KR20100094378A - High refractive index optical resin composition having improved impact resistance, high refractive index plastic optical lens and manufacturing method of the plastic optical lens - Google Patents

Abstract

PURPOSE: A resin composition for a highly refractive optical lens is provided to obtain high refractivity and shock resistance, to have excellent thermal resistance after a multi coating process, to obtain superior optical properties including transparency and Abbe's number. CONSTITUTION: A resin composition for a highly refractive optical lens comprises 40-65 weight% of a diisocyanate mixture and 35-60 weight% of a thiol mixture. The diisocyanate mixture is comprised of 50-85 weight% of dicyclohexylmethanediisocyanate and 15-50 weight% of 1,6-hexamethylene. The thio mixture is comprised of 60-99.9 weight% of 1,2-bis(2-mercaptoethylthio)-3-mercapto and 0.1- 40 weight of pentaerythritoltetrakis(mercaptopropionate) or their mixture.

Description

High Refractive Index Optical Resin Composition Having Improved Impact Resistance, High Refractive Index Plastic Optical Lens and Manufacturing Method of the Plastic Optical Lens

The present invention relates to a resin composition for a high refractive optical lens excellent in impact resistance, a high refractive optical lens using the same, and a method for manufacturing the same. More specifically, optical properties such as lightness, formability and dyeability, and workability such as Abbe number and transparency The present invention relates to a resin composition for high-refractive optical lenses excellent in impact, high heat resistance of a solid resin and not easily cracked by heat even after multi-coating, a high refractive optical lens having excellent impact resistance, and a method of manufacturing the same.

Glass lens, which has been widely used as an optical lens for a long time, has a low coefficient of thermal expansion, so that the lens is less deformed due to external temperature change, and there is less damage due to temperature change of the multi-layer treated on the surface to increase transmittance. However, glass lenses are weak to impact and heavy, and thus are replaced with plastic lenses that are lightweight and have excellent impact resistance as well as excellent processability such as dyeing compared to glass lenses.

In recent years, as the demand for the transmittance and stability level of plastic lenses is increased, multi-coating (SiO ₂ , ZrO _{2) is} applied to both surfaces of the lens in most optical lenses, especially spectacle lenses. Etc.) to increase the transmittance, but this multi-coating layer has a problem that the lens is easily broken by concentrating the impact applied from the outside in one place.

A copolymer of diaryl isophthalate known from Korean Patent Laid-Open Publication No. 1992-0004464, diaryl isophthalate added with dihydric alcohol and diethylene glycol bisaryl carbonate, and xylene diisocyanate known from Korean Patent Publication No. 1994-004010 In the case of plastic spectacle lenses manufactured using 1,2-bismercaptoethyl-3-mercaptopropane and polymethyl methacrylate copolymer, multi-coating to increase the transmittance causes the spectacle lens to break easily. .

In addition, the injection molded polycarbonate optical lens has excellent impact strength after multi-coating, but is severely deformed by heat during use as a thermoplastic resin, and more severely deformed at the center of the thinner lens than the thicker edge. When wearing such spectacle lenses, eye dizziness is caused, and an important optical characteristic, Abbe's number, is lowered.

In order to solve the problems related to the thermal stability of the lens made of the thermoplastic resin, a resin for thermosetting plastic lens has been proposed as an alternative, and in Korean Patent Nos. 0638194 and 0688698, a modified polyol and a diisocyanate are mixed to provide an optical lens. Methods of preparing are known. However, the impact resistance and the heat resistance have been improved, but by casting the optical resin into a flat plate, and then polishing again to manufacture the lens, there is a problem that the cost is high and the refractive index is about 1.523, so that the edge of the lens becomes thick.

In Korean Patent Publication No. 472837, dihydric alcohol was added to diisocyanate, mixed with tetravalent polythiol, and thermally cured to prepare an optical lens, thereby increasing the impact strength of the lens. However, the optical lens composition according to the patent was able to increase the impact strength in the state of the dough (plastic lens without post-processing), but after the multi-coating, the impact resistance is poor, FDA standards (127 cm height, 16.0g) Did not satisfy. In addition, there is also a problem that a lot of defects occur due to the high viscosity of the composition by preparing a monomer composition for an optical lens by adding a dihydric alcohol to diisocyanate in advance. In addition, the optical lens composition is sufficient to make the frameless spectacle lens, but there are many shortages for the spectacle-safe spectacle lens, and there is a problem that the edge of the lens becomes thick due to the low refractive index of about 1.555.

Korean Patent No. 689867 discloses a resin composition for a plastic optical lens and a method of manufacturing an optical lens, which are excellent in light weight, moldability, dyeing property, Abbe number, transparency, etc., and have excellent impact resistance after multi-coating. In addition, the impact resistance after the multi-coating satisfied the FDA standard (127 cm height, 16.0g), but the refractive index is about 1.530 ~ 1.570, the problem of thickening the edge of the lens and low added value remains.

The present inventors have diligently studied to solve the problems of the prior art, and as a result, a specific content in a diisocyanate mixture composed of a specific content of dicyclohexylmethane diisocyanate (H ₁₂ MDI) and 1,6-hexamethylene diisocyanate (HDI) 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane and trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (mercaptopropionate) or mixtures thereof The present invention has found that the resin composition prepared by blending has high general properties required for an optical lens, particularly high refractive index and excellent impact resistance.

Therefore, the object of the present invention is a high refractive index (nE, 20 ℃) of 1.580 or more Excellent impact resistance, impact strength passes the FDA impact test (127 cm height, 16.0g) even after multi-coating, processability of light weight, formability and dyeing, as well as Abbe's number, transparency and UV protection It is to provide a resin composition for high refractive optical lens excellent in optical characteristics such as.

Still another object of the present invention is to provide a high refractive optical lens having a refractive index (nE, 20 ° C.) of 1.580 or more, which is excellent in impact resistance as an optical lens manufactured using the resin composition for an optical lens.

The present invention for solving the above problems is a diisocyanate mixture 40 to 65 consisting of 50 to 85% by weight of dicyclohexyl methane diisocyanate (H ₁₂ MDI) and 15 to 50% by weight of 1,6-hexamethylene diisocyanate (HDI) 60% to 99.9% by weight of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane and trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (mercaptoprop) Pionate) or a mixture of 35 to 60% by weight of a thiol mixture consisting of 0.1 to 40% by weight thereof.

Increasing the amount of 1,6-hexamethylene diisocyanate (HDI) in the diisocyanate mixture increases the impact strength of the lens, but the heat resistance is poor, and when the amount of the dicyclohexyl methane diisocyanate (H ₁₂ MDI) is increased, It was good, but the impact strength fell slightly. On the basis of this, in the resin composition for an optical lens of the present invention, dicyclohexyl methane diisocyanate (H ₁₂ MDI) and 1,6-hexamethylene diisocyanate (HDI) are respectively 50 in consideration of the heat resistance and impact strength of the final lens. It is characterized by the use of ~ 85% by weight and 15-50% by weight.

The thiol mixture is comprised of 60-99.9% by weight, preferably 70-95% by weight of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane and trimethylolpropane tris (mercaptopropionate), Pentaerythritol tetrakis (mercaptopropionate) or a mixture thereof is characterized by consisting of 0.1 to 40% by weight, preferably 5 to 30% by weight. The trimethylolpropane tris (mercaptopropionate) and / or pentaerythritol tetrakis (mercaptopropionate) serves to slightly increase the impact strength without a significant decrease in the heat resistance and refractive index of the final resin composition. It is believed that this is due to the increase of intermolecular mutual attraction due to the presence of ester groups in the polymer forming the lens.

The resin composition for an optical lens obtained by the above method has a liquid refractive index (nD, 20 ° C.) of 1.530 to 1.600, a solid phase refractive index (nE, 20 ° C.) of 1.580 to 1.630, Abbe number 32 to 52, and a liquid viscosity of 20 to 3000. (cps, 20 ° C) and heat cured to obtain a high refractive optical lens having a refractive index (nE, 20 ° C) of 1.580 or more, which was excellent in impact resistance and excellent in heat resistance of a multi-film.

The spectacle lens obtained by thermal curing and post-treatment of the optical lens composition according to the present invention has excellent heat resistance of the multi-film and has impact resistance that complies with the FDA spectacle lens standard (ANS standard, 127 cm height 16.0 g falling ball test), The high refractive index of 1.580 ~ 1.630 provides a safe optical lens for athletes, general athletes who have a lot of exercise, or workers exposed to impacts in the industrial field, even though the edges of the lenses are thin.

A diisocyanate mixture comprising this resin composition for high refractive index optical lens excellent in impact resistance of the present invention includes dicyclohexylmethane diisocyanate (H ₁₂ MDI) and hexamethylene diisocyanate (HDI). The resin composition for an optical lens of the present invention is a resin containing one or two or more diisocyanate compounds selected from the group consisting of alkylene diisocyanate compounds, alicyclic diisocyanate compounds, heterocyclic diisocyanate compounds, and sulfur-containing diisocyanate compounds. It may further comprise an amount of 0.1 to 10% by weight based on the total weight of the composition.

In the alkylene diisocyanate compound, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2-dimethyl Pentane diisocyanate, 2,2,4-trimethylhexanediisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,3,4-trimethylhexamethylene diisocyanate, 1 , 6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8 Diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-1,2- Diiso Nate, 1, 4- butylene glycol dipropyl ether -1,3- diisocyanate, 1, 4- butylene glycol dipropyl ether -1,4- diisocyanate, 1, 4- butylene glycol dipropyl ether -2 , 3-diisocyanate, 1,4-butylene glycol dipropyl ether-2,4-diisocyanate, methyllysine diisocyanate, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexahexa Noate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, mesityrylylenetriisocyanate, 2,6-di (isocyanatomethyl) furan and the like.

Examples of the alicyclic diisocyanate compound include 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane and 3,9-bis (isocyanatomethyl) tri Cyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9-bis (isocyanatomethyl Tricyclo [5,2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) ratio Cyclo [2,2,1] heptane, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethyl methanedi Isocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3 Isocyanato Lofil) -5-isocyanatomethylbicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl ratio Cyclo [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) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocy Anatopropyl) -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-isocy Anatoethyl) -bicyclo [2,2,1] -heptane, 1,3,5-tris (isocyanatome ) Cyclohexane, dicyclohexylmethane-4,4-diisocyanate (H ₁₂ MDI) and the like.

Examples of the heterocyclic diisocyanate compound include thiophene-2,5-diisocyanate, methyl thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1, 4-dithiane-2,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-2 -Methyl-4,5-diisocyanate, ethyl 1,3-dithiolane-2,2-diisocyanate, tetrahydrothiophene-2,5-diisocyanate, methyltetrahydrothiophene-2,5-diisocyanate, Ethyl tetrahydrothiophene-2,5-diisocyanate, methyl tetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate, cyclohexanediisothio Cyanate and the like.

Examples of the sulfur-containing diisocyanate compound include 4-isocyanato-4'-isothiocyanatodiphenyl sulfide and 2-isocyanato-2'-isothiocyanatodiethyl disulfide. Feed, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfon diisocyanate, dithiodimethyl diisocyanate, dithio diethyl diisocyanate, dithio dipropyl diisocyanate, dicyclohexyl sulfi-4, 4'-diisocyanate, 1-isocyanatomethylthia-2,3-bis (2-isocyanatoethylthia) propane, and the like.

The content of dicyclohexyl methane diisocyanate in the diisocyanate mixture is preferably 50 to 85% by weight, more preferably 60 to 80% by weight. If the content of dicyclohexyl methane diisocyanate is less than 50% by weight, the heat resistance of the lens may be drastically deteriorated, and the multi-film on the surface of the lens may be easily cracked, and heat sinking may occur at the center of the lens. In addition, the content of 1,6-hexamethylene diisocyanate in the diisocyanate mixture is preferably 15 to 50% by weight, more preferably 20 to 40% by weight. When the content of 1,6-hexamethylene diisocyanate is less than 15% by weight, the impact strength of the lens is lowered. When the content of 1,6-hexamethylene diisocyanate is more than 50% by weight, the heat resistance of the lens is significantly decreased. On the other hand, alicyclic diisocyanate compounds, alkylene diisocyanate compounds, heterocyclic diisocyanate compounds, sulfur-containing aliphatic poly diisocyanate compounds and the like are added to dicyclohexyl methane diisocyanate and 1,6-hexamethylene diisocyanate in small amounts. This may be a problem, but when used a lot, there may be a problem that the physical properties of the optical lens, such as impact strength degradation, heat resistance or thermal stability of the lens is reduced.

Optical lens may be prepared by adding 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane alone to the diisocyanate mixture, but in the present invention, trimethylolpropane tris is used to enhance impact resistance. (Mercaptopropionate) and / or pentaerythritol tetrakis (mercaptopropionate) are added.

The thiol mixture is preferably used 35 to 60% by weight based on the total weight of the resin composition for the optical lens, more preferably 40 to 50% by weight. When the thiol mixture exceeds 60% by weight relative to the total weight of the resin composition for the optical lens, the lens surface strength is very weak due to uncuring of the lens, so that a lot of absorption occurs on the lens surface during the production process, and the surface is corroded by the cleaning liquid when the lens is washed. This occurs, a problem in which the transparency of the lens sharply drops. In addition, when the thiol mixture is less than 35% by weight, the reaction between the isocyanate compounds occurs, the impact strength of the lens is lowered, and the thermal stability and the light resistance of the lens are sharply lowered by the unreacted isocyanate remaining in the lens.

The resin composition for an optical lens of the present invention comprises 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane and trimethylolpropane tris (mercaptopropionate) and / or penta which constitute the thiol mixture. 2- (2-mercaptoethylthio) propane-1,3-thiol, 2- (2-mercaptoethylthio) -3- [2- (3-mer in addition to erythritol tetrakis (mercaptopropionate) Capto-2- (2-mercaptoethylthio) -propylthio] ethylthio-propane-1-thiol, 2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mer Capto-2- (2-mercaptoethylthio) -propylthio] propylthio} -propane-1-thiol, trimethylolpropane tris (mercaptopropionate, trimethylolethane tris (mercaptopropionate), glycerol Tris (mercaptopropionate), trimethylolchloro tris (mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethyl Olethane tris (mercaptoacetate, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakiscapcaptoacetate, [1,4] dithiane-2-yl-methanethiol, 2- (2-mercapto -Ethylsulfanyl) -propane-1,3-dithiol, 2-([1,4] dithiane-2 ylmethylsulfanyl) -ethanethiol, 3- (3-mercapto-propionylsulfanyl)- Propionic acid 2-hydroxymethyl-3- (3-mercapto-propionyloxy) -2- (3-mercapto-propionyloxymethyl) -propyl ester, 3- (3-mercapto-propionylsulphate Panyl) -propionic acid 3- (3-mercapto-propionyloxy) -2,2-bis- (3-mercapto-propionyloxymethyl) -propyl ester, (5-mercaptomethyl- [1, 4] ditian-2-yl) -methanethiol and one or two or more selected from the group consisting of compounds represented by the following general formula (1) may be further included.

When the trimethylolpropane tris (mercaptopropionate) and / or pentaerythritol tetrakis (mercaptopropionate) compound is used at less than 0.1% by weight, there is no improvement in the impact strength of the lens and exceeds 40% by weight. When used, there is a problem in using an existing mold by lowering the multi heat resistance and refractive index of the lens.

A UV absorber may be further included for improving light resistance and blocking UV rays of the optical lens manufactured from the resin composition for an optical lens of the present invention. As the ultraviolet absorber, any known ultraviolet absorber that can be used for plastic spectacle lenses can be used without limitation. For example, ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H -Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3', 5'-di -t-butylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-t -Octylphenyl) -2H-benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy 2-hydroxybenzophenone, 4-benzooxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2-hydroxy- having good ultraviolet absorption in the wavelength range of 400 or less and having good solubility in the composition of the present invention. 4-methoxybenzophenone, ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole or 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) -2H-benzotriazole, 2- (2 ' -Hydroxy-3,5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 -Chloro-2H-benzotriazole, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be used.

In addition, the resin composition for an optical lens of the present invention may further include a color corrector for correcting the initial color of the lens. As the color corrector, organic dyes, organic pigments, inorganic pigments, and the like may be used. In the embodiment of the present invention, 1-hydroxy-4- (p-toluidin) entraquinone [1-hydroxy-4- (p-toluidin) anthraquinone], perinone dye, etc. were used. By adding 0.1 to 50,000 ppm, preferably 0.5 to 10,000 ppm, of such organic dye per resin composition for optical lenses, it is possible to prevent the lens from becoming yellow by the addition of an ultraviolet absorber, an optical resin, and a monomer.

The resin composition for optical lenses of the present invention may further include a release agent. As the release agent, a silicone-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a fluorine-based surfactant having a phosphate ester group, a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group, an alkyl quaternary ammonium salt, that is, trimethylcetyl A component selected from ammonium salt, trimethyl stearyl, dimethylethyl cetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt, and phosphate ester may be used alone or in combination of two or more thereof. Preferably, phosphate ester is used. As phosphate ester, isopropyl acid phosphate, diisopropyl acid phosphate, butyl acid phosphate, octylic acid phosphate, dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) Phosphates and the like may be used alone or in combination of two or more thereof. As used in the examples of the present invention, it was found that the releasing property when phosphate ester-based ZELEC UN (DUPONT Co., Ltd.) cured the mold from the lens after curing was the best. The addition amount of the release agent may be used in 0.0001 to 10% by weight in the composition, but preferably used in 0.001 to 2% by weight was good demoulding of the mold in the lens and high polymerization yield. If the addition amount of the release agent is less than 0.0001% by weight, a phenomenon occurs when the glass mold surface adheres to the lens when the molded spectacle lens is separated from the glass mold, and when it exceeds 10% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that a stain occurs on the surface.

The resin composition for an optical lens of the present invention may further include a polymerization initiator. As the polymerization initiator, amine-based or tin-based compounds may be used. Examples of the tin compound include butyl tin dilaurate, dibutyl tin dichloride, dibutyl tin diacetate, stannous octylic acid tin, dibutyl tin dilaurate, tetrafluoro tin, tetrachloro tin, tetrabromo tin, tetraiod tin, Methyltin trichloride, butyltin trichloride, dimethyltin dichloride, dibutyltin dichloride, trimethyltin chloride, tributyltin chloride, triphenyltin chloride, dibutyltin sulfide, di (2-ethylsecyl) tin oxide Or the like may be used alone or in combination of two or more thereof. When such a tin compound was used, the polymerization yield was high and there was no bubble generation. The amount used is preferably 0.001 to 4% by weight based on the total weight of the resin composition.

The optical composition, especially the spectacle lens, is obtained by thermal curing the resin composition for an optical lens of the invention. Preferred embodiments for preparing the spectacle lens by thermal curing the composition of the present invention are as follows. First, after the polymerization initiator is finally added to the composition of the present invention, nitrogen is blown to remove air in the mixing vessel, and the mixture is stirred under reduced pressure for 2 to 5 hours, the stirring is stopped, and then degassed under reduced pressure and injected into the mold. do. The mold is preferably a glass mold or a metal mold fixed with a plastic gasket or polyester or polypropylene adhesive tape. The glass mold injected with the mixture was placed in a forced circulation oven, maintained at 33 to 37 ° C. for 2 hours, heated to 38 to 42 ° C. for 3 hours, heated to 80 to 90 ° C. for 10 hours, and heated to 120 to 140 ° C. for 2 to 4 hours. After cooling at 120-140 degreeC for 2 hours, and cooling it for 60 hours at 60-80 degreeC, a solid material is released from a mold and an optical lens is obtained. The optical lens thus obtained is annealed at a temperature of 120 to 140 ° C. for 1 to 4 hours to obtain a final desired plastic spectacle lens (dough).

In addition, the optical lens obtained by the above method can be subjected to hard coating and multi-coating treatment in order to increase the optical characteristics. The hard coat layer may be formed of at least one silane compound having functional groups such as an epoxy group, an alkoxy group, a vinyl group, and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, and aluminum oxide. The coating composition is coated with a thickness of 0.5 to 10 on the surface of the optical lens by impregnation or spin coating, and then heated or UV cured to complete the coating film.

The multi-coating layer, that is, the anti-reflective coating layer may be formed by vacuum deposition or sputtering of metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide and yttrium oxide. Most preferably, the silicon oxide film and the zirconium oxide film are repeatedly vacuum-deposited three or more times on both surfaces of the lens, and then the silicon oxide film is finally vacuum deposited. If necessary, a water film (fluorine resin) layer may be provided at the end, or an ITO layer may be provided between the silicon oxide and the zirconium oxide film.

The optical lens of the present invention may be used after coloring treatment with a disperse dye or a photochromic dye, as necessary.

The resin composition for an optical lens of the present invention is not limited to plastic spectacle lenses, and can be used for various optical products.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.

Example  One

The optical material and the lens of the present invention are prepared by dicyclohexyl methane diisocyanate (H ₁₂ MDI) 38.2 g, 1,6-hexamethylene diisocyanate 16.3 g, 1,2-bis (2-mercaptoethylthio) -3 -34.9 g of mercaptopropane and 10.1 g of pentaerythritol tetrakis (mercaptopropionate) were mixed to prepare a mixture, followed by 2- (2'-hydroxy-5'-methylphenyl) -2H-benzo with a UV absorber. 1.5 g of triazole, 0.1 g of polyoxyethylene octylphenol ether phosphate as a releasing agent, 50 ppm of 1-hydroxy-4- (p-toluidino) anthraquinone (blue) with organic dyes, 10 ppm of perrinone di (red), polymerization 0.1 g of dibutyltin dichloride as an initiator was placed in a mixing vessel equipped with a stirrer, replaced with nitrogen to remove air from the mixing vessel, and then stirred under reduced pressure for 2 hours, and the stirring was stopped, followed by degassing under reduced pressure to fix with polyester adhesive tape. Into a glass mold.

(2) The glass mold in which the mixture was injected was kept at 35 ° C. for 2 hours in a forced circulation oven, 3 hours at 40 ° C., 12 hours at 120 ° C., 2 hours at 120 ° C., and 2 hours at 70 ° C. After cooling to heat curing, the mold was released from the solid to obtain an optical lens having a center thickness of 1.2 to 2.2 mm.

(3) The optical lens obtained in (2) was processed to a diameter of 72 mm and then ultrasonically washed in a caustic soda washing solution, followed by annealing at 120 ° C. for 2 hours.

(4) The surface obtained by (3) is surface-etched in a 5% KOH solution, and then impregnated in hardener of Finecoder Co., Ltd., followed by thermosetting, and silicon oxide, zirconium oxide, silicon oxide, ITO, oxide, and zirconium on both sides. The film, silicon oxide, zirconium oxide, and water film (fluorine resin) were vacuum deposited to obtain a hard coated and multi-coated optical lens.

Property test method

The physical properties of each optical lens were measured by the following physical property test methods, and the results are reported in Table 1 below.

1) Refractive index and Abbe number: Measured using a multi-wavelength Abbe refractometer of Atago's DR-4 model. The specimen contact liquid was monobromonaphthalene.

2) Light transmittance: Measured using a SHIMADZU company UV 2450 model.

3) Specific gravity: Specific gravity was measured using OHAUS VPG214CN model.

4) Multi-film cracking phenomenon by heat: After leaving the lens specimen in an oven at 80 ° C for 60 minutes and visually observing it, if there is no cracking of the multi-film on one lens surface, A, 1 or less cracks of 10 mm or less, B, cracks C was evaluated as 10 or more.

5) Impact resistance: The impact resistance was conducted by a drop ball test with an American Instron Model Mini-Tower Impact Tester (Instron dynatub) at room temperature 22 ℃. When using the US Instron Model Mini-Tower Impact Tester (Instron dynatub), the uncoated lens (dough) was measured by dropping tubs and the multi-coated finished lens by piezo tubs. The impact test of the uncoated lens (dough) is 10 when the lens is dropped at the front of the lens with impact energy 8J, 11J and 14J. When broken, it was marked with X. In addition, the impact test of the multi-coated finished lens is O when 10 lenses (-0.00, 2.2mm center thickness) of the multi-coated finished product are dropped to the front of the lens with impact energy of 0.2J and 0.4J. When broken by 1 or 2, it was indicated by △, and when three or more were broken by X. Drop ball test consists of 10 multi-coated finished lenses (-0.00, center thickness of 2.2 mm), and a ball diameter of 16 g, 5/8 inch (approx. If one lens is not broken by falling, it is indicated by O, or broken by one or two, by Δ, and by three or more broken by X.

Example  2-12

According to the same method as in Example 1, a composition and a lens were prepared using the compositions shown in Table 1, and the experimental results are shown in Table 1.

Comparative example  One

53.6 g of dicyclohexyl methane diisocyanate (H ₁₂ MDI), 3.8 g of 1,6-hexamethylene diisocyanate, 32.7 g of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, pentaerythritol The same procedure as in Example 1 was carried out except that 9.4 g of tetrakis (mercaptopropionate) was mixed to prepare a resin composition for an optical lens, and the characteristics thereof are shown in Table 2.

Comparative example  2 ~ 6

Compositions and lenses were prepared in the compositions shown in Table 2 according to the same method as in Comparative Example 1, and the experimental results are shown in Table 2.

Abbreviation of Tables 1-2

Monomer

IPDI: isophorone diisocyanate

HDI: 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate)

H ₁₂ MDI: dicyclohexyl methane diisocyanate

     (dicyclohexylmethanediisocyanate)

BBH: bis (isocyanatomethyl) bicyclo [2,2,1] heptane

     (bis (isocyanatomethyl) bicyclo [2,2,1] heptane)

GMT: 2- (2-mercaptoethylthio) propane-1,3-dithiol

     (2- (2-mercaptoethylthio) propane-1,3-dithiol)

GST: 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane

     (1,2-bis (2-mercaptoethylthio) -3-mercaptopropane)

ETS: 2- (2-mercaptoethylthio) -3- {2- (3-mercapto-2- (2-mercaptoethylthio)-

     Propylthio) ethylthio} -propane-1-thiol (2- (2-mercaptoethylthio) -3- {2

    -[3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio} propane

    -1-thiol)

TMPMP: trimethylolpropane tris (mercaptopropionate)

     (trimethylolpropane tris (mercaptopropionate))

PETMP: pentaerythritol tetrakis (mercaptopropionate)

    (pentaerylthritoltetrakis (mercaptopropionate))

YIS:

UV absorbers

CBMP: 2- (5-chloro-2H--benzotriazol-2-yl) -4-methyl-6-t-butylphenol

           (2- (5-chloro-2H-benzotriazole-2-yl) -4-methyl-6- (tert-butyl) phenol)

HMBT: 2- (2'-hydroxy-5'-methylphenyl) -2H-benzotriazole

     (2- (2'-hydroxy-5'-methylphenyl) -2H-benzotriazole)

HBCBT: 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole

    (2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole)

HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole

           (2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole)

Release agent

DBP: dibutyl acid phosphate

DIPP: diisopropyl acid phosphate

PENPP: polyoxyethylene octyl phenol ether phosphate (polyoxyethylene octyl

-phenol ether phosphate)

Color correction agent (Organic Dyes)

HTAQ: 1-hydroxy-4- (p-toluidine) entraquinone

   [1-hydroxy-4- (p-toluidine) anthraquinone]

PRD: perinone dye

Polymerization initiator

BTC: dibutyltindichloride

BTL: butyl tin dilaurate

According to the present invention, it is possible to obtain a urethane-based plastic optical lens having a high refractive index and excellent impact resistance after multi-coating and a very low thermal deformation phenomenon, and the optical lens according to the present invention can be particularly applied to spectacle lenses. The present invention can be used in various optical products such as a recording medium substrate, a coloring filter, an ultraviolet absorbing filter used for an optical fiber, an optical disk, a magnetic disk, and the like, as well as a perspective light of a mobile phone.

Claims (11)

40 to 65% by weight of a diisocyanate mixture consisting of 50 to 85% by weight of dicyclohexylmethane diisocyanate (H ₁₂ MDI) and 15 to 50% by weight of 1,6-hexamethylene diisocyanate (HDI), and 1,2-bis 60 to 99.9 wt% of (2-mercaptoethylthio) -3-mercaptopropane, trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (mercaptopropionate) or mixtures thereof Resin composition for a high refractive optical lens comprising 35 to 60% by weight of a thiol mixture consisting of 40% by weight. The resin composition of claim 1, wherein the resin composition is 2- (2-mercaptoethylthio) propane-1,3-thiol, 2- (2-mercaptoethylthio) -3- [2- (3-mercapto- 2- (2-mercaptoethylthio) -propylthio] ethylthio-propane-1-thiol, 2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mercapto- 2- (2-mercaptoethylthio) -propylthio] propylthio} -propane-1-thiol, trimethylolethane tris (mercaptopropionate), glycerol tris (mercaptopropionate), trimethylolchloro tris (Mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), pentaerythritol tetrakismercaptoacetate, [1,4] dithiane-2-yl-methane Thiol, 2- (2-mercapto-ethylsulfanyl) -propane-1,3-dithiol, 2-([1,4] ditian-2 ylmethylsulfanyl) -ethanethiol, 3- (3- Mercapto-propionylsulfanyl) -propionic acid 2-hydr Silmethyl-3- (3-mercapto-propionyloxy) -2- (3-mercapto-propionyloxymethyl) -propyl ester, 3- (3-mercapto-propionylsulfanyl) -propionic acid 3- (3-mercapto-propionyloxy) -2,2-bis- (3-mercapto-propionyloxymethyl) -propyl ester, (5-mercaptomethyl- [1,4] dithiane-2 Resin composition for a high refractive optical lens, characterized in that it further comprises 6 to 28% by weight of one or two or more thiol compounds represented by the following formula (1) (Y1S) and the total weight of the composition:
[Formula 1]

The method of claim 1, wherein the resin composition is 0.1 to 1 or 2 or more of the alkylene diisocyanate compound, alicyclic diisocyanate compound, heterocyclic diisocyanate compound and sulfur-containing diisocyanate compound 0.1 to the total weight of the resin composition A resin composition for high refractive optical lens, characterized in that it further comprises in an amount of 10% by weight. The resin composition for high refractive optical lens according to claim 1, wherein the resin composition further comprises one or two or more additives selected from the group consisting of an ultraviolet absorber, a mold release agent, a polymerization initiator, and a color correcting agent. The method of claim 4, wherein the ultraviolet absorber is 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -2H-benzotria Sol, 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzo 1 selected from the group consisting of hydroxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone The resin composition for high refractive optical lenses characterized by the above-mentioned, or 2 or more types. The method of claim 4, wherein the release agent is isopropyl acid phosphate, diisopropyl acid phosphate, butyric acid phosphate, octylic acid phosphate, dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, tridecanoic acid phosphate, and bis A resin composition for high refractive optical lenses, characterized in that one or two or more phosphate esters selected from the group consisting of (tridecanoic acid) phosphate. The resin composition for high refractive optical lens according to claim 4, wherein the polymerization initiator is a tin-based or amine-based compound. The method of claim 7, wherein the tin compound is butyl tin dilaurate, dibutyl tin dichloride, dibutyl tin diacetate, octylic acid tin, dibutyl dilaurate, tetrafluoro tin, tetrachloro tin, tetrabromo tin, Tetraiodine tin, methyltin trichloride, butyltin trichloride, dimethyltin dichloride, dibutyltin dichloride, trimethyltin chloride, tributyltin chloride, triphenyltin chloride, dibutyltin sulfide, and di- ( Resin composition for a high refractive optical lens, characterized in that one or two or more selected from the group consisting of 2-ethylsecyl) tin oxide. The resin composition for high refractive optical lens according to claim 4, wherein the color corrector is an organic dye. The high refractive optical lens obtained by thermosetting the resin composition for optical lenses of Claim 1. The optical lens according to claim 10, wherein the optical lens is an eyeglass lens.