JPH0733851A - Polyurethane resin for optical material - Google Patents

Abstract

PURPOSE:To obtain an urethane resin having slight discoloration and high whole light transmission free from optical strain. CONSTITUTION:A polyiso(thio)cyanate compound having <=300ppm hydrolyzable chlorine content is reacted with an active hydrogen compound to give a urethane resin for optical material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin for optical materials obtained by reacting a polyiso (thio) cyanate compound with an active hydrogen compound. In particular, the present invention relates to a urethane resin for optical materials, which is less colored and has a high total light transmittance and has no optical distortion.

[0002]

Urethane resins for optical lenses and plastic lenses using the same are obtained by reacting a halogen-containing compound having two or more hydroxyl groups with an isocyanate compound (JP-A-58). -1
No. 64615), a compound obtained by reacting a compound containing a mercapto group with an isocyanate compound (JP-A-60-199016), and a compound obtained by adding a phenolic stabilizer to a polyurethane resin (special A number of applications have been filed, such as Kaihei 5-78441).
A lens having a high refractive index, no coloring, a high total light transmittance, and a small optical distortion has been proposed.

[0003]

However, with respect to optical distortion, there is still no complete solution, and the defective rate in the obtained product is high, and the manufacturing conditions and the like must be changed each time.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding an iso (thio) cyanate compound suitable for obtaining a colorless and transparent urethane resin for optical materials having no optical distortion, the content of hydrolyzable chlorine is determined. It has been found that a polyiso (thio) cyanate compound having a low value is optimally used, and has completed the present invention. That is, the present invention uses a urethane resin for an optical material obtained by reacting a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 300 ppm or less with an active hydrogen compound,
It is intended to provide an optical lens which is less colored and has a high total light transmittance and has no optical distortion.

The polyiso (thio) cyanate compound used in the present invention is selected from the group consisting of polyisocyanate compounds, polyisothiocyanate compounds and isocyanate compounds 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-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,3,5-triisocyanatomethylcyclohexane, 1,8-diisocyanato-4-isocyanatomethyl Octane 2, 5,7-Trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'- Diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-
Aliphatic polyisocyanate such as diisocyanato hexanoate,

Xylylenediisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylenediisocyanate, bis (isocyanatobutyl) benzene, bis Aroaliphatic polyisocyanates such as (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylylene triisocyanate, 2,6
-Di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2 ' -Dimethyldicyclohexyl methane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate 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 [2,2,2]
1] -Alicyclic polyisocyanate such as heptane,

Phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate,
Isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanatomethylbenzene, naphthalene diisocyanate Nato, 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, Tetrahydronaphthalene diisocyanate, Hexahydrobenzenediisocyanate, Hexahydrodiphenylmethane-4,4 ' -Diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate,
Examples thereof include aromatic polyisocyanates such as diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, and dichlorocarbazole diisocyanate.

The polyisocyanate compound used in the present invention may contain a sulfur atom in the molecule. Examples of such polyisocyanate compound include thiodiethylene diisocyanate and thiodipropyl diisocyanate. , Thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and other sulfur-containing aliphatic isocyanates, diphenyl sulfide-2,4'-diisocyanate Nato, diisocyanate, diphenyl sulfide-4,
4'-diisocyanate, 3,3'-dimethoxy-4,
4'-diisocyanato dibenzyl thioether, bis (4-isocyanatomethylphenyl) sulfide, 4,
4'-methoxyphenylthioethylene glycol-3,
Aromatic isocyanate having a sulfide bond 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'-dimethoxydiphenyl disulfide-4,4 '
-Diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate-containing aromatic isocyanate having a disulfide bond, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3, 3'-diisocyanate, benzidine sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,4'-diisocyanate,
4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'- Diisocyanate, 4,4 '
-Di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxyphenylethylenesulfone-3,3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3 Aromatic isocyanate having sulfone bond such as'-diisocyanate, 4
-Methyl-3-isocyanatophenylsulfonyl-4 '
-Isocyanatophenol ester, 4-methoxy-3
-Isocyanatophenylsulfonyl-4'-isocyanatophenol ester-containing aromatic isocyanate having a sulfonate bond, 4-methyl-3-isocyanatophenylsulfonylanilide-3'-methyl-
4'-isocyanate, diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,
Aromatic isocyanate having sulfonic acid amide bond such as 3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3'-isocyanate, thiophene-2,5-diisocyanate Sulfur-containing heterocyclic compounds such as 1,4-dithiane-
2,5-diisocyanate and the like can 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,
A modified burette, a dimerized or trimerized reaction product, etc. can also be used. These may be used alone or in combination of two or more.
Examples of the polyisothiocyanate compound include 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, and 1,6-diisothiocyanate. Hexane, aliphatic isothiocyanate such as p-phenylene isopropylidene diisothiocyanate, alicyclic isothiocyanate such as cyclohexane diisothiocyanate,
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, diphenylether-4. , 4'-diisothiocyanate, diphenylamine-4,4'-diisothiocyanate and other aromatic isothiocyanates, 2,4,5-triisothiocyanate-1,3,5-triazine and other heterocycles Containing isothiocyanates, further, hexanedioil diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate Oceanate, (2,2'-Pypyridine) -4,4'-dicarboni Diisothiocyanate carbonyl isothiocyanate, such as isocyanate and the like.

The aforementioned polyisothiocyanate compound is
It may contain one or more sulfur atoms in addition to the isothiocyanate group, and examples of such polyisothiocyanate include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanate). Ethane), 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 Sulfur-containing aromatic isothiocyanates such as isothiocyanate benzenesulfonyl-4'-isothiocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, thiophenone -2,5-diisothiocyanate, 1,4-dithiane-
Examples include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate. Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products of these polyisothiocyanates, alkyl-substituted products, alkoxy-substituted products, prepolymer-modified products with nitro-substituted products and polyhydric alcohols, carbodiimide-modified products, and urea. Modified products, burette modified products, dimerized or trimerized reaction products and the like can also be used.

In the present invention, examples of the isocyanate compound having an isothiocyanate group include 1-isocyanato-3-isothiocyanatopropane and 1-isocyanate.
Isocyanato-5-isothiocyanatopentane, 1
-Isocyanato-6-isothiocyanatohexane,
Aliphatic compounds such as isothiocyanate carbonyl isocyanate, alicyclic compounds such as 1-isocyanato-4-isothiocyanate cyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-
Aromatic compounds such as isocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and further 4-isocyanate- In addition to isothiocyanate groups such as 4'-isothiocyanate diphenyl sulfide and 2-isocyanato-2'-isothiocyanate diethyl disulfide, compounds containing a sulfur atom and the like can be mentioned. Further, chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds,
Alkoxy-substituted products, nitro-substituted products, prepolymer-type 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. These may be used alone or in combination of two or more. The polyiso (thio) cyanate compound used in the present invention is required to have a hydrolyzable chlorine content of 300 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less. This is because if it exceeds 300 ppm, the lens is colored and optical distortion occurs. The content of hydrolyzable chlorine is measured by a method according to JIS K-1556.

The active hydrogen compound used in the present invention is selected from polyol compounds, polythiol compounds and hydroxythiol compounds. 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, diglycerol, triethylene glycol, polyethylene glycol , Tris (2
- hydroxyethyl) isocyanurate, cycloheptane diol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5,2,3,0 ^2,
6 ] Decane-dimethanol, bicyclo [4,3,0]-
Nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,5]
3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol ,
Aliphatic polyols such as cyclohexanetriol, maltitol, lactose,

Dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2)
-Hydroxyethoxy) benzene, bisphenol A-
Bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-
In addition to aromatic polyols such as bis- (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, polymer polyols such as epoxy resins, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid. Acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-
Bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, a condensation reaction product of an organic acid such as bromophthalic acid and the polyol, an addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide, Addition reaction products of alkylene polyamines with ethylene oxide, alkylene oxides such as propylene oxide, and 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 compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group 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'-thiobis (6-tert
-Butyl-3-methylphenol), 1,3-bis (2
Examples thereof include polyols containing a sulfur atom such as -hydroxyethylthioethyl) -cyclohexane.

Examples of polythiol compounds 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-
Dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,2
1] Pepta-exo-cis-2,3-dithiol, 1,1-
Bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-
Mercaptoacetate), 2,3-dimercapto-1-
Propanol (3-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),
An aliphatic polythiol 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 ) Benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptomethyleneoxy) benzene , 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,
4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris ( Mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3- 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,
1,2,3,4-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'-dimercaptobibenzyl,
2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,
7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-
1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane- Aromatic polythiols such as 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-
1,2-Dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and other chlorine-substituted compounds, bromine-substituted and other halogen-substituted aromatic polythiols, 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-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sy
Polythiols containing a heterocycle such as m-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine, and further 1,2-bis (mercaptomethylthio) benzene and 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 (mercaptoethyl) Thio)
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. Aromatic polythiol containing sulfur atom in addition to mercapto group of nuclear alkylated product, 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-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 sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate) , Hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-
Mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate), 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-mercapto) Ethyl 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 bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester) and the like, an aliphatic polythiol containing a sulfur atom in addition to the mercapto group, 3,4- Thiophenedithiol, 2,5
Examples include heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as dimercapto-1,3,4-thiadiazole.

Examples of hydroxythiol compounds 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), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate) ), Hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-
Mercaptoethylthiobenzene, 4-hydroxy-4 '
-Mercaptodiphenyl sulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane, etc. Is mentioned.

Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds of these active hydrogen compounds may be used. These may be used alone or in combination of two or more. These polyiso (thio)
The ratio of the cyanate compound to the active hydrogen compound is usually 0.5 (iso (thio) cyanate group / active hydrogen group).
To 3.0, preferably 0.5 to 1.5. Further, known chain extenders, cross-linking agents, depending on the purpose,
Various substances such as a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, 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.
The urethane resin thus obtained exhibits a high refractive index and low dispersion and is excellent in optical characteristics, and is suitable for use in optical products such as plastic lenses, prisms, optical fibers, information recording substrates, colored filters and infrared absorption filters. It is preferably used as a material. For example, specifically describing the method for producing a plastic lens, preferably one or more polyiso (thio) cyanate compounds and one or more
After mixing one kind or two or more kinds of active hydrogen compounds and, if necessary, additives, catalysts, etc., they are poured into a mold to react. At this time, a defoaming operation is usually performed before injection to prevent bubbles from entering the resin. The reaction temperature and time will differ depending on the type of raw materials used and additives, but will usually be -50 ° C to 20 ° C.
0 ° C, preferably room temperature to 150 ° C, more preferably 50
Is about 120 ° C., and the time is usually 0.5 to 72 hours. The obtained lens may be annealed if necessary.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations used in the examples are as follows. Abbreviations bis (isocyanatomethyl) cyclohexane H ₆ XDI isophorone diisocyanate IPDI xylylene diisocyanate XDI 1,3,5-triisocyanatomethylcyclohexane H ₆ MTI 1,3,5-triisocyanatomethylbenzene MTI tolylene diisocyanate Nato TDI pentaerythritol tetrakis (3-mercaptopropionate) DETMP bis (2-mercaptoethyl) ether BMEE diethylene glycol DEG Example 1 Hydrolyzable chlorine content (according to JIS K-1556).
The same shall apply hereinafter) is 60 ppm H ₆ XDI and DETMP
The mixture was mixed at a CO group / SH group molar ratio of 1.0, degassed under reduced pressure, and poured into a mold having a thickness of 8 mm and a diameter of 70 mm composed of a glass mold and a gasket, and the temperature was 20 ° C.
To 120 ° C. and heated for 24 hours to cure. After polymerization, the 8 mm-thick flat plate resin obtained by releasing from the mold was visually checked for optical strain (stria). The yellowness was measured according to JIS K-7105 6.3. The results are shown in [Table 1].

Examples 2 to 6 Polymerization was carried out in the same manner as in Example 1 using various polyiso (thio) cyanate compounds having a hydrolyzable chlorine content of 300 ppm or less shown in Table 1 and an active hydrogen compound, and optical distortion ( The presence or absence of striae was measured. Also, the yellow degree is JISK-71.
According to 6.3 of 05. The results are shown in [Table 1]. Comparative Examples 1 to 3 A phenolic stabilizer is added to various polyiso (thio) cyanate compounds having a hydrolyzable chlorine content of more than 300 ppm or polyiso (thio) cyanate compounds having a hydrolyzable chlorine content of more than 300 ppm shown in Table 2. Polymerization was carried out in the same manner as in Example 1 using the above compound and an active hydrogen compound, and the presence or absence of optical strain (stria) was determined. The yellowness is JISK
According to 6.3 of -7105. The results are shown in [Table 2].

[Table 1]

[0022]

[Table 2] In Examples 1 to 6 in which the content of hydrolyzable chlorine in Table 1 is 300 ppm or less, there is no optical distortion, but in Comparative Examples 1 to 3 in which the content of hydrolyzable chlorine in Table 2 exceeds 300 ppm, phenol-based stability Even if the agent was added, optical distortion was observed.

[0023]

EFFECT OF THE INVENTION Urethane resins for optical materials obtained by reacting a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 300 ppm or less with an active hydrogen compound are excellent in colorless transparency and have no optical distortion. It is useful as an optical product such as plastic lens, prism and the like.

Claims (11)

[Claims] 1. A urethane resin for an optical material obtained by reacting a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 300 ppm or less with an active hydrogen compound. 2. The urethane resin for optical materials according to claim 1, wherein the active hydrogen compound is at least one selected from a polyol compound, a polythiol compound and a hydroxythiol compound. 3. The urethane resin for optical materials according to claim 1, wherein the equivalent ratio of iso (thio) cyanate group / active hydrogen group is 0.5 to 3.0. 4. The urethane resin for optical materials according to claim 1, wherein the polyiso (thio) cyanate compound is polyisocyanate. 5. The urethane resin for optical materials according to claim 4, wherein the polyisocyanate is an alicyclic polyisocyanate. 6. The urethane resin for optical materials according to claim 4, wherein the polyisocyanate is an araliphatic polyisocyanate. 7. The urethane resin for optical materials according to claim 1, which is a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 200 ppm or less. 8. The urethane resin for optical materials according to claim 1, which is a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 100 ppm or less. 9. A method for producing a urethane resin for optical materials, which comprises reacting a polyiso (thio) cyanate compound having a hydrolyzable chlorine content of 300 ppm or less with an active hydrogen compound. 10. An optical product using the urethane resin for optical materials according to claim 1. 11. The optical product according to claim 10, which is an optical lens.