TWI466878B - A novel cyclic sulfide compound, a hardened resin composition containing the cyclic sulfide compound, and a hardened product thereof - Google Patents

Description

Novel episulfide compound, curable resin composition containing the episulfide compound, and cured product thereof

The present invention relates to a novel episulfide compound, a curable resin composition containing the episulfide compound and a hardener, and/or an energy ray-sensitive cationic initiator, and a cured product thereof.

Previously, a transparent and high refractive index hardened material was used for an optical material such as a lens. In particular, it is actively developed in the fields of electronic materials and optical materials due to excellent electrical properties, heat resistance, adhesion, optical properties, and the like of a cured resin composition in combination with a curing agent. For example, a semiconductor sealing material, an antireflection film such as a liquid crystal display, a protective film of a color filter, a lens, a mirror surface, and a crucible used in an optical device such as an optical waveguide or a camera can be cited.

A branched alkyl sulfide type episulfide compound is reported in Patent Document 1, and a linear alkyl sulfide type episulfide compound is reported in Patent Document 2, and a bisphenol S type ring is reported in Patent Document 3. Sulfide compound. However, the heat resistance of these compounds is problematic. Further, Patent Document 4 reports an episulfide compound having an anthracene skeleton having high heat resistance as an optical material. However, there is a problem that solubility in a diluent or the like is inferior, and a resin composition for obtaining a cured product exhibiting a high refractive index cannot be produced.

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-071580

Patent Document 2: Japanese Patent Laid-Open No. Hei 9-110979

Patent Document 3: Japanese Patent Laid-Open No. 11-12273

Patent Document 4: Japanese Patent Laid-Open Publication No. 2001-288177

An object of the present invention is to provide a compound which is excellent in curability, transparency, and the like, and is particularly useful for optical use and a curable resin composition using the same.

As a result of intensive studies, the present inventors have found that the epoxy sulfide compound having a specific structure is excellent in solubility, and further, the curable resin composition containing the episulfide compound is excellent in storage stability, and the cured product is high in refraction. The rate is excellent in transparency and the above problems are solved by using it.

The present invention is based on the above findings and provides a novel episulfide compound represented by the following general formula (I) or (II):

(wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (wherein at least one of A ¹ and A ² represents a sulfur atom), and Cy represents a cycloalkyl group having 3 to 10 carbon atoms, and X and Z are each independently represented. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, and a carbon number of 3 to 10 a cycloalkyl or a halogen atom, a methylene group in the alkyl group and the arylalkyl group, and a bond of the aryl group may be interrupted by -O-, -S- or a double bond, and further, Z may be formed by adjacent Z An aromatic ring; the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the aromatic ring formed by the adjacent Z atoms may be substituted by a halogen atom, n represents an integer of 0-10, and p represents 0~ An integer of 5, r represents an integer from 0 to 4; further, the optical isomer present when n is not 0 may be any isomer)

(wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (wherein at least one of A ¹ and A ² represents a sulfur atom), and Y ¹ , Y ² and Z each independently represent an alkyl group having 1 to 10 carbon atoms. An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a halogen atom; The methylene group in the aryl group and the aryl group and the bond of the aryl group may be interrupted by -O-, -S- or a double bond, and the adjacent Y ¹ may be bonded to each other to form a ring, the alkyl group, the aryl group , arylalkyl, heterocyclic and cycloalkyl may be substituted by a halogen atom, n represents an integer from 0 to 10, q represents an integer from 0 to 4, and q' represents an integer from 0 to 8 (where q' is (x) +y) × 2 or less), r represents an integer from 0 to 4, x represents an integer from 0 to 4, y represents an integer from 0 to 4, and the total of x and y is 2 to 4; further, when n is not 0 The optical isomer present may be any isomer).

Moreover, the present invention provides a curable resin composition containing the novel episulfide compound represented by the above formula (I) or (II) and a curing agent.

Further, the present invention provides a curable resin composition comprising the novel episulfide compound represented by the above formula (I) or (II) and an energy ray-sensitive cationic initiator.

Moreover, the present invention provides a cured product obtained by heating and/or irradiating an energy ray to the curable resin composition.

The epoxy sulfide compound of the present invention is excellent in solubility, and further, the curable resin composition containing the episulfide compound is excellent in curability and storage stability, and can provide a cured product having a high refractive index and excellent transparency.

Hereinafter, the episulfide compound, the curable resin composition, and the cured product thereof according to the present invention will be described in detail based on preferred embodiments.

The episulfide compound of the present invention is a novel compound represented by the above formula (I) or (II).

First, the episulfide compound represented by the above formula (I) will be described.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy, X and Z in the above formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group. , cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl and the like.

Examples of the alkyl group having 1 to 10 carbon atoms represented by X and Z in the above formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. And a thiol group, a fluorenyl group, etc., as a group in which the methylene group in the alkyl group is interrupted by -O-, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a methoxymethyl group, Examples of the ethoxymethyl group, the 2-methoxyethyl group, and the like, wherein the methylene group in the alkyl group is interrupted by -S-, a methylthio group, an ethylthio group, a butylthio group, a pentylthio group, etc. Examples of the group in which the methylene group in the alkyl group is interrupted by a double bond include an allyl group, a 3-butenyl group and the like.

Examples of the aryl group having 6 to 20 carbon atoms represented by X and Z in the above formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, and a 1-phenanthryl group. , o-tolyl, m-tolyl, p-tolyl, 3-indenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-dihydroindenyl, 1-indanyl, 2-indanyl, biphenylyl, etc., as a group in which the bonding moiety of the aryl group is interrupted by -O-, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-decyloxy group , 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-decyloxy, 1-indenyloxy, 2-indolyloxy, etc., as a bond of the aryl group The group consisting of -S-interruption may, for example, be a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 1-decylthio group, a 1-phenanthryl group, an o-tolylthio group, an m-tolylthio group, or a pair. a tolylthio group, a 9-fluorenylthio group, a 1-tetrahydronaphthylthio group, a 2-tetrahydronaphthylthio group, a 1-indanylthio group, a 2-indanylthio group, or the like, as a bonding portion of the aryl group The base of the double bond interruption may, for example, be a styryl group or the like.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by X and Z in the above formula (I) include a benzyl group, a phenethyl group, a 2-phenylpropyl group, and a diphenylmethyl group. Triphenylmethyl or the like, as a group in which the methylene group in the arylalkyl group is interrupted by -O-, a benzyloxy group, a phenoxymethyl group, a phenoxyethyl group, a 1-naphthylmethoxy group a group, a 2-naphthylmethoxy group, a 1-fluorenylmethoxy group, etc., as a group in which the methylene group in the arylalkyl group is interrupted by -S-, a benzylthio group, a phenylthiomethyl group, The phenylthioethyl group or the like is a group in which the methylene group in the arylalkyl group is interrupted by a double bond, and examples thereof include a phenylallyl group.

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by X and Z in the above formula (I) include pyrrolyl group, pyridyl group, pyrimidinyl group and fluorene group. Base Base, piperidinyl, pyranyl, pyrazolyl, tri , pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, Thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, Azolyl, benzo Azolyl, isothiazolyl, iso Azolyl, fluorenyl, Ruthenium Olinyl, thio Orolinyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxoimidazolidine-3-yl, 2,4-dioxo Zyridin-3-yl and the like.

Examples of the aromatic ring formed by the adjacent Z in the above formula (I) include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring and the like.

a halogen atom represented by X and Z in the above formula (I), and an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group which may be substituted for X and Z in the above formula (I). Examples of the halogen atom of the aromatic ring formed by the cycloalkyl group and the adjacent Z may be fluorine, chlorine, bromine or iodine.

The aromatic ring formed by the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the Z represented by the above X and Z in the above formula (I) may have a substituent, and for example, a methyl group may be mentioned. , ethyl, propyl, isopropyl, cyclopropyl, butyl, t-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl An alkyl group such as a benzyl group, a trioctyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group or a fluorenyl group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a second group Oxyl, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, third giga Alkoxy groups such as oxy, n-octyloxy, isooctyloxy, trioctyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio , isopropylthio, butylthio, second butylthio, tert-butylthio, isobutylthio, pentylthio, Butylthio, third pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, third heptylthio, n-octylthio, isooctylthio, trioctylthio, An alkylthio group such as 2-ethylhexylthio; vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, dicyclohexenyl, heptenyl, octenyl, nonenyl, ten Alkenyl groups such as pentenyl, behenyl, and behenyl; arylalkyl such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, phenylallyl An aryl group such as a phenyl group or a naphthyl group; an aryloxy group such as a phenoxy group or a naphthyloxy group; an arylthio group such as a phenylthio group or a naphthylthio group; an acetyl group, a 2-chloroethyl group, a propyl group, and a octyl group; , propylene fluorenyl, methacryl fluorenyl, phenylcarbonyl (benzhydryl), phthalic acid, 4-trifluoromethyl benzhydryl, trimethylethyl fluorenyl, o-hydroxybenzoic acid Sulfhydryl, oxalyl, octadecyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl a mercapto group such as an aminomethyl group; an anthracene group such as an ethoxy group or a benzyl group; an amine group; an ethylamino group, a dimethylamino group, a diethylamino group, a butylamino group, and a ring. Amylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidine, methoxyaniline, N-methyl-anilino, diphenylamine Base, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzhydrylamino group, formamidine group, trimethyl group Amidino, laurylamine, amine amidoamine, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, Oleone carbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group , phenoxycarbonylamino group, amine sulfonamide group, N,N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, etc. a substituted amine group; a sulfonylamino group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a decyl group, a guanidino group, an amine group, a sulfonyl group, etc., and the like Replaced. Further, in the case of substituting a substituent having a carbon atom, an alkyl group, an aryl group, an arylalkyl group or a heterocyclic ring represented by X and Z in the above formula (I) containing the substituent is used. The number of carbon atoms of the aromatic ring formed by the group, the cyclohexyl group and the adjacent Z satisfy the predetermined number of carbon atoms.

In the case of the episulfide compound represented by the above formula (I) and the episulfide compound represented by the above formula (II), when n is not 0, an optical isomer may be present, which may be any difference. The structure, the compounds shown herein below are not limited to specific optical isomers.

Examples of the episulfide compound represented by the above formula (I) include compounds represented by the following compounds No. 1 to No. 13. Further, in the following chemical formula, n represents the number from 0 to 10. However, the present invention is not limited by any of the following compounds.

In the episulfide compound represented by the above formula (I), X and Z in the above formula (I) are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and p and r are The compounds having 0 to 2 and n of 0 to 5 are preferable because they have good storage stability, and in particular, the compounds of the following i) to iii) are more preferable because they are easily obtained from raw materials and have good productivity.

i) A compound represented by the following formula (III).

(wherein A ¹ , A ² , Z, r and n are the same as the above formula (I). Further, the optical isomer present when n is not 0 may be any isomer)

Ii) A compound of the above formula (I) wherein X is an aryl group having 6 to 20 carbon atoms, p is 0 or 1, and n is 0 to 2.

Iii) A compound of the above formula (III) wherein n is 0-2.

The method for producing the episulfide compound represented by the above formula (I) is not particularly limited. For example, by reacting the epoxy derivative (1) with thiourea as shown in the following reaction formula, the above can be easily produced. An episulfide compound represented by the formula (I).

Further, by increasing or decreasing the amount of thiourea used in the reaction or the reaction time, the ratio of the oxygen atom in the oxirane ring to the sulfur atom in the epoxy derivative as a raw material can be arbitrarily controlled (sulfur substitution) The ratio may be used as the episulfide compound of the present invention in the state of remaining an epoxy derivative as a part of the raw material or an unsubstituted oxirane ring in the product. The higher the sulfur substitution rate, the higher the refractive index of the cured product, so it is preferably from 50% to 100%, and more preferably from 80% to 100%.

Next, the episulfide compound represented by the above formula (II) will be described. In the following description, the content of the episulfide compound represented by the above formula (I) can be suitably used in the portion which is not particularly described.

The alkyl group having 1 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the above formula (II), and the methylene group in the alkyl group are interrupted by -O-, -S- or a double bond The base of the above formula (I) can be exemplified.

The aryl group having 6 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the above formula (II), and the bond portion of the aryl group are interrupted by -O-, -S- or a double bond The base may be exemplified in the description of the above formula (I).

The arylalkyl group having 7 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the above formula (II), and the methylene group in the arylalkyl group are -O-, -S- The base of the double bond interruption may be exemplified in the description of the above formula (I).

The heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the above formula (II) may, for example, be exemplified in the description of the above formula (I).

The cycloalkyl group having 3 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the above formula (II) may, for example, be exemplified in the description of the above formula (I).

The cyclic structure formed by the adjacent Y ¹ bond in the above formula (II) may be, in addition to those exemplified as the aromatic ring in the above formula (I), a cyclopentane ring or a cyclohexane. Ring, cyclopentene ring, piperidine ring, 5~7 member rings such as porphyrin ring, lactone ring and indoleamine ring, condensed ring such as anthracene ring, anthracene ring, indane ring and tetralin ring.

Examples of the formula (II) in the Y ^1, Y ² and Z shown of a halogen atom, and may be substituted by the general formula (II), the Y ^1, Y ² and Z shown in FIG alkyl, the aryl, The halogen atom of the cyclic structure formed by the alkyl group, the heterocyclic group, the cycloalkyl group and the adjacent Y ¹ bond may be exemplified in the description of the above formula (I).

The cyclic structure formed by the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the adjacent Y ¹ bond represented by Y ¹ , Y ² and Z in the above formula (II) may be There are a substituent, and examples of the substituents include those exemplified in the description of the above formula (I), and the groups may be further substituted. Further, in the case of substituting with a substituent having a carbon atom, an alkyl group, an aryl group or an arylalkyl group represented by Y ¹ , Y ² and Z in the above formula (II) containing the substituent is used. The number of carbon atoms of the cyclic structure formed by the group, the heterocyclic group, the cycloalkyl group, and the adjacent Z may satisfy the range of the predetermined number of carbon atoms.

Examples of the episulfide compound represented by the above formula (II) include compounds represented by the following compounds No. 14 to No. 62. Further, in the following chemical formula, n represents the number from 0 to 10. However, the present invention is not limited by any of the following compounds.

Among the episulfide compounds represented by the above formula (II), the compounds of the following iv) to ix) are preferred because they are easily obtained from raw materials and have good productivity, and a cured product having a high refractive index can be obtained.

Iv) In the above formula (II), x is 2 or 3, y is 0, Y ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or an adjacent Y ¹ is formed. The ring is a group of an aromatic ring, and Y ² and Z are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a compound having q and r of 0 to 2.

v) a compound represented by the following formula (IV).

(wherein Y ^{2 '} is the same as Y ^{2 of the} above formula (II) or represents a hydrogen atom, x' is 1 or 2, and A ¹ and A ² are the same as the above formula (II), Y ¹ , Z, n , q and r are the same as the above formula (II). Further, the optical isomer present when n is not 0 may be any isomer)

Vi) A compound of the above formula (II) or (IV) wherein n is 0-5.

Vii) A compound of the above formula (II) or (IV) wherein Y ² is a phenyl group.

Viii) In the above formula (II) or (IV), q is 0 or 1, and when q is 1, Y ¹ is a compound having an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Ix) A compound of the above formula (II) wherein x is 2, y is 0, Y ² is a phenyl group, q is 0, q' is 0, q is 1, r is 0, and n is 0-2.

The method for producing the episulfide compound represented by the above formula (II) is not particularly limited. For example, by reacting the epoxy derivative (2) with thiourea as shown in the following reaction formula, the above-mentioned pass can be easily produced. An episulfide compound of the formula (II).

The episulfide compound of the present invention can be used for concrete and cement in addition to the curable resin composition described below and the use of the cured product obtained by heating and/or irradiating the curable resin composition. Coatings or adhesives for mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc.; packaging tape, adhesive labels, frozen food labels, removable labels, POS (Point of Sale) Adhesives such as labels, adhesive wallpapers, adhesive flooring, etc.; coated paper, lightweight coated paper, coated paper, coated paperboard, carbonless copy paper, impregnated paper, etc.; natural fiber, synthetic fiber, glass fiber, carbon fiber, A fiber treatment agent such as a sizing agent such as a metal fiber, a smear inhibitor, and a processing agent; a building material such as a sealant, a cement mixture, and a waterproof material; and a wide range of applications such as an electronic and a sealing agent for electrical equipment.

Next, the curable resin composition of the present invention (hereinafter also referred to as a first curable resin composition) containing the novel episulfide compound represented by the above formula (I) or (II) and a curing agent will be described. . In the following description, the description of the above-described episulfide compound can be suitably used for the portion which is not particularly described.

Examples of the curing agent include polyalkyl polyamines such as diethylenetriamine, diethylenetriamine, and tetraethyleneamine; polyether polyamines such as polyoxypropylene diamine and polyoxypropylene triamine. ; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, menthanediamine, norbornene diamine, double (4-Amino-3-methyldicyclohexyl)methane, diamine dicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminomethyl pipe , an alicyclic polyamine such as 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; m-xylenediamine, α -(m-/p-aminophenyl)ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, diaminodiethyldimethylmethane, two Aminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α,α'-bis(4-aminophenyl)-p-isopropylbenzene, dithiodiphenylamine An aromatic polyamine or the like (hereinafter referred to as a polyamine). Further, examples of the polyamines include glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-glycidyl ether, or A polyepoxy addition modification produced by reacting various epoxy resins such as carboxylic acid glycidyl ester; the polyamines and phthalic acid, isophthalic acid, dimer acid are conventionally obtained An imidization modification produced by the reaction of a carboxylic acid; the aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol, resorcinol are conventionally obtained by conventional methods. A Mannich-modified product (hereinafter referred to as a modified product of a polyamine) produced by reacting a phenol having at least one hydroformylation-reactive site in the core. Further, a latent curing agent such as an imidazole such as dicyanodiamine, an acid anhydride or 2-ethyl-4-methylimidazole can also be used. Particularly preferred are the above polyamines, modified polyamines, and imidazoles, and imidazoles are more preferable in terms of storage stability and hardenability.

In the first curable resin composition, the content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the episulfide compound. When the content of the curing agent is less than 0.01 parts by weight, the curing rate is slow or insufficient curing, and if it exceeds 20 parts by weight, the strength of the cured product is insufficient.

Further, the first curable resin composition may contain a curing catalyst as needed; an epoxy compound, an oxetane compound, dioctyl phthalate, dibutyl phthalate, benzyl alcohol Reactive and/or non-reactive diluent (plasticizer) such as coal tar; glass fiber, carbon fiber, cellulose, quartz sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, cerium oxide, a filler or pigment such as fine powder of cerium oxide, titanium dioxide, carbon black, graphite, iron oxide or asphalt; γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-amine Propyltriethoxydecane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxydecane, γ-anilinopropyl Triethoxy decane, γ-glycidoxypropyltriethoxy decane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, vinyltriethoxydecane, N -β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-chloropropyltrimethoxy Baseline, γ-fluorenyl a decane coupling agent such as a trimethoxy decane; a surfactant; a candelabra wax, a carnauba wax, a wood wax, a wax, a beeswax, a lanolin, a cetyl wax, a montan wax, a petroleum wax, a fatty acid wax, a fatty acid ester, Lubricating agent such as fatty acid ether, aromatic ester, aromatic ether; thickener; thixotropic agent; antioxidant; photosensitizer; light stabilizer; ultraviolet absorber; flame retardant; defoamer; rust inhibitor; A commonly used additive such as colloidal cerium oxide or colloidal alumina, and further, an adhesive resin such as xylene resin or petroleum resin may be used in combination. In the first curable resin composition, the additive is preferably 500 parts by mass or less based on 100 parts by mass of the episulfide compound.

Examples of the epoxy compound which can be used as the above-mentioned reactive and/or non-reactive diluent (plasticizer) include hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3. , 4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3 , 4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy 3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3 , 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-intermediate Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane Alkane, dicyclopentadiene diepoxide, ethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, epoxy hexahydroortylene Di-2-ethylhexyl dicarboxylate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, trimethylolpropane A glycidyl ether of a polyhydric alcohol such as triglycidyl ether, tetraglycidyl ether of sorbitol, hexahydroglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, or diglycidyl ether of polypropylene glycol. Further, a polyglycidyl ether of a polyether polyol obtained by adding one or more kinds of alkylene oxides to an aliphatic polyol such as propylene glycol, trimethylolpropane or glycerin, or an aliphatic long-chain dibasic acid Diglycidyl ester, monoglycidyl ether of aliphatic higher alcohol or phenol, cresol, butyl phenol, monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide, and higher fatty acid Glycidyl ester, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene, etc., as a diluent for reactive and/or non-reactive (plasticization) To the oxetane compound, 3-ethyl-3-hydroxymethyloxetane, 3-(methyl)allyloxymethyl-3-ethyloxetane , (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl Benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetane) Alkyl methoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl)ether, isobornyl Oxyethyl (3-ethyl-3-oxetanylmethyl)ether, isobornyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3-Ethyl-3-oxetanylmethyl)ether. Ethylene diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, two Cyclopentyloxyethyl (3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl)ether, Tetrahydrofuranmethyl (3-ethyl-3-oxetanylmethyl)ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl)ether. 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl)ether, tribromophenyl (3-ethyl-3-oxetanylmethyl)ether , 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) Ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether , pentachlorophenyl (3-ethyl-3-oxetanylmethyl)ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl)ether, borneol ( 3-ethyl-3-oxetanylmethyl)ether, 3,7-bis(3-oxetanyl)-5-oxydecane, 3,3'-(1,3 -(2-methylenyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxa) Cyclobutane methoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl Bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) Ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tricyclodecyldiyldimethylene (3-ethyl-3-oxetane) Methyl)ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanyl) Methoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) Ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, Pentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-B) Benzyl-3-oxetanylmethyl)ether, caprolactone modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, caprolactone modified dipentaerythritol (3-ethyl-3-oxetanylmethyl)ether, di-trimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, EO (ethylene oxide , ethylene oxide) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO (propylene oxid e, propylene oxide) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxocycle Butylated alkyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified bisphenol F (3-ethyl-3-oxo Heterocyclic butanylmethyl)ether and the like.

The first curable resin composition may contain no solvent. In this case, the total amount of the above-mentioned episulfide compound and the above-mentioned curing agent is preferably from 5 to 90% by mass, more preferably from 5 to 90% by mass, based on the amount of the solvent. It is in the range of 10 to 50% by mass. Specific examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone. ;ether, two An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid An ester solvent such as isopropyl ester or n-butyl acetate; a cellophane solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n-propanol, An alcohol solvent such as isobutyl or n-butanol or pentanol; a BTX (benzene, toluene and xylene) solvent such as benzene, toluene or xylene; or an aliphatic hydrocarbon solvent such as hexane, heptane, octane or cyclohexane; Terpene hydrocarbon oil such as turpentine, D-limonene, terpene; paraffinic solvent such as mineral oil concentrate, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); tetrachloro a halogenated aliphatic hydrocarbon solvent such as carbon, chloroform, trichloroethylene or dichloromethane; a halogenated aromatic hydrocarbon solvent such as chlorobenzene; a carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N-methylpyrrolidone, etc., among which ketones or cyanobacteria are preferred. Agent. Further, the solvent used in the synthesis of the above episulfide compound may not be removed and may be directly contained in the first curable resin composition.

The first curable resin composition can be cured by heat treatment. The heat treatment is preferably carried out in the range of 100 to 300 ° C for 10 to 240 minutes.

Next, the curable resin composition of the present invention containing the novel episulfide compound represented by the above formula (I) or (II) and an energy ray-sensitive cationic polymerization initiator (hereinafter, also referred to as second hardening) The resin composition) is explained. In the following description, the contents of the above-described episulfide compound and the first curable resin composition can be suitably used in the portions which are not particularly described.

The above-described energy ray-sensitive initiator is a compound which can release a substance which initiates cationic polymerization by irradiation with energy ray sensitivity, more specifically, by irradiation of an energy ray as described below.

Particularly preferred as the energy ray-sensitive cationic polymerization initiator is a double salt which is a sulfonium salt which releases Lewis acid by energy ray-sensitive irradiation, or a derivative thereof. As a representative of the compound, a salt of a cation and an anion represented by the general formula [A] ^{y +} [B] ^{y- can be} mentioned.

Here, the cation [A] ^{y+ is} preferably an anthracene, and its structure can be represented, for example, by [(R) _x Q] ^y+ .

Further, R is an organic group having 1 to 60 carbon atoms and containing atoms other than carbon, and x is an integer of 1 to 5. The x Rs are independent and can be the same or different. Further, it is preferred that at least one of the x R groups is an aromatic group. Q is an atom or an atom group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Further, when the atomic valence of Q in the cation [A] ^y+ is z, the relationship of y=xz is necessary.

Further, it is preferred that the anion [B] ^y- is a halide complex, and its structure can be represented, for example, by [LX _s ] ^y- .

Further, L is a metal or a metalloid which is a central atom of a halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc. , V, Cr, Mn, Co, etc. X is a halogen atom. s is an integer from 3 to 7. Further, when the valence of L in the anion [B] ^y- is t, it is important that the relationship of y = st holds.

Specific examples of the anion [LX _s ] ^y- of the above formula include tetrafluoroborate (BF ₄ ) ^- . Hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- etc., preferably hexafluoroantimonate ( SbF ₆ ) ^- .

Further, as the anion [B] ^y- , a structure represented by [LX _s ^-1 (OH)] ^y- can be used. L, X, and s are the same as described above. Further, examples of other anions which can be used include perchloric acid ions (ClO ₄ ) ^- , trifluoromethyl sulfonium sulfate ions (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ions (FSO ₃ ) ^- , toluenesulfonic acid anions, Trinitrobenzenesulfonic acid anion and the like.

Further, as the anion [B] ^y- , tetrakis(pentafluorophenyl)borate can also be used.

In the present invention, the use of an aromatic onium salt is particularly effective in such an onium salt. Among them, the aromatic halosulfonium salt disclosed in Japanese Patent Laid-Open Publication No. SHO-50-15-1997, Japanese Patent Laid-Open Publication No. SHO-50-158680 Japanese Patent Publication No. Sho 55-158698, Japanese Patent Application Laid-Open No. Hei. No. Hei. The oxyhalide cerium oxide disclosed in Japanese Laid-Open Patent Publication No. SHO 56-8428, Japanese Patent Laid-Open No. Hei 56-149402, and Japanese Patent Laid-Open Publication No. SHO 57-192429 The salt is an aromatic diazonium salt disclosed in Japanese Laid-Open Patent Publication No. SHO49-17040, and the thiopyranium salt disclosed in the specification of U.S. Patent No. 4,139,655.

Particularly preferred among the aromatic phosphonium salts are those having the following formula (V), (VI) or (VII)

(wherein R1 to R14 are each independently or different from a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and Ar is one or more hydrogen atoms. a compound of a phosphonium cation represented by a substituted phenyl group; a compound containing a (triisopropylphenyl) phosphonium cation; a compound containing a bis(t-butylphenyl) phosphonium cation; a compound containing a triphenylphosphonium cation Wait.

For example, 4-(4-benzylidene-phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate; 4,4'-bis[double ((β-hydroxyl) Oxy)phenyl)mercapto]phenylene sulfide-bis-hexafluorophosphate, 4,4'-bis[bis((β-hydroxyethoxy)phenyl)indolyl]phenyl sulfide-bis-six Fluoride; 4,4'-bis[bis(fluorophenyl)indenyl]phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis[bis(fluorophenyl)indenyl]benzenesulfide Ether-bis-hexafluoroantimonate; 4,4'-bis(diphenylmercapto)phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis(diphenylfluorenyl) phenyl sulfide - bis-hexafluoroantimonate; 4-(4-benzylidenephenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-( 4-benzylidene phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate; 4-(4-benzylidenephenylthio)benzene Benzyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimonate; -(4-Benzylmercaptophenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-diphenylphosphonium hexafluoroantimonate; 4-(phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-( Phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate; 4-(phenylthio)phenyl-di-(4-fluorophenyl)fluorene Hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimonate; 4-(phenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(phenylthio)phenyl-diphenylphosphonium hexafluoroantimonate; 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate Phosphate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate; 4-(2-chloro-4-benzhydryl) Phenylthio)phenyldiphenylphosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylphosphonium hexafluoroantimonate; 4-(2-chloro 4-Benzylmercaptophenylthio)phenylbis(4-hydroxyphenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4- Hydroxyphenyl)phosphonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate; (tolylcumyl)phosphonium hexafluorophosphate, (tolylcumene) Hexafluoroantimonate; (tolylcumyl)phosphonium tetrakis(pentafluorophenyl)borate; bis(t-butylphenyl)phosphonium hexafluorophosphate, bis(t-butylbenzene) Base) Hexafluoroantimonate; bis(t-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate; benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, benzyl-4-hydroxyphenyl Methyl hydrazine hexafluoroantimonate; benzyl dimethyl sulfonium hexafluorophosphate, benzyl dimethyl hydrazine hexafluoroantimonate; p-chlorobenzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, p-Chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate; 4-ethyloxyphenyl dimethyl sulfonium hexafluorophosphate, 4-ethyl methoxy phenyl dimethyl hexafluorophosphate Phthalate; 4-methoxycarbonyloxyphenyldimethylphosphonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylhydrazine hexafluoroantimonate; 4-ethoxycarbonyloxy Phenyl phenyl sulfonium hexafluorophosphate, 4-ethoxycarbonyloxy phenyl dimethyl hexafluoroantimonate; α-naphthylmethyl dimethyl hexafluorophosphate, α-naphthalene Methyl dimethyl hydrazine hexafluoroantimonate; α-naphthylmethyltetrahydrothio hexafluorophosphate, α-naphthylmethyltetrahydrothio hexafluoroantimonate; phenylallyl Dimethyl sulfonium hexafluorophosphate, phenallyldimethyl hexafluoroantimonate; phenylallyl tetrahydrothiophosphonium hexafluorophosphate, phenylallyl tetrahydrothio Hexafluoroantimonate; N-(α-phenylbenzyl)cyanopyridinium hexafluorophosphate, N-(α-phenylbenzyl)-2-cyanopyridinium hexafluoroantimonate; N -Phenylpropyl-2-cyanopyridinium hexafluorophosphate, N-phenylallyl-2-cyanopyridinium hexafluoroantimonate; N-(α-naphthylmethyl)-2-cyanide Pyridinium hexafluorophosphate, N-(α-naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate; N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl Benzyl-2-cyanopyridinium hexafluoroantimonate; (4-benzylidene phenylthio)phenyl bis(4-fluorophenyl)phosphonium tetras(3,5-difluoro-4-methoxy Phenyl) borate or the like.

Further, as other preferred ones, xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene- An iron/aromatic hydrocarbon complex such as a cyclopentadienyl iron (II)-tris(trifluoromethylsulfonyl)methide compound, an aluminum complex/photodecomposition telluride initiator, and the like.

The above-mentioned energy ray-sensitive cationic polymerization initiators may be used alone or in combination of two or more. Further, a curing agent used in the first curable resin composition may be used in combination. The amount of use of the energy ray-sensitive cationic polymerization initiator or the total amount of the energy ray-sensitive cationic polymerization initiator and the curing agent is 0.05 to 20 parts by mass based on 100 parts by mass of the episulfide compound. When the amount is less than 0.05 parts by mass, the curing of the curable resin composition is insufficient, and deformation or unevenness or cracking occurs during heating, which is not preferable. In addition, when the amount is more than 50 parts by mass, the content of the ionic substance in the adhesive layer formed by curing the curable resin composition increases, so that the hygroscopic property of the cured product becomes high, and the durability can not be sufficiently obtained. . The amount of use of the energy ray-sensitive cationic polymerization initiator is preferably 0.5 parts by mass to 15 parts by mass based on 100 parts by mass of the episulfide compound.

Further, any additive exemplified in the description of the first curable resin composition may be added to the second curable resin composition. In the second curable resin composition, the above-mentioned optional additives are preferably 500 parts by mass or less based on 100 parts by mass of the above-mentioned episulfide compound.

The second curable resin composition may also contain a solvent. In this case, the amount of the solvent used is preferably such that the total content of the episulfide compound, the energy ray-sensitive cationic polymerization initiator, and/or the curing agent is in the second curable resin composition. It is preferably in the range of 5 to 90% by mass, and more preferably 10 to 50% by mass. Specific examples of the solvent include the solvents exemplified in the first curable resin composition. Among them, ketones or celecoxime-based solvents are preferred. Further, the solvent used in the synthesis of the above episulfide compound may not be removed and may be directly contained in the second curable resin composition.

The second curable resin composition can be cured to a dry state or a solvent-insoluble state, usually after 0.1 second to several minutes, by irradiation with an energy ray such as ultraviolet rays. As an appropriate energy line, any decomposition may be carried out as long as the decomposition of the cationic polymerization initiator is induced, and it is preferred to use an ultra high, high, medium and low pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, or a fluorescent lamp. Lamp, tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, cadmium cadmium laser, krypton laser, strontium ion laser, various semiconductor lasers, YAG (Yttrium Aluminium Garnet, yttrium aluminum garnet laser, energy source or electron beam, X-ray, radiation obtained from a laser, a light-emitting diode, a CRT (Cathode Ray Tube) source, etc., having a wavelength of 2000 Å to 7000 Å. Contour energy line.

Further, the second curable resin composition may be cured by heat treatment. It is preferred that if the heat treatment is appropriately performed before and after the irradiation of the energy ray, a cured product having good quality can be obtained.

The first and second curable resin compositions described above can be used as an ink, a protective film, a paint, a coating agent, an adhesive, an insulating material, a structural material, a compact disc, or the like, in addition to the use of the cured product described below. Sealant, light shaping agent.

Next, the cured product of the present invention obtained by heating and/or irradiating the energy ray of the first and/or second curable resin composition will be described. In the following description, the contents of the above-described episulfide compound and the first and second curable resin compositions can be suitably used in the portions which are not particularly described.

Conditions regarding heating and energy line irradiation, etc., as previously explained.

The shape of the cured product of the present invention is not particularly limited, and examples thereof include a lens shape, a film shape, a braid shape, and a plate shape. Further, other materials may be coated or sealed by hardening them on other materials.

The cured product of the present invention is useful for optical components such as optical lenses, optical films, light guide plates, waveguides, optical elements, and optical connectors.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples and the like. Examples 1-1 to 1-3 show the production examples of the novel episulfide compound of the present invention, and Examples 2-1 to 2-8 show the production examples and evaluation examples of the first and second curable resin compositions. Examples 2-1 to 2-7 show production examples and evaluation examples of the comparative curable resin composition. Examples 3-1 to 3-3 show production examples and evaluation examples of the cured product obtained by curing the first curable resin composition, and Comparative Example 3-1 shows a production example and evaluation example of the comparatively cured product. Examples 4-1 and 4-2 show production examples and evaluation examples of the cured product obtained by curing the second curable resin composition, and Comparative Examples 4-1 to 4-3 show production examples and evaluation examples of the comparatively cured product. .

[Example 1-1] Production of episulfide compound A-1

Add 1,1-bis(4-(2,3-epoxypropoxy)phenyl)-3-phenylindole 100.0 g, tetrahydrofuran 250 g and ethanol to a three-necked flask equipped with a stirring device and a thermometer. 60.0 g, fully stirred to dissolve. 44.2 g of thiourea was added thereto, heated to 45 ° C and stirred for 18 hours. Thereafter, 300 mL of toluene, 200 mL of ethyl acetate, and 300 mL of water were added, and the mixture was washed with a separatory funnel to discard the aqueous layer. Furthermore, the organic layer was washed twice with 300 mL of 10% saline solution, and then sufficiently dried with anhydrous magnesium sulfate to carry out solvent removal to obtain a crude product. This crude product was separated and purified by silica gel column chromatography (developing solvent: toluene) to obtain 73.0 g of a colorless viscous solid (e-sulfide compound (A-1)) in a yield of 69%. As a result of various analyses, it was confirmed that the colorless viscous solid was the episulfide compound of the present invention (the compound of n = 0 in the compound No. 53). The sulfur substitution rate of the oxirane ring substituted by the elemental analysis value to the episulfide ring was 98%. The results of the analysis are shown below.

[化22]

Cyclosulfide compound (compound n=0 in compound No. 53)

(analysis results)

(1) Chemical shift of ¹ H-NMR (DMSO-d6, 35 ° C): (ppm) 2.42 - 2.45 (m: 2H), 2.49 - 2.73 (m: 3H), 3.15 - 3.20 (m: 1H), 3.26 -3.37 (m: 2H), 3.95-4.02 (m: 2H), 4.07-4.16 (m: 3H), 6.78 (d: 1H), 6.86-6.96 (m: 4H), 7.01-7.07 (m: 3H) , 7.08-7.13 (m: 2H), 7.15-7.26 (m: 5H), 7.30-7.35 (m: 2H).

(2) Sulfur content obtained by elemental analysis (measured content obtained by using TOX-100 manufactured by DIA Instruments). Measurement value: 12.1%, theoretical value: 12.3%.

(3) IR (cm ^-1 ) 3027, 2868, 1605, 1579, 1507, 1468, 1454, 1397, 1292, 1245, 1181, 1118, 1032, 1011, 828, 779, 756, 736, 701

[Example 1-2] Production of episulfide compound A-2.

In a three-necked flask equipped with a stirring device and a thermometer, 1,1-bis(4-(2,3-epoxypropoxy)phenyl)-3,5-diphenylindole 50.0 g, tetrahydrofuran 270 was added. g and ethanol 30.0 g were thoroughly stirred to dissolve. 14.8 g of thiourea was added thereto, and the mixture was stirred at room temperature for 48 hours. Thereafter, 1000 mL of toluene and 300 mL of water were added, and the mixture was washed with a separatory funnel to discard the aqueous layer. Furthermore, the organic layer was washed twice with 300 mL of 10% saline solution, and dried sufficiently with anhydrous magnesium sulfate to carry out solvent removal to obtain 50.2 g of a colorless solid in a yield of 95% (cyclosulfide compound (A-2). ). As a result of various analyses, it was confirmed that the colorless solid was the episulfide compound of the present invention (the compound of n = 0 in the compound No. 44). The sulfur substitution rate of the oxirane ring substituted by the elemental analysis value to the episulfide ring was 96%. The results of the analysis are shown below.

[化23]

An episulfide compound (a compound of n=0 in compound No. 44)

(analysis results)

(1) Chemical shift of ¹ H-NMR (DMSO-d6, 35 ° C): (ppm) 2.50 (d: 1H), 2.65 (d: 1H), 2.68-2.71 (m: 2H), 2.76-2.82 (m) : 1H), 3.21-3.36 (m: 3H), 3.80-3.86 (m: 1H), 4.00-4.03 (m: 1H), 4.10-4.15 (m: 1H), 4.18-4.24 (m: 1H), 4.26 -4.31 (m: 1H), 6.88-6.92 (m: 4H), 6.98 (s: 1H), 7.05-7.09 (m: 2H), 7.14-7.20 (m: 3H), 7.25-7.41 (m: 8H) , 7.48-7.55 (m: 3H).

(2) The sulfur content obtained by elemental analysis (measured by the TOX-100 manufactured by DIA Instruments) measured values: 10.3%, theoretical value: 10.7%.

(3) IR (cm ^-1 ) 3027, 2925, 1604, 1579, 1508, 1475, 1298, 1245, 1181, 1035, 914, 830, 763, 701

[Example 1-3] Production of episulfide compound A-3.

In a three-necked flask equipped with a stirring device and a thermometer, bis[4-(2,3-epoxypropoxy)phenyl]cyclohexyl(4-biphenylyl)methane 30.0 g, 1,4-two was added. 150 g of alkane and 30.0 g of ethanol were thoroughly stirred to dissolve. 10.2 g of thiourea was added thereto, and the mixture was stirred at 50 ° C for 24 hours. Thereafter, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, and the mixture was washed with a separating funnel to discard the aqueous layer. Further, the organic layer was washed twice with 300 mL of 10% saline solution, and dried sufficiently with anhydrous magnesium sulfate to carry out solvent removal to precipitate a white powdery crystal. The crystals were washed with toluene and hexane, and sufficiently dried to obtain 22.5 g of colorless crystals (e.g. compound (A-3)). As a result of various analyses, it was confirmed that the colorless crystal was the episulfide compound of the present invention (the compound of n = 0 in the compound No. 1). The sulfur substitution rate of the oxirane ring substituted by the elemental analysis value to the episulfide ring was 92%. The results of the analysis are shown below.

[Chem. 24]

Cyclosulfide compound (compound of n=0 in compound No. 1)

(analysis results)

(1) Chemical shift of ¹ H-NMR (DMSO-d6, 25 ° C): (ppm) 0.99-1.10 (m: 3H), 1.30-1.52 (m: 5H), 2.07 (d: 2H), 2.30 (d) : 2H), 2.51 (d: 2H), 3.14-3.22 (m: 2H), 3.80 (dd: 2H), 3.86 (s: 1H), 3.96 (dd: 2H), 6.61-6.66 (m: 4H), 6.86-6.92 (m: 6H), 7.20-7.25 (m: 1H), 7.31-7.37 (m: 2H), 7.44 (d: 2H), 7.57 (d: 2H).

(2) Sulfur content obtained by elemental analysis (measured by TOX-100 manufactured by DIA Instruments) Actual measured value: 10.1%, theoretical value: 11.0%

(3) IR (cm ^-1 ) 2929, 2845, 1606, 1508, 1236, 1181, 1032, 824, 764, 763

[Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-7] Manufacturing of curable resin compositions No. 1 to No. 8 and comparative curable resin compositions No. 9 to No. 15.

The episulfide compound (A-1) to (A-3) and the diluent (C-1) or (C-2) produced in the above Production Examples 1 to 3 were mixed and heated according to the blending ratio of [Table 1]. After stirring at 100 ° C and dissolving it, the temperature was lowered to 60 ° C, and a thermosetting agent (D-1) or a cationic polymerization initiator (D-2) was added thereto and stirred for 10 minutes to prepare a curable resin composition No. 1 ~No.8. Moreover, the comparative compound (B-1)-(B-3) shown below was used instead of the episulfide compound of the present invention according to the blending ratio of [Table 2], and the comparative hardening resin composition was produced by the same operation. No.9~No.15. The solubility of the obtained composition was evaluated. The results are shown in [Table 1] and [Table 2].

(B-1) 2,2-bis(4-(2,3-cyclothiopropoxy)phenyl)propane

(B-2) 9,9-bis(4-(2,3-cyclothiopropoxy)phenyl)indole

(B-3) 1,1-bis(4-(2,3-epoxypropoxy)phenyl)-3-phenylindole

(C-1) Adeka Resin EP-4100E (made by ADEKA Co., Ltd.): bisphenol A type epoxy resin): thinner

(C-2) Epoxypropyl phenyl ether: thinner

(D-1) 2-ethyl-4-methylimidazole: thermal hardener

(D-2) 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate (Adeka Optomer SP-172, manufactured by ADEKA Co., Ltd. ): Energy line sensitive cationic polymerization initiator

<solubility>

The curable resin composition obtained was stirred at 60 ° C for 10 minutes, and then cooled to room temperature to evaluate the solubility. In addition, the evaluation standard is that ○ is not found even when it is cooled to room temperature, and is dissolved in the case of heating, but after cooling to room temperature, the precipitate is found to be Δ one day, and it is not dissolved even by heating. The case is set to ×.

As is clear from [Table 1] and [Table 2], the composition using the comparative compound (B-2) was inferior in solubility and storage stability, whereas Example 2-1 in which the episulfide compound of the present invention was used was used. The composition of ~2-8 is excellent in solubility to a diluent. Moreover, it was not dissolved in Comparative Examples 2-1 and 2-4, and after cooling to room temperature in Comparative Example 2-7, crystals were precipitated, and thus the curable resin composition was not obtained.

[Examples 3-1 to 3-3 and Comparative Example 3-1]

The curable resin compositions No. 1 to No. 3 and the comparative curable resin composition No. 10 obtained were each heated to 60 ° C and applied onto a glass substrate subjected to mold release treatment. The 1.00 mm spacer was sandwiched and bonded to another glass, heated at 100 ° C for 1 hour, and heated at 150 ° C for 1 hour. The hardened person was set to ○, and the uncured person was set to × to evaluate the hardenability. . Further, the refractive index and transparency were evaluated for those who obtained the cured product. The results are shown in [Table 3]].

<refractive index>

For the obtained cured product, the refractive index n _d and n _e of the D line and the e line at 25 ° C were measured using an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.

According to [Table 3], it is apparent that the episulfide compound A-1 of the present invention is used as compared with the cured product of the comparative curable resin composition No. 10 (Comparative Example 3-1) containing a diluent and a thermosetting agent. The cured product of the curable resin compositions No. 1 to No. 3 (Examples 3-1 to 3-3) of A-3 has a high refractive index.

[Examples 4-1 and 4-2 and Comparative Examples 4-1 to 4-3]

The obtained curable resin compositions No. 4 and No. 5 and comparative curable resin compositions No. 11, No. 13, and No. 14 were each heated to 60 ° C and applied to the glass subjected to mold release treatment. On the substrate. The 1.00 mm spacer was sandwiched and bonded to another glass, and the glass was exposed to one side with a high pressure mercury lamp at 3000 mJ/cm ² (total 6000 mJ/cm ² ), and then treated at 150 ° C for 2 hours. After cooling to room temperature, it was peeled off from the glass substrate. The person who obtained the cured product was set to ○, and the uncured person was set to ×, and the hardenability was evaluated. Further, the refractive index and transparency were evaluated for those obtained as cured products. The results are shown in [Table 4].

<refractive index>

With respect to the obtained cured product, the refractive index n _d and n _e of the D line and the e line at 25 ° C were measured using an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.

<Transparency>

The total light transmittance of the obtained cured product was measured using a fog meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

According to [Table 4], the comparative curable resin composition No. 11 (Comparative Example 4-1) using the comparative compound (B-1) was excellent in solubility, but the curability was poor, and the comparative compound (B-3) was used. Curing of the curable resin composition No. 13 (Comparative Example 4-2) and the comparative curable resin composition No. 14 (Comparative Example 4-3) containing a diluent and an energy ray-sensitive cationic polymerization initiator Good, but poor refractive index and transparency.

On the other hand, the curable resin compositions No. 4 and 5 (Examples 4-4 and 4-5) using the episulfide compound A-1 of the present invention are excellent in curability, refractive index, and transparency.

As apparent from the above, the epoxy sulfide compound of the present invention is excellent in solubility, and the curable resin composition of the present invention characterized by containing such a compound can provide a cured product having excellent curability and transparency and having a high refractive index. Useful for optical materials.

Claims (9)

An episulfide compound represented by the following formula (I): (wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (wherein at least one of A ¹ and A ² represents a sulfur atom), and Cy represents a cycloalkyl group having 3 to 10 carbon atoms, and X and Z are each independently represented. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, and a carbon number of 3 to 10 a cycloalkyl or a halogen atom, a methylene group in the alkyl group and the arylalkyl group, and a bond of the aryl group may be interrupted by -O-, -S- or a double bond, and further, Z may be formed by adjacent Z An aromatic ring; the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the aromatic ring formed by the adjacent Z atoms may be substituted by a halogen atom, n represents an integer of 0-10, and p represents 0~ An integer of 5, r represents an integer from 0 to 4; further, the optical isomer present when n is not 0 may be any isomer). An episulfide compound represented by the following formula (II): (wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (wherein at least one of A ¹ and A ² represents a sulfur atom), and Y ¹ , Y ² and Z each independently represent an alkyl group having 1 to 10 carbon atoms. An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a halogen atom; The methylene group in the aryl group and the aryl group and the bond of the aryl group may be interrupted by -O-, -S- or a double bond, and the adjacent Y ¹ may be bonded to each other to form a ring, the alkyl group, the aryl group , arylalkyl, heterocyclic and cycloalkyl may be substituted by a halogen atom, n represents an integer from 0 to 10, q represents an integer from 0 to 4, and q' represents an integer from 0 to 8 (where q' is (x) +y) × 2 or less), r represents an integer from 0 to 4, x represents an integer from 0 to 4, y represents an integer from 0 to 4, and the total of x and y is 2 to 4; further, when n is not 0 The optical isomer present may be any isomer). An episulfide compound according to claim 1, which is represented by the following formula (III): (wherein A ¹ , A ² , Z, n and r are the same as the above formula (I); further, the optical isomer present when n is not 0 may be any isomer). The episulfide compound of claim 2, which is represented by the following formula (IV): (wherein Y ^{2 '} is the same as Y ^{2 of the} above formula (II) or represents a hydrogen atom, x' is 1 or 2, and A ¹ and A ² are the same as the above formula (II), Y ¹ , Z, n And q and r are the same as the above formula (II); further, the optical isomer present when n is not 0 may be any isomer). The episulfide compound of claim 4, wherein x' of the above formula (IV) is 1. A curable resin composition containing the episulfide compound of claim 1 or 2 and a hardener. A curable resin composition containing the episulfide compound of claim 1 or 2 and an energy ray-sensitive cationic polymerization initiator. A cured product obtained by heating the curable resin composition of claim 6 or 7. A cured product obtained by irradiating an energy ray to the curable resin composition of claim 7.