KR20140031206A - Polyfunctional epoxy compound - Google Patents

Abstract

[PROBLEMS] To provide an epoxy resin composition having low viscosity and high cation curability as well as heat curability.
[Solution]
Formula (1): In formula (1), A is a (n4) valence C2-10 unsaturated hydrocarbon group, (n4) valence C4-20 cyclic hydrocarbon group, (n4) valent nitrogen-containing ring group, (n4) a C3-C10 linear hydrocarbon group or a combination (n4) -valent group which combined these, R <^1> and R <^2> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, and R ³ represents a (n3 + 1) valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2-5, n4 represents an integer of 2-8, n5 represents An integer of 0 or 1 is represented, n6 represents the integer of 0 or 1.] The epoxy compound represented by the following. Curable composition containing the said epoxy compound and an acid generator or hardening | curing agent. The acid generator is a photoacid generator or a thermal acid generator, and the curing agent is an acid anhydride or an amine.

Description

Polyfunctional epoxy compound {POLYFUNCTIONAL EPOXY COMPOUND}

The present invention relates to a light or heat curable epoxy resin composition. More specifically, light or heat curable epoxy resin compositions useful for obtaining cured products having excellent properties such as high adhesion to a substrate, high transparency (transparency to visible light), hard coatability, high heat resistance, and the like (for electronic materials and It relates to a resin composition for an optical material) and its cured product (composite cured product).

Conventionally, epoxy resins are widely used in the field of electronic materials as an epoxy resin composition combined with a curing agent. Among such electronic materials fields, for example, high refractive index layers of antireflection films (antireflection films for liquid crystal displays, etc.), optical thin films (reflective plates, etc.), encapsulants for electronic components, printed wiring boards, interlayer insulating film materials (build-up printed circuit boards) In the case of the application such as an interlayer insulating film material), the molding material is required to have high adhesion to a substrate, hard coat resistance, heat resistance, high transparency to visible light, and the like.

On the other hand, the epoxy resin composition which combined the epoxy compound, the light, and the heat-acid generator not only uses a solvent but can harden | cure an epoxy compound independently, and much examination is made in recent years. In particular, photocation curing by ultraviolet light is very excellent in that it does not require a large curing oven and has a small amount of energy input.

Although the alicyclic epoxy compound which has an epoxy group only in an alicyclic structure is widely used for the cation hardening using light, since the reactivity is high, since the structure is rigid, hardened | cured material tends to be hard and weak.

By the way, the lactone-modified polyfunctional alicyclic epoxy compound, the epoxy resin composition using this epoxy compound, and these manufacturing methods are proposed (refer patent document 1).

On the other hand, glycidyl ester-type epoxy compounds have low reactivity with an acid generator and take a long time to react, and thus have been generally considered unsuitable for cation curing.

As a polyfunctional epoxy compound which has glycidyl ester group, the epoxy resin composition using cyclobutane tetracarboxylic acid tetraglycidyl ester, cyclopentane tetracarboxylic acid tetraglycidyl ester, and cyclohexane tricarboxylic acid triglycidyl ester is mentioned. It is proposed (refer patent document 2, 3).

Moreover, carboxyl group-containing resin which uses the epoxy alkyl ester of cyclohexanedicarboxylic acid which has an epoxy group as a crosslinking | crosslinked compound is proposed (refer patent document 4).

Japanese Patent Application Laid-Open No. H04-069360 Japanese Patent Publication No. S50-010893 Japanese Patent Publication No. 2006-274190 United States Patent No.3565922

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the mother nucleus has various frame | skeleton, and the organic group used as the frame | skeleton has several side chains, and the side chain has a plurality of epoxy groups in a structure which has a plurality of said epoxy groups in 1 molecule. The polyfunctional epoxy compound which has had discovered that not only heat curability but also cation curability are provided.

Accordingly, the present invention is to provide a curable composition having a high cation curability as well as thermosetting in a liquid phase using the epoxy composition and the epoxy compound. The hardened | cured material obtained from this curable composition has high transparency and high heat resistance.

As a 1st viewpoint, this invention is following Formula (1):

[Chemical Formula 1]

[In formula (1), A is a (n4) valent unsaturated hydrocarbon group of 2-10 carbon atoms, (n4) valent C4-C20 cyclic hydrocarbon group, (n4) valent nitrogen-containing ring group, (n4) valent carbon source A linear hydrocarbon group of embroidery 3 to 10 or a (n4) valent group combining these, 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 (n 3+ 1) represents a hydrocarbon group, 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, n5 represents an integer of 0 or 1 And n6 represents an integer of 0 or 1.], an epoxy compound represented by

As a 2nd viewpoint, said Formula (1) is Formula (1-1), Formula (1-2), or Formula (1-3):

(2)

[In Formulas (1-1) and (1-3), A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms having a (n4) valency, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, and a (n4) valence A nitrogen-containing cyclic group, a (n4) valent carbon atom having 3 to 10 carbon atoms, or a (n4) valent group having a combination thereof represented, and in formula (1-2), A 'represents a (n4) valent 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, n1 represents an integer of 2, and n2 represents an integer of 1 , N3 represents an integer of 2 to 5, n4 represents an integer of 2 to 8. The epoxy compound according to the first aspect,

As the third aspect, the epoxy compound according to the first aspect or the second aspect, wherein A is an (n4) valent unsaturated hydrocarbon group obtained by removing (n4) hydrogen atoms from ethylene, propylene, or norbornene,

In a fourth aspect, the A removes (n 4) hydrogen atoms from cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane ( n4) The epoxy compound as described in a 1st viewpoint or a 2nd viewpoint which is a cyclic hydrocarbon group,

As a fifth aspect, A is a (n4) valent nitrogen-containing ring group obtained by removing (n4) hydrogen atoms from trialkylisocyanurate, and A 'isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid. The epoxy compound as described in a 1st viewpoint or the 2nd viewpoint which is a (n4) valent nitrogen-containing ring group which removed (n4) hydrogen atoms from the,

As the sixth aspect, the epoxy compound according to the first aspect or the second aspect, wherein A is a (n4) valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from propane, butane, pentane, or hexane,

As a seventh aspect, the curable composition containing the epoxy compound in any one of a 1st viewpoint thru | or a 6th viewpoint, and a hardening | curing agent,

As a 8th viewpoint, the curable composition as described in a 7th viewpoint that the said hardening | curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, or a polymercaptan,

As a 9th viewpoint, the curable composition as described in a 7th viewpoint or 8th viewpoint which contains the said hardening | curing agent in the ratio of 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups of the said epoxy compound,

As a tenth aspect, the curable composition containing the epoxy compound in any one of a 1st viewpoint thru | or a 6th viewpoint, and an acid generator,

As a 11th viewpoint, the curable composition as described in a 10th viewpoint that the said acid generator is a photo-acid generator or a thermal acid generator,

As a twelfth aspect, the curable composition according to the eleventh aspect, wherein the acid generator is an onium salt,

As a thirteenth aspect, the curable composition according to the eleventh aspect, wherein the acid generator is a sulfonium salt compound or an iodonium salt compound,

As a 14th viewpoint, it is the curable composition in any one of 10th-13th viewpoint which contains the said acid generator in the ratio of 0.1-20 mass% with respect to the mass of the said epoxy compound.

As the epoxy compound having a plurality of epoxy rings bonded to an organic group that is a skeleton via a hydrocarbon group, the longer the hydrocarbon group, the higher the oil-induced degree of the epoxy ring and the higher the reactivity, the more all the epoxy groups are involved in the reaction, and the plurality of epoxy By having a ring, cation curability becomes high.

In addition, when the curable composition containing at least the epoxy compound and the photoacid generator is photocured, it is expected to form a cured product or a cured coating film that can be compatible with excellent mechanical properties and excellent optical properties. In particular, the longer the hydrocarbon group, the higher the toughness of the cured product and the cured coating film is expected to be.

In the epoxy compound of the present invention devised from this viewpoint, the parent nucleus has various skeletons, and the organic group serving as the skeleton has a plurality of side chains, and the side chains have a plurality of epoxy groups via a hydrocarbon group. By having two or more in a molecule | numerator, the characteristic effect which has not only thermosetting but also cation curing is exhibited.

The curable composition of this invention can further contain the epoxy compound represented by said Formula (1), a hardening | curing agent (for example, an amine or an acid anhydride), and in some cases, a hardening adjuvant.

In the present invention, the epoxy compound represented by the formula (1) is intended to be photocured or thermoset using a photoacid generator or a thermal acid generator. Therefore, by using a photoacid generator or a thermal acid generator, even if it does not use the hardening agent (for example, an amine or an acid anhydride) of the epoxy normally used, or even if they are used, since these content is extremely low, since The storage stability of the curable composition is good.

Since the curable composition of this invention is hardened by photocuring by UV irradiation, it is applicable to the material (base material) which is weak to heat.

In addition, since the epoxy compound used in the present invention is a liquid phase, the curable composition of the present invention using the same has good filling properties.

Furthermore, since the curable composition containing the epoxy compound of this invention has characteristics, such as low viscosity and quick-drying, it can be used for coating | covering and bonding an electronic component, an optical component, and a precision instrument component.

This invention is an epoxy compound represented by said Formula (1). In formula (1), A is an unsaturated hydrocarbon group having 2 to 10 carbon atoms having a (n4) valence, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, a nitrogen-containing ring group having a (n4) valence, and a (n4) valence carbon source Embroidery 3-10 represents a linear hydrocarbon group or a (n4) valent group which combined these, R <^1> and R <^2> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, and R <^3> (n3 + 1) represents a hydrocarbon group, 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, n5 represents an integer of 0 or 1 N6 represents the integer of 0 or 1.

Formula (1) contains the epoxy compound represented by said Formula (1-1), Formula (1-2), or Formula (1-3). In formulas (1-1) and (1-3), A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms having a (n4) valence, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, and a nitrogen having a (n4) valence A containing hydrocarbon group, a (n4) valent C3-C10 linear hydrocarbon group, or a combination of these (n4) valent groups, wherein in formula (1-2), A 'represents a (n4) valent 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, n1 represents an integer of 2, and n2 represents an integer of 1 N3 represents the integer of 2-5, n4 represents the integer of 2-8.

In the formulas (1), (1-1) and (1-3), when A is a (n4) valent unsaturated hydrocarbon group, A is, for example, (n4) from ethylene, propylene or norbornene. (N4) valent unsaturated hydrocarbon group which removed the hydrogen atom is mentioned.

In the formulas (1), (1-1) and (1-3), when A is a (n4) valent cyclic hydrocarbon group, as A, for example, cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane And (n4) valent cyclic hydrocarbon groups obtained by removing (n4) hydrogen atoms from alkyl substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane.

In formulas (1), (1-1), (1-2) and (1-3), when A and A 'are (n4) valent nitrogen-containing ring groups, as A, for example, The (n4) valent nitrogen-containing ring group from which (n4) hydrogen atoms have been removed from alkyl isocyanurate is, for example, A ', for example, isocyanuric acid, cyanuric acid, hydantoin, or (n4) from barbituric acid. And a (n4) valent nitrogen-containing cyclic group from which a hydrogen atom is removed.

In the formulas (1), (1-1) and (1-3), when A is a (n4) valent chain hydrocarbon group, as A, for example, from propane, butane, pentane, or hexane to (n4) And (n4) valent chain hydrocarbon groups obtained by removing two hydrogen atoms.

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

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and cyclobutyl Group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2-methyl-2-ethyl-n-propyl group, 2-methyl-2-methyl-n-propyl group, 2, 2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2- Dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl- n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl -n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3 -Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl Group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3- Methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl- Cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl Flag And 2-ethyl-3-methyl-cyclopropyl group.

R ³ represents a (n3 + 1) valent hydrocarbon group, and examples of the hydrocarbon group include a (n3 + 1) valent hydrocarbon group obtained by removing (n3 + 1) hydrogen atoms from the alkyl group.

As B substituted by the said mother-nucleus, the alkylester group, alkyl group, and alkyloxy group which have an epoxy group illustrated below are mentioned. In the following, A represents the mother nucleus.

(3)

[N5 represents the integer of 0 or 1, and n6 represents the integer of 0 or 1 in Formula (2-1)-(2-4).]

In addition, A and A 'which become a mother nucleus can be illustrated as follows. In the following, B represents the above-mentioned polyfunctional epoxy group.

When A represents an unsaturated hydrocarbon group of 2 to 10 carbon atoms having a (n4) valence, it can be exemplified as A as follows.

[Chemical Formula 4]

When A represents a cyclic hydrocarbon group of 4 to 20 carbon atoms having a (n4) valence, it can be exemplified as A as follows.

[Chemical Formula 5]

When A and A 'represent a (n4) valence nitrogen containing ring group, A and A' can be illustrated as follows.

[Chemical Formula 6]

[(In formula (5-1), R represents a hydrogen atom or a C1-C10 alkyl group.]

When A represents a linear hydrocarbon group of 3 to 10 carbon atoms having a (n4) valence, it can be exemplified as A as follows.

[Formula 7]

The compound represented by Formula (1) of this invention is comprised by the combination of the said mother core A and the said substituent B.

The epoxy compound represented by the said Formula (1-1) has a unsaturated bond obtained by making carboxylic acid derivatives, such as carboxylic acid or carboxylic anhydride, which have the structure of said A react, and an alkenol, for example. It can manufacture by making a compound (intermediate) react with a peroxide. In addition, since the intermediate can be produced by any method irrespective of the reaction of carboxylic acid or carboxylic anhydride with alkenol, the intermediate having the unsaturated bond is reacted with a peroxide, and is represented by Formula (1-1). Epoxy compounds can be prepared.

The alkenol corresponding to B (alkyl ester group which has a polyfunctional epoxy group) substituted by the said mother-nucleus A is illustrated below.

[Formula 8]

Carbonic acid or carboxylic anhydride which has a structure of mother-nucleus A is illustrated below.

As carboxylic acid or carboxylic anhydride which A represents a (n4) valent unsaturated hydrocarbon group of 2-10 carbon atoms, it can illustrate as follows.

[Chemical Formula 9]

Examples of the carboxylic acid or carboxylic anhydride in which A represents a (n4) valent hydrocarbon group having 4 to 20 carbon atoms can be exemplified as follows.

[Formula 10]

Examples of the carboxylic acid in which A represents a (n4) valent nitrogen-containing cyclic group include triscarboxyalkyl isocyanurate (wherein the alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms). It is illustrated below.

(11)

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

Examples of the carboxylic acid or carboxylic anhydride in which A represents a (n4) valent linear hydrocarbon group having 3 to 10 carbon atoms can be exemplified as follows.

[Chemical Formula 12]

The compound (intermediate) which has the unsaturated bond obtained by making carboxylic acid or carboxylic anhydride which has the structure of said A react with alkenol can be illustrated by Formula (1-1-1).

[Chemical Formula 13]

[In Formula (1-1-1), A is an unsaturated hydrocarbon group of 2 to 10 carbon atoms having a (n4) valence, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, a nitrogen-containing ring group having a (n4) valence, ( n4) a C3-C10 chain hydrocarbon group or (n4) -valent group which combined these, R <^1> and R <^2> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, and R <^3> Represents a (n3 + 1) valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2-5, n4 represents an integer of 2-8.]

That is, the epoxy compound represented by Formula (1-1) used for this invention uses the epoxy compound represented by Formula (1-1) which consists of a combination of Formula (4-3) and Formula (2-1) as an example. If so, it can be obtained by the following method.

[Formula 14]

The carboxylic anhydride and the alkenol are reacted to synthesize an intermediate (olefin). This reaction is performed for 0 to 100 hours at room temperature (for example, 20 degreeC)-110 degreeC using catalysts, such as paratoluenesulfonic acid and sulfuric acid, in solvents, such as toluene. And an epoxy compound can be obtained by oxidizing this unsaturated compound with a peroxide. As the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be performed at 0-60 degreeC and 1-200 hours in solvents, such as chloroform. The reaction can be carried out by using a dicarboxylic acid compound as a raw material instead of an acid anhydride. In addition, in the case of carboxylic acid which is difficult to dissolve in a solvent such as toluene, a method of esterifying with an alcohol such as methanol and subsequently performing a transesterification reaction with an alkenol or carboxylic acid and alkenol such as carbodiimide The intermediate (olefin) can also be synthesized by a method of reacting with a condensing agent or a method of converting carboxylic acid to acid chloride with thionyl chloride or the like and reacting with alkenol.

The epoxy compound represented by the above formula (1-2) reacts a nitrogen-containing ring compound having a structure of A '(this compound has an NH group) with an alkenol or allyl halide having a leaving group, and the resulting unsaturated bond It can be manufactured by reacting a compound (intermediate) having a peroxide with a peroxide.

In addition, the epoxy compound represented by said formula (1-2) makes the nitrogen compound (this compound has NH group) which has A 'structure, the epoxy compound which has an unsaturated bond react, and the obtained alcohol compound It can also be prepared by reacting an alkenol or an allyl halide having a leaving group with a compound, an intermediate having an unsaturated bond, and a peroxide.

As alkenol or allyl halide which has a leaving group corresponding to B substituted by mother-nucleus A ', it is the said Formula (2-1-1), a formula (2-2-1), a formula (2-3-1), for example. Methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acetic anhydride, trifluoro anhydrous acetic acid, and oxy The following formula (2-1-2), formula (2-2-2), formula (2-) obtained by reacting phosphorus chloride, phosphorus oxybromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like The compound represented by 3-2) and Formula (2-4-2) can be used.

[Chemical Formula 15]

[(In formula (2-1-2), formula (2-2-2), formula (2-3-2), and formula (2-4-2), X is a methanesulfonyloxy group and a trifluoromethane. Sulfonyloxy group, toluenesulfonyloxy group, nitrobenzenesulfonyloxy group, acetyloxy group, trifluoroacetyloxy group, chlorine atom, bromine atom or iodine atom.]

As a nitrogen-containing ring compound (this compound has NH group) which has a structure of mother-nucleus A ', it can illustrate as follows.

[Chemical Formula 16]

A nitrogen-containing ring compound having an A 'structure (this compound has an NH group), and a compound (intermediate) having an unsaturated bond obtained by reacting an alkenol or allyl halide having a leaving group are represented by the formula (1-2-1) It can be illustrated to.

[Chemical Formula 17]

[(In formula (1-2-1), A 'represents a (n4) valent nitrogen-containing ring group. R <^1> and R <^2> respectively independently represents a hydrogen atom or an alkyl group of 1-10 carbon atoms, and R is ³ represents a (n3 + 1) valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2-5, n4 represents an integer of 2-8.]

That is, the epoxy compound represented by Formula (1-2) used for this invention uses the epoxy compound represented by Formula (1-2) which consists of a combination of Formula (5-6) and Formula (2-1) as an example. If so, it can be obtained by the following method.

[Chemical Formula 18]

A nitrogen-containing ring compound (this compound has an NH group) and an alkenol having a leaving group are reacted to synthesize an intermediate (olefin). This reaction is carried out in a solvent such as DMF, using a base such as sodium hydride, potassium carbonate, t-butoxy potassium, triethylamine, or the like at room temperature (for example, 20 ° C.) to the boiling point temperature of the solvent for 0 to 100 hours. Is done. And an epoxy compound can be obtained by oxidizing this unsaturated compound with a peroxide. As the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be performed at 0-60 degreeC and 1-200 hours in solvents, such as chloroform.

Furthermore, the epoxy compound represented by the said Formula (1-3) is a compound (intermediate) which has an unsaturated bond obtained by making the alcohol which has the structure of said A, the alkenol and allyl halide which have a leaving group react, for example; The peroxide can be reacted to produce it.

As alkenol or allyl halide which has a leaving group corresponding to B substituted by mother-nucleus A, for example, said Formula (2-1-1), Formula (2-2-1), Formula (2-3-1) And methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide, acetyl halide, acetic anhydride, trifluoro anhydrous acetic acid, and oxychloride in the compound represented by (2-4-1). Formula (2-1-2), formula (2-2-2), formula (2-3) obtained by reacting phosphorus, phosphorus oxybromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like -2) and the compound represented by formula (2-4-2) can be used.

The alcohol which has a structure of mother-nucleus A is illustrated below.

Examples of the alcohol in which A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms having a (n4) valence can be exemplified as follows.

[Chemical Formula 19]

Examples of the alcohol in which A represents a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence can be exemplified as follows.

[Chemical Formula 20]

Examples of alcohols in which A represents a (n4) valent nitrogen-containing ring group can be exemplified as follows.

[Chemical Formula 21]

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

Examples of the alcohol in which A represents a chain hydrocarbon group having 3 to 10 carbon atoms having a (n4) valence can be exemplified as follows.

[Chemical Formula 22]

The compound (intermediate) which has an unsaturated bond obtained by making the alcohol which has the structure of said A, and the alkenol and allyl halide which have a leaving group react is illustrated in Formula (1-3-1).

(23)

[In Formula (1-3-1), A is an unsaturated hydrocarbon group of 2 to 10 carbon atoms having a (n4) valence, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, a nitrogen-containing ring group having a (n4) valence, ( n4) a C3-C10 chain hydrocarbon group or (n4) -valent group which combined these, R <^1> and R <^2> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, and R <^3> Represents a (n3 + 1) valent hydrocarbon group, n1 represents an integer of 2, n2 represents an integer of 1, n3 represents an integer of 2-5, n4 represents an integer of 2-8.]

That is, the epoxy compound represented by Formula (1-3) used for this invention uses the epoxy compound represented by Formula (1-3) which consists of a combination of Formula (4-4) and Formula (2-1) as an example. If so, it can be obtained by the following method.

&Lt; EMI ID =

An alcohol (alkenol) having a leaving group is reacted to synthesize an intermediate (olefin). This reaction is carried out at a room temperature (for example, 20 ° C.) to a boiling point temperature of a solvent using a base such as sodium hydroxide, potassium carbonate, t-butoxy potassium or triethylamine in a solvent such as ether or amide. For 100 hours. And an epoxy compound can be obtained by oxidizing this unsaturated compound with a peroxide. As the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid and the like can be used. This reaction can be performed at 0-60 degreeC and 1-200 hours in solvents, such as chloroform.

Examples of the epoxy compound represented by the formula (1-3) include cyanuric chloride, formula (2-1-1), formula (2-2-1), formula (2-3-1), and The compound (intermediate) having an unsaturated bond obtained by reacting allyl alcohol represented by formula (2-4-1) or the like and a peroxide may be produced by reacting as described above.

(25)

Moreover, this invention is the curable composition containing the epoxy compound represented by said formula (1), and a hardening | curing agent.

Furthermore, this invention is a curable composition containing the epoxy compound represented by said formula (1), and an acid generator.

The curable composition of this invention can contain a solvent, another epoxy compound, a hardening | curing agent, surfactant, an adhesion promoter, etc. further as needed.

The ratio of solid content in the curable composition of this invention can be 1-100 mass%, or 5-100 mass%, or 50-100 mass%, or 80-100 mass%.

Solid content is the ratio of the remaining component which removed the solvent from the curable composition. In this invention, since a liquid epoxy compound is used and a hardening | curing agent or an acid generator is mixed here, it is not necessary to use a solvent fundamentally, but it is possible to add a solvent as needed. For example, the acid generator is a solid, and the acid generator can be dissolved in a solvent such as propylene carbonate and mixed with a liquid epoxy compound to produce a curable compound. Moreover, also when dissolving an acid generator in a liquid epoxy compound, a general solvent can be added for viscosity adjustment of the curable composition obtained.

Content of the epoxy compound represented by said formula (1) in the curable composition of this invention is 8-99.9 mass%, Preferably 40-99 mass%, More preferably, based on content of solid content of the said curable composition. Preferably it is 70-99 mass%.

Moreover, content of the acid generator in the curable composition of this invention can be 0.1-20 mass% or 0.1-10 mass% based on content of solid content of the said curable composition.

The curable composition of this invention can contain an acid generator in the ratio of 0.1-20 mass% or 0.1-10 mass% with respect to the mass of the epoxy compound represented by said Formula (1).

In this invention, the epoxy compound represented by said formula (1) and an epoxy compound other than that can be used together. The epoxy compound represented by said formula (1) and an epoxy compound other than that can be used in the range of 1: 0.1-1: 10 by molar ratio of an epoxy group.

As epoxy compounds other than the epoxy compound represented by said formula (1), it can illustrate as follows.

Solid epoxy compound, Tris- (2, 3- epoxypropyl)-isocyanurate (formula (7-1), brand name TEPIC, Nissan Chemical Industries, Ltd. make).

(26)

Liquid epoxy compound, brand name EPIKOTE 828 (formula (7-2), the product made by Japan Epoxy Resins Co., Ltd.).

(27)

Liquid epoxy compound, brand name YX8000 (formula (7-3), the Japan Epoxy Resins Co., Ltd. product).

(28)

Liquid epoxy compound, brand name DME100 (formula (7-4), New Japan Chemical Co., Ltd. product).

[Chemical Formula 29]

Liquid epoxy compound, brand name CE-2021P (formula (7-5), Daicel Corporation make).

(30)

In the present invention, the following tris- (3,4-epoxybutyl) -isocyanurate (formula (7-6)) and tris- (4,5-epoxypentyl) -isocysis are liquid phase compounds. Anurate (formula (7-7)), tris- (5,6-epoxyhexyl) -isocyanurate (formula (7-8)), tris (glycidyloxyethyl) isocyanurate (formula ( 7-9)).

(31)

Liquid epoxy compound modified by adding 0.8 mol of propionic anhydride to 1 mol of tris- (2,3-epoxypropyl) -isocyanurate (formula (7-10), manufactured by Nissan Chemical Industries, Ltd., trade name: TEPIC- PAS B22). In formula (7-10), (7-10-1) :( 7-10-2) :( 7-10-3) :( 7-10-4) is a molar ratio of about 35%: 45%: 17 It is contained in%: 3% ratio.

(32)

Liquid epoxy compound modified by adding 0.4 mol of propionic anhydride to 1 mol of tris- (2,3-epoxypropyl) -isocyanurate (Formula (7-11), manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC-PAS) B26). Formula (7-11) contains (7-11-1) :( 7-11-2) :( 7-11-3) in a molar ratio of about 60%: 32%: 8%.

(33)

In this invention, a vinyl ether compound, an oxetane compound, etc. can be used as a cation curable monomer other than an epoxy compound.

The vinyl group-containing compound (vinyl ether compound, etc.) is not particularly limited as long as it is a compound having a vinyl group. For example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxy Oxybutyl vinyl ether (HBVE) and triethylene glycol divinyl ether. Moreover, the vinyl compound which has substituents, such as an alkyl group and an allyl group, in the (alpha) and / or (beta) position can also be used. Moreover, the vinyl ether compound containing cyclic ether groups, such as an epoxy group and / or an oxetane group, can be used, For example, oxynorbornene divinyl ether and 3, 3- dimethanol oxetane divinyl ether are mentioned. Moreover, the hybrid compound which has a vinyl group and a (meth) acryl group can be used, For example, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl (VEEA, VEEM) etc. are mentioned. These can be used individually or in combination of 2 or more types.

The oxetanyl group-containing compound (oxetane compound) is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3- (phenoxymethyl) oxetane (POX) and di [1-ethyl (3-ox) Cetanyl)] methyl ether (DOX), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl } Oxetane (TESOX), oxetanyl silsesquioxane (OX-SQ), phenol novolak oxetane (PNOX-1009), etc. are mentioned. In addition, a hybrid compound (1-ethyl-3-oxetanylmethyl (meth) acrylate) having an oxetanyl group and a (meth) acryl group can be used. These oxetane type compounds can be used individually or in combination of 2 or more types.

In this invention, the curable composition containing the epoxy compound represented by said formula (1), and a hardening | curing agent can be obtained.

As a hardening | curing agent, an acid anhydride, an amine, a phenol resin, a polyamide resin, imidazole, or a polymer captan can be used. Among these, especially acid anhydride and an amine are preferable. Even if it is a solid, these hardening | curing agents can melt | dissolve in a solvent and can be used. However, since the intensity | strength fall and water resistance fall by the density | concentration fall of hardened | cured material and generation | occurrence | production of pores by evaporation of a solvent, it is preferable that hardening | curing agent itself is a liquid at normal temperature and normal pressure.

A hardening | curing agent can contain 0.5-1.5 equivalent, Preferably it is 0.8-1.2 equivalent with respect to 1 equivalent of epoxy groups of an epoxy compound. The equivalent of the curing agent relative to the epoxy compound is represented by the equivalent ratio of the curing group of the curing agent to the epoxy group.

As a phenol resin, a phenol novolak resin, a cresol novolak resin, etc. are mentioned, for example.

As the amine, for example, piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, isophoronediamine, Diaminodicyclohexyl methane, 1,3-diaminomethylcyclohexane, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mensendiamine, Isophorone diamine, diamino dicyclohexyl methane, etc. can be used preferably.

Polyamide resin is produced | generated by condensation of dimer acid and a polyamine, and is a polyamide amine which has a primary amine and a secondary amine in a molecule | numerator.

As imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2- undecyl imidazolium trimellitate, an epoxy imidazole adduct, etc. Can be mentioned.

For example, a mercaptan group exists in the terminal of a polypropylene glycol chain, or a mercaptan group exists in the terminal of a polyethylene glycol chain, and it is preferable that it is liquid.

As the acid anhydride, anhydrides of compounds having a plurality of carboxyl groups in one molecule are preferable. As these acid anhydrides, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetra Hydrophthalic anhydride, endo methylene tetrahydro phthalic anhydride, methyl endo methylene tetrahydro phthalic anhydride, methyl butenyl tetrahydro phthalic anhydride, dodecenyl anhydrous succinic acid, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, succinic anhydride, methylcyclohexene dicaca Carboxylic acid anhydride, chloric acid anhydride, and the like.

Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methylnadic acid anhydride, methylhybic anhydride), liquid hydride methylnadic acid anhydride, and methyl butenyl at room temperature and atmospheric pressure Tetrahydrophthalic anhydride, dodecenyl anhydrous succinic acid, methylhexahydrophthalic anhydride, a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride is preferred. These liquid acid anhydrides have a viscosity of about 10 mPas to 1000 mPas when measured at 25 ° C. In acid anhydride groups, one acid anhydride group is calculated as one equivalent.

Moreover, when obtaining hardened | cured material from the curable composition of this invention, a hardening adjuvant may be used together suitably.

Examples of the curing aid include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, tetrabutylphosphonium dithiophosphate and 1,8-diazabi Cyclo [5,4,0] undecane-7-ene, 1,8-diazabicyclo [5,4,0] undecane-7-ene and salts of octylic acid, zinc octylate, tetrabutylammonium bromide and the like And quaternary ammonium salts. These hardening aids can be used in the ratio of 0.001-0.1 mass part with respect to 1 mass part of hardening agents.

In this invention, a curable composition is obtained by mixing the epoxy compound represented by said Formula (1), the said hardening | curing agent, and a hardening adjuvant as needed. These mixing is not particularly limited as long as it can be mixed uniformly, but can be performed using, for example, a reaction flask, a stirring blade or a mixer.

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

The obtained curable composition has a suitable viscosity for use as a liquid sealing material. Since the curable composition of this invention can be adjusted to arbitrary viscosity, and is used for transparent sealing materials, such as LED by the casting method, the potting method, the dispenser method, the printing method, etc., partial sealing is possible at the arbitrary places. The curable composition is directly mounted on an LED or the like in a liquid state by the above-described method, and then dried and cured to obtain an epoxy resin cured product.

The hardened | cured material obtained from a curable composition is obtained by apply | coating the said curable composition to a base material, or inject | pouring into the mold plate which apply | coated the mold release agent, precuring at the temperature of 100-120 degreeC, and obtaining it by postcure at the temperature of 120-200 degreeC. Lose.

Heating time is 1 to 12 hours, Preferably it is about 2 to 5 hours.

The thickness of the coating film obtained from the curable composition of this invention can be selected in the range of 0.01 micrometer-about 10 mm according to the use of hardened | cured material.

The said curable composition can contain a solvent as needed.

Examples of the solvent include ethylene glycol alkyl ethers such as ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. Diethylene glycols such as acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol Propylene glycol monoalkyl ethers such as 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, and propylene glycol butyl ether acetate Propylene glycol alkyl ether acetates, toluene and xyl, such as len glycol alkyl ether acetates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate Aromatic hydrocarbons such as ethylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, and methyl acetate, ethyl acetate, propyl acetate, butyl acetate and 2-hydroxypropionic acid Ethyl, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate Methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropion Acid propyl, 3-hydroxy butyl propionate, 2-hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate, ethoxy acetic acid Ethyl, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butoxy acetate Butyl, 2-methoxy methyl propionate, 2-methoxy ethylpropionate, 2-methoxy propylpropionate, 2-methoxy propylpropionate, 2-ethoxy propylpropionate, 2-ethoxy propylpropionate, 2-ethoxy propylpropionate Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-Ethoxypropionate, 3-propoxy propionate, 3-propoxypropionate, 3-propoxypropionate, 3-propoxypropionate, 3-butoxypropionate, methyl 3-butoxypropionate, 3 And esters such as propyl butoxypropionate and butyl 3-butoxypropionate.

In this invention, the curable composition containing the epoxy compound represented by said 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 generates acid directly or indirectly by light irradiation or heating.

Specific examples of the photoacid generator include onium salts such as triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, iodonium salts, sulfonium salts, phosphonium salts and selenium salts, and metals. Rosene complex, iron arene complex, etc. are mentioned.

The onium salt used as the photoacid generator is, for example, diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodide. Nium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, Bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p- tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluorobolay It can be given. Furthermore, bis (alkylphenyl) iodonium salts, such as bis (4-t- butylphenyl) iodonium hexafluoro phosphate, and alkoxycarbonyl alkoxy- trialkyl aryl iodonium salts (for example, 4-[(1-ethoxycarba) Bonyl-ethoxy) phenyl]-(2,4,6-trimethylphenyl) -iodonium hexafluorophosphate, etc., bis (alkoxyaryl) iodonium salt (for example, (4-methoxyphenyl) phenyl iodonium And bis (alkoxyphenyl) iodonium salts such as hexafluoroantimonate).

Examples of the sulfonium salt include triphenylsulfonium chloride, triphenylsulfonium bromide, tri (p-methoxyphenyl) sulfoniumtetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, Triphenylsulfonium salts such as tri (p-ethoxyphenyl) sulfoniumtetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, and ( 4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide-bis- Sulfo, such as hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl) diphenylsulfonium hexafluoroantimonate) A tan salt is mentioned.

Examples of the phosphonium salt include triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, and tri (p-methoxyphenyl) phosphonium hexafluorophosphonate And phosphonium salts such as tri (p-ethoxyphenyl) phosphoniumtetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate and benzyltriphenylphosphonium hexafluoroantimonate.

As said selenium salt, selenium salts, such as a triphenyl selenium hexafluoro phosphate, are also (eta5 or (eta) 6-isopropylbenzene) ((eta5-cyclopentadienyl) iron (II) hexa as a said metallocene complex. Metallocene complexes, such as a fluorophosphate, are mentioned.

In addition, the following compounds can also be used as a photo-acid generator.

(34)

(35)

(36)

[Formula 37]

(38)

[Chemical Formula 39]

(40)

(41)

(42)

As a photo-acid generator, a sulfonium salt compound and an iodonium salt compound are preferable. These anion species ^{_{include, CF 3 SO 3 -, C}} 4 F 9 SO 3 -, C 8 F 17 SO 3 -, camphor-sulfonic acid anion, tosyl acid anion, BF ₄ ^-, PF ₆ ^-, AsF ₆ ^- and SbF ₆ ^- and the like. In particular, anionic species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are preferable.

And as a photo-acid generator, the said Formula (8-1), (8-2), (8-3), (8-8), (8-9), and (8-10) are preferable, for example. Especially, formula (8-1) and (8-2) are preferable.

These photoacid generators can be used individually or in combination of 2 or more types.

Examples of the thermal acid generator include sulfonium salts and phosphonium salts, and sulfonium salts are preferably used.

In addition, the following compounds can be illustrated as a thermal acid generator.

(43)

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

These thermal acid generators can be used individually or in combination of 2 or more types.

The said composition may contain the usual additive as needed. Such additives include, for example, pigments, colorants, thickeners, sensitizers, antifoams, leveling agents, applicability improving agents, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, Fillers, antistatic agents, curing agents and the like. These additives may be used alone or in combination of two or more.

In this invention, the curable composition containing the epoxy compound represented by said Formula (1) and a photo-acid generator can be apply | coated on a board | substrate, and it can harden | cure by light irradiation. It may also be heated before or after light irradiation.

Moreover, in this invention, the curable composition containing the epoxy compound represented by said Formula (1) and a thermal acid generator can be apply | coated on a board | substrate, and it can harden | cure by heating.

Furthermore, the curable composition containing the epoxy compound represented by said Formula (1), a thermal acid generator, and a photo-acid generator can be apply | coated on a board | substrate, and it can harden | cure by light irradiation after heating.

The curable composition may include a solvent. The solvent can use the above-mentioned solvent.

As a method of applying the curable composition of the present invention to a substrate, for example, a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, and gravure A coating method, a dipping method, a slit method, etc. are mentioned.

The thickness of the coating film formed from the curable composition of this invention can be selected in the range of about 0.01 micrometer-about 10 mm according to the use of hardened | cured material, For example, when using it as a photoresist, it is 0.05-10 micrometers (especially 0.1- 5 μm), and when used as a printed wiring board, it may be about 10 μm to 5 mm (particularly 100 μm to 1 mm), and when used as an optical thin film, 0.1 to 100 μm (particularly 0.3 to 50 μm) I can do that.

As light to irradiate or expose when a photo-acid generator is used, gamma ray, an X-ray, an ultraviolet-ray, a visible ray, etc. are mentioned, for example, Visible light or an ultraviolet-ray, especially ultraviolet-ray are used in many cases.

The wavelength of light is 150-800 nm, for example, Preferably it is 150-600 nm, More preferably, it is 200-400 nm, Especially about 300-400 nm.

The amount of irradiation light depends on the thickness of the coating film, and can be, for example, about 2 to 20000 mJ / cm 2, preferably about 5 to 5000 mJ / cm 2.

The light source can be selected according to the type of light to be exposed. For example, in the case of ultraviolet light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a deuterium lamp, a halogen lamp, and a laser light (helium-cadmium laser, excimer) Laser, etc.) etc. can be used. By such light irradiation, the curing reaction of the composition proceeds.

In the case of using a thermal acid generator or heating the coating film as necessary after light irradiation using a photoacid generator, the heating is performed at, for example, room temperature to about 250 ° C. Heating time can be selected in the range of 3 second or more (for example, about 3 second-about 5 hours), for example, about 5 second-about 2 hours.

And when forming a pattern or an image (for example, when manufacturing a printed wiring board etc.), the coating film formed on the base material can also be pattern-exposed. This pattern exposure may be performed by scanning of laser light, or may be performed by irradiating light through a photomask. A pattern or an image can be formed by developing (or dissolving) the non-irradiation area | region (unexposed part) produced | generated by such pattern exposure with the developing solution.

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

As aqueous alkali solution, aqueous solution of alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, aqueous solution of quaternary ammonium hydroxides, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, ethanolamine, propylamine, ethylene Amine aqueous solution, such as diamine, is mentioned.

It is common that the said alkaline developing solution is 10 mass% or less aqueous solution, Preferably 0.1-3.0 mass% aqueous solution etc. are used. And although alcohol and surfactant can also be added and used for the said developing solution, these addition amounts are respectively 0.05-10 mass parts with respect to 100 mass parts of developing solutions. In this, 0.1-2.38 mass% tetramethylammonium hydroxide aqueous solution can be used.

Moreover, although the organic solvent as a developing solution can use a general organic solvent, For example, acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, 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, etc. are mentioned. These can be used individually or as a mixture of 2 or more types. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. can be used preferably.

Surfactant can also be added to the curable composition of this invention for the purpose of improving applicability | paintability. Such surfactants include, but are not limited to, fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like. The said surfactant can be used individually or in combination of 2 or more types.

Among these surfactants, fluorine-based surfactants are preferable because of their high applicability improving effect. As a specific example of a fluorine-type surfactant, brand name: EFTOP [trademark] EF301, EF303, EF352 (made by Mitsubishi Materials Electronic Chemicals Co., Ltd. (Tochem Products Co., Ltd.)), brand name: MEGAFAC [registered trademark] F171, F173, R-30, R-08, R-90, BL-20, F-482 (manufactured by DIC Corporation (Dainippon Ink and Chemicals, Inc.)), trade name: FLUORAD FC430, FC431 (manufactured by Sumitomo 3M Ltd.) ), Trade name: ASAHI GUARD [registered trademark] AG710, SURFLON [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like, and the like. It is not limited.

The addition amount of surfactant in the curable composition of this invention is 0.0008-4.5 mass%, Preferably it is 0.0008-2.7 mass%, More preferably, it is 0.0008-1.8 mass% based on content of solid content of the said curable composition. .

An adhesion promoter can be added to the curable composition of this invention for the purpose of improving adhesiveness with the board | substrate after image development. These adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane and dimethylvinyl. Alkoxysilanes such as oxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole Silazanes, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Silanes such as (N-piperidinyl) propyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mer Captobenzoxazole, right Heterocyclic compounds, such as a azole, a thiouracil, a mercaptoimidazole, and a mercapto pyrimidine, urea, such as 1, 1- dimethyl urea and a 1, 3- dimethyl urea, or a thiourea compound is mentioned. The adhesion promoter can be used alone or in combination of two or more kinds.

The addition amount of the adhesion promoter in the curable composition of this invention is 18 mass% or less normally, based on content of solid content of the said curable composition, Preferably it is 0.0008-9 mass%, More preferably, it is 0.04-9 mass%. .

The curable composition of this invention may contain the sensitizer. Examples of the sensitizer that can be used include anthracene, phenothiazine, perylene, thioxanthone and benzophenone thioxanthone. Examples of the sensitizing dye include thiopyryllium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, and cyanine dyes. A dye, a rhodamine type pigment, a pyryllium salt type pigment, etc. can be illustrated. Particularly preferred is an anthracene-based sensitizer, and in combination with a cationic curing catalyst (sensitizing cationic polymerization initiator), the sensitivity is dramatically improved and also has a radical polymerization initiation function. In the hybrid type that uses, the catalyst species can be simplified. As a specific compound of anthracene, dibutoxy anthracene, dipropoxy cyanquinone, etc. are effective.

The addition amount of the sensitizer in the curable composition of this invention is 0.01-20 mass% based on content of solid content of the said curable composition, Preferably it is 0.01-10 mass%.

Example

For each measurement, the following instruments were used, respectively.

NMR: FT-NMR (ECX300) manufactured by JEOL Ltd.

LC-MS: Liquid Chromatograph Mass Spectrometer (Alliance-ZQ-LC-MS)

Gc-ms: gas chromatograph mass spectrometer (gc-ms qp5050a) made by shimadzu corporation

TOF-MS (MALDI): MALDI-TOF mass spectrometer (autoflexIII) manufactured by Bruker Daltonics Inc.

Viscosity measurement: Type E viscometer (VISCONIC ED type) made by Tokimec Inc.

Transmittance measurement: ultraviolet, visible, near-infrared spectrophotometer (UV-3600) made by Shimadzu Corporation

Bending test: precision universal testing machine (AGS-X series) made by Shimadzu Corporation

Linear expansion coefficient, glass transition temperature measurement: Thermometer measuring device (TMA Q400) made by TA Instruments, Inc.

The following epoxy compounds were prepared.

[Preparation of Epoxy Compound]

Synthesis Example 1

Synthesis of Bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester

10 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1.2 g of paratoluenesulfonic acid monohydrate, 100 mL of toluene, and trimethylolpropane diallyl in a reactor equipped with a Dean-Stark device and a cooler 34 g of ether (90%) was added and reacted at reflux for 15 hours. After completion of the reaction, sodium bicarbonate water washing and water washing were performed, and the resultant was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 80:20) to obtain bis (2,2-bis (allyloxymethyl). 38 g of butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid esters were obtained as a pale yellow liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.92 to 5.80 (m, 4H), 5.66 (s, 2H), 5.27 to 5.11 (m, 8H), 4.12 to 3.98 (m, 4H), 3.93 to 3.91 ( m, 8H), 3.30 (s, 8H), 3.03 (m, 2H), 2.56-2.25 (m, 4H), 1.46-1.39 (q, 4H), 0.87-0.82 (t, 6H)

GC-MS (CI): m / z = 563 (M + l).

35 g of bis (2,2-bis (allyloxymethyl) butyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester, 300 mL of chloroform, and 86 g of metachloroperbenzoic acid were added to the reactor and allowed to react for 2 days. . After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, and sodium bicarbonate water was added and extracted. The organic layer was distilled off from the solvent to obtain a crude substance. Purification by silica gel chromatography (hexane: ethyl acetate = 50: 50 → 10: 90) afforded 32 g of a pale yellow liquid.

The obtained compound is bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl)-corresponding to a combination of formula (4-3) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. It was 4, 5- epoxycyclohexane-1, 2-dicarboxylic acid ester.

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The viscosity was 2867 mPa · s at 25 ° C. This epoxy compound was set to (i-1).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.11 to 3.98 (m, 4H), 3.74 to 3.68 (m, 4H), 3.42 to 3.30 (m, 12H), 3.23 (s, 2H), 3.13 to 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 + l).

Synthesis Example 2

Synthesis of bis (3- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester

8.0 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, 2.0 g of paratoluenesulfonic acid monohydrate, 150 mL of toluene, and pentaerythritol triallyl ether (70%) in a reactor equipped with a Dean stark apparatus and a cooler 39 g was added and reacted at reflux for 35 hours. After completion of the reaction, sodium bicarbonate was washed, water was washed, concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 90: 10) to obtain bis (3- (allyloxy) 2,2-bis (allyloxy 17 g of methyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid esters were obtained as a colorless liquid.

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

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

To the reactor, 16 g of bis (3- (allyloxy) 2,2-bis (allyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester, 500 mL of chloroform and 60 g of metachloroperbenzoic acid were added. It was made to react for 5 days. After completion of the reaction, the mixture was quenched with an aqueous sodium thiosulfate solution, and sodium bicarbonate water was added, followed by extraction. The organic layer was solvent-distilled to obtain a crude substance. Purification by silica gel chromatography (ethyl acetate = 100) gave 22 g of a colorless liquid.

The obtained compound is bis (3- (2,3-epoxypropyloxy) -2,2-bis (2) corresponding to the combination of formula (4-3) corresponding to the mother nucleus and formula (2-2) corresponding to the substituent. , 3-epoxypropyloxymethyl) propyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester.

[Chemical Formula 45]

The viscosity was 15808 mPa · s at 25 ° C. This epoxy compound was set to (i-2).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.22 to 4.10 (q, 4H), 3.74 to 3.69 (m, 6H), 3.53 to 3.44 (m, 12H), 3.36 to 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 / z = 759 (M + l).

Synthesis Example 3

Synthesis of Tris (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3-propanetricarboxylic acid ester

12 g of propane-1,2,3-tricarboxylic acid, 2.6 g of paratoluene sulfonic acid monohydrate, 200 mL of toluene, 49 g of trimethylolpropanediallyl ether (90%) were added to a reactor equipped with a Dean stark apparatus and a cooler. The reaction was carried out at reflux for 24 hours. After completion of the reaction, sodium bicarbonate was washed, water was washed, concentrated, purified by silica gel chromatography (hexane: ethyl acetate = 80: 20), and tris (2,2-bis (allyloxymethyl) butyl) -1. 46 g of 2, 3- propane tricarboxylic acid esters were obtained as a yellow liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.92 to 5.79 (m, 6H), 5.27 to 5.12 (m, 12H), 4.06 to 4.05 (m, 6H), 3.93 to 3.91 (m, 12H), 3.30 to 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 + l).

45 g of tris (2,2-bis (allyloxymethyl) butyl) -1,2,3-propanetricarboxylic acid ester, 600 mL of chloroform, and 87 g of metachloroperbenzoic acid were added to the reactor and reacted for 4 days. After completion of the reaction, the mixture was quenched with an aqueous sodium thiosulfate solution, and sodium bicarbonate water was added, followed by extraction. The organic layer was solvent-distilled to obtain a crude substance. Purification by silica gel chromatography (hexane: ethyl acetate = 70:30) afforded 22 g of a colorless liquid.

The obtained compound is tris (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1 corresponding to the combination of formula (6-1) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. It was a 2, 3- propane tricarboxylic acid ester. The viscosity was 5421 mPa * s at 25 degreeC. This epoxy compound was set to (i-3).

(46)

H-NMR (300 MHz, CDCl ₃ ): δ = 4.05 to 4.04 (m, 6H), 3.73 to 3.68 (m, 6H), 3.42 to 3.24 (m, 19H), 3.12 to 3.10 (m, 6H), 2.83 to 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 / z = 861 (M + l).

Synthesis Example 4

Synthesis of Tetra (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1,2,3,4-butanetetracarboxylic acid ester

Dean-Stark apparatus, 7 g of butane-1,2,3,4-tetracarboxylic dianhydride, 0.7 g of paratoluene sulfonic acid monohydrate, 150 mL of toluene, trimethylolpropanediallyl ether (90%) 35 g was added and reacted for 51 hours at reflux temperature. After completion of the reaction, sodium bicarbonate was washed, water was washed, concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 90: 10) to give tetra (2,2-bis (allyloxymethyl) butyl) -1. 20 g of 2,3,4-butane tetracarboxylic acid esters were obtained as a yellow liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.92 to 5.79 (m, 8H), 5.27 to 5.12 (m, 16H), 4.13 to 4.00 (m, 8H), 3.95 to 3.91 (m, 16H), 3.32 to 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 tetra (2,2-bis (allyloxymethyl) butyl) -1,2,3,4-butanetetracarboxylic acid esters, 500 mL of chloroform, and 42 g of metachloroperbenzoic acid were added to the reactor and reacted for 9 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, and sodium bicarbonate water was added and extracted. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 20:80), and after concentration, 170 g of toluene and 3.4 g of activated carbon were added, followed by stirring for 3 hours. Activated carbon was filtered off and the solvent was distilled off to obtain 16 g of a pale yellow liquid.

The obtained compound is tetra (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -1 corresponding to the combination of formula (6-2) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. It was 2,3,4- butane tetracarboxylic ester.

(47)

The viscosity was 12186 mPa * s at 25 degreeC. This epoxy compound was set to (i-4).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.15 to 3.97 (m, 8H), 3.72 to 3.68 (d, 8H), 3.42 to 3.32 (m, 26H), 3.13 to 3.09 (m, 8H), 2.85 to 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-tris [2- [2,2-bis (2,3-epoxypropyloxymethyl) butyloxy] carbonylethyl] isocyanurate

45 g of trimethylolpropanediallyl ether, 360 mL of dichloromethane, 23 g of 4-dimethylaminopyridine, 36 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, tris (2-carboxyethyl) isocyanuric acid 18 g was added and reacted for 3 days at room temperature. After completion of the reaction, the organic layer was washed with hydrochloric acid and sodium bicarbonate water and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 80: 20 → 50: 50) gave 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) butyloxy 27 g of carbonylethyl] isocyanurate were obtained as a colorless liquid.

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 / z = 935 (M + l).

27 g of 1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) butyloxy] carbonylethyl] isocyanurate, 530 mL of chloroform and 50 g of metachloroperbenzoic acid were added to the reactor And it was made to react at room temperature for 3 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution and washed with sodium bicarbonate water and water. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 40: 60 → 0: 100), and after concentration, 250 mL of toluene and 5 g of activated carbon were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 23 g of a colorless liquid.

The obtained compound is 1,3,5-tris [2- [2,2-bis (2,3-) corresponding to the combination of formula (5-2) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. Epoxypropyloxymethyl) butyloxy] carbonylethyl] isocyanurate.

(48)

The viscosity was 14464 mPa * s at 30 degreeC. This epoxy compound was set to (i-5).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.20 to 4.16 (m, 6H), 4.06 (s, 6H), 3.73 to 3.67 (m, 6H), 3.44 to 3.31 (m, 18H), 3.14 to 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

Of 1,3,5-tris [2- [2,2-bis (2,3-epoxypropyloxymethyl) -3- (2,3-epoxypropyloxy) propyloxy] carbonylethyl] isocyanurate synthesis

56 g of pentaerythritol, 400 mL of dichloromethane, 29 g of 4-dimethylaminopyridine, 46 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and 25 g of isocyanuric acid tris (2-carboxyethyl) were added thereto. It was made to react overnight at room temperature. After completion of the reaction, the organic layer was washed with hydrochloric acid and sodium bicarbonate water and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 90: 10 → 80: 20 → 60: 40) gave 1,3,5-tris [2- [2,2-bis (2,3-propenyloxy). 24 g of methyl) -3- (2,3-propenyloxy) propyloxy] carbonylethyl] isocyanurate was obtained as a colorless liquid.

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

TOF-MS (MALDI): m / z = 1082.43 (M + Na)

1,3,5-tris [2- [2,2-bis (2,3-propenyloxymethyl) -3- (2,3-propenyloxy) propyloxy] carbonylethyl] isocyanu to the reactor 23 g of rate, 1 L of chloroform, and 63 g of metachloroperbenzoic acid were added, and the mixture was reacted at room temperature for 6 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution and washed with sodium bicarbonate water and water. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 20: 80 → 0: 100), and after concentration, 500 mL of toluene and 4 g of activated carbon were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 33 g of a colorless liquid.

The obtained compound is 1,3,5-tris [2- [2,2-bis (2,3-) corresponding to the combination of formula (5-2) corresponding to the mother nucleus and formula (2-2) corresponding to the substituent. Epoxypropyloxymethyl) -3- (2,3-epoxypropyloxy) propyloxy] carbonylethyl] isocyanurate.

(49)

The viscosity was 15462 mPa · s at 30 ° C. This epoxy compound was set to (i-6).

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

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

Synthesis Example 7

Synthesis of 1,3,5-tris [2- [1- (2,3-epoxypropyloxymethyl) -2- (2,3-epoxypropyloxy) ethyloxy] carbonylethyl] isocyanurate

55 g of isocyanuric acid tris (2-carboxyethyl) and 170 mL of N, N-dimethylformamide were added to the reactor, and after confirming dissolution, 63 g of thionyl chloride was added dropwise. The mixture was stirred at room temperature for 1 hour, and the precipitated solid was filtered, washed with chloroform and dried to obtain 54 g of 1,3,5-tris (2-chloroformylethyl) isocyanurate as a white solid.

100 mL of chloroform, 37 g of glycerol-α, α'-diallyl ether and 17 g of pyridine were added to the reactor, followed by stirring. 20 g of 1,3,5-tris (2-chloroformylethyl) isocyanurate was added little by little. It was. It was made to react at 65 degreeC for 3 hours. After distilling off the solvent, the precipitated salt was filtered off, chloroform was added to the filtrate, and washed with water. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50) to give 1,3,5-tris [2- [1- (2,3-propenyloxymethyl) 27 g of 2- (2,3-propenyloxy) ethyloxy] carbonylethyl] isocyanurate were obtained as a colorless liquid.

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

27 g of 1,3,5-tris [2- [1- (2,3-propenyloxymethyl) -2- (2,3-propenyloxy) ethyloxy] carbonylethyl] isocyanurate in the reactor, 1 L of chloroform and 59 g of metachloro and benzoic acid were added and reacted at room temperature for 4 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution and washed with sodium bicarbonate water and water. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica 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 were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 12 g of a colorless liquid.

The obtained compound is 1,3,5-tris [2- [1- (2,3-epoxypropyloxy) corresponding to the combination of formula (5-2) corresponding to the mother nucleus and formula (2-3) corresponding to the substituent. Methyl) -2- (2,3-epoxypropyloxy) ethyloxy] carbonylethyl] isocyanurate.

(50)

The viscosity was 18061 mPa · s at 30 ° C. This epoxy compound was set to (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, 18 H)

LC-MS (ESI): m / z = 905 (M + H)

Synthesis Example 8

Synthesis of 1,3,5-tris [2,3-bis (2,3-epoxypropyloxy) propyl] isocyanurate

30 g of isocyanuric acid, 5 g of tetramethylammonium chloride, 300 mL of 1,3-dimethyl-2-imidazolidinone, and 95 g of allylglycidyl ether were added to the reactor and reacted at 100 ° C for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, and the organic layer was washed with sodium bicarbonate water and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 30:70) gave 37 g of 1,3,5-tris [2-hydroxy-3- (2,3-propenyloxy) propyl] isocyanurate. Obtained as a colorless liquid.

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

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

11 g of sodium hydride and 700 mL of dimethylformamide were added to the reactor, and 1,3,5-tris [2-hydroxy-3- (2,3-propenyloxy) propyl] isocyanurate was stirred at 0 ° C. 35 g and allyl bromide 54 g were dripped, and it was made to react at room temperature for 1 day. After completion of the reaction, it was quenched with water, extracted with toluene, the organic layer was washed with brine and concentrated. Purification by silica gel chromatography (hexane: ethyl acetate = 80: 20 → 50: 50) yields 1,3,5-tris [2,3-bis (2,3-propenyloxy) propyl] isocyanurate 13 g was obtained as a colorless liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.94 to 5.79 (m, 6H), 5.27 to 5.81 (m, 12H), 4.19 to 3.94 (m, 18H), 3.86 to 3.83 (m, 3H), 3.52 to 3.51 (m, 6H)

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

21 g of 1,3,5-tris [2,3-bis (2,3-propenyloxy) propyl] isocyanurate, 630 mL of chloroform, and 59 g of metachloroperbenzoic acid were added to the reactor and allowed to react at room temperature for 4 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution and washed with sodium bicarbonate water and water. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 20:80), and after concentrating, 320 mL of toluene and 7 g of activated carbon were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 30 g of a colorless liquid.

The obtained compound is 1,3,5-tris [2,3-bis (2,3-epoxypropyloxy) corresponding to the combination of formula (5-6) corresponding to the mother nucleus and formula (2-4) corresponding to the substituent. ) Propyl] isocyanurate.

(51)

The viscosity was 17011 mPa · s at 25 ° C. This epoxy compound was set to (i-8).

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

LC-MS (ESI): m / z = 688 (M + l).

Synthesis Example 9

Synthesis of Bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -adamantane-1,3-dicarboxylic acid ester

20 g of 1,3-adamantanedicarboxylic acid, 200 g of methanol, and 0.8 g of concentrated sulfuric acid were added to the reactor, and the mixture was reacted at reflux for 2 hours. The reaction solution was concentrated, 200 mL of toluene was added, washed with sodium bicarbonate water and then water. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 3: 1) to give 21 g of 1,3-adamantanedicarboxylic acid methyl ester as a white solid.

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

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

20 g of 1,3-adamantanedicarboxylic acid methyl ester, 12 g of paratoluene sulfonic acid hydrate, 200 mL of toluene, and 70 g of trimethylolpropane diallyl ether (90%) were added to the reactor and allowed to react at reflux for 26 days. The reaction solution was concentrated and washed with sodium bicarbonate water and aqueous sodium hydroxide solution. The organic layer was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 100: 0 → 95: 5 → 80: 20) to give bis (2,2-bis (propenyloxymethyl) butyl) -adamantane. 14 g of -1,3-dicarboxylic acid esters were obtained as a brown liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.91 to 5.82 (m, 4H), 5.27 to 5.13 (m, 8H), 3.97 (s, 4H), 3.94 to 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 (CI): m / z = 618 (M + H)

13 g of bis (2,2-bis (propenyloxymethyl) butyl) -adamantane-1,3-dicarboxylic acid ester, 500 mL of chloroform, and 47 g of metachloroperbenzoic acid were added to the reactor and allowed to react at room temperature for 3 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution and washed with sodium bicarbonate water and water. The organic layer was distilled off with a solvent to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50 → 30: 70 → 10: 90), and after concentration, 130 mL of toluene and 3 g of activated carbon were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 9 g of a pale yellow liquid.

The obtained compound is bis (2,2-bis (2,3-epoxypropyloxymethyl) butyl) -a corresponding to the combination of formula (4-1) corresponding to the mother nucleus and formula (2-1) corresponding to the substituent. Tan-1,3-dicarboxylic acid ester.

(52)

The viscosity was 2609 mPa · s at 25 ° C. This epoxy compound was set to (i-9).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.00 (s, 4H), 3.72 to 3.67 (m, 4H), 3.44 to 3.32 (m, 12H), 3.10 (s, 4H), 2.79 to 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 / z = 682 (M + H)

Comparative Synthesis Example 1

Synthesis of bis (2,3-epoxypropyl) -4,5-epoxycyclohexane-1,2-dicarboxylic acid ester

15 g of cis-4-cyclohexene-1,2-dicarboxylic acid, 37 g of potassium carbonate, 255 mL of dimethylformamide, and 32 g of allyl bromide were added to the reactor and allowed to react at room temperature for 15 hours. After completion | finish of reaction, it filtered and toluene and water were added and extracted. After washing with water and concentrating, the residue was purified by silica gel chromatography (hexane: ethyl acetate = 75: 25), and 21 g of bis (2-propenyl) -4-cyclohexene-1,2-dicarboxylic acid ester was pale yellow. Obtained as a liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.96 to 5.82 (m, 2H), 5.68 to 5.57 (m, 2H), 5.33 to 5.19 (m, 4H), 4.60 to 4.58 (m, 4H), 3.11 to 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-dicarboxylic acid ester and 300 mL of chloroform were added to a reactor, after cooling to 0-10 degreeC, 87 g of metachloro perbenzoic acid were added, and it heated up to room temperature. The reaction was carried out for 5 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, and sodium bicarbonate water was added and extracted. The organic layer was washed with sodium bicarbonate water, washed with water, dried, and the solvent was distilled off to obtain a crude substance. Purification by silica gel chromatography (hexane: ethyl acetate = 50: 50 → 10: 90) gave 20 g of a colorless liquid.

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

(53)

The viscosity was 1992 mPa · s at 25 ° C. This epoxy compound was set to (i-10).

H-NMR (300 MHz, CDCl ₃ ): δ = 4.51 to 4.41 (m, 2H), 3.96 to 3.74 (m, 2H), 3.25 to 3.19 (m, 4H), 3.01 to 2.98 (m, 2H), 2.84 to 2.81 (m, 2H), 2.66-2.61 (m, 2H), 2.27-2.20 (m, 4H),

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

Comparative Synthesis Example 2

Synthesis of Tetra (2,3-epoxypropyl) -1,2,3,4-butanetetracarboxylic acid ester

53 g of 1,2,3,4-butanetetracarboxylic acid, 155 g of potassium carbonate, 892 mL of N, N-dimethylformamide, and 177 g of allyl bromide were added to the reactor and reacted at 68 ° C for 11 hours. After the reaction was completed, water was washed with toluene, concentrated, purified by silica gel chromatography (hexane: ethyl acetate = 80: 20), and tetra (2-propenyl) -1,2,3,4-butane. 71 g of tetracarboxylic acid ester was obtained as a pale yellow liquid.

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

GC-MS (CI): m / z = 395 (M + H),

40 g of tetra (2-propenyl) -1,2,3,4-butanetetracarboxylic acid ester and 800 mL of chloroform were added, after cooling to 0-10 degreeC, 112 g of metachloro and benzoic acid were added, and it heated up to room temperature. The reaction was carried out for 96 hours. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, and sodium bicarbonate water was added and extracted. The organic layer was washed with water, and the solvent was distilled off to obtain a crude substance. Purification by silica gel chromatography (hexane: ethyl acetate = 20:80) gave 22 g of a colorless liquid. As a result of standing at room temperature, crystals precipitated, which was then washed with ethanol (エ ノ タ ー ル) to obtain a white solid. The melting point of the crystal was measured by DSC and found to be 49.6 ° C. The obtained compound was tetra (3,4-epoxypropyl) -1,2,3,4-butanetetracarboxylic acid ester.

[Formula 54]

This epoxy compound was set to (i-11).

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

LC-MS (ESI): m / z = 481.2 (M + Na).

Comparative Synthesis Example 3

Synthesis of Bis (2,3-epoxypropyl) -adamantane-1,3-dicarboxylic acid ester

20 g of 1,3-adamantanedicarboxylic acid, 32 g of potassium carbonate, 500 mL of N, N-dimethylformamide and 32 g of allyl bromide were added to the reactor and allowed to react 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 obtain 28 g of bis (2,3-propenyl) -adamantane-1,3-dicarboxylic acid ester as a yellow liquid.

H-NMR (300 MHz, CDCl ₃ ): δ = 5.97-5.84 (m, 2H), 5.33-5.20 (m, 4H), 4.58-5.45 (m, 4H), 2.17-1.69 (m, 14H)

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

27 g of bis (2,3-propenyl) -adamantane-1,3-dicarboxylic acid ester, 62 g of metachloroperbenzoic acid, and 500 mL of chloroform were added to the reactor, and the mixture was allowed to react at room temperature for 5 days. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, and sodium bicarbonate water was added and extracted. The organic layer was washed with water, and the solvent was distilled off to obtain a crude substance. Purification was carried out by silica gel chromatography (hexane: ethyl acetate = 70: 30 → 50: 50), and after concentration, 250 mL of toluene and 5 g of activated carbon were added and stirred. Activated carbon was filtered off and the solvent was distilled off to obtain 20 g of a colorless liquid.

The obtained compound was bis (2,3-epoxypropyl) -adamantane-1,3-dicarboxylic acid ester.

(55)

The viscosity was 207 mPa · s at 25 ° C. This epoxy compound was set to (i-12).

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

GC-MS (CI): m / z = 336 (M)

As the liquid epoxy compound, 3,4-epoxycyclohexenylmethyl-3 'and 4'-epoxycyclohexene carboxylate of the formula (7-5) were prepared. This epoxy compound was set to (i-13).

Hydrogenated bisphenol A diglycidyl ether of Formula (7-3) was prepared as a liquid epoxy compound. This epoxy compound was set to (i-14).

[Preparation of Photoacid Generator]

A propylene carbonate solution of a sulfonium salt (formula (8-2), active ingredient 50%, trade name CPI-101A, manufactured by San-Apro Ltd.) was prepared. This was made into the photo-acid generator (ii-1).

A propylene carbonate solution of sulfonium salt (formula (8-1), active ingredient 50%, trade name CPI-100P, manufactured by San-Apro Ltd.) was prepared. This was made into the photo-acid generator (ii-2).

[Preparation of Curable Composition and Photocurability Test]

Example 1

The epoxy compound and the photoacid generator are blended in the ratios shown in Table 1, mixed with an apparatus for stirring and defoaming (trade name: Awatori Rentaro, manufactured by Thinky Corporation), and degassed to form a curable composition. It prepared. The compounding amounts were all described in parts by mass, and the epoxy compound and the photoacid generator described parts by mass of the active ingredient. The photoacid generators (ii-1) and (ii-2) of the propylene carbonate solution were used as they are.

UV (ultraviolet ray) irradiation was carried out to the prepared curable composition from a distance of 9.5 cm, the photocuring behavior was observed with a rheometer (viscometer), and the time when the storage modulus reached a fourth power Pa (1 × 10 ⁴ Pa) of 10 (seconds) ) Was defined as curing time (seconds). UV irradiation was performed up to 600 seconds.

The rheometer was made of Reologica Instruments AB (trade name VAR-50 type), and the lamp was Hg-Xe lamp. The UV wavelength to be irradiated was 365 nm and the irradiation amount was 20 mW / cm 2. The irradiation window material in UV irradiation used the hard glass of thickness 3mm, and the film thickness of the coating film formed from the curable composition was 50 micrometers. The photocuring time of the curable composition was measured and listed in Table 1.

Example 2-Example 8 and Comparative Examples 1-5

In the same manner as in Example 1, the curable composition was prepared at the blending ratios shown in Tables 1 to 4, the photocuring time of the curable composition was measured, and listed in Tables 1 to 4.

Example 9

In the same manner as in Example 1, the curable composition prepared at the blending ratio shown in Table 5 was applied to a PET film (Toyobo Co., Ltd. A4100 125 µm) with a 75 µm applicator, and UV (ultraviolet) irradiation was performed from a distance of 26.5 cm. It carried out with the following accumulated light quantity, and performed the tack-free test (touch-drying time test) immediately after irradiation.

The UV irradiator uses a batch furnace type ultraviolet curing device (manufactured by Eye Graphics Co., Ltd.) for a 2kW × 1 lamp, and the lamp is a Hg lamp (H02-L41 2.0kW, Eye Graphics Co., Ltd.). Agent), and roughness was performed at 20 mW / cm 2 (365 nm). As the irradiation window in the UV irradiation, quartz glass was used. The tack-free time of the curable composition was evaluated and listed in Table 5.

Example 10, Comparative Example 6- Comparative Example 9

In the same manner as in Example 9, the curable composition was prepared at the blending ratio shown in Table 5, and the tack-free time of the curable composition was evaluated and described in Table 5.

On the other hand, the evaluation criteria in Table 5 are five stages of curing (◎), slightly sticking (○), finger marks (△), surface hardening but internal uncured (△ ×), uncured (×) Evaluated as.

[Making of thermosets]

Example 11

24.6 g of epoxy compound (i-1) and 31.3 g of an acid anhydride curing agent RIKACID MH-700 (trade name, manufactured by New Japan Chemical Co., Ltd., the component of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride) Was mixed at a molar ratio of 70:30) and degassed by stirring at room temperature for 30 minutes under reduced pressure. 0.25 g of HISHICOLIN PX-4ET (trade name, manufactured by Nippon Chemical Industrial Co., Ltd., a component of tetrabutylphosphonium diethylphosphorodithioate) was added as a curing accelerator, and the mixture was stirred for 5 minutes. The mixture was placed between a release-treated glass plate (release agent SR-2410 (trade name) manufactured by Dow Corning Toray Co., Ltd.) at 150 ° C. for 1 hour using a release rubber containing 3 mm of silicone rubber. It poured and hardened for 2 hours at 100 degreeC of precure, and 5 hours at 150 degreeC of this hardening.

Example 12

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

Example 13

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

Example 14

10.2 g of epoxy compound (i-4), 11.7 g of RIKACID MH-700 and 0.11 g of HISHICOLIN PX-4ET were added in the same manner as in Example 1 to obtain a cured product.

Example 15

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

Example 16

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

Example 17

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

Example 18

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

Comparative Example 10

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

Comparative Example 11

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

About the obtained hardened | cured material, the three-point bending test (bending strength and bending elastic modulus), transmittance | permeability, linear expansion rate, and glass transition temperature were measured.

(Measurement of bending characteristics)

It measured on the basis of JIS K-6911 by the universal testing machine.

The height and width of the test piece were measured, the test piece was supported, a load was applied to the center with a pressure wedge, the load when the test piece was bent was measured, and the bending strength σ was calculated.

Bending strength σ: (MPa) {kgf / mm 2},

P: load (N) when the test piece is bent {kgf},

L: distance between points (mm),

W: width of the test piece (mm),

h: height of test piece (mm)

Respectively.

σ = (3PL) / (2Wh ² )

Flexural modulus (E): (MPa) {kgf / mm 2} is taken as F / Y: inclination (N / mm) {kgf / mm} of the linear portion of the load-bending curve,

E = [L ³ / (4Wh ³ )] × (F / Y)

(Measurement of transmittance)

The transmittance of 400 nm was measured using a spectrophotometer.

(Measurement of linear expansion rate)

The linear expansion coefficient was measured based on JIS K-6911.

The thickness of the test piece was accurately measured and measured by TMA (thermomechanical analysis) expansion / compression method with a load of 0.05 N and a heating rate of 5 ° C./min.

The linear expansion coefficient (alpha) 1 was calculated | required as the variation amount ((DELTA) L1) of the length of 30-80 degreeC / initial length (L) x50 = (alpha) 1 of a test piece.

(Measurement of Glass Transition Temperature (Tg))

The thickness of the test piece was measured accurately, and measured by 0.05N load and a temperature increase rate of 5 degree-C / min by TMA expansion and compression method. A tangent line was drawn on the curve before and after the glass transition point, and Tg was calculated | required from the intersection of this tangent line.

[Industrial applicability]

The curable composition comprising the epoxy compound of the present invention has light and heat curability, and has excellent characteristics such as high adhesion to a substrate, high transparency (transparency to visible light), hard coat resistance, high heat resistance, and the like. It can be used for coating or bonding optical parts and precision instrument parts. For example, lenses of mobile phones and cameras, optical elements such as light emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, components such as lenses and prisms of cameras, magnetic components of hard disks such as personal computers, It can be used to bond CDs and DVD players (parts that take in optical information reflected from the disc), cones and coils of speakers, magnets of motors, circuit boards, electronic parts, and parts inside engines such as automobiles. .

For hard coat materials for surface protection of automobile bodies, lamps, telephones, building materials, plastics, etc., for example, automobiles, body of bikes, lenses or mirrors of headlights, plastic lenses of eyeglasses It can be applied to mobile phones, game machines, optical films, ID cards, etc.

For ink materials for printing on metals such as aluminum and plastics, such as credit cards, membership cards, etc., switches for telephone products and OA devices, ink for printing on keyboards, ink for inkjet printers on CDs and DVDs Application is mentioned.

In addition, the curable composition of the present invention is combined with three-dimensional CAD to cure the resin to form a complex three-dimensional object, application to optical molding such as model production of industrial products, coating, bonding of optical fibers, optical waveguide, thick film resist (For MEMS), etc. are mentioned.

Claims (14)

The following formula (1)
[Chemical Formula 1]

[In formula (1), A is a (n4) valent unsaturated hydrocarbon group of 2-10 carbon atoms, (n4) valent C4-C20 cyclic hydrocarbon group, (n4) valent nitrogen-containing ring group, (n4) valent carbon source A linear hydrocarbon group of embroidery 3 to 10 or a (n4) valent group combining these, 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 (n 3+ 1) represents a hydrocarbon group, 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, n5 represents an integer of 0 or 1 And n6 represents the integer of 0 or 1.] The epoxy compound represented by the following.
The method of claim 1,
Formula (1) is formula (1-1), formula (1-2), or formula (1-3):
(2)

[In Formulas (1-1) and (1-3), A represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms having a (n4) valency, a cyclic hydrocarbon group having 4 to 20 carbon atoms having a (n4) valence, and a (n4) valence A nitrogen-containing cyclic group, a (n4) valent C3-C10 linear hydrocarbon group, or a combination thereof (n4) a valent group, wherein A 'represents a (n4) valent 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, n1 represents an integer of 2, and n2 represents an integer of 1 And n3 represents the integer of 2-5, n4 represents the integer of 2-8.] The epoxy compound represented by the following.
3. The method according to claim 1 or 2,
The epoxy compound in which A is a (n4) valent unsaturated hydrocarbon group obtained by removing (n4) hydrogen atoms from ethylene, propylene, or norbornene.
3. The method according to claim 1 or 2,
A is a (n4) valent cyclic hydrocarbon in which (n4) hydrogen atoms are removed from cyclobutane, cyclopentane, cyclohexane, epoxycyclohexane, alkyl-substituted epoxycyclohexane, bicycloheptene, bicyclooctene, or adamantane Group, epoxy compound.
3. The method according to claim 1 or 2,
Wherein A is a (n4) valent nitrogen-containing ring group having (n4) hydrogen atoms removed from trialkylisocyanurate, and A 'is (n4) from isocyanuric acid, cyanuric acid, hydantoin, or barbituric acid Epoxy compound which is (n4) valent nitrogen-containing ring group which removed hydrogen atom.
3. The method according to claim 1 or 2,
The epoxy compound in which A is a (n4) valent chain hydrocarbon group obtained by removing (n4) hydrogen atoms from propane, butane, pentane, or hexane.
The curable composition containing the epoxy compound as described in any one of Claims 1-6, and a hardening | curing agent.
8. The method of claim 7,
Curable composition whose said hardening | curing agent is an acid anhydride, an amine, a phenol resin, a polyamide resin, imidazole, or a polymercaptan.
9. The method according to claim 7 or 8,
Curable composition containing the said hardening | curing agent in the ratio of 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups of the said epoxy compound.
The curable composition containing the epoxy compound as described in any one of Claims 1-6, and an acid generator.
11. The method of claim 10,
Curable composition, wherein the acid generator is a photoacid generator or a thermal acid generator.
12. The method of claim 11,
Curable composition, wherein the acid generator is an onium salt.
12. The method of claim 11,
The said acid generator is a sulfonium salt compound or an iodonium salt compound, The curable composition.
14. The method according to any one of claims 10 to 13,
The curable composition containing the said acid generator in the ratio of 0.1-20 mass% with respect to the mass of the said epoxy compound.