JP2000186086A - 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 thiocyanate 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 thiocyanate compound in a mixed solvent of an organic solvent in which the epoxy compound can be dissolved (preferably an alcohol, especially an alcohol having <=3C) with water (preferably a volume ratio of water/organic solvent is 0.1-10.0) at 10-40 deg.C.

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 an episulfide compound, to improve the reaction yield, and to obtain a high refractive index and Abbe which were impossible in the prior art. It is to improve the quality of a high-refractive-index optical material having a balance between numbers.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an episulfide compound having an epithio structure represented by the following formula (2) by reacting a thiocyanate with an epoxy compound represented by the following formula (1). In the production method, in a mixed solvent of an organic solvent and water in which the epoxy compound can be dissolved,
The problem was solved by a production method characterized in that the reaction was carried out at a temperature of 10 to 40 ° C.

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. )

Embedded image (Wherein, R ¹ is a hydrocarbon having 1 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. )

[0005]

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

The episulfide compound having a structure represented by the above formula (1) of the present invention includes all organic compounds satisfying the above conditions, and more preferably the above (1)
It is a compound having two or more structures represented by the formulas. Specific examples of the compound having the structure represented by the above formula (1) are as follows. (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 such as sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, or urethane 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-epithiopropyl) 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-tris (β-epithiopropyl) propane,
1,3-bis (β-epithiopropyl) -1- (β-epithiopropyl) -2-thiapropane, 1,5-bis (β-epithiopropyl) -2,4-bis (β-epithio Propyl) -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 structure such as dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, and 2,2-bis [4- (epithioethyl) cyclohexyl] Propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- (epithioethyl) cyclohexyl] methane, bis [4- (β
Compounds having two aliphatic cyclic structures, such as -epithiopropyl) cyclohexyl] methane, 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, neo 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, hetonic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenedicarboxylic acid, diphthic acid 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, , 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 a primary diamine such as 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2- (4,4'-diaminodiphenyl) 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)-
Amine-based epoxy compounds produced by condensation of a secondary diamine such as propane or 1,4-di- (4-piperidyl) -butane with epihalohydrin;
Urethane epoxy compounds produced from phenol compounds, diisocyanates, glycidol and the like can be mentioned. If you take a more specific example method,
The following can be given as typical examples. Organic compound having a linear 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) -2-[[2- (2-
chain organic compounds such as β-epithiopropyloxyethyl) oxyethyl] oxy] ethane and the like; tetrakis (β-epithiopropyloxymethyl) methane;
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, 8-
Bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy)-
4,5 bis (β-epithiopropyloxymethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -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, 1,11
-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, 1,1
1-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9
Compounds having an aliphatic cyclic skeleton, such as -trithiaundecane: 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)
A compound having one aromatic skeleton such as 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,
Compounds having two aromatic skeletons, such as 4,4'-bis (β-epithiopropyloxy) biphenyl. Moreover,
Compounds in which at least one hydrogen of the epithio group of these compounds is substituted with 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-epithiopropylthio) -2-
(Β-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, 1,8-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-epithio Propylthio) -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-epi Thiopropylthio) -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, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropyl Thiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-tri Thiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[(2-β
-Epithiopropylthioethyl) thiomethyl] -3,
An ester group such as 6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane A chain compound having an epithioalkylthio group: tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1,1-tri [2- (β-epithiopropylthio) acetylmethyl] propane, Compounds having an aliphatic cyclic skeleton such as tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane: 1,3 or 1,4-
Bis (β-epithiopropylthio) cyclohexane,
1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithio Propylthioethylthiomethyl) -1,
Aliphatics such as 4-dithia 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithia Compounds having one cyclic skeleton, bis [4-
(Β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio)
Compounds having two aliphatic cyclic skeletons such as cyclohexyl] propane and bis [4- (β-epithiopropylthio) cyclohexyl] sulfide. Compounds having an aromatic skeleton: aromatics such as 1,3 or 1,4-bis (β-epithiopropylthio) benzene and 1,3 or 1,4-bis (β-epithiopropylthiomethyl) benzene Compounds having one skeleton or bis [4
-(Β-epithiopropylthio) phenyl] methane,
2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] Compounds having two aromatic skeletons, such as sulfone and 4,4′-bis (β-epithiopropylthio) biphenyl. Furthermore, 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). Preferred specific examples of these include vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, allylthioglycidyl ether and the like.

Other specific examples of the compound having one epithio group include compounds such as ethylene sulfide, propylene sulfide, and thioglycidol; And thioglycidyl ethers such as glycidyl esters, methylthioglycidyl ether, ethylthioglycidyl ether, propylthioglycidyl ether, and butylthioglycidyl ether.

Of the above, more preferred are (B) an organic compound having an epithioalkyloxy group, (C) an organic compound having an epithioalkylthio group, (D) an organic compound having an epithioalkylseleno group, or (E)
An organic compound having an epithioalkyl telluro group,
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 a chain compound having a β-epithiopropylthio group or a β-epithiopropylseleno group, a branched compound, an aliphatic cyclic compound, an aromatic compound, and a heterocyclic ring having the above-described specific examples. And the like.

In the present invention, the corresponding epoxy compound represented by the formula (1), which is used as a raw material when producing the episulfide compound represented by the formula (2), is a compound in which the sulfur atom in the three-membered ring represented by the formula (2) is oxygen. Just replacing the atom does not change other structures. That is, R ¹ , R ² , R ³ , R ⁴ and Y in the formula are the same.

In the present invention, the corresponding epoxy compound of the formula (1), which is used as a raw material in producing the episulfide compound of the formula (2), is a compound having a carbanion represented by alkyl lithium or Grignard or a compound having a hydroxyl group (water Or a metal salt thereof, such as a sulfur compound having a mercapto group (including hydrogen sulfide) or a metal salt thereof, a selenium compound having a selenol group or a metal salt thereof, or a tellurium compound having a tellurol group or these And 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 is a sulfur compound having a mercapto group (including hydrogen sulfide), such as the above-mentioned alkyl lithium or a carbanion represented by Grignard, a compound having a hydroxy group (including water) or a metal salt thereof, or These metal salts, such as selenium compounds having a selenol group or these metal salts,
Or, for a tellurium compound having a telluryl group or a metal salt thereof, a stoichiometric amount or more is used.
Lower or higher amounts 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, ethers, aromatic hydrocarbons, halogenated hydrocarbons, and the like. 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 the epoxy compound of the formula (1), there is also a method of producing the corresponding unsaturated compound represented by the formula (3) by oxidation with an organic peracid, alkyl hydroperoxide, hydrogen peroxide or the like. can give.

Embedded image (Wherein, R ¹ is a hydrocarbon having 0 to 10 carbon atoms, R ² , R ³ ,
R ⁴ represents 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 production of the episulfide compound of the formula (2) from the epoxy compound of the formula (1) in the present invention, thiocyanic acid is used as a thiating agent for converting the ether structure of the epoxy compound into a sulfide structure. Use salt. As the thiocyanate to be used, an alkali or alkaline earth metal thiocyanate or ammonium thiocyanate may be used, and these may be used in combination. Specific preferred thiocyanates are potassium thiocyanate, sodium thiocyanate, calcium thiocyanate, barium thiocyanate, and ammonium thiocyanate. For the thiocyanate, a mole number corresponding to the number of epoxy groups of the epoxy compound of the formula (1), that is, a stoichiometric amount, is used. Less or more may 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.

The reaction for producing the episulfide compound of the formula (2) according to the present invention comprises the steps of:
(1) The reaction is performed in a mixed solvent of an organic solvent capable of dissolving the epoxy compound represented by the formula. Usually, water / organic solvent = 0.1 to
It is used at a volume ratio of 10.0, but preferably at a water / organic solvent = 0.2-5.0 volume ratio. When the volume ratio is less than 0.1, the thiocyanate is insufficiently dissolved and the reaction does not proceed sufficiently, so that the yield decreases and the
If it exceeds 300, the production of the polymer becomes remarkable.

Specific examples of the organic solvent capable of dissolving the epoxy compound as a raw material in the present specification include alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, methylcellosolve and ethylcellosolve. , Hydroxy ethers such as butyl cellosolve, aliphatic hydrocarbons such as pentane, hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, and halogenated hydrocarbons such as dichloroethane, chloroform and chlorobenzene. No. Among the above, alcohols having 3 or less carbon atoms are preferable, and methanol or ethanol is more preferable.

For the purpose of improving the reaction efficiency, a phase transfer catalyst typified by tetrabutylammonium bromide, a surfactant and the like may be added to the reaction solution as needed.

In the production method of the present invention, the reaction temperature is very important. Specifically, the reaction temperature ranges from 10 to 40.
Performed at ° C. When the reaction temperature is lower than 10 ° C., the reaction yield is remarkably reduced, and at the same time, the oxidation resistance of the obtained optical material is lowered. The optical material becomes cloudy, and further causes a decrease in heat resistance. The reaction time may be any time as long as the reaction is completed under the above-mentioned temperature conditions, but is usually preferably 20 hours or less.

The stability of the episulfide compound of the formula (2) can be improved by washing the reaction product with an acidic aqueous solution. Specific examples of the acid used for the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid,
Examples include 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 an effect at pH 6 or lower, but the more effective range is pH 3-0.

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, the distillation is carried out at 0-100 ° C. under reduced pressure of 0.1-10000 Pa. Filtration is performed with a filter having a pore size of about 0.05 to 10 micron, and filters impurities and polymers at a freezing point of about 50 ° C.

The curing catalyst used for producing the optical material from the episulfide compound of the formula (2) in the present invention includes amines, phosphines, mineral acids, Lewis acids,
Organic acids, silicic acids, tetrafluoroboric acid and the like can be mentioned. 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, a tertiary polyamine, 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) Usually used in an amount of 0.0001 mol to 1.0 mol, preferably 0.0001 mol to 0.5 mol, more preferably 0 mol, to 1 mol of the episulfide compound having the structure represented by the formula. 0.0001 mol to 0.1 mol, most preferably 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. Also, 0.0
If the amount is less than 001 mol, the composition is not sufficiently cured and the heat resistance becomes insufficient.

The composition of the present invention may be a compound having one or more functional groups capable of reacting with the epithio group in the formula (2), or one or more of these functional groups and another functional group capable of homopolymerization. And a compound having at least one functional group capable of homopolymerization, and a compound having one functional group capable of reacting with an epithio group and capable of homopolymerization. it can. Specific examples of these compounds include those described in JP-A-9-255781.

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 the polymerization, and in some cases, using or adding a known external and / or internal adhesiveness improving agent to improve the adhesion between the obtained cured material and the mold. It is also effective to improve it.

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.
Specific examples of compounds having at least one active hydrogen other than an SH group per molecule include alcohols, phenols, mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, Carboxylic acids, amides, 1,3-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, phenols, mercapto alcohols, hydroxythiophenols, carboxylic acids, and mercaptocarboxylic acids , Hydroxycarboxylic acids, amides, 1,3-diketones, 1,3-dicarboxylic acids and esters thereof, 3-ketocarboxylic acids and esters thereof, and the like. Specific examples include those described in JP-A-9-255781.

In the present invention, the method for producing an optical material comprises the steps of: using a compound having one or more structures represented by the formula (2) as a raw material alone or a composition and a catalyst thereof; A compound having at least two functional groups capable of reacting, a compound having at least one functional group capable of at least one of these functional groups and another functional group capable of at least one homopolymer, a compound having at least one functional group capable of homopolymerizing, A compound having one functional group capable of reacting with a group and capable of being homopolymerized, furthermore, the above-mentioned antioxidant component, a component for improving performance such as dyeability and strength, an adhesion improver, Additives such as antioxidants, ultraviolet absorbers, radical polymerization initiators, and various performance improvers other than the aforementioned antioxidant components are used in an amount of 0.001 to 80% by weight, preferably 0.01% by weight, based on the total composition. % 50 wt%, more preferably 0.
After mixing from 01% by weight to 30% by weight, 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.

The compound having one or more of the structure represented by the formula (1) in one molecule or a part or the whole of the composition may be mixed with a catalyst before casting, in the presence or absence of a catalyst, under stirring, or 0.1 to 72 at −100 to 160 ° C. without stirring.
After preliminarily polymerizing over time, the composition can be prepared and cast. The preliminary polymerization conditions are:
Preferably, the reaction is carried out at -10 to 100 ° C for 1 to 48 hours, more preferably at 0 to 60 ° C for 1 to 48 hours. The curing time is from 0.1 to 100 hours, usually from 1 to 48 hours, and the curing temperature is from -10 to 160C, usually from -10 to 140C. The polymerization is carried out at a predetermined polymerization temperature for a predetermined period of time.
The temperature can be increased by 1 ° C. to 100 ° C./h, decreased by 0.1 ° C. to 100 ° C./h, or a combination thereof. After the curing, the material is heated at a temperature of 50 to 150 ° C. for 10 minutes.
Performing the annealing treatment for about a minute to about 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 the catalyst and optionally used epithio groups, or compounds having one or more of these functional groups and one or more other homopolymerizable functional groups, homopolymerizable Compounds having one or more functional groups, one functional group capable of reacting with an epithio group and capable of homopolymerization
Compounds having the same, and further used as desired, antioxidant components, performance improving components such as dyeability and strength, as well as adhesion improvers, stabilizers, radical polymerization initiators, etc., are all contained in the same container. The ingredients may be mixed at the same time under stirring, or the respective raw materials may be added and mixed stepwise, or the several components may be separately mixed and then remixed in the same container. 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 5 ° C.
0 ° 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 casting and 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, by developing appropriate reaction conditions for an episulfide compound having an epithio structure represented by the formula (2) of the present invention, it is possible to improve the reaction yield and to reduce the yellowing of an optical material obtained from the compound. Clouding and reduction in heat resistance were prevented. 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 1 516.0 g of bis (β-epoxypropylthio) ethane was placed in a flask equipped with a stirrer, thermometer and nitrogen inlet tube.
(2.5 mol) and 971.8 g of potassium thiocyanate
(10 mol), 1.6 l of water and 1.6 l of methanol were further charged as solvents, and 1
The reaction was performed for 5 hours. No precipitation of polymer was observed during the reaction. After the reaction, the reaction product was extracted with 4.3 l of toluene.
After washing with 520 ml of a 0% aqueous sulfuric acid solution and four times with 520 ml of water, excess solvent was distilled off to obtain 459.0 g of bis (β-epithiopropicathio) ethane (yield 77%). Next, 0.9 parts by weight of triethylamine as a catalyst was mixed with 100 parts by weight of the obtained bis (β-epithiopropylthio) ethane, and the mixture was stirred at room temperature to obtain a uniform liquid. Then, after defoaming and filtering, the mixture was poured into a mold for a flat lens having a thickness of 2.5 mm, and was heated from 20 ° C. to 90 ° C. in an oven.
The temperature was raised over 0 hours to carry out polymerization and curing to produce 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. yield,
Table 2 shows the evaluation results of the yellowness and white turbidity of the lens.

Examples 2 to 10 Table 1 was placed in a flask equipped with a stirrer, thermometer and nitrogen inlet tube.
Example 1 except that 2.5 mol of various epoxy compounds, 10 mol of thiocyanate, and 3.2 l of the solvent shown in Table 1 were used to change the reaction temperature, reaction time, type of thiocyanate, and the ratio of water to the organic solvent shown in Table 1. Was repeated to produce an episulfide compound shown in Table 1, from which a lens was produced. In Examples 9 and 10, some precipitation of polymer was observed during the reaction, but in Examples 2 to 8, no precipitation of polymer was observed. The obtained lens shows good heat resistance and physical properties, and has a refractive index of 1.70 to
Not only had excellent optical properties of 1.71 and Abbe number of 36, but also the surface condition was good, and striae and surface deformation were hardly observed. Table 2 shows the evaluation results of the yield, the yellowness of the lens, and the cloudiness.

Comparative Examples 1 and 2 Example 1 was repeated except that the reaction temperature and reaction time for producing bis (β-epithiopropylthio) ethane were changed as shown in Table 1. In Comparative Example 2, polymer precipitation was observed during the reaction. As shown in Table 2, the obtained lenses had significantly reduced yield and extremely high yellowness of the lenses because the reaction temperature was outside the range of the present invention. When the reaction temperature was 45 ° C., the lens became cloudy and the heat resistance was lowered.

Comparative Example 3 Example 2 was repeated except that the ratio of the solvent for producing bis (β-epithiopropylthio) ethane was changed to water / methanol = 1/15. Precipitation of the polymer was observed during the reaction. As shown in Table 1, the obtained lenses had high yellowness.

Comparative Example 4 Example 2 was repeated except that the ratio of the solvent for producing bis (β-epithiopropylthio) ethane was changed to water / methanol = 15/1. As shown in Table 1, since the reaction temperature was high and water was excessive with respect to the organic solvent, the polymer precipitated vigorously during the reaction, and bis (β-epithiopropylthio) ethane was not obtained.

[0042]

[Table 1]

[0043]

[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 (4)

[Claims] 1. A method of producing an episulfide compound having a structure represented by the following formula (2) by reacting a thiocyanate with an epoxy compound having a structure represented by the following formula (1): A method for producing an episulfide compound, wherein the reaction is carried out at a temperature of 10 to 40 ° C. in a mixed solvent of a soluble organic solvent and water. 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. The method for producing an episulfide compound according to claim 1, wherein the mixing ratio of the mixed solvent is 0.1 to 10.0 in terms of volume ratio of water / organic solvent. 3. The method for producing an episulfide compound according to claim 1, wherein the organic solvent is an alcohol. 4. The method for producing an episulfide compound according to claim 3, wherein the alcohol has 3 or less carbon atoms.