JPH0912663A - Photopolymerized urethane-containing plastic lens - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a sulfur-containing urethane resin composition and a plastic lens. [Structure] A polyiso (thio) cyanate compound, a polythiol compound and a compound containing two or more reactive unsaturated groups, and the molar ratio of [-SH group / (-NCO group + -NCS group)] is 1.16 or more. A sulfur-containing urethane resin composition which gives a resin having a refractive index of 1.59 or more and having a compound having a reactive unsaturated group of 3.00 or less and 10 to 50% by weight of the total amount, and reacting the composition. A resin thus obtained and a plastic lens made of the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin plastic lens having good optical properties required for various optical lenses such as spectacle lenses and excellent impact resistance, heat resistance and scratch resistance. And a method for producing the lens by short-time polymerization using photopolymerization.

[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.

As a resin widely used for these purposes at present, 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 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 as small as nd = 1.50 as compared with an inorganic lens (nd = 1.52), and in order to obtain the same optical characteristics as a glass lens,
It is necessary to increase the center thickness, the edge thickness, and the curvature of the lens, and it is inevitable that the lens becomes thick overall. Therefore, a plastic lens having excellent physical properties equivalent to that of a DAC resin and having a higher refractive index than an inorganic lens (nd = 1.52) has been desired.

Polyurethane type plastic lenses are known as lenses which satisfy this requirement. The inventors of the present invention have proposed, as the polyurethane lens, for example, in JP-A-63-46213, a polyurethane lens composed of a polymer of a xylylene diisocyanate compound and a polythiol compound. It is widely used as an optical lens.

However, these polyurethane lenses are generally used in order to obtain a lens having satisfactory optical distortion and striae when used as a plastic lens as compared with a radical polymerization type resin of an olefin group, for example, a DAC resin. Since long-term polymerization of 8 hours or more is required, its improvement has been desired. Further, since the surface of the obtained lens is soft and easily scratched, a protective coat was required on the surface of the lens.

Further, the inventors of the present invention disclosed in Japanese Patent Application Laid-Open No. 1-96208 that a polymer of a polyisocyanate compound, a polythiol compound and a compound containing a hydroxyl group or a mercapto group and an acrylic group, a methacryl group or a styryl group in one molecule. The following lens composition is proposed. However, when a resin was prepared using the composition described in the publication, optical inhomogeneity (stria) was likely to occur when polymerized at high speed.

Further, JP-A-5-025240 proposes a lens composition comprising a polymer of a polyisocyanate compound, a polythiol compound and a polyene compound. However, it is described in the publication that the amount of the polyene compound used is preferably 50% by weight or more, and if the amount of the polyene compound used is reduced, sufficient heat resistance and surface hardness cannot be obtained. However, in the range of use of the polyene compound described, the impact resistance was 32 g at most in an iron ball drop test from 127 cm, and it could not be said that the polyene compound had sufficient impact resistance. The obtained lens was also fragile. Further, the resin in the publication has a small refractive index and is only 1.588 at the maximum, and a lens having a higher refractive index has been desired.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polyiso (thio) cyanate compound, a polythiol compound,
To provide a sulfur-containing polyurethane lens that is composed of a compound containing two or more reactive unsaturated groups, is excellent in impact resistance, heat resistance, and scratch resistance, and can be polymerized in a short time by photopolymerization, and a method for producing the same. is there.

[0010]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that polyiso (thio)
In producing a sulfur-containing urethane plastic lens from a cyanate compound and a compound containing a thiol, 10 to 50% by weight of a compound containing two or more reactive unsaturated groups
By adding the [-SH group / (-NCO group + -NCS group)] ratio to 1.16 or more and 3.00 or less, excellent impact resistance, scratch resistance, and heat resistance are achieved, and excellent optical properties are obtained. The inventors have found that a sulfur-containing urethane-based plastic lens having physical properties can be produced in a short time, and arrived at the present invention.

That is, the present invention comprises a polyiso (thio) cyanate compound, a polythiol compound and a compound containing two or more reactive unsaturated groups, and [-SH group / (-NC
O group + -NCS group)] molar ratio is 1.16 or more and 3.00 or less, and the amount of the compound containing the reactive unsaturated group is 10% of the total amount.
A plastic lens obtained by polymerizing a sulfur-containing urethane resin composition that gives a resin having a refractive index of 1.59 or more in an amount of ˜50% by weight and a method for producing the lens.

Further, it comprises a polyiso (thio) cyanate compound, a polythiol compound and a compound containing two or more reactive unsaturated groups, and [-SH group / (-NCO group + -NC
S group)] The molar ratio is 1.16 or more and 3.00 or less, and the compound containing a reactive unsaturated group is 10 to 29% by weight of the total amount.
A plastic lens obtained by polymerizing the sulfur-containing urethane-based resin composition and a method for producing the lens.

Hereinafter, the present invention will be described in detail. The polyiso (thio) cyanate compound used in the present invention is a polyisocyanate compound or a polyisothiocyanate compound, and specifically, the following compounds are exemplified.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and 2,2. '-Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4 -Trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7- Trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω′-diisocyanate, lysine di Isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-
Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, 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, mesitylene triisocyanate Nart 2,
Aliphatic polyisocyanates such as 6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane Diisocyanate, 2,2 '
-Dimethyldicyclohexylmethane diisocyanate,
Bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate dimer, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-
Isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2
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) -6- (2-isocyanatoethyl) -bicyclo [2,2,1]- Heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatomethyl-2- (3- Isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) ) -Acycloaliphatic polyisocyanate such as bicyclo [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, methylnaphthalene diisocyanate,
Biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, dibenzyl-4,4′-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3 ′
-Dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6. 4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ',
4 ', 6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthylenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, Diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3
-Aromatic polyisocyanates such as propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, thiodiethyl Diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, dicyclohexyl sulfide-4,4'- Sulfur-containing aliphatic isocyanate such as diisocyanate, diphenyl sulfide-2,
4'-diisocyanate, diphenyl sulfide-4,
4'-diisocyanate, 3,3'-dimethoxy-4,
4'-diisocyanato dibenzyl thioether, bis (4-isocyanatomethylbenzene) sulfide, 4,
4'-methoxybenzenethioethylene glycol-3,
Aromatic sulfide-based isocyanates such as 3′-diisocyanate, diphenyldisulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyldisulfide-5,5′-diisocyanate, 3,3′- Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,
6'-diisocyanate, 4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,
3'-dimethoxydiphenyldisulfide-4,4'-
Aromatic disulfide-based isocyanates such as diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate, diphenylsulfone-
4,4'-diisocyanate, diphenyl sulfone-
3,3'-diisocyanate, benzidine sulfone-
4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethanesulfone-2,4'-diisocyanate, 4,
4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-di Isocyanate,
4,4'-di-tert-butyldiphenylsulfone-
3,3′-diisocyanate, 4,4′-methoxybenzeneethylenedisulfone-3,3′-diisocyanate, 4,4′-dichlorodiphenylsulfone-3,3 ′
-Aromatic sulfone type isocyanate such as diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester Sulfonate ester-based isocyanates such as 4-methyl-3-isocyanatobenzenesulfonylanilide-3′-methyl-4′-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4′-diisocyanate, 4,4 Aromatic sulfonic acid amides such as'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate, thiophene-2, 5
-Diisocyanate, thiophene-2,5-diisocyanatomethyl, 1,4-dithiane-2,5-diisocyanate, 4,5-bis (isocyanatomethyl) -1,3-
Dithiolane, bis (isocyanatomethyl) tetrahydrothiophene, 2,5-bis (isocyanatomethyl)-
Examples thereof include sulfur-containing heterocyclic compounds such as 1,4-dithiane.

Further, these chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds,
Nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, buret-modified products, dimerization or trimerization reaction products, and the like can also be used.

The polyisothiocyanate compound used in the present invention is a compound containing two or more -NCS groups in one molecule, and may further contain a sulfur atom in addition to the isothiocyanate group.

Specifically, for example, 1,2-diisothiocyanatopropane, 1,3-isothiocyanatopropane,
Aliphatic isothiocyanates such as 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylene diisopropylidene diisothiocyanate, and cycloaliphatic isothiocyanates such as cyclohexane diisothiocyanate Nato, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato -M-xylene, 4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylenebis (4-isothiocyanatobenzene), 1,1'-methylenebis (4-isothiocyanato-2-) Methylbenzene), 1,1′-methylenebis (4-isothiocyanato-3-methylbenzene),
1,1 ′-(1,2-ethanediyl) bis (4-isothiocyanatobenzene), 4,4′-diisothiocyanatobenzophenone, 4,4′-diisothiocyanato-3,
3'-dimethylbenzophenone, benzanilide-3,
4'-diisothiocyanate, diphenyl ether-
4,4'-diisothiocyanate, diphenylamine-
Aromatic isothiocyanates such as 4,4′-diisothiocyanate, 2,4,6-triisothiocyanato-1,
Heterocyclic ring-containing isothiocyanates such as 3,5-triazine, and further hexanedioyl diisothiocyanate,
Nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2′-bipyridine) -4,
Carbonyl isothiocyanates such as 4'-dicarbonyl diisothiocyanate can be mentioned.

Examples of the bifunctional or higher polyisothiocyanate having at least one sulfur atom in addition to the isothiocyanate group used as a raw material in the present invention include, for example, thiobis (3-isothiocyanatopropane) and thiobis. (2
-Isothiocyanatoethane), dithiobis (2-isothiocyanatoethane), and other sulfur-containing aliphatic isothiocyanates, 1-isothiocyanato-4-{(2-isothiocyanato) sulfonyl} benzene, thiobis (4-isothiocyanatobenzene) ), Sulfonylbis (4-isothiocyanatobenzene), sulfinylbis (4-isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato-1-{(4-isothiocyanatophenyl) sulfonyl. } -2-Methoxy-
Benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isothiocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, etc. Sulfurized aromatic isothiocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithiane-
Examples thereof include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate. Furthermore, chlorine substitution products of these polyisothiocyanates, halogen substitution products such as bromine substitution products, alkyl substitution products, alkoxy substitution products, nitro substitution products, prepolymer modified products with polyhydric alcohols, carbodiimide modified products, Urea modified products, buret modified products, dimerized or trimerized reaction products and the like can also be used. Examples of the isothiocyanate compound having an isocyanate group used as a raw material in the present invention include 1-isothiocyanato-3-isothiocyanatopropane and 1-isothiocyanatopropane.
Isothiocyanato-5-isothiocyanatopentane, 1
-Isothiocyanato-6-isothiocyanatohexane,
Isothiocyanatocarbonyl isothiocyanate, 1-
Aliphatic or alicyclic compounds such as isothiocyanato-4-isothiocyanatocyclohexane, 1-isothiocyanato-4-isothiocyanatobenzene, 4-methyl-
Aromatic compounds such as 3-isothiocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,5-diisocyanato-1,3,5-triazine, and further 4-isocyanato-4′-isothiocyanate Ocyanato diphenyl sulfide, 2-isocyanato-2'-
In addition to the isothiocyanato group such as isocyanatodiethyldisulfide, a compound containing a sulfur atom may be mentioned.

Further, halogen-substituted compounds such as chlorine-substituted compounds, bromine-substituted compounds, etc., alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer modified products with polyhydric alcohols, carbodiimide modified products, and urea modified products of these compounds. body,
Bullet modified products, dimerization or trimerization reaction products, and the like can also be used.

These polyisocyanate compounds may be used alone or in admixture of two or more.

Of these, considering the price and availability, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, α, α, α ',
α'-Tetramethylxylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and bis (isocyanatomethyl) cyclohexane are preferred. Especially xylylene diisocyanate or α, α, α ',
The use of α'-tetramethylxylylene diisocyanate is particularly preferable because a lens having a high refractive index can be obtained and there is little yellowing.

The polythiol compound used in the present invention may contain a hydroxyl group. For example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-
Propanedithiol, 2,2-propanedithiol,
1,6-hexanedithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane,
1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3
-Dithiol, 3,4-dimethoxybutane-1,2-dithiol, 3,6-dioxaoctane-1,8-dimercaptan, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] Hepta-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 '
-Mercaptoacetate), diethylene glycol bis (2'-mercaptoacetate), diethylene glycol bis (3'-mercaptopropionate), 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 tris (2'-mercaptoacetate), trimethylolpropane tris (3'-mercaptopropionate), pentaerythritol tetrakis (2'-mercaptoacetate), pentaerythritol tetrakis (3'-mercaptopropionate).
Such as aliphatic polythiol, 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 (2'-mercaptoethyl) benzene, 1,3-bis (2'-mercaptoethyl) benzene, 1,4-bis (2'-mercaptoethyl) benzene, 1,2-bis (mercaptomethyloxy) benzene, 1,3-bis (mercaptomethyloxy) benzene, 1,4-bis (mercaptomethyloxy) benzene, 1,2-bis (mercaptoethyloxy) benzene, 1,3-bis (mercaptoethyloxy) benzene, 1, 4-bis (mercaptoethyloxy) 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 (2'-mercaptoethyl) benzene,
1,2,4-tris (2′-mercaptoethyl) benzene, 1,3,5-tris (2′-mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyloxy) benzene, 1,2,2 4-tris (mercaptomethyloxy) benzene, 1,3,5-tris (mercaptomethyloxy) benzene, 1,2,3-tris (mercaptoethyloxy) benzene, 1,2,4-tris (mercaptoethyloxy) benzene Benzene, 1,3,5-tris (mercaptoethyloxy) benzene, 1,2,3,4
-Tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3, 5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2'-mercaptoethyl) benzene, 1,2,2
3,5-tetrakis (2'-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2'-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2'-
Mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyloxy) benzene, 1,2,
4,5-Tetrakis (mercaptomethyloxy) benzene, 1,2,3,4-tetrakis (mercaptoethyloxy) benzene, 1,2,3,5-tetrakis (mercaptoethyloxy) benzene, 1,2,4 5-tetrakis (mercaptoethyloxy) benzene, 2,2'-
Dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptodibenzyl, 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 (4'-methoxyphenyl) propane-
2,2-dithiol, 1,3-diphenylpropane-
Aromatic polythiols such as 2,2-dithiol, phenylmethane-1,1-dithiol and 2,4-di (4'-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3-dithiol, 1 , 3-di (4'-chlorophenyl) propane-2,2-dithiol, 3,4
5-tribromo-1,2-dimercaptobenzene, 2,
Halogen-substituted aromatic polythiols such as chlorine-substituted compounds such as 3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and bromine-substituted compounds, and 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-4,6-dithiol-sym-
A polythiol containing a heterocycle such as triazine, further 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 (2'-mercaptoethylthio) benzene, 1,
2,4-tris (2'-mercaptoethylthio) benzene, 1,3,5-tris (2'-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 (2'-mercaptoethylthio) benzene, 1,2,3,5-tetrakis (2'-mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2'-mercapto) Aromatic polythiols containing a sulfur atom in addition to the mercapto group such as ethylthio) benzene, bis (4-mercaptophenyl) sulfide, and their nuclear alkylated products, bis (mercaptomethyl)
Sulfide, bis (2'-mercaptoethyl) sulfide, bis (3'-mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2'-mercaptoethylthio) methane, bis (3'-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2'-mercaptoethylthio)
Ethane, 1,2- (3'-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane,
1,3-bis (2'-mercaptoethylthio) propane, 1,3-bis (3'-mercaptopropylthio) propane, 1,2-bis (2'-mercaptoethylthio)
-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 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 (2 '-Mercaptoethyl) disulfide, bis (3'
-Mercaptopropyl) disulfide and the like, and esters of these thioglycolic acid and mercaptopropionic acid, hydroxymethylsulfide-bis (2'-mercaptoacetate), hydroxymethylsulfide-bis (3'-mercaptopropionate), hydroxyethyl Sulfide-bis (2'-mercaptoacetate),
Hydroxyethylsulfide-bis (3'-mercaptopropionate), hydroxypropylsulfide-bis (2'-mercaptoacetate), hydroxypropylsulfide-bis (3'-mercaptopropionate), hydroxymethyldisulfide-bis (2 '-Mercaptoacetate), hydroxymethyldisulfide-bis (3'-mercaptopropionate), hydroxyethyldisulfide-bis (2'-mercaptoacetate), hydroxyethyldisulfide-bis (3'-
Mercaptopropionate), hydroxypropyldisulfide-bis (2'-mercaptoacetate), hydroxypropyldisulfide-bis (3'-mercaptopropionate), 2-mercaptoethylether-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), thioglycolic 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), dithioglycolic acid- Aliphatic polythiols containing sulfur atoms in addition to mercapto groups such as bis (2 ', 3'-dimercaptopropyl ester) and dithiodipropionic acid (2', 3'-dimercaptopropyl ester), 3,4-thiophene Dithiol,
2,5-bis (mercaptomethyl) tetrahydrothiophene, bis (mercaptomethyl) -1,3-dithiolane, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane, 2,5
Examples include heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as -dimercaptomethyl-1,4-dithiane. Examples of the polythiol compound containing a hydroxyl group include thioglycerol and 2,3-dihydroxy-
1-mercaptobutane, 2,3-dihydroxy-1-mercaptopentane, 3,4-dihydroxy-1-mercaptobutane, 3,4-dihydroxy-1-mercaptopentane, 3,4-dihydroxy-1-mercaptohexane, etc. Mercaptodiol compound, 2-hydroxy-
1,3-dimercaptopropane, 1-hydroxy-2,
3-dimercaptopropane, 2-hydroxy-1,3-
Dimercaptobutane, 1-hydroxy-2,3-dimercaptobutane, 2-hydroxy-1,3-dimercaptopentane, 2-hydroxy-1,3-dimercaptohexane, 3-hydroxy-1,4-dimercapto butane,
3-hydroxy-1,4-dimercaptopentane, 3-
Examples thereof include dimercapto alcohol compounds such as hydroxy-1,4-dimercaptohexane.

Considering the ease of handling of the monomer, the high refractive index of the lens obtained by polymerization, and the heat resistance among these,
2,3-dimercapto-1-propanol (2'-mercaptoacetate), 2,3-dimercapto-1-propanol (3'-mercaptopropionate), ethylene glycol bis (2'-mercaptoacetate), ethylene glycol bis (3′-mercaptopropionate), trimethylolpropane tris (2′-mercaptoacetate), trimethylolpropane tris (3 ′)
-Mercaptopropionate), pentaerythritol tetrakis (2'-mercaptoacetate), pentaerythritol tetrakis (3'-mercaptopropionate), 1,3-bis (mercaptomethyl) benzene,
1,4-bis (mercaptomethyl) benzene, 1,3-
Bis (2'-mercaptoethyl) benzene, 1,4-bis (2'-mercaptoethyl) benzene, 1,3,5-
Tris (mercaptomethyl) benzene, 1,3,5-tris (2′-mercaptoethyl) benzene, bis (mercaptomethyl) sulfide, bis (2′-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2,5 -Dimercapto-1,4-dithiane, 2,
5-dimercaptomethyl-1,4-dithiane is preferred.

The compound containing two or more reactive unsaturated groups used in the present invention is a compound having two or more reactive unsaturated groups such as an acryl group, a methacryl group, a vinyl group and an allyl group. The compounds containing the same reactive unsaturated group or the compounds containing different reactive unsaturated groups may be used.

Specifically, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4
-Butanediol acrylate, 1,3-butylene glycol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate,
1,6-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, decanediol diacrylate,
Tetradecanediol diacrylate, pentadecanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene Glycol diacrylate, bis (acryloxy neopentyl glycol) adipate, hydroxypivalate neopentyl glycol diacrylate, glycerin triacrylate, methacryloyl glycerin diacrylate, diethylene glycol bis (hydroxypropyl acrylate), trimethylolpropane triacryl , Ethoxylated trimethylolpropane triacrylate, hydroxypropylated trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, stearic acid modified Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, alkylated dipentaerythritol pentaacrylate, dialkylated dipentaerythritol tetraacrylate, trialkylated dipentaerythritol triacrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol Li hexaacrylate, dicyclopentanyl diacrylate, dicyclopentanyl oxyethyl diacrylate,
Dicyclopentanyl methyl diacrylate, ethoxylated hydrogenated bisphenol A diacrylate, allyl acrylate, acryloxytriethylene glycol vinyl ether, allylated cyclohexyl diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, Tris (Acryloxyethyl) isocyanurate, bis (acryloxyethyl) alkoxyethyl isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, bisphenol A diacrylate, bisphenol F diacrylate, bisphenol S diacrylate, tetrabromobisphenol A di Acrylate, tetrabromobisphenol F diacrylate, tetrabromobi Phenol S diacrylate,
Ethoxylated bisphenol A diacrylate, ethoxylated bisphenol F diacrylate, ethoxylated bisphenol S diacrylate, ethoxylated tetrabromobisphenol A diacrylate, ethoxylated tetrabromobisphenol F diacrylate, ethoxylated tetrabromobisphenol S diacrylate, propoxylated Such as bisphenol A diacrylate, propoxylated bisphenol F diacrylate, propoxylated bisphenol S diacrylate, propoxylated bisphenol A bis (hydroxypropyl acrylate), tris (acryloxyethoxy) phosphine oxide, tris (acryloxyethoxybutoxy) phosphine oxide Acrylic esters, ethylene glycol dimethacrylate, propylene Glycol dimethacrylate,
1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,5-pentanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,7-heptanediol dimethacrylate ,
1,8-octanediol dimethacrylate, decanediol dimethacrylate, tetradecanediol dimethacrylate, pentadecanediol dimethacrylate,
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate,
Tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, bis (methacryloxy neopentyl glycol) adipate, hydroxypivalate neopentyl glycol dimethacrylate, glycerin trimethacrylate, diethylene glycol bis (hydroxypropyl methacrylate), tri Methylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, hydroxypropylated trimethylolpropane trimethacrylate, ethylene oxide modified trimethylolpropane trimethacrylate, propylene oxide modified trimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate , Pentaerythritol tetramethacrylate, stearic acid modified pentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, alkylated dipentaerythritol pentamethacrylate, dialkylated dipentaerythritol tetra-methacrylate, trialkylated dipentaerythritol trimethacrylate, caprolactone modified dimethacrylate Pentaerythritol hexamethacrylate, caprolactone modified dipentaerythritol hexamethacrylate, dicyclopentanyl dimethacrylate, dicyclopentanyloxyethyl dimethacrylate, dicyclopentanylmethyl dimethacrylate, ethoxylated hydrogenated bisphenol A dimethacrylate, allyl methacrylate, methacrylic acid Roxytriethylene glyco Vinyl ether, allylated cyclohexyl dimethacrylate, methoxylated cyclohexyl dimethacrylate, neopentyl glycol modified trimethylolpropane dimethacrylate, tris (methacryloxyethyl) isocyanurate, bis (methacryloxyethyl) alkoxyethyl isocyanurate, caprolactone modified tris (methacryl Roxyethyl) isocyanurate, bisphenol A dimethacrylate, bisphenol F dimethacrylate,
Bisphenol S dimethacrylate, tetrabromobisphenol A dimethacrylate, tetrabromobisphenol F dimethacrylate, tetrabromobisphenol S dimethacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol F dimethacrylate, ethoxylated bisphenol S dimethacrylate, ethoxylated tetra Bromobisphenol A dimethacrylate, ethoxylated tetrabromobisphenol F dimethacrylate, ethoxylated tetrabromobisphenol S dimethacrylate, propoxylated bisphenol A
Methacrylic acid such as dimethacrylate, propoxylated bisphenol F dimethacrylate, propoxylated bisphenol S dimethacrylate, propoxylated bisphenol A bis (hydroxypropyl methacrylate), tris (methacryloxyethoxy) phosphine oxide, tris (methacryloxyethoxybutoxy) phosphine oxide Examples thereof include vinyl compounds such as esters, divinylbenzene, trivinylbenzene, divinylcyclohexane, trivinylcyclohexane, vinylcyclohexene and divinyl ether, and allyl compounds such as diallyl phthalate, diallyl isophthalate, diallyl ether and diallyl sulfide.

The compounds having these reactive unsaturated groups are
Each may be used alone, or two or more kinds may be mixed and used.

A compound having a monofunctional reactive unsaturated group may be added to the above monomer mixture for the purpose of modifying the resin.

The plastic lens according to the present invention is made of a urethane resin, a sulfide resin and a polyvinyl resin, that is, a thiourethane bond by an iso (thio) cyanato group and a mercapto group, and a reactivity with the mercapto group. Mainly consists of a sulfide bond due to an unsaturated group and a polyvinyl bond due to a reactive unsaturated group, but depending on the purpose, it may of course contain an alohanate bond, a urea bond, a thiourea bond, a buret bond, etc. . Alternatively, a urea bond or a biuret bond may be used by partially using an amine or the like. When using a compound other than the active hydrogen compound that reacts with the iso (thio) cyanate compound, it is necessary to pay particular attention to the coloring point.

If the compounding ratio of the polyiso (thio) cyanate compound and the polythiol compound is [-SH group / (-NCO group + -NCS group)] ratio is less than 1.16, the obtained lens is colored yellow. Cheap. On the other hand, [-SH group / (-
NCO group + -NCS group)] ratio is 1.16 or more and 3.00 or less, the obtained lens is not only colorless and transparent, but also has high impact resistance.

However, the mixing ratio of the isocyanate compound, the thiol compound and the compound having a reactive unsaturated group is such that the functional group molar ratio is [[(-NCO group + -NCS group) + (unsaturated group)] / (-SH group + -OH group)} and 1.0 or more and 3.0
The following is preferred. If it is less than 1.0, unreacted thiol groups remain, and the heat resistance of the resin decreases as the molar ratio decreases. If it exceeds 3.0, the impact resistance decreases.

Depending on the purpose, various kinds of internal release agents, chain extenders, cross-linking agents, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, etc. can be used in the same manner as in known molding methods. The substance may be added.

In order to adjust the reaction rate to a desired value, a known urethane reaction catalyst or radical polymerization catalyst may be added as appropriate.

The lens of the present invention is usually obtained by cast polymerization. Specifically, a polyiso (thio) cyanate compound, a polythiol compound, and a compound having a reactive unsaturated group are mixed, the mixture is defoamed by an appropriate method as needed, and then a photopolymerization catalyst is added. , Degassing with further stirring,
It is injected into a mold, irradiated with ultraviolet rays or visible rays to undergo photopolymerization, and then polymerized at a temperature from room temperature to about 180 ° C. At this time, a known release treatment may be applied to the mold in order to facilitate the release property after the polymerization.

This photopolymerization can be polymerized by light using a high-pressure mercury lamp, a low-pressure mercury lamp, a halogen lamp, a xenon lamp, a tungsten lamp, a fluorescent lamp, or sunlight as a light source, like the conventional photopolymerizable material.

At this time, a polymerization initiator is used if necessary, but the polymerization catalyst is not particularly limited, and a known radical generator or a photosensitizer which generates a radical upon irradiation with light is used.

Further, by cooling and removing heat during photopolymerization, a lens having no optical distortion or striae can be obtained.

The urethane resin according to the present invention thus obtained is colorless and transparent, and has the characteristics of high refractive index and low dispersion, and is used as a material for optical elements such as eyeglass lenses and camera lenses, and a glazing material. It is suitable as a material for paints and adhesives. In addition, the lens made of the urethane resin according to the present invention may be improved in antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, or fashionability as required. Therefore, physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, light control treatment can be applied.

[0038]

The present invention will be described below in more detail with reference to examples and comparative examples. Refractive index of the obtained lens, Abbe number,
The heat resistance and appearance were evaluated by the following test methods. Refractive index, Abbe number: 20 ° C. using a Pulfrich refractometer
Was measured. Appearance: Visual observation. Dyeability: MLP-Yellow 2, M which is a disperse dye for plastic lenses manufactured by Mitsui Toatsu Dye Co., Ltd.
5 g / each using LP-Red2 and MLP-Blue2
A plate having a thickness of 9 mm was immersed for 5 minutes in a 90 ° C. dyeing bath adjusted to an aqueous solution of 1 l, and then the dyeability of the lens was visually observed. Dyeing heat resistance: A flat plate having a thickness of 1.2 mm was immersed in a dyeing bath at 90 ° C. for 5 minutes, and then it was visually observed whether or not the lens was deformed. Scratch resistance: No. Using 00 steel wool, the manner of scratching when worn was visually observed. Impact resistance: Drop an iron ball from a height of 127 cm into a minus lens with a center thickness of 1.5 mm, and divide it with 114 g for those that will not break ◎, 67 g for those that will not break, for 36 g that will not break with Δ, and divide by 36 g The thing was expressed by x.

Example 1 m-xylylene diisocyanate (hereinafter abbreviated as XDI)
31.3 parts, pentaerythritol tetrakis (3-mercaptopropionate) (hereinafter abbreviated as PEMP) 4
8.7 parts of 2,2-bis [4- (acryloxyethoxy) phenyl] propane (hereinafter abbreviated as BisAE2PP) 20.0 parts and dibutyltin dichloride 0.02% by weight (based on the entire mixture) were mixed. After forming a uniform solution and sufficiently defoaming, 0.5 part of Darocurure 1173 (manufactured by Ciba Geigy) was added in a dark room, further stirred, and poured into a mold made of a mold-treated glass mold and a gasket. Then, light was irradiated for 15 minutes using a high-pressure mercury lamp, and further heated and cured in an oven at 120 ° C. for 2 hours. After completion of the polymerization, the lens was cooled and the lens was taken out of the mold. At this time, the ratio of -SH group / -NCO group was 1.2. The obtained plastic lens was colorless and transparent, had almost no optical distortion or striae, and had a refractive index nd = 1.590 and an Abbe number νd = 39. When dyed in a dyeing bath at 90 ° C., the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. In the iron ball drop test, it did not crack even at 114 g.

Example 2 As in Example 1, 31.8 parts of XDI, 48.2 parts of pentaerythritol tetrakis (thioglyconate) (hereinafter abbreviated as PETG) and trimethylolpropane trimethacrylate (hereinafter abbreviated as TMPTMA) 20.0. Parts and 0.02% by weight dibutyltin dichloride (based on the total mixture) and 0.5 part Darocurure 1173 to make a lens. At this time, the ratio of -SH group / -NCO group was 1.2. The obtained plastic lens is colorless and transparent, has almost no optical distortion or striae, and has a refractive index nd.
= 1.590 and Abbe number νd = 38. Again 90
When dyed in a dyeing bath at ℃, the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. In the iron ball drop test, it did not crack even at 114 g.

Example 3 As in Example 1, 39.1 parts of XDI, 47.9 parts of trimethylolpropane tris (thioglyconate) (hereinafter abbreviated as TMPTG), 13.0 parts of BisAE2PP and 0.02% by weight of dibutyltin dichloride. A lens was made using (relative to the entire mixture) and 0.5 part of Darocur 1173. At this time, the ratio of -SH group / -NCO group was 1.2. The obtained plastic lens is colorless and transparent, has almost no optical distortion or striae, and has a refractive index nd.
= 1.592 and Abbe number νd = 39. Again 90
When dyed in a dyeing bath at ℃, the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. In the iron ball drop test, it did not crack even at 114 g.

Examples 4 to 20 Lenses were prepared in the same manner as in Example 1 except that the monomer was changed, and the optical properties, dyeability, heat resistance and impact resistance of the obtained lenses were measured. The results are shown in Table 1.

Comparative Example 1 A lens was prepared in the same manner as in Example 1 except that 52.0 parts of XDI, 48.0 parts of GST and 0.02% by weight of butyltin dichloride (based on the entire mixture) were used. At this time, in order to obtain a lens with no optical distortion or striae, the temperature should be 20 to 120 ° C.
It was necessary to raise the temperature over 10 hours. The obtained plastic lens is colorless and transparent, has almost no optical distortion or striae, and has a refractive index nd = 1.660 and an Abbe number νd.
= 33. When dyed in a 90 ° C. dyeing bath, the dyeability was good, but the lens was deformed. Further, in the iron ball drop test, it did not break even at 114 g, but it was greatly scratched when worn with steel wool.

Comparative Example 2 Similarly, 17.0 parts of XDI, 23.0 parts of PEMP and UM
(Urethane dimethacrylate obtained by reacting 2,6-tolylene diisocyanate with 2-hydroxypropyl methacrylate) 40.0 parts, phenyl methacrylate 20.0 parts and tributyltin chloride 0.05 parts. After mixing to make a uniform solution and thoroughly defoaming it, leave it in the dark room for 2, 4, 6
-Trimethylbenzoyldiphenylphosphine oxide (0.1 part) and 2-hydroxybenzophenone (0.1 part) were added, and the mixture was further stirred and poured into a mold made of a glass mold and a gasket which were subjected to a mold release treatment. Then
Irradiate light for 15 minutes using a high pressure mercury lamp, and
It was heat-cured in an oven at 0 ° C. for 2 hours. After completion of the polymerization, the lens was cooled and the lens was taken out of the mold.
The ratio of -SH group / -NCO group at this time was 1.05. The obtained plastic lens is colorless and transparent, has almost no optical distortion or striae, and has a refractive index nd = 1.58.
7. Abbe number νd = 40. When dyed in a dyeing bath at 90 ° C., the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. However, in the iron ball drop test, it cracked at 36 g.

Comparative Example 3 As in Comparative Example 2, 20.0 parts of XDI and 30.0% of PEMP were used.
Parts and UM 35.0 parts, phenyl methacrylate 15.0
Part, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.1 part), and 2-hydroxybenzophenone (0.1 part) were used to prepare a lens. At this time
The ratio of SH group / -NCO group was 0.94. The obtained plastic lens is colorless and transparent, has almost no optical distortion or striae, and has a refractive index nd = 1.588 and an Abbe number ν.
It was d = 40. When dyeing in a 90 ° C dyeing bath,
The dyeability was good and the lens did not deform. Also, it was not scratched when worn with steel wool. However, in the iron ball drop test, it cracked at 36 g.

Comparative Example 4 As in Example 1, 32.1 parts of XDI and 47.9 of PEMP were used.
Parts, 200 parts BisAE2PP, 0.02 wt% dibutyltin dichloride (based on the total mixture) and 0.5 part Darocurure 1173 were used to make lenses. At this time, the SH / NCO ratio was 1.15. The obtained plastic lens had almost no optical distortion or striae, a refractive index nd = 1.590 and an Abbe number νd = 39, but was colored yellow. When dyed in a dyeing bath at 90 ° C., the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. However, in the iron ball drop test, it cracked at 67 g.

Comparative Example 5 As in Example 1, 36.8 parts of XDI and 43.2 of PETG were used.
Parts, TMPTMA 20.0 parts, dibutyltin dichloride 0.02% by weight (based on the total mixture) and Darocurure 1173 0.5 parts were used to make lenses. At this time, the ratio of -SH group / -NCO group was 1.15. The obtained plastic lens had almost no optical distortion or striae, a refractive index nd = 1.599 and an Abbe number νd = 38, but was colored yellow. When dyed in a dyeing bath at 90 ° C., the dyeability was good and the lens was not deformed. Also, it was not scratched when worn with steel wool. However, in the iron ball drop test, it cracked at 67 g.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

EGDMA; ethylene glycol dimethacrylate BisME4PP; 2,2-bis (methacryloxyethoxyethoxyphenyl) propane TG; thioglycerin IPDI; isophorone diisocyanate GDTG; glycerin bis (thioglycolate) TEGDMA; triethylene glycol dimethacrylate DCPDA; dicyclopentanyl diacrylate TMPTG; trimethylolpropane tris (thioglycolate) PET; pentaerythrithiol DTG; dithioglycerin TTG; trithioglycerin DPHA; dipentalerythritol hexaacrylate DPMAPA; dipentaerythritol monoalkyl Pentaacrylate

[0052]

As is apparent from the examples, the urethane resin type plastic lens according to the present invention has good optical properties and excellent impact resistance, heat resistance and scratch resistance, and is photopolymerized. Therefore, it can be polymerized in a short time, and is suitable as a material for optical elements such as spectacle lenses and camera lenses, glazing materials, paints, and adhesives.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Teruyuki Nagata 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (8)

[Claims] 1. A composition comprising a polyiso (thio) cyanate compound, a polythiol compound and a compound containing two or more reactive unsaturated groups, wherein [-SH group / (-NCO group + -NCS
Group)] The molar ratio is 1.16 or more and 3.00 or less, and the compound containing the reactive unsaturated group is 10 to 50% by weight of the total amount.
And a sulfur-containing urethane resin composition that gives a resin having a refractive index of 1.59 or more. 2. A compound comprising a polyiso (thio) cyanate compound, a polythiol compound and two or more reactive unsaturated groups, wherein [-SH group / (-NCO group + -NCS
Group)] A sulfur-containing urethane resin composition having a molar ratio of 1.16 to 3 and a compound containing a reactive unsaturated group of 10 to 29% by weight based on the total amount. 3. A resin obtained by polymerizing the resin composition according to claim 1. 4. A resin obtained by polymerizing the resin composition according to claim 2. 5. A plastic lens made of the resin according to claim 3. 6. A plastic lens made of the resin according to claim 4. 7. A method for producing a plastic lens, which comprises polymerizing the resin composition according to claim 1 by photopolymerization and / or thermal polymerization. 8. A method for producing a plastic lens, which comprises polymerizing the resin composition according to claim 2 by photopolymerization and / or thermal polymerization.