JP2001166102A - Optical material and method for producing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a lens having improved weather resistance in the production of a lens comprising an episulfide resin using an episulfide compound as a starting material. SOLUTION: A hard coat layer containing a UV absorber is disposed on an episulfide resin substrate obtained by polymerizing a polymerizable composition containing a compound having two or more episulfide groups in one molecule to obtain the objective episulfide resin optical material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an episulfide-based resin material obtained by polymerizing a polymerizable composition containing a compound having two or more episulfide groups in a molecule in the production of an episulfide-based optical material. The present invention relates to an optical material provided with a hard coat layer containing an ultraviolet absorber and a method for producing the same.

[0002]

2. Description of the Related Art Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed. Therefore, plastic lenses have recently been rapidly used in optical elements such as spectacle lenses and camera lenses. Further higher performance is required for plastic lens resins, and higher refractive index, higher Abbe number, lower specific gravity, higher heat resistance, and the like have been required. Until now, various resin materials for lenses have been developed and used. Currently, resins widely used for these purposes include diethylene glycol bis (allyl carbonate) (hereinafter, referred to as “diethylene glycol bis (allyl carbonate)”).
D. A. C) is radically polymerized.
This resin has various characteristics such as being excellent in impact resistance, being lightweight, being excellent in dyeing properties, being excellent in workability such as cutting property and polishing property, and the like. .
However, this resin has a refractive index nd as low as about 1.50, increases the center thickness and edge thickness of the lens, and a resin for a lens having a higher refractive index has been desired.

[0003] D. A. C. As a resin having a higher refractive index than the resin, a polythiourethane resin (Japanese Patent Application Laid-Open No. 63-46213) or a sulfur-containing O- (meth) acrylate resin (Japanese Patent Application Laid-Open No. 12896
6, JP-A-3-217412 and JP-A-4-217.
No. 161410, etc.) and thio (meth) acrylate resins (JP-A-63-188660, JP-B-3-59).
060 is known. Among them, polythiourethane resin has a high refractive index and good impact resistance,
It is a well-balanced resin.

However, it is very difficult to improve both the refractive index and the Abbe number at the same time because they have conflicting physical properties such that the Abbe number decreases as the refractive index increases. Therefore, studies for increasing the refractive index while suppressing a decrease in the Abbe number have been actively conducted.

[0005] The most typical proposal in these studies is:
JP-A-9-110979, JP-A-9-71580
, Japanese Patent Application Laid-Open No. 9-255781, WO 89/1
0575, JP-A-11-14070, JP-A-11-140070
It is a method using an episulfide compound as described in JP-A-1-183702, JP-A-11-189592, and Japanese Patent Application No. 11-68448.

[0006] In recent years, studies have been actively conducted to provide these plastic lenses with an ultraviolet absorbing ability not only to improve the light resistance of the resin itself against ultraviolet rays caused by sunlight or the like but also to protect eyes. In these studies, various ultraviolet absorbers have been used to impart ultraviolet absorption capability.

According to these episulfide resins, a high refractive index can be realized while having a relatively high Abbe number. Therefore, the weather resistance improvement of episulfide resin and
There is a need to study episulfide resins and optical materials that take into account the ability to absorb ultraviolet light for the purpose of protecting the eyes.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a lens made of an episulfide resin, the lens having further improved weather resistance.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by providing a hard coat layer containing an ultraviolet absorber on an episulfide resin base material, Furthermore, they have found that an episulfide-based lens with improved weather resistance can be produced, and have completed the present invention.

The present invention provides a hard coat layer containing an ultraviolet absorber on an episulfide resin substrate obtained by polymerizing a polymerizable composition containing a compound having two or more episulfide groups in a molecule. And a method for manufacturing an optical material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

Specific examples of the compound having two or more episulfide groups in a molecule used in the present invention include bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, Bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-
Bis (2,3-epithiopropylthio) propane, 1,
3-bis (2,3-epithiopropylthio) propane,
1,3-bis (2,3-epithiopropylthio) -2-
Methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3-bis (2
3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-
Bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropyl Thio) hexane, 1,6-bis (2,3-
Epithiopropylthio) -2-methylhexane, 3,8
-Bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3-epithio Propylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3
-Epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl ) -3-Thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3- Epithiopropylthio) -2,
2-bis (2,3-epithiopropylthiomethyl) -4
-Thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3
-Epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8
-Bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-
Dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3 -Epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4 5-tris (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,
1-tris [｛2- (2,3-epithiopropylthio)
Ethyl {thiomethyl] -2- (2,3-epithiopropylthio) ethane, 1,1,2,2-tetrakis [{2-
(2,3-epithiopropylthio) ethyl {thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithiopropylthiomethyl) -3 , 6,9-Trithiaundecane, 1,1
1-bis (2,3-epithiopropylthio) -4,7-
Bis (2,3-epithiopropylthiomethyl) -3,
6,9-trithiaundecane, 1,11-bis (2,3
A chain aliphatic 2,3-epithiopropylthio compound such as -epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane; And 1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthio) Methyl) cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [{2- (2,3-epithiopropylthio) ethyl}
Thiomethyl] -1,4-dithiane, 2,5-bis (2,
Cycloaliphatic 2,3-epithiopropylthio compounds such as 3-epithiopropylthiomethyl) -2,5-dimethyl-1,4-dithiane, and 1,2-bis (2,3-epithio) Propylthio) benzene, 1,3-bis (2,3
-Epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene, 1,2-
Bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropylthiomethyl) benzene, Bis {4- (2,3-epithiopropylthio) phenyl} methane, 2,2-bis {4
-(2,3-epithiopropylthio) phenyl} propane, bis {4- (2,3-epithiopropylthio) phenyl} sulfide, bis {4- (2,3-epithiopropylthio) phenyl} sulfone , 4,4'-bis (2,3-epithiopropylthio) biphenyl and other aromatic 2,3-epithiopropylthio compounds, but are not limited to these exemplified compounds only. Absent. These compounds may be used alone or in combination of two or more.

The polymerizable composition of the present invention includes not only a mixture of these episulfide resins, but also other polysulfide oligomers such as dimers, trimers, and tetramers of these resins, and the synthesis of episulfide resins. Episulfide resins having a mercapto group generated when epihalohydrin is deficient, as well as organic and inorganic compounds such as inorganic acids and organic acids, solvents, unreacted raw materials and other by-products and impurities used in the synthesis of episulfide, and impurities. It may be included in a range that does not result in

The polymerizable composition of the present invention is mainly used to adjust the optical properties such as the refractive index of the obtained resin, and to adjust various properties such as impact resistance and specific gravity. A resin modifier can be added for the purpose of improving the monomer system and the resin, for example, for adjusting the viscosity and other handling properties.

As the resin modifier, episulfide compounds and amine compounds other than those contained in the polymerizable composition of the present invention, epoxy compounds, polyphenols, thiol compounds, mercapto organic acids, organic acids and anhydrides, Examples include olefins including (meth) acrylates, amino acids, and mercaptoamines.

Specific examples of preferable amine compounds as the resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine, and
c-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine,
1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine, 2-, 3-, or 4-methyl Benzylamine, o-, m-, or p-
Methylaniline, o-, m- or p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol,
1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine , 3-isopropoxypropylamine, 3-isobutoxypropylamine, monofunctional primary amine compounds such as 2,2-diethoxyethylamine, ethylenediamine,
2- or 1,3-diaminopropane, 1,2-,
1,3- or 1,4-diaminobutane, 1,5-
Diaminopentane, 1,6-diaminohexane, 1,7
-Diaminoheptane, 1,8-diaminooctane, 1,
10-diaminodecane, 1,2-, 1,3- or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4 -Or 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'- or 4,4'-diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5
-, 1,8- or 2,3-diaminonaphthalene,
2,3-, 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m
-Or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3- or 1,4-diaminomethylcyclohexane, 2-,
Or a primary polyamine compound such as 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, diethylamine, dipropylamine, Di-n-butylamine, di-sec-butylamine, diisobutylamine,
Di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, Monofunctional secondary amine compounds such as N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine and morpholine N, N'-dimethylethylenediamine, N, N'-dimethyl-1,2-diaminopropane, N, N'-dimethyl-1,3-diaminopropane,
N, N'-dimethyl-1,2-diaminobutane, N,
N'-dimethyl-1,3-diaminobutane, N, N'-
Dimethyl-1,4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-
1,6-diaminohexane, N, N'-dimethyl-1,
7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1,3-diaminopropane,
N, N′-diethyl-1,2-diaminobutane, N,
N'-diethyl-1,3-diaminobutane, N, N'-
Diethyl-1,4-diaminobutane, N, N′-diethyl-1,5-diaminopentane, N, N′-diethyl-
1,6-diaminohexane, N, N′-diethyl-1,
7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4 -Piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4
Examples thereof include secondary polyamine compounds such as -di- (4-piperidyl) butane and tetramethylguanidine, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, more preferred are benzylamine and piperazines.

Specific examples of preferred epoxy compounds as the resin modifier include a phenolic epoxy compound obtained by a condensation reaction of a polyhydric phenol compound such as bisphenol A glycidyl ether and an epihalohydrin compound, hydrogenated bisphenol A Alcohol-based epoxy compounds obtained by condensation of a polyhydric alcohol compound such as glycidyl ether and an epihalohydrin compound, 3,4-epoxycyclohexylmethyl-3 ′,
4'-epoxycyclohexanecarboxylate and 1,
Glycidyl ester epoxy compounds obtained by condensation of polyhalogenated organic acid compounds such as 2-hexahydrophthalic acid diglycidyl ester and epihalohydrin compounds, and amine epoxy compounds obtained by condensation of primary and secondary diamine compounds with epihalohydrin compounds Etc.,
Examples include aliphatic polyepoxy compounds such as vinylcyclohexene diepoxide, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Polyphenols as a resin modifier include:
It has one or more phenolic hydroxyl groups in the aromatic ring, and monophenols are phenol, o
-Cresol, m-cresol, p-cresol, 3-
Methoxyphenol, 4-ethoxyphenol, 4-n
-Propoxyphenol, 3-butoxyphenol, nonylphenol, 2-n-propylphenol, 2,
3,4,6-tetrachlorophenol, 2,3,5,6
-Tetrafluorophenol, 2,4,6-tribromophenol, 2,6-dichloro-4-fluorophenol, 2,6-dichloro-4-nitrophenol, 2,
3,4-trichlorophenol, 4-bromo-2-chlorophenol, 2,4-dibromophenol, 2-chloro-4-nitrophenol, 2,3-dichlorophenol, 2-fluoro-4-nitrophenol, 3, 5-xylenol, 2,3-difluorophenol, 2,4-
Dinitrophenol, 2-bromophenol, 2-amino-4-chloro-5-nitrophenol, 2-chlorophenol, 4-amino-2,6-dichlorophenol,
2-nitrophenol, 2-amino-4-nitrophenol, thymol, carvacrol, α-naphthol, 2
-Aminophenol and the like, and polyphenols include catechol, 3-chlorocatechol, resorcin, hydroquinone, chlorohydroquinone, pyrogallol, fluoroglucin and the like, but are not limited to these exemplified compounds. These polyphenol compounds may be used alone or in combination of two or more.

Specific examples of preferred thiol compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, , 4-butanedithiol, 1,2,3
-Trimercaptopropane, tetrakis (mercaptomethyl) methane, 1,2-dimercaptocyclohexane,
Bis (2-mercaptoethyl) sulfide, 2,3-dimercapto-1-propanol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoglycolate) ),
Pentaerythritol tetrakis (2-mercaptothioglycolate), pentaerythritol tetrakis (3
-Mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris (3-mercaptopropionate), 1,1,1-trimethylmercaptoethane, 1,
1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane, 4-mercaptomethyl-
1,8-dimercapto-3,6-dithiaoctane, 2,
5-dimercaptomethyl-1,4-dithiane, 2,5-
Bis {(2-mercaptoethyl) thiomethyl} -1,4
-Dithiane, 1,3-cyclohexanedithiol, 1,
4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11
-Dimercapto-3,6,9-trithiaundecane,
Aliphatic thiols such as 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and benzylmercaptan, thiophenol;
2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis ( Mercaptomethyl) benzene, 2,2′-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, 2,2-bis (4-mercaptophenyl) propane, , 2,3-trimercaptobenzene, 1,2,2
Examples thereof include aromatic thiols such as 4-trimercaptobenzene and 1,2,5-trimercaptobenzene, but are not limited to these exemplified compounds. Also,
These may be used alone or in combination of two or more.

Specific examples of preferred mercapto organic acid compounds include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but are not limited to these exemplified compounds. Not something. In addition, these may be used alone or 2
More than one kind may be mixed and used.

Specific examples of preferred organic acids and anhydrides thereof include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydroacid. Examples thereof include phthalic anhydride, methylnorbornene anhydride, methylnalbornanoic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferred olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. , Phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate , Bisphenol A dimethacrylate,
2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2- Bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate,
1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1- Bis (4-methacryloxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
Such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, etc. (Meth) acrylate compounds, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, allyl compounds such as diethylene glycol bisallyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene,
Examples thereof include vinyl compounds such as 3,9-divinylspirobi (m-dioxane), diisopropenylbenzene, and the like, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Any of the above resin modifiers can be used alone or in combination of two or more.

As the curing catalyst used for producing the episulfide resin of the present invention, amines, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used. For example, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, t-butylamine, cyclohexylamine, 2-aminoethanol, dibutylamine, triethylamine, tri-n-butylamine, tri-n
-Hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N,
N-diethylethanolamine, N, N-di-n-butylethanolamine, N, N-dimethylbenzylamine,
Diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine,
N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, N, N
-Dimethylaniline, β-picoline, piperidine, 2,
2'-bipyridyl, dicyandiamide, hexamethylenetetramine, 1,8-diazabicyclo (5,4,0)-
Amines such as 7-undecene, trimethylphosphine,
Triethylphosphine, tri-n-propylphosphine,
Triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane,
Phosphines such as 1,2-bis (dimethylphosphino) ethane, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin, dibutyltin oxide, zinc chloride, zinc acetylacetone;
Lewis acids such as aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate, 2,
2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4
-Dimethylvaleronitrile), t-butylperoxy-
Radical polymerization catalysts such as 2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, Cationic polymerization catalysts such as diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, and triphenylsulfonium hexafluoroarsenic acid are exemplified, but not limited to these exemplified compounds. These may be used alone or in combination of two or more.

The curing catalyst is used in an amount of 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total weight of the composition comprising the episulfide resin. . When the addition amount of the curing catalyst is less than 0.001% by mass, it may cause poor polymerization. On the other hand, even if it exceeds 10% by mass, the pot life is shortened, and inconveniences such as a decrease in transparency, optical properties, or weather resistance may occur.

A typical polymerization method for obtaining the episulfide resin of the present invention includes cast polymerization. That is, the polymerizable composition is injected between molding molds held by gaskets or tapes. At this time, a curing catalyst and a resin modifier may be mixed in the polymerizable composition as necessary. Next, the resin is cured by heating in a heatable device such as an oven or water, and the resin can be taken out.

The conditions for the heat polymerization of the polymerizable composition of the present invention injected into the molding mold include the type of compound having two or more episulfide groups in the molecule, the type of resin modifier, the type of curing catalyst, Although the condition cannot be limited because the conditions are largely different depending on the shape of the mold, etc., it is approximately −50 to 200
The reaction is carried out at a temperature of ° C. for 0.1 to 100 hours.

In some cases, preferable results may be obtained by maintaining the temperature in the range of 10 ° C. to 150 ° C. or by gradually increasing the temperature and polymerizing for 1 to 80 hours.

Further, the polymerization time of the polymerizable composition of the present invention can be reduced by irradiation with ultraviolet rays or the like. At this time, a curing catalyst such as a radical polymerization catalyst may be added.

When molding the resin of the present invention, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, an anti-coloring agent, a dye, a filler may be used in the same manner as in a known molding method depending on the purpose. Various substances such as an internal and / or external release agent, an internal and / or external adhesion improver, and a compound having a hydroxyl group as a dyeability improver may be added. Further, separately from the hard coat layer, an ultraviolet absorber having high compatibility with the episulfide resin base material may be added, and together with the ultraviolet absorber contained in the hard coat layer, higher weather resistance and ultraviolet absorption can be obtained. Noh is obtained.

Further, with respect to the resin molded product taken out,
If necessary, a process such as annealing may be performed. Furthermore, the resin of the present invention can be obtained as molded articles of various forms by changing the molding mold at the time of casting polymerization, and can be used for spectacle lenses, camera lenses, light emitting diodes (LEs).
It can be used for various applications as an optical material such as D) and a transparent resin. In particular, it is suitable as an optical material for eyeglass lenses, camera lenses, and the like.

The optical material obtained in the present invention is obtained by providing a hard coat layer containing an ultraviolet absorber on the above-mentioned episulfide resin base material, and these base materials can be used without treatment. Alternatively, alkali treatment may be performed as a pretreatment before use. Performing the alkali treatment of the base material has an effect of increasing the adhesion of the hard coat layer.

The hard coat layer containing the ultraviolet absorbent in the present invention is not particularly limited as long as it is obtained from a thermosetting silicone resin, acrylic resin or epoxy resin. Resins are preferably used, and in general, (A) an organic silicon compound represented by the following formula (2): R _n Si (OR ′) _4-n (2) 6, an alkyl group, a vinyl group, an aryl group, or a vinyl group, a methacryloxy group, an epoxy group, an amino group, a mercapto group, an alkyl group having a fluorine atom or a chlorine atom, a cycloalkyl group or an aryl group; Represents a hydrogen atom, an alkyl group or an acyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or 2. When n is 2, R may be the same or different.) B) colloidally dispersed silica sol,
(C) a curing catalyst (D) at least one organic solvent,
(E) A cured layer obtained by subjecting a hard coat composition containing an ultraviolet absorber and a coating layer thereof to a heat curing treatment.

The mixing ratio of each component of the hard coat composition is appropriately determined depending on the physical properties, thickness, etc. of the obtained hard coat layer, and cannot be unconditionally limited, but is usually (A)
The component is 20 to 200 parts by mass, and the component (B) is 40 to 200 parts by mass.
Parts by mass, the component (C) is 0.1 to 20 parts by mass, the component (D) is 1 to 500 parts by mass, and the component (E) is a coating solution prepared from (A) to (D). It is used in a ratio of 0.1 to 5% by mass.

As the organosilicon compound of the component (A) represented by the general formula (2), γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane Silane, γ-methacryloxypropyltriethoxysilane,
γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (3,4-epoxycyclohexyl) ethyltriethoxysilane, phenyltrimethoxysilane, Examples include phenylmethyldimethoxysilane, vinyltriethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, and methyltrimethoxysilane. These can be used alone or in combination of two or more.

These organosilicon compounds may be used as they are, but are preferably used as hydrolysates. The hydrolyzate is obtained by substituting a part or all of an alkoxy group or an acyloxy group in the silicon compound with a hydroxyl group, and also includes a product in which the substituted hydroxyl groups partially condense naturally. These hydrolysates are obtained, for example, by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid.

The colloidally dispersed silica sol as the component (B) is also called colloidal silica.
It is a sol obtained by dispersing ultrafine particles of silica having a particle size of 1 to 100 nm in water or an alcohol-based dispersion medium or a dry powder obtained by removing the dispersion medium from this sol, and commercially available ones can be used.

The curing catalyst of the component (C) is a catalyst necessary for curing the mixture of the above components. In the present invention, from the viewpoint of the stability of the composition for hard coat, curability, etc., for example, a Lewis acid catalyst, an organoaluminum compound,
Organic titanium compounds and the like are preferably used. Specifically, aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum isopropoxide, aluminum acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate and the like are exemplified.
Aluminum acetylacetonate is preferred.

The organic solvent of component (D) used in the present invention includes alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids,
Aromatic compounds and the like can be mentioned, and these alone,
Alternatively, it can be used as a mixed solvent of two or more.
In particular, methanol, ethanol, propanol, isopropanol, lower alcohols such as butanol, methyl cellosolve, ethyl cellosolve, cellosolves such as butyl cellosolve, formic acid, acetic acid, lower alkyl carboxylic acids such as propylene acid, toluene, aromatic compounds such as xylene, And esters such as ethyl acetate and butyl acetate are preferably used alone or as a mixed solvent.

As the ultraviolet absorber of component (E), benzotriazole-based, benzophenone-based, cyanoacrylate-based, benzoate-based, and triazine-based ultraviolet absorbers can be used. These UV absorbers can be used alone or in combination of two or more. It is preferable to dissolve the ultraviolet absorber in the composition for hard coat in advance to give a preferable result. Among the ultraviolet absorbers, a benzotriazole-based ultraviolet absorber is preferable, but is appropriately determined in consideration of the solubility in the hard coat composition (coating solution).

The hard coat layer of the present invention is prepared by coating the above-mentioned composition for hard coat by an ordinary coating method such as a dipping method, a spraying method, a roller coating method, a spin coating method or a flow coating method. After applying to the surface of the material, the curing temperature (for example, 130 ° C.)
It is formed by baking and curing for 1 hour, preferably for 5 to 20 minutes.

The thickness of the hard coat layer is not particularly limited as long as it does not impair the intrinsic optical properties of the episulfide resin base material, but is preferably 0.1 to 0.1.
It is 10 μm, more preferably 1-3 μm. The hard coat layer is preferably formed on both surfaces of the episulfide resin base material, but may be formed on only one surface depending on the purpose of use.

In order to improve the adhesion between the episulfide resin substrate and the hard coat layer, a primer layer may be provided between the resin substrate and the hard coat layer. The primer layer is not particularly limited as long as it can improve the adhesion between the resin base material and the hard coat layer, and a silicone resin, an acrylic resin, an epoxy resin, or the like is used. In order to improve the impact resistance of the obtained lens, a primer layer of a urethane resin may be provided.

Further, in the lens using the cured resin of the present invention, if necessary, improvements such as antireflection, high hardness, high abrasion resistance, high chemical resistance, high antifogging property, and high fashionability are provided. To perform a physical or chemical treatment such as surface polishing, antistatic treatment, antireflection coating treatment, and dyeing treatment, and these treatments can be performed before or after the formation of the hard coat layer. Alternatively, the hard coat layer may also have a function for the above improvement.

[0045]

The present invention will be described below in more detail with reference to examples.

Example 1 (1) Preparation of episulfide resin base material (lens) Bis (2,3-epithiopropyl) disulfide 100
g, 4,8or4,7or5,7-dimercaptomethyl-1,11-mercapto-3,6,9 as a resin modifier
-10 g of trithiaoundecan, 2- as an ultraviolet absorber
After sufficiently mixing 1.0 g of (5-tertbutyl-2-hydroxyphenyl) benzotriazole, 0.1 g of N, N-dimethylcyclohexylamine was used as a curing catalyst.
Was added and mixed, and the mixture was defoamed under reduced pressure for 0.2 hours and poured into a mold composed of a glass mold and a gasket. This mold was gradually heated from 30 ° C. to 120 ° C.
Polymerization was carried out over a period of time. After completion of the polymerization, the obtained molded body was released from the mold to obtain a lens made of an episulfide resin.

(2) Preparation of Hard Coating Solution γ-Glycidoxypropyltrimethoxysilane
While maintaining 2 g at 10 ° C., 24.3 g of a 0.01 N hydrochloric acid aqueous solution was gradually added dropwise with stirring. After the completion of the dropwise addition, the cooling was stopped to obtain a silane hydrolyzate. 125.4 g of methanol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name “methanol silica sol”, solid content: 30%, average particle diameter: 13 ± 1 nm) was added to this solution with stirring, and then methanol was added. 5 g, 12.5 g of diethylene glycol dimethyl ether and 0.4 g of a silicone-based surfactant were added, and 3.8 g of aluminum acetylacetonate was further added, followed by sufficiently stirring and mixing to prepare a composition for hard coat. Prepared composition for hard coat 100
0.5 g of "Tinuvin 1130" (Ciba Specialty Co.) as an ultraviolet absorber was added to the resulting mixture, and the mixture was sufficiently stirred and dissolved to obtain a hard coat liquid.

(3) Coating and Hardening of Hard Coat Solution The episulfide resin lens polymerized in (1)
The hard coat liquid prepared in (2) was applied by a spinner method (rotation speed: 1500 min ^-1 ). 3 at room temperature after application
After air drying for 0 minutes and further drying at 100 ° C. for 5 minutes,
Heat treatment was performed at 120 ° C. for 60 minutes.

(4) Evaluation The obtained lens was subjected to a weather resistance test using a carbon arc fade meter, and evaluated by the magnitude of the hue change Δb * before and after irradiation for 20 hours. Hue change Δb * is 0.1
It was 2.

Comparative Example 1 (2) Preparation and coating of episulfide resin base material (lens) in the same manner as in Example 1 except that no ultraviolet absorber was added to the prepared hard coat composition in the preparation of the hard coat liquid Preparation of a liquid and application and curing of a coating liquid were performed.

The obtained lens was subjected to a weather resistance test using a carbon arc fade meter and evaluated based on the magnitude of the hue change Δb * before and after irradiation for 20 hours. As a result, the hue change Δb * was 0.23. Compared with No. 1, the hue change was large.

[0052]

According to the present invention, in the production of a lens made of an episulfide resin, a lens having further improved weather resistance can be produced.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Morijiri 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Chemicals, Inc. 72) Inventor Akinori Ryu 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Chemicals, Inc. (72) Inventor Nobuo Kawato 30-Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. 30 Asamuta-cho, Omuta-shi Mitsui Chemicals, Inc. F term (reference) 2K009 AA15 BB11 CC09 CC42 CC47 DD02 DD06 4J030 BA04 BA05 BB03 BC12 BC13 BC15 BC21 BF05 BG25

Claims (8)

[Claims] 1. A hard coat layer containing an ultraviolet absorber is provided on an episulfide resin substrate obtained by polymerizing a polymerizable composition containing a compound having two or more episulfide groups in a molecule. An optical material characterized by the above. 2. The optical material according to claim 1, wherein the compound having two or more episulfide groups in the molecule is an episulfide compound having a disulfide bond in the molecule. 3. The optical material according to claim 1, wherein the compound having two or more episulfide groups in the molecule is an episulfide compound represented by the following formula (1). Embedded image 4. The optical material according to claim 1, wherein the hard coat layer containing the ultraviolet absorbent is made of a thermosetting silicone resin as a base material. 5. After hardening a polymerizable composition containing a compound having two or more episulfide groups in a molecule to obtain an episulfide resin base material, a hard coat composition containing an ultraviolet absorber is obtained. A method for producing an optical material, wherein the method is applied on the substrate and heat-cured to form a hard coat layer. 6. The method for producing an optical material according to claim 5, wherein the compound having two or more episulfide groups in the molecule is an episulfide compound having a disulfide bond in the molecule. 7. The method for producing an optical material according to claim 5, wherein the compound having two or more episulfide groups in the molecule is an episulfide compound represented by the following formula (1). Embedded image 8. The method for producing an optical material according to claim 5, wherein the composition for a hard coat containing an ultraviolet absorber comprises a thermosetting silicone resin as a base material.