JPH05297201A - Sulfuric plastic lens and manufacture thereof - Google Patents

Abstract

PURPOSE:To reduce or deodorize the bad smell or offensive smell to be produced at the time when a sulfuric lens is worked. CONSTITUTION:At least one kind of compound selected among caproic acid methyl, caproic acid vinyl, caproic acid ethyl, caproic acid isopropyl, or 5-tert- butyl-2,4,6-trinitro-m-xylene of 0.005 to 0.5% by weight is included in a sulfuric lens. Thereby, bad smell or offensive smell specific to sulfur can be reduced or deodorized, so that workers can carry out lens working without feeling discomfort.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high refractive index sulfur-containing plastic lens. More specifically, the present invention relates to a plastic lens which is obtained by casting polymerization and does not give off a peculiar odor or bad odor peculiar to sulfur when the molded body is cut and polished, and a method for producing the same. The sulfur-containing plastic lens of the present invention is used for spectacles, optical materials and the like.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight and less likely to break than inorganic lenses and can be dyed, and thus have been rapidly popularized in optical elements such as spectacle lenses and camera lenses in recent years. Currently, as the resin most widely used for these purposes, there is a resin obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC). This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and excellent workability such as machinability and abrasiveness. .. However, this DAC lens has a refractive index n _D as compared with an inorganic lens (n _D = 1.52).
= 1.50, it is necessary to increase the center thickness, edge thickness, and curvature of the lens in order to obtain optical properties equivalent to those of a glass lens. Therefore, a lens resin having a higher refractive index is desired.

Attempts have been made to introduce sulfur atoms in order to increase the refractive index of the resin. For example, a sulfur-containing urethane resin comprising polyisocyanate and polythiol (Japanese Patent Laid-Open No. Sho 60).
-199016, JP-A-62-267316, JP-A-6
3-46213), polythio (meth) acrylate resin (JP-A-64-26613, JP-A-64-31759,
JP-A-63-188660) or sulfur-containing poly (meth)
Acrylate resins (JP-A-62-283109, JP-A-63-268707) and the like have been proposed. However, since these resins contain a sulfur atom,
When the lens was cut or polished, a peculiar odor or a bad odor specific to sulfur was generated, and the operator sometimes felt a strong discomfort.

For plastic lenses, a processing method for reducing or eliminating the offensive odor and malodor generated during cutting and polishing is desired and proposed. For example, in the production of a radical polymerization type high refractive index plastic lens having a crosslinked structure with a refractive index of 1.50 or more, by using a resin containing 0.05% to 1% of an aroma imparting compound, Japanese Patent Publication No. 2-56641 discloses a technique for mitigating an offensive odor during cutting and polishing. However, as a result of the present inventors' investigations on sulfur-containing plastic lenses using the aroma imparting compounds disclosed herein, these aroma imparting compounds reduce the offensive odor and malodor peculiar to sulfur, or It was found to be insufficient for deodorizing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sulfur-containing plastic lens having a high refractive index, which reduces or eliminates the offensive odor and malodor peculiar to sulfur during processing such as cutting and polishing. And a method of manufacturing the lens.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have used a compound of a certain kind to produce a peculiar offensive odor of sulfur generated at the time of processing a lens, The inventors have found that a bad odor can be reduced or deodorized, and have completed the present invention. That is, the present invention is
In a high-refractive index sulfur-containing plastic lens having a cross-linking structure with a refractive index of 1.50 or more, methyl caproate, vinyl caproate, ethyl caproate, isopropyl caproate or 5-tert-butyl-2,4,6-trinitro The present invention relates to a sulfur-containing plastic lens containing 0.005 to 0.5% by weight of at least one compound selected from -m-xylene. Further, in the method for producing a high refractive index sulfur-containing plastic lens having a crosslinked structure with a refractive index of 1.50 or more, the monomer mixture contains methyl caproate, vinyl caproate, ethyl caproate, isopropyl caproate or 5-tert. −
At least one compound selected from butyl-2,4,6-trinitro-m-xylene is added in an amount of 0.005 to 0.5
The present invention relates to a method for producing a sulfur-containing plastic lens which is added by weight% and polymerized by heating. Furthermore, the sulfur-containing plastic lens in which the sulfur-containing plastic lens is a sulfur-containing urethane resin and the method for producing a sulfur-containing plastic lens in which the monomer mixture is a monomer mixture consisting of a bifunctional or higher functional polyisocyanate compound and a bifunctional or higher functional polythiol compound It is about.

According to the present invention, it is possible to process the sulfur-containing lens without any discomfort for the operator by reducing or eliminating the offensive odor and bad odor characteristic of sulfur generated during cutting and polishing of the lens. .. The compound used in the present invention is at least one compound selected from methyl caproate, vinyl caproate, ethyl caproate, isopropyl caproate or 5-tert-butyl-2,4,6-trinitro-m-xylene. The amount used varies depending on the type of compound and the sulfur-containing lens used, but is usually 0.005 to 0.5% by weight. These compounds are commercially available and are easily available.

The sulfur-containing lens used in the present invention is made of sulfur-containing urethane resin, sulfur-containing epoxy resin, polythio (meth) acrylate resin, and sulfur-containing poly (meth) acrylate resin. For example, the sulfur-containing urethane resin is a resin obtained by reacting polyisocyanate with a polyol having a sulfur atom, a polythiol, a mercapto compound having a hydroxy group, or the like. Specifically, as the polyisocyanate, for example, ethylene diisocyanate, trimethylene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate Isocyanate, butene diisocyanate, 1,3-butadiene-1,4-
Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4- Isocyanatomethyl octane, 2,5,7-trimethyl-1,8
-Diisocyanate-5-isocyanatomethyl octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine diisocyanate Nato methyl ester, lysine triisocyanate, 2-isocyanatoethyl-
2,6-Diisocyanate hexanoate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α , Α, α ', α'-Tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityl Lentriisocyanate, aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan,

Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2 '
-Dimethyldicyclohexyl methane diisocyanate,
Bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate dimerate, 2-isocyanatomethyl-3- (3-isocyanatopropyl)
-5-isocyanatomethyl-bicyclo- [2,2,
1] -heptane, 2-isocyanatomethyl-3- (3
-Isocyanatopropyl) -6-isocyanatomethyl-bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)
-5-isocyanatomethyl-bicyclo- [2,2,
1] -heptane, 2-isocyanatomethyl-2- (3
-Isocyanatopropyl) -6-isocyanatomethyl-bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl)
-5- (2-isocyanatoethyl) -bicyclo-
[2,2,1] -Heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2- Isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) ) -6- (2-Isocyanatoethyl) -bicyclo-
Alicyclic polyisocyanate such as [2,2,1] -heptane,

Phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate,
Isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate , Toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) Ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diester Phenylmethane-2,4
4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-
Diphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate, phenylisocyanate methylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthylenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane- 4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole di For example, isocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, etc. Aromatic polyisocyanate,

Sulfur containing thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, etc. Aliphatic isocyanate, diphenyl sulfide-2,4'-
Diisocyanate, diphenyl sulfide-4,4'-
Diisocyanate, 3,3'-dimethoxy-4,4'-
Diisocyanate dibenzyl thioether, bis (4-
Isocyanatomethylbenzene) sulfide, 4,4 '
-Methoxybenzenethioethylene glycol-3,3 '
-Aromatic sulfide-based isocyanates such as diisocyanate, diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl Disulfide-5,5'-diisocyanate,
3,3'-Dimethyldiphenyldisulfide-6,6'-
Diisocyanate, 4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3 Aromatic disulfide-based isocyanates such as 3'-diisocyanate,

Diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate Nato, 4-methyldiphenylsulfone-2,4 '
-Diisocyanate, 4,4'-dimethoxydiphenyl sulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl sulfone, 4,4'-dimethyldiphenyl sulfone -3
3'-diisocyanate, 4,4'-di (tert-butyl) diphenylsulfone-3,3'-diisocyanate, 4,4'-methoxybenzeneethylenedisulfone-
Aromatic sulfone-based isocyanates such as 3,3′-diisocyanate and 4,4′-dichlorodiphenylsulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanate Sulfonic acid ester-based isocyanates such as natophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanatophenolester, 4-methyl-3-isocyanatobenzenesulfonylanilide-3′-methyl-4 ′ -Isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate,
Aromatic sulfonic acid amides such as 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3′-isocyanate, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and others, 1, 4-dithian-2,5-diisocyanate and the like can be mentioned. Further, these chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds and prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette modified products Body, dimerization or trimerization reaction products and the like can also be used.

Examples of the polyol having a sulfur atom include bis- [4- (hydroxyethoxy) phenyl]
Sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4- (2,3-
Dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide, and the average per hydroxyl group of these compounds Compounds to which 3 or less molecules of ethylene oxide and / or propylene oxide are added, di- (2-hydroxyethyl) sulfide, 1,
2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,
4-dithian-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone [trade name, bisphenol S],
Contains sulfur atoms such as tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane The polyols mentioned can also be used. These polyols may use halogen-substituted products such as chlorine-substituted products and bromine-substituted products. These may be used alone or in combination of two or more.

Examples of polythiols include methanedithiol, 1,2-ethanedithiol, 1,1-
Propanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethyl Propane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-2,3- Dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester),
2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropanoate) Pionate), 1,2-dimercaptopropyl methyl ether,
2,3-dimercaptopropyl methyl ether, 2,2
-Bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis ( 2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) and other aliphatic polythiols,

1,2-dimercaptobenzene, 1,3-
Dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,
3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene ) Benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene , 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,
2,4-Trimercaptobenzene, 1,3,5-Trimercaptobenzene, 1,2,3-Tris (mercaptomethyl) benzene, 1,2,4-Tris (mercaptomethyl) benzene, 1,3,5- Tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,2. 3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) Benzene, 1,2,4-
Tris (mercaptoethyleneoxy) benzene, 1,
3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,
2,3,5-tetramercaptobenzene, 1,2,4
5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene,

1,2,4,5-Tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1, 2,4,5-Tetrakis (mercaptoethyl) benzene, 1,2,3,4
-Tetrakis (mercaptomethyleneoxy) benzene,
1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,
2,3,5-Tetrakis (mercaptoethyleneoxy)
Benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4 '
-Dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-
Naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol, 9,
10-anthracene dimethanethiol, 1,3-di (p
-Methoxyphenyl) propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-
Aromatic polythiols such as mercaptophenyl) pentane,

2-methylamino-4,6-dithiol-
sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4,
6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym
-Triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-
A polythiol containing a heterocycle such as 4,6-dithiol-sym-triazine,

1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene,
1,2-bis (mercaptoethylthio) benzene, 1,
3-bis (mercaptoethylthio) benzene, 1,4-
Bis (mercaptoethylthio) benzene, 1,2,3-
Tris (mercaptomethylthio) benzene, 1,2,4
-Tris (mercaptomethylthio) benzene, 1,3
5-tris (mercaptomethylthio) benzene, 1,
2,3-tris (mercaptoethylthio) benzene,
1,2,4-Tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5 -Tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4
-Tetrakis (mercaptoethylthio) benzene, 1,
Aromatic aromatic compounds containing sulfur atoms in addition to mercapto groups such as 2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and their nuclear alkylated products. Polythiol,

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2
-Mercaptoethylthio) ethane, 1,2-bis (3-
Mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3- Tris (mercaptomethylthio) propane, 1,2,3-tris (2
-Mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) ) Methane, bis (2,3-dimercaptopropyl) sulfide, 2,5
-Dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide and the like, and esters of these thioglycolic acid and mercaptopropionic acid,

Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate) , Hydroxypropylsulfide bis (2-mercaptoacetate), hydroxypropylsulfide bis (3-mercaptopropionate), hydroxymethyldisulfidebis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-
Mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate),

Thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis ( 2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester),
4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycol Acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester), etc. Aliphatic polythiol containing sulfur atom in addition to mercapto group, 3,4-thiophenedithiol, Examples include heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole. Furthermore, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds of these polythiols may be used. These may be used alone or in combination of two or more.

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol and 3
-Mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto- 2-propanol, 1,3-dimercapto-2-propanol, 2,3
-Dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate),
Pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxy Ethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenyl sulfone, 2-
Examples thereof include (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), dimercaptoethane mono (salicylate), and hydroxyethylthiomethyl-tris (mercaptoethylthiomethyl) methane. Further, halogen-substituted products of these chlorine-substituted products and bromine-substituted products may be used. These may be used alone or in combination of two or more.

Further, among the sulfur-containing lens materials used in the present invention, the sulfur-containing epoxy resin comprises an active hydrogen compound and an epoxy resin having two or more epoxy groups in one molecule. Examples of the active hydrogen compound include polythiols, mercapto compounds having a hydroxy group, sulfur-containing polyols, thiosalicylic acid, thioglycolic acid, 3,3-dithioisobutyric acid, and thiol among the compounds listed above as the raw materials for the sulfur-containing urethane-based resin. Lactic acid, mercaptocarboxylic acid such as thiomalic acid, hydroxycarboxylic acid containing a sulfur atom such as 3- (hydroxysulfoxy) propionic acid, m-benzenedisulfonic acid, o-benzenedisulfinic acid, 4-aminobenzenesulfonic acid, 2-Aminoethylsulfonic acid, 1,4-disulfophenol, 4-sulfobenzoic acid, 4-mercaptobenzenesulfonic acid, sulfonic acid compounds such as bis (4-sulfobenzene) disulfide and sulfinic acid compounds, bis (2-amino Ethyl) disulfide, bis (3-
Aminopropyl) sulfide, 4-aminobenzenethiophenol, 3,5-dihydroxybenzenesulfonamide, cystathionine, cystine, lanthionine, methionine, 2-sulfonylamidothiazole-5-benzoic acid, 3- (hydroxysulfonyloxy) propionic acid, Examples thereof include amines and amides having a sulfur atom such as N-ethyl-N′-methylsulfoamide.

Specific examples of the epoxy resin having two or more epoxy groups in one molecule include (1) diaminodiphenylmethane, metaxylylenediamine, paraxylylenediamine, metaaminobenzylamine and paraaminobenzyl. Amine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane,
1,3-diaminocyclohexane, 1,4-diaminocyclohexane, metaphenylenediamine, paraphenylenediamine, benzylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl ketone, naphthalenediamine, aniline, toluidine, metaaminophenol , Para-aminophenol, aminonaphthol, phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, para-hydroxybenzamide,
Epoxy resin produced by a known production method from compounds having an amino group or an amide group such as metahydroxybenzamide,

(2) Hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, brominated bisphenol A, novolac resin, cresol novolac resin, tetraphenylethane, triphenylethane, etc. Epoxy resin produced (3) ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dibromo Neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone, polytetramethylene ether glyco , Polybutadiene glycol, hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, and other polyhydric alcohols, and polyester polyols made from these polyhydric alcohols and polycarboxylic acids Epoxy resin produced by a known production method from alcohols of

(4) Cyclopentadiene epoxide, epoxidized soybean oil epoxidized polybutadiene, vinyl cyclohexene epoxide, trade name E of Union Carbide
RL-4221, ERL-4234, ERL-4299
Epoxy compounds of unsaturated compounds known as, (5) adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, Het acid, nadic acid, maleic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, butanetetracarboxylic acid, benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexene- Epoxy resin produced by a known production method from polyvalent carboxylic acids such as 1,2-dicarboxylic acid,

(6) A compound having an active hydrogen group such as a hydroxy group, an amino group and an amide group and a polyisocyanate having two or more functional groups (for example, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexa). Methylene diisocyanate, isophorone diisocyanate,
Urethane-based epoxy resin produced from xylylene diisocyanate, naphthalene diisocyanate, etc.) and glycidol or 3-hydroxypropylene sulfide,
(7) 3,4-Epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) dichlorohexane-meta -Alicyclic epoxy resins such as dioxane and bis (3,4-epoxycyclohexyl) adipate,
(8) Other epoxy resins include trisepoxy isocyanurate, glycidyl (meth) acrylate copolymer, 1,2-propylene sulfide (meth) acrylate copolymer, and further the above-mentioned epoxy polyisocyanate, dicarboxylic acid, and polycarboxylic acid. Examples thereof include modified resins with dihydric phenol and the like.

Among the materials for the sulfur-containing lens used in the present invention, the raw material monomer for the polythio (meth) acrylate resin is the polythiol or hydroxy group among the compounds listed above as the raw material for the sulfur-containing urethane resin. An acrylic ester or a methacrylic ester of a mercapto compound having Furthermore, among the materials for the sulfur-containing lens used in the present invention, as the raw material monomer for the sulfur-containing poly (meth) acrylate resin, among the compounds listed above as the raw material for the sulfur-containing urethane-based resin, a polythiol having a sulfur atom is used. Acrylic ester or methacrylic ester of Any plastic lens made of these resins has a refractive index of 1.5.
It is a high refractive index plastic lens of 0 or more.

The sulfur-containing plastic lens of the present invention is
Usually obtained by cast polymerization. Specifically, the monomer mixture is thoroughly mixed with the above-mentioned compound used in the present invention, and if necessary, this mixture is defoamed by an appropriate method, then poured into a mold and heated. Polymerize. At this time, in order to facilitate the mold release after the polymerization, the mold may be subjected to a known mold release treatment. Further, a known catalyst may be appropriately added to adjust the reaction rate to a desired value. The polymerization temperature and the polymerization time are appropriately determined depending on the combination of the monomers used and the type of the compound to be added, and the polymerization can be carried out at 20 to 200 ° C. for 0.5 to 100 hours.

When the sulfur-containing plastic lens of the present invention is, for example, a plastic lens composed of a sulfur-containing urethane resin, when the compound used in the present invention is a compound having active hydrogen, it is previously reacted with an isocyanate compound. You can also leave it. Further, if necessary, as in the known molding method, an internal release agent, a chain extender, a cross-linking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye,
Various substances such as fillers may be added. In addition, the sulfur-containing plastic lens of the present invention is surface-polished in order to improve antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, fashionability, etc., if necessary. A physical or chemical treatment such as an antistatic treatment, a hard coat treatment, a non-reflective coat treatment, a dyeing treatment and a light control treatment can be applied.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 46.5 parts by weight of m-xylylene diisocyanate, pentaerythritol tetrakis (thioglycolate) 5
After thoroughly mixing 3.5 parts by weight, 0.1% by weight of dibutyltin dilaurate and 0.1% by weight of ethyl caproate and thoroughly defoaming, this mixture was poured into a mold that had been subjected to a mold release treatment. .. Initially, heat at 50 ° C for 5 hours, then 90 ° C for 5 hours, 100 ° C for 5 hours, 120 ° C for 5 hours.
Polymerization was carried out by heating for an hour. After the completion of polymerization, gradually cool,
The polymer was removed from the mold. The obtained lens is
It was colorless and transparent, and no odor was felt even when it was brought close to the nose. When this was cut and polished with an edger for processing spectacle lenses, the bad odor peculiar to sulfur originally possessed was almost disappeared, and the operator did not feel any discomfort.

Example 2 A lens was obtained in the same manner as in Example 1 except that 0.1% by weight of isopropyl caproate was used instead of ethyl caproate. The obtained lens is used in Example 1.
As a result of cutting and polishing in the same manner as above, the malodor inherent to sulfur, which was originally possessed, was almost eliminated, and the worker did not feel any discomfort.

Example 3 In Example 1, instead of ethyl caproate,
Using 0.01% by weight of tert-butyl-2,4,6-trinitro-m-xylene in the same manner as in Example 1,
Got the lens. When the obtained lens was cut and polished in the same manner as in Example 1, the inherent malodor of sulfur originally possessed was
Almost disappeared, and the worker did not feel any discomfort.

Comparative Example 1 Instead of the ethyl caproate used in Example 1, 1-bornyl acetate, which is the aroma imparting compound disclosed in Japanese Patent Publication No. 256641, was used. Similarly, a lens was obtained. When the obtained lens was cut and polished in the same manner as in Example 1, a bad odor peculiar to sulfur was strongly generated, and the operator felt a strong discomfort. Comparative Example 2 A lens was obtained in the same manner as in Example 1 without using ethyl caproate. When the obtained lens was cut and polished in the same manner as in Example 1, a bad odor peculiar to sulfur was strongly generated, and the operator felt a strong discomfort.

[0035]

The sulfur-containing plastic lens of the present invention is
Little or no offensive odor peculiar to sulfur is generated at the time of processing such as cutting or polishing a sulfur-containing lens. Therefore, it is possible to process the sulfur-containing lens without the operator feeling uncomfortable, and since there is no odor at the time of normal wearing of the eyeglass lens, it can be handled in the same manner as the conventional product. ..

Claims (4)

[Claims] 1. A high-refractive-index sulfur-containing plastic lens having a cross-linking structure with a refractive index of 1.50 or more, wherein methyl caproate, vinyl caproate, ethyl caproate, isopropyl caproate or 5-tert-butyl- is used.
A sulfur-containing plastic lens comprising 0.005 to 0.5% by weight of at least one compound selected from 2,4,6-trinitro-m-xylene. 2. In the manufacture of a high refractive index sulfur-containing plastic lens having a crosslinked structure having a refractive index of 1.50 or more,
To the monomer mixture, methyl caproate, vinyl caproate, ethyl caproate, isopropyl caproate or 5-tert-butyl-2,4,6-trinitro-m-
At least one compound selected from xylene is used as
A method for producing a sulfur-containing plastic lens, which comprises adding 005 to 0.5% by weight and polymerizing by heating. 3. The sulfur-containing plastic lens according to claim 1, wherein the sulfur-containing plastic lens is a plastic lens made of a sulfur-containing urethane resin. 4. The method for producing a sulfur-containing plastic lens according to claim 2, wherein the monomer mixture is a monomer mixture composed of a bifunctional or higher functional polyisocyanate compound and a bifunctional or higher functional polythiol compound.