JP5103788B2 - Resin composition - Google Patents

Description

The present invention relates to an inorganic compound having a sulfur atom and / or a selenium atom, which is a raw material of an optical material having a high refractive index and an Abbe number, and an optical material obtained using the same. This optical material is useful for optical products such as plastic lenses, prisms, optical fibers, information recording bases, filters, adhesives, and in particular, plastic lenses 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. The most important performance required for optical materials, particularly spectacle lenses, is a high refractive index and a high Abbe number, which enables the lens to be thinned, and a high Abbe number reduces the chromatic aberration of the lens. In recent years, many polyepisulfide compounds excellent in the balance between the refractive index and the Abbe number have been reported for the purpose of high refractive index and high Abbe number (see, for example, Patent Documents 1-3). Although the optical material obtained from the polyepisulfide compound of these inventions has achieved a high refractive index and a high Abbe number of 1.7 or more, a material having a higher refractive index has been demanded.
From such a background, an optical material using an inorganic compound having a sulfur atom and / or a selenium atom has been proposed in order to further increase the refractive index (see Patent Document 4). In this case, in order to ensure the transparency of the obtained optical material, preparation of the composition of the compound required a prepolymerization reaction and a degassing treatment (see Patent Documents 5 and 6). However, when these prepolymerization reaction and deaeration treatment are performed, the viscosity of the composition increases, and further, the viscosity increase after about 3 hours, which is an injection time necessary for producing an optical material industrially, is extremely high. Intense and normal casting polymerization operations such as filtration and mold injection were difficult. In particular, when the compounding amount of the inorganic compound having a sulfur atom and / or selenium atom is increased to aim for a high refractive index, the above operation is difficult.

JP-A-9-71580 Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 9-255781 Japanese Patent No. 3738817 JP 2004-197005 A Japanese Patent Laid-Open No. 2004-137482

An object of the present invention is to provide a viscosity of a resin composition using an inorganic compound having a sulfur atom and / or a selenium atom to create a high refractive index optical material, and an injection time required for producing an optical material industrially. It is to reduce the viscosity for about 3 hours after making the composition, and to enable cast polymerization operation.

The inventor conducted intensive research to solve the problems of the present invention,
(A) an inorganic compound having 1 to 50 parts by weight of a sulfur atom and / or a selenium atom (hereinafter referred to as (a) compound),
(B) 50 to 99 parts by weight of a compound represented by the following formula (1) (hereinafter referred to as (b) compound) and
(C) It has been found that a resin composition comprising a compound having 1 to 20 parts by weight of NH group and / or NH2 group (hereinafter referred to as (c) compound) has a low viscosity and is easy for cast polymerization operation. The present invention has been reached.

The composition of the present invention reduces the viscosity of a resin composition using an inorganic compound having a sulfur atom and / or selenium atom, and facilitates cast polymerization operation.

The low-viscosity resin composition for the purpose of the present invention is not particularly limited as long as it is a viscosity at which casting polymerization can be performed satisfactorily, but preferably has a viscosity of 200 mPa · s or less, more preferably 150 mPa · s or less. It is. Usually, when the viscosity is 100 mPa · s or less, the casting polymerization operation is easy, and when the viscosity exceeds 200 mPa · s, the casting polymerization operation (filtration) becomes difficult. Especially when the viscosity exceeds 1000 mPa · s, the casting polymerization operation (filtration) Is impossible. In view of industrial mass production, it takes about 3 hours as the time required for casting, and it is preferable that the viscosity of the resin composition does not increase during this period. That is, the resin composition needs to have a viscosity of 1000 cps or less for 3 hours after the composition is formed, and is usually preferably 200 cps or less.
The inorganic compound having a sulfur atom and / or selenium atom as the compound (a) used in the present invention includes all inorganic compounds having one or more sulfur atoms and / or selenium atoms. The term “inorganic compound” as used herein is as described in “Standard Chemistry Dictionary” (edited by Chemical Society of Japan (1991) Maruzen). The compound (a) preferably has a total weight ratio of sulfur atoms and / or selenium atoms in the compound of 30% or more. When this ratio is less than 30%, the increase in the ratio of the weight of sulfur atoms and / or selenium atoms in the composition for optical materials is small, so the effect of increasing the refractive index of the resin is small. . The amount of the compound (a) added is 1 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 45 parts when the total of the compounds (a) and (b) is 100 parts by weight. Part by weight, particularly preferably 15 to 40 parts by weight, most preferably 20 to 35 parts by weight. The refractive index of the target resin is preferably 1.72 or more, more preferably 1.73 or more, particularly preferably 1.74 or more, and most preferably 1.75 or more. The higher the refractive index, the present invention. The effect of appears.

Specific examples of the inorganic compound having a sulfur atom include sulfur, hydrogen sulfide, carbon disulfide, selenocarbon sulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide and other sulfur oxides, thiocarbonate, sulfuric acid and salts thereof, sulfuric acid Hydrogen salt, sulfite, hyposulfite, persulfate, thiocyanate, thiosulfate, halides such as sulfur dichloride, thionyl chloride, thiophosgene, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide, arsenic sulfide, Examples thereof include metal sulfides and metal hydrosulfides. Among these, sulfur, carbon disulfide, phosphorus sulfide, selenium sulfide, metal sulfide and metal hydrosulfide are preferable, sulfur, carbon disulfide and selenium sulfide are more preferable, and sulfur is particularly preferable. .
The inorganic compound having a selenium atom includes all inorganic compounds satisfying this condition except for selenocarbon sulfide and selenium sulfide, which are listed as specific examples of the inorganic compound containing a sulfur atom. Specific examples include selenium oxides such as selenium, hydrogen selenide, selenium dioxide, carbon diselenide, ammonium selenide, selenium dioxide, selenic acid and salts thereof, selenite and salts thereof, hydrogen selenate salts, seleno Examples thereof include sulfuric acid and its salts, selenopyrosulfuric acid and its salts, halides such as selenium tetrabromide and selenium oxychloride, selenocyanate, boron selenide, phosphorus selenide, arsenic selenide, metal selenide and the like. Among these, preferred are selenium, carbon diselenide, phosphorus selenide, and metal selenide, and particularly preferred are selenium and carbon diselenide. These inorganic compounds having a sulfur atom and a selenium atom may be used alone or in combination of two or more.

The amount of the compound (b) used in the present invention is 50 to 99 parts by weight, preferably 50 to 95 parts by weight, when the total of the compounds (a) and (b) is 100 parts by weight. The amount is preferably 60 to 90 parts by weight, particularly preferably 65 to 85 parts by weight, and most preferably 70 to 80 parts by weight.
(B) Specific examples of the compound include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, and bis (β-epithiopropylthio). Methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1,4 -Episulfides such as bis (β-epithiopropylthio) butane and bis (β-epithiopropylthioethyl) sulfide. (A) The compounds may be used alone or in combination of two or more. Among them, preferred specific examples are bis (β-epithiopropyl) sulfide and / or bis (β-epithiopropyl) disulfide, and the most preferred specific example is bis (β-epithiopropyl) sulfide.

In order to obtain a low yellow optical material from the resin composition comprising the compound (a) and the compound (b), it is necessary to add a compound having at least one group having active hydrogen. As a result of intensive studies on a compound having at least one group having active hydrogen that realizes a low-viscosity resin composition that is the object of the present invention, it is a compound having at least one NH group and / or NH2 group (c ) The compound was found to be effective. With a compound having two or more SH groups recommended in Patent Document 6 or the like, a low-viscosity resin composition cannot be obtained. (C) The addition amount of the compound is 1 to 20 parts by weight, preferably 2 to 18 parts by weight, more preferably 3 to 15 parts when the total of the compounds (a) and (b) is 100 parts by weight. Part by weight, particularly preferably 4 to 12 parts by weight, most preferably 5 to 10 parts by weight.

In addition, among the compounds (c), it was revealed that the compound (c) having a specific structure is preferable in consideration of the high refractive index and low yellow of the obtained optical material and the handling of the compound (c). That is, as the compound (c), the compound (c) having an aromatic ring is preferable in order to maintain the high refractive index of the optical material, and NH group and / or NH2 is used in order to obtain a lower viscosity resin composition. The number of groups is preferably one, and more preferably one NH group. (C) The molecular weight of the compound is preferably less than 200, and in order to realize a low yellow color of the optical material, the compound (c) The molecular weight of is preferably less than 200, and the molecular weight of the compound (c) is preferably 100 or more from the viewpoint that the compound is liquid or solid and has a weak odor and is easy to handle.
(C) Specific examples of the compound include 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, amino Hexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethyl Xyloxy) propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aniline, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine, ethylenediamine, 1,2-diaminopropane, 1,3-diamino Propane, 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 '- Tylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisamino Ethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-amino Ethylpiperidine, 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'-diamino Diphenylmethane, 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-teto Oxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-amino Compounds having an NH2 group such as propylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-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, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, Secondary amines such as dibenzylamine, N-methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine; N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4 -Diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N, N'- Methyl-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, , 3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane, tetramethylguanidine, and other compounds having an NH group. (C) The compounds may be used alone or in combination of two or more. Among these, preferred examples are aniline, N-methylaniline, diphenylamine, benzylamine, N-methylbenzylamine, and dibenzylamine.

When polymerizing and curing the resin composition of the present invention, a compound (d) that is a polymerization catalyst can be added as necessary. Polymerization catalysts include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, condensates of aldehydes and amine compounds, salts of carboxylic acids and ammonia, urethanes, thiourethanes, guanidines, Thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoride Examples thereof include boric acids, peroxides, azo compounds, and acidic phosphate esters. The typical examples of the compound (d) are shown below.
(1) Ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mistyri Ruamine, 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 Primary amines such as ethylene, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine; 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'-dimethyl Propane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisamino Ethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-amino Ethylpiperidine, 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-tetrao Saspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-amino Primary polyamines such as propylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone; Dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methyl Ruhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine , Methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine and other secondary amines; 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-methyl Piperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- ( Secondary polyamines such as 4-piperidyl) propane, 1,4-di- (4-piperidyl) butane, 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-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanol Ruamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N , N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl Tertiary amines such as 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, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, heptamethyliso Tertiary polyamines such as biguanides; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N -Undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole, N- (2'-cyanoethyl)- -Methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis- (2-ethyl-4-methylimidazolyl) methane 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 2-mercaptobenzimidazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-mercapto-1-methyl-tetrazole, 2 , 5-dimercapto-1,3,4-thiadiazole, imidazoles such as an adduct of alkyl imidazole and isocyanuric acid, a condensate of alkyl imidazole and formaldehyde; 3,5-dimethylpyrazole, 3,5-di (2- Pyridyl) pyrazole, 3,5-dimethyl-1-hydroxymethylpyrazo , 3,5-diisopropylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 3-methylpyrazole, 4-methylpyrazole, N-methylpyrazole, 5- (thienyl) pyrazole and other pyrazoles; 1,8- Such as diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5, 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7 Amines such as amidines;

(2) 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) phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexyl Phosphines such as phenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine and chlorodiphenylphosphine.
(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 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, trimethyldecylammonium chloride, trimethyldodecylammonium chloride, trimethylcetylammonium chloride, trimethyllaurylammonium chloride, trimethylbenzylammonium chloride, trimethyl Benzyl ammonium bromide, trie Ru-n-octylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tri-n-butyl-n-octylammonium chloride, tri-n-butylbenzylammonium fluoride, tri-n-butylbenzylammonium chloride, tri -N-butylbenzylammonium bromide, tri-n-butylbenzylammonium iodide, n-butyldimethylbenzylammonium chloride, n-octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium Chloride, lauryldimethylbenzylammonium chloride, methyl Rutriphenylammonium chloride, methyltribenzylammonium chloride, methyltriphenylammonium bromide, methyltribenzylammonium bromide, ethyltriphenylammonium chloride, ethyltribenzylammonium chloride, ethyltriphenylammonium bromide, ethyltribenzylammonium bromide, n-butyl Triphenylammonium chloride, n-butyltribenzylammonium chloride, n-butyltriphenylammonium bromide, n-butyltribenzylammonium bromide, 1-methylpyridinium chloride, 1-methylpyridinium bromide, 1-ethylpyridinium chloride, 1-ethyl Pyridinium bromide, 1-n-butyl Lidinium chloride, 1-n-butylpyridinium bromide, 1-n-hexylpyridinium chloride, 1-n-hexylpyridinium bromide, 1-n-octylpyridinium bromide, 1-n-dodecylpyridinium chloride, 1-n-dodecylpyridinium Bromide, 1-n-cetylpyridinium chloride, 1-n-cetylpyridinium bromide, 1-phenylpyridinium chloride, 1-phenylpyridinium bromide, 1-benzylpyridinium chloride, 1-benzylpyridinium bromide, 1-methylpicolinium chloride, 1 -Methylpicolinium bromide, 1-ethylpicolinium chloride, 1-ethylpicolinium bromide, 1-n-butylpicolinium chloride, 1-n-butyl Rupicolinium bromide, 1-n-hexylpicolinium chloride, 1-n-hexylpicolinium bromide, 1-n-octylpicolinium chloride, 1-n-octylpicolinium bromide, 1-n-dodecylpicolinium chloride, 1-n-dodecylpicolinium bromide, 1-n-cetylpicolinium chloride, 1-n-cetylpicolinium bromide, 1-phenylpicolinium chloride, 1-phenylpicolinium bromide 1-benzylpicolinium chloride, 1-benzyl Quaternary ammonium salts such as picolinium 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-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.
(5) Reaction product of acetaldehyde and ammonia, condensate of formaldehyde and paraylidine, condensate of acetaldehyde and paraylidine, reaction product of formaldehyde and aniline, reaction product of acetaldehyde and aniline, reaction product of butyraldehyde and aniline, formaldehyde and acetaldehyde Reaction product of aniline, reaction product of acetaldehyde, butyraldehyde and aniline, condensation product of butyraldehyde and monobutylamine, reaction product of butyraldehyde and butylideneaniline, reaction product of heptaldehyde and aniline, reaction of tricrotonylidene-tetramine , Condensates of aldehydes and amine compounds, such as condensates of α-ethyl-β-propylacrolein and aniline, condensates of formaldehyde and alkylimidazoles.

(6) Salts of carboxylic acid and ammonia such as ammonium acetate, ammonium benzoate, ammonium carbamate, ammonium trifluoroacetate and the like.
(7) Urethanes obtained by reaction of alcohol and isocyanate.
(8) Thiourethanes obtained by reaction of mercaptans with isocyanates.
(9) Diphenylguanidine, phenyltolylguanidine, phenylxylylguanidine, tolyloxysilylguanidine, diortolylguanidine, orthotolylguanide, diphenylguanidine phthalate, tetramethylguanidine, guanidine thiocyanate, triphenylguanidine, aminoguanidine sulfate, Guanidines such as 1,3-diphenylguanidine sulfate and diortolylguanidine salt of dicatecholboric acid.
(10) Thiocarbonanilide, diortolylthiourea, ethylenethiourea, diethylthiourea, dibutylthiourea, dilaurylthiourea, trimethylthiourea, dimethylethylthiourea, tetramethylthiourea, 1,3-diphenyl-2-thiourea, 1 -Thioureas such as allyl-2-thiourea and guanylthiourea.
(11) 2-mercaptobenzothiazole, dibenzothiazyl disulfide, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenylthio) benzothiazole, 2- (morpholinodithio) benzothiazole, 2- ( 2,6-dimethyl-4-morpholinothio) benzothiazole, N, N-diethylthiocarbamoyl-2-benzothiazolyl sulfide, 1,3-bis (2-benzothiazolylmercaptomethyl) urea, benzothiadiadi Ruthiobenzoate, 2-mercaptothiazoline, 2-mercapto-5-methyl-1,3,4-thiadiazole, 2-mercapto-5-methylthio-1,3,4-thiadiazole, 2- (morpholinothio) benzothiazole, 2 -Natrium of mercaptobenzothiazole Salts, thiazoles, such as 2-mercaptobenzimidazole zinc salt of benzothiazole, complex salts of dibenzothiazyl disulfide and zinc chloride.
(12) N-cyclohexyl-2-benzothiazylsulfenamide, N-tert-butyl-2-benzothiazylsulfenamide, N-tert-octyl-2-benzothiazylsulfenamide, N-oxydiethylene 2-benzothiazylsulfenamide, N, N-diethyl-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazylsulfenamide, N, N-dicyclohexyl-2-benzothia Sulfenamides such as dirusulfenamide.
(13) Tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetrabutylthiuram monosulfide, dipentamethylenethiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl-N, Thiurams such as N′-diphenylthiuram disulfide, N, N′-diethyl-N, N′-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, and cyclic thiuram.
(14) Sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium pentamethylenedithiocarbamate, sodium cyclohexylethyldithiocarbamate, potassium dimethyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diphenyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc dimethylpentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, bismuth dimethyldithiocarbamate, cadmium diethyldithiocarbamate, pentamethylenedithiocarb Cadmium minate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, iron dimethyldithiocarbamate, copper dimethyldithiocarbamate, diethylammonium diethyldithiocarbamate, N, N-cyclohexylammonium dibutyldithiocarbamate, Dithiocarbamic acid such as piperidine pentamethylenedithiocarbamate, cyclohexylethylammonium cyclohexylethyldithiocarbamate, pipecocholine methylpentamethylenedithiocarbamate, pipecolylpipecolyldithiocarbamate, zinc N-phenyldithiocarbamate, complex of zinc pentamethylenedithiocarbamate and piperidine salts.
(15) Xanthates such as sodium isopropylxanthate, zinc isopropylxanthate, zinc butylxanthate, and dibutylxanthate disulfide.
(16) 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, and triphenylsulfonium iodide.
(17) Secondary iodonium salts such as diphenyliodonium chloride, diphenyliodonium bromide, and diphenyliodonium iodide.
(18) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and half esters thereof.
(19) Lewis acids represented by boron trifluoride, boron trifluoride etherate, and the like.
(20) Organic acids and their half esters.
(21) Silicic acid and tetrafluoroboric acid.
(22) Cumyl peroxyneodecanoate, diisopropyl peroxydicarbonate, diallyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimyristyl peroxydicarbonate, cumyl peroxyneohexanoate, tert- Hexyl peroxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyneohexanoate, tert-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide Peroxides such as dicumyl peroxide and di-ter-butyl peroxide; peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide.
(23) 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1- [ (1-Cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile 2, 2′-azobis (2-methylpropane), 2,2′-azobis ( 2, 4, 4-trimethylpentane) and the like.
(24) mono- and / or dimethyl phosphate, mono- and / or diethyl phosphate, mono- and / or dipropyl phosphate, mono- and / or dibutyl phosphate, mono- and / or dihexyl phosphate, mono- and / Or acid such as dioctyl phosphate, mono- and / or didecyl phosphate, mono- and / or didodecyl phosphate, mono- and / or diphenyl phosphate, mono- and / or dibenzyl phosphate, mono- and / or didecanol phosphate Phosphate esters.
The compound (d) has been exemplified above, but the compound is not limited to these listed compounds as long as it exhibits polymerization and curing. These (d) compounds may be used alone or in combination of two or more. Among these, preferred specific examples include tetra-n-butylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, quaternary ammonium salts such as 1-n-dodecylpyridinium chloride, tetra-n-butylphosphonium bromide, Quaternary phosphonium salts such as tetraphenylphosphonium bromide can be mentioned. Among these, further preferred specific examples are triethylbenzylammonium chloride and / or tetra-n-butylphosphonium bromide, and the most preferred specific example is tetra-n-butylphosphonium bromide.
The amount of the compound (d) added is 0.001 to 5 parts by weight, preferably 0.002 to 5 parts by weight, more preferably 100 parts by weight of the total of the compounds (a) and (b). Is 0.005 to 3 parts by weight.
When polymerizing and curing the resin composition, the compound (e), which is a polymerization regulator, can be added as necessary for the purpose of extending the pot life or dispersing the polymerization heat. Examples of the polymerization regulator include halides of Groups 13 to 16 in the long-term periodic table. The typical examples of these are shown below.

(1) Silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, propyltrichlorosilane, dipropyldichlorosilane, tripropylchlorosilane, n-butyltrichlorosilane, di-n -Butyldichlorosilane, tri-n-butylchlorosilane, t-butyltrichlorosilane, di-t-butyldichlorosilane, tri-t-butylchlorosilane, octyltrichlorosilane, dioctyldichlorosilane, trioctylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, Triphenylchlorosilane, allylchlorodimethylsilane, trichloroallylsilane, t-butylchlorodimethylsilane, diphenyl-t- Tylchlorosilane, t-butoxychlorodiphenylsilane, trimethyl (2-chloroallyl) silane, trimethylchloromethylsilane, n-butylchlorodimethylsilane, compounds in which all or part of these chlorines are changed to fluorine, bromine, iodine, etc. Silane halides.
(2) Germanium tetrachloride, methylgermanium trichloride, dimethylgermanium dichloride, trimethylgermanium chloride, ethylgermanium trichloride, diethylgermanium dichloride, triethylgermanium chloride, propylgermanium trichloride, dipropylgermanium dichloride, tripropylgermanium chloride, n- Butyl germanium trichloride, di n-butyl germanium dichloride, tri n-butyl germanium chloride, t-butyl germanium trichloride, di-t-butyl germanium dichloride, tri-t-butyl germanium chloride, amyl germanium trichloride, diamyl germanium dichloride, Triamyl germanium chloride Octyl germanium trichloride, dioctyl germanium dichloride, trioctyl germanium chloride, phenyl germanium trichloride, diphenyl germanium dichloride, triphenyl germanium chloride, toluyl germanium trichloride, ditoluyl germanium dichloride, tritoluyl germanium chloride, benzyl germanium trichloride, dibenzyl Germanium dichloride, tribenzylgermanium chloride, cyclohexylgermanium trichloride, dicyclohexylgermanium dichloride, tricyclohexylgermanium chloride, vinylgermanium trichloride, divinylgermanium dichloride, trivinylgermanium chloride, ali Trichlorogermane, bis (chloromethyl) dimethylgermane, chloromethyltrichlorogermane, t-butyldimethylchlorogermane, carboxyethyltrichlorogermane, chloromethyltrimethylgermane, dichloromethyltrimethylgermane, 3-chloropropyltrichlorogermane, phenyldimethylchlorogermane, Germanium halides such as 3- (trichlorogermyl) propionyl chloride and compounds obtained by changing all or part of these chlorines to fluorine, bromine or iodine.
(3) Tin tetrachloride, diethyldichlorosilane, dimethyltin dichloride, trimethyltin chloride, ethyltin trichloride, diethyltin dichloride, triethyltin chloride, propyltin trichloride, dipropyltin dichloride, tripropyltin chloride, n-butyltin Trichloride, di-n-butyltin dichloride, tri-n-butyltin chloride, t-butyltin trichloride, di-t-butyltin dichloride, tri-t-butyltin chloride, amyltin trichloride, diamyltin dichloride, triamyltin chloride, octyltin Trichloride, dioctyltin dichloride, trioctyltin chloride, phenyltin trichloride, diphenyltin dichloride, triphenyl Zuclochloride, Toluoyl Tin Trichloride, Ditoluoyl Tin Dichloride, Tritoluoyl Tin Chloride, Benzyl Tin Trichloride, Dibenzyl Tin Dichloride, Tribenzyl Tin Chloride, Cyclohexyl Tin Trichloride, Dicyclohexyl Tin Dichloride, Tricyclohexyl Tin Chloride, Vinyl Tin Tri Chloride, divinyltin dichloride, trivinyltin chloride, butylchlorodihydroxytin, bis (2,4-pentadionato) dichlorotin, carbomethoxyethyltrichlorotin, chloromethyltrimethyltin, diallyldichlorotin, dibutylbutoxychlorotin, tri-n -Halo of tin such as pentylchlorotin and compounds in which all or part of these chlorines are changed to fluorine, bromine or iodine Down monster.
(4) Antimony pentachloride, methyl antimony tetrachloride, dimethyl antimony trichloride, trimethyl antimony dichloride, tetramethyl antimony chloride, ethyl antimony tetrachloride, diethyl antimony trichloride, triethyl antimony dichloride, tetraethyl antimony chloride, butyl antimony tetrachloride, dibutyl Convert all or part of antimony trichloride, tributylantimony dichloride, tetrabutylantimony chloride, phenylantimony tetrachloride, diphenylantimony trichloride, triphenylantimony dichloride, tetraphenylantimony chloride, and all or part of these chlorines to fluorine, bromine, iodine Antimony halo compounds Down monster.
(5) chlorides such as aluminum chloride, indium chloride, thallium chloride, phosphorus trichloride, phosphorus pentachloride, bismuth chloride, etc., and compounds in which all or part of these chlorines are changed to fluorine, bromine, iodine, diphenylchloroboron, Phenyldichloroboron, diethylchlorogallium, dimethylchloroindium, diethylchlorothallium, diphenylchlorothallium, ethyldichlorophosphine, butyldichlorophosphine, triphenylphosphinedichloride, diphenylchloroarsenic, tetraphenylchloroarsenic, diphenyldichloroselenium, phenylchloroselenium, Compounds having halogen and hydrocarbon groups, such as diphenyldichlorotellurium, and compounds in which all or part of these chlorines are changed to fluorine, bromine, iodine, chlorophenol, dichlorophenol Nord, trichlorophenol, chloroaniline, dichloroaniline, chloronitrobenzene, dichloronitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloroacetophenone, chlorotoluene, chloronitroaniline, chlorobenzyl cyanide, chlorobenzaldehyde, chlorobenzotrichloride, chloronaphthalene , Dichloronaphthalene, chlorothiophenol, dichlorothiophenol, methallyl chloride, benzyl chloride, benzyl chloride, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, chlorosuccinic acid, oxalic acid dichloride, triglycol dichloride, methanesulfonyl chloride, chlorobenzoic acid , Chlorosalicylic acid, 4,5-dichlorophthalic acid, 3,5-dichlorosalicyl , Isopropyl chloride, allyl chloride, epichlorohydrin, chloromethylthiirane, propylene chlorohydrin, chloranil, dichlorodicyanobenzoquinone, dichlorophen, dichloro-1,4-benzoquinone, dichlorobenzophenone, N-chlorophthalimide, 1,3- Halogen-substituted hydrocarbons such as dichloro-2-propanol, methyl 2,3-dichloropropionate, p-chlorobenzenesulfonic acid, ethyl 2-chloropropionate, dichloromethane, chloroform, carbon tetrachloride, benzoic acid chloride, phthalic acid Chloride, isophthalic acid chloride, terephthalic acid chloride, methacrylic acid chloride, succinic acid chloride, fumaric acid chloride, nicotinic acid chloride, chloronicotinic acid chloride, oleic acid Examples thereof include organic halides typified by acid chlorides such as chloride, benzoyl chloride, chlorobenzoyl chloride, and propionic acid chloride, and other halogen compounds in which all or part of these chlorines are changed to fluorine, bromine, and iodine.
These (e) compounds may be used alone or in combination of two or more. Of these, preferred are halides of silicon, germanium, tin and antimony. More preferred are chlorides of silicon, germanium, tin and antimony, and further preferred are chlorides of germanium, tin and antimony having an alkyl group. Specific examples of the most preferred are dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyldichlorogermanium, butyltrichlorogermanium, diphenyldichlorogermanium, phenyltrichlorogermanium, triphenylantimony dichloride.
(E) The addition amount of a compound is 0.001-5 weight part with respect to a total of 100 weight part of (a) and (b) compound, Preferably it is 0.002-5 weight part, More preferably Is 0.005 to 3 parts by weight.

In the present invention, prepolymerizing the compound (a) and the compound (b) for 1 minute to 24 hours at 0 ° C. to 150 ° C. is an effective means for handling the solid (a) compound. In addition, transparency of the obtained optical material is improved. At this time, a prepolymerization reaction catalyst for promoting the reaction between the compound (a) and the compound (b) may be added. Examples of the prepolymerization reaction catalyst include the compound (d) described above, among which compounds containing nitrogen or phosphorus atoms are preferred, and compounds containing nitrogen or phosphorus atoms and having an unsaturated bond are more preferred. Particularly preferred are imidazoles, and most preferred is 2-mercapto-1-methylimidazole. The amount of the prepolymerization reaction catalyst added is 0.001 to 5 parts by weight, preferably 0.002 to 5 parts by weight, based on 100 parts by weight of the total of the compounds (a) and (b). Preferably it is 0.005-3 weight part.
A method of adding a prepolymerization reaction catalyst that promotes the reaction between the compounds (a) and (b) and reacting them will be described in detail. (A) The compound and (b) compound are partially or entirely reacted in the presence or absence of a prepolymerization reaction catalyst with stirring or without stirring at 0 ° C. to 150 ° C. for 1 minute to 72 hours. To obtain a resin composition. The reaction time is 1 minute to 72 hours, preferably 10 minutes to 48 hours, and more preferably 30 minutes to 24 hours. The reaction temperature is 0 ° C to 150 ° C, preferably 10 ° C to 120 ° C, more preferably 20 ° C to 100 ° C. Furthermore, it is preferable that (a) the compound is allowed to react for 10% or more (100% before the reaction) by this reaction, and more preferably 20% or more. The reaction may be carried out in an atmosphere such as air, presence of a gas such as nitrogen or oxygen, sealed under normal pressure or increased or reduced pressure, or any atmosphere such as reduced pressure. In this reaction, (c) a part or all of the compound, (d) compound, (e) compound, a compound capable of reacting with some or all of the composition components used as a performance improving agent described later, You may carry out by adding various additives, such as a ultraviolet absorber. In addition, liquid chromatography and / or measuring the viscosity and / or specific gravity and / or refractive index of this reaction product are preferable for controlling the reaction progress and obtaining a homogeneous resin composition. Among them, liquid chromatography and / or a method for measuring a refractive index is preferable because of high sensitivity, and further, a method for measuring a refractive index is more preferable because it is simple. When measuring the refractive index, it is preferable to use an inline refractometer because the progress of the reaction can be confirmed in real time.

For the purpose of improving various performances such as oxidation resistance, weather resistance, dyeability, strength, refractive index and the like, it is also possible to add a compound capable of reacting with a part or all of the components of the composition component and to cure by polymerization. In this case, a known polymerization catalyst can be added separately as necessary for the reaction.
Compounds having an SH group, epoxy compounds, iso (thio) cyanates, carboxylic acids, carboxylic anhydrides, phenols, vinyl compounds, allyl compounds as compounds capable of reacting with some or all of the composition components , Acrylic compounds, methacrylic compounds and the like. The typical examples of these are shown below.
(1) Bis (2-mercaptoethyl) sulfide, bis (2,3-dimercaptopropyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 2- (2-mercaptoethylthio) -1, 3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-bis (mercaptomethyl) -1,5-dimercapto-3-thiapentane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-bis (mercaptomethyl) -1,11 Dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-to Thiaundecane, 1,2,7-trimercapto-4,6-dithiaheptane, 1,2,9-trimercapto-4,6,8-trithianonane, 1,2,8,9-tetramercapto-4,6- Dithianonane, 1,2,10,11-tetramercapto-4,6,8-trithiaundecane, 1,2,12,13-tetramercapto-4,6,8,10-tetrathiatridecane, tetrakis (4 -Mercapto-2-thiabutyl) methane, tetrakis (7-mercapto-2,5-dithiaheptyl) methane, 1,5-dimercapto-3-mercaptomethylthio-2,4-dithiapentane, 3,7-bis (mercaptomethylthio)- 1,9-dimercapto-2,4,6,8-tetrathianonane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5 Bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (2-mercaptoethyl) -1-thiane, bis (4-mercaptophenyl) ) Compounds having an SH group such as sulfide, bis (4-mercaptomethylphenyl) sulfide, 3,4-thiophenedithiol, and the like.
(2) Manufactured by condensation of polyhalogen compounds such as ethylene oxide and propylene oxide, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol ether, halogenated bisphenol A, novolac resin and epihalohydrin Phenolic epoxy compounds, methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythrito 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, etc. Alcohol-based epoxy compound produced by condensation of a compound and epihalohydrin, urethane-based epoxy compound produced from the above alcohol and phenol compound and diisocyanate, acetic acid, propionic acid, benzoic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, Dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benze Glycidyl ester epoxy compounds produced by condensation of carboxylic acid compounds such as tetracarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric 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, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2 , 2'-dimethylpropane, 1,2-, 1,3- or 1 4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m-, or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m-, or p-xylylenediamine Amine, 1,5- or 2,6-naphthalenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 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-Dimethylpi Razine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- (4-piperidyl) -ethane, 1,3-di- (4-piperidyl) -propane, 1,4 -Amine-type epoxy compounds produced by condensation of di- (4-piperidyl) -butane and epihalohydrin, bis (β-epoxypropyl) sulfide, bis (β-epoxypropyl) disulfide, bis (β-epoxypropylthio) methane Bis (β-epoxypropyldithio) methane, 1,2-bis (β-epoxypropylthio) ethane, 1,3-bis (β-epoxypropylthio) propane, 1,2-bis (β-epoxypropylthio) ) Propane, 1- (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) propane, 1,4-bis (β-epoxypro) Ruthio) butane, 1,3-bis (β-epoxypropylthio) butane, 1- (β-epoxypropylthio) -3- (β-epoxypropylthiomethyl) butane, 1,5-bis (β-epoxypropyl) Thio) pentane, 1- (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) pentane, 1,6-bis (β-epoxypropylthio) hexane, 1- (β-epoxypropylthio)- 5- (β-epoxypropylthiomethyl) hexane, 1- (β-epoxypropylthio) -2-[(2-β-epoxypropylthioethyl) thio] ethane, 1- (β-epoxypropylthio) -2 -[[2- (2-β-epoxypropylthioethyl) thioethyl] thio] ethane, tetrakis (β-epoxypropylthiomethyl) methane, 1,1,1- Lis (β-epoxypropylthiomethyl) propane, 1,5-bis (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) -3-thiapentane, 1,5-bis (β-epoxypropylthio) ) -2,4-bis (β-epoxypropylthiomethyl) -3-thiapentane, 1- (β-epoxypropylthio) -2,2-bis (β-epoxypropylthiomethyl) -4-thiahexane, 5,6-Tris (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) ) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,5bis (β-epoxypropylthiomethyl) -3,6-dithiaoct 1,8-bis (β-epoxypropylthio) -4,4-bis (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2, 4,5-tris (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2,5-bis (β-epoxypropylthiomethyl) -3,6 -Dithiaoctane, 1,9-bis (β-epoxypropylthio) -5- (β-epoxypropylthiomethyl) -5-[(2-β-epoxypropylthioethyl) thiomethyl] -3,7-dithianonane, 1 , 10-bis (β-epoxypropylthio) -5,6-bis [(2-β-epoxypropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epoxy Propylthio) -4,8-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7-bis (β-epoxypropyl) Thiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7-[(2-β-epoxypropylthioethyl) thiomethyl] -3,6,9 -Trithiaundecane, 1,11-bis (β-epoxypropylthio) -4,7-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,3 and 1,4- Bis (β-epoxypropylthio) cyclohexane, 1,3 and 1,4-bis (β-epoxypropylthiomethyl) cyclohexane, bis [4- (β-epoxypropylthio) cyclohexane Sil] methane, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] sulfide, 2,5-bis (β-epoxypropylthiomethyl) ) -1,4-dithiane, 2,5-bis (β-epoxypropylthioethylthiomethyl) -1,4-dithiane, 1,3 and 1,4-bis (β-epoxypropylthio) benzene, 1, 3, and 1,4-bis (β-epoxypropylthiomethyl) benzene, bis [4- (β-epoxypropylthio) phenyl] methane, 2,2-bis [4- (β-epoxypropylthio) phenyl] propane Bis [4- (β-epoxypropylthio) phenyl] sulfide, bis [4- (β-epoxypropylthio) phenyl] sulfone, 4,4 ′ Sulfur-containing epoxy compounds such as bis (β-epoxypropylthio) biphenyl, 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5 , 5-spiro-3,4-epoxycyclohexane-meta-dioxane, alicyclic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate, cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide Epoxy compounds produced by epoxidation of unsaturated compounds such as vinyl phenyl glycidyl ether, vinyl benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether Epoxy compounds having an unsaturated group such as epoxy compounds.

(3) methyl isocyanate, ethyl isocyanate, propyl isocyanate, iso-propyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, Monoisocyanates such as toluyl isocyanate, diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane , Isophoro Diisocyanate, 2,5-bis (isocyanatomethyl) norbornene, 2,6-bis (isocyanatomethyl) decahydronaphthalene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 2,6-bis (isocyanatomethyl) -1,4-dithiane, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4 , 4′-diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2′-isocyanatocyclohexyl) propyl isocyanate, tris (phenylisocyanate) thiophosphate, isopropylidenebis (cyclohexyl isocyanate), 2,2′-bis (4-i Cyanate phenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4 '-Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, dicyclohexylmethane-4,4' -Diisocyanato, 1,1'-methylenebis (4-isocyanatobenzene), 1,1'-methylenebis (3-methyl-4-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3 -Bis (1-isocyanate-1-me Ruethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, , 5-Naphthalene diisocyanate, bis (isocyanatemethyl) tetrahydrodicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) tetrahydrothiophene, bis (isocyanatemethyl) thiophene, 2,5-diisocyanatemethylnorbornene, bis ( Isocyanatomethyl) adamantane, 3,4-diisocyanateselenophan, 2,6-diisocyanate-9-selenabicyclononane, bis (isocyanatomethyl) selenophan, 3,4-diisocyanate -2,5-diselenolane, dimer acid diisocyanate, polyisocyanates such as 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, dimers of these polyisocyanates by a bullet-type reaction, these polyisocyanates Cyclic trimers of isocyanates and isocyanates such as adducts of these polyisocyanates and alcohols or thiols, and all or part of the isocyanate groups of compounds having one or more of the above isocyanate groups per molecule Isothiocyanates obtained by changing to an isothiocyanate group.
(4) Carboxylic acids exemplified as the starting material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (2).
(5) Carboxylic anhydrides exemplified as the raw material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (2).
(6) Phenols exemplified as the raw material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (2).
(7) Vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, vinyl glycidyl ether, vinyl alcohol, methyl vinyl carbinol, ethylene glycol monovinyl ether, ethylene glycol Divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, tetramethylene glycol monovinyl ether, divinyl sulfide, vinyl ethyl sulfide, vinyl phenyl sulfide, methyl vinyl ketone, divinyl dicarbonate, vinyl diglycol carbonate, vinylene carbonate, vinyl acetate, chloro Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl 2-ethylhexanoate, divinyl adipate, vinyl benzoate, vinyl salicylate, vinyl acrylate, vinyl methacrylate, vinyl bromide, vinyl iodide, vinyl phosphate, Vinylurea, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4,6-trimethylstyrene, 4-t-butylstyrene, stilbene, vinylphenol, 3-vinylbenzyl Alcohol, 4-vinylbenzyl alcohol, 2- (4-vinylphenylthio) ethanol, 2- (3-vinylphenylthio) ethanol, 2- (4-vinylbenzylthio) ethanol, 2- (3-vinylbenzylthio) Ethanol, 1,3-bis (4- Vinylbenzylthio) -2-propanol, 1,3-bis (3-vinylbenzylthio) -2-propanol, 2,3-bis (4-vinylbenzylthio) -1-propanol, 2,3-bis (3 -Vinylbenzylthio) -1-propanol, cinnamyl alcohol, cinnamaldehyde, 1,3-divinylbenzene, 1,4-divinylbenzene, trivinylbenzene, divinylphthalate, 2-chlorostyrene, 3-chlorostyrene, 4- Chlorostyrene, 3-chloromethylstyrene, 4-chloromethylstyrene, 4-aminostyrene, 3-cyanomethylstyrene, 4-cyanomethylstyrene, 4-vinylbiphenyl, 2,2'-divinylbiphenyl, 4,4'- Divinylbiphenyl, 2,2'-distyryl ether, 4,4'-distyryl ether 2,2′-distyryl sulfide, 4,4′-distyryl sulfide, 2,2-bis (4-vinylphenyl) propane, bis (4-vinylphenyl) ether, 2,2-bis (4-vinyl) Vinyl compounds such as (roxyphenyl) propane;

(8) Allyl compounds in which some or all of the vinyl groups of the compounds exemplified as the vinyl compounds of (7) are replaced with allyl groups.
(9) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 3-phenoxy-2-hydroxypropyl acrylate, trimethylolpropane mono Acrylate, 2-hydroxyethyl isocyanurate monoacrylate, 2-hydroxyethyl isocyanurate diacrylate, 2-hydroxyethyl cyanurate monoacrylate, 2-hydroxyethyl cyanurate diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,3 -Butylene glycol diacrylate, triethylene glycol diacrylate Polyethylene glycol diacrylate, propylene glycol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate Acrylate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) Cyclohexyl] propane, 2,2-bis [4- (2-hydroxy-3-acryloxypropoxy) phenyl] propane, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [ 4- (Acryl Polyethoxy) phenyl] propane, trimethylolpropane triacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaacrylate of bis (2,2,2-trimethylolethyl) ether , Acrylic compounds such as hexaacrylate of bis (2,2,2-trimethylolethyl) ether, bis (4-acryloylthiophenyl) sulfide.
(10) Methacrylic compounds in which part or all of the acrylic groups of the compounds exemplified as the acrylic compounds of (9) are replaced with methacrylic groups.
In the optical material manufacturing method of the present invention, it is of course possible to further improve the practicality of the material obtained by adding various additives such as known antioxidants, bluing agents, ultraviolet absorbers, deodorants and the like. It is. Further, when the optical material of the present invention is easily peeled off from the mold during polymerization, a known external and / or internal adhesion improver is added, or when it is difficult to peel off from the mold, a known external and / or internal mold release is added. It is also effective to add a property improver to improve the adhesiveness or releasability between the resulting optical material and the mold.
It is preferable to degas the resin composition in advance from the viewpoint of achieving high transparency of the optical material. The deaeration treatment is performed before mixing the compound (a), the compound (b), the compound (c), a compound capable of reacting with some or all of the composition components, the compound (d), the compound (e), and various additives. It is performed under reduced pressure during or after mixing. Preferably, it is performed under reduced pressure during or after mixing. The deaeration treatment conditions are 0 to 100 ° C. for 1 minute to 24 hours under a reduced pressure of 0.001 to 50 torr. The degree of decompression is preferably 0.005 to 25 torr, more preferably 0.01 to 10 torr, and the degree of decompression may be varied within these ranges. The deaeration time is preferably 5 minutes to 18 hours, more preferably 10 minutes to 12 hours. The temperature at the time of deaeration is preferably 5 ° C. to 80 ° C., more preferably 10 ° C. to 60 ° C., and the temperature may be varied within these ranges. In the deaeration process, renewing the interface of the resin composition by stirring, blowing of gas, vibration by ultrasonic waves, or the like is a preferable operation for enhancing the deaeration effect. The components removed by the degassing treatment are mainly dissolved gases such as hydrogen sulfide and low-boiling substances such as low molecular weight mercaptans, but the types are particularly limited as long as the effects of the degassing treatment are expressed. Not.

The manufacturing method of the optical material will be described in detail as follows. (A) compound and (b) compound and / or reactant obtained by prepolymerization reaction of (a) compound and (b) compound, (c) compound, compound capable of reacting with part or all of composition component, Various additives such as (d) compound, (e) compound, adhesion improver or releasability improver, antioxidant, bluing agent, ultraviolet absorber, deodorant, etc. are all contained in the same container. They may be mixed under stirring at the same time, each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. Each raw material, additive and the like may be mixed in any order. Further, two or more kinds of each component may be mixed after the preliminary reaction is performed by the above-described method in advance. 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 about −50 ° C. to 100 ° C., preferably −30 ° C. to 70 ° C., more preferably −5 ° C. to 50 ° C. The mixing time is 1 minute to 12 hours, preferably 5 minutes to 10 hours, and most preferably about 5 minutes to 6 hours. If necessary, the active energy ray may be blocked and mixed. Then, you may perform a deaeration process with the above-mentioned method. Immediately before the casting operation, it is necessary to purify these resin compositions by filtering impurities and the like with a filter in order to further improve the quality of the optical material of the present invention. The pore size of the filter used here is about 0.05 to 10 μm, and generally 0.1 to 1.0 μm is used, and the filter material is preferably PTFE, PET, PP or the like. The When filtration is not performed, or when filtration is performed with a filter having a pore diameter exceeding 10 μm, foreign substances are mixed into the resin or transparency is lowered, so that it is usually unusable as an optical material. The resin composition thus obtained is injected into a glass or metal mold and then polymerized and cured by an electric furnace or an active energy ray generator. The polymerization time is usually from 0.1 to 100 hours. The polymerization temperature is -10 to 160 ° C, usually -10 to 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 polymerization is completed, annealing the material at a temperature of 50 to 150 ° C. for about 5 minutes to 5 hours is a preferable treatment for removing distortion of the optical material. Furthermore, surface treatments such as dyeing, hard coating, antireflection, antifogging, antifouling and impact resistance 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. In addition, evaluation of the viscosity of the composition, the refractive index and Abbe number of the obtained cured product, heat resistance and color tone was performed by the following methods.
The viscosity was measured using a B-type viscometer immediately after degassing and after 3 hours at 20 ° C. Usually, when the viscosity is 200 mPa · s or less, the casting polymerization operation is easy. When the viscosity exceeds 200 mPa · s, the casting polymerization operation (filtration) becomes difficult. When the viscosity exceeds 1000 mPa · s, the casting polymerization operation (filtration) is difficult. It becomes impossible.
The refractive index and Abbe number were measured at 20 ° C. using an Abbe refractometer.
For heat resistance, a sample was cut to a thickness of 3 mm, a 10 g weight was applied to a 1 mmφ pin, the temperature was raised from 30 ° C. to 10 ° C./min, TMA measurement was performed, and the softening point was measured. Usually, 50 degreeC or more is preferable and 70 degreeC or more is more preferable. If it is less than 30 ° C., it is difficult to put it into practical use as a lens.
For the color tone, the YI value of a 2.5 mm flat plate was measured using a colorimeter. The higher the YI value, the more yellow the lens, usually 5 or less, and more preferably 3 or less. If it is 10 or more, it is difficult to put it into practical use as a lens.

<Example 1>
(A) 20 parts by weight of sulfur (hereinafter referred to as a-1 compound) as the compound and (b) 80 parts by weight of bis (β-epithiopropyl) sulfide (hereinafter referred to as b-1 compound) as the compound may be at 65 ° C. Mix and make uniform. Subsequently, 0.5 part by weight of 2-mercapto-1-methylimidazole was added and reacted at 60 ° C. for about 1 hour until the refractive index (20 ° C.) reached 1.679. Thereafter, the obtained resin composition was cooled to 20 ° C. Thereto, 5 parts by weight of N-methylaniline (hereinafter referred to as c-1 compound) as compound (c), 0.03 parts by weight of triethylbenzylammonium chloride as compound (d), and di-n-butyltin dichloride as compound (e) 0.2 parts by weight was added and mixed well, and a uniform solution was added to obtain a uniform resin composition. The resulting resin composition was degassed at 20 ° C. for 10 torr for 10 minutes. This composition was filtered through a membrane filter made of PTFE of 0.5 μm, poured into a 2.5 mm-thick flat plate mold composed of two glass plates and a gasket, heated at 30 ° C. for 10 hours, Thereafter, the temperature was raised from 30 ° C. to 100 ° C. over a period of 10 hours to 100 ° C., and finally heated at 100 ° C. for 1 hour to be cured by polymerization. After cooling to room temperature, the mold was released from the mold to obtain a cured optical material. Table 1 shows the evaluation results of the viscosity of the resin composition immediately after the degassing treatment and after 3 hours, the refractive index and Abbe number of the obtained cured product, heat resistance and color tone.

<Comparative example 1>
(C) Example 1 was repeated except that no compound was used. (C) Since the compound was not used, the viscosity of the resin composition immediately after the degassing treatment and after 3 hours was high, particularly the viscosity of the resin composition after 3 hours was extremely high, and filtration was impossible. Table 1 shows the evaluation results of the viscosity of the resin composition immediately after the degassing treatment and after 3 hours, the refractive index and Abbe number of the obtained cured product, heat resistance and color tone. The lens was remarkably bad in color tone (high YI value), yellow, and not a practical lens.

<Comparative example 2>
(C) Example 1 was repeated except that 5 parts by weight of bis (2-mercaptoethyl) sulfide (hereinafter referred to as o-1 compound) was used as the other compound instead of the compound. (C) Since the compound is not used, the viscosity of the resin composition immediately after the deaeration treatment and after 3 hours is high, particularly the viscosity of the resin composition after 3 hours is extremely high, and filtration is impossible. . Table 1 shows the evaluation results of the viscosity of the resin composition immediately after the degassing treatment and after 3 hours, the refractive index and Abbe number of the obtained cured product, heat resistance and color tone.

Claims (9)

(A) 1 to 50 parts by weight of an inorganic compound having a sulfur atom and / or selenium atom (hereinafter referred to as (a) compound) and (b) 50 to 99 parts by weight of a compound represented by the following formula (1) (hereinafter referred to as ( b) Compound)
Preliminarily reacted for 1 minute to 72 hours at 0 ° C to 150 ° C in the presence of imidazoles as prepolymerization reaction catalysts ;

(C) NH Motoma other compounds that one have the NH2 group having an aromatic ring of 1 to 20 parts by weight (excluding a compound having a halogeno group) (hereinafter compound (c)) and
(D), comprising a polymerization catalyst (hereinafter referred to as (d) compound) comprising 0.001 to 5 parts by weight of a quaternary ammonium salt or a quaternary phosphonium salt ,
A resin composition characterized by being degassed at 0 to 100 ° C for 1 minute to 24 hours under a reduced pressure of 0.001 to 50 torr, and having a viscosity of 1000 mPa · s or less after 3 hours from preparation object. The resin composition according to claim 1, wherein the prepolymerization reaction is a reaction of (a) the compound by 10% or more (previous reaction is 100%). The resin composition according to claim 1 or 2, wherein the compound (a) is sulfur. The resin composition according to claim 1 or 2, wherein the compound (b) is bis (β-epithiopropyl) sulfide and / or bis (β-epithiopropyl) disulfide. (C) The resin composition according to claim 1 or 2, wherein the compound has a molecular weight of 100 or more and less than 200. Furthermore , the resin composition of Claim 1 or 2 which added (e) 0.001-5.0 weight part polymerization regulator (henceforth (e) compound). The manufacturing method of the optical material which polymerizes and cures the resin composition in any one of Claims 1-6 . An optical material obtained by the method of claim 7 . An optical lens made of the optical material according to claim 8 .