 7 or 8, wherein the hardener is contained in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group of the epoxy compound. A curable composition comprising the epoxy compound and the acid generator according to any one of claims 1 to 6. The sclerosing composition of claim 10, wherein the acid generator is a photoacid generator or a thermal acid generator. The sclerosing composition of claim 11, wherein the acid generator is a cerium salt. The sclerosing composition of claim 11, wherein the acid generator is an onium salt compound or an iodonium salt compound. The curable composition according to any one of claims 10 to 13, wherein the acid generator is contained in a ratio of 0.1 to 20% by mass based on the mass of the epoxy compound.