JP5501710B2 - Novel episulfide compound, curable resin composition containing the episulfide compound, and cured product thereof - Google Patents

Description

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

  Conventionally, transparent and high refractive index cured products have been used for optical materials such as lenses. In particular, active development has been made in the field of electronic materials and optical materials due to the excellent electrical properties, heat resistance, adhesiveness, optical properties and the like of the cured resin combined with a curing agent. Examples thereof include a semiconductor sealing material, an antireflection film such as a liquid crystal display, a protective film for a color filter, an optical waveguide, and a lens, mirror, and prism that are used in an optical device such as a camera.

  Patent Document 1 reports branched alkyl sulfide type episulfide compounds, Patent Document 2 reports linear alkyl sulfide type episulfide compounds, and Patent Document 3 reports bisphenol S type episulfide compounds. However, these compounds have a problem in heat resistance. Patent Document 4 reports an episulfide compound having a fluorene skeleton having high heat resistance as an optical material. However, there is a problem that a resin composition for obtaining a cured product exhibiting a high refractive index cannot be produced due to poor solubility in a diluent or the like.

JP-A-9-071580 Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 11-12273 JP 2001-288177 A

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

  As a result of intensive studies, the present inventors have found that an episulfide compound having a specific structure is excellent in solubility, and further that a curable resin composition containing the episulfide compound is excellent in storage stability, and that the cured product is high. It was found that it is a refractive index and excellent in transparency, and it was found that the above problem can be solved by using this.

  The present invention has been made based on the above findings, and the first embodiment of the present invention is an episulfide compound represented by the following general formula (I) or (II).

（式中、Ａ¹及びＡ²は酸素原子又は硫黄原子を表し（但し、Ａ¹及びＡ²の少なくとも一つは硫黄原子を表す）、Ｃｙは炭素原子数３〜１０のシクロアルキル基を示し、Ｘ及びＺはそれぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、炭素原子数３〜１０のシクロアルキル基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基並びに該アリール基の結合部は−Ｏ−、−Ｓ−又は二重結合で中断されてもよく、また、Ｚは隣接するＺ同士で芳香環を形成してもよい。該アルキル基、アリール基、アリールアルキル基、複素環基、シクロアルキル基及び隣接するＺ同士で形成される芳香環はハロゲン原子で置換されてもよく、ｎは０〜１０、ｐは０〜５、ｒは０〜４の整数を表す。尚、ｎが０でないときに存在する光学異性体は、どの異性体でもよい。）

(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), Cy represents a cycloalkyl group having 3 to 10 carbon atoms. , X and Z are each independently 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, or a heterocyclic ring having 2 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 10 carbon atoms, or a halogen atom, the methylene group in the alkyl group and the arylalkyl group and the bond part of the aryl group interrupted by -O-, -S- or a double bond Z may form an aromatic ring with adjacent Z. The alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Z are formed with each other. Aromatic ring is halogen source And n represents an integer of 0 to 10, p represents an integer of 0 to 5, and r represents an integer of 0 to 4. The optical isomer present when n is not 0 may be any isomer. )

（式中、Ａ¹及びＡ²は酸素原子又は硫黄原子を表し（但し、Ａ¹及びＡ²の少なくとも一つは硫黄原子を表す）、Ｙ¹、Ｙ²及びＺは、それぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、炭素原子数３〜１０のシクロアルキル基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基並びに該アリール基の結合部は−Ｏ−、−Ｓ−又は二重結合で中断されてもよく、隣接するＹ¹は、互いに結合して環を形成してもよく、該アルキル基、アリール基、アリールアルキル基、複素環基及びシクロアルキル基はハロゲン原子で置換されてもよく、ｎは０〜１０、ｑは０〜４、ｑ’は０〜８（但し、ｑ’は（ｘ＋ｙ）×２以下である）、ｒは０〜４、ｘは０〜４、ｙは０〜４の整数を表し、ｘとｙの合計は２〜４である。尚、ｎが０でないときに存在する光学異性体は、どの異性体でもよい。）

(Wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (provided that at least one of A ¹ and A ² represents a sulfur atom), Y ¹ , Y ² and Z are each independently, 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 cyclohexane having 3 to 10 carbon atoms. Represents an alkyl group or a halogen atom, the methylene group in the alkyl group and arylalkyl group, and the bond part of the aryl group may be interrupted by —O—, —S— or a double bond, and adjacent Y ¹ is May combine with each other to form a ring, and the alkyl group, aryl group, arylalkyl group, heterocyclic group and cycloalkyl group may be substituted with a halogen atom, n is 0 to 10, and q is 0. -4, q 'is 0-8 (where q' is (x y) × 2 or less), r is 0 to 4, x is 0 to 4, y is an integer of 0 to 4, and the sum of x and y is 2 to 4. When n is not 0 The optical isomer present in can be any isomer.)

  The second embodiment of the present invention is a curable resin composition containing the episulfide compound and the curing agent according to the first embodiment.

  The third embodiment of the present invention is a curable resin composition containing the episulfide compound according to the first embodiment and an energy ray-sensitive cation initiator.

  The fourth embodiment of the present invention is a cured product obtained by heating and / or irradiating energy beams to the curable resin composition according to the second and / or third embodiment.

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

Hereinafter, the episulfide compound, curable resin composition, and cured product thereof of the present invention will be described in detail based on preferred embodiments.
The episulfide compound which is the first embodiment of the present invention is a novel compound represented by the above general formula (I) or (II).
First, the episulfide compound represented by the general formula (I) will be described.

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

  Examples of the alkyl group having 1 to 10 carbon atoms represented by X and Z in the general formula (I) include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Examples of the group in which the methylene group in the alkyl group is interrupted by —O— include methoxy, ethoxy, propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl, and the like. Examples of the group in which the methylene group is interrupted by -S- include methylthio, ethylthio, butylthio, pentylthio and the like. Examples of the group in which the methylene group in the alkyl group is interrupted by a double bond include allyl and 3-butenyl. Etc.

  Examples of the aryl group having 6 to 20 carbon atoms represented by X and Z in the general formula (I) include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 1-phenanthryl, o-tolyl, Examples include m-tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, biphenyl, and the like. Are groups interrupted by —O— such as phenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluore Nyloxy, 1-indanyloxy, 2-indanyloxy and the like, and the bond part of the aryl group is -S. And the groups interrupted by phenylthio, 1-naphthylthio, 2-naphthylthio, 1-anthrylthio, 1-phenanthrylthio, o-tolylthio, m-tolylthio, p-tolylthio, 9-fluorenylthio, 1-tetrahydronaphthylthio, 2 -Tetrahydronaphthylthio, 1-indanylthio, 2-indanylthio and the like are exemplified, and examples of the group in which the bond part of the aryl group is interrupted by a double bond include styryl and the like.

  Examples of the arylalkyl group having 7 to 20 carbon atoms represented by X and Z in the general formula (I) include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, and the like. Examples of the group in which the methylene group in the arylalkyl group is interrupted by -O- include benzyloxy, phenoxymethyl, phenoxyethyl, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy, and the like. Examples of the group in which the methylene group in the arylalkyl group is interrupted by -S- include benzylthio, phenylthiomethyl, phenylthioethyl, etc., and the methylene group in the arylalkyl group is interrupted by a double bond. Examples of the group include cinnamyl.

  Examples of the heterocyclic group having 2 to 20 carbon atoms represented by X and Z in the general formula (I) include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, and quinolyl. , Isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, etc. It is below.

  Examples of the aromatic ring formed by adjacent Zs in the general formula (I) include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.

  The halogen atom represented by X and Z in the above general formula (I), and the alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and X and Z represented by the above general formula (I) and Examples of the halogen atom that may substitute the aromatic ring formed between adjacent Zs include fluorine, chlorine, bromine, and iodine.

  The alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the aromatic ring formed between Z and represented by X and Z in the general formula (I) may have a substituent. , Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1 -Alkyl groups such as methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl; methyloxy, ethyloxy, propyl Oxy, isopropyloxy, butyloxy Sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyl Alkoxy groups such as oxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio Alkylthio such as heptylthio, isoheptylthio, tertiary heptylthio, n-octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio Vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl Alkenyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl; aryl groups such as phenyl, naphthyl; phenoxy, naphthyloxy Arylthio groups such as phenylthio and naphthylthio; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), Acyl groups such as phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxy Carbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, laur Ileamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl -Substituted amino groups such as methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, A cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, etc., and these groups may be further substituted. There. In addition, when substituted with a substituent having a carbon atom, the alkyl group, aryl group, arylalkyl group, heterocyclic group, cyclohexyl represented by X and Z in the general formula (I) including the substituent The number of carbon atoms of the aromatic ring formed by the group and adjacent Zs shall satisfy the specified range of the number of carbon atoms.

  In the episulfide compound represented by the general formula (I) and the episulfide compound represented by the general formula (II) described later, when n is not 0, an optical isomer may exist. The compounds shown in the following text are not limited to specific optical isomers.

  As the episulfide compound represented by the general formula (I), for example, the following compound No. 1-No. The compound shown by 13 is mentioned. In the following chemical formula, n represents a number from 0 to 10. However, the present invention is not limited by the following compounds.

（式中、Ａ¹、Ａ²、Ｚ、ｒ及びｎは上記一般式（Ｉ）と同じである。尚、ｎが０でないときに存在する光学異性体は、どの異性体でもよい。）
ii）上記一般式（Ｉ）中、Ｘが炭素原子数６〜２０のアリール基であり、ｐが０又は１であり、ｎが０〜２である化合物。
iii）上記一般式（III）中、ｎが０〜２である化合物。 Among the episulfide compounds represented by the general formula (I) of the present invention, in the general formula (I), X and Z are alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 20 carbon atoms. In addition, a compound in which p and r are 0 to 2 and n is 0 to 5 is preferable because of good storage stability. In particular, the following compounds i) to iii) are readily available as raw materials and are productive. Is preferable because it is good.
i) A compound represented by the following general formula (III).

(In the formula, A ¹ , A ² , Z, r and n are the same as those in the general formula (I). The optical isomer present when n is not 0 may be any isomer.)
ii) A compound in which, in the general formula (I), 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 in which n is 0 to 2 in the general formula (III).

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

  In addition, by changing the amount of thiourea used in the reaction and the reaction time, it is possible to arbitrarily control the ratio of substitution of oxygen atoms to sulfur atoms in the oxirane ring (sulfur substitution rate) in the epoxy derivative as a raw material. Depending on the purpose, it may be used as an episulfide compound of the present invention while leaving an unsubstituted oxirane ring in the product, or an epoxy derivative as a part of the raw material. The higher the sulfur substitution rate, the higher the refractive index of the cured product. Therefore, the sulfur substitution rate is preferably 50% to 100%, and more preferably 80% to 100%.

  Next, the episulfide compound represented by the general formula (II) will be described. In the following description, the contents of the description in the episulfide compound represented by the above general formula (I) are appropriately applied to portions not specifically described.

The alkyl group having 1 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the methylene group in the alkyl group are —O—, —S—, or a double bond. Examples of the interrupted group include the groups exemplified in the description of the general formula (I).

The aryl group having 6 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the bond part of the aryl group are interrupted by —O—, —S— or a double bond. Examples of the group include those exemplified in the description of the general formula (I).

The arylalkyl group having 7 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the methylene group in the arylalkyl group are —O—, —S— or a double bond Examples of the group interrupted in the above include the groups exemplified in the description of the general formula (I).

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II) include groups exemplified in the description of the general formula (I).

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II) include the groups exemplified in the description of the general formula (I).

The ring structure formed by bonding adjacent Y ¹ in the general formula (II) includes, in addition to those exemplified as the aromatic ring in the general formula (I), a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, Examples thereof include 5- to 7-membered rings such as piperidine ring, morpholine ring, lactone ring and lactam ring, and condensed rings such as fluorene ring, acenaphthene ring, indane ring and tetralin ring.

The halogen atom represented by Y ¹ , Y ² and Z in the general formula (II), and the alkyl group, aryl group, arylalkyl group represented by Y ¹ , Y ² and Z in the general formula (II); Examples of the halogen atom that may substitute the ring structure formed by bonding of the heterocyclic group, the cycloalkyl group and the adjacent Y ¹ include the groups exemplified in the description of the general formula (I).

Ring structure formed by bonding of alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Y ¹ represented by Y ¹ , Y ² and Z in the general formula (II) May have a substituent, and examples of these substituents include the groups exemplified in the description of the general formula (I), and these groups may be further substituted. In addition, when substituted with a substituent having a carbon atom, an alkyl group represented by Y ¹ , Y ² and Z, an aryl group, an arylalkyl group, which can be placed in the general formula (II) including the substituent, The number of carbon atoms in a ring structure formed by a heterocyclic group, a cycloalkyl group, and adjacent Z's shall satisfy the specified range of carbon atoms.

  As the episulfide compound represented by the general formula (II), for example, the following compound No. 14-No. The compound shown by 62 is mentioned. In the following chemical formula, n represents a number from 0 to 10. However, the present invention is not limited by the following compounds.

（式中、Ｙ²’は上記一般式（II）のＹ²と同じ又は水素原子を表し、ｘ’は１又は２であり、Ａ¹及びＡ²は上記一般式（II）と同じであり、Ｙ¹、Ｚ、ｎ、ｑ及びｒは上記一般式（II）と同じである。尚、ｎが０でないときに存在する光学異性体は、どの異性体でもよい。）
vi）上記一般式（II）又は（IV）中、ｎが０〜５である化合物。
vii）上記一般式（II）又は（IV）中、Ｙ²がフェニル基である化合物。
viii）上記一般式（II）又は（IV）中、ｑが０又は１であり、ｑが１の時、Ｙ¹が炭素原子数１〜１０のアルキル基又は炭素原子数６〜２０のアリール基である化合物。
ix）上記一般式（II）中、ｘは２であり、ｙは０であり、Ｙ²はフェニル基であり、ｑは０であり、ｑ’は０であり、ｑは１であり、ｒは０であり、ｎは０〜２である化合物。 Among the episulfide compounds represented by the above general formula (II) of the present invention, the following compounds iv) to ix) are easy to obtain raw materials, have good productivity, and obtain a cured product having a high refractive index. preferable.
iv) In the general 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 adjacent Y A ring formed by ¹ is a group that becomes an aromatic ring, Y ² and Z are an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and q and r are 0 to 2 A compound.
v) A compound represented by the following general formula (IV).

(In the formula, Y ² ′ is the same as Y ^{2 in the} general formula (II) or represents a hydrogen atom, x ′ is 1 or 2, and A ¹ and A ² are the same as those in the general formula (II). , Y ¹ , Z, n, q and r are the same as those in the general formula (II), and the optical isomers present when n is not 0 may be any isomers.)
vi) A compound wherein n is 0 to 5 in the general formula (II) or (IV).
vii) A compound wherein Y ² is a phenyl group in the above general formula (II) or (IV).
viii) In the general formula (II) or (IV), when q is 0 or 1 and q is 1, Y ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. A compound that is
ix) In the general formula (II), x is 2, y is 0, Y ² is a phenyl group, q is 0, q ′ is 0, q is 1, r Is a compound in which n is 0 and n is 0-2.

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

  The episulfide compound which is the first embodiment of the present invention is a curable resin composition which is the second or third embodiment described below, and the curable resin composition is heated and / or irradiated with energy rays. In addition to the use as a cured product according to the fourth embodiment obtained in this manner, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; for packaging Adhesive tape, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive flooring, etc .; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper Processed paper such as natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fiber treatment agents such as fusing agents, anti-fraying agents, processing agents, etc .; sealing agents, cement admixture , Building materials such as waterproof material; may be used for a wide range of applications such as electronic and electrical equipment sealants.

  Next, the curable resin composition which is the 2nd Embodiment of this invention is demonstrated. In the following description, the contents of the description in the first embodiment are appropriately applied to portions that are not particularly described.

  The curable resin composition according to the second embodiment of the present invention is a curable resin composition comprising the episulfide compound according to the first embodiment and a curing agent. Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; polyether polyamines such as polyoxypropylenediamine and polyoxypropylenetriamine; 1,2-diaminocyclohexane, 1, 4-diamino-3,6-diethylcyclohexane, isophoronediamine, mensendiamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminomethylpiperazine Alicyclic polyamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; m-xylenediamine, α- (m / paminophen) Nyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α'-bis (4-aminophenyl) -p-diisopropyl Examples include aromatic polyamines such as benzene and dithiodianiline (hereinafter referred to as polyamines). In addition, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-glycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acids are used in a conventional manner. Polyepoxy addition-modified products produced by reacting; amidation-modified products produced by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; Polyamines and aldehydes such as formaldehyde and phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, t-butylphenol, and resorcinol are reacted in a conventional manner. Mannich-modified products such as produced by Rukoto the like (hereinafter referred to as modified products of polyamines). Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles such as 2-ethyl-4methylimidazole can also be used. In particular, the polyamines, modified products of the polyamines, and imidazoles are preferable, and imidazoles are more preferable in terms of storage stability and curability.

  In the curable resin composition according to the second embodiment of the present invention, the content of the curing agent is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the episulfide compound according to the first embodiment. More preferably, it is 0.1 to 5 parts by weight. When the content of the curing agent is less than 0.01 parts by weight, the curing rate is slow or the curing is insufficient, and when it exceeds 20 parts by weight, the strength of the cured product is insufficient.

  In addition, the curable resin composition according to the second embodiment of the present invention includes, if necessary, a curing catalyst; reactivity such as an epoxy compound, an oxetane compound, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar. And / or non-reactive diluent (plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black , Graphite, iron oxide, bituminous fillers or pigments; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N '-Β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropi Triethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-amino Silane coupling agents such as propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; surfactants; candelilla wax, carnauba wax, wax , Ibotaro, Beeswax, Lanolin, Whale wax, Montan wax, Petroleum wax, Fatty acid wax, Fatty acid ester, Fatty acid ether, Aromatic ester, Aromatic ether, etc. Lubricant; Thickener; Thixotropic agent; Antioxidant; Light Sensitizer; light stabilizer; Flame absorbing agent; Antifoaming agent; Rust preventive agent; Storage stabilizer; Common additives such as colloidal silica and colloidal alumina may be contained, and adhesive resin such as xylene resin and petroleum resin It can also be used in combination. In the curable resin composition according to the second embodiment of the present invention, these optional additives are preferably 500 parts by mass or less in total with respect to 100 parts by mass of the episulfide compound according to the first embodiment. .

  Examples of the epoxy compound that may be used as the reactive and / or non-reactive diluent (plasticizer) include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. 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-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4 -Epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipe One or two glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of taerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol obtained by adding more than one kind of alkylene oxide, diglycidyl ester of aliphatic long chain dibasic acid, monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol, etc. Monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide, glycidyl ester of higher fatty acid, epoxidized soybean Examples of the oxetane compound that may be used as a reactive and / or non-reactive diluent (plasticizer) include oil, octyl epoxy stearate, butyl epoxy stearate, and epoxidized polybutadiene. -Hydroxymethyloxetane, 3- (meth) 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-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl- 3-oxetanylmethyl) ether, isobornyloxyethyl (3- Ru-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether Dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofur Furyl (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, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- ( 2-Methylenyl) propanediylbis (oxymethylene) Bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) 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, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, Trimethylolpropane tris (3-ethyl-3-oxy) Cetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) 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, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, Dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis ( -Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified Examples thereof include hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.

  The curable resin composition according to the second embodiment of the present invention may contain a solvent. In this case, the use amount of the solvent is preferably 5 to 90% by mass in the total content of the episulfide compound according to the first embodiment and the curing agent in the curable resin composition according to the second embodiment. More preferably, the content 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; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-diethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, and n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyla Alcohol solvents such as coal; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents such as Mineral Spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride Solvent: Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N-methylpyrrolidone, etc. , Ketones or cellosolve solvents It is preferred. Moreover, you may make it contain in the curable resin composition which is 2nd Embodiment as it is, without removing the solvent used when synthesize | combining the episulfide compound which is 1st Embodiment.

  The curable resin composition according to the second embodiment of the present invention can be cured by heat treatment. The heat treatment is preferably performed in the range of 100 to 300 ° C. for 10 to 240 minutes.

  Next, the curable resin composition which is the 3rd Embodiment of this invention is demonstrated. In the following description, the contents of the description in the first and second embodiments are appropriately applied to portions that are not particularly described.

  The curable resin composition according to the third embodiment of the present invention is a curable resin composition comprising the episulfide compound according to the first embodiment and an energy ray-sensitive cationic polymerization initiator. The energy beam sensitive initiator is a compound capable of releasing a substance that initiates cationic polymerization by energy beam sensitive irradiation, more specifically, energy beam irradiation as described later.

Particularly preferable examples of the energy ray-sensitive cationic polymerization initiator include a double salt that is an onium salt that releases a Lewis acid by energy ray-sensitive irradiation, or a derivative thereof. A typical example of such a compound is a salt of a cation and an anion represented by the general formula [A] ^{y +} [B] ^y- .

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

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

The anion [B] ^y− is preferably a halide complex, and the structure thereof can be represented by [LX _s ] ^y− , for example.

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

Specific examples of the anion [LX _s ] ^y− of the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate. (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like can be mentioned, and hexafluoroantimonate (SbF ₆ ) ⁻ is preferable.

As the anion [B] ^y− , a structure represented by [LX _s ⁻¹ (OH)] ^y− can also be used. L, X, and s are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. And trinitrobenzenesulfonic acid anion.

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

  In the present invention, it is particularly effective to use an aromatic onium salt among such onium salts. Of these, aromatic halonium salts described in JP-A-50-151997, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899, JP-A-56- No. 55420, JP-A No. 55-125105, etc., Group VIA aromatic onium salts, JP-A No. 50-158698, Group VA aromatic onium salts, JP-A No. 56-8428, Oxosulfoxonium salts described in JP-A-56-149402, JP-A-57-192429, etc., aromatic diazonium salts described in JP-A-49-17040, US Pat. No. 4,139,655 The thiopyrylium salt described in 1 is preferable.

（式中、Ｒ1〜Ｒ14は各々同一でも異なっていてもよい水素原子、ハロゲン原子或いは酸素原子又はハロゲン原子を含んでもよい炭化水素基、若しくは置換基がついてもよいアルコキシ基、Ａｒは１以上の水素原子が置換されてもよいフェニル基である。）で表されるスルホニウム陽イオンを有する化合物；（トリクミル）ヨードニウム陽イオンを有する化合物；ビス（ｔ−ブチルフェニル）ヨードニウム陽イオンを有する化合物；トリフェニルスルホニウム陽イオンを有する化合物等が挙げられる。 Of these aromatic onium salts, the following general formula (V), (VI) or (VII) is particularly preferable.

(Wherein R1 to R14 may be the same or different from each other, a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may contain a halogen atom, or an alkoxy group which may have a substituent, Ar is one or more. A hydrogen atom is a phenyl group which may be substituted.) A compound having a sulfonium cation represented by: a compound having a (tricumyl) iodonium cation; a compound having a bis (t-butylphenyl) iodonium cation; Examples thereof include a compound having a phenylsulfonium cation.

  For example, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate; 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis- Hexafluorophosphate, 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate; 4,4′-bis [bis (fluorophenyl) sulfonio] phenyl sulfide- Bis-hexafluorophosphate, 4,4′-bis [bis (fluorophenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate; 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophos Fate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoro Phosphate, 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) ) Sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexaful Orophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (phenylthio) ) Phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (phenylthio) phenyl-di -(4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl-diphenyls Rufonium hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4 -Fluorophenyl) sulfonium hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) Phenyl bis (4-hydroxyphenyl) sulfonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate; (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexafluoroantimonate; (tolylcumyl) iodonium tetrakis (Pentafluorophenyl) borate; bis (tertiarybutylphenyl) iodonium hexafluorophosphate, bis (tertiarybutylphenyl) iodonium hexafluoroantimonate; bis (tertiarybutylphenyl) iodonium tetrakis (pentafluorophenyl) borate; benzyl- 4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; benzyldimethylsulfonium hexafluorophosphate, benzyldimethylsulfonium hexafluoroantimonate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-chloro Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; 4-acetoxyphenyldimethylsulfonium hexafluorophosphate; 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate; 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyl Oxyphenyl dimethyl sul 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate; α-naphthylmethyldimethylsulfonium hexafluorophosphate, α-naphthylmethyldimethylsulfonium hexafluoro Antimonate; α-naphthylmethyltetrahydrothiophenium hexafluorophosphate, α-naphthylmethyltetrahydrothiophenium hexafluoroantimonate; cinnamyldimethylsulfonium hexafluorophosphate, cinnamyldimethylsulfonium hexafluoroantimonate; cinnamyltetrahydrothiophene Ni-hexafluorophosphate Cinnamyltetrahydrothiophenium hexafluoroantimonate; N- (α-phenylbenzyl) cyanopyridinium hexafluorophosphate, N- (α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate; N-cinnamyl-2- Cyanopyridinium hexafluorophosphate, N-cinnamyl-2-cyanopyridinium hexafluoroantimonate; N- (α-naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, N- (α-naphthylmethyl) -2-cyanopyridinium hexa Fluoroantimonate; N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2-cyanopyridinium hexafluoroantimonate; (4-benzoylphenyl) E) phenyl bis (4-fluorophenyl) sulfonium tetrakis (3,5-difluoro-4-methoxyphenyl) can be given borate.

  Other preferred examples include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) -tris ( Examples thereof include iron / allene complexes such as (trifluoromethylsulfonyl) methanide, aluminum complexes / photolytic silicon compound-based initiators, and the like.

  The energy ray-sensitive cationic polymerization initiator can be used alone or in combination of two or more. Further, the curing agent used in the second embodiment can also be mixed and used. The amount of the energy ray sensitive cationic polymerization initiator used or the total amount of the energy ray sensitive cationic polymerization initiator and the curing agent used is 0.05 to 20 mass with respect to 100 parts by mass of the episulfide compound according to the first embodiment. Part. When the amount used is less than 0.05 parts by mass, the curable resin composition is not sufficiently cured, and distortion or unevenness occurs, or cracks occur during heating. When the amount used exceeds 50 parts by mass, the content of the ionic substance in the adhesive layer formed by curing the curable resin composition increases, so the hygroscopicity of the cured product increases and the durability performance is sufficient. Can't get. The more preferable usage-amount of the said energy-beam sensitive cationic polymerization initiator is 0.5 mass part-15 mass parts with respect to 100 mass parts of episulfide compounds which are 1st Embodiment.

  Moreover, you may add the arbitrary additives illustrated by description of the curable resin composition which is 2nd Embodiment to the curable resin composition which is the 3rd Embodiment of this invention. In the curable resin composition which is 3rd Embodiment, these arbitrary additives are preferably 500 mass parts or less in total with respect to 100 mass parts of episulfide compounds which are 1st Embodiment.

  The curable resin composition that is the third embodiment of the present invention may contain a solvent. In this case, the amount of the solvent used is the curable resin in which the total content of the episulfide compound according to the first embodiment, the energy ray-sensitive cationic polymerization initiator and / or the curing agent is the third embodiment. In the composition, it is preferably 5 to 90% by mass, more preferably 10 to 50% by mass. Specific examples of the solvent include the solvents exemplified in the curable resin composition according to the second embodiment, and among them, ketones or cellosolve solvents are preferable. Moreover, you may make it contain in the curable resin composition which is 3rd Embodiment as it is, without removing the solvent used when synthesize | combining the episulfide compound which is 1st Embodiment.

  The curable resin composition according to the third embodiment of the present invention can be cured into a dry-to-touch state or a solvent-insoluble state usually after 0.1 seconds to several minutes by irradiation with energy rays such as ultraviolet rays. it can. Any suitable energy ray may be used as long as it induces decomposition of the cationic polymerization initiator, but preferably an ultra-high, high, medium, low-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, From 2000 angstroms obtained from tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, etc. High energy rays such as electromagnetic energy having a wavelength of 7000 angstroms, electron beams, X-rays, and radiation are used.

  Moreover, the curable resin composition which is the 3rd Embodiment of this invention can be hardened also by heat processing. Preferably, when a heat treatment is appropriately performed before and after the energy beam irradiation, a cured product with good quality can be obtained.

  The curable resin composition according to the second and third embodiments of the present invention described above is used as a cured product according to the fourth embodiment described below, as well as an ink, a protective film, a paint, and a coating agent. It can also be used as an adhesive, an insulating material, a structural material, an optical disk, a sealing agent, and an optical modeling agent.

  Next, the cured product according to the fourth embodiment will be described. In the following description, the contents of the description in the first to third embodiments are appropriately applied to portions that are not particularly described.

  The cured product according to the fourth embodiment of the present invention is a cured product obtained by heating and / or irradiating energy rays with the curable resin composition according to the second and / or third embodiment. Conditions such as heating and energy beam irradiation are as described above.

  The shape of the cured product according to the fourth embodiment of the present invention is not particularly limited, and examples thereof include a lens shape, a film shape, a prism shape, and a plate shape. Furthermore, the material may be coated or sealed by curing on other materials.

  The cured product according to the fourth embodiment of the present invention is useful for optical components such as an optical lens, an optical film, a light guide plate, a waveguide, an optical element, and an optical connector.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these Examples etc. Examples 1-1 to 1-3 show production examples of the episulfide compound according to the first embodiment of the present invention, and Examples 2-1 to 2-8 are the second and third embodiments of the present invention. The manufacture example and evaluation example of curable resin composition which are are shown, and Comparative Examples 2-1 to 2-7 show the manufacture example and evaluation example of a comparative curable resin composition. Examples 3-1 to 3-3 show the manufacture example and evaluation example of the hardened | cured material which is 4th Embodiment which hardened the 2nd Embodiment of this invention, and Comparative Example 3-1 is comparative hardening. The manufacture example and evaluation example of a thing are shown. Examples 4-1 and 4-2 show the manufacture example and evaluation example of the hardened | cured material which is 4th Embodiment which hardened the 3rd Embodiment of this invention, and Comparative Examples 4-1 to 4-3. These show the manufacture example and evaluation example of a comparative hardened | cured material.

[Example 1-1] Production of episulfide compound A-1 In a three-necked flask equipped with a stirrer and a thermometer, 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane was added. 100.0 g of tetrahydrofuran, 250 g of tetrahydrofuran, and 60.0 g of ethanol were charged and dissolved with sufficient stirring. This was charged with 44.2 g of thiourea, 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, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline, and then thoroughly dried over anhydrous magnesium sulfate, and the solvent was removed 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 (episulfide compound (A-1)) in a yield of 69%. As a result of various analyses, it was confirmed that the colorless viscous solid was an episulfide compound of the present invention (a compound of n = 0 in Compound No. 53). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 98%. The analysis results are shown below.

(result of analysis)
(1) ¹ H-NMR chemical shift (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 by elemental analysis (measured content by TOX-100 manufactured by Diainstruments)
Found: 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.
To a three-necked flask equipped with a stirrer and a thermometer, 50.0 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3,5-diphenylindane, 270 g of tetrahydrofuran, and 30. 0 g was charged and dissolved by stirring well. This was charged with 14.8 g of thiourea and stirred at room temperature for 48 hours. Thereafter, 1000 mL of toluene and 300 mL of water were added, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline and dried well over anhydrous magnesium sulfate, and then the solvent was removed to obtain 50.2 g of a colorless solid (episulfide compound (A-2)) in a yield of 95. %. As a result of various analyses, it was confirmed that the colorless solid was an episulfide compound of the present invention (a compound of n = 0 in Compound No. 44). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 96%. The analysis results are shown below.

(result of analysis)
(1) ¹ H-NMR chemical shift (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) Sulfur content by elemental analysis (measured content by TOX-100 manufactured by Diainstruments)
Actual value: 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 stirrer and a thermometer, 30.0 g of bis [4- (2,3-epoxypropyloxy) phenyl] cyclohexyl (4-biphenyl) methane, 150 g of 1,4-dioxane, and ethanol 30. 0 g was charged and dissolved by stirring well. This was charged with 10.2 g of thiourea and stirred at 50 ° C. for 24 hours. After that, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline, dried thoroughly with anhydrous magnesium sulfate, and then the solvent was removed to precipitate white powdery crystals. The crystals were washed with toluene and hexane and dried well to obtain 22.5 g of colorless crystals (episulfide compound (A-3)) with a yield of 71%. As a result of various analyses, it was confirmed that the colorless crystals were the episulfide compound of the present invention (the compound of n = 0 in Compound No. 1). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from elemental analysis values was 92%. The analysis results are shown below.

(result of analysis)
(1) ¹ H-NMR chemical shift (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 by elemental analysis (measured content by TOX-100 manufactured by Diainstruments)
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] Curable resin composition No. 1-No. 8 and comparative curable resin composition No. 9-No. Production of 15 The episulfide compounds (A-1) to (A-3) and the diluent (C-1) or (C-2) produced in the above Production Examples 1 to 3 were mixed according to the mixing ratio of [Table 1]. After heating to 100 ° C. and dissolving with stirring, the temperature was lowered to 60 ° C., a thermosetting agent (D-1) or a cationic polymerization initiator (D-2) was added, and the mixture was stirred for 10 minutes. Item No. 1-No. 8 was produced. Further, according to the blending ratio of [Table 2], the comparative curable resin composition was prepared in the same manner using the comparative compounds (B-1) to (B-3) shown below instead of the episulfide compound of the present invention. No. 9-No. 15 was produced. 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-epithiopropyloxy) phenyl) propane (B-2) 9,9-bis (4- (2,3-epithiopropyloxy) phenyl ) Fluorene (B-3) 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane (C-1) Adeka Resin EP-4100E (manufactured by ADEKA Corporation): Bisphenol A Type epoxy resin): diluent (C-2) glycidyl phenyl ether: diluent (D-1) 2-ethyl-4-methylimidazole: thermosetting agent (D-2) 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (Adekaoptomer SP-172, manufactured by ADEKA Corporation): Energy ray sensitive cation Polymerization initiator

<Solubility>
The obtained curable resin composition was stirred at 60 ° C. for 10 minutes, cooled to room temperature, and evaluated for solubility. The evaluation criteria are ○ when the precipitate is not confirmed even after cooling to room temperature, △ when the precipitate is confirmed after cooling to room temperature but one day after cooling to room temperature, when it does not dissolve even when heated Is x.

  As is clear from [Table 1] and [Table 2], the composition using the comparative compound (B-2) is poor in solubility and storage stability, whereas the example using the episulfide compound of the present invention. In the composition of 2-1 to 2-8, it is excellent in the solubility with respect to a diluent. Moreover, since it did not melt | dissolve in Comparative Example 2-1 and 2-4, and since the crystal | crystallization precipitated after cooling to room temperature in Comparative Example 2-7, the curable resin composition was not obtained.

[Examples 3-1 to 3-3 and Comparative example 3-1]
The obtained curable resin composition No. 1-No. 3 and comparative curable resin composition No. Each 10 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. The glass was sandwiched with another glass with a 1.00 mm spacer and bonded together, and heated at 100 ° C. for 1 hour and at 150 ° C. for 1 hour. The cured product was evaluated as ◯, and the cured product was evaluated as ×. Moreover, what was obtained as hardened | cured material evaluated the refractive index and transparency. The results are shown in [Table 3].

<Refractive index>
At resulting cured product for Atago Co. Abbe refractometer DR-M2, it was measured D line and e-line refractive index n _d and n _e at 25 ° C..

  From [Table 3], comparative curable resin composition No. consisting of a diluent and a thermosetting agent was used. 10 (Comparative Example 3-1) compared with the cured product, the curable resin composition No. 1 using the episulfide compounds A-1 to A-3 of the present invention was used. 1-No. It is clear that the cured product of No. 3 (Examples 3-1 to 3-3) has a high refractive index.

[Examples 4-1 and 4-2 and Comparative Examples 4-1 to 4-3]
The obtained curable resin composition No. 4 and no. 5 and comparative curable resin composition No. 11, No. 13, and No. 11; Each 14 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. Laminated by sandwiching the other piece of glass with 1.00mm spacer, which after exposure at 3000 mJ / cm ² per glass sided high pressure mercury lamp (total 6000 mJ / cm ^2), for 2 hours at 0.99 ° C., cooled to room temperature And peeled from the glass substrate. The curability was evaluated as ◯ for those obtained as cured products, and x for those that were not cured. Moreover, what was obtained as hardened | cured material evaluated the refractive index and transparency. The results are shown in [Table 4].

<Refractive index>
The obtained cured product at Atago Co. Abbe refractometer DR-M2, were measured D line and e-line refractive index n _d and n _e at 25 ° C..

<Transparency>
The total light transmittance of the resulting cured product was measured with a haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

From [Table 4], comparative curable resin composition No. using comparative compound (B-1). 11 (Comparative Example 4-1) has good solubility but poor curability, and the curable resin composition No. 11 using the comparative compound (B-3). 13 (Comparative Example 4-2), and comparative curable resin composition No. consisting of a diluent and an energy ray-sensitive cationic polymerization initiator. 14 (Comparative Example 4-3) has good curability but is inferior in refractive index and transparency.
In contrast, the curable resin composition No. 1 using the episulfide compound A-1 of the present invention was used. 4 and 5 (Examples 4-4 and 4-5) are clearly excellent in curability, refractive index and transparency.

  From the above, the episulfide compound of the present invention is excellent in solubility, and the curable resin composition of the present invention characterized by containing these compounds is a cured product having a high refractive index excellent in curability and transparency. Obviously, it is useful for optical material applications.

Claims (9)

Episulfide compounds represented by the following general 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), Cy represents a cycloalkyl group having 3 to 10 carbon atoms. , X and Z are each independently 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, or a heterocyclic ring having 2 to 20 carbon atoms. Group, a cycloalkyl group having 3 to 10 carbon atoms, or a halogen atom, the methylene group in the alkyl group and the arylalkyl group and the bond part of the aryl group interrupted by -O-, -S- or a double bond Z may form an aromatic ring with adjacent Z. The alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Z are formed with each other. Aromatic ring is halogen source And n represents an integer of 0 to 10, p represents an integer of 0 to 5, and r represents an integer of 0 to 4. The optical isomer present when n is not 0 may be any isomer. ) An episulfide compound represented by the following general formula (II).

(Wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (provided that at least one of A ¹ and A ² represents a sulfur atom), Y ¹ , Y ² and Z are each independently, 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 cyclohexane having 3 to 10 carbon atoms. Represents an alkyl group or a halogen atom, the methylene group in the alkyl group and arylalkyl group, and the bond part of the aryl group may be interrupted by —O—, —S— or a double bond, and adjacent Y ¹ is May combine with each other to form a ring, and the alkyl group, aryl group, arylalkyl group, heterocyclic group and cycloalkyl group may be substituted with a halogen atom, n is 0 to 10, and q is 0. -4, q 'is 0-8 (where q' is (x y) × 2 or less), r is 0 to 4, x is 0 to 4, y is an integer of 0 to 4, and the sum of x and y is 2 to 4. When n is not 0 The optical isomer present in can be any isomer.) The episulfide compound of Claim 1 represented by the following general formula (III).

(In the formula, A ¹ , A ² , Z, n and r are the same as those in the general formula (I). Note that the optical isomer present when n is not 0 may be any isomer.) The episulfide compound of Claim 2 represented by the following general formula (IV).

(In the formula, Y ² ′ is the same as Y ^{2 in the} general formula (II) or represents a hydrogen atom, x ′ is 1 or 2, and A ¹ and A ² are the same as those in the general formula (II). , Y ¹ , Z, n, q and r are the same as those in the general formula (II), and the optical isomers present when n is not 0 may be any isomers.)   The episulfide compound according to claim 4, wherein x 'in the general formula (IV) is 1.   A curable resin composition comprising the episulfide compound according to any one of claims 1 to 5 and a curing agent.   A curable resin composition comprising the episulfide compound according to claim 1 and an energy ray-sensitive cationic polymerization initiator.   A cured product obtained by heating the curable resin composition according to claim 6.   A cured product obtained by irradiating the curable resin composition according to claim 7 with energy rays.