JP2005113156A - Method for producing resin having high refractive index and excellent in color tone and transparency - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin with a high refractive index, having high transparency and good color tone which are not obtained by conventional technologies, from an episulfide compound or a composition containing the compound, wherein the episulfide compound is a raw material for resins with a high refractive index and has an epithio structure represented by formula (1). <P>SOLUTION: The method for producing a resin for optical materials and having high refractive index comprises polymerizing and curing an episulfide compound or a composition containing the compound in the presence of 0.001-3.0 pts.wt. quaternary ammonium salt. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

In recent years, plastic materials have been widely used in various optical materials, particularly eyeglass lenses, because they are light and tough and easy to dye. In addition to low specific gravity, the performance required especially for optical materials, especially spectacle lenses, is high transparency and low yellowness, high refractive index and high Abbe number as optical performance, and high refractive index reduces lens thickness. A high Abbe number reduces the chromatic aberration of the lens. The inventors of the present application have found a novel episulfide compound that enables an optical material having a thin thickness and low chromatic aberration and having a refractive index of 1.7 or more and an Abbe number of 35 or more. 1-3).
The appearance of the optical material obtained by these inventions is of sufficient quality as a normal plastic material. However, it is needless to say that a resin whose appearance is more colorless and transparent is more preferably used for optical materials such as plastic lenses for spectacles.

JP-A-9-71580 Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 9-255781

  The object of the present invention is to solve the above-mentioned problems in the prior art and from an episulfide compound having an epithio structure represented by the following formula (1), which is a raw material for a high refractive index resin, or a composition containing the compound: An object of the present invention is to provide a method for producing a high refractive index resin having high transparency and good color tone that has not been achieved by the prior art.

The present inventors have earnestly studied on a method for producing a high refractive index resin having high transparency and good color tone from an episulfide compound having an epithio structure represented by the following formula (1) or a composition containing the compound. As a result of use of at least one selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt and a secondary iodonium salt as a polymerization catalyst, a high degree of transparency is achieved. The inventors have found that a high refractive index resin having a good color tone can be obtained, and have reached the present invention.
That is, the present invention provides 0.001 to 3.0 parts by weight of at least one polymerization catalyst selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, and a secondary iodonium salt. And 100 parts by weight of an episulfide compound having at least one epithio structure represented by the above formula (1) in one molecule or a composition containing 10% by weight or more of the compound is polymerized and cured. The present invention relates to a method for producing a refractive index resin. ,

(In the formula, R ¹ represents a hydrocarbon having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ each represent a hydrocarbon group or hydrogen having 1 to 10 carbon atoms. Y represents O, S or Se. n and m each represents 0 or 1)

  The quaternary ammonium salt, quaternary phosphonium salt, and tertiary sulfonium salt are added to 100 parts by weight of an episulfide compound having an epithio structure represented by the formula (1) of the present invention or a composition containing 10 wt% or more of the compound. Alternatively, by using a production method in which 0.001 to 3.0 parts by weight of a secondary iodonium salt as a catalyst is added and polymerized and cured, it is possible to produce a high refractive index resin having high transparency and good color tone that is not a conventional technique. became.

The episulfide compound produced in the present invention expresses a high refractive index, a high Abbe number, and a good balance between the two when used as an optical material. Therefore, R ¹ in the formula (1) is preferably methylene and ethylene. In the formula (1), R ² , R ³ and R ⁴ are each preferably hydrogen or a methyl group. More preferably R ¹ is methylene and R ² , R ³ and R ⁴ are hydrogen. n represents 0 or 1, but n is preferably 1. m represents 0 or 1, but m is preferably 1. Y may be any of O, S, Se, or Te, but S or Se is advantageous when a high refractive index is desired.

The episulfide compound having a structure represented by the formula (1) of the present invention includes all organic compounds satisfying this condition, but more preferably a compound having two or more structures represented by the formula (1). is there. Specific examples of the compound having the structure represented by the formula (1) are as follows. (A) Organic compound having an epithio group (B) Organic compound having an epithioalkyloxy group (C) Organic compound having an epithioalkylthio group (D) Organic compound having an epithioalkylseleno group (E) Epithioalkyl Organic compounds having tellurium groups The organic compounds of (A), (B), (C), (D), and (E) are chain compounds, branched compounds, aliphatic cyclic compounds, aromatic compounds, or nitrogen , Oxygen, sulfur, selenium, a heterocyclic compound containing a tellurium atom as a main skeleton, an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group, and an epithioalkyltelluro group. You may have in a molecule | numerator simultaneously. Furthermore, these compounds may contain bonds such as sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, urethane, etc. in the molecule.

A preferred specific example of the organic compound having one or more epithio groups in (A) is a compound in which one or more epoxy groups of a compound having an epoxy group (not a glycidyl group) are substituted with epithio groups. Can do. If a more specific example method is taken, the following can be given as representative examples.
Organic compounds having a chain aliphatic skeleton:
1,1-bis (epithioethyl) methane 1- (epithioethyl) -1- (β-epithiopropyl) methane 1,1-bis (β-epithiopropyl) methane 1- (epithioethyl) -1- (β-epi Thiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane 1- (epithioethyl) -3- (β-epithiopropyl) butane, 1,3-bis (β-epithiopropyl) propane, -(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-epithio) Opropyl) 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,

Compounds 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-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, etc. Compounds having one cyclic structure, 2,2-bis [4- (epithioethyl) cyclohexyl] propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- (epithioethyl) Cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) A compound having two aliphatic cyclic structures such as (l) 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-epithio) Propyl) biphenyl, a compound having two aromatic skeleton and the like. Furthermore, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also exemplified.

  In a preferred specific example of the organic compound having one or more epithioalkyloxy groups in (B), one or more glycidyl groups of the epoxy compound derived from epihalohydrin are substituted with epithioalkyloxy groups (thioglycidyl groups). Compounds can be given as representative examples.

  Specific examples of the epoxy compound are produced by condensation of a polyhydric phenol compound such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, novolac resin, and epihalohydrin. 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-ma Of 1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, and the like and epihalohydrins Alcohol-based 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, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphth Glycidyl ester epoxy compounds produced by condensation of polycarboxylic acid compounds such as nildicarboxylic acid and epihalohydrins; 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, 1 , 2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1,4-bisamino Cyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethyl Chlorohexane, 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, Primary diamines such as 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 Amine-based epoxy compounds produced by condensation of secondary diamines such as piperidyl) -propane and 1,4-di- (4-piperidyl) -butane with epihalohydrins; from the aforementioned polyhydric alcohols, phenol compounds and diisocyanates and glycidol The urethane type epoxy compound etc. which are manufactured can be mention | raise | lifted.

  If a more specific example method is taken, the following can be given as representative examples. Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) 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, , 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-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane Chain organic compounds such as tetrakis (β-epithiopropyloxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epi Thiopropyloxy) -2- (β-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiop) Pyroxymethyl) -3-thiapentane, 1- (β-epithiopropyloxy) -2,2-bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epi Thiopropyloxy) -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-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiop (Lopyloxymethyl) -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-epithiopropyl) Oxy) -4,8-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β- Epithiop (Lopyloxymethyl) -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, etc.

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-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2 , 5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane,
Compounds having an aromatic skeleton: 1, 3 or 1,4-bis (β-epithiopropyloxy) benzene, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) benzene, etc. Compounds having one skeleton, bis [4- (β-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (β-epithiopropyloxy) phenyl] propane, bis [4- (β Two aromatic skeletons such as -epithiopropyloxy) phenyl] sulfide, bis [4- (β-epithiopropyloxy) phenyl] sulfone, 4,4'-bis (β-epithiopropyloxy) biphenyl Having compound. Furthermore, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also exemplified.

  A preferred specific example of the organic compound having one or more epithioalkylthio groups in (C) is an epoxyalkylthio group (specifically, β-epoxypropylthio group) of an epoxy compound derived from a compound having a mercapto group and an epihalohydrin. As a representative example, a compound in which one or more of ()) is substituted with an epithioalkylthio group. If a more specific example method is taken, the following can be given as representative examples.

Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) Methane, bis (β-epithiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β-epithiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1, 2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithio Propylthio) -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-epithiopropyl) Thio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethane, tetrakis (β-epithiopropylthiomethyl) methane, tetrakis (β-epithiopropyldithio) Til) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,5-bis (β-epithiopropyl) Thio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3- Thiapentane, 1,6-bis (β-epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 1- (β-epithiopropylthio) -2,2-bis (Β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8- Bi (Β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β-epithio) Propylthiomethyl) -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-epithiopropylthioe L) 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-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-epithiopropylthio) Methyl) -3,6,9-trichiau Ndecane etc.

Chain compounds having an ester group and an epithioalkylthio group: tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio) acetylmethyl ] An aliphatic cyclic skeleton such as propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane Compound having: 1,3 or 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane 2,5-bis (β-epi Thiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis ( compounds having one aliphatic cyclic skeleton such as β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, Bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] A compound having two aliphatic cyclic skeletons such as sulfide.

Compound having aromatic skeleton: 1,3 or 1,4-bis (β-epithiopropylthio) benzene, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) benzene, 1,3 or Compounds having one aromatic skeleton such as 1,4-bis (β-epithiopropyldithiomethyl) benzene, 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] sulfone, 4,4 ′ -A compound having two aromatic skeletons such as bis (β-epithiopropylthio) biphenyl. Furthermore, compounds in which at least one of hydrogens in the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

  (D) Preferred specific examples of organic compounds having an epithioalkylseleno group include epoxy compounds derived from selenium compounds such as metal selenium, alkali metal selenides, alkali metal selenols, alkyl (aryl) selenols, hydrogen selenides, and epihalohydrins. A representative example is a compound in which one or more of the epoxyalkylseleno groups (specifically, β-epoxypropylseleno group) are substituted with epithioalkylseleno groups. If a more specific example method is taken, the following can be given as representative examples:

Organic compounds having a chain 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-epithiopropylseleno) Methyl) propane, 1,5-bis (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) -3-thiapentane, 1,5-bis (β-epi) Thiopropylseleno) -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) -4,5bis (β-epithiopropylselenomethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,4-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Lopyrseleno) -2,4,5-tris (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,5-bis (β-epithio) Propylselenomethyl) -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, 1,11-bis (β-epi Opropylseleno) -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) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylseleno) acetylmethyl] Propane, tetra [2- (β-epithiopropylselenomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylselenomethyl) acetylmethyl] propa Bis (5,6-epithio-3-selenohexyl) 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-tellapropane, bis (4,5-thioepoxy-2-selenopentyl)- 3,6,9-triteraoundedecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis ( 6,7-thioepoxy-1-tellla-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-tella-6-thiaoctane-1,8-bis ( , 4-thioepoxy-1-Serenobuchiru) etc.

Compounds having an aliphatic cyclic skeleton: (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, (2,3 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-diselenolane, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1, 3-diselenolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-selenolane, (2,4 or 2,5 or 4, 5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-selenolane, 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) selenophan, (2,3 or 2,4 or 2,5 or 3,4) -bis (4,5-epithio-2-selenopentyl) selenophan , 2- (4,5- (Oepoxy-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-diterlan, (2,3 or 2,5 or 2,6) -bis (4,5-epithio-2-selenopentyl) -1,4-diterlan, (2,4 or 2,5 or 5, 6)- (3,4-epithio-1-selenobutyl) -1,3-diterlan, (2,4 or 2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl) -1,3 Diterlan, (2,3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-4-tellane, (2,3 or 2,5 Or 2,6 or 3,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-4-terlan, (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-thio A-3-tellurolane, (2,4 or 2,5 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-tellurolane, 2,6-bis (4 5-epithio-2-selenopentyl-1,3,5-triterulan, bis (3,4-epithio-1-selenobutyl) tricyclotellaoctane, bis (3,4-epithio-1-selenobutyl) dicyclotellanonane , (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) tellurophane, 2- (4,5-thioepoxy-2-selenopentyl) -5- (3,4-thioepoxy-1-selenobutyl) -1-tellacyclohex (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-tellulacyclohexane, (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-tellulacyclohexane, etc.

Compounds having an aromatic 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-epithiopropylseleno) biphenyl, and the like, as well as the hydrogen of the β-epithiopropyl group of these compounds. A compound in which at least one is substituted with a methyl group is also a specific example.

(E) Preferred specific examples of the organic compound having an epithioalkyltelluro group include epoxy compounds derived from tellurium compounds such as metal tellurium, alkali metal telluride, alkali metal tellurol, alkyl (aryl) tellurol, hydrogen telluride and epihalohydrin. A representative example is a compound in which one or more of the epoxyalkyltelluro groups (specifically, β-epoxypropyltelluro group) are substituted with epithioalkyltelluro groups. If a more specific example method is taken, the following can be given as representative examples.
Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) telluride, bis (β-epithiopropyl) ditelluride, bis (β-epithiopropyl) tritellide, 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-epithiopropyltelluro) Methyl) propane, 1,5-bis (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) -3-thiapentane, 1,5-bis (β-epi Thiopropyltelluro) -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) -4,5bis (β-epithiopropyltelluromethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,4-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Lopyrteluro) -2,4,5-tris (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,5-bis (β-epithio) Propyltelluromethyl) -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, 1,11-bis (β-epi Opropyltelluro) -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) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluro) acetylmethyl] Propane, tetra [2- (β-epithiopropyltelluromethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluromethyl) acetylmethyl] propa Bis (5,6-epithio-3-tellohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-telluroheptyl) -1- (3,4-thioepoxy-1-tellulobutyl) propane 1,1,3,3-tetrakis (4,5-thioepoxy-2-tellopentyl) -2-selenapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6,9-triselenaundecane -1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7-thioepoxy-1-selena -4-telloheptyl) butane, tris (4,5-thioepoxy-2-tellopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thioepoxy) -1-tellulobutyl), bis (5,6-epithio-3-tellurohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellla-4-telluroheptyl) -1- (3,4-thioepoxy- 1-tellulobutyl) propane, 1,1,3,3, -tetrakis (4,5-thioepoxy-2-tellopentyl) -2-tellapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6 9-triteraoundedecane-1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7- Thioepoxy-1-tellla-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellopentyl) -3-tella-6-thiaoctane-1,8-bis ( , 4-thioepoxy-1-Terurobuchiru) etc.

Compounds having an aliphatic cyclic skeleton: (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-tellulobutyl) -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-tellulobutyl) -1,3- Diselenane, (2,4 or 2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3-diselenane, (2,3 or 2,5 or 2,6 or 3, 5) -Bis (3,4-epithio-1-tellulobutyl) -1-thia-4-selenane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio- 2-tellopentyl) -1-thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1,3-diselenolane, (2,4 or 4,5 ) -Bis (4,5-epithio-2-terlopentyl) -1, 3-diselenolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-3-selenolane, (2,4 or 2,5 or 4, 5) -bis (4,5-epithio-2-tellopentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-tellopentyl-1,3,5-triselenane, bis ( 3,4-epithio-1-tellulobutyl) tricycloselenaoctane, bis (3,4-epithio-1-tellurobutyl) dicycloselenanane, (2,3 or 2,4 or 2,5 or 3,4)- Bis (3,4-epithio-1-tellulobutyl) selenophane, (2,3 or 2,4 or 2,5 or 3,4) -bis (4,5-epithio-2-telluropentyl) selenophane, 2- (4,5- Oepoxy-2-tellulopentyl) -5- (3,4-thioepoxy-1-tellulobutyl) -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-tellulobutyl) -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-tellulobutyl) -1 , 4-diterlan, (2,3 or 2,5 or 2,6) -bis (4,5-epithio-2-telluropentyl) -1,4-diterlan, (2,4 or 2,5 or 5,6 ) − (3,4-epithio-1-tellurobutyl) -1,3-diterlan, (2,4 or 2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3- Diterlan, (2,3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-4-tellane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-terlopentyl) -1-thia-4-tellane, (2,4 or 4,5) -bis (3,4-epithio-1- Tellurobutyl) -1,3-ditellurolane, (2,4 or 4,5) -bis (4,5-epithio-2-telluropentyl) -1,3-ditellurolane, (2,4 or 2,5 or 4,5 ) -Bis (3,4-epithio-1-tellulobutyl) -1-thio A-3-tellurolane, (2,4 or 2,5 or 4,5) -bis (4,5-epithio-2-tellopentyl) -1-thia-3-tellurolane, 2,6-bis (4,5 -Epithio-2-tellulopentyl-1,3,5-tritelllane, bis (3,4-epithio-1-tellulobutyl) tricyclotellulaoctane, bis (3,4-epithio-1-tellulobutyl) dicyclotelllanonane, 2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-tellulobutyl) tellurophane, (2,3 or 2,4 or 2,5 or 3,4) -bis (4,5-epithio-2-tellopentyl) tellurophan, 2- (4,5-thioepoxy-2-tellopentyl) -5- (3,4-thioepoxy-1-tellulobutyl) -1-tellulacyclohex (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-tellulobutyl) -1-tellulacyclohexane, (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-tellulacyclohexane, etc.

Compounds having an aromatic 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-epithiopropyltelluro) biphenyl, and the like, and hydrogen of β-epithiopropyl group of these compounds A compound in which at least one of these is substituted with a methyl group is also a specific example.

  Furthermore, organic compounds having an unsaturated group are also included in the above (A) to (E). Specific examples of these include vinyl phenyl thioglycidyl ether, vinyl benzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, and allyl thioglycidyl ether.

  In addition, other specific examples of compounds having one epithio group include compounds such as ethylene sulfide, propylene sulfide, and thioglycidol, and thioglycidyl esters of monocarboxylic acids such as acetic acid, propionic acid, and benzoic acid. And thioglycidyl ethers such as methylthioglycidyl ether, ethylthioglycidyl ether, propylthioglycidyl ether, and butylthioglycidyl ether.

  Of these, (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 epithioalkyltelluro group, particularly preferred is (C) an organic compound having an epithioalkylthio group or (D) an organic compound having an epithioalkylseleno group. Specific examples of particularly preferable examples include the above-described specific examples of a chain compound having a β-epithiopropylthio group or β-epithiopropylseleno group, a branched compound, an aliphatic cyclic compound, an aromatic compound, and a heterocyclic ring. Compounds and the like.

Examples of the curing catalyst used for producing an optical material having good transparency and color tone according to the present invention include quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, and secondary iodonium salts. . Specific examples are given below.
(1) 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 hydrogensal Fight, tetra-n-butylammonium tetrafluoroborate, tetra-n-butyl Ruammonium tetraphenylborate, tetra-n-butylammonium paratoluenesulfonate, tetra-n-hexylammonium chloride, tetra-n-hexylammonium bromide, tetra-n-hexylammonium acetate, tetra-n-octylammonium chloride, Tetra-n-octylammonium bromide, tetra-n-octylammonium acetate, trimethyl-n-octylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, triethyl-n-octylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium Bromide, tri-n-butyl-n-octylammoni Muchloride, 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-dode Silpyridinium bromide, 1-n-phenylpyridinium bromide, 1-methylpicolinium bromide, 1-ethylpicolinium bromide, 1-n-butylpicolinium bromide, 1-n-hexylpicolinium bromide, 1-n-octylpicoly Quaternary ammonium salts such as nium bromide, 1-n-dodecylpicolinium bromide, 1-n-phenylpicolinium bromide.

  (2) 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-butyltri Phenylphosphonium iodide, n-hexyltriphenylphosphonium bromide De, n- octyl triphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxymethyl phosphonium bromide, tetrakis hydroxyethyl phosphonium chloride, quaternary phosphonium salts such as tetrakis hydroxybutyl phosphonium chloride.

(3) Trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, tri-n- Tertiary sulfonium salts such as hexylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide.

(4) Secondary iodonium salts such as diphenyliodonium chloride, diphenyliodonium bromide, and diphenyliodonium iodide. Among these, the quaternary phosphonium salt and the tertiary sulfonium salt are preferable from the viewpoint of the color tone of the cured resin, and the quaternary phosphonium salt is most preferable. These may be used alone or in combination of two or more.

  The amount of the catalyst used in the present invention is 0.001 with respect to 100 parts by weight of an episulfide compound having one or more epithio structures represented by formula (1) or a composition containing 10 wt% or more. It is -3.0 weight part, Preferably it is 0.005-2.0 weight part.

  In addition, the composition containing an episulfide compound having one or more epithio structures represented by the formula (1) in one molecule in the present invention means that the epithio structure represented by the formula (1) is one in one molecule. An episulfide compound having at least one compound, a compound having at least one functional group capable of reacting with an epithio group in the formula (1), one or more functional groups capable of reacting with an epithio group and one other functional group capable of homopolymerization. It consists of a compound having one or more, a compound having one or more functional groups capable of homopolymerization, or a compound having one functional group capable of reacting with an epithio group and capable of homopolymerization. Specific examples of these compounds include those described in JP-A-9-255781.

  When using a compound having an unsaturated group, it is a preferred method to use a radical polymerization initiator as a polymerization accelerator. Any radical polymerization initiator may be used as long as it generates radicals by heating or ultraviolet rays or electron beams. Specific examples thereof include those described in JP-A-9-255781.

  In order to give good oxidation resistance to the cured material, it is also possible to use a compound having one or more SH groups as an anti-oxidation component alone or in combination with a known antioxidant. The compound having at least one SH group mentioned here includes mercaptans, thiophenols, mercaptans having unsaturated groups such as vinyl, aromatic vinyl, methacryl, acryl, and allyl, and thiophenols. It is done. Specific examples include those described in JP-A-9-255781.

  It is also possible to use a compound having one or more active hydrogens other than SH groups for the purpose of improving performance such as dyeability and strength. The active hydrogen referred to here is, for example, a hydroxyl group, a carboxyl group, an amide group hydrogen, a 1,3-diketone, a 1,3-dicarboxylic acid and an ester thereof, a hydrogen at the 2-position of a 3-ketocarboxylic acid and an ester thereof, or the like. The compounds having at least one active hydrogen per molecule are alcohols, phenols, mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides, 1,3-diketones. 1,3-dicarboxylic acid and esters thereof, 3-ketocarboxylic acid and esters thereof, alcohols having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, allyl, phenols, mercapto alcohol , Hydroxythiophenols, carboxylic acids, Mercaptoethyloleates carboxylic 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.

  Furthermore, it is also possible to use a compound having one or more isocyanate groups for the purpose of improving the strength. Specific examples of the compound having one or more isocyanate groups include those described in JP-A No. 11-292950.

  In the present invention, when a composition having at least one structure represented by the formula (1) in one molecule is used as a composition as described above, at least the same compound is used at 10 wt% or more, preferably 20 wt% or more. More preferably 30 wt% or more. When it is less than 10 wt%, the balance between the high refractive index and the high Abbe number cannot be maintained.

  In the optical material manufacturing method of the present invention, it is of course possible to further improve the practicality of the resulting material by adding additives such as known antioxidants and ultraviolet absorbers. In addition, the optical material of the present invention tends to be peeled off from the mold during the polymerization. In some cases, a known external and / or internal adhesion improver is used or added to improve the adhesion between the obtained cured material and the mold. It is also effective to improve it.

  In the present invention, the optical material production method comprises a composition containing only one compound having at least one structure represented by the formula (1) as a raw material in one molecule or a compound, a catalyst, an adhesion improver, Additives such as antioxidants, UV absorbers, radical polymerization initiators, various performance improvers, etc. are mixed and homogenized, and then injected into a glass or metal mold, followed by polymerization and curing reaction by heating. Manufactured by removing from.

  (1) A compound having one or more of the structures represented by the formula in one molecule alone or a part or all of the composition containing the compound is stirred in the presence or absence of a catalyst before casting. It is also possible to perform casting by preliminarily polymerizing at −100 to 160 ° C. over 0.1 to 72 hours with or without stirring, and then preparing a composition and performing casting. This preliminary polymerization condition is preferably 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 manufacturing method of the curable resin optical material of the invention will be described in more detail as follows.
As described above, the main raw material and the auxiliary raw material are mixed and then injected and cured into a mold, but the compound having one or more structures represented by the formula (1) in one molecule alone or the compound part thereof A compound containing two or more functional groups capable of reacting with an epithio group used optionally and a catalyst, or one or more of these functional groups and one or more other functional groups capable of homopolymerization Compound, compound having one or more functional groups capable of homopolymerization, compound having one functional group capable of reacting with epithio group and capable of homopolymerization, and further used as desired, antioxidant component, dyeing Performance improving components such as property and strength, as well as adhesion improvers, stabilizers, radical polymerization initiators, etc. are all mixed in the same container while stirring at the same time, but each raw material is added and mixed in stages. Even after mixing several ingredients separately It may be re-mixed in the same vessel. Each raw material and auxiliary raw material may be mixed in any order.

In mixing, the set temperature, the time required for this, etc., basically need only be the conditions that each component is sufficiently mixed, but the excessive temperature, time is an undesirable reaction between each raw material and additive, Furthermore, the viscosity is increased, making the casting operation difficult, and so on.
The mixing temperature should be in the range of about -50 ° C to 100 ° C, the preferred temperature range is -30 ° C to 50 ° C, and 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 the degassing operation under reduced pressure before, during or after mixing the raw materials and additives is a preferable method from the viewpoint of preventing the generation of bubbles during the subsequent medium-size polymerization curing. The degree of decompression at this time is about 0.1 mmHg to 700 mmHg, and preferably 10 mmHg to 300 mmHg.

Furthermore, it is preferable to further refine the quality of the optical material of the present invention by purifying the mixture or the main and sub raw materials before mixing with a filter having a pore size of about 0.05 to 3 μm to purify impurities and the like. .
After pouring into a glass or metal mold, polymerization and curing is performed with an electric furnace or the like. The curing time is 0.1 to 100 hours, usually 1 to 48 hours, and the curing temperature is −10 to 160 ° C., usually −10. ~ 140 ° C. The polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature from 0.1 ° C to 100 ° C / h, lowering the temperature from 0.1 ° C to 100 ° C / h, and a combination thereof.
In addition, 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. Furthermore, surface treatments such as dyeing, hard coating, antireflection, and imparting antifogging properties can be performed as necessary.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The obtained lens was evaluated by the following method.
1. Refractive index, Abbe number (ND, νD) Measured at 25 ° C. using an Abbe refractometer.
2. The δYI value of a 2.5 mm thick lens was measured using a color tone colorimeter. If the δYI value is 1.5 or less, it can be used as an optical material for glasses, but the smaller the value, the better the color tone. In a transparent dark room, the presence of white turbidity of a 10 mm thick lens was observed under irradiation with a projector light. Regarding transparency, it can be used as an optical material even if light turbidity is observed in this observation (light), but it is better not to observe white turbidity.
None: Not observed Light: Light turbidity observed Dark: White turbidity observed

Example 1
100 parts by weight of bis (β-epithiopropylthio) ethane was mixed with 0.1 part by weight of tetrabutylammonium bromide as a catalyst and stirred at room temperature to obtain a uniform solution. Next, this was degassed and filtered, and then poured into 2.5 mm and 10 mm thick flat lens molds, heated in an oven from 20 ° C. to 90 ° C. over 20 hours, polymerized and cured to produce a lens. . The obtained lens showed good heat resistance and physical properties, the surface condition was good, and striae and surface deformation were hardly observed. Table 3 shows the evaluation results of the refractive index, Abbe number, yellowness and cloudiness of the lens.

Examples 2-13
A lens was manufactured by repeating Example 1 except that the composition containing the compound shown in Table 1 and a catalyst were used. Table 3 shows the evaluation results of the refractive index, Abbe number, yellowness and cloudiness of the lens.

Comparative Example 1
Example 1 was repeated except that the amount of tetrabutylammonium bromide added was 5 parts by weight. As a result, gelation occurred during stirring and mold injection could not be performed.

Comparative Example 2
Example 1 was repeated except that the amount of tetrabutylammonium bromide added was 0.0005 parts by weight. The obtained lens was a yellow rubber-like soft resin, and the optical properties could not be measured.

Comparative Example 3
Example 1 was repeated except that 0.1 parts by weight of triethylamine was used instead of 0.1 parts by weight of tetrabutylammonium bromide. As shown in Table 3, thin turbidity was observed in the obtained lens.

Comparative Examples 4-6
A lens was manufactured by repeating Example 1 except that the composition containing the compound of formula (1) shown in Table 1 and a catalyst were used. Table 3 shows the evaluation results of the refractive index, Abbe number, yellowness and cloudiness of the lens.

The production method of the present invention is suitably used for a method of producing an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, and a filter, particularly a plastic lens for spectacles.

Claims (2)

In the presence of 0.001 to 3.0 parts by weight of a quaternary ammonium salt, 100 parts by weight of an episulfide compound having one or more epithio structures represented by the following formula (1) in one molecule and one or more SH groups A method for producing a resin for a high refractive index optical material, comprising polymerizing and curing a composition containing the compound.

(In the formula, R ¹ represents a hydrocarbon having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ each represent a hydrocarbon group or hydrogen having 1 to 10 carbon atoms. Y represents O, S or Se. n and m each represents 0 or 1) The production method according to claim 1, wherein the composition contains 10 wt% or more of an episulfide compound having one or more epithio structures represented by the formula (1) in one molecule.