WO2009107946A2 - Super-high refractive index optical resin composition having high heat deflection temperature and excellent thermal stability, optical lens using same and method for manufacturing the optical lens - Google Patents

Abstract

The present invention relates to a urethane-based optical resin composition having a high heat deflection temperature and a method for manufacturing an optical lens using the composition. A monomer composition for a plastic optical lens according to the present invention is lightweight and has excellent plasticity, dyeability, transparency, shock resistance, etc., and especially has a high initial heat deflection temperature, thereby reducing central deformation of the lens and cracking of the multi-film of the lens due to heat. Further, the monomer composition has excellent thermal stability to reduce discoloration of the lens due to heat.

Description

Ultra high refractive optical resin composition having high thermal deformation temperature and excellent thermal stability, optical lens using same and manufacturing method thereof

The present invention relates to an optical resin composition for an ultra high refractive urethane plastic optical lens, an optical lens using the same, and a manufacturing method thereof.

Urethane-based plastic optical lenses have excellent transparency, Abbe's number, and tensile strength as compared with other plastic lenses, and have been recognized for their superiority as optical lens materials. However, urethane-based plastic optical lenses have a low heat distortion temperature, which causes problems with the center deformation of the lens during hard and multi-coating (anti-reflective coating) on the lens surface after casting, and is also exposed to high temperature and high humidity or heat in a sauna. In this case, the thermal deformation of the lens is severe and the multi-film is severely cracked. This causes a problem of deterioration of the transparency of the lens sharply by forming a cloudy film on the lens surface.

In Korean Patent Application Publication No. 1987-0008928, 0.05 mol of xylene diisocyanate and 0.025 mol of pentaerythritol tetrakiscapcappropionate are thermally cured to produce a urethane-based high refractive plastic optical lens having excellent transparency, Abbe number, and tensile strength. However, the urethane-based high refractive plastic optical lens manufactured as described above has a problem in that the thermal deformation is severe when exposed to high temperature, so that the multi-film is easily cracked, and the center portion of the lens is deformed during hard and multi-coating on the len surface, and the refractive index is as low as 1.594.

Korean Patent Publication No. 1993-0006918 discloses an alicyclic diisocyanate compound and a pentaerythritol tetrakismercaptopropionate or 1,2-bis (2-mercaptoethylthio) in order to solve the central deformation problem of a urethane optical lens. 3-mercaptopropane is thermosetted, and the urethane plastic optical lens is manufactured. Although the urethane-based plastic optical lens manufactured is slightly higher in heat deformation temperature, the film is easily cracked when exposed to high temperature due to severe heat deformation, and also the lens center part is hard on the lens surface when the heat deformation temperature is low. Deformed The problem remains, and the refractive index is as low as 1.597.

Also in Korean Patent Publication No. 1992-0005708, xylene diisocyanate and 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane are thermally cured to obtain a urethane-based ultrahigh refractive plastic optical lens. This lens has a high refractive index of 1.655, There is a problem in that the lens center portion is deformed during hard and multi-coating on the lens surface, and there is a problem in that the multi-film is easily cracked due to severe thermal deformation when exposed to high temperature.

In Korean Patent Publication No. 10-0704314, a urethane-based high refractive plastic optical lens was manufactured by mixing a trivalent isocyanate compound with a divalent isocyanate compound in order to increase the heat deformation temperature of the lens, but this also has a problem of low refractive index.

In the present invention, while having excellent light weight, moldability, dyeability, transparency, impact resistance Monomer composition for plastic optical lenses having a high refractive index of 1.630 or more, high initial thermal deformation temperature of the solid resin, less multi-film cracking of the lens surface after multi-coating, and less central strain due to heat when hard and multi-coating the lens surface; An object of the present invention is to provide an optical lens using the same and a method of manufacturing the same.

In addition, in the present invention, the equivalent ratio of -SH (and -OH) /-NCO is 1.00 to 1.30, and alicyclic diisocyanate, alkylene diisocyanate, and the like are mixed with tolylene diisocyanate to improve thermal stability and storage stability of the lens. An object of the present invention is to provide an excellent monomer composition for plastic optical lenses and an ultra high refractive optical lens using the same.

In the present invention, to achieve the above object

(a) (i) alkylene diisocyanate compounds; Alicyclic diisocyanate compounds; Heterocyclic diisocyanate compounds; 25 to 65% by weight of a compound obtained by adding one or two or more diisocyanate compounds selected from sulfur-containing aliphatic diisocyanate compounds to tolylene diisocyanate, and (ii) 35 to 75% by weight of one or two or more mercapto compounds having at least one sulfur atom in the molecule, and (iii) an ultraviolet absorber; Mold release agents; And a polymerization initiator,

(b) the equivalent ratio of -SH (and -OH) /-NCO is between 1.00 and 1.30,

(c) liquid phase refractive index (Ne, 20 ° C) 1.550 to 1.660; Solid phase refractive index (Ne, 20 ° C) 1.630 to 1.685; Abbe number (20 degreeC) 24-50; And a monomer composition for an optical lens having a liquidus viscosity (20 ° C.) of 10 to 1,000 cps.

In addition, the present invention provides a plastic optical lens obtained by heat curing the monomer composition for an optical lens and a method of manufacturing the same.

The monomer composition for an optical lens and the optical lens using the same according to the present invention have a high refractive index (Ne, 20 ° C.) of 1.630, It has excellent optical properties such as excellent light weight, moldability, dyeability, Abbe's number, transparency and impact resistance. Also, early It has a high heat deformation temperature, a small multi-film cracking phenomenon on the lens surface, and less deformation due to heat, so there is no heat-centered deformation during post-processing such as hard and multi coating.

Examples of the diisocyanate compound which can be used in admixture with tolylene diisocyanate include alkylene diisocyanate compounds, alicyclic diisocyanate compounds, heterocyclic diisocyanate compounds, and aliphatic diisocyanate compounds containing sulfur.

In the alkylene diisocyanate compound, for example, Ethylene diisocyanate; Trimethylene diisocyanate; Tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; Octamethylene diisocyanate; Nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexanediisocyanate; Decamethylene diisocyanate; Butene diisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-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-diisocyanate; 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-diisocyanatohexanoate; 2-isocyanatopropyl-2,6-diisocyanatohexanoate; Mesityrylylenetriisocyanate; 2,6-di (isocyanatomethyl) furan and the like.

In the alicyclic diisocyanate compound, for example, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane; 3,9-bis (isocyanatomethyl) tricyclo [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) bicyclo [2,2,1] heptane; Isophorone diisocyanate; Bis (isocyanatomethyl) cyclohexane; Dicyclohexyl methane diisocyanate; Cyclohexanediisocyanate; Methylcyclohexanediisocyanate; Dicyclohexyldimethylmethane diisocyanate; 2,2'-dimethyldicyclohexylmethane diisocyanate; Bis (4-isocyanato-n-butylidene) pentaerythritol; Dimer acid diisocyanate; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [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-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 1,3,5-tris (isocyanatomethyl) -cyclohexane; Dicyclohexylmethane-4,4-diisocyanate (H₁₂MDI) and the like.

Heterocyclic diisocyanate compounds include, for example, 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; Cyclohexanediisothiocyanate, and the like.

Examples of the sulfur-containing aliphatic diisocyanate compound include 4-isocyanato-4'-isothiocyanatodiphenylsulfide; 2-isocyanato-2'-isothiocyanatodiethyl disulfide; Thiodiethyl diisocyanate; Thiodipropyl diisocyanate; Thiodihexyl diisocyanate; Dimethyl sulfon diisocyanate; Dithiodimethyl diisocyanate; Dithiodiethyl diisocyanate; Dithiodipropyl diisocyanate; Dicyclohexylsulphi-4,4'- diisocyanate; 1-isocyanatomethylthia-2,3-bis (2-isocyanatoethylthia) propane and the like.

Preferably, the diisocyanate compound added to tolylene diisocyanate is isophorone diisocyanate; 1,6-hexamethylene diisocyanate; Dicyclohexyl methane diisocyanate; 2,4-trimethyl-1,6-diisocyanate hexane; Bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane; And bis (isocyanatomethyl) bicyclo [2,2,1] heptane.

The content of tolylene diisocyanate in the total diisocyanate compound is preferably 25 to 85% by weight, more preferably 35 to 80% by weight. If the content of tolylene diisocyanate in the diisocyanate content is 25% by weight or less, the initial heat deformation temperature may drop sharply, and thus the multi-film on the surface of the lens may be easily cracked, and thermal depression may occur in the center of the lens. If the content of tolylene diisocyanate is 85% or more, there is a problem in that the color change due to heat and the yellowing phenomenon due to ultraviolet light appear severely. On the other hand, the content of alicyclic diisocyanate, alkylene diisocyanate heterocyclic diisocyanate compound, sulfur-containing aliphatic poly diisocyanate and the like added to tolylene diisocyanate is preferably 15 to 75% by weight, more preferably 20 65 wt%. When 75 wt% or more, the refractive index is lowered, and in the case of isophorone diisocyanate, when 75 wt% or more is used, bubbles may occur at the edge of the lens. In addition, when 1,6-hexamethylene diisocyanate is used in an amount of 75% by weight or more, there is a problem in that the initial heat deformation temperature of the lens drops sharply.

The mercapto compound used in the monomer composition of the present invention is a compound having a sulfur atom in at least one molecule. Preferably, 2- (2-mercaptoethylthio) propane-1,3-thiol; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 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 Use more than one species.

The equivalent ratio of -SH (and -OH) /-NCO of the isocyanate compound and the mercapto compound is set to 1.00 to 1.30. When the equivalent ratio of -SH is less than 1.00, thermal stability, storage stability, and weather resistance are drastically decreased. When the equivalent ratio of -SH is more than 1.30, the thermal resistance is rapidly decreased. More preferably, the equivalent ratio of -SH (and -OH) /-NCO is 1.05 to 1.30.

In the monomer composition of the present invention, the ultraviolet absorber is 0.005 to 6% by weight (50 to 60,000 ppm), preferably 0.01 to 3% by weight (100 to 30,000 ppm), based on the total weight of the mixed composition of the diisocyanate compound and the mercapto compound. Is added. If the amount of the ultraviolet absorber is less than 0.005% by weight, no effective ultraviolet absorbing capacity can be obtained, and yellowing may be severe when the lens is exposed to ultraviolet rays. In addition, when it is 6% by weight or more, not only it is difficult to dissolve in the composition, but also poor polymerization may occur during curing. As the ultraviolet absorbent, any known ultraviolet absorbent usable for spectacle lenses can be used without limitation. For example, 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'-t-octylphenyl) -2H-benzotriazole having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like can be used.

The monomer composition of the present invention may include a color corrector for color correction of the lens. The color corrector corrects the initial color of the lens due to the color of the ultraviolet absorber or the monomer itself or other additives such as green or yellow, and gives a color without aesthetic rejection such as colorless, white or blue. By raising the value of goods. As the color correcting agent, organic dyes, organic pigments, inorganic pigments, and the like may be used. Preferably, organic dyes may be used. The organic dye is used in the spectacle lens Known organic dyes can be used. In the embodiment of the present invention, 1-hydroxy-4- (p-toluidine) anthraquinone (1-hydroxy-4- (p-toluidine) anthraquinone) of Kyungin Yang Co., Ltd. perinone dye) and the like. By adding 0.5 to 10,000 ppm, preferably 5 to 1,000 ppm, of such organic dye per kg of the monomer, it is possible to prevent the optical lens from becoming yellow by the addition of an ultraviolet absorber.

In the present invention, the release agent may be used one or two or more selected from fluorine nonionic surfactants, silicone nonionic surfactants, alkyl quaternary ammonium salts, and phosphate esters. Preferably acidic phosphate ester is used. Application of the release agent to metals or glass molds also provides good deforming. As phosphate ester, Isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl acid phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. As a result of use in the embodiment of the present invention, when using the phosphate ester ZELEC UN (DUPONT) and KPSS-1000, the deforming when the mold is demolded in the lens after curing was the best. The amount of the releasing agent added may be used in an amount of 0.001 to 5% by weight based on the total weight of the isocyanate compound, but preferably 0.005 to 2% by weight of the mold is good in the mold deforming and high polymerization yield.

The polymerization initiator used in the present invention may be an amine-based or tin-based compound. The amount used is preferably 0.001 to 5% by weight relative to the diisocyanate compound.

Examples of the amine compound include triethylamine; Tripropylamine; Dipropylethylamine; Tributylamine; Trihexylamine; Dimethylcyclohexylamine; Dicyclohexylethylamine; Tricyclohexylamine; Diethylcyclohexylamine; Dipropylcyclohexylamine; Dicyclohexylpropylamine; Dibutylcyclohexylamine; Dicyclohexylbutynamine; N, N-dimethylbenzylamine; N, N-diethylbenzylamine; N, N-dipropylbenzylamine; N, N-dibutylbenzylamine; N-methylbenzylamine; 2-dimethylaminomethylphenol; 2,4,6-tris (N, N-dimethylaminomethyl) phenol; Triethylenediamine; Tetramethylethylenediamine; Tetraethylethylenediamine; N, N-dimethylcyclohexylamine; N, N-dicyclohexylmethylamine; Tetrapropylethylenediamine; Tetrabutylethylenediamine; Pentamethyldiethylenetriamine; Pentaethyldiethylenetriamine; Pentapropyldiethylenetriamine; Pentabutyldiethylenetriamine; N-methylpiperidine; N-ethylpiperidine; N-propylpiperidine; N-butyl piperidine; N, N-dimethylpiperazine; N, N-diethylpiperazine; N, N-dipropylpyrazine; N, N-dibutylpiperazine; Hexamethylenetetramine; Dimethylaminoethyl acetate; Diethylaminoethyl acetate; Dimethylaminopropionitrile; Diethylaminopropionitrile; N-methylmorpholine; N-ethyl morpholine; N-propylmorpholine; N-butylmorpholine; N-cyclohexylmorpholine; N-methylpiperidone; N-ethylpiperidone; N-propylpiperidone; N-butyl piperidone; N-methylpyrrolidine; N-ethylpyrrolidine; N-propylpyrrolidine; N-butylpyrrolidine; N-methylpyrrolidone; N-ethylpyrrolidone; N-propylpyrrolidone and N-butylpyrrolidone. Examples of aromatic tertiary amines include N, N-dimethylaniline; N, N-diethylaniline; N, N-dipropylaniline; N, N-dibutylaniline; N, N-cyclohexylmethylaniline; N, N-dicyclohexyl aniline; Diphenylmethylamine; Diphenylethylamine; Triphenylamine; N, N-dimethyltoluidine; N, N-diethyltoluidine; N-cyclohexyl-N-methyltoluidine; N, N-dicyclohexyl toluidine; N, N-dimethylnaphthylamine; N, N-diethylnaphthylamine; N, N-dimethylanisidine; N, N-diethylanisidine and N, N, N ', N'-tetramethylphenylenediamine. Moreover, pyridine; Picoline; Dimethylpyridine; 2,2'-bipyridine; 4,4'-bipyridine; Pyradine; N-methylpyrazole; N-ethylpyrazole; N-propylpyrazole; N-butylpyrazole; N-cyclosecsilpyrazole; Pyridazine; Pyrimidine; Pyrinoline; Oxazole; Thiazole; 1-methylimidazole; 1-benzylimidazole; 1-methyl-2-methylimidazole; 1-benzyl-2-methylimidazole; 1-ethyl-4-methylimidazole; 1-ethyl-2-ethyl-4-methylol; N-methylpyrrole; N-ethylpyrrole; N-butylpyrrole; N-methylpyrroline; N-ethylpyrroline; N-butylpyrroline; Pyrimidine; Furin; Quinoline; Isoquinoline; N-methylcarbazole; N-ethylcarbazole; N-butylcarbazole and the like can be used.

As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octylic acid; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; Di (2-ethylsecyl) tin oxide and the like may be used alone or in combination of two or more thereof. When such a tin compound is used, the polymerization yield is high and there is no bubble generation.

Monomer composition of the present invention is liquid refractive index (Ne, 20 ℃) 1.550 ~ 1.660, solid state refractive index (Ne, 20 ℃) 1.630 ~ 1.685, Abbe water (20 ℃) 24 ~ 50, liquid viscosity (20 ℃) 10 ~ 1000cps, The specific gravity has a liquid specific gravity of 1.05 to 1.40 and a solid specific gravity of 1.15 to 1.55, and more preferably has a liquid viscosity of 20 to 600 cps.

The optical resin composition of the present invention is thermally cured to obtain plastic optical lenses, in particular spectacle lenses. Preferred embodiments for preparing the spectacle lens by thermal curing the composition of the present invention are as follows. First, after finally adding the polymerization initiator to the composition of the present invention, by substituting with nitrogen to remove air in the mixing vessel (reactor), stirring under reduced pressure for 2 to 5 hours, stopping stirring, and then degassing under reduced pressure Inject into the mold. 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 115 to 125 ° C. for 12 hours, and maintained at 115 to 125 ° C. for 2 hours. After cooling at 60-90 degreeC over 2 hours, solids are released from a mold, and an optical lens is obtained. The optical lens thus obtained is subjected to annealing for 1 to 4 hours at a temperature of 100 to 120 ° C. to obtain the final desired plastic optical lens.

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. After coating the coating composition to a thickness of 0.5 ~ 10㎛ on the surface of the optical lens by impregnation or spin coating method, by heating or ultraviolet curing 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 times on both surfaces of the lens and 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.

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

The optical resin composition of the present invention is not limited to plastic eyeglass lenses, and can be used in various optical products.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the scope of the present invention is not limited by the following examples, and those skilled in the art to which the present invention pertains should be within the equivalent scope of the technical concept of the present invention and the claims to be described below. Of course, various modifications and variations are possible.

Example 1

(1) To 24.000 g of tolylene diisocyanate, 16.000 g of 1,6-hexamethylene diisocyanate, 11.000 g of isophorone dicyanate, and 49.000 g of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane To this, 1.500 g of 2- (2′-hydroxy-5-methylphenyl) -2H-benzotriazole as a UV absorber, 0.100 g of diisopropyl acid four state as a release agent, and an organic dye as a color correcting agent 75 ppm of 1-hydroxy-4- (p-toluidine) anthraquinone (blue), 40 ppm of perrinone dyes (Red), 0.050 g of dibutyltin dichloride as a polymerization initiator were placed in a mixing vessel equipped with a stirrer and replaced with nitrogen. After removing the air in the mixing vessel, stirring was carried out for 2 hours, the stirring was stopped, degassing under reduced pressure, and injected into a glass mold fixed with a polyester adhesive tape (diopta -5.00).

(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 mm.

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

(4) The lens obtained in (3) was impregnated with a hard coat of Finecoder ST11 Water-8H, and then thermally cured, and silicon oxide → zirconium oxide → silicon oxide → ITO → zirconium oxide → silicon oxide → zirconium oxide on both surfaces. Vacuum deposition in the order of the water film (fluorine resin) to obtain a hard-coated and multi-coated optical lens.

Experiment method

The physical properties of each optical lens were measured by the following experimental method, and the results are reported in Table 1.

1. Refractive index and Abbe number: Measured using an Abbe refractometer, an Atacota Co 1T model.

2. Light transmittance: It measured using the spectrophotometer.

3. Initial Heat Deflection Temperature: Measurement was made using a Thermo Mechanical Analyzer (TMA).

4. Color Stability to Heat (Δ YI): After placing the 2 mm thick specimens in an oven at 120 ° C. for 12 hours, the values of Δ YI before and after being put into the oven using a colorimeter were measured and recorded.

5. Specific gravity: The volume and weight of the optical lens were measured using an underwater substitution method.

6. Multi-film cracking phenomenon by heat: After leaving the lens specimen in an oven at 90 ° C for 60 minutes and visually observing no cracking of the multi-film on the lens surface, A, 1 or less cracks of 10 mm or less B, and The above was described as C.

Examples 2-16

According to the method similar to Example 1, the monomer composition and the lens were manufactured with the composition of Tables 1-2, respectively, and the experiment result was described in Tables 1-2.

Comparative Example 1

The same procedure as in Example 1 was conducted except that 50.068 g of tolylene diisocyanate and 49.931 g of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane were mixed to prepare a monomer composition. Is shown in Table 3.

Comparative Examples 2-7

According to the same method as in Comparative Example 1, a composition and a lens were prepared using the compositions shown in Table 3, and the experimental results are shown in Table 3.

Table 1

TABLE 2

TABLE 3

Abbreviation of Tables 1 to 3

Monomer

TDI: tolylene diisocyanate

IPDI: isophorone diisocyanate

HDI: 1,6-hexamethylene diisocyanate

H ₁₂ MDI: dicyclohexylmethane diisocyanate

XDI: xylylene diisocyanate

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

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

ETS4: 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)

GMS5: 2- (2-mercaptoethylthio) -3- {2-mercapto-3- (3-mercapto-2- (2-mercaptoethylthio) -propylthio) propylthio} -propane-1 -Thiol (2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) propylthio] propylthio} propane-1-thiol)

UV absorbers

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-benzotriazole2- (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)

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)

DHBP: 2,4-dihydroxybenzophenone

HOOBP: 2-hydroxy-4-octyloxybenzophenone

DHMBP: 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-dihydroxy-4,4'-dimethoxybenzophenone)

THBP: 2,2 ', 4,4'-tetrahydroxybenzophenone (2,2', 4,4'-tetrahydroxy benzophenone)

HMBP: 2-hydroxy-4-methoxy benzophenone

Release agent

OP: octyl acid phosphate

DOP: dioctyl acid phosphate

IDP: isodecyl acid phosphate

DIPP: diisopropyl acid phosphate

DBP: dibutyl acid phosphate

PENPP: polyoxyethylene-octyl phenol ether phosphate

Color Corrector (Organic Dyes)

HTAQ: 1-hydroxy-4- (p-toluidine) entraquinone [1-hydroxy-4- (p-toluidin-e) anthraquinone]

PRD: perinone dye

Polymerization initiator

BTL: butyl tin dilaurate

BTC: dibutyltindichloride

BTA: dibutyltindiacetate

According to the present invention, the problem of the center deformation caused by heat, which is a problem of the urethane-based plastic optical lens, can be solved, and a urethane-based plastic optical lens, in particular, an eyeglass lens, having a very low thermal deformation phenomenon can be obtained. In addition, the monomer composition for an optical lens of the present invention may be used for various optical products such as recording medium substrates, coloring filters, ultraviolet absorbing filters, etc. used for prisms, optical fibers, optical disks, magnetic disks, etc., in addition to the manufacture of spectacle lenses.

Claims (14)

1. (a) (i) alkylene diisocyanate compounds; Alicyclic diisocyanate compounds; Heterocyclic diisocyanate compounds; 25 to 65% by weight of a compound obtained by adding one or two or more diisocyanate compounds selected from sulfur-containing aliphatic diisocyanate compounds to tolylene diisocyanate, (ii) Have at least one sulfur atom in the molecule One or two or more mercapto compounds 35 to 75 wt%, and (iii) an ultraviolet absorber; Mold release agents; And a polymerization initiator,

   (b) the equivalent ratio of -SH (and -OH) /-NCO is between 1.00 and 1.30,

   (c) liquid phase refractive index (Ne, 20 ° C) 1.550 to 1.660; Solid phase refractive index (Ne, 20 ° C) 1.630 to 1.685; Abbe number (20 degreeC) 24-50; And a liquid phase viscosity (20 ° C.) 10-1,000 cps monomer composition for an optical lens.
2. According to claim 1, 0.005 to 6% by weight of the ultraviolet absorbent to the total weight of the mixture of (i) and (ii); 0.001 to 5% by weight release agent; 0.001 to 5 wt% of a polymerization initiator; And 0.5-10,000 ppm color corrector of the lens,

   A monomer composition for an optical lens having a liquid specific gravity of 1.05 to 1.40 and a solid phase specific gravity of 1.15 to 1.55.
3. The diisocyanate compound of claim 1, wherein the diisocyanate compound added to tolylene diisocyanate is isophorone diisocyanate (IPDI); 1,6-hexamethylene diisocyanate (HDI); Dicyclohexyl methane diisocyanate (H₁₂MDI); 2,4-trimethyl-1,6-diisocyanate hexane (TMDI); Bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane; And bis (isocyanatomethyl) bicyclo [2,2,1] heptane, or a monomer composition for an optical lens, characterized in that at least two kinds thereof.
4. The method of claim 1, wherein the mercapto compound is 2- (2-mercaptoethylthio) propane-1,3-thiol; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2- (2-mercaptoethylthio) propylthio] ethylthio} -propane-1-thiol; And 2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) propylthio] propylthio} -propane-1-thiol A monomer composition for an optical lens, characterized in that one or two or more selected from the group consisting of.
5. The method of claim 1, wherein the ultraviolet light absorber, 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; And 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a monomer composition for an optical lens.
6. The monomer composition for an optical lens according to any one of claims 1 to 5, wherein the release agent is a phosphate ester.
7. The method of claim 6, wherein the phosphate ester is isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl acid phosphate; Tridecanoic acid phosphate; And at least one selected from the group consisting of bis (tridecanoic acid) phosphate, and a monomer composition for an optical lens.
8. The monomer composition of claim 1, wherein the polymerization initiator is a tin-based or amine-based compound.
9. The method of claim 8, wherein the tin compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octylic acid; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; And di (2-ethylsecyl) tin oxide, or a monomer composition for an optical lens, characterized in that at least two kinds thereof.
10. 3. The monomer composition of claim 2, wherein the color corrector is an organic dye.
11. The plastic optical lens obtained by thermosetting the monomer composition for optical lenses of claim 1.
12. 12. The plastic optical lens according to claim 11, wherein the optical lens is an eyeglass lens.
13. (a) (i) alkylene diisocyanate compounds; Alicyclic diisocyanate compounds; Heterocyclic diisocyanate compounds; One or two or more diisocyanates selected from sulfur-containing aliphatic diisocyanate compounds 25 to 65% by weight of the compound added to tolylene diisocyanate, (ii) Have at least one sulfur atom in the molecule One or two or more mercapto compounds 35 to 75% by weight, and (iii) 0.5 to 10,000 ppm color corrector of the lens relative to the total weight of the mixture of (i) and (ii); 0.005-6% by weight of ultraviolet absorbent; 0.001 to 5% by weight release agent; And 0.001 to 5% by weight of a polymerization initiator,

    (b) the mold injected with the mixture was placed in an oven, held at 33-37 ° C. for 2 hours, heated at 38-42 ° C. for 3 hours, heated at 115-125 ° C. for 12 hours, held at 115-125 ° C. for 2 hours, Cooling at 60 to 90 ° C. over 2 hours to release the solids from the mold to obtain an optical lens, and

    (c) a method for producing a plastic optical lens comprising annealing the released optical lens at a temperature of 100 to 140 ° C. for 1 to 4 hours.
14. The method of manufacturing a plastic spectacle lens according to claim 13, further comprising a hard coating and a multi coating step after the step (c).