JP3222182B2 - Plastic lens made of resin with improved hue, total light transmittance and optical distortion of urethane resin for optical use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin obtained by reacting an isocyanate compound with an active hydrogen compound, and more particularly to a urethane resin for optical use having little coloring, high total light transmittance and no optical distortion. The present invention relates to a plastic lens that requires high colorless and transparent homogeneity.

[0002]

2. Description of the Related Art The present applicant has already filed a number of applications concerning a resin for a plastic lens obtained by reacting an isocyanate compound with an active hydrogen compound, a lens made of the resin, and a method for producing the lens. 1-295
201, 1-302202, 2-153302, 2-295202, 2-802, 2-167330
However, the isocyanate compound used in the present invention has a drawback that it is unstable due to the high reactivity of the isocyanate group, and is liable to cause coloration or cloudiness due to self-polymerization. Therefore, the addition of a stabilizer that suppresses coloring and polymerization has been indispensable.

[0003] Various compounds are already known as stabilizers for isocyanate compounds.
2,6-Ditert-butyl-p-cresol (USP 3,
And phosphites such as triphenyl phosphite (JP-B-45-33438).

In addition, ureas, carbamates, acid amides (Japanese Patent Publication No. 45-7044, Japanese Patent Application Laid-Open No. Sho 50-365)
46), acidic substances such as perchloric acid and trifluoromethanesulfonic acid (DEP. 2837770), carbon dioxide and sulfur dioxide (US Pat. No. 3,247,236), organic amines (JP-A-50-101344), acid chloride ( JP-A-63-179917), siloxane (BEP. 8)
58921), organotin compounds (EP 20387)
4), acyl isocyanate compounds (JP-B-48-38)
Numerous stabilizers such as 25) are known.

[0005]

However, the effect of the isocyanate compound stabilizer on the yellowness, total light transmittance and optical homogeneity of the urethane resin obtained by reacting the isocyanate compound with the active hydrogen compound is discussed. Was not recognized at all.

[0006] Coloring and polymerization of the isocyanate compound itself due to aging can be considerably suppressed by adding known stabilizers. However, even though the isocyanate compound itself was colorless and transparent, it was found that the yellowness and total light transmittance of the urethane resin obtained by reacting with the active hydrogen compound differed depending on the type of the stabilizer. It was also found that the stabilizer of the isocyanate compound affected the presence or absence of optical distortion of the obtained urethane resin. Therefore, particularly in the production of optical materials such as plastic lenses that require colorless, transparent, and homogeneity, the selection of an isocyanate compound stabilizer is a very important issue.

[0007]

Means for Solving the Problems The present inventors diligently studied a stabilizer of an isocyanate compound suitable for obtaining a colorless and transparent urethane resin for optical use having no optical distortion, and phenol was added as a stabilizer. It has been found that a urethane resin obtained by reacting an isocyanate compound with an active hydrogen compound has a low yellowness, a high total light transmittance, and no optical distortion, and has completed the present invention.

[0008]

That is , in the present invention, the phenol is 10 to 10
One or two selected from the group consisting of xylylene diisocyanate added at 5000 ppm and a polyol compound, a polythiol compound and a hydroxythiol compound
NCO / (OH + SH) with at least one kind of active hydrogen compound
The present invention relates to a plastic lens made of an optical urethane resin having improved hue, total light transmittance and optical distortion, which is obtained by reacting at a functional group molar ratio of 0.5 to 3.0.

Phenol is preferably added in an amount of 10 to 5000 ppm based on the isocyanate compound. If it is less than 10 ppm, the stability of the isocyanate compound itself is poor and the total light transmittance of the urethane resin is low. If it exceeds 5000 ppm, the isocyanate compound itself is not used. This tends to promote the coloring of the urethane resin and the coloring of the urethane resin, which is not preferred.

The isocyanate compound used in the present invention is selected from the group consisting of a polyisocyanate compound and an isocyanate compound having an isothiocyanate group.
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-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1, 8-diisocyanato-5-i Socyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butyleneglycol dipropylether-α, α'-diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate Nate, 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, mesitylylene triisocyanate, 2,6
-Di (isocyanatomethyl) furan, isophoronediisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethanediisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2 ' -Dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate diisocyanate, 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- [2,2,1] -heptane, 2,5 ( Or 6)
-Bis (isocyanatomethyl) -bicyclo [2,2,
1]-aliphatic polyisocyanates such as heptane, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate Notate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl Diphenylmethane-
4,4'-diisocyanate, bibenzyl-4,4'-
Diisocyanate, bis (isocyanatophenyl) ethylene, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, triphenylmethane triisocyanate, polymeric MDI (diphenylmethane diisocyanate), naphthalene triisocyanate, Diphenylmethane 2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ',
4 ', 6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthalenediisocyanate, 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, dibenzofurandi isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, and dichlorocarbazole diisocyanate. .

Examples of the polyisocyanate compound containing a sulfur atom include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, and dithiodimethyl diisocyanate. Sulfur-containing aliphatic isocyanates such as diethyl diisocyanate and dithiodipropyl diisocyanate, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy Aroma having a sulfide bond such as -4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3,3'-diisocyanate Tribe isocyanate Chromatography, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyl diphenyl 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-3,3'-diisocyanate Aromatic isocyanates having a disulfide bond, such as nathate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethane Sulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,4'-
Diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4'-dimethyldiphenylsulfone-3 , 3 '
-Diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-methoxyphenylethylene sulfone-3,
Aromatic isocyanate having a sulfone bond such as 3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3
Aromatic isocyanates having a sulfonic acid ester bond, such as -isocyanatophenylsulfonyl-4'-isocyanatophenol ester and 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methyl-3 -Isocyanatophenylsulfonylanilide-3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine-
4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3'-isocyanate Such as aromatic isocyanates having a sulfonic acid amide bond, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and 1,4-dithiane-2,5-diisocyanate.

Further, as the isocyanate compound having an isothiocyanato group, for example, 1-isocyanato-
3-isothiocyanatopropane, 1-isocyanato-
5-isothiocyanatopentane, 1-isocyanato-6
Aliphatic compounds such as -isothiocyanatohexane, isothiocyanatocarbonylisocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1- Aromatic compounds such as isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and 4-isocyanato-4′-isothiocyanatodiphenyl Sulfide, 2-isocyanato-2 '
And compounds containing a sulfur atom in addition to an isothiocyanato group such as -isothiocyanatodiethyl disulfide.

Further, halogen-substituted compounds such as chlorine-substituted and bromine-substituted products of these isocyanate compounds, furthermore, their buret-forming reaction products, adduct reaction products with trimethylolpropane, dimerization or trimerization reaction products Objects can also be used. These may be used alone or in combination of two or more.

The active hydrogen compound used in the present invention is selected from a polyol compound, a polythiol compound and a hydroxythiol compound. Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol,
Tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol,
Iditol, glycol, inositol, hexanetriol, triglycerose, diglyperol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, Cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,
0 ^2,6 ] decane-dimethanol, bicyclo [4,3
0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1] dodecane-diethanol, hydroxy Aliphatic polyols such as propyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol, cyclohexanetriol, maltitol and lactose , Dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol,
Biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) benzene,
Aromatic polyols such as bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis- (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, and epoxy resins Oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, A condensation reaction product of an organic acid such as bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, or bromophthalic acid with the polyol, and a mixture of the polyol with ethylene oxide or propylene oxide; Id and addition reaction products of an alkylene oxide, or alkylene polyamine with ethylene oxide, propylene oxide addition reaction products of an alkylene oxide, further, bis - [4- (hydroxyethoxy) phenyl] sulfide, bis - [4
-(2-hydroxypropoxy) phenyl] sulfide, bis- [4- (2,3-dihydroxypropoxy)
Phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis-
[2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and a compound in which ethylene oxide and / or propylene oxide having an average of 3 molecules or less per hydroxyl group are added to these compounds, di- (2-
Hydroxyethyl) sulfide, 1,2-bis- (2-
Hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,
5-diol, bis (2,3-dihydroxypropyl)
Sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (trade name: bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4′-
Examples thereof include polyols containing a sulfur atom such as thiobis (6-tert-butyl-3-methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Examples of the polythiol 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, bis (2-mercaptoethyl ester) thiomalate, 2,3-
Dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-
Mercapto acetate), 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),
Aliphatic polythiols such as 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 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, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercapto) Ethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, , 3,5-trimercaptobenzene, 1,2,2
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, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3 1,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3
4-tetrakis (mercaptoethyl) 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′-di Mercaptobibenzyl, 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
Anthracenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,
Aromatic polythiols such as 3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3 -Dithiol,
1,3-di (p-chlorophenyl) propane-2,2-
Dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4,6-tetrachloro-1,
A halogen-substituted aromatic polythiol such as a chlorine-substituted product such as 5-bis (mercaptomethyl) benzene and a bromine-substituted product;
Also, 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-
Polythiol containing a heterocycle such as dithiol-sym-triazine, furthermore, 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, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and the like, and the like. Aromatic polythiol containing a sulfur atom in addition to a mercapto group such as an alkylated nucleus, bis (mercaptomethyl) sulfide,
Bis (mercaptoethyl) sulfide, bis (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, 1,2,3-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 thioglycolic acid and mercapto thereof Esters of propionic acid, hydroxymethyl sulfide bis (2-
Mercapto acetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-
Mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyldisulfidebis (2-mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate) ), Hydroxyethyl disulfide bis (3-mercaptopropionate),
Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfidebis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-
Mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (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-thiodibutyl acid bis (2-mercapto Ethyl ester), bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptoethyl ester) dithiodipropionate, 4,4-
Bis (2-mercaptoethyl ester) dithiodibutyrate, bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3 thiodipropionate)
Aliphatic polythiol containing a sulfur atom in addition to a mercapto group such as dimercaptopropyl ester), bis (2,3-dimercaptopropyl ester) dithioglycolate, and dithiodipropionic acid (2,3-dimercaptopropyl ester) , 3,4-thiophenedithiol,
Heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole, and the like.

Examples of the hydroxy thiol compound include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, and 2,4-dimercapto. Phenol, 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), pentaerythritolbis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate) ), Hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-
Mercaptoethylthiobenzene, 4-hydroxy-4 '
-Mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyltris (mercaptoethylthio) methane, etc. Is mentioned.

Further, chlorine-substituted active hydrogen compounds and halogen-substituted bromine-substituted compounds may be used.
These may be used alone or in combination of two or more. The use ratio of these isocyanate compounds and active hydrogen compounds is (NCO + NCS)
/ (OH + SH) functional group molar ratio is usually 0.5 to 3.0
, Preferably in the range of 0.5 to 1.5.

Depending on the purpose, a known chain extender, crosslinking agent, light stabilizer, ultraviolet absorber, antioxidant, oil-soluble dye,
Various substances such as a filler and an internal release agent may be added.
In order to adjust the reaction rate, a known reaction catalyst used in the production of polyurethane can be appropriately added.

More specifically, the method for producing a plastic lens of the present invention preferably comprises one or more isocyanate compounds, one or more active hydrogen compounds, and if necessary, additives and catalysts. After mixing, the mixture is poured into a mold and polymerized. At this time, a defoaming operation is usually performed before injection to prevent foam from entering the resin.

The polymerization temperature and time vary depending on the type of monomer and additives, but are usually -50 ° C to 200 ° C.
Preferably from room temperature to 150 ° C, more preferably from 50 to 12
0 ° C. and the time is usually 0.5 to 72 hours.
The polymerized lens may be annealed as needed.

[0022]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. Examples 1 to 3 Various isocyanate compounds to which a phenol stabilizer shown in Table 1 was added and an active hydrogen compound were mixed, defoaming was performed under reduced pressure, and a 9 m-thick glass mold and gasket was formed.
m, poured into a 70 mm diameter mold, from room temperature to 12
The temperature was gradually increased to 0 ° C. and the mixture was cured in 48 hours. After polymerization, the mold was released from the mold, and the yellowness (6.3 of JIS-K-7105) and the total light transmittance (5.5 of JIS-K-7105) of the obtained 9 mm-thick plate resin were measured. . Further, the presence or absence of optical distortion was determined by the orthogonal Nicol method using a Toshiba strain tester (SVP-100). The results are shown in Table 1.

Comparative Examples 1 to 17 Using various isocyanate compounds to which known stabilizers other than phenol shown in Table 2 were added, the yellowness, the total light transmittance and the presence or absence of optical distortion of the plate resin were determined in the same manner as in the Examples. It was measured. The results are shown in Table 2. Examples 1-3 and Comparative Examples 1-1
As is clear from the comparison with 7, when phenol is used as the stabilizer for the isocyanate compound, the urethane resin obtained by reacting the isocyanate compound with the active hydrogen compound has excellent yellowness and total light transmittance. And no optical distortion was observed.

That is, phenol is used as a stabilizer in an amount of 10 to 5
The urethane resin of the present invention obtained by reacting an isocyanate compound added with 000 ppm and an active hydrogen compound is a conventional urethane resin obtained by reacting an isocyanate compound added with a stabilizer other than phenol with an active hydrogen compound. It is clear that it is superior in colorless transparency and has no optical distortion compared to urethane resin, and is useful as an optical material such as a plastic lens.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

According to the present invention, phenol is used as a stabilizer in an amount of 10 to 500.
An optical urethane resin obtained by reacting an isocyanate compound added with 0 ppm with an active hydrogen compound is excellent in colorless and transparent, has no optical distortion, and is useful as an optical material such as a plastic lens.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-167330 (JP, A) JP-A-52-76398 (JP, A) JP-B-41-14752 (JP, B1) US Patent 3,356,650 (US U.S. Pat. No. 3,137,381 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 G02B 1/04 G02C 7/02

Claims (1)

(57) [Claims] 1. An xylylene diisocyanate to which 10 to 5000 ppm of phenol is added, and one or more active hydrogen compounds selected from the group consisting of a polyol compound, a polythiol compound and a hydroxythiol compound, are mixed with NCO / ( OH + SH) functional group molar ratio 0.5
A plastic lens made of an urethane resin for optics having improved hue, total light transmittance and optical distortion, obtained by reacting at a ratio of up to 3.0.