JP3325561B2 - Method for improving 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 which is less colored, has a high total light transmittance and has no optical distortion. How to get.

[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.

[0007] Therefore, in the production of optical materials such as plastic lenses that require colorless, transparent, and homogenous properties, selection of a stabilizer for an isocyanate compound is a very important issue.

[0008]

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 phenols were added as a stabilizer. An isocyanate compound;
It has been found that a urethane resin obtained by reacting an active hydrogen compound has a small yellowness, a high total light transmittance, and no optical distortion, and has completed the present invention.

That is, the present invention relates to a polyisocyanate compound and one or more isocyanate compounds selected from the group consisting of isocyanate compounds having an isothiocyanate group, and a group consisting of a polyol compound, a polythiol compound and a hydroxythiol compound. In producing an optical urethane resin by reacting one or more selected active hydrogen compounds, (NCO + NC
S) / (OH + SH) functional group molar ratio of 0.5 to 3.0 and using an isocyanate compound to which phenol is added in an amount of 10 to 5000 ppm. A method for improving transmittance and optical distortion is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The phenols referred to in the present invention are compounds having a phenolic hydroxyl group. Specifically, phenol and cresol, ethylphenol, isopropylphenol, tert-butylphenol, hexylphenol, cyclohexylphenol, 2,2 6-di-tert-butyl-p-cresol, guaiacol,
Substituted phenols such as eugenol, catechol, resorcin, hydroquinone, tertiary butyl catechol,
Polyphenols such as pyrogallol, biphenols such as biphenol and dimethylbiphenol, bisphenols such as bisphenol A, bisphenol F, bisphenol S, methylene-bis (methyl-tert-butylphenol), and thio-bis (methyl-tert-butylphenol) And naphthols such as naphthol and dihydroxynaphthalene. Further, these fluorine, chlorine and bromine substituted products are also effective. Among these phenols, phenol is preferred, and a target substance having excellent yellowness and total light transmittance without optical distortion can be obtained.

These phenols are preferably added in an amount of 10 to 5000 ppm based on the isocyanate compound.
If the amount is less than ppm, the stability of the isocyanate compound itself is poor and the total light transmittance of the urethane resin is low, and the
If it exceeds pm, the coloring of the isocyanate compound itself and the coloring of the urethane resin tend to be accelerated, 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-diisocyanate 4-isocyanatomethyloctane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butyleneglycoldipropylether-α, α′-diisocyanate, lysinediamine Isocyanate methyl 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, mesylate Tyrylene triisocyanate,
2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate,
Cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,2'-dimethyl dicyclohexyl methane 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
Aliphatic polyisocyanates such as 2,1] -heptane, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate,
Diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine 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 (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'-di Isocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate,
Aromatic polyisocyanates such as diethylene glycol diphenyl ether diisocyanate, dibenzofurandi isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, and dichlorocarbazole diisocyanate are exemplified.

The polyisocyanate compound containing a sulfur atom includes, for example, thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, 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.

In addition, halogen-substituted compounds such as chlorine-substituted and bromine-substituted products of these isocyanate compounds, buret-forming reaction products thereof, 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,
0,6] 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 is 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, tetra Methyl bisphenol S, 4,
Examples thereof include a polyol containing a sulfur atom such as 4′-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 (mercaptoethyleneoxy) benzene 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,2
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, 1,2,3- 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, 1,2,2
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 1,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,2
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, , 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- Aromatic polythiols such as methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di (p-mercaptophenyl) pentane ,

Further, 2,5-dichlorobenzene-1,3
-Dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
Halogen-substituted aromatic polythiols such as chlorine-substituted products such as 1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene, and bromine-substituted products, and 2-methyl Amino-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-s
ym-triazine, 2-thiobenzeneoxy-4,6-
Heterocycle-containing polythiols such as dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine; furthermore, 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercapto) Methylthio) 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 (mercapto Ethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 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 aromatic polythiols containing a sulfur atom in addition to a mercapto group such as an alkylated product thereof;

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- (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, 1,2,2 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-mercaptopropylthio) Methyl) 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 sulfidebis (2-mercaptoacetate), hydroxyethyl sulfidebis (3-mercaptopropionate) , Hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfidebis (2-mercaptoacetate),
Hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-
Mercaptopropionate), 2-mercaptoethylether bis (2-mercaptoacetate), 2-mercaptoethyletherbis (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),
Bis (2-mercaptoethyl ester) thiodipropionate, bis (2-mercaptoethyl ester) 4,4-thiodibutylate, bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptodithiodipropionate) Ethyl ester), bis (2-mercaptoethyl ester) 4,4-dithiodibutyrate, bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate ), Bis (2,3-dimercaptopropyl ester) dithioglycolate, aliphatic polythiol containing sulfur atom in addition to mercapto group such as dithiodipropionic acid (2,3-dimercaptopropyl ester), 3,4- Thiophenedithiol, 2,5
And heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as -dimercapto-1,3,4-thiadiazole.

Examples of the hydroxythiol 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, a chlorine-substituted form of these active hydrogen compounds and a halogen-substituted form of bromine-substituted form may be used.
These may be used alone or in combination of two or more.

The ratio of the isocyanate compound and the active hydrogen compound used is (NCO + NCS) / (OH + S
The functional group molar ratio of H) is usually in the range of 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 according to 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.

[0030]

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 11 Various isocyanate compounds to which a phenolic stabilizer shown in Table 1 was added and an active hydrogen compound were mixed, and defoaming operation was performed under reduced pressure.
mm, 70 mm diameter mold,
The temperature was gradually increased to 20 ° C. and the mixture was cured for 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 1-21 Various isocyanate compounds to which known stabilizers other than phenols shown in Table 2 were added were used, and 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. Was measured. The results are shown in Table 2.

As is clear from the comparison between Examples 3 to 5 and Comparative Examples 1 to 17 and Examples 2, 6, 7, and 8 and Comparative Examples 18 to 21, phenols are used as stabilizers for the isocyanate compound. In this case, the urethane resin obtained by reacting the isocyanate compound with the active hydrogen compound was excellent in yellowness and total light transmittance, and no optical distortion was observed.

That is, phenols are used as stabilizers
The urethane resin of the present invention obtained by reacting an isocyanate compound added with 5000 ppm with an active hydrogen compound is a conventional type obtained by reacting an isocyanate compound added with a stabilizer other than phenols with an active hydrogen compound. Clearly, it is excellent in colorless transparency and has no optical distortion as compared with the urethane resin, and is useful as an optical material such as a plastic lens.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

According to the present invention, a phenol is used as a stabilizer in an amount of 10 to 50.
An optical urethane resin obtained by reacting an isocyanate compound added with 00 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 Continued on the front page (72) Inventor Teruyuki Nagata 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (56) References JP-A-2-167330 (JP, A) JP-A-52-76398 JP, A) JP-B-41-14752 (JP, B1) US Pat. No. 3,356,650 (US, A) US Pat. No. 3,137,381 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18 / 00-18/87 C08K 5/13 C08L 75/04-75/12 G02B 1/04

Claims (3)

(57) [Claims] 1. One or two or more isocyanate compounds selected from the group consisting of a polyisocyanate compound and an isocyanate compound having an isothiocyanato group, and a compound selected from the group consisting of a polyol compound, a polythiol compound and a hydroxythiol compound. One or two
In producing an optical urethane resin by reacting with at least one kind of active hydrogen compound, (NCO + NCS) / (OH +
SH) a hue, total light transmittance and optical properties of the urethane resin for optical use, wherein an isocyanate compound having a functional group molar ratio of 0.5 to 3.0 and phenol added to 10 to 5000 ppm is used. How to improve distortion. 2. The method according to claim 1, wherein the isocyanate compound is an aliphatic polyisocyanate. 3. The method according to claim 1, wherein the isocyanate compound is xylylene diisocyanate.