JP2000186087A - Production of episulfide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful for an optical material of a high quality having high refractive index at a high yield by reacting a specific epoxy compound with a thiourea compound in a specific solvent at a specific range of temperature. SOLUTION: This compound has a structure of formula II and is obtained by reacting an epoxy compound (e.g. an organic compound having an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group or an epithioalkyltelluro group) having a structure of formula I [R1 is a 0-10C hydrocarbon; R2-R4 are each a 1-10C hydrocarbon group or H; Y is O, S, Se or Te; (n) is 0 or 1] with a thiourea compound in a mixed solvent of a polar solvent in which the thiourea compound can be dissolved (e.g. an alcohol) with a non-polar organic solvent in which the epoxy compound can be dissolved (e.g. an aromatic hydrocarbon) (preferably a volume ratio of water/ organic solvents is 0.1-10.0) at 10-30 deg.C preferably in the presence of an acid and/or an acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic lens,
The present invention relates to a method for manufacturing optical materials such as a prism, an optical fiber, an information recording substrate, and a filter, particularly, a plastic lens for eyeglasses.

[0002]

2. Description of the Related Art Plastic materials have been widely used in recent years for various optical materials, particularly for spectacle lenses, because they are lightweight, rich in toughness and easy to dye. Optical materials, especially the performance required especially for spectacle lenses, have low specific gravity, high transparency and low yellowness, and high refractive index and high Abbe number as optical performance. Enable and high Abbe number reduce chromatic aberration of the lens. The present inventors have a refractive index having a small thickness and a low chromatic aberration.
A novel episulfide compound capable of producing an optical material having a molecular weight of 7 or more and an Abbe number of 35 or more has been found, and patent applications have been filed earlier (Japanese Patent Application Laid-Open Nos. 9-71580 and 9-11097).
9, JP-A-9-255781). However, the episulfide compound found here is colored and polymer is formed depending on the reaction conditions. As a result, the reaction yield is reduced and the optical material obtained by polymerizing the compound is yellowed or clouded, and furthermore heat-resistant. As a result, the quality of the lens deteriorated. Therefore, it has been desired to optimize the reaction conditions when producing an episulfide compound.

[0003]

The problem to be solved by the present invention is to develop an appropriate reaction condition for producing an episulfide compound having a structure represented by the following formula (2), and to reduce the reaction yield. An object of the present invention is to improve the quality of a high-refractive-index optical material having a high refractive index and a balance between Abbe's number, which is impossible with the prior art.

[0004]

An object of the present invention is to provide an epoxy compound having a structure represented by the following formula (2) by reacting thiourea with an epoxy compound having a structure represented by the following formula (1). In the method for producing a compound, if necessary, in the presence of an acid and / or an acid anhydride, a mixed solvent of a polar organic solvent in which thiourea can be dissolved and a non-polar organic solvent in which an epoxy compound can be dissolved, has a concentration of 10 to 30. Solved by carrying out the reaction at a temperature of ° C.

Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² and R ³
And R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te, and n
Represents 0 or 1. )

Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² and R ³
And R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te, and n
Represents 0 or 1. )

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The episulfide compound produced by the present invention exhibits a high refractive index, a high Abbe number and a good balance between the two when used as an optical material.
R ¹ in the formula (2) is preferably methylene and ethylene, and R ² , R ³ and R ⁴ in the formula (2) are each preferably hydrogen or a methyl group. More preferably, R ¹ is methylene and R ² , R ³ and R ⁴ are each hydrogen. n represents 0 to 1, preferably n is 1
It is. Y may be any of O, S, Se or Te, but S, Se or Te is more advantageous when a high refractive index is desired.

The episulfide compound having the structure represented by the formula (2) of the present invention includes all organic compounds having at least one structure represented by the formula (2) in one molecule, but is more preferable. Is a compound having two or more structures represented by the formula (2) in one molecule. (2) Specific examples of the episulfide compound having the structure represented by the formula include the following. (A) Organic compound having epithio group (B) Organic compound having epithioalkyloxy group (C) Organic compound having epithioalkylthio group (D) Organic compound having epithioalkyl seleno group (E) Epithioalkyl Organic compound having telluro group The above organic compounds (A), (B), (C), (D) and (E) are chain compounds, branched compounds, aliphatic cyclic compounds, aromatic compounds, or nitrogen. , Oxygen, sulfur, selenium,
Having a heterocyclic compound containing a tellurium atom as a main skeleton and having an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group, and an epithioalkyltelluro group simultaneously in one molecule. It doesn't matter. Further, these compounds may contain a bond of sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, urethane or the like in the molecule.

A preferred specific example of the organic compound (A) having one or more epithio groups is a compound having one or more epoxy groups substituted with an epithio group in a compound having an epoxy group (not a glycidyl group). Can be given as Taking a more specific example method, the following can be given as typical examples. Organic compound having a linear aliphatic skeleton: 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1-
(Β-epithiopropyl) methane, 1,1-bis (β-
Epithiopropyl) methane, 1- (epithioethyl)-
1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane 1- (epithioethyl) -3- (β-epithiopropyl) butane, 1,3-bis (β-epi Thiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane, 1,4-bis (β-epithiopropyl) butane, 1- (epithioethyl) -5- (β-epithiopropyl ) Hexane, 1- (epithioethyl)-
2- (γ-epithiobutylthio) ethane, 1- (epithioethyl) -2- [2- (γ-epithiobutylthio) ethylthio] ethane, tetrakis (β-epithiopropyl) methane, 1,1,1 -Tris (β-epithiopropyl) propane, 1,3-bis (β-epithiopropyl)
-1- (β-epithiopropyl) -2-thiapropane,
1,5-bis (β-epithiopropyl) -2,4-bis (β-epithiopropyl) -3-thiapentane, a compound having an aliphatic cyclic skeleton: 1,3 or 1,4-
Bis (epithioethyl) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyl) cyclohexane, 2,5-bis (epithioethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyl ) -1,4-
Compounds having one aliphatic cyclic skeleton such as dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, bis [4- (epithioethyl) cyclohexyl] methane, bis [ 4- (β-epithiopropyl) cyclohexyl] methane, 2,2-bis [4- (epithioethyl)
Cyclohexyl] propane, 2,2-bis [4- (β-
Compounds having two aliphatic cyclic skeletons, such as epithiopropyl) cyclohexyl] propane, bis [4- (β-epithiopropyl) cyclohexyl] sulfide, and bis [4- (epithioethyl) cyclohexyl] sulfide. Compounds having an aromatic skeleton: compounds having one aromatic skeleton such as 1,3 or 1,4-bis (epithioethyl) benzene, 1,3 or 1,4-bis (β-epithiopropyl) benzene, , Bis [4- (epithioethyl)
Phenyl] methane, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (epithioethyl) phenyl] propane, 2,2-bis [4- (β
-Epithiopropyl) phenyl] propane, bis [4-
(Epithioethyl) phenyl] sulfide, bis [4-
(Β-epithiopropyl) phenyl] sulfide, bis [4- (epithioethyl) phenyl] sulfone, bis [4- (β-epithiopropyl) phenyl] sulfone, 4,4′-bis (epithioethyl) biphenyl,
4,4′-bis (β-epithiopropyl) biphenyl,
And other compounds having two aromatic skeletons. Further, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also exemplified.

Preferred specific examples of the organic compound (B) having one or more epithioalkyloxy groups include an epoxy compound derived from epihalohydrin in which one or more glycidyl groups are replaced with an epithioalkyloxy group (thioglycidyl group). A typical example is a compound substituted with: Specific examples of the epoxy compound include those produced by condensing epihalohydrin with polyhydric phenol compounds such as hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, and novolak resin. Phenolic epoxy compounds; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Pentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- Is a polyhydric alcohol compound such as 1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, and epihalohydrin. Alcoholic epoxy compounds produced by condensation; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid , Hexahydroterephthalic acid, hexic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenedicarboxylic acid, diph Glycidyl ester epoxy compounds produced by condensation of a polycarboxylic acid compound such as nildicarboxylic acid and epihalohydrin; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3 -Diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis- (3-aminopropyl) ether, ,
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-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-
Bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5-
Or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2- (4,4'-diaminodiphenyl)
Primary diamine such as propane, 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,
Amine-based epoxy compounds produced by condensation of a secondary diamine such as 1,4-di- (4-piperidyl) -butane with epihalohydrin; urethane-based compounds produced from the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates and glycidol Epoxy compounds and the like can be given. If a more specific example method is used, the following can be given as typical examples. Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyloxy) ether, bis (β-epithiopropyloxy) methane, 1,2-bis (β-epithiopropyloxy) ethane, 1,3- Bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-epithiopropyloxy) butane, 1,3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β
-Epithiopropyloxymethyl) butane, 1,5-bis (β-epithiopropyloxy) pentane, 1- (β
-Epithiopropyloxy) -4- (β-epithiopropyloxymethyl) pentane, 1,6-bis (β-epithiopropyloxy) hexane, 1- (β-epithiopropyloxy) -5- (β -Epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy)
-2-[(2-β-epithiopropyloxyethyl) oxy] ethane, 1- (β-epithiopropyloxy)-
Linear organic compounds such as 2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane and the like; tetrakis (β-epithiopropyloxymethyl) methane, 1,1,1 -Tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (β
-Epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3-thiapentane, 1-
(Β-epithiopropyloxy) -2,2-bis (β-
Epithiopropyloxymethyl) -4-thiahexane,
1,5,6-tris (β-epithiopropyloxy)-
4- (β-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,5bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio Propyloxy) -4,4-bis (β
-Epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy)
-2,4,5-tris (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-
Epithiopropyloxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane,
1,9-bis (β-epithiopropyloxy) -5
(Β-epithiopropyloxymethyl) -5-[(2-
β-epithiopropyloxyethyl) oxymethyl]-
3,7-dithianonane, 1,10-bis (β-epithiopropyloxy) -5,6-bis [(2-β-epithiopropyloxyethyl) oxy] -3,6,9-trithiadecane, 11-bis (β-epithiopropyloxy) -4,8-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β
-Epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-[(2-β-epithiopropyloxyethyl) oxymethyl ] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-
Bis (β-epithiopropyloxy) cyclohexane,
1,3 or 1,4-bis (β-epithiopropyloxymethyl) cyclohexane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyl) Oxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2,5-bis (β-
Epithiopropyloxymethyl) -1,4-dithiane,
Compounds having an aromatic skeleton such as 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane: 1,3 or 1,4-bis (β-epithiopropyloxy) benzene, 1,3 or 1,4-bis (β-epithiopropyloxymethyl)
Benzene, bis [4- (β-epithiopropyloxy)
Phenyl] methane, 2,2-bis [4- (β-epithiopropyloxy) phenyl] propane, bis [4- (β
-Epithiopropyloxy) phenyl] sulfide, bis [4- (β-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (β-epithiopropyloxy) biphenyl and the like. Compounds in which at least one of the group's hydrogens has been replaced by a methyl group are also examples.

Preferred specific examples of the organic compound (C) having one or more epithioalkylthio groups include a compound having a mercapto group and an epoxyalkylthio group of an epoxy compound derived from epihalohydrin (specifically, β
-Epoxypropylthio group) can be exemplified by a compound in which one or more are substituted with an epithioalkylthio group. If a more specific example method is used, the following can be given as typical examples. Organic compounds having a linear aliphatic skeleton: bis (β-epithiopropylthio) sulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3- Bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2
-(Β-epithiopropylthiomethyl) propane, 1,
4-bis (β-epithiopropylthio) butane, 1,3
-Bis (β-epithiopropylthio) butane, 1- (β
-Epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β -Epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (Β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epi Thiopropylthioethyl) thioethyl] thio] ethane tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithi Propylthio)-2-(beta-epithiopropylthiomethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,2 -Bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β -Epithiopropylthiomethyl) -3,6-dithiaoctane,
1,8-bis (β-epithiopropylthio) -4,4-
Bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3, 6-dithiaoctane, 1,8-bis (β
-Epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane,
1,9-bis (β-epithiopropylthio) -5- (β
-Epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,1
1-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11
-Bis (β-epithiopropylthio) -5,7-[(2
-Β-epithiopropylthioethyl) thiomethyl]-
3,6,9-trithiaundecane, 1,11-bis (β
-Epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane A chain compound having an ester group and an epithioalkylthio group: tetra [2- ( β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio) acetylmethyl] propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl Methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane, etc. Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-
Bis (β-epithiopropylthio) cyclohexane,
1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyl) Thio) cyclohexyl]
Propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-
Bis (β-epithiopropylthioethylthiomethyl)-
Compounds having an aromatic skeleton such as 1,4-dithiane: 1,3 or 1,4-bis (β-epithiopropylthio) benzene, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) Benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl Phenyl] sulfide, bis [4-
(Β-epithiopropylthio) phenyl] sulfone,
4,4′-bis (β-epithiopropylthio) biphenyl and the like Further, compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

(D) Preferred specific examples of the organic compound having an epithioalkylseleno group include selenium compounds such as metal selenium, alkali metal selenide, alkali metal selenol, alkyl (aryl) selenol, hydrogen selenide and epihalohydrin. A typical example is a compound in which one or more epoxyalkylseleno groups (specifically, β-epoxypropylseleno groups) of an epoxy compound are substituted with epithioalkylseleno groups.
If a more specific example method is used, the following can be given as typical examples. Organic compounds having a linear aliphatic skeleton: bis (β-epithiopropyl) selenide, bis (β-epithiopropyl)
Diselenide, bis (β-epithiopropyl) triselenide, bis (β-epithiopropylseleno) methane, 1,
2-bis (β-epithiopropylseleno) ethane, 1,
3-bis (β-epithiopropylseleno) propane,
1,2-bis (β-epithiopropylseleno) propane, 1- (β-epithiopropylseleno) -2- (β-
Epithiopropylselenomethyl) propane, 1,4-bis (β-epithiopropylseleno) butane, 1,3-bis (β-epithiopropylseleno) butane, 1- (β-
Epithiopropylseleno) -3- (β-epithiopropylselenomethyl) butane, 1,5-bis (β-epithiopropylseleno) pentane, 1- (β-epithiopropylseleno) -4- (β- Epithiopropylselenomethyl) pentane, 1,6-bis (β-epithiopropylseleno) hexane, 1- (β-epithiopropylseleno)
-5- (β-epithiopropylselenomethyl) hexane, 1- (β-epithiopropylseleno) -2-[(2
-Β-epithiopropylselenoethyl) thio] ethane,
1- (β-epithiopropylseleno) -2-[[2-
(2-β-epithiopropylselenoethyl) selenoethyl] thio] ethane, tetrakis (β-epithiopropylselenomethyl) methane, 1,1,1-tris (β-epithiopropylselenomethyl) propane, 1,5 -Bis (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) -3-thiapentane, 1,5-
Bis (β-epithiopropylseleno) -2,4-bis (β-epithiopropylselenomethyl) -3-thiapentane, 1- (β-epithiopropylseleno) -2,2-
Bis (β-epithiopropylselenomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl)
-3-Thiahexane, 1,8-bis (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,5 bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,
8-bis (β-epithiopropylseleno) -4,4-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,4 , 5-Tris (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,5-bis (β-
Epithiopropylselenomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylseleno)-
5- (β-epithiopropylselenomethyl) -5
[(2-β-epithiopropylselenoethyl) selenomethyl] -3,7-dithianonane, 1,10-bis (β-
Epithiopropylseleno) -5,6-bis [(2-β-
Epithiopropylselenoethyl) thio] -3,6,9-
Trithiadecane, 1,11-bis (β-epithiopropylseleno) -4,8-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, 1,1
1-bis (β-epithiopropylseleno) -5,7-bis (β-epithiopropylselenomethyl) -3,6,9
-Trithiaundecane, 1,11-bis (β-epithiopropylseleno) -5,7-[(2-β-epithiopropylselenoethyl) selenomethyl] -3,6,9-trithiaundecane, 1, 11-bis (β-epithiopropylseleno) -4,7-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropylseleno) acetyl Methyl] methane, 1,1,1-tri [2- (β-epithiopropylseleno) acetylmethyl] propane, tetra [2
-(Β-epithiopropylselenomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylselenomethyl) acetylmethyl] propane, bis (5,6-epithio-3-seleno) Hexyl) selenide,
2,3-bis (6,7-thioepoxy-1-selena-4
-Selenoheptyl) -1- (3,4-thioepoxy-1
-Selenobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl)-
2-Selenapropane, bis (4,5-thioepoxy-2
-Selenopentyl) -3,6,9-triselenaundecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1)
-Selenobutyl) -2,3-bis (6,7-thioepoxy-1-selena-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-
Selena-6-thiaoctane-1,8-bis (3,4-thioepoxy-1-selenobutyl), bis (5,6-epithio-3-selenohexyl) telluride, 2,3-bis (6,7-thioepoxy- 1-tellura-4-selenoheptyl) -1- (3,4-thioepoxy-1-selenobutyl) propane, 1,1,3,3-tetrakis (4,5
-Thioepoxy-2-selenopentyl) -2-tellurapropane, bis (4,5-thioepoxy-2-selenopentyl) -3,6,9-tritereoundecane-1,11
-Bis (3,4-thioepoxy-1-selenobutyl),
1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis (6,7-thioepoxy-1-tellura-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-) Selenopentyl) -3-tellura-6
Thiaoctane-1,8-bis (3,4-thioepoxy-
Compounds having an aliphatic cyclic skeleton such as 1-selenobutyl): (1,3 or 1,
4) -Bis (β-epithiopropylseleno) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl) cyclohexane, bis [4- (β
-Epithiopropylseleno) cyclohexyl] methane,
2,2-bis [4- (β-epithiopropylseleno)
Cyclohexyl] propane, bis [4- (β-epithiopropylseleno) cyclohexyl] sulfide, 2,5
-Bis (β-epithiopropylselenomethyl) -1,4
-Dithiane, 2,5-bis (β-epithiopropylselenoethylthiomethyl) -1,4-dithiane, (2,3 or 2,5 or 2,6) -bis (3,4-epithio-
1-selenobutyl) -1,4-diselenane, (2,3 or 2,5 or 2,6) -bis (4,5-epithio-
(2-selenopentyl) -1,4-diselenane, (2,4
Or 2,5 or 5,6) -bis (3,4-epithio-1-selenobutyl) -1,3-diselenane, (2,4
Or 2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl) -1,3-diselenane,
3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-
4-selenane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-4-selenane, (2,4 or 4 ,
5) -Bis (3,4-epithio-1-selenobutyl)-
1,3-diselenolan, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1,3-
Diselenolan, (2,4 or 2,5 or 4,5)-
Bis (3,4-epithio-1-selenobutyl) -1-thia-3-selenolan, (2,4 or 2,5 or 4,
5) -Bis (4,5-epithio-2-selenopentyl)
-1-thia-3-selenolan, 2,6-bis (4,5-
Epithio-2-selenopentyl-1,3,5-triselenane, bis (3,4-epithio-1-selenobutyl) tricycloselenaoctane, bis (3,4-epithio-1
-Selenobutyl) dicycloselenanane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-
Epithio-1-selenobutyl) selenophane, (2,3
Or 2,4 or 2,5 or 3,4) -bis (4,
5-epithio-2-selenopentyl) selenophane, 2
-(4,5-thioepoxy-2-selenopentyl) -5
-(3,4-thioepoxy-1-selenobutyl) -1-
Selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-1-selenobutyl) -1-selenacyclohexane , (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-
2-selenopentyl) -1-selenacyclohexane,
(2,3 or 2,5 or 2,6) -bis (3,4-
Epithio-1-selenobutyl) -1,4-ditelluran,
(2,3 or 2,5 or 2,6) -bis (4,5-
Epithio-2-selenopentyl) -1,4-ditelluran, (2,4 or 2,5 or 5,6) -bis (3,
4-epithio-1-selenobutyl) -1,3-ditelluran, (2,4 or 2,5 or 5,6) -bis (4
5-epithio-2-selenopentyl) -1,3-ditelluran, (2,3 or 2,5 or 2,6 or 3,
5) -Bis (3,4-epithio-1-selenobutyl)-
1-thia-4-telluran, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-
Selenopentyl) -1-thia-4-telluran, (2,4
Or 4,5) -bis (3,4-epithio-1-selenobutyl) -1,3-ditellolane, (2,4 or 4,
5) -Bis (4,5-epithio-2-selenopentyl)
-1,3-ditellolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-tellurolan, (2,4 or 2,
5 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-tellurolan, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,3)
5-tritellurane, bis (3,4-epithio-1-selenobutyl) tricyclotelluraoctane, bis (3,4-
Epithio-1-selenobutyl) dicyclotelluranonane,
(2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-selenobutyl) tellurophane, (2,3 or 2,4 or 2,5 or 3,4)
-Bis (4,5-epithio-2-selenopentyl) tellurophan, 2- (4,5-thioepoxy-2-selenopentyl) -5- (3,4-thioepoxy-1-selenobutyl) -1-telluracyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-
1-selenobutyl) -1-telluracyclohexane,
(2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2-selenopentyl) -1-telluracyclohexane and the like Compound having group skeleton: (1,3 or 1,4)-
Bis (β-epithiopropylseleno) benzene, (1,
3 or 1,4) -bis (β-epithiopropylselenomethyl) benzene, bis [4- (β-epithiopropylseleno) phenyl] methane, 2,2-bis [4- (β-
Epithiopropylseleno) phenyl] propane, bis [4- (β-epithiopropylseleno) phenyl] sulfide, bis [4- (β-epithiopropylseleno) phenyl] sulfone, 4,4′-bis (β- Further, specific examples thereof include compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group.

(E) Preferred examples of the organic compound having an epithioalkyltelluro group include a tellurium compound such as metal tellurium, alkali metal telluride, alkali metal tellurol, alkyl (aryl) tellurol, hydrogen telluride and epihalohydrin. A typical example is a compound in which one or more epoxyalkyltelluro groups (specifically, β-epoxypropyltelluro group) of an epoxy compound are substituted with epithioalkyltelluro groups.
If a more specific example method is used, the following can be given as typical examples. Organic compounds having a linear aliphatic skeleton: bis (β-epithiopropyl) telluride, bis (β-epithiopropyl)
Ditelluride, bis (β-epithiopropyl) tritelluride, bis (β-epithiopropyltelluro) methane, 1,
2-bis (β-epithiopropyltelluro) ethane, 1,
3-bis (β-epithiopropyltelluro) propane,
1,2-bis (β-epithiopropyltelluro) propane, 1- (β-epithiopropyltelluro) -2- (β-
Epithiopropyltelluromethyl) propane, 1,4-bis (β-epithiopropyltelluro) butane, 1,3-bis (β-epithiopropyltelluro) butane, 1- (β-
Epithiopropyltelluro) -3- (β-epithiopropyltelluromethyl) butane, 1,5-bis (β-epithiopropyltelluro) pentane, 1- (β-epithiopropyltelluro) -4- (β- Epithiopropyltelluromethyl) pentane, 1,6-bis (β-epithiopropyltelluro) hexane, 1- (β-epithiopropyltelluro)
-5- (β-epithiopropyltelluromethyl) hexane, 1- (β-epithiopropyltelluro) -2-[(2
-Β-epithiopropyltelluroethyl) thio] ethane,
1- (β-epithiopropyltelluro) -2-[[2-
(2-β-epithiopropyltelluroethyl) telluroethyl] thio] ethane, tetrakis (β-epithiopropyltelluromethyl) methane, 1,1,1-tris (β-epithiopropyltelluromethyl) propane, 1,5 -Bis (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) -3-thiapentane, 1,5-
Bis (β-epithiopropyltelluro) -2,4-bis (β-epithiopropyltelluromethyl) -3-thiapentane, 1- (β-epithiopropyltelluro) -2,2-
Bis (β-epithiopropyltelluromethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl)
-3-Thiahexane, 1,8-bis (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,5 bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,
8-bis (β-epithiopropyltelluro) -4,4-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,4 , 5-Tris (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,5-bis (β-
Epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropyltelluro)-
5- (β-epithiopropyltelluromethyl) -5-
[(2-β-epithiopropyltelluroethyl) selenomethyl] -3,7-dithianonane, 1,10-bis (β-
Epithiopropyltelluro) -5,6-bis [(2-β-
Epithiopropyltelluroethyl) thio] -3,6,9-
Trithiadecane, 1,11-bis (β-epithiopropyltelluro) -4,8-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, 1,1
1-bis (β-epithiopropyltelluro) -5,7-bis (β-epithiopropyltelluromethyl) -3,6,9
-Trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -5,7-[(2-β-epithiopropyltelluroethyl) selenomethyl] -3,6,9-trithiaundecane, 1, 11-bis (β-epithiopropyltelluro) -4,7-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropyltelluro) acetyl Methyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluro) acetylmethyl] propane, tetra [2
-(Β-epithiopropyltelluromethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluromethyl) acetylmethyl] propane, bis (5,6-epithio-3-tellulohexyl) ) Selenide,
2,3-bis (6,7-thioepoxy-1-selena-4
-Telluroheptyl) -1- (3,4-thioepoxy-1
-Tellurobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-tellulopentyl)-
2-Selenapropane, bis (4,5-thioepoxy-2
-Telluropentyl) -3,6,9-triselenaundecane-1,11-bis (3,4-thioepoxy-1-tellurobutyl), 1,4-bis (3,4-thioepoxy-1)
-Tellurobutyl) -2,3-bis (6,7-thioepoxy-1-selena-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellulopentyl) -3-
Selena-6-thiaoctane-1,8-bis (3,4-thioepoxy-1-tellurobutyl), bis (5,6-epithio-3-tellurohexyl) telluride, 2,3-bis (6,7-thioepoxy-1) -Tellura-4-telluroheptyl) -1- (3,4-thioepoxy-1-tellurobutyl) propane, 1,1,3,3-tetrakis (4,5
-Thioepoxy-2-telluropentyl) -2-tellurapropane, bis (4,5-thioepoxy-2-telluropentyl) -3,6,9-tritereoundecane-1,11
-Bis (3,4-thioepoxy-1-tellurobutyl),
1,4-bis (3,4-thioepoxy-1-tellurobutyl) -2,3-bis (6,7-thioepoxy-1-tellura-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellulopentyl) ) -3-tellura-6
Thiaoctane-1,8-bis (3,4-thioepoxy-
Compounds having an aliphatic cyclic skeleton such as 1-tellurobutyl): (1, 3 or 1,
4) -Bis (β-epithiopropyltelluro) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl) cyclohexane, bis [4- (β
-Epithiopropyltelluro) cyclohexyl] methane,
2,2-bis [4- (β-epithiopropyltelluro)
Cyclohexyl] propane, bis [4- (β-epithiopropyltelluro) cyclohexyl] sulfide, 2,5
-Bis (β-epithiopropyltelluromethyl) -1,4
-Dithiane, 2,5-bis (β-epithiopropyltelluroethylthiomethyl) -1,4-dithiane, (2,3 or 2,5 or 2,6) -bis (3,4-epithio-
1-tellurobutyl) -1,4-diselenane, (2,3 or 2,5 or 2,6) -bis (4,5-epithio-
(2-telluropentyl) -1,4-diselenane, (2,4
Or 2,5 or 5,6) -bis (3,4-epithio-1-tellurobutyl) -1,3-diselenane, (2,4
Or 2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3-diselenane,
3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-tellurobutyl) -1-thia-
4-selenane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-tellulopentyl) -1-thia-4-selenane, (2,4 or 4,
5) -Bis (3,4-epithio-1-tellurobutyl)-
1,3-diselenolane, (2,4 or 4,5) -bis (4,5-epithio-2-telluropentyl) -1,3-
Diselenolan, (2,4 or 2,5 or 4,5)-
Bis (3,4-epithio-1-tellurobutyl) -1-thia-3-selenolan, (2,4 or 2,5 or 4,
5) -Bis (4,5-epithio-2-telluropentyl)
-1-thia-3-selenolan, 2,6-bis (4,5-
Epithio-2-tellulopentyl-1,3,5-triselenane, bis (3,4-epithio-1-tellurobutyl) tricycloselenaoctane, bis (3,4-epithio-1
-Tellurobutyl) dicycloselennananan, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-
Epithio-1-tellurobutyl) selenophane, (2,3
Or 2,4 or 2,5 or 3,4) -bis (4,
5-epithio-2-telluropentyl) selenophane, 2
-(4,5-thioepoxy-2-telluropentyl) -5
-(3,4-thioepoxy-1-tellurobutyl) -1-
Selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-1-tellurobutyl) -1-selenacyclohexane , (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-
2-telluropentyl) -1-selenacyclohexane,
(2,3 or 2,5 or 2,6) -bis (3,4-
Epithio-1-tellurobutyl) -1,4-ditellurane,
(2,3 or 2,5 or 2,6) -bis (4,5-
Epithio-2-telluropentyl) -1,4-ditelluran, (2,4 or 2,5 or 5,6) -bis (3,
4-epithio-1-tellurobutyl) -1,3-ditelluran, (2,4 or 2,5 or 5,6) -bis (4
5-epithio-2-telluropentyl) -1,3-ditellurane, (2,3 or 2,5 or 2,6 or 3,
5) -Bis (3,4-epithio-1-tellurobutyl)-
1-thia-4-telluran, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-
Telluropentyl) -1-thia-4-telluran, (2,4
Or 4,5) -bis (3,4-epithio-1-tellurobutyl) -1,3-ditellolane, (2,4 or 4,
5) -Bis (4,5-epithio-2-telluropentyl)
-1,3-ditellolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-tellurobutyl) -1-thia-3-tellurolan, (2,4 or 2,
5 or 4,5) -bis (4,5-epithio-2-telluropentyl) -1-thia-3-tellurolan, 2,6-bis (4,5-epithio-2-tellulopentyl-1,3,3)
5-tritellurane, bis (3,4-epithio-1-tellurobutyl) tricyclotelluraoctane, bis (3,4-
Epithio-1-tellurobutyl) dicyclotelluranonane,
(2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-tellurobutyl) tellurophan, (2,3 or 2,4 or 2,5 or 3,4)
-Bis (4,5-epithio-2-telluropentyl) tellurophan, 2- (4,5-thioepoxy-2-tellulopentyl) -5- (3,4-thioepoxy-1-tellurobutyl) -1-telluracyclohexane, (2 , 3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-
1-tellurobutyl) -1-telluracyclohexane,
(2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2-tellulopentyl) -1-telluracyclohexane Compound having a skeleton: (1,3 or 1,4)-
Bis (β-epithiopropyltelluro) benzene, (1,
3 or 1,4) -bis (β-epithiopropyltelluromethyl) benzene, bis [4- (β-epithiopropyltelluro) phenyl] methane, 2,2-bis [4- (β-
Epithiopropyltelluro) phenyl] propane, bis [4- (β-epithiopropyltelluro) phenyl] sulfide, bis [4- (β-epithiopropyltelluro) phenyl] sulfone, 4,4′-bis (β- Further, specific examples thereof include compounds in which at least one hydrogen of the β-epithiopropyl group in these compounds is substituted with a methyl group.

Further, organic compounds having an unsaturated group are also included in the above (A) to (E). Specific preferred examples thereof include vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, and allylthioglycidyl ether.

Other specific examples of the compound having one epithio group include compounds such as ethylene sulfide, propylene sulfide and thioglycidol, and thiol of monocarboxylic acid such as acetic acid, propionic acid and benzoic acid. Examples thereof include glycidyl esters, thioglycidyl ethers such as methylthioglycidyl ether, ethylthioglycidyl ether, propylthioglycidyl ether, and butylthioglycidyl ether.

Of the above, more preferred are (B) an organic compound having an epithioalkyloxy group, and (C) an organic compound having an epithioalkylthio group.
(D) an organic compound having an epithioalkylseleno group,
(E) An organic compound having an epithioalkyltelluro group, and particularly preferred are (C) an organic compound having an epithioalkylthio group, and (D) an organic compound having an epithioalkylseleno group. Specific examples of particularly preferable ones are β-epithiopropylthio group, a chain compound having a β-epithiopropylseleno group, a branched compound, an aliphatic cyclic compound, an aromatic compound having the above-described specific examples,
It is a heterocyclic compound.

In the present invention, when producing an episulfide compound having the structure of formula (2), the corresponding (1)
The epoxy compound having the structure of the formula has the same structure as that of the formula (1) except that the sulfur atom in the three-membered ring is replaced by an oxygen atom. That is, R ¹ , R ² , R ³ , R
⁴ and Y are the same.

In the present invention, when producing an episulfide compound having the structure of the formula (2), the corresponding (1) is used as a raw material.
The epoxy compound having the structure of the formula is a sulfur compound having a mercapto group (including hydrogen sulfide) such as a carbanion represented by alkyl lithium or Grignard, a compound having a hydroxy group (including water) or a metal salt thereof. Alternatively, it is produced by reacting a selenium compound having a selenol group, a metal salt thereof, or the like, or a tellurium compound having a tellurol group, a metal salt thereof, or the like, with epihalohydrin or alkyl epihalohydrin. In this reaction, a phase transfer catalyst typified by tetrabutylammonium bromide, a surfactant, an alkali or the like may be used as necessary. The epichlorohydrin or alkyl epihalohydrin compound may be a carbanion, a compound having a hydroxy group (including water) or a metal salt thereof, a mercapto group-containing sulfur compound (including hydrogen sulfide) or a metal salt thereof, such as a selenol group. The selenium compound or a metal salt thereof or the like, or a tellurium compound having a tellurol group or a metal salt thereof or the like is used in a stoichiometric amount or more, but since the purity of the product, the reaction rate, economic efficiency, etc. are emphasized, If so, less or more may be used. That is, if importance is placed on the purity of the product, the reaction rate, the economic efficiency, etc., it is permissible to use less or more. The reaction is preferably carried out using a stoichiometric amount to 10 times the stoichiometric amount. More preferably, the reaction is carried out using a theoretical amount to 5 times the molar amount of the theoretical amount. The reaction may be carried out without solvent or in a solvent. Specific examples include water, alcohols,
Examples include ethers, aromatic hydrocarbons, and halogenated hydrocarbons. The reaction is usually carried out at a temperature of 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time may be any time as long as the reaction is completed under the above-mentioned various conditions, but usually is suitably 10 hours or less.

As another method for producing an epoxy compound having the structure of the formula (1), a corresponding unsaturated compound represented by the following formula (3) is prepared by using an organic peracid, an alkyl hydroperoxide,
There is also a method of producing by oxidation with hydrogen peroxide or the like.

Embedded image (Wherein, R ¹ is a hydrocarbon having 0 to 10 carbon atoms, R ² , R ³
And R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te, and n
Represents 0 or 1. )

In the present invention, when an episulfide compound having a structure represented by the formula (2) is produced from an epoxy compound having a structure represented by the formula (1), the ether structure of the epoxy compound is converted into a sulfide structure. Thiourea is used as the thialating agent. The thiourea used is
(1) The number of moles corresponding to the number of epoxy groups of the epoxy compound having the structure represented by the formula, that is, a theoretical amount is used. However, larger amounts can be used. The reaction is preferably carried out using a stoichiometric amount to 5 times the molar amount of the stoichiometric amount. More preferably, the reaction is carried out using a stoichiometric amount to 2.5 times the molar amount of the stoichiometric amount.

As the solvent for producing the episulfide compound having the structure represented by the formula (2) of the present invention, a polar organic solvent capable of dissolving thiourea and an epoxy compound having the structure represented by the formula (1) Use a mixed solvent of a non-polar organic solvent in which is soluble. Usually, a polar organic solvent / non-polar organic solvent is used in a volume ratio of 0.1 to 10.0, but preferably, a polar organic solvent / non-polar organic solvent = 0.2 to 5.0.
The volume ratio is used. Also in this case, when the volume ratio is less than 0.1, the thiourea is insufficiently dissolved and the reaction does not proceed sufficiently, resulting in a decrease in the yield. When the volume ratio exceeds 10.0, the production of the polymer becomes remarkable.

As used herein, the term "organic solvent" refers to a polar organic solvent or a non-polar organic solvent. The polar organic solvent is a water-soluble organic solvent, and the non-polar organic solvent is a non-water-soluble organic solvent. Specific examples of the polar organic solvent include alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, and hydroxyethers such as methylcellosolve, ethylcellosolve and butylcellosolve. Specific examples of the non-polar organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as dichloroethane, chloroform, and chlorobenzene. can give.

The addition of an acid and / or acid anhydride as a polymerization inhibitor to the reaction solution is an effective means from the viewpoint of improving the reaction results. Specific examples of acids and acid anhydrides include nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, and pyrophosphoric acid. Acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide,
Phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, silica gel, silica alumina,
Inorganic acidic compounds such as aluminum chloride and zinc chloride, formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptopropio Catenate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, Salicylic acid,
2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, anhydride Organic carboxylic acids such as butyric acid, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, trifluoroacetic anhydride, mono, di and trimethyl phosphate, mono, di and triethyl Phosphates such as phosphate, mono, di and triisobutyl phosphate, mono, di and tributyl phosphate, mono, di and trilauryl phosphate, and phosphites in which these phosphate moieties are phosphites, typified by dimethyldithiophosphoric acid Dialkyl Organic phosphorus compounds such as dithiophosphoric acids, phenol, catechol, t-butylcatechol, 2,6-di-t-butylcresol, 2,6-di-
t-butylethylphenol, resorcin, hydroquinone, phloroglucin, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic amide, methyl hydroxyphenylacetate, methylhydroxyphenylacetate,
Hydroxyphenethyl alcohol, hydroxyphenethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, 2,2′-methylene-bis (4-methyl-6-t-butylphenol), bisphenol-F, bisphenol-S, α-naphthol,
phenols such as β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o
-Toluenesulfonic acid, m-toluenesulfonic acid, p-
Toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
p-phenolsulfonic acid, o-cresolsulfonic acid, metanylic acid, sulfanilic acid, 4B-acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, lauric acid, phenyl Examples thereof include sulfonic acids such as J acid, and some of them can be used in combination. The addition amount is usually 0.001 to 1 with respect to the total amount of the reaction solution.
Although it is used in the range of 0 wt%, it is preferably 0.01 to
5 wt%. When the addition amount is 0.001 wt% or less, the production of the polymer becomes remarkable, the reaction yield decreases, and 10 w
Above t%, the yield is significantly reduced.

In the production method of the present invention, the reaction temperature is very important. Specifically, the reaction is carried out at a reaction temperature of 10 to 30C. When the reaction temperature is lower than 10 ° C., the thiourea becomes insufficiently dissolved in addition to the decrease in the reaction rate, and the reaction does not proceed sufficiently. If the amount exceeds the above range, the polymer precipitates, which lowers the reaction yield, causing the optical material to become cloudy, and further causes the heat resistance to decrease. The reaction time may be any time as long as the reaction is completed under the above-mentioned temperature conditions, but usually is suitably 20 hours or less.

The reaction product can be washed with an acidic aqueous solution to improve the stability of the obtained compound. Specific examples of the acid used for the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids usually have a pH
The effect is exhibited at pH 6 or less, but the more effective range is pH 3 or less.

If water or an organic solvent remains in the reaction mixture after washing, distilling it off under reduced pressure is effective in improving the quality of the obtained optical material such as transparency and heat resistance. Means. The distillation under reduced pressure is usually 0.1 to
It is carried out at 10,000 Pa at 10-100 ° C. The distillation time may be any time as long as the distillation is completed under the above-mentioned various conditions, but usually 24 hours or less is appropriate.

Purification of the episulfide compound obtained by the production method of the present invention by distillation, filtration or the like is preferable from the viewpoint of further improving the quality of the optical material. Usually, distillation is carried out at 0 to 100 ° C. under reduced pressure of 0.01 to 10000 Pa. Filtration uses a filter having a pore size of about 0.05 to 10 microns, and filters impurities, polymers, and the like at a freezing point of about 50 ° C.

In the present invention, curing catalysts used for producing an optical material from an episulfide compound having a structure represented by the formula (2) include amines, phosphines, and the like.
Examples thereof include mineral acids, Lewis acids, organic acids, silicic acids, and boric acid tetrafluoride. Specific examples include (1) ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, Laurylamine, mystyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine,
Aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-
Isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine, etc. Primary amines: ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl) 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-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-amino Methylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylpiperidine, N-
Aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine, o-, m- or p-phenylenediamine, 2,4- or 2, 6-tolylenediamine, 2,
4-toluenediamine, m-aminobenzylamine, 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'-diaminoditolylsulfone, methylenebis (o-chloroaniline), 3,9-bis (3-
Aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, Pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4 Primary polyamines such as -diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, 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 and 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-
Secondary polyamines such as piperidyl) butane and tetramethylguanidine; trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3
-Methoxypropylamine, tri-n-butylamine,
Tri-iso-butylamine, tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecylamine, Tri-laurylamine, dicyclohexylethylamine, cyclohexyldiethylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanol Amine, N, N-dimethylethanolamine, N-ethyldiethanolamine, 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
Tertiary amines such as -methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N, N'- Bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ′, N′-tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N,
Tertiary polyamines such as N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole;
2-methylimidazole, 4-methylimidazole,
N-ethylimidazole, 2-ethylimidazole, 4
-Ethylimidazole, N-butylimidazole, 2-
Butyl imidazole, N-undecyl imidazole, 2
-Undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-
Methyl imidazole, N- (2'-cyanoethyl) -2
-Methylimidazole, N- (2'-cyanoethyl)-
2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis- (2
-Ethyl-4-methylimidazolyl) methane, various imidazoles such as adducts of alkylimidazole and isocyanuric acid, and condensates of alkylimidazole and formaldehyde; Amidines such as 1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; amine compounds represented by the above. (2) The amines of (1), a mineral acid, a Lewis acid, an organic acid,
Salts with silicic acid, tetrafluoroboric acid, etc. (3) 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 -Hexyl ammonium bromide, tetra-n-hexylammonium acetate,
Tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-
Octyl ammonium acetate, trimethyl-n-octyl ammonium chloride, trimethyl benzyl ammonium chloride, trimethyl benzyl ammonium bromide, triethyl-n-octyl ammonium chloride, triethyl benzyl ammonium chloride, triethyl benzyl ammonium bromide, tri-n-butyl-n-octyl ammonium Chloride,
Tri-n-butylbenzylammonium fluoride,
Tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium 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-hexylpyridinium 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-
quaternary ammonium salts such as n-phenylpicolinium bromide; (4) 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, Ethyltriphenylphosphonium iodide, n-butyltriphenylphosphonium bromide, n-butyltriphenylphosphonium iodide, n-hexyltriphenylphosphonium bromide, n-octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakishydroxymethylphosphonium chloride , Tetrakishydroxymethylphosphonium bromide, tetrakis Hydroxyethyl phosphonium chloride, phosphonium salts such as tetrakis hydroxybutyl phosphonium chloride. (5) trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butylsulfonium iodide, tri-
n-butylsulfonium tetrafluoroborate, tri-n-hexylsulfonium bromide, tri-n-
Sulfonium salts such as octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, and triphenylsulfonium iodide. (6) iodonium salts such as diphenyliodonium chloride, diphenyliodonium bromide and diphenyliodonium iodide. (7) Complex of the amines of (1) with borane and boron trifluoride. (8) trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-
Butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine , Tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl)
Phosphines such as phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, and chlorodiphenylphosphine; (9) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid and half esters thereof. (10) Lewis acids represented by boron trifluoride etherate of boron trifluoride. (11) Organic acids and their half esters. (12) Silicic acid, boric acid tetrafluoride. (13) Tin compounds such as dibutyltin dilaurate, dibutyltin dichloride and tributyltin chloride. And so on. Among these, those having less coloring of the cured product and preferable are primary monoamine, secondary monoamine, tertiary monoamine, tertiary polyamine, imidazoles, amidines, quaternary ammonium salts, phosphine, tin compounds,
A quaternary phosphonium salt, a tertiary sulfonium salt, and a secondary iodonium salt, more preferably a compound having one or less group capable of reacting with an episulfide group, a secondary monoamine, a tertiary monoamine, and a tertiary monoamine Polyamines, imidazoles, amidines, quaternary ammonium salts, phosphines, quaternary phosphonium salts, tertiary sulfonium salts,
Grade iodonium salt. These may be used alone or in combination of two or more. The above curing catalyst is
(2) It is usually used in an amount of 0.0001 mol to 1.0 mol, preferably 0.000 mol, per 1 mol of the episulfide compound having one or more structures represented by the formula per molecule.
1 mol to 0.5 mol, more preferably 0.0001 mol
It is used in an amount of from 0.1 mol to 0.1 mol, most preferably from 0.0001 mol to 0.05 mol. When the amount of the curing catalyst is more than 1.0 mol, the refractive index and heat resistance of the cured product are reduced, and the cured product is colored. On the other hand, if the amount is less than 0.0001 mol, the composition is not cured sufficiently and the heat resistance becomes insufficient.

The composition of the present invention may be a compound having at least one functional group capable of reacting with the epithio group in the structure represented by the formula (2), or one or more of these functional groups and another compound. A compound having one or more polymerizable functional groups, a compound having one or more homopolymerizable functional groups, and a compound having one functional group capable of reacting with an epithio group and capable of being homopolymerized. It can also be produced by curing polymerization. Specific examples of these compounds are disclosed in
No. 2,558,781.

When a compound having an unsaturated group is used, it is preferable to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator is not particularly limited as long as it generates a radical by heating or ultraviolet rays or electron beams.
No. 781.

In the method for producing an optical material of the present invention, it is of course possible to further improve the practicality of the obtained material by adding known additives such as an antioxidant and an ultraviolet absorber. Further, the optical material of the present invention tends to peel off from the mold during polymerization, and in some cases, using or adding a known external and / or internal adhesiveness improving agent, to obtain the adhesion between the obtained cured material and the mold. It is also effective to improve.

The composition of the present invention comprises a compound having at least one SH group as an antioxidant component, alone or in combination with a known antioxidant, in order to impart good oxidation resistance to the material after curing. It is also possible to use. Examples of the compound having one or more SH groups include mercaptans, thiophenols, and mercaptans and thiophenols having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, and allyl. Can be
Specific examples include those described in JP-A-9-255781.

It is also possible to use a compound having at least one active hydrogen other than the SH group for the purpose of improving the performance such as dyeability and strength. The term "active hydrogen" used herein means, for example, hydrogen of a hydroxyl group, a carboxyl group, an amide group, and 1,2-diketone, 1,3-dicarboxylic acid and its ester, and 3-ketocarboxylic acid and its ester.
Compounds having at least one active hydrogen per molecule include alcohols, phenols, mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides, and the like. , 3-Diketones, 1,3-dicarboxylic acids and esters thereof, 3-ketocarboxylic acids and esters thereof, and alcohols having unsaturated groups such as vinyl, aromatic vinyl, methacryl, acryl, and allyl, and phenol , Mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides,
Examples thereof include 1,3-diketones, 1,3-dicarboxylic acid and esters thereof, and 3-ketocarboxylic acid and esters thereof. A specific example is disclosed in Japanese Patent Application Laid-Open No. 9-2557.
No. 81 publication.

In the present invention, the method for producing an optical material is a method for producing an episulfide compound having a structure represented by the formula (2) alone or a composition thereof, a catalyst and a functional group capable of reacting with an epithio group optionally used. Or a compound having at least one of these functional groups and one or more other homopolymerizable functional groups, a compound having at least one homopolymerizable functional group, or a compound capable of reacting with an epithio group. And a compound having one functional group capable of homopolymerization,
Furthermore, the above-mentioned antioxidant components used as required, components for improving performance such as dyeability and strength, adhesion improvers, antioxidants other than the above-described antioxidant components, ultraviolet absorbers, radical polymerization initiators 0.001% to 80%, preferably 0.01% to 5%, of additives such as various performance improvers based on the total composition.
After mixing 0%, more preferably 0.01% to 30%, the mixture is polymerized and cured as described below to obtain an optical material such as a lens. That is, the raw material after mixing is poured into a glass or metal mold, the polymerization and curing reaction is advanced by heating, and then the mold is removed from the mold.

(2) An episulfide compound having a structure represented by the formula alone or a part or the whole amount of the composition is poured into a mixture in the presence or absence of a catalyst, with or without stirring, in the range of -100 to 100% before casting. After preliminarily polymerizing at 160 ° C. for 0.1 to 72 hours, it is also possible to prepare a composition and perform casting. The preliminary polymerization conditions are preferably at -10 to 100C for 1 to 48 hours, more preferably 0 to 100 hours.
Performed at ６０60 ° C. for 1-48 hours. Curing time is 0.1
~ 100 hours, usually 1-48 hours, the curing temperature is-
It is 10 to 160 ° C, usually -10 to 140 ° C. The polymerization is held at a predetermined polymerization temperature for a predetermined time, and 0.1 ° C. to 10 ° C.
The temperature can be increased by 0 ° C./h, decreased by 0.1 ° C. to 100 ° C./h, or a combination thereof. After the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Further, if necessary, a surface treatment such as dyeing, hard coating, antireflection, imparting anti-fogging property can be performed.

The method for producing the cured resin optical material of the present invention comprises:
The details are as follows. As described above, the mixture is prepared by mixing the main raw material and the auxiliary raw material, and then injecting and hardening the mixture into a mold. Compounds having two or more functional groups capable of reacting with an epithio group, compounds having one or more of these functional groups and one or more other functional groups capable of homopolymerization, and one or more functional groups capable of homopolymerization Compound, a compound having one functional group capable of reacting with an epithio group and capable of homopolymerization, and further, an antioxidant component, a component for improving performance such as dyeability and strength, and a cohesion, which are used as desired. The solubility improver, stabilizer, radical polymerization initiator, etc. may be mixed together in the same container under stirring at the same time, or each raw material may be added and mixed in a stepwise manner. Remix within It may be. The respective raw materials and the auxiliary raw materials may be mixed in any order. Upon mixing, the set temperature, the time required for the mixing, etc. may be basically any conditions under which each component is sufficiently mixed, but an excessive temperature and time may cause an undesired reaction between each raw material and additive, Further, it is not appropriate, for example, because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of -50 ° C to about 100 ° C, and the preferred temperature range is -30 ° C to 50 ° C.
° C, more preferably -5 ° C to 30 ° C. The mixing time is 1 minute to 5 hours, preferably 5 minutes to 2 hours, more preferably 5 minutes to 30 minutes, and most preferably about 5 minutes to 15 minutes. Performing a degassing operation under reduced pressure before, during or after the mixing of the raw materials and additives is a preferable method from the viewpoint of preventing the formation of bubbles during the subsequent medium-sized polymerization curing. The degree of pressure reduction at this time is 0.1 mm
Hg to about 700 mmHg, preferably 1
It is 0 mmHg to 300 mmHg. Further, the mixture or the main and auxiliary raw materials before mixing may be used in an amount of 0.05 to 3
Filtration and purification of impurities and the like with a filter having a pore size of about μm is also preferable from the viewpoint of further improving the quality of the optical material of the present invention.

[0035]

According to the present invention, since the reaction conditions for producing the episulfide compound having the structure represented by the formula (2) of the present invention have been developed, the reaction yield of the episulfide compound has been improved, and The resulting optical material was prevented from yellowing or clouding and from decreasing heat resistance. As a result, the quality of a high-refractive-index optical material having a high balance between the refractive index and the Abbe number is significantly improved as compared with the related art.

[0036]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, evaluation of the obtained lens was performed by the following method. 1. Yellowness The δYI value of the lens was measured using a colorimeter. The lower the δYI value, the better the yellowness.
If it is the following, it can be used as an optical material for glasses. 2. Cloudiness The lens was observed for cloudiness under irradiation of a fluorescent lamp in a dark room. No: not observed Yes: white turbidity is observed Heat resistance The elastic modulus at 90 ° C. was measured using a dynamic viscoelasticity measuring device. Usually, if this elastic modulus is 250 MPa or more, it can be used as an optical material for glasses.

Example 1 365.0 g of bis (β-epoxypropyl) sulfide was placed in a flask equipped with a stirrer, thermometer and nitrogen inlet tube.
(2.5 mol) and 761.2 g of thiourea (10 mo
l) and 43.8 g (0.43 mol) of acetic anhydride and 1.7 l of toluene and 3.4 methanol as solvents.
and then reacted at 20 ° C. for 10 hours under a nitrogen atmosphere. No precipitation of polymer was observed during the reaction. After the reaction, the reaction product was extracted with 4.3 l of toluene, washed with 520 ml of a 10% aqueous sulfuric acid solution, and washed four times with 520 ml of water. After removing the excess solvent, 338.8 g of bis (β-epithiopropyl) sulfide was removed. Yield 76%). Next, the obtained bis (β-epithiopropylthio) sulfide 1
To 0.1 part by weight of triethylamine as a catalyst was mixed with 00 parts by weight and stirred at room temperature to form a uniform liquid. Then, after defoaming and filtering, the mixture was poured into a 2.5 mm-thick flat lens mold and heated in an oven from 20 ° C. to 90 ° C. over 20 hours to polymerize and cure, thereby producing a lens. The obtained lens has good heat resistance and physical properties, and has not only excellent optical properties such as a refractive index of 1.71 and an Abbe number of 36 but also a good surface condition. Almost no deformation was observed. Table 2 shows the evaluation results of the yellowness, cloudiness, and heat resistance of the lens.

Examples 2 to 14 2.5 mol of the epoxy compound described in Table 1 and thiourea 76 were placed in a flask equipped with a stirrer, thermometer and nitrogen inlet tube.
Example 1 was repeated except that 1.2 g (10 mol) and further 5.1 l of the solvent were changed in the reaction temperature, the reaction time, the type and amount of the thiocyanate and the type and amount of the acidic substance, the type and the ratio of the solvent shown in Table 1. Was repeated to produce various episulfide compounds described in Table 1, and lenses were produced therefrom. In Examples 11 to 13, some precipitation of the polymer was observed during the reaction, but in Examples 2 to 10, no precipitation of the polymer was observed. The obtained lens shows good heat resistance and physical properties, and has not only excellent optical properties such as a refractive index of 1.70 to 1.71 and an Abbe number of 36, but also a good surface state. Striae and surface deformation were hardly observed. Table 2 shows the evaluation results of the reaction yield and the yellowness, cloudiness and heat resistance of the lens.

Comparative Example 1 Example 2 was repeated except that the reaction temperature and reaction time for producing bis (β-epithiopropylthio) ethane were changed. As shown in Table 1, the obtained lens had a remarkably high yellowness because the reaction temperature was below the range of the present invention.

Comparative Example 2 Example 2 was repeated except that the reaction temperature and the reaction time for producing bis (β-epithiopropylthio) ethane were changed. Precipitation of the polymer was observed during the reaction. As shown in Table 2, the reaction temperature of the obtained lens was higher than the range of the present invention, so that the yield was greatly reduced, and the obtained lens became cloudy and had low heat resistance.

Comparative Examples 3 and 4 Comparative Example 2 was repeated except that the solvent for preparing bis (β-epithiopropyl) sulfide and the acidic substance were changed. Precipitation of the polymer was observed during the reaction. As shown in Table 2, the yield was extremely reduced, and the obtained lens became cloudy.

Comparative Example 5 When preparing bis (β-epithiopropyl) sulfide, Comparative Example 3 was repeated without adding an acidic substance. The polymer precipitated in large quantities and no bis (β-epithiopropyl) sulfide was obtained.

[0043]

[Table 1]

[0044]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tokiki Niimi 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory (72) Inventor Yu Horikoshi 6-chome, Shinjuku, Katsushika-ku, Tokyo No. 1-1 Inside the Tokyo Research Laboratory, Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Masanori Shimuta 1-327, Funamachi, Taisho-ku, Osaka City Inside Naniwa Plant, Mitsubishi Gas Chemical Co., Ltd. (72) Nobuyuki Uemura, Taisho Osaka City 1-3-27, Funamachi, Ward Mitsubishi Gas Chemical Co., Ltd. Naniwa Plant

Claims (6)

[Claims] 1. A method for producing an episulfide compound having a structure represented by the following formula (2) by reacting an thiourea with an epoxy compound having a structure represented by the following formula (1): In a mixed solvent of a soluble polar organic solvent and a non-polar organic solvent in which the epoxy compound can be dissolved,
A method for producing an episulfide compound, wherein the reaction is carried out at a temperature of 10 to 30C. Embedded image (Wherein, R ¹ is a hydrocarbon having 0 to 10 carbon atoms, R ² , R ³
And R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te, and n
Represents 0 or 1. ) (Wherein, R ¹ is a hydrocarbon having 0 to 10 carbon atoms, R ² , R ³
And R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te;
n represents 0 or 1. ) 2. A method for producing an episulfide compound having a structure represented by the above formula (2) by reacting an thiourea with an epoxy compound having a structure represented by the above formula (1). Or an episulfide compound characterized in that the reaction is carried out at a temperature of 10 to 30 ° C. in a mixed solvent of a polar organic solvent in which thiourea can be dissolved and a nonpolar organic solvent in which an epoxy compound can be dissolved in the presence of an acid anhydride. Manufacturing method. 3. The method for producing an episulfide compound according to claim 1, wherein the mixing ratio of the mixed solvent is from 0.1 to 10.0 in terms of a volume ratio of a polar organic solvent / a non-polar organic solvent. 4. The method for producing an episulfide compound according to claim 1, wherein the polar organic solvent is an alcohol. 5. The method for producing an episulfide compound according to claim 1, wherein the non-polar organic solvent is an aromatic hydrocarbon. 6. The method for producing an episulfide compound according to claim 2, wherein the acid and / or acid anhydride is 0.001 to 10% by weight based on the total amount of the reaction solution.