JP4783697B2 - Polymerizable composition comprising polythiol compound and polyiso (thio) cyanate compound - Google Patents

Description

  The present invention relates to a polymerizable composition comprising a polythiol and a polyiso (thio) cyanate compound used for a polyurethane-based resin giving good optical properties.

  In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.

  Plastic lens resins are required to have higher performance, and higher refractive index, higher Abbe number, lower specific gravity, higher heat resistance, and the like have been demanded. Various resin materials for lenses have been developed and used so far.

  Among them, proposals relating to polyurethane resins have been actively made, and the present inventors have also made various proposals relating to plastic lenses using the polyurethane resins.

Among the polyurethane-based resins, the resin obtained by reacting polythiol and polyiso (thio) cyanate compound as the most typical resin is colorless and transparent, has a high refractive index and low dispersion, has a small optical distortion, has an impact property, It is one of the most suitable resins for plastic lenses with excellent dyeability and processability.
Furthermore, there has been proposed an ultraviolet absorber added to such a plastic lens to protect the eyes and the like from damage caused by ultraviolet rays. In particular, ultraviolet rays having a wavelength of 400 nm or less are known to adversely affect the cornea and the crystalline lens, and a high light cut rate is required. (See Patent Documents 1, 2, and 3)
JP-A-11-231102 JP 11-295502 A Japanese Patent Laid-Open No. 10-186219

  When the addition amount of the ultraviolet absorber is increased in order to increase the ultraviolet cut rate, problems such as yellowing of the plastic lens may occur, which may affect the lens performance. Resins obtained by these inventions are required to have high transparency in the case of lens applications.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have to add a large amount of benzotriazole-based ultraviolet absorber in order to increase the light cut rate at a wavelength of 400 nm, and accordingly It has been clarified that not only the yellowness of the resin deteriorates but also the optical properties, particularly the Abbe number, decrease. As a result of further intensive studies, by selecting a specific benzotrizol-based UV absorber, the cut rate at a wavelength of 400 nm can be increased even with a small amount of addition, and further added without deteriorating the yellowness of the resin. It has been found that since the amount can be reduced, it is possible to suppress a decrease in optical properties, particularly Abbe number. In other words, by adding a specific benzotriazole UV absorber to iso (thio) cyanate and polythiol, which are polyurethane resin raw materials, and producing a polyurethane resin, the above problems are solved and colorless and transparent with no deterioration in optical properties The inventors have found that a high-performance polyurethane resin having a high UV cut rate can be obtained, and have completed the present invention.

That is, the present invention
1) a polythiol compound comprising 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and pentaerythritol tetrakis (β-mercaptopropionate);
A polyiso (thio) cyanate compound comprising bis (isocyanatomethyl) norbornane;
2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, isooctyl-3- (3- (2H-benzotriazole- consisting of 2-yl) -5-t-butyl-4-hydroxyphenyl propionate, and 2- [2-hydroxy-3,5-bis (dimethylbenzyl) phenyl] one selected from -2H- benzotriazole A benzotriazole-based ultraviolet absorber, and a polymerizable composition for lenses,
Wherein the light-cutting at a wavelength 400nm of the resin plate having a thickness of 9mm obtained from the composition is 99.8% or more, about lenses for polymerizable compositions.
Further, the following 2) to 5 ) are each one of preferred embodiments of the present invention.

2) A method for producing a resin for curing the polymerizable composition for lenses described in 1 ) above.
3) A resin obtained by curing the polymerizable composition for lenses described in 1 ) above.
4) An optical element made of the resin described in 3 ) above.
5) A lens made of the resin described in 3 ) above.
In the above 4) and 5) , “made of resin” means that the entire optical element or lens is made of the resin, and that a part of the optical element or lens is made of the resin. If it is, it is intended to include both.

  The present invention provides a high-performance polyurethane-based lens that has low chromatic aberration, is transparent, and has a high UV cut rate, and contributes to the development of this field.

The present invention is specified by selecting the type of benzotrizol-based UV absorber, and even with a small amount of addition, the light cut rate at a wavelength of 400 nm can be 99.5% or more, and furthermore, the amount of addition can be made small. The polymerizable composition is characterized in that it suppresses the decrease in optical properties, particularly Abbe number.
If the polymerizable composition is characterized in that the light-cut rate at a wavelength of 400 nm is 99.5% or more and the Abbe number is not lowered by containing an ultraviolet absorber, the chromatic aberration is low, and it is transparent and has a high UV-cut rate. A high-performance polyurethane-based resin having can be obtained.

  Examples of the ultraviolet absorber used in the present invention include 2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, isooctyl. -3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionate, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole 2- (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 , 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, at least one selected from the group consisting of Masui.

  More preferably, 2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, isooctyl-3- (3- (2H -Benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenylpropionate, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,

  Particularly preferably 2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, isooctyl-3- (3- (2H- At least one from the group consisting of benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenylpropionate, 2- [2-hydroxy-3,5-bis (dimethylbenzyl) phenyl] -2H-benzotriazole It is to select the species.

The addition amount of the ultraviolet absorber in the present invention is preferably 0.03 to 1.5 wt%, and more preferably 0.05 to 0.5 wt% with respect to the polymerizable composition.
The polyurethane lens of the present invention is obtained by reacting polythiol and a polyiso (thio) cyanate compound.

  The polyiso (thio) cyanate compound that can be used in the present invention is a compound having at least two or more iso (thio) cyanate groups in one molecule and is not particularly limited. Specifically, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane 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, bis (isocyanatoethyl) carbonate, bis ( Isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine Li diisocyanate, bis (isocyanatomethyl) norbornane, bis (isocyanatomethyl) cyclohexane, aliphatic such as dicyclohexylmethane diisocyanate polyisocyanate compound;

  1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylpheny Range isocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis (phenyl isocyanate), 4 , 4′-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4′-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, bis Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanate) A polyisocyanate compound having an aromatic ring compound of natomethylphenyl) ether, bis (isocyanatoethyl) phthalate, 2,6-di (isocyanatomethyl) furan, o-xylylene diisocyanate;

  Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis ( Isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatomethylthio) ethane, 1, 5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1 , 2,6 7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia-1,7-heptanediisocyanate, 2,5-diisocyanatomethylthiophene, 4-isocyanatoethylthio-2, Sulfur-containing aliphatic polyisocyanate compounds such as 6-dithia-1,8-octane diisocyanate;

  Aromatic sulfide polyisocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) sulfide;

  Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanatophenyl) Aromatic disulfide polyisocyanate compounds such as disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide;

  2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanate Natomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl A sulfur-containing alicyclic polyisocyanate compound such as -1,3-dithiolane;

  Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane, 1,6-diisothiocyanatohexane, alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate, 1,2-di Isothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 4, 4'-methylenebis (phenylisothiocyanate), 4,4'-methylenebis (2-methylphenylisothiocyanate), 4,4'-methylenebis (3-methylphenylisothiocyanate), 4,4'-diisothi Oceanatobenzophenone, 4,4′-diisothiocyanato-3,3′-dimethylbenzophenone, bis (4 Isothiocyanatophenyl) aromatic poly isothiocyanate compounds such as ether;

  Furthermore, carbonyl isothiocyanes such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-dicarbonyldiisothiocyanate, etc. Sulfur-containing aliphatic isothiocyanate compounds such as nate compounds, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane);

  Sulfur-containing aromas such as 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene) Sulfur-containing alicyclic compounds such as aromatic polyisothiocyanate compounds, 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane;

  1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2- Isocyanato groups such as isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl sulfide, 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide And compounds having an isothiocyanato group, but are not limited to these exemplified compounds.

  Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products and the like can also be used. These compounds may be used alone or in combination of two or more. More preferably, m-xylylene diisocyanate, bis (isocyanatomethyl) norbornane, bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, particularly preferably bis (isocyanatomethyl) norbornane Is mentioned.

  The polythiol compound that can be used in the present invention is a compound having at least two thiol groups in one molecule and is not particularly limited. Specifically, for example, methanedithiol, 1,2-ethanedithiol, 1, 1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis ( Mercaptomethyl) cyclohexane, bis-thiomalate (2-mercaptoethyl ester), 2,3-di Mercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), 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 bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythris Tall tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercaptomethyl) aliphatic polythiol compounds such as methane;

  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, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Puttoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane;

  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) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylates;

  Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, 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-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- Lucaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, 1,2-bis [ (2-Mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11- Mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethyl) Thiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopro Pyr) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl- Aliphatic polythiol compounds containing sulfur atoms other than mercapto groups such as 2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and the like Of 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 Dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic 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-dithio Dibutyl 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 mercapto groups, and other aliphatic polythiol compounds containing a sulfur atom and an ester bond;

A heterocyclic compound containing a sulfur atom in addition to a mercapto group such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole;
2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol 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, pentaerythritol tris (3-mercapto Propionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3 Mercaptopropionate), hydroxymethyl - tris (mercaptoethylthiomethyl) methane, compounds containing 1-hydroxyethyl-thio-3-mercaptoethyl hydroxy group other than the mercapto group of thio benzene;

  1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-Dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4- Bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-propa Dithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercapto) Methylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis ( Mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) me , Tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1 , 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12, 14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8, 10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2 , 5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4, 6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7-mercapto -2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-dithi Nilthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-bis (mercaptomethylthio) propane, 1- { 4- (6-Mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetra Thiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -2,4 , 6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithieta L)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3- Dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -6 -{4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1 , 11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Zimmerka Put-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl-1,9-dimercapto-2,4,6 , 8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1,3 -Dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis (mercaptomethyl) H ) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8 -Mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithia Hexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} mercaptomethylthiomethyl-1,3-dithietane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio} mercapto Tylthiomethyl-1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1, 3-dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- ( 1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [ Bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithietane, 4- {4- (5-mercaptomethylthio-1,3-dithio Ranyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and dithioacetal or dithioketal skeletons such as oligomers thereof A compound having:

  Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis (4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl) (mercaptomethylthio) methane, tris (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl) methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris ((4-mercaptomethyl-2,5-dithi Cyclohexyl-1-yl) methylthio) methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2 -(2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4- Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris (2,2-bis (mercaptomethylthio) -1-thiaethyl) methane, tris (3,3- Bis (mercaptomethylthio) -2-thiapropyl) methane, tris (4,4-bis (mercaptomethylthio) -3-thiabutyl) me 2,4,6-tris (3,3-bis (mercaptomethylthio) -2-thiapropyl) -1,3,5-trithiacyclohexane, tetrakis (3,3-bis (mercaptomethylthio) -2-thiapropyl ) Compounds having an ortho trithioformate skeleton such as methane and further oligomers thereof;

  3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof. Examples include compounds having an orthotetrathiocarbonate skeleton, but are not limited to these exemplary compounds. These exemplary compounds may be used alone or in combination of two or more. More preferably, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis (β -Mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, particularly preferably 1,2-bis [(2-mercaptoethylthio) -3-mercaptopropane, pentaerythritol tetrakis (β -Mercaptopropionate), bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol.

  The ratio of the polythiol and polyiso (thio) cyanate compound used in the present invention is usually within the range of SH group / NCO group = 0.5 to 3.0, preferably 0.6 to 2.0, more preferably 0.8. It is in the range of 8-1.3.

  In addition to polythiol compounds and polyiso (thio) cyanate compounds that form urethane resins, active hydrogen typified by amines, etc., for the purpose of improving various physical properties, operability, polymerization reactivity, etc. of the polyurethane-based resin of the present invention. You may add 1 type (s) or 2 or more types other than urethane formation raw materials, such as a compound, an epoxy compound, an olefin compound, a carbonate compound, an ester compound, a metal, a metal oxide, an organometallic compound, and an inorganic substance.

Further, in the same manner as in known molding methods depending on the purpose, in addition to the ultraviolet absorber of the present invention, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, an oil-soluble dye, a filler, a release agent, Various substances such as a bluing agent may be added. In order to adjust to a desired reaction rate, a thiocarbamic acid S-alkyl ester or a known reaction catalyst used in the production of polyurethane can be appropriately added.
The polyurethane resin and lens of the present invention are usually obtained by cast polymerization.

  The temperature for preparing a polymerizable composition by mixing isocyanates, thiols, UV absorbers, and other additives such as a catalyst is usually 25 ° C. or lower. From the viewpoint of the pot life of the composition, it may be preferable to lower the temperature further. However, when the solubility of the ultraviolet absorber, catalyst, or additive in the monomer is not good, it is possible to preheat and dissolve the monomer in the isocyanates or thiols, or the monomer mixture.

  Casting polymerization is mentioned as a manufacturing method of the polythiourethane resin of this invention. That is, the polymerizable composition according to the present invention is injected between molding molds held by a gasket or a tape. At this time, depending on the physical properties required of the plastic lens to be obtained, it is often preferable to perform a defoaming treatment under reduced pressure, a filtration treatment such as pressurization or reduced pressure, and the like.

The polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., but it takes approximately 1-50 hours at a temperature of -50 to 150 ° C. Done. Depending on the case, it is preferable to hold or gradually raise the temperature in a temperature range of 10 to 150 ° C. and cure in 1 to 25 hours.
About the obtained polythiourethane resin, you may perform processes, such as annealing, as needed. The treatment temperature is usually 50 to 150 ° C, preferably 90 to 140 ° C, and more preferably 100 to 130 ° C.

The polyurethane resin of the present invention thus obtained has a high refractive index, low dispersion, excellent heat resistance and durability, light weight and excellent impact resistance, and has a hue. It is favorable and suitable as an optical element material such as a spectacle lens or a camera lens.
It can be obtained as molded products of various shapes by changing the mold during casting polymerization, and can be used for various applications as optical resins such as spectacle lenses, camera lenses, and light emitting diodes (LEDs). . In particular, it is suitable for optical materials and optical elements such as spectacle lenses, camera lenses, and light emitting diodes.

The plastic lens using the polythiourethane resin of the present invention is antireflective, imparted with high hardness, improved wear resistance, improved chemical resistance, imparted antifogging, or imparted fashionability or photochromic properties as necessary. Therefore, physical or chemical treatments such as surface polishing, antistatic treatment, coating treatment on one or both sides, dyeing treatment, and light control treatment can be performed.
Examples of the coating layer applied by the coating treatment include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, a stainproof layer, and a water repellent layer. Each of these coating layers may be used alone, or a plurality of coating layers may be used in multiple layers. When a coating layer is applied to both sides, a similar coating layer or a different coating layer may be applied to each surface.

  Each of these coating layers is an ultraviolet absorber for the purpose of protecting the lens and eyes from ultraviolet rays, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer, an antioxidant, and a lens for the purpose of improving the weather resistance of the lens. For the purpose of enhancing fashionability, dyes and pigments, photochromic dyes and photochromic pigments, antistatic agents, and other known additives for enhancing the performance of the lens may be used in combination. For the layer to be coated by coating, various leveling agents for the purpose of improving coating properties may be used.

  The primer layer is usually formed between a hard coat layer described later and the optical lens. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer formed thereon and the lens, and in some cases, the impact resistance can also be improved.

  Any material can be used for the primer layer as long as it has high adhesion to the obtained optical lens, but usually it is mainly composed of urethane resin, epoxy resin, polyester resin, melanin resin, and polyvinyl acetal. A primer composition or the like is used. The primer composition may use an appropriate solvent that does not affect the lens for the purpose of adjusting the viscosity of the composition. Of course, you may use it without a solvent.

  The primer composition can be formed by either a coating method or a dry method. When using a coating method, a primer layer is formed by solidifying after applying to a lens by a known coating method such as spin coating or dip coating. When performing by a dry method, it forms by well-known dry methods, such as CVD method and a vacuum evaporation method. When forming the primer layer, the surface of the lens may be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary for the purpose of improving adhesion.

  The hard coat layer is a coating layer for the purpose of imparting functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, and weather resistance to the lens surface.

  The hard coat layer is generally composed of an organic silicon compound having a curing property and an element selected from the element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A hard coat composition containing at least one kind of oxide fine particles and / or at least one kind of fine particles composed of a composite oxide of two or more elements selected from these element groups is used. In addition to the above components, the hard coat composition includes at least amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, perchloric acid salts, acids, metal chlorides and polyfunctional epoxy compounds. It is preferable to include any of them. An appropriate solvent that does not affect the lens may be used in the hard coat composition. Of course, you may use it without a solvent.

  The hard coat layer is usually formed by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Examples of the curing method include thermal curing, a curing method by irradiation with energy rays such as ultraviolet rays and visible rays, and the like. In order to suppress the occurrence of interference fringes, the refractive index of the hard coat layer is preferably in the range of ± 0.1 in the difference in refractive index from the lens.

The antireflection layer is usually formed on the hard coat layer as necessary. The antireflection layer includes an inorganic type and an organic type. In the case of an inorganic type, an inorganic oxide such as SiO ₂ or TiO ₂ is used, and a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method is used. It is formed by the dry method. In the case of an organic type, it is formed by a wet method using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.

The antireflection layer has a single layer and a multilayer, and when used in a single layer, the refractive index is preferably at least 0.1 lower than the refractive index of the hard coat layer. In order to effectively exhibit the antireflection function, a multilayer antireflection film is preferably used. In that case, a low refractive index film and a high refractive index film are alternately laminated. Also in this case, the difference in refractive index between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O _5, and examples of the low refractive index film include an SiO ₂ film. .

  On the antireflection film layer, an antifogging coating film layer, a contamination prevention layer, and a water repellent layer may be formed as necessary. As a method for forming the antifogging coat layer, the antifouling layer, and the water repellent layer, there is no particular limitation on the treatment method, treatment material, and the like as long as the antireflection function is not adversely affected. A coating treatment method, antifouling treatment method, water repellent treatment method, and material can be used. For example, in the anti-fogging coat and anti-fouling treatment method, a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it water-absorbing, a method of covering the surface with fine irregularities and increasing water absorption, Examples thereof include a method of absorbing water using photocatalytic activity and a method of preventing water droplet adhesion by applying a super water-repellent treatment. Further, in the water repellent treatment method, a method of forming a water repellent treatment layer by vapor deposition or sputtering of a fluorine-containing silane compound or the like, or a method of forming a water repellent treatment layer by coating after dissolving the fluorine-containing silane compound in a solvent Etc.

Although the lens can be dyed by a known dyeing method, it is usually carried out by the following method.
(1) A method of immersing a lens in a dyeing solution, (2) A method of coating using a coating agent containing a dye, or a method of providing a dyeable coating layer and dyeing the coating layer, (3) Raw material monomer (4) A method in which a sublimable dye is heated and sublimated.

  In the method (1), generally, a lens fabric finished with a predetermined optical surface is immersed (dyeing step) in a dyeing solution in which a dye to be used is dissolved or uniformly dispersed, and then as required. In this method, the lens is heated to fix the dye (annealing step after dyeing). The pigment used in the dyeing process is not particularly limited as long as it is a known pigment, but usually an oil-soluble dye or a disperse dye is used. The solvent used in the dyeing process is not particularly limited as long as the dye used is soluble or can be uniformly dispersed. In this dyeing process, a surfactant for dispersing the dye in the dyeing solution or a carrier for promoting dyeing may be added as necessary. In the dyeing step, a dyeing bath is prepared by dispersing a dye and an optionally added surfactant in water or a mixture of water and an organic solvent, and an optical lens is immersed in the dyeing bath, and a predetermined temperature is set. And dye for a predetermined time. Although the dyeing temperature and time vary depending on the desired color density, it is usually from 120 ° C. or less to several minutes to several tens of hours, and the dye concentration in the dye bath is 0.01 to 10% by weight. Moreover, when dyeing is difficult, you may carry out under pressure. The post-dyeing annealing step performed as necessary is a step of performing heat treatment on the dyed lens fabric. The heat treatment is performed by removing water remaining on the surface of the lens fabric dyed in the dyeing process with a solvent or air-drying the solvent, and then, for example, in a furnace such as an infrared heating furnace in an atmospheric atmosphere or a resistance heating furnace. Let it stay for a predetermined time. In the post-dyeing annealing step, color loss of the dyed lens fabric is prevented (color loss prevention treatment), and moisture that has penetrated into the lens fabric during dyeing is removed.

  In the method (2), the dyed coating layer is applied to the lens surface by applying an organic coating liquid in which the pigment is dispersed or dissolved to the plastic lens, and then curing it, instead of directly dyeing the plastic lens material. This is a method of forming, or a method of (1) after forming a dyeable coating layer on the surface of a plastic lens, that is, a method of dyeing by immersing a plastic lens in a dyeing solution and heating.

  The method (3) is a method in which a dye is previously dissolved in a raw material monomer for a plastic lens and then polymerized. The dye to be used is not particularly limited as long as it can be uniformly dissolved in the raw material monomer or dispersed so as not to impair the optical properties.

  The method (4) includes (a) a method of dyeing a plastic lens by sublimating a solid sublimable dye, and (b) a substrate formed by applying a solution containing the sublimable dye is opposed to the plastic lens in a non-contact state. And a method of dyeing by heating the substrate and the lens, and (c) a method of dyeing by heating after transferring a transfer layer composed of a colored layer containing a sublimable dye and an adhesive layer to a plastic lens. Yes, the optical lens of the present invention may be dyed by any method. The dye to be used is not particularly limited as long as it has a sublimation property.

Hereinafter, the present invention will be specifically described by way of examples. Light cut rate of plastic lens, Abbe number, Y. I value was evaluated by the following method.
-Light cut rate: A 9 mm thick flat resin was analyzed with a spectrophotometer, and the light cut rate at 400 nm was measured.
Abbe number: Measured at 20 ° C. using a Purichrich refractometer.
・ Y. I value: Y. The I value is a yellow index in hue evaluation and can be measured with a color difference meter. Using a color difference meter (CR-200, CT-210) manufactured by Minolta, a circular flat plate having a thickness of 9 mm and a diameter of 75 mm was prepared by cast polymerization and measured.

[ Comparative Example 4 ]
(Manufacture of plastic lenses)
50.6 parts by weight of bis (isocyanatomethyl) norbornane, 0.06 parts by weight of dibutyltin dichloride as a curing catalyst, 0.12 parts by weight of Zelec UN (trade name, acidic phosphate ester) manufactured by Stepan, manufactured by Ciba Specialty Chemicals Tinuvin 327 (trade name, UV absorber) 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (0.05 parts by weight) was mixed and dissolved at 15 to 20 ° C. . 2. 25.6 parts by weight of polythiol based on 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, and polythiol based on pentaerythritol tetrakis (β-mercaptopropionate). 9 parts by weight was charged and mixed to obtain a mixed homogeneous liquid. This uniform liquid was defoamed at 600 Pa for 1 hour, filtered through a 1 μm PTFE filter, and then poured into a mold mold composed of a glass mold and tape having a diameter of 75 mm and a thickness of 9 mm, thereby producing a lens. The mold was put into an oven, gradually heated from 20 ° C. to 120 ° C., and polymerized in 20 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 130 ° C. for 4 hours. The resulting resin had a light beam cut rate at 400 nm of 99.7%, an Abbe number of 40.6, I value: 6.4. The results are shown in Table 1.

[Example 2]
In place of the UV absorber used in Comparative Example 4 , Tinuvin 384 (trade name, UV absorber) isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-t-butyl manufactured by Ciba Specialty Chemicals Co., Ltd. Except having used 0.50 weight part of -4-hydroxyphenyl propionate, it carried out similarly to the comparative example 4. The evaluation result of the obtained plastic lens is shown in Table 1.

[Example 3]
In place of the UV absorber used in Comparative Example 4 , Tinuvin 234 (trade name, UV absorber) 2- [2-hydroxy-3,5-bis (dimethylbenzyl) phenyl] -2H-benzotriazole manufactured by Ciba Specialty Chemicals The same procedure as in Comparative Example 4 was performed except that 0.25 parts by weight was used. The evaluation results of the obtained plastic lens are shown in Table 1.

[Example 4]
In place of the ultraviolet absorber used in Comparative Example 4 , Tinuvin 928 (trade name, ultraviolet absorber) 2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3) manufactured by Ciba Specialty Chemicals 3-tetramethylbutyl) phenyl] -2H-benzotriazole The same procedure as in Comparative Example 4 was performed except that 0.20 part by weight was used. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 1]
In place of the ultraviolet absorber used in Comparative Example 4 , 2.50 parts by weight of Biosorb 583 (trade name, ultraviolet absorber) 2- (2-hydroxy-5-t-octylphenyl) benzotriazole manufactured by Kyodo Yakuhin Co., Ltd. was used. Others were the same as in Comparative Example 4 . The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 2]
Instead of the ultraviolet absorber used in Comparative Example 4 , Tinuvin 320 (trade name, ultraviolet absorber) 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole 0.65 manufactured by Ciba Specialty Chemicals The same procedure as in Comparative Example 4 was performed except that parts by weight were used. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 3]
Other than using 1.22 parts by weight of Seesorb 707 (trade name, ultraviolet absorber) 2- (4-octyloxy-2-hydroxyphenyl) benzotriazole manufactured by Sipro Kasei Co., Ltd. instead of the ultraviolet absorber used in Comparative Example 4 Were performed in the same manner as in Comparative Example 4 . The evaluation results of the obtained plastic lens are shown in Table 1.

[Reference example]
A resin was prepared in the same manner as in Comparative Example 4 without adding any ultraviolet absorber used in Comparative Example 4 . The evaluation results of the obtained plastic lens are shown in Table 1.
In the system to which no ultraviolet absorber was added, the light cut rate at 400 nm was 13.2%, and the Abbe number was 40.5.

In the polyurethane resin to which 2.5% of Viosorb 583 was added in Comparative Example 1, the light ray cut rate at 400 nm was very high at 99.9%, but the Abbe number was 38.7, and the Abbe number of the reference example was 40.5. A significant decrease was seen in comparison. Furthermore, even in the polyurethane resin to which 1.22% of Seesorb 707 was added in Comparative Example 3, the light cut rate at 400 nm was very high at 99.9%, but the Abbe number was 39.4, and the Abbe number of the reference example was 40.5. The Abbe number decreased. In Comparative Example 2, the polyurethane resin to which 0.65% of Tinuvin 320 was added had a very high light cut rate of 99.9%, and the Abbe number was not decreased. I value rose to 8.3 and the deterioration of yellowness was confirmed. In Examples 1 to 4, by appropriately selecting the type and addition amount of the ultraviolet absorber, it was possible to have a high light cut rate and a high Abbe number and to suppress the yellowness to 6.5 or less. That is, it was found that a polyurethane resin having low chromatic aberration and high transparency can be provided by using a polymerizable composition to which a specific benzotriazole ultraviolet absorber is added.

Polyurethane resins obtained by reacting polythiols with polyiso (thio) cyanate compounds are colorless and transparent, have a high refractive index and low dispersion, and are ideal resins for plastic lenses with excellent impact, dyeability, and processability. One. The present invention provides a high-performance polyurethane-based lens that has low chromatic aberration, is transparent, and has a high UV cut rate, and contributes to the development of this field.

Claims (5)

A polythiol compound consisting of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and pentaerythritol tetrakis (β-mercaptopropionate);
A polyiso (thio) cyanate compound comprising bis (isocyanatomethyl) norbornane;
2- [2-hydroxy-3- (dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H-benzotriazole, isooctyl-3- (3- (2H-benzotriazole- consisting of 2-yl) -5-t-butyl-4-hydroxyphenyl propionate, and 2- [2-hydroxy-3,5-bis (dimethylbenzyl) phenyl] one selected from -2H- benzotriazole A benzotriazole-based ultraviolet absorber, and a polymerizable composition for lenses,
Wherein the light-cutting at a wavelength 400nm of the resin plate having a thickness of 9mm obtained from the composition is 99.8% or more, lenses for the polymerizable composition. The manufacturing method of resin which hardens the polymeric composition for lenses of Claim 1 . A resin obtained by curing the polymerizable composition for lenses according to claim 1 . An optical element made of the resin according to claim 3 . A lens made of the resin according to claim 3 .