JPH05307101A - Production of lens made of polyurethane resin - Google Patents

Abstract

PURPOSE:To industrially efficiently produce the lens having excellent optical homogeneity by putting a mold set in which a monomer is poured into a specific medium and polymerizing the monomer by heating. CONSTITUTION:The mold set in which the monomer is poured is put into the medium having >=0.1Wm<-1>K<-1> thermal conductivity and >=120 deg.C b.p. to polymerize the monomer by heating at the time of producing the lens made of a polyurethane resin. The medium to be used is generally liquid at room temp. and includes, for example, ethylene glycol, diethylene glycol, glycerol, various silicone oils, etc. The lens made of the polyurethane resin to be used is obtd. by bringing >=1 kinds of active hydrogen compds. selected from a polyisocyanate compd. having >=2 pieces of isocyanate groups in one molecule, a polyol compd. having >=2 pieces of hydroxyl groups in one molecule, a polythiol compd. having >=2 pieces of mercapto groups in one molecule and a mercapto compd. having a hydroxyl group in one molecule into reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane resin lens having excellent optical homogeneity. More specifically, the present invention relates to a method for producing a lens for spectacles and a lens made of polyurethane resin useful as an optical lens.

[0002]

2. Description of the Related Art Conventionally, polymerization of diethylene glycol bis (allyl carbonate) most commonly used as a plastic lens in water has been generally performed mainly in Europe and America. This is especially important in the production of thick lenses, where the heat control of the resin during polymerization is important. In that case, it is easier to control the heat by using water as a medium than in air, which has a low thermal conductivity. This is because it is easy to obtain a high-quality lens in terms of homogeneity. On the other hand, although the polyurethane resin lens is partially polymerized in water, it is generally polymerized in an air oven. The reason for this is that in the case of a polyurethane resin lens, 120 ° C at the final stage of polymerization.
It is necessary to heat to a certain degree, and when water is used as the heating medium, it is necessary to heat while pressurizing or to perform polymerization in water up to about 80 ° C and then transfer to an air oven to complete the polymerization. This is because it is industrially extremely complicated.

[0003]

The object of the present invention is to carry out polymerization in a single polymerization tank from the beginning to the end of the polymerization to obtain a polyurethane resin lens with improved optical homogeneity. It is to provide a method.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies on a method for producing a polyurethane resin lens having improved optical homogeneity, and as a result, have completed the present invention. It was. That is, in the present invention, in the production of a lens made of a polyurethane resin, a mold set in which a monomer is injected has a thermal conductivity of 0.1 Wm ^-1 K ^-1 or more
In addition, the present invention relates to a method for producing a polyurethane resin lens which is heated and polymerized in a medium having a boiling point of 120 ° C. or higher. The medium used in the present invention is a medium having a thermal conductivity of 0.1 Wm ⁻¹ K ⁻¹ or more and a boiling point of 120 ° C. or more, and is generally a liquid at room temperature, for example, ethylene glycol, diethylene glycol, Glycerin,
Examples include various silicone oils. These are commercially available and are easily available.

The polyurethane resin lens used in the present invention comprises a polyisocyanate compound having two or more isocyanate groups in one molecule and two in one molecule.
A polyol compound having two or more hydroxyl groups, a polythiol compound having two or more mercapto groups in one molecule,
It is obtained by reacting one or more active hydrogen compounds selected from mercapto compounds having a hydroxy group in one molecule.

Examples of the polyisocyanate used in the present invention include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate,
Hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-
Dimethyl pentane 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-diisocyanate Nato-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 diisocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanato hexanoate, 2-isocyanate Propyl-
2,6-diisocyanate hexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α,
α, α ', α'-Tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitilerent Liisocyanate, aliphatic polyisocyanate such as 2,6-di (isocyanatomethyl) furan,

Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate Nato, 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- [2,2,1] -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]-
Alicyclic polyisocyanate such as heptane,

Phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate,
Isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate , Toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4 '
-Diisocyanate, bis (isocyanatophenyl)
Ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate,
Polymeric MDI, naphthalene triisocyanate,
Diphenylmethane-2,4,4'-triisocyanate, 3-
Methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate, phenylisocyanate methylisocyanate, phenylisocyanate ethylisocyanate , Tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, Benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate Aromatic polyisocyanates such as dichloro carbazole diisocyanate,

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

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'-diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3 ' -Diisocyanate, 4,4'-di (tert-butyl) diphenylsulfone-3,3'-diisocyanate, 4,
4'-methoxybenzene ethylenedisulfone-3,3'-diisocyanate, 4,4'-dichlorodiphenylsulfone-3,
Aromatic sulfone-based isocyanates such as 3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4-
Methoxy-3-isocyanatobenzenesulfonyl-4 '
-Sulfonic acid ester-based isocyanate such as isocyanate phenol ester, 4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-
Isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide- Aromatic sulfonic acid amides such as 4-methyl-3'-isocyanate, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, etc. Is mentioned. Also,
These chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds,
An alkyl-substituted product, an alkoxy-substituted product, a nitro-substituted product, a prepolymer modified product with a polyhydric alcohol, a carbodiimide modified product, a urea modified product, a buret modified product, a dimerized or trimerized reaction product and the like can also be used.

The polyol compound used in the present invention is a bifunctional or higher functional polyol, and includes a compound having a sulfur atom in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2
-Methyl glucoside, 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, cyclobutanediol, cyclopentanediol, Cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0 ^2,6 ] decane-dimethanol, bicyclo [4,
3,0] -nonanediol, dicyclohexanediol,
Tricyclo [5,3,1,1] dodecanediol, bicyclo [4,
3,0] Nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo
[5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol,

1,1-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, 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-bis-
(2-hydroxyethyl ether), dibromoneopentyl glycol, epoxy resin and other polyols, as well as oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid A condensation reaction product of the above-mentioned polyol with an organic polybasic acid such as isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycolic acid, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, bromophthalic acid,
An addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide,
Examples thereof include addition reaction products of alkylene polyamines and alkylene oxides such as ethylene oxide and propylene oxide. Furthermore, these chlorine substitution products,
You may use halogen substitution products, such as a bromine substitution product. These may be used alone or in combination of two or more.

Examples of the bifunctional or higher functional polyol containing a sulfur atom include, for example, bis- [4- (hydroxyethoxy) phenyl] sulfide and 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 these compounds have an average of 3 per hydroxyl group.
Compounds to which ethylene oxide and / or propylene oxide below the molecule are added, 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-hydroxyethylthioethyl) -cyclohexane and the like. .. Furthermore, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds may be used. These may be used alone or in combination of two or more.

Further, the polythiol compound used in the present invention is a polythiol having two or more functional groups, and includes those containing at least one sulfur atom in addition to the mercapto group. Examples of bifunctional or higher polythiols include methanedithiol, 1,2-ethanedithiol, 1,1
-Propanedithiol, 1,2-Propanedithiol, 1,
3-propanedithiol, 2,2-propanedithiol,
1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-
Dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-2,3-dithiol, 1,1- Bis (mercaptomethyl) cyclohexane,
Thiomalic acid bis (2-mercaptoethyl ester),
2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2
-Mercaptoacetate), 2,3-dimercapto-1-
Propanol (3-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-mercapto) Propionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) and other aliphatic polythiols, 1,2-bis [(2-mercaptoethyl) thio] -3-mercapto Propane and halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds thereof,

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 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, 1,2,4-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 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3, 4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-
Tetrakis (mercaptomethyleneoxy) benzene,
1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2, 2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5 −
Naphthalenedithiol, 2,6-naphthalenedithiol,
2,7-naphthalenedithiol,

2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10
-Anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4 -Aromatic polythiols such as di (p-mercaptophenyl) pentane, 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 halogen-substituted aromatic polythiols, 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- Thiol-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,
Examples thereof include heterothiol-containing polythiols such as 2-thiobutyloxy-4,6-dithiol-sym-triazine, and halogen-substituted compounds such as chlorine-substituted and bromine-substituted polythiols thereof. These may be used alone or in combination of two or more.

As the bifunctional or higher polythiol containing at least one sulfur atom in addition to the mercapto group,
For example, 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-teto Tetrakis (mercaptoethylthio) benzene, and aromatic, such as these nuclear alkylated polythiol,

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2 -Bis (3-mercaptopropylthio) 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, etc., and thioglycolic acid thereof And an ester of mercaptopropionic acid,

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

Thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis ( 2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester),
4,4-Dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-
Dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester), and other aliphatic polythiols, 3,4-thiophenedithiol, bismuthiol And other heterocyclic compounds. Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds thereof may be used. These may be used alone or in combination of two or more.

The thiol compound having a hydroxy group used in the present invention also includes a thiol compound containing at least one sulfur atom in addition to the mercapto group. For example, 2
-Mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3, 4-dimercapto-2-propanol, 1,3-dimercapto-2
-Propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, trimethylolpropane bis (thioglycolate), trimethylolpropane mono (thioglycolate), trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane mono (3-mercaptopropionate), trimethylolethane bis (thioglycolate), trimethylolethane mono (thioglycolate), trimethylolethane bis (3-mercapto) Propionate), trimethylolethane mono (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercapto). Mercaptopropionate),
Pentaerythritol tris (thioglycolate), dipentaerythritol 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 (mercaptoethyl) Thiomethyl)
Examples include methane. Further, halogen-substituted products of these chlorine-substituted products and bromine-substituted products may be used. These may be used alone or in combination of two or more.

The ratio of the active hydrogen compound to the polyisocyanate compound used is such that the NCO / (SH + OH) functional group molar ratio is usually in the range of 0.5 to 3.0, preferably in the range of 0.5 to 1.5. Further, in the invention of the present application, the matching property between the mold and the gasket and the heat resistance of the gasket are important. From that point, a rubber-modified polypropylene that is soft and has good heat resistance is preferably used. For example,
Such as Mitsui Petrochemical's Mirastomer.

In the method of the present invention, at least one of the above-mentioned polyisocyanate compound and active hydrogen compound is first mixed. At that time, a compound such as a catalyst, a release agent, an ultraviolet absorber, a cross-linking agent, a chain extender, a light stabilizer, an antioxidant, an oil-soluble dye, a filler, and a fragrance may be appropriately added depending on the purpose. .. This monomer mixture is degassed by an appropriate method, if necessary, and then injected into a mold for polymerization.
Polymerization is generally carried out when the thermal conductivity filled in a polymerization tank equipped with a heating, cooling and stirring device is 0.1 Wm ⁻¹ K ⁻¹ or more,
In addition, it is usually carried out in a medium having a boiling point of 120 ° C. or higher, but usually 1
Starting from a low temperature of about 0 ° C to 20 ° C, gradually raising the temperature and heating up to about 120 ° C, the process ends.

In the present invention, the reason why a lens having excellent optical homogeneity can be obtained by polymerizing in the above-mentioned medium is that the heat conduction of the medium is larger than that of air, and therefore the heat control of the polymerization reaction is easy. Because there is. In particular,
In the polymerization of a polyurethane resin lens which is an exothermic reaction, the polymerization time can be shortened as compared with polymerization in air, which is economically advantageous. In addition, the polyurethane resin lens thus obtained is a lens of excellent quality, which has better optical homogeneity than a lens polymerized in an air oven under the same heating conditions, and is a spectacle lens, a camera. It is suitable as an optical element such as a lens.

The polyurethane resin lens obtained in the present invention is improved in antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, fashionability, etc., as required. Therefore, surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment,
Physical or chemical treatment such as light control treatment can be performed.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The optical uniformity of the obtained lens was evaluated using an optical strain meter. Example 1 50 kg of m-xylylene diisocyanate, pentaerythritol tetrakis (3-mercaptopropionate)
A mixture of 65 kg and 92 g of dibutyltin dilaurate,
The mixture was poured into 1000 mold sets for semi-finished lenses consisting of a milastomer and a glass mold, and the polymerization was completed in 48 hours while gradually raising the temperature from 10 ° C to 120 ° C in silicone oil. The obtained lens is 10
All of the 00 pieces were optically uniform.

Comparative Example 1 Polymerization was completed in the same temperature conditions as in Example 1 in an air oven using the same mold set with the same monomer composition as in Example 1. The 210 lenses thus obtained were optically non-uniform and were unsuitable as spectacle lenses.

[0029]

According to the present invention, a lens having excellent optical homogeneity can be industrially and efficiently manufactured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08J 5/00 CFF 9267-4F

Claims (2)

[Claims] 1. In the production of a polyurethane resin lens, a mold set in which a monomer is injected is placed in a medium having a thermal conductivity of 0.1 Wm ⁻¹ K ⁻¹ or more and a boiling point of 120 ° C. or more, A method for producing a lens made of a polyurethane resin, which comprises heat-polymerizing. 2. The method for producing a polyurethane resin lens according to claim 1, wherein the medium is any one of ethylene glycol, glycerin or silicone oil.