KR20120058635A - Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It - Google Patents
Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It Download PDFInfo
- Publication number
- KR20120058635A KR20120058635A KR1020100078120A KR20100078120A KR20120058635A KR 20120058635 A KR20120058635 A KR 20120058635A KR 1020100078120 A KR1020100078120 A KR 1020100078120A KR 20100078120 A KR20100078120 A KR 20100078120A KR 20120058635 A KR20120058635 A KR 20120058635A
- Authority
- KR
- South Korea
- Prior art keywords
- optical lens
- polythiol compound
- compound
- diisocyanate
- bis
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Abstract
Description
The present invention relates to the production of polythiol compounds and resin compositions thereof, which are widely used as materials for optical lenses.
Plastic lenses are lightweight and have excellent impact resistance, and are easily dyed and excellent in processability compared to glass lenses, and are widely used as spectacle lenses and camera lenses today. Materials for plastic optical lenses are usually polyethylene glycol bisallylcarbonate, polymethyl methacrylate (PMMA), mixtures of allyl ester oligoma compounds and allyl carbonate compounds, polythiol compounds, polyisocyanate compounds or polythiocyanates Compounds are widely used. Among these, urethane-based optical lenses using a polythiol compound, a polyisocyanate compound or a polythiocyanate compound are excellent in refractive index, Abbe number, tensile strength, processability, and the like, and their use has been gradually expanded. In addition, in the production of optical lenses, in order to produce ease of production and colorless transparent quality, a clear colorless transparent optical lens resin and its resin composition are required. In particular, in order to produce a lens with uniform color and clearness, a clear optical resin composition is required as well as color uniformity of the optical resin composition as a main material of the optical lens.
The present inventors prepared the optical lens using an allyl ester oligoma compound and an allyl carbonate compound or an allyl ester oligoma compound, an allyl carbonate compound, and a resin composition for an optical lens composed of a maleate compound prior to the present invention. Korean Patent No. 10-0897407 has been filed, which relates to a method for obtaining a clear lens free of yellow color, and also a method for producing a resin composition for an optical lens and an optical lens using a polythiol compound and a polyisocyanate compound. Korean Patent Application No. 10-2008-0017382, 10-2009-001059, 10-2007-0077515, 10-2006-00 85437, 10-2006-0125651, 10-2007-0136578, 10-2009-0021331 To prepare resin compositions and optical lenses for urethane-based optical lenses having excellent optical properties such as refractive index, Abbe's number, tensile strength, impact strength, processability, and the like. The proposed law. In the production of a urethane-based lens, it is important to produce a clear resin composition without variation in color for each production lot since the color and clearness of the resin composition have a significant influence on the color of the optical lens.
In order to achieve the above object, in the present invention, the thiourea used in the production of polythiol is purified to have a metal content of 2% or less, in particular, a calcium content of 0.95% by weight or less, and a raw material of a polythiol compound. Phosphorus 2-mercaptoethanol controls the production of bis (2-hydroxyethyl) disulfide, which is oxidized by oxygen or moisture, to less than 0.50% by weight in GC analysis, while at the same time isotiu, an intermediate produced during thiol production The rhonium salt was hydrolyzed with 25% ammonia water dissolved in a high purity water containing 2% by weight or less of an organic or metallic material as an impurity instead of an aqueous solution of basic alkali and alkaline earth metal hydroxides to obtain a clear and transparent polythiol resin for an optical lens.
In order to reduce uneven production-specific color variation of the polythiol compound, the removal of impurities of thiourea, the improvement of the purity of 2-mercaptoethanol, and the hydrolysis process were simultaneously introduced to prepare a uniform and colorless transparent polythiol compound.
In addition, the present invention provides a plastic spectacle lens obtained by thermosetting a resin composition for an optical lens comprising the polythiol compound.
The optical resin composition and the optical lens including the bright clear transparent polythiol compound and the polyisocyanate compound obtained in the present invention are bright and transparent, and have excellent optical properties such as impact resistance, heat resistance, moldability, dyeability, light transmittance, Abbe's number, and the like. . Polythiol resin for urethane optical lens requires new high performance and various lens resin materials such as high refractive index, high Abbe, low specific gravity, high heat resistance, high transmittance, high transparency and high impact resistance have been developed and used. have. Among them, transparency of the optical lens resin and the composition is very important. In the present invention, the production yield of the polythiol compound, which is a resin for an optical lens, can be increased and stably produce a transparent and transparent lens material, thereby reducing production costs and maximizing the quality of an optical lens.
The present invention is to improve the purity of the raw material causing the coloration in the manufacturing process and to cope with ammonia, which is a non-metallic compound rather than a metal hydroxide in order to overcome the production-specific variations due to the production of the polythiol compound, the production-specific variation due to the coloring of the resin It corresponds to the obtained resin composition for optical lenses containing the uniform, colorless and transparent polythiol compound and polyisocyanate compound.
As mentioned above, attempts were made to improve the manufacturing process in order to reduce the variation in production when producing the polythiol compound, but the color variation in the manufacturing process did not find a solution. The present inventors have found a technique for producing a uniform, clear and colorless transparent polythiol resin as a result of the continuous research to obtain a uniform polythiol resin using the prepared polythiol resin. Reducing the content of alkaline earth metals in thiourea, which causes coloring in the production of polythiol compounds, and reducing the content of bis (2-hydroxyethyl) sulfide in 2-mercaptoethanol, and at the same time aqueous alkaline and alkaline earth metal hydroxide solutions Instead, a clear, colorless and transparent polythiol compound was prepared by coping with ammonia, a nonmetallic compound.
Thiourea is prepared from lime nitrogen, hydrogen sulfide and calcium sulfide, and is mainly produced by reacting lime nitrogen with hydrogen sulfide. There are unreacted lime nitrogen and by-product calcium hydroxide as impurities. The metal ions contained are purified on strong ionic basic ion exchange resins, and the polyurethane resins produced using them are colorless, transparent, low-dispersion, plastic lens resins with excellent impact, dyeability and processability. It is suggested in 9-110955, 9-110956, and 7-252207, but there were many coloring problems and manufacturing variations. Therefore, the calcium component of thiourea is a factor influencing the coloring, and if it is more than a specific amount, the (poly) thiol compound is colored and the obtained polythiol resin is colored or turbid. From the standpoint of suppression of coloring and clouding of the calcium amount of thiourea, the content is preferably 10 ppm to 10,000 ppm or less, more preferably 10 ppm to 5,000 ppm or less, still more preferably 10 ppm to 2,000 ppm or less. If the calcium content of thiourea is 0.95% by weight or less, the coloring of the thiol compound is suppressed and is colorless and transparent. Calcium content was measured by ICP method, and the method of reducing calcium content was possible by purification, acid treatment, recrystallization, etc., and hydrochloric acid treatment and recrystallization from water lowered calcium content of thiourea.
2-mercaptoethanol, a raw material of the polythiol compound, is easily produced by bis (2-hydroxyethyl) disulfide by oxygen, which causes coloration of the thiol compound for optical lenses, and the color is good when it is below a certain amount. The polythiol compound for optical lenses can be obtained. The content of bis (2-hydroxyethyl) disulfide contained in 2-mercaptoethanol is preferably 10 ppm to 5,000 ppm or less, more preferably 10 ppm to 4,500 ppm or less, and more preferably 100 ppm to 3,500 ppm or less. When the bis (2-hydroxyethyl) disulfide content in 2-mercaptoethanol is 0.95% by weight or less, the coloring of the thiol compound is suppressed and is colorless and transparent. The content of bis (2-hydroxyethyl) disulfide was determined by GC analysis.
2-mercaptoethanol is oxidized in the presence of oxygen or moisture to produce bis (2-hydroxyethyl) disulfide, and the formation is faster at the presence of metals such as iron or at higher temperatures. To prevent this oxidation, air is replaced with nitrogen or argon, which are inert gases, and stored in a metal container such as polyethylene or below 30oC. In order to reduce bis (2-hydroxyethyl) disulfide content in 2-mercaptoethanol, the content of bis (2-hydroxyethyl) disulfide was reduced by distillation or column chromatography.
The base used to hydrolyze the isothiuronium salt, which is an intermediate of the polythiol compound, to obtain a polythiol compound includes metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, triethylamine and tributylamine. Although there are amines and the like, ammonia water is required to obtain a polythiol compound having a better color. Ammonia water was prepared by dissolving ammonia gas having a purity of 99% or higher in deionized tertiary distilled water.
Toluene used in the preparation of the polythiol compound of the present invention was used having a purity of 99% or more, caustic soda was used having a purity of 98% or more. 25% caustic soda solution was prepared by dissolving more than 98% caustic soda in deionized tertiary distilled water, and epichlorohydrin with 99% purity. 36% aqueous hydrochloric acid solution was used that contains less than 10 ppm organic or inorganic, water was used as a solvent and washing in the preparation of polythiol compound using deionized tertiary distilled water.
In addition, the polythiol compound of the present invention may be used in the air, but if the whole is carried out in a nitrogen atmosphere or argon atmosphere is more preferable in terms of color.
The present invention obtains a polyurethane optical lens in the reaction of a polythiol compound and a polyisocyanate compound.
The polythiol compound is a compound having at least one sulfur atom in a molecule. Preferably, 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) -ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, 2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mercapto-2 -(2-mercaptoethylthio) -propylthio] propylthio} -propane-1-thiol; 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester; 2- (2-mercaptoethylthio) -3- (2- {2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio} ethylthio) propane-1-thiol Use one or two or more of them.
Or the polythiol compound includes a thiol ester compound. For example, thiol ester compounds are trimethylolpropane tris (mercaptopropionate), trimethylol ethane tris (mercaptopropionate), glycerol tris ( Mercaptopropionate), trimethylolchlorotris (mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), and the like. As pentaerythritol tetrakis (mercaptopropionate) (PETMP), pentaerythritol tetrakis (mercaptoacetate) (PETMA), bispentaerythritol ether hexakis (mercaptopropionate) (BPEHMP) , Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA), bispentaerythritol hexa (2-mercapto Cetate) (BPEMA), bistrimethylolpropane tetrakis (3-mercaptopropionate) (BTMPMP), bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA), etc. alone or in combination Can be mixed
Examples of the polyisocyanate compound include an alkylene diisocyanate compound, an aromatic diisocyanate compound, an alicyclic diisocyanate compound, a heterocyclic diisocyanate compound, and an aliphatic polyiso (thio) cyanate compound.
Examples of the alkylene diisocyanate compound include 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.
Examples of the aromatic diisocyanate compound include xylylene diisocyanate, tolylene-2,4-diisocyanate, 1,2-diisocyanate, 1,3-diisocyanate, 1,4-diisocyanatobenzene, and the like. , 4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenyl isocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate , Toluidine diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2-phenylphenylisocyanate), bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl Ether, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylenedi Isocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, bis (isocyanatoethyl) phthalate, and the like.
Examples of the alicyclic diisocyanate compound include 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.
Aliphatic (thio) isocyanate compounds include, for example, 4-isocyanato-4'-isothiocyanatodiphenyl sulfide; 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 isoprone diisocyanate; 1,3-cyclohexane-bismethylisocyanate, 1,6-hexamethylenedisocyananeate; Xylylene diisocyanate (XDI); 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; 1 type, or 2 or more types are selected from the group which consists of tolylene-2, 4- diisocyanate (TDI) and 4,4'- dicyclohexyl methane diisocyanate (H12MDI).
The molar ratio of the functional group of (NCO) / (OH + SH) of the polyisocyanate compound with respect to a polythiol compound is the range of 0.5-3.0 normally, Preferably it is 0.5-1.5.
The resin composition of the present invention obtained by reacting 30 to 70 wt% of the polythiol compound and 30 to 70 wt% of the polyisocyanate compound has a solid phase refractive index (nD, 20 ° C.) of 1.560 to 1.680, a liquid refractive index of 1.520 to 1.650, and a solid phase specific gravity of 1.15 to 1.40, Abbe number 25-50 of solid resin, and liquid viscosity (20 degreeC) 5-1000 cps.
The resin composition of the present invention may include from 0.0007 to 9% by weight of the ultraviolet absorber based on the total weight of the reaction mixture, preferably 0.5 to 3% by weight in order to improve the light stability of the prepared resin. If the UV absorber is used in a smaller amount than the above range, it is difficult to effectively block ultraviolet rays harmful to the eyes, and when it is used beyond this range, it is difficult to dissolve in the optical lens composition, and spot patterns appear on the surface of the cured optical lens or transparency of the optical lens. Problem may occur. As the ultraviolet absorbent, any known ultraviolet absorbent surface usable for the optical lens can be used. For example, ethyl-2-cyano-3,3-diphenyl acrylate; 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-benzoxoxy-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 nm 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; 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 and 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like These may be used alone or in combination of two or more.
The lightweight resin for an optical lens of the present invention may include a known organic dye for improving the initial color of the lens and satisfying consumer's preference. In the embodiment of the present invention 1-hydroxy-4- (para- toluidine) anthraquinone [1-hydroxy-4- (p-toluidine) -anthra quinone], perinone dye (perinone dye) and the like composition for an optical lens By adding 0.001 to 10,000 ppm, preferably 0.005 to 1,000 ppm per kg, it is possible to prevent the optical lens from becoming yellow by the addition of an ultraviolet absorber.
In addition, the resin composition of the present invention may further include an internal mold release agent. Examples of the internal mold release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; The component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types. Preferably, acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. In the embodiment of the present invention, ZELEC UN ™ (DUPONT, Inc.), which is an acidic phosphate ester, showed the best demolding when demolding the mold from the lens after curing. The internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent in the lens has a high polymerization yield. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.
As the polymerization initiator used to react the polythiol compound and the polyisocyanate compound, an amine-based or tin-based compound may be used. As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous oxide; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraidotin; 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 was used, the polymerization yield was high and there was no bubble generation. The amount of use is preferably 0.0001 to 10% by weight based on the total weight of the reaction mixture.
When the resin composition for optical lenses of the present invention is thermoset, a plastic optical lens is obtained. Such plastic optical lenses include eyeglass lenses in particular. Preferred embodiments for preparing the spectacle lens by thermal curing the composition of the present invention are as follows. First, a polymerization initiator is finally added to the composition constituting the resin of the present invention, substituted with nitrogen to remove air in the mixing vessel (reactor), and then stirred under reduced pressure for 2 to 5 hours, and the stirring is stopped, followed by degassing under reduced pressure. Inject into the mold. The mold is preferably a glass mold or a metal mold fixed with polyester, polypropylene adhesive tape, or plastic gasket. The glass mold infused 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 120 to 140 ° C. for 2 to 4 hours. After raising the temperature at 120 to 140 ° C. for 2 hours and cooling at 60 to 80 ° C. for 2 hours, the solid is released from the mold to obtain an optical lens. 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 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 impregnating the lens into the coating composition or by spin coating to form a coating layer with a thickness of 0.5 ~ 10㎛ on the surface of the optical lens, the coating film is completed by heating or UV curing.
The multi-coating layer, that is, the anti-reflective coating layer, may be formed by vacuum deposition or sputtering metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide, and yttrium oxide. Can be. Most preferably, the silicon oxide film and the zirconium oxide film are alternately vacuum-deposited three times or more on both surfaces of the hard coating film of the lens, and finally, the silicon oxide film is vacuum deposited. In addition, an indium tin oxide (ITO) layer may be further provided as a water film layer between the final silicon oxide and the zirconium oxide film as necessary. The optical lens of the present invention may be used after coloring by adding a disperse dye or a photochromic dye to the hard liquid, if necessary.
Polythiol resins for urethane lenses require new high performance, and various resin materials for lenses such as high refractive index, high Abbe, low specific gravity, high heat resistance, high transmittance, high transparency and high impact resistance have been developed and used. . Among them, transparency of the resin for the lens and the composition is very important. By increasing the yield of lens resin and providing resin for clear, colorless and transparent lens, it is possible to stably reduce the production cost and maximize the quality of lens by producing clear and transparent lens.
[ Example ]
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are not intended to more specifically describe the present invention, the scope of the present invention is not limited by these examples.
Property evaluation
Calcium content in thiourea: Reduction of calcium content of thiourea was used by hydrochloric acid treatment of 99% pure thiourea and recrystallization in aqueous solution. The calcium content of 0.01% thiourea, which is the reference, was burned to 100 g of purified thiourea, and the remaining ash was used as an aqueous solution. Spectroscope) analysis method. The calcium content was calculated by adding calcium chloride dihydrate (CaCl 2.2 H 2 O) with a purity of 99% to thiourea. The calcium content of 0.20, 0.50, 0.6, 0.70, 0.80, 0.9, and 1.20% of thiourea used in Table 1 was 99% pure calcium chloride dihydrate in thiourea including 0.01% calcium obtained by purification. CaCl2.2H2O) was added to prepare a thiourea containing the corresponding calcium content.
Bis (2-hydroxyethyl) disulfide content in 2-mercaptoethanol: The reduction of the content of bis (2-hydroxyethyl) disulfide in 2-mercaptoethanol is distilled from 2-mercaptoethanol having a purity of 99% After purification by column chromatography on silica gel, 2-mercaptoethanol having 0.10 wt% of bis (2-hydroxyethyl) disulfide in 2-mercaptoethanol was obtained by GC analysis. The content of bis (2-hydroxyethyl) disulfide was determined by GC analysis with an acetone solvent using a 7890A GC instrument from Agilent Technologies. Increasing the content of bis (2-hydroxyethyl) disulfide in 2-mercaptoethanol shows that the bis (2-hydroxyethyl) disulfide in 2-mercaptoethanol prepared above is 0.10% by weight of bis ( 2-Mercaptoethanol was prepared having the contents of 0.30, 0.40, 0.45 and 0.60% by weight as 2-hydroxyethyl) disulfide.
YI (Yellow Index) was taken as a value for the color of polythiol and lens.
(1) Color of polythiol (YI or dYI): In the present invention, the YI value is determined by using a color analyzer equipped with an IRS-2200 condenser mounted on a model UV-2450 of SHIMADZU Co., Ltd. Distilled water was added and the base line was set, and polythiol was added to the silica cell containing distilled water, and the color YI value was measured. In the color evaluation, the YI value indicates the yellow index and can be measured by the color chrominometer. The smaller the YI value, the better the color.
(2) Color (YI or dYI) of the polythiourethane-based plastic lens: In the present invention, the YI value was used as a color analyzer equipped with an IRS-2200 condenser in the SHIMADZU Model UV-2450 and the measurement method was based on air. The color YI value was measured by fixing to the device to fix the lens. In the color evaluation, the value of YI represents the yellow index and can be measured by the color chrominometer. The smaller the value of YI, the better the color.
APHA was taken as a value for the color of the polythiol and the optical lens.
(1) APHA of polythiol compound: In the present invention, APHA was measured by inserting a sample into a quartz cell having a permeation length of 1 cm using Hunterlab's ColorQuest XE instrument. This data was obtained by measuring the concentration of the standard solution prepared by dissolving the reagents of platinum and cobalt, and measuring the APHA value obtained by comparing the built-in program with the sample solution. The smaller the measured value, the better the color.
(2) APHA of the polythiourethane-based plastic optical lens: In the present invention, the APHA value was measured using a ColorQuest XE instrument from Hunterlab, which was directly inserted into a plastic optical lens. This data was obtained by measuring the concentration of the standard solution prepared by dissolving the reagents of platinum and cobalt, and measuring the APHA value obtained by comparing the built-in program with the sample solution. The smaller the measured value, the better the color of the optical lens.
Resin Preparation of Polythiol Compound
Example 1
Polythiol Preparation of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol)
Under a nitrogen stream, 2-mercaptoethanol (53.20 g, 0.681 mol) containing 0.10% by weight of bis (2-hydroxyethyl) disulfide was added to a 2 L three-necked flask, followed by 25% aqueous NaOH solution (53.91 g, 0.337 mol). ) Is added to form a uniform aqueous solution, and then slowly added dropwise epichlorohydrin (30.00 g, 0.324 mol) while maintaining the internal temperature at 40 ℃. After the addition, the reaction solution is stirred at 45oC for 1 hour, GC checks whether new species are produced by GC, and when the starting material is completely gone, proceed to the next reaction. At the end of the reaction, the reaction mixture was cooled to room temperature and refluxed at 110 ° C for 4 hours with the addition of thiourea (92.60 g, 0.912 mol) and 36% concentrated hydrochloric acid (126.88 g, 1.46 mol) containing 0.02 wt% calcium. give. The reaction solution is cooled to room temperature and 25% ammonia water (128.88 g, 1.89 mol) is slowly added dropwise not to exceed 30 ° C. After the dropwise addition, toluene (150 g, 1.628 mol) is added and the reaction solution is hydrolyzed at 80 ° C. for 1 hour and 30 minutes, cooled to room temperature, and the organic layer is separated. The separated organic layer is washed twice with concentrated hydrochloric acid, then twice with water and the solvent is removed to give the desired GST (75.60 g, 0.290 mol, 90%). The polythiol compound prepared was AHPA 6 and YI 0.65.
Manufacture of Optical Lens
38.83 g of a prepared thiol compound GST; 7.36 g PETMP; 45.18 g of isophorone diisocyanate; 8.63 g of hexamethylene diisocyanate; 1.50 g of 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole as an ultraviolet absorber; 1.0 g of polyoxyethylene nonylphenyl phosphate as a releasing agent; 0.1 g of dibutyltin dichloride as a polymerization initiator was placed in a mixing vessel equipped with a stirrer, and replaced with nitrogen to remove air in the mixing vessel, followed by stirring under reduced pressure for 2 hours. The mixture was injected into a glass mold (diopta-5.00, center thickness 1.2 mm) fixed by using nitrogen gas. The glass mold injected with the mixture was placed in a forced circulation oven, maintained at 33 ° C. for 2 hours, heated at 33 ° C. to 40 ° C. for 3 hours, heated at 40 ° C. to 90 ° C. for 10 hours, and heated at 90 ° C. to 130 ° C. for 4 hours, After holding for 2 hours at 130 ° C and cooling for 2 hours at 130 ° C to 70 ° C, the glass mold was detached to obtain a plastic optical lens. The prepared optical lens had APHA of 9 and YI of 0.80.
Example 2-5
Polythiol Preparation of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol)
In the same manner as in Example 1, Example 2-5 was identical except that 2-mercaptoethanol using different amounts of thiourea and bis (2-hydroxyethanol) disulfide, which differed by weight percent of calcium, was used. Synthesized The results are shown in Table 1.
Manufacture of Optical Lens
An optical lens was manufactured in the same manner as in Example 1, and the results of the plastic optical lens manufactured using the polythiol compound obtained in Example 2-5 are shown in Table 1.
Example 6
Poly of ETS-4 (2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2- (2-mercaptoethylthio) propylthio] ethylthio} propane-1-thiol) Thiol manufacturers
Under a nitrogen stream, 2-mergaethanol (453.2 g, 5.80 mol) and triethyleneamine (0.1 g) containing 0.10% by weight of bis (2-hydroxyethyl) sulfide were added to a 1 L four-necked round flask and stirred for 10 minutes. do. Epichlorohydrin (536.7 g, 5.80 mol) is slowly added dropwise over 2-3 hours without exceeding the internal temperature of 40 ° C. After the dropwise addition, the mixture is stirred for 1 hour at 40oC. Colorless and transparent 1-chloro- synthesized prior to the homogeneous solution obtained by adding 1,2-ethanedithiol (267.4 g, 2.84 mol) to a 10 L four-necked flask and slowly adding 24.5% aqueous NaOH solution (924.3 g, 5.66 mol) 3- (2-Hydroxyethylthio) -propan-2-ol (967.6 g, 5.67 mol) is slowly added in 6-7 portions at about 150 g, not exceeding 70 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, cooled to 30 ° C., and then thiourea (973.30 g, 12.77 mol) containing 36% concentrated hydrochloric acid (1774.00 g, 17.51 mol) and 0.02% by weight of calcium was added. It is refluxed for 3 hours and 30 minutes at internal temperature of 110 degreeC. After completion of the reaction, cool to 30 ℃ and add 25% ammonia water (1583.72 g, 23.29 mol) to the internal temperature not more than 30 ℃ and add toluene (1600.00 g, 17.36 mol) at the end of the dropwise addition. The solution is hydrolyzed at an internal temperature of 80 ° C. for 1 hour 30 minutes. After hydrolysis, cool to room temperature and add the reaction solution to the separatory funnel. After separating the layers, the water layer is discarded and the separated organic layer is washed once with 36% concentrated hydrochloric acid (250 mL) and twice with saturated brine. Removal of the solvent under low pressure of the obtained organic layer gave a polythiol compound (1163.59 g, 2.726 mol, 94%). The polythiol compound prepared had an AHPA of 5 and a YI of 0.0.59.
Manufacture of Optical Lens
An optical lens was manufactured in the same manner except for using the same composition ratio as in Example 1. The prepared optical lens had an APHA of 7 and a YI of 0.73.
Example 7-10
Poly of ETS-4 (2- (2-mercaptoethylthio) -3- {2- [3-mercapto-2- (2-mercaptoethylthio) propylthio] ethylthio} propane-1-thiol) Thiol manufacturers
In the same manner as in Example 6, Example 7-10 was the same except that 2-mercaptoethanol using different amounts of thiourea and bis (2-hydroxyethanol) disulfide was used. Synthesized The results are shown in Table 1.
Manufacture of Optical Lens
In the same manner as in Example 6, the results of the plastic optical lens manufactured using the polythiol compound obtained in Example 7-10 are shown in Table 1.
Example 11
Preparation of Polythiol Compounds
In the same manner as in Example 1, Example 11 was used except that 2-mercaptoethanol contained thiourea containing 0.70 wt% calcium and 0.40 wt% bis (2-hydroxyethanol) disulfide Was synthesized in the same manner. The polythiol compound prepared had an AHPA of 17 and a YI of 1.37.
Manufacture of Optical Lens
As in Example 1, the results of the plastic optical lens manufactured using the obtained polythiol compound are shown in Table 1. The obtained optical lens had an APHA of 19 and a Y.I of 1.55.
Example 12
Preparation of Polythiol Compounds
In the same manner as in Example 1, Example 12 was used except that 2-mercaptoethanol contained thiourea containing 0.80 wt% calcium and 0.30 wt% bis (2-hydroxyethanol) disulfide Was synthesized in the same manner. The polythiol compound prepared had an AHPA of 18 and a YI of 1.44.
Manufacture of Optical Lens
As in Example 1, the results of the plastic optical lens manufactured using the obtained polythiol compound are shown in Table 1. The optical lens obtained had an APHA of 19 and a YI of 1.57.
Comparative Example 1
Preparation of Polythiol Compounds
In the same manner as in Example 11, Comparative Example 1 prepared a polythiol compound in the same manner as in Comparative Example 1 except that 50% aqueous solution of soda soda instead of ammonia was used to hydrolyze the isotyuronium salt. The polythiol compound prepared had an AHPA of 23 and a YI of 1.95.
Manufacture of Optical Lens
As in Example 1, the results of the plastic optical lens manufactured using the obtained polythiol compound are shown in Table 1. The optical lens obtained had an APHA of 32 and a YI of 3.15.
Comparative Example 2
Preparation of Polythiol Compounds
In the same manner as in Example 12, Comparative Example 2 was prepared in the same manner except that a 50% aqueous solution of soda soda instead of ammonia was used to hydrolyze the isothiuronium salt. The polythiol compound prepared had an AHPA of 22 and a YI of 1.88.
Manufacture of Optical Lens
As in Example 1, the results of the plastic optical lens manufactured using the obtained polythiol compound are shown in Table 1. The prepared optical lens had an APHA of 30 and a YI of 2.68.
Comparative Example 3-7
Polythiol Preparation of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol)
In the same manner as in Example 1, Comparative Example 3-7 was the same except that 2-mercaptoethanol using different amounts of thiourea and bis (2-hydroxyethanol) disulfide, which differed in weight% of calcium, was used. Synthesized The results are shown in Table 1.
Manufacture of Optical Lens
As in Example 1, the results of the plastic optical lens manufactured using the polythiol compound obtained in Comparative Example 3-7 are shown in Table 1.
division
Polythiol
For raw materials of compounds
Polythiol
Color of the compound and its plastic optical lens
Calcium content in Tiyourea (wt%)
Ss * amount in 2-mercaptoethanol
(weight%)
Hydrolysis
matter
Color of polythiol
Color of plastic optical lens
APHA
YI
APHA
YI
The results of Table 1 show that the polythiol prepared by treating with ammonia when the calcium content is less than 0.90% by weight and the content of bis (2-hydroxyethyl) disulfide is less than 0.45% by weight and hydrolyzes the isoturonium salt The compound had a good color and the plastic lens made of this polythiol compound was clear and colorless and transparent. When the calcium content of the raw material used in the preparation of the polythiol compound is 0.10% by weight or more, or the content of bis (2-hydroxyethyl) disulfide is 0.50% by weight or more, the color of the polythiol compound is deteriorated and is also produced using the same. Optical lenses lack color or transparency. The color of the polythiol compound obtained according to the hydrolysis method of the polyalcohol and thiourea in Examples 11 and 12 and Comparative Examples 1 and 2 has a relatively better color of ammonia than caustic soda. Compared with the optical lens manufactured using the same, the APHA value or YI value was low, and the color and transparency were excellent. In Examples and Comparative Examples (in Table 1), the polythiol compound and the optical lens of the Example were relatively lower in APHA and YI values, better colors, clearer, and colorless transparent optical lenses compared to those of the Comparative Examples. .
Production of a colorless transparent polythiol compound of the present invention can produce a colorless transparent optical lens, and also to prepare a urethane lens having excellent optical properties and physical properties such as high transmittance, high refractive index low dispersion, dyeability, processability, etc. It is an indispensable being. Since the color and clearness of the resin composition greatly affect the color of the optical lens, it is important to provide a clear resin composition without color variation for each lot. The present invention is a resin manufacturing technique for optical lenses required for the production of lenses, because the present invention provides a transparent and transparent optical lens material, so that it is possible to stably produce a transparent and transparent lens. This is expected to be widely used in the field of optical lens because the yield of optical lens is high and stable and clear and transparent lens can be produced.
Claims (7)
Using a thiourea refined to less than 2% by weight of metal and less than 0.95% by weight of calcium, the content of bis (2-hydroxyethyl) disulfide contained in 2-mercaptoethanol is reduced to less than 0.5% by weight A method for producing a polythiol compound, wherein the isothiuronium salt, which is an intermediate product, is hydrolyzed with ammonia water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100078120A KR20120058635A (en) | 2010-08-13 | 2010-08-13 | Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100078120A KR20120058635A (en) | 2010-08-13 | 2010-08-13 | Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20120058635A true KR20120058635A (en) | 2012-06-08 |
Family
ID=46610075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100078120A KR20120058635A (en) | 2010-08-13 | 2010-08-13 | Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20120058635A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5319037B1 (en) * | 2012-08-14 | 2013-10-16 | 三井化学株式会社 | Method for producing polythiol compound |
| JP5319036B1 (en) * | 2012-08-14 | 2013-10-16 | 三井化学株式会社 | Method for producing polythiol compound |
| WO2014027427A1 (en) * | 2012-08-14 | 2014-02-20 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| KR20150032250A (en) * | 2012-08-14 | 2015-03-25 | 미쓰이 가가쿠 가부시키가이샤 | Polythiol composition, polymerizable composition for optical materials, and use of polymerizable composition for optical materials |
| JP2015086204A (en) * | 2013-11-01 | 2015-05-07 | 三菱瓦斯化学株式会社 | Method of producing polythiol compound for optical material |
| KR20160073958A (en) * | 2013-10-15 | 2016-06-27 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Optical material composition and optical material using same |
| US9567479B2 (en) | 2012-08-23 | 2017-02-14 | Lg Chem, Ltd. | Hard coating film |
| US9765234B2 (en) | 2012-08-23 | 2017-09-19 | Lg Chem, Ltd. | Laminated hard coating film |
| US9777186B2 (en) | 2012-08-23 | 2017-10-03 | Lg Chem, Ltd. | Hard coating film |
| US9783698B2 (en) | 2012-08-23 | 2017-10-10 | Lg Chem, Ltd. | Hard coating film |
| WO2018003059A1 (en) * | 2016-06-30 | 2018-01-04 | ホヤ レンズ タイランド リミテッド | Method for preparing polythiol compound, method for preparing curable composition, and method for producing cured product |
| US9902868B2 (en) | 2012-08-23 | 2018-02-27 | Lg Chem, Ltd. | Hard coating film |
| US9909026B2 (en) | 2012-08-23 | 2018-03-06 | Lg Chem, Ltd. | Hard coating film |
| WO2018043901A1 (en) * | 2016-08-30 | 2018-03-08 | 에스케이씨 주식회사 | Method for preparing polythiol compound for optical material |
| WO2018043896A1 (en) * | 2016-08-30 | 2018-03-08 | 에스케이씨 주식회사 | Polythiol composition for optical material and method for preparing same |
| JP2018058774A (en) * | 2016-09-30 | 2018-04-12 | ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ | Method for producing polythiol compound for optical material |
| WO2018173820A1 (en) | 2017-03-24 | 2018-09-27 | 三井化学株式会社 | Method for producing polythiol compound, polymerizable composition and use thereof |
| US10280330B2 (en) | 2012-08-23 | 2019-05-07 | Lg Chem, Ltd. | Hard coating film |
| WO2019189762A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for manufacturing polythiol compound, method for manufacturing curable composition, and method for manufacturing cured material |
| WO2019189761A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| US10723697B2 (en) * | 2017-03-31 | 2020-07-28 | Skc Co., Ltd. | Preparation method of polythiol for optical lenses by using metal sulfide |
| CN113061252A (en) * | 2019-12-13 | 2021-07-02 | Skc株式会社 | Process for preparing polythiol compositions |
| KR20220013950A (en) * | 2019-12-13 | 2022-02-04 | 에스케이씨 주식회사 | Manufacturing method of polythiol composition |
-
2010
- 2010-08-13 KR KR1020100078120A patent/KR20120058635A/en not_active Application Discontinuation
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5319037B1 (en) * | 2012-08-14 | 2013-10-16 | 三井化学株式会社 | Method for producing polythiol compound |
| JP5319036B1 (en) * | 2012-08-14 | 2013-10-16 | 三井化学株式会社 | Method for producing polythiol compound |
| WO2014027427A1 (en) * | 2012-08-14 | 2014-02-20 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| WO2014027428A1 (en) * | 2012-08-14 | 2014-02-20 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| KR20140142375A (en) | 2012-08-14 | 2014-12-11 | 미쓰이 가가쿠 가부시키가이샤 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| CN104321307A (en) * | 2012-08-14 | 2015-01-28 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| KR20150032250A (en) * | 2012-08-14 | 2015-03-25 | 미쓰이 가가쿠 가부시키가이샤 | Polythiol composition, polymerizable composition for optical materials, and use of polymerizable composition for optical materials |
| EP2845847A4 (en) * | 2012-08-14 | 2015-04-29 | Mitsui Chemicals Inc | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| US10858473B2 (en) | 2012-08-14 | 2020-12-08 | Mitsui Chemicals, Inc. | Polythiol composition, polymerizable composition for optical material and use thereof |
| US9181179B2 (en) | 2012-08-14 | 2015-11-10 | Mitsui Chemicals, Inc. | Method for producing polythiol compound, polymerizable composition for optical material, and uses thereof |
| US9181180B2 (en) | 2012-08-14 | 2015-11-10 | Mitsui Chemicals, Inc. | Method for producing polythiol compound, polymerizable composition for optical material, and uses thereof |
| KR20160028487A (en) | 2012-08-14 | 2016-03-11 | 미쓰이 가가쿠 가부시키가이샤 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| KR20160028486A (en) | 2012-08-14 | 2016-03-11 | 미쓰이 가가쿠 가부시키가이샤 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| US10858472B2 (en) | 2012-08-14 | 2020-12-08 | Mitsui Chemicals, Inc. | Polythiol composition, polymerizable composition for optical material and use thereof |
| CN104321307B (en) * | 2012-08-14 | 2016-08-17 | 三井化学株式会社 | The manufacture method of multi-thioalcohol compound, polymerizable composition for optical material and application thereof |
| CN105906773A (en) * | 2012-08-14 | 2016-08-31 | 三井化学株式会社 | Method for producing polythiol compound, polymerizable composition for optical material, and uses thereof |
| EP3093282A1 (en) * | 2012-08-14 | 2016-11-16 | Mitsui Chemicals, Inc. | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| KR20180090898A (en) * | 2012-08-14 | 2018-08-13 | 미쓰이 가가쿠 가부시키가이샤 | Polythiol composition, polymerizable composition for optical materials, and use of polymerizable composition for optical materials |
| US9605105B2 (en) | 2012-08-14 | 2017-03-28 | Mitsui Chemicals, Inc. | Method for producing polythiol compound, polymerizable composition for optical material, and uses thereof |
| US9637584B2 (en) | 2012-08-14 | 2017-05-02 | Mitsui Chemicals, Inc. | Method for producing polythiol compound, polymerizable composition for optical material, and uses thereof |
| CN105906773B (en) * | 2012-08-14 | 2018-05-29 | 三井化学株式会社 | The manufacturing method of multi-thioalcohol compound, polymerizable composition for optical material and application thereof |
| US9902868B2 (en) | 2012-08-23 | 2018-02-27 | Lg Chem, Ltd. | Hard coating film |
| US9783698B2 (en) | 2012-08-23 | 2017-10-10 | Lg Chem, Ltd. | Hard coating film |
| US10280330B2 (en) | 2012-08-23 | 2019-05-07 | Lg Chem, Ltd. | Hard coating film |
| US9777186B2 (en) | 2012-08-23 | 2017-10-03 | Lg Chem, Ltd. | Hard coating film |
| US9909026B2 (en) | 2012-08-23 | 2018-03-06 | Lg Chem, Ltd. | Hard coating film |
| US10087340B2 (en) | 2012-08-23 | 2018-10-02 | Lg Chem, Ltd. | Hard coating film |
| US9567479B2 (en) | 2012-08-23 | 2017-02-14 | Lg Chem, Ltd. | Hard coating film |
| US9765234B2 (en) | 2012-08-23 | 2017-09-19 | Lg Chem, Ltd. | Laminated hard coating film |
| KR20160073958A (en) * | 2013-10-15 | 2016-06-27 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Optical material composition and optical material using same |
| JP2015086204A (en) * | 2013-11-01 | 2015-05-07 | 三菱瓦斯化学株式会社 | Method of producing polythiol compound for optical material |
| US10975026B2 (en) | 2016-06-30 | 2021-04-13 | Hoya Lens Thailand Ltd. | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| JPWO2018003059A1 (en) * | 2016-06-30 | 2019-01-17 | ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| WO2018003059A1 (en) * | 2016-06-30 | 2018-01-04 | ホヤ レンズ タイランド リミテッド | Method for preparing polythiol compound, method for preparing curable composition, and method for producing cured product |
| WO2018043896A1 (en) * | 2016-08-30 | 2018-03-08 | 에스케이씨 주식회사 | Polythiol composition for optical material and method for preparing same |
| WO2018043901A1 (en) * | 2016-08-30 | 2018-03-08 | 에스케이씨 주식회사 | Method for preparing polythiol compound for optical material |
| JP2018058774A (en) * | 2016-09-30 | 2018-04-12 | ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ | Method for producing polythiol compound for optical material |
| KR20190122729A (en) | 2017-03-24 | 2019-10-30 | 미쯔이가가꾸가부시끼가이샤 | Process for preparing polythiol compound, polymerizable composition and use thereof |
| WO2018173820A1 (en) | 2017-03-24 | 2018-09-27 | 三井化学株式会社 | Method for producing polythiol compound, polymerizable composition and use thereof |
| US10723697B2 (en) * | 2017-03-31 | 2020-07-28 | Skc Co., Ltd. | Preparation method of polythiol for optical lenses by using metal sulfide |
| JP2019172630A (en) * | 2018-03-29 | 2019-10-10 | ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| JP2019172631A (en) * | 2018-03-29 | 2019-10-10 | ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| WO2019189761A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for producing polythiol compound, method for producing curable composition, and method for producing cured product |
| WO2019189762A1 (en) * | 2018-03-29 | 2019-10-03 | ホヤ レンズ タイランド リミテッド | Method for manufacturing polythiol compound, method for manufacturing curable composition, and method for manufacturing cured material |
| CN113061252A (en) * | 2019-12-13 | 2021-07-02 | Skc株式会社 | Process for preparing polythiol compositions |
| KR20220013950A (en) * | 2019-12-13 | 2022-02-04 | 에스케이씨 주식회사 | Manufacturing method of polythiol composition |
| US11578038B2 (en) | 2019-12-13 | 2023-02-14 | Skc Co., Ltd. | Method for preparing polythiol composition |
| CN113061252B (en) * | 2019-12-13 | 2023-09-29 | Skc株式会社 | Process for the preparation of polythiol compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20120058635A (en) | Preparation of Polythiol Compound for Optical Lens and Polymerizable Composition Comprising It | |
| KR101594407B1 (en) | Method of Preparing Clear and Transparent Polythiol Compound Resin Composition Including the Polythiol Compound for Optical Lens and Preparation Method of the Optical Lens | |
| KR102074091B1 (en) | Polythiol composition, polymerizable composition for optical materials, and use of polymerizable composition for optical materials | |
| KR101807584B1 (en) | A method of preparing polythiol compounds, and composition for optical material using it | |
| KR101400358B1 (en) | Method of producing polythiol compound for optical material and polymerizable composition for optical material comprising the polythiol compound | |
| EP3486272B1 (en) | Aromatic polythiol compound for optical material | |
| KR101074450B1 (en) | Resin Composition Using New Thiol Compound for Optical Lens Having Light Weight and High Refractive Index, and the Optical Lens Using It | |
| KR20100094378A (en) | High refractive index optical resin composition having improved impact resistance, high refractive index plastic optical lens and manufacturing method of the plastic optical lens | |
| KR20140029298A (en) | A method of preparing thiourethane based optical material | |
| KR101455645B1 (en) | Preparation method of polythiol compound and polymerizable composition for optical material comprising it | |
| US20150018507A1 (en) | Method for producing polythiol compound for optical materials and composition comprising same for optical materials | |
| EP2757115B1 (en) | Method for producing urethane optical member | |
| KR101157497B1 (en) | Resin Composition Having High Heat Resistance and Good Reactivity for Urethane Optical Lens | |
| KR20150014418A (en) | Preparation method of polythiol compounds by ring open and the polythiol compounds, and the resin composition for optical material using it | |
| WO2015190809A1 (en) | Novel thiol compound and polymerizable composition containing same | |
| US10669367B2 (en) | Polythiol composition for plastic lens | |
| KR20120060254A (en) | Resin Composition of Superhigh Refractive Index Having Excellent Thermal Stable for Urethane Optical Lens and Optical Lens Using It | |
| KR101813258B1 (en) | Siloxane thiol oligomer for optical materials | |
| KR20210121873A (en) | Thiourethane based resin composition for optical materials and method of manufacturing thiourethane based optical material resin | |
| KR101745469B1 (en) | Resin Composition Having Superhigh Refractive Index for Urethane Optical Lens and Optical Lens Using It | |
| KR20170090393A (en) | Resin Composition of Superhigh Refractive Index Having Excellent Thermal Stable for Urethane Optical Lens and Optical Lens Using It | |
| KR20140001808A (en) | A method of preparing thiourethane based optical material | |
| KR101883811B1 (en) | Siloxane thiol oligomer for optical materials | |
| JP2018058773A (en) | Method for producing polythiol compound for optical material | |
| KR20120063026A (en) | Resin composition of superhigh refractive index having high heat distortion temperature and excellent thermal stable for urethane optical lens and optical lens using it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |