JP2019008289A - Episulfide compound having alicyclic ring, curable episulfide resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a curable episulfide resin composition capable of forming a cured product (particularly, plastic for an optical lens) having a high bending rate, a high number of abbreviations, and a good balance between the two and having excellent optical characteristics. To provide an episulfide compound having an episulfide group useful as a component, a curable episulfide resin composition containing the episulfide compound, and a cured product thereof. SOLUTION: The present invention is an alicyclic episulfide compound having one or more alicyclics (aliphatic hydrocarbon ring) and one or more episulfide groups in a molecule (in one molecule). A curable episulfide resin composition containing an episulfide compound and a cured product thereof are provided. [Selection diagram] None

Description

  The present invention relates to an episulfide compound having an alicyclic skeleton and one or more episulfide groups in the molecule, a curable episulfide resin composition containing the episulfide compound, a cured product of the curable episulfide resin composition, and the like.

  Since plastic is lighter, harder to break, and easier to dye than glass, in recent years, plastics are widely used as various optical materials such as eyeglass lenses, camera lenses, optical fiber cables, prisms, information recording boards, and filters. Optical properties required when plastics are used for optical materials, especially for eyeglass lenses, are plastic materials that have a high refractive index so that the lens thickness can be reduced and a high Abbe number to reduce chromatic aberration. ing. However, the optical properties of general resins tend to decrease the Abbe number as the refractive index increases, and the development of plastic lens materials that achieve both a high refractive index and a high Abbe number is energetically advanced. .

  In recent years, in order to improve the refractive index and the Abbe number in a well-balanced manner, a technique for introducing a compound having a sulfur atom (sulfur-containing compound) having high atomic refraction and relatively small dispersion into a resin composition has been studied. For example, in Patent Document 1, a thiourethane resin obtained by reacting a polythiol compound with a polyisocyanate compound as a sulfur-containing compound, and in Patent Documents 2 and 3, an episulfide resin obtained by curing polymerization of a linear alkyl sulfide episulfide compound as a sulfur-containing compound Resin materials containing sulfur-containing compounds such as these have been reported.

JP-A-60-199016 Japanese Patent Publication No. 9-110979 Japanese Patent Publication No. 10-298287

  The thiourethane resin described in Patent Document 1 exhibits a high refractive index of about 1.60 when xylylene diisocyanate is used as the polyisocyanate to be reacted with the polythiol compound, while the Abbe number is increased due to the influence of the aromatic ring of the xylylene group. There was a problem of rainbow generation due to chromatic aberration. The episulfide resins described in Patent Documents 2 and 3 form a cured product having a very high refractive index of about 1.7 because the linear alkyl sulfide type episulfide compound, which is a sulfur-containing compound, has a high sulfur concentration. The Abbe number is about 35, the balance of optical properties is poor, and it has been limited to use as an additive for adjusting the refractive index.

Accordingly, an object of the present invention is to provide various optical materials (for example, optical lenses such as glasses and cameras, optical fiber cables, etc.) with excellent optical properties that have a high refractive index, a high Abbe number, and a balance between the two. And a compound having an episulfide group (episulfide compound) useful as a component of a curable episulfide resin composition capable of forming a cured product suitable for a prism, an information recording substrate, a filter, and the like.
In addition, another object of the present invention is to provide a high refractive index, a high Abbe number, and an excellent optical characteristic in which both are balanced, and various optical materials (for example, optical lenses such as glasses and cameras, It is to provide a curable episulfide resin composition capable of forming a cured product suitable for an optical fiber cable, a prism, an information recording substrate, a filter and the like.
In addition, another object of the present invention is to provide a high refractive index, a high Abbe number, and an excellent optical characteristic in which both are balanced, and various optical materials (for example, optical lenses such as glasses and cameras, It is to provide a cured product suitable for an optical fiber cable, a prism, an information recording base, a filter, and the like.

  As a result of intensive studies to solve the above problems, the present inventor, as a compound having an episulfide group, a compound having one or more alicyclic rings and one or more episulfide groups in the molecule (hereinafter referred to as “ According to the alicyclic episulfide compound (A) ”, the cured product of the curable episulfide resin composition containing the alicyclic episulfide compound has a high refractive index, a high Abbe number, and a balance between the two. The present invention has been completed by finding that it exhibits excellent optical properties and can be suitably used as plastics for various optical materials such as optical lenses such as glasses and cameras, optical fiber cables, prisms, information recording boards, filters, and the like.

  That is, the present invention provides an alicyclic episulfide compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more episulfide groups in the molecule (in one molecule).

（式中、Ｙは単結合又は連結基を示す。Ｘ¹及びＸ²は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ¹及びＸ²の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。但し、Ｙが−ＣＨ₂−Ｏ−Ｃ（＝Ｏ）−で表される二価の基である場合、シクロヘキサン環にアルキル基が結合しており、かつＸ¹及びＸ²は共に硫黄原子である。） The alicyclic episulfide compound may be a compound represented by the following formula (2).

(In the formula, Y represents a single bond or a linking group. X ¹ and X ² each independently represents an oxygen atom or a sulfur atom, and at least one of X ¹ and X ² is a sulfur atom. A substituent may be bonded to one or more carbon atoms constituting the alicyclic ring, provided that Y is a divalent group represented by —CH ₂ —O—C (═O) —. An alkyl group is bonded to the cyclohexane ring, and X ¹ and X ² are both sulfur atoms.)

（式中、Ｘ³及びＸ⁴は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ³及びＸ⁴の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。） The alicyclic episulfide compound may be a compound represented by the following formula (2a).

(In the formula, X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one of X ³ and X ⁴ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)

（式中、Ｚは単結合又は連結基を示す。Ｘ²⁵及びＸ²⁶は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ²⁵及びＸ²⁶の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。但し、Ｚが−Ｃ（ＣＨ₃）₂−で表される基である場合は、Ｘ²⁵及びＸ²⁶の一方が硫黄原子、他方が酸素原子である。） The alicyclic episulfide compound may be a compound represented by the following formula (4).

(In the formula, Z represents a single bond or a linking group. X ²⁵ and X ²⁶ each independently represents an oxygen atom or a sulfur atom, and at least one of X ²⁵ and X ²⁶ is a sulfur atom. A substituent may be bonded to one or more of the carbon atoms constituting the alicyclic ring, provided that when Z is a group represented by —C (CH ₃ ) ₂ —, X ²⁵ and X ²⁶ One of these is a sulfur atom and the other is an oxygen atom.)

（式中、Ｘ²⁷及びＸ²⁸は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ²⁷及びＸ²⁸の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。） The alicyclic episulfide compound may be a compound represented by the following formula (4-1).

(In the formula, X ²⁷ and X ²⁸ each independently represent an oxygen atom or a sulfur atom, but at least one of X ²⁷ and X ²⁸ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)

  The present invention also provides an alicyclic episulfide compound (A) having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more episulfide groups in the molecule (in one molecule), a curing catalyst, and the like. A curable episulfide resin composition comprising (B) is provided.

  The curable episulfide resin composition may further contain a curing agent (C).

  In the curable episulfide resin composition, the curing agent (C) may be a thiol compound.

（式中、Ｙ'は単結合又は連結基を示す。Ｘ^1'及びＸ^2'は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ^1'及びＸ^2'の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。但し、Ｙ'が−ＣＨ₂−Ｏ−Ｃ（＝Ｏ）−で表される二価の基である場合は、Ｘ^1'及びＸ^2'は、共に硫黄原子である。） In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (2 ′).

(In the formula, Y ′ represents a single bond or a linking group. X ^{1 ′} and X ^{2 ′} each independently represents an oxygen atom or a sulfur atom, and at least one of X ^{1 ′} and X ^{2 ′} represents A substituent may be bonded to one or more carbon atoms constituting the alicyclic ring, provided that Y ′ is represented by —CH ₂ —O—C (═O) —. In the case of a valent group, X ^{1 ′} and X ^{2 ′} are both sulfur atoms.)

In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (2-1).

（式中、Ｘ³及びＸ⁴は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ³及びＸ⁴の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。） In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (2a).

(In the formula, X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one of X ³ and X ⁴ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)

（式中、脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。） In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (1-1).

(In the formula, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring.)

（式中、Ｚは単結合又は連結基を示す。Ｘ²⁵及びＸ²⁶は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ²⁵及びＸ²⁶の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。但し、Ｚが−Ｃ（ＣＨ₃）₂−で表される基である場合は、Ｘ²⁵及びＸ²⁶の一方が硫黄原子、他方が酸素原子である。） In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (4).

(In the formula, Z represents a single bond or a linking group. X ²⁵ and X ²⁶ each independently represents an oxygen atom or a sulfur atom, and at least one of X ²⁵ and X ²⁶ is a sulfur atom. A substituent may be bonded to one or more of the carbon atoms constituting the alicyclic ring, provided that when Z is a group represented by —C (CH ₃ ) ₂ —, X ²⁵ and X ²⁶ One of these is a sulfur atom and the other is an oxygen atom.)

（式中、Ｘ²⁷及びＸ²⁸は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ²⁷及びＸ²⁸の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。） In the curable episulfide resin composition, the alicyclic episulfide compound (A) may be a compound represented by the following formula (4-1).

(In the formula, X ²⁷ and X ²⁸ each independently represent an oxygen atom or a sulfur atom, but at least one of X ²⁷ and X ²⁸ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)

The curable episulfide resin composition may be a resin composition for optical lenses.
The curable episulfide resin composition may be a resin composition for eyeglass lenses.

  The present invention also provides a cured product of the curable episulfide resin composition.

  Moreover, this invention provides the optical lens shape | molded with the hardened | cured material of the said curable episulfide resin composition.

  Furthermore, this invention provides the spectacles lens shape | molded with the hardened | cured material of the said curable episulfide resin composition.

  Since the alicyclic episulfide compound (A) of the present invention has the above-described configuration, the cured product of the curable episulfide resin composition containing the alicyclic episulfide compound has an optimized alicyclic structure and a sulfur concentration. It has excellent optical properties with a high refractive index, a high Abbe number, and a balance between the two. Therefore, it can be suitably used as a plastic material for various optical materials such as optical lenses such as glasses and cameras, optical fiber cables, prisms, information recording boards, and filters.

1 is a chart of the ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 1. FIG. FIG. 2 is a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 2. FIG. 3 is a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 3. FIG. 4 is a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound (product 1) obtained in Example 4. FIG. 5 is a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound (product 2) obtained in Example 4.

[Alicyclic episulfide compound (A)]
The alicyclic episulfide compound (A) of the present invention is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more episulfide groups in the molecule (in one molecule). The number of episulfide groups possessed by the alicyclic episulfide compound (A) is not particularly limited as long as it is 1 or more. However, the cured product has high refractive index, high Abbe number, balance between refractive index and Abbe number, heat resistance, Two or more are preferable from the viewpoint of mechanical strength and the like.

The alicyclic ring (aliphatic hydrocarbon ring) possessed by the alicyclic episulfide compound (A) is not particularly limited, but is a 3- to 10-membered cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. , Norbornane ring, adamantane ring, bridged hydrocarbon ring such as tricyclo [5.2.1.0 ^2,6 ] decane ring, etc., and the curability and the high refractive index of the cured product, high Abbe number, In view of the balance between the refractive index and the Abbe number, a 5- or 6-membered cycloalkane is preferable.

  Examples of the alicyclic episulfide compound (A) include (i) at least one alicyclic episulfide group (an episulfide group composed of two adjacent carbon atoms and sulfur atoms constituting the alicyclic ring) in the molecule. (Ii) a compound having an episulfide group directly bonded to the alicyclic ring by a single bond; (iii) a compound having an alicyclic ring and a 2,3-episulfidepropyl group, etc. .

The alicyclic episulfide group possessed by the compound having at least one alicyclic episulfide group in the molecule (i) is not particularly limited, but among them, the curability and the high refractive index of the cured product, the high Abbe number, From the viewpoint of the balance between the refractive index and the Abbe number, an episulfide cyclohexyl group (an episulfide group composed of two adjacent carbon atoms and sulfur atoms constituting the cyclohexane ring) is preferable. That is, (i) the compound having at least one alicyclic episulfide group in the molecule is preferably a compound having at least one episulfide cyclohexyl group in the molecule. Specific examples include compounds represented by the following formula (1).

  In the above formula (1), X represents a monovalent organic group. Examples of the monovalent organic group include a hydrocarbon group (monovalent hydrocarbon group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an alkylthio group, an alkenylthio group, and an arylthio group. Aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, glycidyl group, epoxy group, episulfide group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, and these groups Examples include a group to which a linking group described later (a divalent group having one or more atoms) is bonded. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring in the formula (1).

  Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include C _1-20 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group include vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, and 2-pentenyl groups. C _2-20 alkenyl groups such as 3-pentenyl group, 4-pentenyl group, and 5-hexenyl group. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group.

As the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, C _3-12 cycloalkyl groups such as cyclododecyl; cycloalkenyl C _3-12, such as cyclohexenyl group Group; C _4-15 bridged cyclic hydrocarbon group such as bicycloheptanyl group and bicycloheptenyl group.

As said aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, C _7-18 aralkyl groups such as benzyl group and phenethyl group, and C _6-10 aryl-C _2-6 alkenyl groups such as cinnamyl group. And C _1-4 alkyl-substituted aryl groups such as a tolyl group and C _2-4 alkenyl-substituted aryl groups such as a styryl group.

The hydrocarbon group may have a substituent. Although carbon number of the substituent in the said hydrocarbon group is not specifically limited, 0-20 are preferable, More preferably, it is 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Especially C _1-6 alkoxy group); alkenyloxy group such as allyloxy group (particularly C _2-6 alkenyloxy group); C _1-4 alkyl on aromatic ring such as phenoxy group, tolyloxy group, naphthyloxy group, etc. Group, C _2-4 alkenyl group, halogen atom, aryloxy group which may have a substituent such as C _1-4 alkoxy group (especially C _6-14 aryloxy group); benzyloxy group, phenethyloxy aralkyloxy group (particularly, C _7-18 aralkyloxy group) of the group or the like; an acetyl group, propionyloxy group, (meth) Akuriroiruo Shi group, an acyloxy group such as a benzoyloxy group (in particular, C _1-12 acyloxy group); a mercapto group; methylthio group, an alkylthio group such as an ethylthio group (particularly, C _1-6 alkylthio group); arylthio alkenylthio groups such as Group (especially C _2-6 alkenylthio group); C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group on the aromatic ring such as phenylthio group, tolylthio group, naphthylthio group, etc. An arylthio group (particularly a C _6-14 arylthio group) optionally having a substituent such as aralkylthio group (particularly a C _7-18 aralkylthio group) such as a benzylthio group or a phenethylthio group; a carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl alkoxycarbonyl group such as a group (in particular, C _1-6 alkoxy - Carbonyl group); phenoxycarbonyl group, a tolyl group, an aryloxycarbonyl group such as a naphthyloxycarbonyl group (particularly, C _6-14 aryloxy - carbonyl group); aralkyloxycarbonyl group such as benzyloxycarbonyl group (especially, C _7-18 aralkyloxy - carbonyl group); an amino group; methylamino group, ethylamino group, dimethylamino group, mono- or dialkylamino groups such as diethylamino group (especially, mono- or di -C _1-6 alkylamino group) An acylamino group such as an acetylamino group, a propionylamino group or a benzoylamino group (particularly a C _1-11 acylamino group); an epoxy group-containing group such as an epoxy group, a glycidyl group, a glycidyloxy group or a cyclohexene oxide group; an episulfide group; 2,3-episulfide pro Episulfide group-containing groups such as ethyl group, 2,3-episulfidepropyloxy group, episulfide cyclohexyl group; oxetanyl group-containing groups such as ethyl oxetanyloxy group; acyl groups such as acetyl group, propionyl group, benzoyl group; oxo group; Or a group in which two or more of these are bonded via a C _1-6 alkylene group, if necessary.

As a preferable embodiment of X in the above formula (1), an aliphatic hydrocarbon group is preferable, a C _2-20 alkenyl group is more preferable, and a vinyl group is more preferable. That is, as the compound (i) having at least one alicyclic episulfide group in the molecule, a compound represented by the following formula (1-1) is preferable.

In addition, as a preferable embodiment of the compound represented by the above formula (1), in particular, from the viewpoint of the high refractive index, high Abbe number, balance between the refractive index and Abbe number of the cured product, heat resistance, light resistance, etc. A compound represented by the following formula (2) is also preferable.

In the above formula (2), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is episulfidized, a carbonyl group (—CO—), an ether bond (—O—), Examples include an ester bond (—COO—), an amide group (—CONH—), a carbonate group (—OCOO—), a sulfonyl group (—SO ₂ —), and a group in which a plurality of these are linked. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring in the formula (2).

In the above formula (2), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ¹ and X ² is a sulfur atom. However, when Y is a divalent group represented by —CH ₂ —O—C (═O) —, an alkyl group is bonded to the cyclohexane ring, and X ¹ and X ² are both sulfur atoms. is there.

（式中、Ｙ'は単結合又は連結基を示す。Ｘ^1'及びＸ^2'は、それぞれ独立して、酸素原子又は硫黄原子を示すが、Ｘ^1'及びＸ^2'の少なくとも１つは硫黄原子である。脂環を構成する炭素原子の１以上には、置換基が結合していてもよい。但し、Ｙ'が−ＣＨ₂−Ｏ−Ｃ（＝Ｏ）−で表される二価の基である場合は、Ｘ^1'及びＸ^2'は、共に硫黄原子である。） In addition, as a preferable embodiment of the compound represented by the above formula (1), in particular, from the viewpoint of the high refractive index, high Abbe number, balance between the refractive index and Abbe number of the cured product, heat resistance, light resistance, etc. A compound represented by the following formula (2 ′) is also preferable.

(In the formula, Y ′ represents a single bond or a linking group. X ^{1 ′} and X ^{2 ′} each independently represents an oxygen atom or a sulfur atom, and at least one of X ^{1 ′} and X ^{2 ′} represents A substituent may be bonded to one or more carbon atoms constituting the alicyclic ring, provided that Y ′ is represented by —CH ₂ —O—C (═O) —. In the case of a valent group, X ^{1 ′} and X ^{2 ′} are both sulfur atoms.)

The formula (2 ') Y in', X 1 ^'and X ^2' is, Y in the formula (2), and X ¹ and X ² are those similar respectively are exemplified. However, when Y ′ is a divalent group represented by —CH ₂ —O—C (═O) —, X ^{1 ′} and X ^{2 ′} are both sulfur atoms. The compound represented by the above formula (2 ′) includes a compound represented by the following formula (2-1) as a preferred embodiment in addition to the compound represented by the above formula (2).

Examples of the alicyclic episulfide compound (A) in which Y and Y ′ in formulas (2) and (2 ′) are single bonds include compounds represented by the following formula (2a).

In the formula (2a), X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ³ and X ⁴ is a sulfur atom. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring in the formula (2a).

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is episulfided or epoxidized (sometimes referred to as “episulfided alkenylene group”) include, for example, vinylene group, propenylene group, 1 -Butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, etc., linear or branched alkenylene groups having 2 to 8 carbon atoms (including alkapolyenylene groups), etc. Is mentioned. In particular, as the episulfide alkenylene group, an alkenylene group in which all carbon-carbon double bonds are episulfided or epoxidized is preferable, and more preferably, all carbon-carbon double bonds are episulfided or epoxidized. It is an alkenylene group having 2 to 4 carbon atoms.

  As the linking group Y and Y ′, a linking group containing an oxygen atom is particularly preferable. Specifically, for example, —CO—, —O—CO—O—, —COO—, —O—, — CONH—; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the alicyclic episulfide compound (A) represented by the above formula (2) or (2 ′) include 2,2-bis (3,4-episulfidecyclohexane-1-yl) propane, -(3,4-episulfidecyclohexane-1-yl) -2- (3,4-epoxycyclohexane-1-yl) propane, bis (3,4-episulfidecyclohexylmethyl) ether, (3,4-episulfidecyclohexylmethyl) ) (3,4-epoxycyclohexylmethyl) ether, 1,2-bis (3,4-episulfidecyclohexane-1-yl) ethane, 1- (3,4-episulfidecyclohexane-1-yl) -2- (3 , 4-Epoxycyclohexane-1-yl) ethane, 1,2-episulfide-1,2-bis (3,4-episulfide) Cyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-episulfidecyclohexane-1-yl) ethane, 1,2-episulfide-1- (3,4-episulfidecyclohexane -1-yl) -2- (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1- (3,4-episulfidecyclohexane-1-yl) -2- (3,4 And epoxycyclohexane-1-yl) ethane, compounds represented by the following formulas (2a) and (2-1) to (2-10). In addition, l in the following formula (2-5) and m in (2-7) each represent an integer of 1 to 30. R in the following formula (2-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (2-9) and (2-10) each represent an integer of 1 to 30. In the following formula (2a), X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ³ and X ⁴ is a sulfur atom. In the following formula (2-3), X ⁵ and X ⁶ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ⁵ and X ⁶ is a sulfur atom. . In the following formula (2-4), X ⁷ and X ⁸ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ⁷ and X ⁸ is a sulfur atom. . In the following formula (2-5), X ⁹ and X ¹⁰ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ⁹ and X ¹⁰ is a sulfur atom. . In the following formula (2-6), X ¹¹ and X ¹² each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ¹¹ and X ¹² is a sulfur atom. . In the following formula (2-7), X ¹³ and X ¹⁴ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ¹³ and X ¹⁴ is a sulfur atom. . In the following formula (2-8), X ¹⁵ and X ¹⁶ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ¹⁵ and X ¹⁶ is a sulfur atom. . In the following formula (2-9), X ¹⁷ , X ¹⁸ and X ¹⁹ each independently represent an oxygen atom or a sulfur atom, but at least one of X ¹⁷ , X ¹⁸ and X ¹⁹ (preferably 2 Is one or more sulfur atoms. In the following formula (2-10), X ²⁰ , X ²¹ , X ²² and X ²³ each independently represent an oxygen atom or a sulfur atom, but at least one of X ²⁰ , X ²¹ , X ²² and X ²³ One (preferably two or more) is a sulfur atom.

  Examples of the alicyclic episulfide compound (A) represented by the above formulas (2a) and (2-1) to (2-10) include trade names “Celoxide 8000”, “Celoxide 2021P”, and “Celoxide 2081”. The above can be produced by using a commercially available corresponding alicyclic epoxy compound such as (manufactured by Daicel Co., Ltd.) or the like as a raw material by the “method for producing alicyclic episulfide compound (A)” described later.

Examples of the compound (ii) having an episulfide group directly bonded to the alicyclic ring by a single bond include compounds represented by the following formula (3).

In the formula (3), R ′ is a group obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol (p-valent organic group) in the structural formula, and p and q each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably from 1 to 6, and q is preferably from 1 to 30. When p is 2 or more, q in each [] (inside parentheses) may be the same or different. In the above formula (3), plural (p × q) X ^{24 s} independently represent an oxygen atom or a sulfur atom, and at least one (preferably two or more) of X ²⁴ is a sulfur atom. is there. Specific examples of the compound represented by the above formula (3) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Using a commercially available corresponding cycloaliphatic epoxy compound such as “EHPE3150” (manufactured by Daicel Corporation), etc. as a raw material by “manufacturing method of cycloaliphatic episulfide compound (A)” described later. Can do.

Examples of the compound (iii) having an alicyclic ring and a 2,3-episulfidepropyl group include compounds represented by the following formula (4).

  In the above formula (4), Z represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group represented by Z include those similar to the linking group represented by Y in the above formula (2). In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring in the formula (4).

In the formula (4), X ²⁵ and X ²⁶ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ²⁵ and X ²⁶ is a sulfur atom. However, when Z is a group represented by —C (CH ₃ ) ₂ —, one of X ²⁵ and X ²⁶ is a sulfur atom and the other is an oxygen atom.

(Iii) Specific examples of the compound having an alicyclic ring and a 2,3-episulfidepropyl group include 2- [4- (2,3-episulfidepropoxy) cyclohexyl] -2- [4- (2,3 -Epoxypropoxy) cyclohexyl] propane, bis [2- (2,3-episulfidepropoxy) cyclohexyl] methane, [2- (2,3-episulfidepropoxy) cyclohexyl] [2- (2,3 -Epoxypropoxy) cyclohexyl] methane, [2- (2,3-episulfidepropoxy) cyclohexyl] [4- (2,3-episulfidepropoxy) cyclohexyl] methane, [2- (2,3- Episulfidepropoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, [2- (2,3-epoxypro) Xyl) cyclohexyl] [4- (2,3-episulfidepropoxy) cyclohexyl] methane, bis [4- (2,3-episulfidepropoxy) cyclohexyl] methane, [4- (2,3-episulfide) Propoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-episulfidepropoxy) cyclohexyl] methane, [3, 5-dimethyl-4- (2,3-episulfidepropoxy) cyclohexyl] [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, hydrogenated bisphenol F type episulfide resin (Hydrogenated bisphenol F type episulfide resin), etc .; hydrogenated biphenol type episulfide resin; hydrogenated novo Obtained from a hydrogenated naphtholene type episulfide resin, such as hydrogenated phenol novolak type episulfide resin, hydrogenated cresol novolak type episulfide resin, hydrogenated cresol novolak type episulfide resin of bisphenol A, etc .; Examples thereof include hydrogenated epoxy resins of episulfide resins. Here, the episulfide resin is a compound in which at least one of the epoxy groups contained in the corresponding epoxy resin is substituted with an episulfide group. Especially, the hydrogenated biphenol type | mold episulfide resin represented by a following formula (4-1) is preferable.

In the formula (4-1), X ²⁷ and X ²⁸ each independently represent an oxygen atom or a sulfur atom, but at least one (preferably two) of X ²⁷ and X ²⁸ is a sulfur atom. . In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring in the formula (4-1).

  As the alicyclic episulfide compound (A) represented by the above formula (4), for example, trade name “YX8000”, trade name “YX8034”, trade name “YL-6753” (above, manufactured by Mitsubishi Chemical Corporation) ) And other commercially available corresponding alicyclic epoxy compounds, etc., as raw materials, can be produced by the “method for producing alicyclic episulfide compound (A)” described later.

  Other examples of the alicyclic episulfide compound (A) include 1,2,8,9-diepisulfide limonene, 1,2-episulfide-8,9-epoxylimonene, and 8,9-episulfide-1,2. -Epoxy limonene etc. are mentioned, It can manufacture by the below-mentioned "manufacturing method of an alicyclic episulfide compound (A)" by using 1,2,8,9-diepoxy limonene etc. as a raw material.

[Method for producing alicyclic episulfide compound (A)]
The alicyclic episulfide compound (A) of the present invention has a corresponding alicyclic epoxy compound (a compound in which all of the sulfur atoms of the alicyclic episulfide compound (A) are substituted with oxygen atoms. It may be produced by reacting a cycloaliphatic epoxy compound (A) ”(sometimes referred to as“ alicyclic epoxy compound (A) ”) with a chelating agent.

  The alicyclic epoxy compound (A), which is a raw material for producing the alicyclic episulfide compound (A) of the present invention, can be produced by a known method, and the trade names “Celoxide 2021P”, “Celoxide 2081”, Commercial products such as “Celoxide 2000”, “Celoxide 8000”, and “EHPE3150” (manufactured by Daicel Corporation) can also be used.

  The thiating agent used in the production of the alicyclic episulfide compound (A) of the present invention reacts with the epoxy group of the alicyclic epoxy compound (A) to produce an episulfide group (hereinafter referred to in this specification). The compound is not particularly limited as long as it is a compound that may promote an “episulfidation reaction”. One kind of thiating agent may be used alone, or two or more kinds of thiating agents may be used in combination.

Examples of the thiating agent used in the episulfidation reaction of the present invention include thiocyanate and thioureas.
Examples of the thiocyanate include lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, cesium thiocyanate, silver thiocyanate, cobaltous thiocyanate, mercuric thiocyanate, thallium thiocyanate, thiocyanate. Examples include cuprous acid, lead dithiocyanate, nickel dithiocyanate, barium dithiocyanate, ammonium thiocyanate, and guanidine thiocyanate, which are easy to obtain and have excellent reactivity.Sodium thiocyanate, thiocyanic acid Potassium and ammonium thiocyanate are preferred.

  Examples of the thioureas include thiourea, N, N′-dimethylthiourea, N, N, N ′, N′-tetramethylthiourea, N, N′-diethylthiourea, propylthiourea, N, N′-diisopropylthio. Urea, N, N′-dibutylthiourea, N-methyl-N ′-(2-methyl-2-propenyl) thiourea, N-phenylthiourea, N, N′-diphenylthiourea, 1-methyl-2-imidazo Lidinthione, 1-benzyl-2-thiourea, N- (3,5-dimethylphenyl) thiourea, N- (2,6-dimethylphenyl) thiourea, N- (2,3-dimethylphenyl) thio Urea, N- (2,4,6-trimethylphenyl) thiourea, N, N′-bis (2-methylphenyl) thiourea, N, N′-bis (3,5-dimethylphenyl) thiourea, N , N′-bis (2,6 Dimethylphenyl) thiourea, N, N′-bis (2,4,6-trimethylphenyl) thiourea, N- (2-chlorophenyl) thiourea, N- (3-chlorophenyl) thiourea, N- (4- Chlorophenyl) thiourea, N- (3,4-dichlorophenyl) thiourea, N- (3,5-dichlorophenyl) thiourea, N- (2,6-dichlorophenyl) thiourea, N- (2,4,6- Trichlorophenyl) thiourea, N, N′-bis (2-chlorophenyl) thiourea, N, N′-bis (3,5-dichlorophenyl) thiourea, N, N′-bis (2,6-dichlorophenyl) thio Urea, N- (2-fluorophenyl) thiourea, N- (3-fluorophenyl) thiourea, N- (4-fluorophenyl) thiourea, N- [2- (trifluoromethyl) pheny ] Thiourea, N- [3- (trifluoromethyl) phenyl] thiourea, N- [4- (trifluoromethyl) phenyl] thiourea, N- (2,6-difluorophenyl) thiourea, N- ( 2,4-difluorophenyl) thiourea, N- (2,3-difluorophenyl) thiourea, N- (2,4,6-trifluorophenyl) thiourea, N, N′-bis (2-fluorophenyl) ) Thiourea, N, N′-bis (2,6-difluorophenyl) thiourea, N, N′-bis (2,4,6-trifluorophenyl) thiourea, N- (2-cyanophenyl) thio Urea, N- (3-cyanophenyl) thiourea, N- (4-cyanophenyl) thiourea, N- (3,5-dicyanophenyl) thiourea, N, N′-bis (4-cyanophenyl) thio Urea, N, N′-bis ( , 5-dicyanophenyl) thiourea, N- (2-methoxyphenyl) thiourea, N- (3-methoxyphenyl) thiourea, N- (4-methoxyphenyl) thiourea, N- (2,6-dimethoxy) Phenyl) thiourea, N- (3,5-dimethoxyphenyl) thiourea, N- (2,4,6tridimethoxyphenyl) thiourea, N, N′-bis (4-methoxyphenyl) thiourea, N, N′-bis (2,6-dimethoxyphenyl) thiourea, N, N′-bis (2,4,6tridimethoxyphenyl) thiourea, N- (2-nitrophenyl) thiourea, N- (3- Nitrophenyl) thiourea, N- (4-nitrophenyl) thiourea, N- (3,5-dinitrophenyl) thiourea, N, N′-bis (3,5-dinitrophenyl) thiourea and the like. Economics, Thiourea is preferred from the viewpoint of refractoriness.

  The amount of the thiating agent used in the episulfation reaction of the present invention is not particularly limited as long as the episulfation reaction proceeds, but the total molar amount of epoxy groups contained in the alicyclic epoxy compound (A) used as a raw material 100-2000 mol% is preferable with respect to (100 mol%), and 105-1000 mol% is more preferable. If the amount of the thialating agent used is 100 mol% or more, the episulfidation reaction proceeds well. On the other hand, even if the amount of the chelating agent used exceeds 2000 mol%, there is little influence on the progress of the episulfidation reaction, which is economically disadvantageous.

  The episulfidation reaction of the present invention can be performed in the presence or absence of a solvent. Among these, it is preferable to perform in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol , Water and the like. Among these solvents, alcohol is preferable. A solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The usage-amount of a solvent is not specifically limited, According to desired reaction time etc. in the range of 0-2000 weight part with respect to 100 weight part of alicyclic epoxy compounds (A), it can adjust suitably. it can.

  Although the reaction temperature of the episulfidation reaction is not particularly limited, it is preferably −100 to 150 ° C., more preferably 10 to 80 ° C. Moreover, the reaction time of the episulfidation reaction is not particularly limited, but is preferably 1 to 100 hours, and more preferably 3 to 50 hours. Moreover, the episulfidation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the said episulfidation reaction is not specifically limited, For example, any of inert gas atmosphere, such as nitrogen atmosphere and argon atmosphere, oxygen presence, such as under air, may be sufficient.

  The alicyclic episulfide compound (A) of the present invention is obtained by the episulfidation reaction. After completion of the episulfidation reaction, for example, the alicyclic episulfide compound (A) of the present invention is washed with water, acid, alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Separation / purification may be performed by the separation means described above, a separation means combining these, or the like.

  Since the alicyclic episulfide compound (A) of the present invention has the above-described configuration, a curable composition containing this as an essential component (hereinafter sometimes referred to as “the curable episulfide resin composition of the present invention”). By curing, a cured product having a high refractive index and a high Abbe number and an excellent balance between the refractive index and the Abbe number can be formed.

<Curable episulfide resin composition>
The curable episulfide resin composition of the present invention is a resin composition containing an alicyclic episulfide compound (A) and a curing catalyst (B) as essential components. The curable episulfide resin composition of the present invention may further contain, as an optional component, an episulfide compound other than the curing agent (C) and the alicyclic episulfide compound (A).

  In the curable episulfide resin composition of the present invention, the alicyclic episulfide compound (A) can be used alone or in combination of two or more.

  The content (blending amount) of the alicyclic episulfide compound (A) in the curable episulfide resin composition of the present invention is not particularly limited, but the total amount of compounds having episulfide groups contained in the curable episulfide resin composition (total Episulfide compound) is preferably 30 to 100% by weight, more preferably 40 to 95% by weight, still more preferably 50 to 90% by weight, and particularly preferably 60 to 85% by weight with respect to 100% by weight. When the content of the alicyclic episulfide compound (A) is less than 30% by weight, the refractive index of the cured product, the Abbe number, the balance between the refractive index and the Abbe number, light resistance, and the like may decrease. In addition, when using 2 or more types as an alicyclic episulfide compound (A), it is preferable that the total amount of these alicyclic episulfide compounds (A) satisfy | fills the said range.

  The content (blending amount) of the alicyclic episulfide compound (A) in the curable episulfide resin composition (100 wt%) of the present invention is not particularly limited, but is preferably 30 wt% or more and less than 100 wt%. Preferably it is 40 to 90 weight%, More preferably, it is 50 to 80 weight%. When the content of the alicyclic episulfide compound (A) is less than 30% by weight, the refractive index, Abbe number, heat resistance, and light resistance of the cured product may be lowered. In addition, when using 2 or more types as an alicyclic episulfide compound (A), it is preferable that the total amount of these alicyclic episulfide compounds (A) satisfy | fills the said range.

[Curing catalyst (B)]
The curable episulfide resin composition of the present invention contains a curing catalyst (B) as an essential component. By using the curing catalyst (B), the curing reaction of the compound having an episulfide group can proceed to obtain a cured product. Although it does not specifically limit as a curing catalyst (B), Amines; Phosphines; Organic acid, its salt, or its ester; Inorganic acid; Quaternary ammonium salt; Quaternary phosphonium salt; Tertiary sulfonium salt, Secondary iodonium Salts; Lewis acids; radical polymerization catalysts; cationic polymerization catalysts and the like can be used. In addition, a curing catalyst (B) can be used individually by 1 type or in combination of 2 or more types.

  As the amines (amine-based curing catalyst) as the curing catalyst (B), a known or conventional amine-based curing catalyst can be used, and is not particularly limited. For example, ethylamine, n-propylamine, sec-propylamine, n -Butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mistyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2- Ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxy Propylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, Primary amines such as α-phenylethylamine, naphthylamine, furfurylamine; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diamino Butane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopro Pyr) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, aminoethylethanolamine, 1,2-, 1 , 3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bis Aminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropyl Piperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoro Diamine, Menthanediamine, 1,4-Bisaminopropylpiperazine, o-, m-, or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminobenzyl Amine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-, or p-xylylenediamine, 1,5- or 2 , 6-Naphthalenediamine, benzidine, 4,4'-bis (o-toluidine), dianisidine, 4,4'-diaminodiphenylmethane, 2,2- (4,4'-diaminodiphenyl) propane, 4,4'- Diaminodiphenyl ether, 4,4′-thiodianiline, 4,4′-diaminodiphenylsulfone, 4,4′-dia Noditolyl sulfone, methylene bis (o-chloroaniline), 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methylimino Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4 -Primary polyamines such as bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutyl Amines, Di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2, Secondary amines such as 4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine; N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1,6-diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl- 1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6 -Dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4- Di- (4-pipe Zyl) butane, tetramethylguanidine, and other secondary polyamines; trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n -Butylamine, tri-isobutylamine, tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecyl Amine, tri-laurylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, N-methyldicyclohexylamine Triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N -Dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1 , 3,2-dioxabornane and the like; tetramethylethylenediamine, pyrazine, N, N′-dimethylpiperazine, N, N′-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ′, N′-tetramethyl-1,3-butanamine, 2-dimethyl Such as ruamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, heptamethylisobiguanide, etc. Tertiary polyamine; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N-undecyl Imidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole, N- (2′-cyanoethyl) -2-methyl Midazole, N- (2′-cyanoethyl) -2-undecylimidazole, N- (2′-cyanoethyl) -2-phenylimidazole, 3,3-bis- (2-ethyl-4-methylimidazolyl) methane, alkyl Various imidazoles such as an adduct of imidazole and isocyanuric acid, a condensate of alkyl imidazole and formaldehyde; 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] Examples thereof include amidines such as nonene-5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7.

  As the phosphine (phosphine-based curing catalyst) as the curing catalyst (B), a known or conventional phosphine-based curing catalyst can be used, and is not particularly limited. n-butylphosphine, tri-n-cyclohexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, di Black hexyl phenyl phosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, chlorodiphenylphosphine, and the like.

  Although it does not specifically limit as organic acid, its salt, or its ester as a curing catalyst (B), For example, sulfonic acid, carboxylic acid, and its ester are preferable, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid , P-toluenesulfonic acid, 10-camphorsulfonic acid, and methyl and ethyl esters thereof.

  The inorganic acid as the curing catalyst (B) is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid.

  The quaternary ammonium salt as the curing catalyst (B) is not particularly limited. For example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetra- n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylammonium borohydride, tetra -N-butylammonium hexafluorophosphite, tetra-n-butylammonium hydrogensulfite Tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium tetraphenylborate, tetra-n-butylammonium paratoluenesulfonate, tetra-n-hexylammonium chloride, tetra-n-hexylammonium bromide, tetra -N-hexylammonium acetate, tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-octylammonium acetate, trimethyl-n-octylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, triethyl -N-octylammonium chloride, triethylbenzylammonium chloride, trie Rubenzylammonium bromide, tri-n-butyl-n-octylammonium chloride, tri-n-butylbenzylammonium fluoride, tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butyl Benzylammonium iodide, methyltriphenylammonium chloride, methyltriphenylammonium bromide, ethyltriphenylammonium chloride, ethyltriphenylammonium bromide, n-butyltriphenylammonium chloride, n-butyltriphenylammonium bromide, 1-methylpyridinium bromide 1-ethylpyridinium bromide, 1-n-butylpyridinium bromide, 1-n-hexylpi Lidinium bromide, 1-n-octylpyridinium bromide, 1-n-dodecylpyridinium bromide, 1-n-phenylpyridinium bromide, 1-methylpicolinium bromide, 1-ethylpicolinium bromide, 1-n-butylpicolinium bromide 1-n-hexylpicolinium bromide, 1-n-octylpicolinium bromide, 1-n-dodecylpicolinium bromide, 1-n-phenylpicolinium bromide and the like.

  Although it does not specifically limit as quaternary phosphonium salts as a curing catalyst (B), For example, tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride, tetra-n -Butylphosphonium bromide, tetra-n-butylphosphonium iodide, tetra-n-hexylphosphonium bromide, tetra-n-octylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, ethyl Triphenylphosphonium iodide, n-butyltriphenylphosphonium bromide, n-butyltri Enylphosphonium iodide, n-hexyltriphenylphosphonium bromide, n-octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakishydroxymethylphosphonium chloride, tetrakishydroxymethylphosphonium bromide, tetrakishydroxyethylphosphonium chloride, tetrakishydroxybutylphosphonium chloride, etc. Is mentioned.

  The tertiary sulfonium salt as the curing catalyst (B) is not particularly limited, and examples thereof include trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butyl. Examples include sulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, tri-n-hexylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, and triphenylsulfonium iodide.

  The secondary iodonium salts as the curing catalyst (B) are not particularly limited, and examples thereof include diphenyliodonium chloride, diphenyliodonium bromide, and diphenyliodonium iodide.

  The Lewis acid as the curing catalyst (B) is not particularly limited, and examples thereof include boron trifluoride, boron trifluoride etherate, dibutyltin dichloride, and dibutyltin dilauric acid.

  As the radical polymerization catalyst (radical polymerization initiator) as the curing catalyst (B), a known or conventional radical polymerization initiator can be used, and is not particularly limited. For example, photo radical polymerization initiator, thermal radical polymerization initiator. Etc.

  Examples of the photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, Orthobenzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name) “Kayacure DETX”, etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Gaigi Co., Ltd., trade name “Irgacure 907”, etc.), 1-hydroxycyclo F 2-amino-2-benzoyl-1- such as silphenylketone (Ciba-Geigy Co., Ltd., trade name “Irgacure 184”, etc.), 2-dimethylamino-2- (4-morpholino) benzoyl-1-phenylpropane, etc. Aminobenzene derivatives such as phenylalkane compounds, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2, 2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (made by Hodogaya Chemical Co., Ltd., trade name “B-CIM”, etc.), etc. 1,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine Halomethyl triazines compounds of 2-trichloromethyl-5- (2-benzofuran-2-yl - ethenyl) -1,3,4 oxadiazole, and the like halomethyl oxadiazole compounds, and the like. Moreover, a photosensitizer can be added as needed.

  Examples of the thermal radical polymerization initiator include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, peroxyketal, and ketone peroxide (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butylperoxybenzoate, t-butylperoxide, cumene hydro Peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di (2-t- Butyl peroxyisopropyl) benzene, , 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc.) Mention may be made of peroxides.

  As the cationic polymerization catalyst (cationic polymerization initiator) as the curing catalyst (B), a known or commonly used cationic polymerization initiator can be used, and is not particularly limited, but examples thereof include a photocationic polymerization initiator and a thermal cationic polymerization initiator. Etc.

  Examples of the photocationic polymerization initiator include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and the like. Examples of the cationic catalyst include trade name “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.), trade name “CD-1010”, trade name “CD-1011”, trade name “CD-1012” (above, the United States). Commercial products such as Sartomer), trade name “Irgacure 264” (manufactured by BASF), and trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Examples of the thermal cationic polymerization initiator include aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, allene-ion complexes, and the like. Trade names “PP-33”, trade names “CP-66”, trade names “ CP-77 "(manufactured by ADEKA Corporation), trade name" FC-509 "(manufactured by 3M), trade name" UVE1014 "(manufactured by GE), trade name" Sun Aid SI-60L ", trade name" Sun Aid " "SI-80L", trade name "Sun-Aid SI-100L", trade name "Sun-Aid SI-110L", trade name "Sun-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.), trade name "CG-24-61" ”(Manufactured by Ciba Japan) and the like can be preferably used. Furthermore, a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S The compound with phenols, such as these, may be sufficient.

As the curing catalyst (B), a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, a secondary iodonium salt from the viewpoint of the high refractive index, high Abbe number, and balance between the refractive index and the Abbe number of the cured product, Lewis acids are preferred, more preferably quaternary ammonium salts, quaternary phosphonium salts, and even more preferably quaternary phosphonium.
Preferred examples include quaternary ammonium salts such as tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, and tetra-n-butyl. And quaternary phosphonium salts such as phosphonium bromide and tetraphenylphosphonium bromide.

  The content (blending amount) of the curing catalyst (B) is not particularly limited, but is 0.01 to 15 weights with respect to the total amount (100 parts by weight) of the compound having an episulfide group contained in the curable episulfide resin composition. Part is preferable, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (B) within the above range, a cured product having a high refractive index, a high Abbe number, a good balance between the refractive index and the Abbe number, and excellent heat resistance, light resistance, and transparency can be obtained. be able to. In addition, when using 2 or more types as a curing catalyst (B), it is preferable that the total amount of these curing catalysts (B) satisfy | fills the said range.

[Curing agent (C)]
The curable episulfide resin composition of the present invention may further contain a curing agent (C). The curing agent (C) in the curable episulfide resin composition of the present invention is a compound having a function of reacting and curing with a compound having an episulfide group. As the curing agent (C), known or conventional curing agents can be used as episulfide resin curing agents, such as thiol compounds, isocyanate compounds, thioisocyanate compounds, epoxy compounds, acid anhydrides, polyhydric phenol compounds. Etc.

  As the curing agent (C), a thiol compound is preferable. By using a thiol compound as the curing agent (C), the mercapto group is excellent in reactivity to the episulfide group, so that the curability is improved, and by adjusting the sulfur concentration in the cured product, a high refractive index, A cured product having a high Abbe number and a good balance between the refractive index and the Abbe number can be formed.

  Although it does not specifically limit as a thiol compound as a hardening | curing agent (C), For example, thiophenols, thiols, mercapto alcohols, hydroxythiophenols, mercapto organic acids, mercaptoamines etc. are mentioned.

  Although it does not specifically limit as thiophenol, For example, thiophenol, 4-tert- butylthiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, o-dimercaptobenzene, m-dimercaptobenzene , P-dimercaptobenzene, 1,3,5-trimercaptobenzene and the like.

  Examples of thiols include, but are not limited to, for example, til mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan. , N-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, benzyl mercaptan, 4-chlorobenzyl mercaptan, methylthioglycoglycan Rate, ethyl thioglycolate, n-butyl thioglycolate, n-octyl thioglycolate, methyl (3- Lucaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3-mercaptopropionate) Monothiols) such as pionate) and n-octyl (3-mercaptopropionate), methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1, 2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 1,5 -Dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2- Methylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl 1,4-dimercaptopropane, 2- ( 2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) ) Methane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3 -Tetrakis (mercaptomethylthio) propane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol Bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3- Mercaptopropionate), 1,1-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3- (Mercaptomethyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (mercaptoethyl) -1,4-dithiane, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) ether 2,2-bis (4-mercaptophenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, etc. Valent thiols and the like.

  Although it does not specifically limit as mercapto alcohol, For example, 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropanol, 2-hydroxypropyl mercaptan, 2-phenyl-2-mercaptoethanol, 2-phenyl-2-hydroxy Ethyl mercaptan, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, 2,3-dimercaptopropanol, 1,3-dimercapto-2-propanol, 2,2-dimethylpropane- Examples include 1,3-diol and glyceryl dithioglycolate.

  Although it does not specifically limit as hydroxythiophenol, For example, 2-hydroxythiophenol, 3-hydroxythiophenol, 4-hydroxythiophenol etc. are mentioned.

  Although it does not specifically limit as mercapto organic acids, For example, mercaptocarboxylic acids, such as 2-mercaptoacetic acid (thioglycolic acid) and 3-mercaptopropionic acid, are mentioned.

  The mercaptoamines are not particularly limited, and examples thereof include mercaptoalkylamines such as 2-mercaptoethylamine, 3-mercaptopropylamine and 3-mercaptobutylamine; and aminothiophenols such as 4-aminothiophenol. .

  The isocyanate compound as the curing agent (C) is not particularly limited. For example, diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o -Tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3- (2'-isocyanate Tocyclohexyl) propyl isocyanate, tris (phenylisocyanate) thiophosphate, isopropylidenebis (cyclohexylisocyanate), 2,2′-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) Phenylmethane, 4,4 ', 4 "-triisocyanate-2,5-dimethoxyphenylamine, 3,3'-dimethoxybenzidine-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate 4,4′-diisocyanatobiphenyl, 4,4′-diisocyanate-3,3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanate base) Zen), 1,1'-methylenebis (3-methyl-4-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene 1,4-bis (1-isocyanato-1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1, 5-Naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) norbornene, bis (isocyanatomethyl) adamantane , Dimer acid dii Cyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, bis [(4-isocyanatomethyl) phenyl] sulfide, 2,5-diisocyanate -1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyanate methylthiophene, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and the like. Among the above, polyisocyanates include isocyanates such as dimers, cyclized trimers and adducts of alcohols or thiols by burette type reaction.

  Although it does not specifically limit as a thioisocyanate compound as a hardening | curing agent (C), For example, the compound which changed all or one part of the isocyanate group of the said isocyanate compound into the isothiocyanate group is mentioned.

  Although it does not specifically limit as an epoxy compound as a hardening | curing agent (C), For example, phenol, cresol, xylenol, naphthol, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated Phenolic epoxy compounds produced by condensation of aromatic hydroxy compounds such as bisphenol A and novolac resins and epihalohydrins, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, isopropyl alcohol, isobutyl alcohol, tert -Butanol, neopentyl alcohol, ethylene glycol, diethylene glycol, trie Lenglycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, Of 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct and the like and epihalohydrin Alcohol epoxy compounds produced by condensation, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, isobutyric acid, isovaleric acid, benzoic acid, benzoylacetic acid, naphtho Phosphorus carboxylic acid, adipic acid, sebacic acid, dodecyl carboxylic acid, dimer acid, phthalic acid, isoterephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, het acid Glycidyl ester produced by condensation of carboxylic acid compounds such as nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid and epihalohydrin Epoxy compound, methylamine, ethylamine, propylamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-di Aminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis (3-aminopropyl) ether, 1,2-bis (3-aminopropoxy) Ethane, 1,3-bis (3-aminopropoxy) -2,2'-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bis Aminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, isophoronediamine, 1,4-bis Aminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or 1 such as xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2- (4,4′-diaminodiphenyl) propane Primary amine, dimethylamine, diethylamine, dibutylamine, methylethylamine, methylpropylamine, methylbutylamine, methylpentylamine, methylhexylamine, ethylpropylamine, ethylbutylamine, ethylpentylamine, ethylhexylamine, N, N'-dimethylethylenediamine N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl- 1,5-diaminopentane, N, N′-dimethyl -1,6-diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl -1,3-diaminopropane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl-1,5-diaminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di (4-piperidyl) methane, 1, Acetates produced by condensation of secondary amines such as 2-di (4-piperidyl) ethane, 1,3-di (4-piperidyl) propane, 1,4-di (4-piperidyl) butane and epihalohydrins Epoxy compounds, cycloaliphatic epoxy compounds (compounds in which the sulfur atom of the above cycloaliphatic episulfide compound (A) is substituted with oxygen atoms, etc.), styrene oxide, cyclopentadiepoxide, epoxidized soybean oil, epoxidized polybutadiene And an epoxy compound produced by epoxidation of an unsaturated compound such as vinylcyclohexene epoxide, the above-mentioned polyhydric alcohol, a urethane-based epoxy compound produced from a phenol compound, diisocyanate, glycidol and the like.

  As the acid anhydride as the curing agent (C), known or conventional acid anhydride curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl anhydride Acid, liquid acid anhydride such as methylendomethylenetetrahydrophthalic anhydride at 25 ° C .; succinic anhydride, hydrogenated pyromellitic anhydride, hydrogenated biphenyl dianhydride, phthalic anhydride, tetrahydrophthalic anhydride (for example, 1 , 2,3,6-tetrahydrophthalic anhydride), hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride and the like, and the like (solid-state acid anhydrides) at 25 ° C. Moreover, as said acid anhydride type hardening catalyst, the polyhydric carboxylic acid condensate etc. of Unexamined-Japanese-Patent No. 2011-219534 etc. can also be used, for example.

  Although it does not specifically limit as a polyhydric phenol compound as a hardening | curing agent (C), For example, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, novolak resin, etc. Is mentioned.

  A hardening | curing agent (C) can be used individually by 1 type or in combination of 2 or more types. The curing agent (C) is preferably a polyvalent thiol compound from the viewpoint of high refractive index, high Abbe number, balance between refractive index and Abbe number, heat resistance, and light resistance of the cured product. In addition, 2 to 6 compounds are preferable. Specific examples thereof include bis (2-mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 2,5-bis (mercaptomethyl) -1,4- Dithiane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3- Tetrakis (mercaptomethylthio) propane, 1,3-bis (mercaptomethyl) benzene, 1,4-bis Include mercaptomethyl) benzene.

  When the curable episulfide resin composition of the present invention contains a curing agent (C), the content (blending amount) is not particularly limited, but the episulfide group contained in the curable episulfide resin composition of the present invention is not limited. The amount is preferably 10 to 200 parts by weight, and more preferably 30 to 150 parts by weight, based on 100 parts by weight of the total amount of the compound. More specifically, it should be used at a ratio of 0.1 to 1.5 equivalents of mercapto group per equivalent of epoxy group in the compound having all episulfide groups contained in the curable episulfide resin composition of the present invention. Is preferred. When the content of the curing agent (C) is less than 10 parts by weight, curing is insufficient, and the refractive index, Abbe number, and toughness of the cured product tend to decrease. On the other hand, if the content of the curing agent (C) exceeds 200 parts by weight, the balance between the refractive index and the Abbe number of the cured product may be deteriorated. In addition, when using 2 or more types as a hardening | curing agent (C), it is preferable that the total amount of these hardening | curing agents (C) satisfy | fills the said range.

[Other episulfide compounds]
The curable episulfide resin composition of the present invention may contain an episulfide compound other than the alicyclic episulfide compound (A) (sometimes referred to as “other episulfide compound”). Examples of the other episulfide compounds include aromatic thioglycidyl ether episulfide compounds [for example, bisphenol A type episulfide compounds, bisphenol F type episulfide compounds, biphenol type episulfide compounds, phenol novolak type episulfide compounds, cresol novolak type episulfide compounds, Bisphenol A cresol novolac type episulfide compound, naphthalene type episulfide compound, episulfide compound obtained from trisphenolmethane, etc.], aliphatic thioglycidyl ether type episulfide compound [eg, aliphatic 2,3-episulfide propyl ether, etc.], thioglycidyl Ester episulfide compounds, thioglycidylamine episulfides Compound, isocyanurate compound having episulfide group [for example, diallyl mono (2,3-episulfidepropyl) isocyanurate compound, monoallyldi (2,3-episulfidepropyl) isocyanurate compound, tri (2,3-episulfidepropyl) isocyanurate Compound, etc.], 2,2-bis [4- (2,3-episulfidepropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-episulfidepropoxy) cyclohex Xyl] propane, hydrogenated bisphenol A type episulfide resin (hydrogenated bisphenol A type episulfide resin), a compound represented by the above formula (2), wherein Y is —CH ₂ —O—C (═O ) - in a divalent group represented by and one of which vulcanization of X ¹ and X ² Atom and the other like compounds is an oxygen atom. Other episulfide compounds include compounds in which a part of the episulfide group is replaced with an epoxy group.

  Representative examples of the monoallyldi (2,3-episulfidepropyl) isocyanurate compound include monoallyldi (2,3-episulfidepropyl) isocyanurate, 1-allyl-3,5-bis (2-methyl-2,3 -Episulfidepropyl) isocyanurate, 1- (2-methylpropenyl) -3,5-di (2,3-episulfidepropyl) isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methyl) -2,3-episulfidepropyl) isocyanurate and the like.

  The monoallyldi (2,3-episulfidepropyl) isocyanurate compound may be modified in advance by adding a compound that reacts with an episulfide group, such as alcohol or acid anhydride.

  In the curable episulfide resin composition of the present invention, the other episulfide compounds can be used alone or in combination of two or more. Among these, the other episulfide compounds include 2,2-bis [] in terms of the high refractive index of the cured product, a high Abbe number, the balance between the refractive index and the Abbe number, transparency, and mechanical properties (for example, toughness). 4- (2,3-episulfidepropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-episulfidepropoxy) cyclohexyl] propane, bisphenol A type episulfide resin Hydrogenated one (hydrogenated bisphenol A type episulfide resin) is preferred.

  When the curable episulfide resin composition of the present invention contains the other episulfide compound, the content (blending amount) is not particularly limited, but is 5 for 100 parts by weight of the alicyclic episulfide compound (A). -150 weight part is preferable, More preferably, it is 10-100 weight part.

[Additive]
In addition to the above, the curable episulfide resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used as the additive, the reaction can be allowed to proceed slowly. In addition, amino acids, olefins such as (meth) acrylates, inorganic substances such as sulfur, silicone-based and fluorine-based antifoaming agents, leveling agents, and γ-glycidoxy as long as viscosity and transparency are not impaired. Silane coupling agents such as propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, surfactants, inorganic fillers such as alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbers, pigments, Conventional additives such as mold release agents can be used.

  The curable episulfide resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary. In addition, the curable episulfide resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

  Although the viscosity in 25 degreeC of the curable episulfide resin composition of this invention is not specifically limited, 100-10000 mPa * s is preferable, More preferably, it is 200-9000 mPa * s, More preferably, it is 300-8000 mPa * s. There exists a tendency for the heat resistance of hardened | cured material to fall that the viscosity in 25 degreeC is less than 100 mPa * s. On the other hand, when the viscosity at 25 ° C. exceeds 10,000 mPa · s, workability at the time of casting tends to be reduced, or defects derived from poor casting tend to occur in the cured product. The viscosity at 25 ° C. of the curable episulfide resin composition is, for example, using a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25. It can be measured under the conditions of ° C. and rotation speed: 0.5 to 10 rpm.

<Hardened product>
By curing the curable episulfide resin composition of the present invention, a cured product having a high refractive index, a high Abbe number, and a good balance between the refractive index and the Abbe number can be obtained with high productivity. In particular, when the curable episulfide resin composition of the present invention contains the above-described curing agent (C), the cured product exhibits a higher refractive index and a higher Abbe number. Although the heating temperature (curing temperature) in the case of hardening is not specifically limited, 10-200 degreeC is preferable, More preferably, it is 20-190 degreeC, More preferably, it is 30-180 degreeC. In addition, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased.

<Optical material>
A cured product obtained by curing the curable episulfide resin composition of the present invention (hereinafter sometimes referred to as “cured product of the present invention”) exhibits a high refractive index and a high Abbe number, Since it has an excellent Abbe number balance, it can be suitably used as various optical materials, for example, optical lenses such as glasses and cameras, optical fiber cables, prisms, information recording boards, and plastics for filters. Here, being excellent in the balance between the refractive index and the Abbe number means that the refractive index and the Abbe number are respectively adjusted to ranges that are satisfactory as an optical material while exhibiting high values. In the cured product of the present invention, the refractive index (ne) of the cured product at e-line (546.1 nm) is 1. It is preferable that it is 50-1.80, and 1.55-1.75 is more preferable. Further, from the viewpoint of effectively preventing rainbow generation due to chromatic aberration, the Abbe number (νe) at the e-line (546.1 nm) is preferably 30 to 60, and more preferably 40 to 55. As described above, the cured product of the present invention has a high refractive index, a high Abbe number, and good optical characteristics that satisfy the balance of both at the same time. It is. The refractive index and Abbe number of the cured product are values measured using a prism coupler. Specifically, the refractive index of the cured product at a wavelength of 546.1 nm (ne), the refractive index at 488 nm (nF ′), and the refractive index at 643.9 nm (nC ′) are obtained, and the Abbe number = (ne −1) / (nF′−nC ′) is substituted for the Abbe number (νe).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Measurement of ¹ H-NMR)
The ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in the examples was measured under the following conditions.
Equipment: JEOL 400MHz
Solvent: Deuterated chloroform (containing tetramethylsilane)

(Measurement of refractive index and Abbe number of cured product)
The refractive index (ne) and Abbe number (νe) of the cured product obtained by polymerization were measured using a Prism Coupler Model 100 manufactured by Metricon.

Example 1
3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (5.0 g) and ammonium thiocyanate (9.05 g) were reacted in methanol solvent (50 mL) at 25 ° C. for 36 hours. . The reaction mixture was extracted with dichloromethane, washed with water, and concentrated, and the extract obtained was purified by silica gel column purification (elution solvent: dichloromethane) to obtain 4.76 g of product. By NMR measurement, the product could be identified as 3,4-episulfide cyclohexylmethyl (3,4-episulfide) cyclohexanecarboxylate (compound represented by (2-1) above).
A chart of ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 1 is shown in FIG.

Example 2
4-vinylcyclohexene-1,2-epoxide (239 g) and ammonium thiocyanate (293 g) were reacted in a methanol solvent (2.9 L) at 43 ° C. for 4 hours. The reaction mixture was extracted with dichloromethane, washed with water, and concentrated, and the resulting extract was purified by silica gel column (elution solvent: dichloromethane) to obtain 170 g of product. By NMR measurement, the product could be identified as 4-vinylcyclohexene-1,2-episulfide (compound represented by (1-1) above).
A chart of the ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 2 is shown in FIG.

Example 3
Hydrogenated biphenol (100 g) was reacted with sodium hydride (26.6 g) and allyl bromide (152.5 g) in THF solvent (1 L) at 50 ° C. for 20 hours. The reaction mixture was washed with water, THF was concentrated, and the concentrate was separated and purified with a silica gel column (elution solvent: THF). As a result, hydrogenated biphenyl diallyl ether (78 g) and hydrogenated biphenol monoallyl ether (40 g) were obtained.
The obtained hydrogenated biphenyl diallyl ether (78 g) and metachloroperbenzoic acid (120.8 g) were reacted in a dichloromethane solvent (2 L) at room temperature for 18 hours. The reaction mixture was washed with water, dichloromethane was concentrated, and the concentrate was separated and purified with a silica gel column (elution solvent dichloromethane). As a result, 75 g of hydrogenated biphenyl diglycidyl ether was obtained.
The obtained hydrogenated biphenyl diglycidyl ether (3 g) and ammonium thiocyanate (4.41 g) were reacted in a methanol solvent (30 mL) at room temperature for 36 hours. The reaction mixture was extracted with dichloromethane, washed with water and concentrated, and the extract obtained was purified by silica gel column purification (elution solvent: dichloromethane) to obtain 0.90 g of product. NMR measurement, the product (represented by the above (4-1), X ²⁷ and X ²⁸ are both compounds is a sulfur atom) hydrogenated biphenyl di (2,3- polyepisulfide propyl) ether could be identified with.
A chart of ¹ H-NMR spectrum of the alicyclic episulfide compound obtained in Example 3 is shown in FIG.

Example 4
A 1000 ml three-necked round bottom flask equipped with a thermometer, a dropping funnel and a reflux tube was charged with ammonium thiocyanate (NH ₄ SCN, 78 g, 4.0 equivalents) and methanol (750 ml). Stir until the solid is dissolved while flowing nitrogen into the reaction system at room temperature, and then add (3,4,3 ′, 4′-diepoxy) bicyclohexyl (50 g, 0.26 mol) in a dropping funnel over 2 minutes. The reaction solution (pale yellow) was stirred at 25 ° C. for 18 hours (precipitation of insoluble components was observed). The reaction solution was extracted 6 times with petroleum ether (PE) (300 ml, 60 to 90 ° C.). The extract was dehydrated with sodium sulfate (Na ₂ SO ₄ ) and then concentrated at 30 ° C. Purification (silica gel, developing solution: PE / ethyl acetate = 20/1), and product 1 (7.2 g, yield 12%) and product 2 (0.8 g, yield 1) as colorless oily liquid .3%) was obtained.
By NMR measurement, product 1 was (3,4,3 ′, 4′-diepisulfide) bicyclohexyl (a compound represented by (2a) above, wherein X ³ and X ⁴ are both sulfur atoms), product 2 can be identified as (3,4-episulfide-3 ′, 4′-epoxy) bicyclohexyl (a compound represented by (2a) above, wherein one of X ³ and X ⁴ is a sulfur atom and the other is an oxygen atom). It was.
FIG. 4 shows a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound (product 1) obtained in Example 4, and FIG. 5 shows a chart of ¹ H-NMR spectrum of the alicyclic episulfide compound (product 2). Respectively.

Example 5
As an alicyclic episulfide compound (A), 35 g of 3,4-episulfide cyclohexylmethyl (3,4-episulfide) cyclohexanecarboxylate synthesized in Example 1 was used, and tetrabutylphosphonium bromide was added as a curing catalyst (B). 35 g was used.
These were blended using “Awatori Nertaro” manufactured by Shinky Co., Ltd. by mixing with stirring at room temperature for 20 minutes to obtain a curable episulfide resin composition.
The obtained curable episulfide resin composition was poured into a glass mold (thickness 3 mm). The glass mold was gradually heated from 30 ° C. over 19 hours to increase to 80 ° C., held at 80 ° C. for 2 hours, and further cured at 120 ° C. for 3 hours. The obtained cured product was excellent in transparency and free from distortion, and had good appearance as a spectacle lens. The refractive index (ne) was 1.602 and the Abbe number (νe) 45.

Example 6
As the alicyclic episulfide compound (A), 19.8 g of 4-vinylcyclohexene-1,2-episulfide synthesized in Example 2 was used, and 0.20 g of tetrabutylphosphonium bromide was used as the curing catalyst (B). As C), 15.2 g of pentaerythritol tetrakis (2-mercaptoacetate) was used.
These were blended using “Awatori Nertaro” manufactured by Shinky Co., Ltd. by mixing with stirring at room temperature for 20 minutes to obtain a curable episulfide resin composition.
The obtained curable episulfide resin composition was poured into a glass mold (thickness 3 mm). The glass mold was gradually heated from 30 ° C. over 19 hours to increase to 80 ° C., held at 80 ° C. for 2 hours, and further cured at 120 ° C. for 3 hours. The obtained cured product was excellent in transparency and free from distortion, and had good appearance as a spectacle lens. Further, the refractive index (ne) was 1.652 and the Abbe number (νe) 44.

Comparative Example 1
For alicyclic epoxy compound, 35 g of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, and for curing catalyst, 0.21 g of Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) It was.
These were blended using “Awatori Nertaro” manufactured by Shinky Co., Ltd. by mixing with stirring at room temperature for 20 minutes to obtain a curable epoxy resin composition.
The obtained curable epoxy resin composition was poured into a glass mold (thickness 3 mm). The glass mold was kept at 65 ° C. for 2 hours and 150 ° C. for 2 hours. The obtained cured product was excellent in transparency but distorted, and was difficult to use as a spectacle lens. Further, the refractive index (ne) was 1.520 and the Abbe number (νe) was 55.

Claims (19)

  An alicyclic episulfide compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more episulfide groups in the molecule (in one molecule). The alicyclic episulfide compound according to claim 1, which is a compound represented by the following formula (2).

(In the formula, Y represents a single bond or a linking group. X ¹ and X ² each independently represents an oxygen atom or a sulfur atom, and at least one of X ¹ and X ² is a sulfur atom. A substituent may be bonded to one or more carbon atoms constituting the alicyclic ring, provided that Y is a divalent group represented by —CH ₂ —O—C (═O) —. An alkyl group is bonded to the cyclohexane ring, and X ¹ and X ² are both sulfur atoms.) The alicyclic episulfide compound according to claim 2, which is a compound represented by the following formula (2a).

(In the formula, X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one of X ³ and X ⁴ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.) The alicyclic episulfide compound according to claim 1, which is a compound represented by the following formula (4).

(In the formula, Z represents a single bond or a linking group. X ²⁵ and X ²⁶ each independently represents an oxygen atom or a sulfur atom, and at least one of X ²⁵ and X ²⁶ is a sulfur atom. A substituent may be bonded to one or more of the carbon atoms constituting the alicyclic ring, provided that when Z is a group represented by —C (CH ₃ ) ₂ —, X ²⁵ and X ²⁶ One of these is a sulfur atom and the other is an oxygen atom.) The alicyclic episulfide compound according to claim 4, which is a compound represented by the following formula (4-1).

(In the formula, X ²⁷ and X ²⁸ each independently represent an oxygen atom or a sulfur atom, but at least one of X ²⁷ and X ²⁸ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)   In the molecule (in one molecule), an alicyclic episulfide compound (A) having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more episulfide groups, and a curing catalyst (B) are included. Curable episulfide resin composition.   The curable episulfide resin composition according to claim 6, further comprising a curing agent (C).   The curable episulfide resin composition according to claim 7, wherein the curing agent (C) is a thiol compound. The said alicyclic episulfide compound (A) is a compound represented by following formula (2 '), The curable episulfide resin composition of any one of Claims 6-8.

(In the formula, Y ′ represents a single bond or a linking group. X ^{1 ′} and X ^{2 ′} each independently represents an oxygen atom or a sulfur atom, and at least one of X ^{1 ′} and X ^{2 ′} represents A substituent may be bonded to one or more carbon atoms constituting the alicyclic ring, provided that Y ′ is represented by —CH ₂ —O—C (═O) —. When it is a valent group, X ¹⁾ and X ^{2 ′} are both sulfur atoms. ) The curable episulfide resin composition according to claim 9, wherein the alicyclic episulfide compound (A) is a compound represented by the following formula (2-1).

The curable episulfide resin composition according to claim 9, wherein the alicyclic episulfide compound (A) is a compound represented by the following formula (2a).

(In the formula, X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, but at least one of X ³ and X ⁴ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.) The said alicyclic episulfide compound (A) is a compound represented by following formula (1-1), The curable episulfide resin composition of any one of Claims 6-8.

(In the formula, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring.) The said alicyclic episulfide compound (A) is a compound represented by following formula (4), The curable episulfide resin composition of any one of Claims 6-8.

(In the formula, Z represents a single bond or a linking group. X ²⁵ and X ²⁶ each independently represents an oxygen atom or a sulfur atom, and at least one of X ²⁵ and X ²⁶ is a sulfur atom. A substituent may be bonded to one or more of the carbon atoms constituting the alicyclic ring, provided that when Z is a group represented by —C (CH ₃ ) ₂ —, X ²⁵ and X ²⁶ One of these is a sulfur atom and the other is an oxygen atom.) The curable episulfide resin composition according to claim 13, wherein the alicyclic episulfide compound (A) is a compound represented by the following formula (4-1).

(In the formula, X ²⁷ and X ²⁸ each independently represent an oxygen atom or a sulfur atom, but at least one of X ²⁷ and X ²⁸ is a sulfur atom. One or more carbon atoms constituting the alicyclic ring May be bonded to a substituent.)   It is a resin composition for optical lenses, The curable episulfide resin composition of any one of Claims 6-14.   The curable episulfide resin composition according to any one of claims 6 to 14, which is a spectacle lens resin composition.   Hardened | cured material of the curable episulfide resin composition of any one of Claims 6-16.   An optical lens molded from a cured product of the curable episulfide resin composition according to claim 15.   An eyeglass lens formed from a cured product of the curable episulfide resin composition according to claim 16.

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