CN101984758B - Resin composition for a high refractive index optical lens having superior impact resistance, high refractive index optical lens using same, and method for producing same - Google Patents
Resin composition for a high refractive index optical lens having superior impact resistance, high refractive index optical lens using same, and method for producing same Download PDFInfo
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- CN101984758B CN101984758B CN201080000831.9A CN201080000831A CN101984758B CN 101984758 B CN101984758 B CN 101984758B CN 201080000831 A CN201080000831 A CN 201080000831A CN 101984758 B CN101984758 B CN 101984758B
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/52—Polythioethers
Abstract
The present invention relates to a resin composition for a high refractive index optical lens having superior impact resistance, to a high refractive index optical lens using same, and to a method for producing same. More particularly, the present invention relates to a resin composition for an optical lens which has superior impact resistance and heat resistance after being multicoated, which is lightweight, and which has superior workability including formability, dyeability, etc., and superior optical properties including Abbe number, transparency, ultraviolet barrier properties, etc. The present invention also relates to a high refractive index optical lens using same.
Description
Technical field
The present invention relates to possess the high refractive index optical lens resin combination of superior impact resistance, utilize high refractive index optical lens and the manufacture method thereof of above-mentioned composition, especially possessing outstanding light weight, in the time of the optical characteristics such as the processibility such as plasticity-and dyeability and high Abbe number and the transparency, the thermotolerance that cause possesses superior impact resistance and solid resin is high, therefore after multilayer film, multilayer film be difficult for the being heated high refractive index optical lens resin combination of cracking utilizes the high refractive index optical lens and the manufacture method thereof that possess superior impact resistance of above-mentioned composition.
Background technology
Just begin to be widely used as from way back the glass lens of optical lens, therefore with low uncertainty with the number of degrees of the lens of exterior temperature change because its thermal expansivity is little, and for improving transmissivity to be plated on the temperature variant damage of its surperficial multilayer film less.But a little less than the shock-resistance of glass lens, proportion is high, therefore now gradually by lightweight, shock-resistance is high, and replace than the plastic lens that glass lens has outstanding processibilities such as dyeability.
Recently, along with the transmissivity of plastic lens and the requirement of level of stability are become more and more higher, most of optical lens, especially ophthalmic lens are by carrying out multilayer film (SiO in its lens both side surface
2, ZrO
2Deng inorganics) improve transmissivity, but such multilayer film will concentrate on from the impact of outside a place, therefore easily cause lens cracked.
Korea S publication 1992-0004464 number disclosed diallyl isophthalate (diallyl isophthalate), add the diallyl isophthalate of bivalent alcohol and the multipolymer of glycol ether diallyl carbonic ether (diethylene glycol bis allylcarbonate), Korea S publication 1994-0004010 number disclosed Xylene Diisocyanate (xylenediisocyanate), 1,2-dimercapto ethyl-3-sulfydryl propane (1,2-bismercaptoethyl-3-mercaptopropane) and the plastic spectacle lens that is made of polymethylmethacrylate (polymethylmethacrylate) multipolymer, carry out multilayer film for improving transmissivity, but have the frangible problem of ophthalmic lens.
In addition, the polycarbonate of extrusion moulding (polycarbonate) optical lens, although the shock-resistance after the multilayer film is better, if but use as thermoplastic resin, then because of easily temperature distortion, the central part distortion that the edge that its thickness is thicker is thinner than lens thickness is larger, therefore, if wear such eyeglass, then will cause dizzy, and lower as the Abbe number of important optical properties.
For solving the thermostability of the lens that formed by above-mentioned thermoplastic resin manufacturing, develop thermosetting resin lens resin as countermeasure, in Korean registered patent No. 0638194 and No. 0688698, disclose to mix and used sex change polyvalent alcohol (polyol) and vulcabond (diisocyanate) to make the method for optical lens.But, although improved shock-resistance and thermotolerance, need after optical resin is cast as flat board, grind again the manufacturing lens, thereby cost to be higher, and its specific refractory power drops to about 1.523, so the edge of lens is with thickening.
No. the 472837th, Korea S's publication is added in vulcabond after the bivalent alcohol, carries out hybrid reaction with tetravalence polythiol (polythiol) and carries out thermofixation and make optical lens, thereby improved the shock-resistance of lens.But the optical lens composition of above-mentioned patent is although can improve shock-resistance under blank eyeglass (without the plastic lens of following process) state, but after multilayer film, because its shock-resistance reduces, thus can't satisfy the FDA specification (the 127cm height, 16.0g).In addition, prepare the optical lens composition because adding in advance bivalent alcohol in the vulcabond, therefore, the high viscosity owing to composition easily occurs bad.In addition, above-mentioned optical lens composition although possess the intensity that is enough to make the no-frame glasses sheet, can not be can be regarded as the preferably ophthalmic lens of safety of shock-resistance, and owing to specific refractory power drops to about 1.555, so the edge of lens is thicker.
The Korean registered patent discloses for No. 689867 when possessing outstanding light weight, plasticity-, dyeability, Abbe number and the transparency, in the manufacture method of the plastic optical lens that has superior impact resistance after multilayer film with resin combination and optical lens thereof.(the 127cm height 16.0g), also is low to moderate about 1.530～1.570 owing to specific refractory power, so the edge thickening of lens, and added value is low although the shock-resistance behind the above-mentioned patent multilayer film satisfies the FDA specification.
Summary of the invention
For overcoming the problem of prior art, the inventor is through further research discovery, to dicyclohexyl methane diisocyanate (the dicyclohexylmethanediisocyanate) (H by certain content
12MDI) and 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate) the mixtures of diisocyanates of (HDI) formation, cooperate 1 of certain content, 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1,2-bis (2-mercaptoethylthio)-3-mercaptopropane) and trimethylolpropane tris (mercaptopropionic acid ester) (trimethylol propane tris (mercaptopropionate)), the resin combination that the mixture manufacturing of tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)) or above-mentioned substance forms, possess optical lens required various characteristics, especially high refractive index and outstanding shock-resistance.
Therefore, the object of the present invention is to provide a kind of high refractive index optical lens resin combination, it has 1.580 above high refractive index (nE, 20 ℃) time, has outstanding shock-resistance, thereby the shock strength after the multilayer film can be passed through the shock-resistant experiment of FDA (127cm height, 16.0g), and its multilayer film good heat resistance not only, but also possess processibility and the optical characteristics such as high Abbe number, the transparency and ultraviolet resistance such as outstanding light weight, plasticity-and dyeability.
Another object of the present invention is to provide a kind of optical lens that utilizes above-mentioned optical lens to form with the resin combination manufacturing, it has superior impact resistance and 1.580 above high refractive index (nE, 20 ℃).
For achieving the above object, the invention provides a kind of optical lens resin combination, comprising: the mixtures of diisocyanates of 40～65 % by weight, it is by the dicyclohexyl methane diisocyanate (H of 50～85 % by weight
12MDI) and 15～50 % by weight 1,6-hexamethylene diisocyanate (HDI) consists of; The mercaptan mixture of 35～60 % by weight, it is by 1 of 60～99.9 % by weight, and the mixture of front three hydroxy propane three (mercaptopropionic acid ester), tetramethylolmethane four (mercaptopropionic acid ester) or the above-mentioned substance of 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane and 0.1～40 % by weight consists of.
In above-mentioned mixtures of diisocyanates, if increase by the usage quantity of 1,6-hexamethylene diisocyanate (HDI), then increase the shock strength of lens, but reduce thermotolerance; And if increase dicyclohexyl methane diisocyanate (H
12MDI) usage quantity then improves thermotolerance, but reduces shock strength.Based on this, with in the resin combination, consider thermotolerance and the shock strength of final produced lens, dicyclohexyl methane diisocyanate (H at optical lens of the present invention
12MDI) and the usage quantity of 1,6-hexamethylene diisocyanate (HDI) be respectively 50～85 % by weight and 15～50 % by weight.
Above-mentioned mercaptan mixture, by being preferably 60～99.9 % by weight, more preferably 1 of 70～95 % by weight, 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane and be preferably 0.1～40 % by weight, more preferably the mixture of the trimethylolpropane tris of 5～30 % by weight (mercaptopropionic acid ester), tetramethylolmethane four (mercaptopropionic acid ester) or above-mentioned substance consists of.The effect of above-mentioned front three hydroxy propane three (mercaptopropionic acid ester) and/or tetramethylolmethane four (mercaptopropionic acid ester) is, under the prerequisite of the final resin combination thermotolerance of not obvious reduction and specific refractory power, improves shock strength.This is because have ester group in the polymer of formation lens, thereby improves intermolecular attractive interaction.
The optical lens resin combination that forms by the aforesaid method manufacturing, its liquid refractivity (nD, 20 ℃) be 1.530～1.600, solid specific refractory power (nE, 20 ℃) is 1.580～1.630, Abbe number is 32～52, liquid viscosity is 20～3000 (cps, 20 ℃), and has superior impact resistance and multilayer film good heat resistance by the manufacturing of thermofixation above-mentioned composition, and its specific refractory power (nE, 20 ℃) is the high refractive index optical lens more than 1.580.
By thermofixation optical lens of the present invention with composition and carry out the ophthalmic lens that subsequent disposal obtains, the good heat resistance of its multilayer film, has the FDA of meeting ophthalmic lens specification (ANS specification, the 127cm height, 16.0g the shock-resistance falling sphere experiment), and owing to having 1.580～1.630 high refractive index, so its edge is thinner, thereby the optical lens that is suitable for the large the general population of sportsmen or amount of exercise or impacts more operation field workman's etc. safety can be provided.
Embodiment
Consist of the high refractive index optical lens with superior impact resistance of the present invention mixtures of diisocyanates of resin combination, comprise dicyclohexyl methane diisocyanate (H
12MDI) and 1,6-hexamethylene diisocyanate (1,6-hexamethylenediisocyanate) (HDI).Optical lens resin combination of the present invention, also can comprise one or more diisocyanate cpds in vulcabond (diisocyanate) compound that is selected from alkylene vulcabond (alkylene diisocyanate) compound, alicyclic diisocyanate (alicyclic diisocyanate) compound, heterocycle vulcabond (heterocyclic diisocyanate) compound and sulfur-bearing, and its content is 0.1～10 % by weight with respect to the resin combination gross weight.
Above-mentioned alkylene diisocyanate cpd, for example be ethylidene diisocyanate (ethylene diisocyanate), trimethylene diisocyanate (trimethylenediisocyanate), tetramethylene diisocyanate (tetramethylene diisocyanate), 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate), inferior octyl diisocyanate (octamethylene diisocyanate), nonamethylene vulcabond (nonamethylene diisocyanate), 2,2-dimethylpentane vulcabond (2,2-dimethylpentane diisocyanate), 2,2,4-trimethyl cyclohexane vulcabond (2,2,4-trimethylhexane diisocyanate), decamethylene vulcabond (decamethylene diisocyanate), butene diisocyanate (butenediisocyanate), 1,3-divinyl-1,4-vulcabond (1,3-butadiene-1,4-diisocyanate), 2,3,4-trimethylammonium hexylidene diisocyanate (2,3,4-trimethyl hexamethylene diisocyanate), 1,6,11-undecane triisocyanate (1,6,11-undecane triisocyanate), 1,3,6-hexylidene triisocyanate (1,3,6-hexamethylene triisocyanate), 1,8-two isocyanatos-4-isocyanato methyloctane (1,8-diisocyanato-4-isocyanato methyloctane), 2,5,7-trimethylammonium-1,8-two isocyanatos-5-isocyanato methyloctane (2,5,7-trimethyl-1,8-diisocyanato-5-isocyanato methyloctane), two (isocyanato ethyl) carbonic ether (bis (isocyanato ethyl) carbonate), two (isocyanato ethyl) ether (bis (isocyanato ethyl) ether), 1,4-butyleneglycol dipropyl ether-1,2-vulcabond (1,4-butylene glycol dipropylether-1,2-diisocyanate), 1,4-butyleneglycol dipropyl ether-1,3-vulcabond (1,4-butylene glycol dipropyl ether-1,3-diisocyanate), 1,4-butyleneglycol dipropyl ether-1,4-vulcabond (1,4-butylene glycol dipropylether-1,4-diisocyanate), 1,4-butyleneglycol dipropyl ether-2,3-vulcabond (1,4-butylene glycol dipropyl ether-2,3-diisocyanate), 1,4-butyleneglycol dipropyl ether-2,4-vulcabond (1,4-butylene glycol dipropylether-2,4-diisocyanate), methyllysine vulcabond (methyllysinediisocyanate), Lysine triisocyanate (lysine triisocyanate), 2-isocyanato ethyl-2,6-two isocyanato capronate (2-isocyanato ethyl-2,6-diisocyanato hexanoate), 2-isocyanato propyl group-2,6-two isocyanato capronate (2-isocyanatopropyl-2,6-diisocyanato hexanoate), sym-trimethylbenzene triisocyanate (mesitylene triisocyanate), 2,6-two (isocyanato methyl) furans (2,6-di (isocyanato methyl) furan) etc.
Above-mentioned alicyclic diisocyanate (alicyclic diisocyanate) compound, for example be 3,8-two (isocyanato methyl) three rings [5,2,1,02,6] decane (3,8-bis (isocyanatomethyl) tricyclo[5,2,1,02,6] decane), 3,9-two (isocyanato methyl), three rings [5,2,1,02,6] decane (3,9-bis (isocyanato methyl) tricyclo[5,2,1,02,6] decane), 4,8-two (isocyanato methyl) three rings [5,2,1,02,6] decane (4,8-bis (isocyanato methyl) tricyclo[5,2,1,02,6] decane), 4,9-two (isocyanato methyl), three rings [5,2,1,02,6] decane (4,9-bis (isocyanato methyl) tricyclo[5,2,1,02,6] decane), 2,5-two (isocyanato methyl) two rings [2,2,1] heptane (2,5-bis (isocyanato methyl) bicyclo[2,2,1] heptane), 2,6-two (isocyanato methyl), two rings [2,2,1] heptane (2,6-bis (isocyanato methyl) bicyclo[2,2,1] heptane), isophorone diisocyanate (isophoronediisocyanate), two (isocyanato methyl) hexanaphthene (bis (isocyanato methyl) cyclohexane), dicyclohexyl methane diisocyanate (dicyclohexyl methanediisocyanate), cyclohexyl diisocyanate (cyclohexane diisocyanate), methylcyclohexane diisocyanate (methyl cyclohexane diisocyanate), dicyclohexyl dimethylmethane vulcabond (dicyclohexyl dimethyl methanediisocyanate), 2,2 '-dimethyl dicyclohexyl methane diisocyanate (2,2 '-dimethyldicyclohexyl methane diisocyanate), two (4-isocyanato-n-butylidene) tetramethylolmethane (bis (4-isocyanato-n-butylidene) pentaerythritol), dimer acid diisocyanate (dimer acid diisocyanate), 2-isocyanato methyl-3-(3-isocyanato propyl group)-5-isocyanato methyl bicyclic [2,2,1]-heptane (2-isocyanato methyl-3-(3-isocyanato propyl)-5-isocyanato methylbicyclo[2,2,1]-heptane), 2-isocyanato methyl-3-(3-isocyanato propyl group)-6-isocyanato methyl bicyclic [2,2,1]-heptane (2-isocyanato methyl-3-(3-isocyanato propyl)-6-isocyanatomethylbicyclo[2,2,1]-heptane), 2-isocyanato methyl-2-(3-isocyanato propyl group)-5-isocyanato methyl-two ring [2,2,1]-heptane (2-isocyanato methyl-2-(3-isocyanato propyl)-5-isocyanato methyl-bicyclo[2,2,1]-heptane), 2-isocyanato methyl-2-(3-isocyanato propyl group)-6-isocyanato methyl-two ring [2,2,1]-heptane (2-isocyanato methyl-2-(3-isocyanato propyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane), 2-isocyanato methyl-3-(3-isocyanato propyl group)-6-(2-isocyanato ethyl)-two ring [2,2,1]-heptane (2-isocyanato methyl-3-(3-isocyanato propyl)-6-(2-isocyanato ethyl)-bicyclo[2,2,1]-heptane), 2-isocyanato methyl-3-(3-isocyanato propyl group)-6-(2-isocyanato ethyl)-two ring [2,2,1]-heptane (2-isocyanato methyl-3-(3-isocyanato propyl)-6-(2-isocyanato ethyl)-bicyclo[2,2,1]-heptane), 2-isocyanato methyl-2-(3-isocyanato propyl group)-5-(2-isocyanato ethyl)-two ring [2,2,1]-heptane (2-isocyanato methyl-2-(3-isocyanato propyl)-5-(2-isocyanato ethyl)-bicyclo[2,2,1]-heptane), 2-isocyanato methyl-2-(3-isocyanato propyl group)-6-(2-isocyanato ethyl)-two ring [2,2,1]-heptane (2-isocyanato methyl-2-(3-isocyanato propyl)-6-(2-isocyanato ethyl)-bicyclo[2,2,1]-heptane), 1,3,5-three (isocyanato methyl)-hexanaphthene (1,3,5-tris (isocyanato methyl)-cyclohexane), dicyclohexyl methyl hydride-4,4-vulcabond (dicyclohexyl methane-4,4-diisocyanate) (H
12MDI) etc.
Above-mentioned heterocycle vulcabond (heterocyclic diisocyanate) compound; thiophene-2 is for example arranged; 5-vulcabond (thiophene-2; 5-diisocyanate); thiotolene-2; 5-vulcabond (methyl thiophene-2; 5-diisocyanate); 1; 4-dithiane-2; 5-vulcabond (1; 4-dithiane-2; 5-diisocyanate); methyl 1; 4-dithiane-2; (methyl 1 for the 5-vulcabond; 4-dithiane-2; 5-diisocyanate); 1; 3-dithiolane-4; 5-vulcabond (1; 3-dithiolan-4; 5-diisocyanate); methyl 1; 3-dithiolane-4; (methyl 1 for the 5-vulcabond; 3-dithiolan-4; 5-diisocyanate); methyl 1; 3-dithiolane-2-methyl-4; 5-vulcabond (methyl1; 3-dithiolan-2-methyl-4; 5-diisocyanate); ethyl 1; 3-dithiolane-2; (ethyl 1 for the 2-vulcabond; 3-dithiolan-2; 2-diisocyanate); tetramethylene sulfide-2; 5-vulcabond (tetrahydro thiophene-2; 5-diisocyanate); methyl tetramethylene sulfide-2; 5-vulcabond (methyl tetrahydro thiophene-2; 5-diisocyanate); ethyl tetramethylene sulfide-2; 5-vulcabond (ethyl tetrahydro thiophene-2; 5-diisocyanate); methyl tetramethylene sulfide-3; 4-vulcabond (methyltetrahydrothiophene-3; 4-diisocyanate); 1; 2-two isocyanide acyl group ethane (1; 2-diisocyanato ethane); 1; 3-two isocyanide acyl group propane (1; 3-diisocyanatopropane); 1; 4-two isocyanide acyl group butane (1; 4-diisocyanato butane); 1; 6-two isocyanide acyl group hexanes (1,6-diisocyanato hexane); p-phenylene diisopropylidene diisothio-cyanate (p-phenylene diiso propylidene diisothiocyanate); hexanaphthene diisothio-cyanate (cyclohexane diisothiocyanate) etc.
The diisocyanate cpd of above-mentioned sulfur-bearing, for example be 4-isocyanato-4 '-isocyanato diphenyl sulfide (4-isocyanato-4 '-isocyanato diphenyl sulphide), 2-isocyanato-2 '-the isocyanato diethyl sulfide (2-isocyanato-2 '-isocyanatodiethyl sulphide), sulfo-diethyl vulcabond (thiodiethyl diisocyanate), sulfo-dipropyl vulcabond (thiodipropyl diisocyanate), sulfo-dihexyl vulcabond (thiodihexyl diisocyanate), dimethyl sulfone vulcabond (dimethylsulfone diisocyanate), dithio dimethyl vulcabond (dithiodimethyldiisocyanate), dithio diethyl vulcabond (dithiodiethyl diisocyanate), dithio dipropyl group diisocyanate (dithiodipropyl diisocyanate), dicyclohexyl sulfide-4,4 '-vulcabond (dicyclohexyl sulphide-4,4 '-diisocyanate), 1-isocyanato methyl thia-2,3-two (2-isocyanato ethyl thia) propane (1-isocyanato methylthia-2,3-bis (2-isocyanato ethylthia) propane) etc.
In above-mentioned vulcabond (diisocyanate) mixture, the content of dicyclohexyl methane diisocyanate (dicyclohexylmethane diisocyanate) is preferably 50～85 % by weight, is more preferred from 60～80 % by weight.If the content of dicyclohexyl methane diisocyanate (dicyclohexylmethane diisocyanate) is lower than 50 % by weight, then the thermotolerance of lens sharply descends, thereby easily cause lens surface cracking, and at the central part of lens, the depressed phenomenon that occurs being heated and cause.In above-mentioned vulcabond (diisocyanate) mixture, the content of 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate) is preferably 15～50 % by weight, is more preferred from 20～40 % by weight.If the content of 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate) is lower than 15 % by weight, then reduce the shock strength of lens, and if above 50 % by weight, then obviously reduce the thermotolerance of lens.In addition, can be to dicyclohexyl methane diisocyanate (dicyclohexylmethanediisocyanate) and 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate), add a small amount of alkylene vulcabond (alkylene diisocyanate) compound, alicyclic diisocyanate (alicyclicdiisocyanate) compound, vulcabond (diisocyanate) compound of heterocycle vulcabond (heterocyclic diisocyanate) compound and sulfur-bearing uses, if but usage quantity is excessive, then will reduce the shock strength of lens, and reduce the important physical property of the optical lenses such as thermotolerance or thermostability.
In above-mentioned vulcabond (diisocyanate) mixture, add 1 separately, 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1,2-bis (2-mercaptoethylthio)-3-mercaptopropane) also can make optical lens, but in the present invention, add trimethylolpropane tris (mercaptopropionic acid ester) (trimethylol propanetris (mercaptopropionate)) and/or tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)) for improving shock-resistance.
The content of above-mentioned mercaptan (thiol) mixture is preferably with respect to 35～60 % by weight of above-mentioned optical lens with the resin combination gross weight, is more preferred from 40～50 % by weight.If the content of above-mentioned mercaptan (thiol) mixture surpasses with respect to 60 % by weight of above-mentioned optical lens with the resin combination gross weight, then will cause insufficient curing of lens, thereby because of the lens surface weak strength, easily in production process, produce cut at lens surface, and when washing, easily be washed liquid at surperficial corrosion, thereby sharply reduce the transparency of lens.In addition, if the content of above-mentioned mercaptan mixture is lower than 35 % by weight, then because of the reaction between isocyanic ester (isocyanate) compound, reduce the shock strength of lens, and residue in unreacting isocyanate (isocyanate) in the lens, cause the thermostability of lens and photostabilization sharply to descend.
Optical lens resin combination of the present invention; except 1 of above-mentioned formation mercaptan (thiol) mixture; 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1; outside 2-bis (2-mercaptoethylthio)-3-mercaptopropane) and trimethylolpropane tris (mercaptopropionic acid ester) (trimethylol propane tris (mercaptopropionate)) and/or the tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)); also can comprise the propane-1 from 2-(2-mercaptoethyl sulfo-); 3-mercaptan (2-(2-mercaptoethylthio) propane-1; 3-thiol); 2-(2-mercaptoethyl sulfo-)-3-[2-(3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] ethylenebis dithiocarbamate-propane-1-mercaptan (2-(2-mercaptoethylthio)-3-[2-(3-mercapto-2-(2-mercaptoethylthio)-propylthio] ethylthio-propane-1-thiol); 2-(2-mercaptoethyl sulfo-)-3-{2-sulfydryl-3-[3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] propyl dithiocarbamate }-propane-1-mercaptan (2-(2-mercaptoethylthio)-3-{2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio] propylthio}-propane-1-thiol); trimethylolpropane tris (mercaptopropionic acid ester) (trimethylolpropane tris (mercaptopropionate)); trimethylolethane trimethacrylate (mercaptopropionic acid ester) (trimethylolethane tris (mercaptopropionate)); three (thiohydracrylic acid) glyceryl ester (glycerol tris (mercaptopropionate)); trishydroxymethyl chloro three (mercaptopropionic acid ester) (trimethylolchloro tris (mercaptopropionate)); trimethylolpropane tris alcohol (thioglycollate) (trimethylolpropane tris (mercaptoacetate)); trimethylolethane trimethacrylate (thioglycollate) (trimethylolethane tris (mercaptoacetate)); tetramethylolmethane four mercaptopropionic acid esters (pentaerythritoltetrakis mercaptopropionate); tetramethylolmethane four thioglycollates (pentaerythritoltetrakis mercaptoacetate); [1; 4] dithiane-2-base-thiomethyl alcohol ([1; 4] dithiane-2-yl-methanethiol); 2-(2-sulfydryl-ethylsulfonyl)-propane-1; 3-two mercaptan (2-(2-mercapto-ethylsulfanyl)-propane-1; 3-dithiol); 2-([1; 4] dithiane-2 ylmethyl alkylsulfonyl)-(2-([1 for sulfur alcohol; 4] dithiane-2ylmethylsulfanyl)-ethanethiol); 3-(3-sulfydryl-propionyl alkylsulfonyl)-propionic acid 2-hydroxymethyl-3-(3-sulfydryl-propionyloxy)-2-(3-sulfydryl-propionyloxy methyl)-propyl diester (3-(3-mercapto-propionylsulfanyl)-propionic acid2-hydroxyl methyl-3-(3-mercapto-propionyloxy)-2-(3-mercapto-propionyloxymethyl)-propyl ester); 3-(3-sulfydryl-propionyl alkylsulfonyl)-propionic acid 3-(3-sulfydryl-propionyloxy)-2; 2-two-(3-sulfydryl-propionyloxy methyl)-propyl diester (3-(3-mercapto-propionylsulfanyl)-propionic acid 3-(3-mercapto-propionyloxy)-2; 2-bis-(3-mercapto-propionyloxymethyl)-propyl ester); (5-mercapto methyl-[1; 4] dithiane-2-yl)-thiomethyl alcohol ((5-mercaptomethyl-[1,4] dithiane-2-yl)-methanethiol) and in the compound shown in the following Chemical formula 1 (Y1S) select one or more.
[Chemical formula 1]
If the content of trimethylolpropane tris (mercaptopropionic acid ester) (trimethylol propane tris (mercaptopropionate)) and/or tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)) compound is lower than 0.1 % by weight, then can not improve the shock strength of lens, if and surpass 40 % by weight, then because reducing multilayer film thermotolerance and specific refractory power, thereby can't use existing mold.
Optical lens with optical lens of the present invention is made with resin combination for improving photostabilization and antiultraviolet, also can comprise UV light absorber.UV light absorber can be used the published any UV light absorber that can be used for plastic spectacle lens.For example, can be used alone or as a mixture ethyl-2-cyano group-3,3-diphenylacrylate ester (ethyl-2-cyano-3,3-diphenylacrylate), 2-(2 '-hydroxy-5-methyl base phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5-methylphenyl)-2H-benzotriazole), 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl phenyl)-5-chloro-2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-butylphenyl)-5-chloro-2H-benzotriazole), 2-(2 '-hydroxyl-3 '-tert-butyl-5 '-aminomethyl phenyl)-5-chloro-2H-benzotriazole (2-(2 '-hydroxy-3 '-t-butyl-5 '-methylphenyl)-5-chloro-2H-benzotriazole), 2-(2 '-hydroxyl-3 ', 5 '-two-uncle-pentyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-amylphenyl)-2H-benzotriazole), 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-butylphenyl)-2H-benzotriazole), 2-(2 '-hydroxyl-5 '-the t-butyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5 '-t-butylphenyl)-2H-benzotriazole), 2-(2 '-hydroxyl-5 '-uncle-octyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5 '-t-octylphenyl)-2H-benzotriazole), 2,4-dihydroxy-benzene ketone (2,4-dihydroxybenzophenone), 2-hydroxyl-4-anisole ketone (2-hydroxy-4-methoxybenzophenone), 2-hydroxyl-4-octyloxy benzophenone (2-hydroxy-4-octyloxybenzophenone), 4-dodecyloxy-2-Viosorb 110 (4-dodecyloxy-2-hydroxybenzophenone), 4 benzoic acid base-2-Viosorb 110 (4-benzoxy-2-hydroxybenzophenone), 2,2 ', 4,4 '-tetrahydroxy phenol ketone (2,2 ', 4,4 '-tetrahydroxybenzophenone), 2,2 '-dihydroxyl-4,4 '-dimethoxy benzophenone (2,2 '-dihydroxy-4,4 '-dimethoxybenzophenone) etc.Preferably, use in 400 following frequency bands, have good anti-ultraviolet function and to composition of the present invention have the 2-(2 '-hydroxy-5-methyl base phenyl) of good solubility-2H-benzotriazole (2-(2 '-hydroxy-5-methylphenyl)-2H-benzotriazole), 2-hydroxyl-4-anisole ketone (2-hydroxy-4-methoxybenzophenone), ethyl-2-cyano group-3,3-diphenylacrylate ester (ethyl-2-cyano-3,3-diphenylacrylate), 2-(2 '-hydroxyl-5 '-uncle-octyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5 '-t-octylphenyl)-2H-benzotriazole) or 2,2 '-dihydroxyl-4,4 '-dimethoxy benzophenone (2,2 '-dihydroxy-4,4 '-dimethoxybenzophenone), 2-(2 '-hydroxyl-3 ', 5 '-two-uncle-amyl group phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-amylphenyl)-2H-benzotriazole), 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl phenyl)-5-chloro-2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-butylphenyl)-5-chloro-2H-benzotriazole), 2-(2 '-hydroxyl-3 '-tert-butyl-5 '-aminomethyl phenyl)-5-chloro-2H-benzotriazole (2-(2 '-hydroxy-3 '-t-butyl-5 '-methylphenyl)-5-chloro-2H-benzotriazole), 2,2 '-dihydroxyl-4,4 '-dimethoxy benzophenone (2,2 '-dihydroxy-4,4 '-dimethoxybenzophenone) etc.
In addition, optical lens resin combination of the present invention is for the correction of priming color also can comprise the color control agent.The color control agent can use organic dye, pigment dyestuff and mineral dye etc.In an embodiment of the present invention, use 1-hydroxyl-4-(p-Tolylamine) anthraquinone (1-hydroxy-4-(p-toluidine) anthraquinone), cyclic ketones dyestuff (perinonedye) etc.The addition of above-mentioned organic dye is that 000ppm is preferably 0.5～10000ppm with respect to optical lens 0.1～50 of 1 part of resin combination, thereby when adding UV light absorber, optical resin and monomer, prevents the lens flavescence.
Optical lens of the present invention also can comprise releasing agent with resin combination.Releasing agent can use from containing the fluorine class nonionogenic tenside of perfluoroalkyl (Perfluoroalkyl), hydroxyalkyl (hydroxyalkyl) or phosphate-based (phosphoric ester); The silicon class nonionogenic tenside that contains dimethylpolysiloxane--based (dimethyl polysiloxane), hydroxyalkyl (hydroxyalkyl) or phosphate-based (phosphoric ester); Trimethylammonium hexadecyl ammonium salt (trimethylcetyl ammonium salt), trimethylammonium octadecyl (trimethylstearyl), dimethyl ethyl hexadecyl ammonium salt (dimethylethylcetylammonium salt), triethyl dodecyl ammonium salt (triethyldodecyl ammoniumsalt), tricaprylmethylammonium salt (trioctylmethyl ammonium salt), diethyl hexamethylene dodecyl ammonium salt (diethylcyclohexadodecyl ammonium salt), one or more that select in the alkyl quaternary ammonium saltss such as phosphoric acid ester (phosphoric ester).Preferably, use phosphoric acid ester.Phosphoric acid ester can be used from p isopropylbenzoic acid ester (isopropylphosphate), di-isopropyl phosphoric acid ester (diisopropyl phosphate), dibutyl phosphate (dibutyl phosphate), octyl phosphate (octyl phosphate), dioctylphosphoric acid ester (dioctyl phosphate), phosphoric acid isodecyl ester (isodecyl phosphate), di(2-ethylhexyl)phosphate isodecyl ester (diisodecyl phosphate), phosphoric acid tridecanol ester (tridecanolphosphate), one or more that select in di(2-ethylhexyl)phosphate (tridecanol acid) ester (bis (tridecanol acid) phosphate).The result who uses in an embodiment of the present invention shows, with lens during from mold releasability, its release property is best after curing for the ZELEC UN of phosphoric acid ester (DUPONT company).The addition of releasing agent is 0.0001～10 % by weight of composition, is preferably 0.001～2 % by weight, and the lens release of this moment is good and percent polymerization is high.If the addition of releasing agent is lower than 0.0001 % by weight, then when the ophthalmic lens after the moulding is separated from glass mold, surface of glass die will be attached to lens, if and surpass 10 % by weight, then in the mould polymerization process, because lens separate from mould, thereby produce spot at lens surface.
Optical lens of the present invention also can comprise polymerization starter with resin combination.Polymerization starter can use amine compound or tin compound.Tin compound can use from two lauric acid butyl tin (butyltindilaurate), dichloride dibutyl tin (dibutyltindichloride), dibutyltin diacetate (dibutyltindiacetate), stannous octoate (stannous octylate), dibutyl tin laurate (dilauricaciddibutyltin), tin tetrafluoride (tetrafluorotin), tin tetrachloride (tetrachlorotin), tin tetrabromide (tetrabromotin), tin tetraiodide (tetraiodtin), methyl tin chloride (methyltintrichloride), tri-chlorination butyl tin (butyltintrichloride), dichloride tin methide (dimethyltindichloride), dichloride dibutyl tin (dibutyltindichloride), trimethyltin chloride (trimethyltinchloride), tributyltin chloride (tributyltinchloride), triphenyltin chloride (triphenyltinchloride), butyl disulfide tin (dibutyltinsulphide), one or more that select in oxidation two (2-ethylhexyl) tin (di (2-ethylhexyl) tinoxide) etc.If use above-mentioned tin compound, then percent polymerization is high, does not produce bubble.Its usage quantity is preferably 0.001～4 % by weight with respect to resin combination.
Make optical lens by thermofixation optical lens of the present invention with resin combination, especially ophthalmic lens.The preferred embodiment of making ophthalmic lens by thermofixation composition of the present invention is as follows: at first, after composition of the present invention adds polymerization starter at last, be blown into nitrogen and remove the interior air of spice bucket, the decompression of then carrying out 2～5 hours is stirred, wait to stir after the end, vacuum deaerator injects mould.At this moment, preferably, mould uses and utilizes plastic gasket or polyester or fixing glass mold or the metal die of polypropylene sealing tape.The glass mold that injects mixture is put into the forced cyclic type baking oven, keeping 2 hours with 33～37 ℃, heated up 3 hours with 38～42 ℃, heated up 10 hours with 80～90 ℃, heated up 2～4 hours with 120～140 ℃, kept 2 hours with 120～140 ℃, after 60～80 ℃ of coolings 2 hours, solid substance is made optical lens from mold releasability.With the above-mentioned optical lens that makes, under 120～140 ℃ of temperature condition, carry out 1～4 hour slow cooling, make plastic spectacle lens (blank eyeglass) with this.
In addition, for improving the optical characteristics of the optical lens of making by aforesaid method, can carry out the processing of dura mater coating and multilayer film and process.The method that forms the dura mater coating is as follows: pass through the methods such as dipping or rotary coating on the optical lens surface, to paint after the thickness of 0.5～10 μ m as the plated film compound of main component with at least a metal oxide colloids such as at least a silane compound that contains the functional groups such as epoxy resin-matrix, epoxy group(ing), vinyl and silicon oxide, titanium oxide, weisspiessglanz, stannic oxide, Tungsten oxide 99.999, aluminum oxide, and utilize heating or ultraviolet curing to finish and film.
Multilayer film, namely anti-reflection coating can utilize the metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium white, titanium oxide, tantalum oxide, yttrium oxide, forms by vacuum moulding machine or spraying plating.Preferably, on the dura mater coating on lens two sides, more than three times after repeating vacuum cvd silicon oxide and the zirconium oxide film, last vacuum moulding machine silicon oxide film.In addition, can form at last as required moisture film (fluoro-resin) layer, or between silicon oxide and zirconium oxide film, form the ITO layer.
Optical lens of the present invention can utilize dispersed dye or phototropic dyestuff to carry out painted afterwards use as required.
Optical lens resin combination of the present invention, unrestricted in plastic spectacle lens, can be applicable to various optical articles.
Below, the present invention is described in detail in conjunction with specific embodiments.But these embodiment are intended to be described in more detail the present invention, but not limit the scope of the invention.
Embodiment 1
(1) method of manufacturing optical material of the present invention and lens is as follows: dicyclohexyl methane diisocyanate (dicyclohexylmethane the diisocyanate) (H that mixes 38.2g
12MDI), 16.3g 1,6-hexamethylene diisocyanate (1,6-hexamethylenediisocyanate), 34.9g 1,2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1, after tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)) the preparation mixture of 2-bis (2-mercaptoethylthio)-3-mercaptopropane) and 10.1g, as UV light absorber get 1.5g 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5 '-methylphenyl)-2H-benzotriazole), get the polyoxyethylene octyl phenol ether phosphate (polyoxyethylene octylphenol ether phosphate) of 0.1g as releasing agent, get 1-hydroxyl-4-(p-Tolylamine) anthraquinone (1-hydroxy-4-(p-toluidine) anthraquinone) (blueness) of 50ppm and the cyclic ketones dyestuff (perinone dye) (redness) of 10ppm as organic dye, get the dichloride dibutyl tin (dibutyltindichloride) of 0.1g as polymerization starter, input is provided with the spice bucket of agitator and utilizes nitrogen replacement to remove after the interior air of spice bucket, the decompression of carrying out 2 hours is stirred, wait to stir after the end, vacuum deaerator injects with the fixing glass mold of polyester adhesive adhesive tape.
The glass mold that (2) will inject mixture is put into the forced cyclic type baking oven, keeping 2 hours with 35 ℃, heated up 3 hours with 40 ℃, heated up 12 hours with 120 ℃, kept 2 hours with 120 ℃, after 70 ℃ of coolings 2 hours, solid substance is made the optical lens that center thickness is 1.2～2.2mm from mold releasability.
(3) will be processed into the 72mm diameter from the optical lens that (2) make and utilize the caustic soda washings to carry out after the ultrasonic washing, the slow cooling of carrying out under 120 ℃ of temperature condition 2 hours is processed.
(4) optical lens that makes from (3) is carried out the surface etching processing and impregnated in (strain) Fine Coat dura mater masking liquid carrying out after the thermofixation, at two sides vacuum moulding machine silicon oxide, zirconium white, ITO, moisture film (fluoro-resin), carry out the optical lens that the dura mater coating is processed and multilayer film is processed thereby make.
The physical property experiment method
By following physical property experiment method measure the physical property of each optical lens and with its outcome record in table 1.
1) specific refractory power and Abbe number: utilize the DR-4 model multi-wavelength Abbe refractometer of Atago company to measure.The test piece Fluid Contacting uses monobromination naphthalene (monobromonaphthalene).
2) optical transmittance: utilize UV 2450 models of SHIMADZU company to measure.
3) proportion: utilize the VPG214CN of OHAUS company to measure.
4) the multilayer film cracking phenomena that is heated: the baking oven of the lens test piece being put into 80 ℃ detects by an unaided eye after roasting 60 minutes, if lens surface then is chosen as A without the multilayer film cracking phenomena, if the following cut of 1mm at 10 with the next B that is chosen as, if cut then is being chosen as C more than 10.
5) shock-resistance: shock-resistance is under 22 ℃ of conditions of normal temperature, measures by American I nstronModel Mini-Tower Impact Tester (Instron dynatub) and falling sphere (drop ball) test.When using American I nstron Model Mini-Tower Impact Tester (Instron dynatub), utilize groove (tubs) without the lens of filming (blank eyeglass), measure in the lens front and the finished lens of multilayer film utilizes indent (piezo tubs) to land.Without the test of the impact of the lens of filming (blank eyeglass), land in the lens front with the impact energy of 8J, 11J and 14J to 10 lens, if 1 not crackedly then is chosen as zero, if cracked 1～2 then is chosen as △, if the cracked X that then is chosen as more than 3.In addition, the impact test of the finished lens of multilayer film, finished lens (0.00 to 10 multilayer films, center thickness 2.2mm) lands in the lens front with the impact energy of 0.2J and 0.4J, then be not chosen as zero if 1 cracked, if cracked 1～2 then is chosen as △, if the cracked X that then is chosen as more than 3.Regulation according to FDA, fall sphere test is to the finished lens (0.00 of 10 multilayer films, center thickness 2.2mm), be 5/8 inch (approximately 16mm) with diameter), weight is the steel ball of 16g, lands in the lens front at the height of 127cm, if 1 not crackedly then is chosen as zero, if cracked 1～2 then is chosen as △, if the cracked X that then is chosen as more than 3.
Embodiment 2～12
Utilize the method identical with embodiment 1, with the composition manufacturing shown in the table 1 separately composition and lens and experimental result is recorded in table 1.
Comparative example 1
Except dicyclohexyl methane diisocyanate (the dicyclohexylmethanediisocyanate) (H that mixes 53.6g
12MDI), 1 of 3.8g, 6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate), 1 of 32.7g, 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1, tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritol tetrakis (mercaptopropionate)) the preparation optical lens of 2-bis (2-mercaptoethylthio)-3-mercaptopropane) and 9.4g is with outside the resin combination, the method identical with embodiment 1 implement and with its characteristic records in table 2.
Comparative example 2～6
Utilize the method identical with comparative example 1, with the composition manufacturing shown in the table 2 separately composition and lens and experimental result is recorded in table 2.
[table 1]
[table 2]
Abbreviation in table 1～2
Monomer
IPDI: isophorone diisocyanate (isophorone diisocyanate)
HDI:1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate)
H
12MDI: dicyclohexyl methane diisocyanate (dicyclohexylmethanediisocyanate)
BBH: two (isocyanato methyl) two ring [2,2,1] heptane (bis (isocyanatomethyl) bicyclo[2,2,1] heptane)
GMT:2-(2-mercaptoethyl sulfo-) propane-1,3-two mercaptan (2-(2-mercaptoethylthio) propane-1,3-dithiol)
GST:1,2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane (1,2-bis (2-mercaptoethylthio)-3-mercaptopropane)
ETS:2-(2-mercaptoethyl sulfo-)-3-{2-[3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] ethylenebis dithiocarbamate } propane-1-mercaptan (2-(2-mercaptoethylthio)-3-{2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio] ethylthio}propane-1-thiol)
TMPMP: trimethylolpropane tris (mercaptopropionic acid ester) (trimethylolpropanetris (mercaptopropionate))
PETMP: tetramethylolmethane four (mercaptopropionic acid ester) (pentaerythritoltetrakis (mercaptopropionate))
Y1S：
UV light absorber
CBMP:2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6-(tertiary butyl) phenol (2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6-(tert-butyl) phenol)
HMBT:2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-the 2H-benzotriazole (2-(2 '-hydroxy-5 '-methylphenyl)-2H-benzotriazole)
HBCBT:2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl phenyl)-5-chloro-2H-benzotriazole (2-(2 '-hydroxy-3 ', 5 '-di-t-butylphenyl)-5-chloro-2H-benzotriazole)
HOPBT:2-(2 '-hydroxyl-5 '-uncle-octyl phenyl) benzotriazole (2-(2 '-benzotriazole of hydroxy-5 '-tert-octylphenyl))
Releasing agent
DBP: dibutyl phosphate (dibutyl phosphate)
DIPP: di-isopropyl phosphoric acid ester (diisopropyl acid phosphate)
PENPP: polyoxyethylene octyl phenol ether phosphate (polyoxyethyleneoctylphenol ether phosphate)
Color control agent (organic dye)
HTAQ:1-hydroxyl-4-(p-Tolylamine) anthraquinone (1-hydroxy-4-(p-toluidine) anthraquinone)
PRD: cyclic ketones dyestuff (perinone dye)
Polymerization starter
BTC: dichloride dibutyl tin (dibutyltindichloride)
BTL: two lauric acid butyl tin (dibutyltindilaurate)
Industrial applicibility
Can make when having high refractive index according to the present invention, after carrying out multilayer film, has outstanding shock-resistance and thermal distortion phenomenon amino formate plastic optical lens seldom, and optical lens of the present invention is particularly useful for ophthalmic lens, and except ophthalmic lens, also can be used for using the various optical articles such as perspective light at recording medium substrate, colour filter, ultraviolet absorbing filter and the mobile phone of prism, fiber optics, CD, disk etc.
Claims (11)
1. a high refractive index optical lens resin combination is characterized in that, comprises:
The mixtures of diisocyanates of 40～65 % by weight, it is by the dicyclohexyl methane diisocyanate (H of 50～85 % by weight
12MDI) and 15～50 % by weight 1,6-hexamethylene diisocyanate (HDI) consists of;
The mercaptan mixture of 35～60 % by weight, it is by 1 of 60～99.9 % by weight, and the trimethylolpropane tris (mercaptopropionic acid ester) of 2-two (2-mercaptoethyl sulfo-)-3-sulfydryl propane and 0.1～40 % by weight, tetramethylolmethane four (mercaptopropionic acid ester) or their mixture consist of.
2. resin combination according to claim 1; it is characterized in that: described resin combination also comprises with respect to the mercaptan compound of 6～28 % by weight of described resin combination gross weight with by in the compound shown in the following Chemical formula 1 (Y1S) one or more; the gross weight of all components is by weight 100% in the described resin combination; described mercaptan compound is selected from the propane-1 by 2-(2-mercaptoethyl sulfo-); 3-mercaptan; 2-(2-mercaptoethyl sulfo-)-3-[2-(3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] ethylenebis dithiocarbamate-propane-1-mercaptan; 2-(2-mercaptoethyl sulfo-)-3-{2-sulfydryl-3-[3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] propyl dithiocarbamate }-propane-1-mercaptan; trimethylolethane trimethacrylate (mercaptopropionic acid ester); three (thiohydracrylic acid) glyceryl ester; trishydroxymethyl chloro three (mercaptopropionic acid ester); trimethylolpropane tris (thioglycollate); trimethylolethane trimethacrylate (thioglycollate); tetramethylolmethane four mercaptoacetates; [1; 4] dithiane-2-base-thiomethyl alcohol; 2-(2-sulfydryl-ethylsulfonyl)-propane-1; 3-two mercaptan; 2-([1; 4] dithiane-2-ylmethyl alkylsulfonyl)-sulfur alcohol; 3-(3-sulfydryl-propionyl alkylsulfonyl)-propionic acid 2-hydroxymethyl-3-(3-sulfydryl-propionyloxy)-2-(3-sulfydryl-propionyloxy methyl)-propyl diester; 3-(3-sulfydryl-propionyl alkylsulfonyl)-propionic acid 3-(3-sulfydryl-propionyloxy)-2; 2-pair-(3-sulfydryl-propionyloxy methyl)-propyl diester; (5-mercapto methyl-[1; 4] dithiane-2-yl)-and group that thiomethyl alcohol forms, Chemical formula 1 is
3. resin combination according to claim 1, it is characterized in that: with respect to described resin combination gross weight, described resin combination also comprises in the group that is comprised of alkylene diisocyanate cpd, alicyclic diisocyanate compound, heterocycle diisocyanate cpd and sulfur-bearing diisocyanate cpd one or more of being selected from of 0.1～10 % by weight, the gross weight of all components is by weight 100% in the described resin combination.
4. resin combination according to claim 1, it is characterized in that: described resin combination also comprises at least a additive, and described additive is selected from the group that is comprised of UV light absorber, releasing agent, polymerization starter and color control agent.
5. resin combination according to claim 4, it is characterized in that: described UV light absorber is selected from by 2-(2 '-hydroxy-5-methyl base phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chloro-2H-benzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chloro-2H-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl)-the 2H-benzotriazole, 2,4-dihydroxy-benzene ketone, 2-hydroxyl-4-anisole ketone, 2-hydroxyl-4-octyloxy benzophenone, 4-dodecyloxy-2-Viosorb 110,4-benzoyloxy-2-Viosorb 110,2,2 ', 4,4 '-the tetrahydroxy phenol ketone, 2,2 '-dihydroxyl-4,4 '-group of the compositions of mixtures of dimethoxy benzophenone and they.
6. resin combination according to claim 4 is characterized in that: described releasing agent is to be selected from least a in the group that is comprised of p isopropylbenzoic acid ester, di-isopropyl phosphoric acid ester, dibutyl phosphate, octyl phosphate, dioctylphosphoric acid ester, phosphoric acid isodecyl ester, di(2-ethylhexyl)phosphate isodecyl ester, phosphoric acid tridecanol ester, di(2-ethylhexyl)phosphate (tridecanol) ester.
7. resin combination according to claim 4, it is characterized in that: described polymerization starter is tin compound or amine compound.
8. resin combination according to claim 7 is characterized in that: described tin compound is selected from the group by two lauric acid butyl tin, dichloride dibutyl tin, dibutyltin diacetate, stannous octoate, dibutyl tin laurate, tin tetrafluoride, tin tetrachloride, tin tetrabromide, tin tetraiodide, methyl tin chloride, tri-chlorination butyl tin, dichloride tin methide, dichloride dibutyl tin, trimethyltin chloride, tributyltin chloride, triphenyltin chloride, butyl disulfide tin, oxidation two (2-ethylhexyl) tin and their compositions of mixtures.
9. resin combination according to claim 4, it is characterized in that: described color control agent is organic dye.
10. the high refractive index optical lens of making by thermofixation resin combination claimed in claim 1.
11. optical lens according to claim 10 is characterized in that: described optical lens is ophthalmic lens.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2009-0012990 | 2009-02-17 | ||
| KR20090012990 | 2009-02-17 | ||
| PCT/KR2010/000930 WO2010095837A2 (en) | 2009-02-17 | 2010-02-12 | Resin composition for a high refractive index optical lens having superior impact resistance, high refractive index optical lens using same, and method for producing same |
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| CN101984758A CN101984758A (en) | 2011-03-09 |
| CN101984758B true CN101984758B (en) | 2013-02-20 |
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| KR (1) | KR101142266B1 (en) |
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| KR101389356B1 (en) * | 2011-01-20 | 2014-04-28 | 주식회사 케이오씨솔루션 | Preparation of 3-mercapto(meta)propionic acid and (meta)carbonic acid ester compound bearing mercapto group using it |
| JP6276754B2 (en) | 2012-04-23 | 2018-02-07 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Light-resistant polyurethane composition |
| CN102660115B (en) * | 2012-05-23 | 2014-01-08 | 江苏明月光电科技有限公司 | Combination for preparing lens with good safety and preparation method of lens |
| KR102097174B1 (en) * | 2012-08-27 | 2020-04-06 | 주식회사 케이오씨솔루션 | Polymerizable composition based on epoxy acryl compounds with improved storage stability and method of preparing optical material based on the epoxy acryl compounds |
| WO2015002301A1 (en) * | 2013-07-05 | 2015-01-08 | 味の素株式会社 | Thiol-group-containing compound and single-liquid epoxy resin composition |
| WO2015046540A1 (en) | 2013-09-30 | 2015-04-02 | ホヤ レンズ タイランド リミテッド | Transparent plastic substrate and plastic lens |
| KR101952270B1 (en) * | 2015-02-04 | 2019-02-28 | 케이에스랩(주) | Polythiourethane polymerization compositions having high impact resistance and preparation method of optical resin using them |
| CN105482070B (en) * | 2015-12-08 | 2017-08-18 | 江苏乾元新材料科技有限公司 | It is a kind of to use optical resin composition with high impact resistance, heat resistance and refractive index of organic and inorganic hybridization and preparation method thereof |
| CN105837793A (en) * | 2016-04-08 | 2016-08-10 | 扬州大学 | A preparing method of a sulfur-containing epoxy resin optical lens material with a high refractive index |
| CN107118322A (en) * | 2017-06-30 | 2017-09-01 | 山东益丰生化环保股份有限公司 | A kind of high refractive power resin of polyurethanes and preparation method thereof |
| CN108503794A (en) * | 2018-04-14 | 2018-09-07 | 上海伟星光学有限公司 | One kind having diffusing reflection high transmittance polyurethane film and preparation method thereof |
| CN111333803B (en) * | 2018-12-19 | 2022-02-18 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material and application thereof |
| KR102062134B1 (en) * | 2019-01-16 | 2020-01-03 | 주식회사 신아티앤씨 | Composition for optical material comprising a ester polythiol mixture, Method for producing the ester polythiol mixture, Quantum dot film, Backlight unit, and Liquid crystal display |
| JP6691990B1 (en) * | 2019-04-26 | 2020-05-13 | 三井化学株式会社 | Thiol-containing composition for optical material, polymerizable composition for optical material |
| CN111077732A (en) * | 2019-12-20 | 2020-04-28 | 深圳市华星光电半导体显示技术有限公司 | Material composition of light coupling-out lens and manufacturing method thereof |
| KR102152125B1 (en) * | 2019-12-26 | 2020-09-04 | 주식회사 신아티앤씨 | Composition for optical material comprising a ester polythiol mixture, Quantum dot film, Backlight unit, and Liquid crystal display |
| KR102152126B1 (en) * | 2019-12-26 | 2020-09-04 | 주식회사 신아티앤씨 | Composition for optical material comprising a ester polythiol mixture, Quantum dot film, Backlight unit, and Liquid crystal display |
| KR102217688B1 (en) * | 2019-12-26 | 2021-02-19 | 주식회사 신아티앤씨 | Method for producing the ester polythiol mixture |
| WO2022138865A1 (en) * | 2020-12-25 | 2022-06-30 | 三井化学株式会社 | Polythiol composition, polymerizable composition, resin, molded article, optical material, and lens |
| CN112794985B (en) * | 2020-12-30 | 2022-11-25 | 温州大学新材料与产业技术研究院 | Transparent polyurethane optical material and preparation method thereof |
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| KR100912274B1 (en) * | 2007-08-01 | 2009-08-17 | 주식회사 신대특수재료 | Resin Composition for Optical Lens Having Light Weight and High Refractive Index, and the Optical Lens Using It |
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2010
- 2010-02-12 CN CN201080000831.9A patent/CN101984758B/en not_active Expired - Fee Related
- 2010-02-12 KR KR1020100013636A patent/KR101142266B1/en active IP Right Grant
- 2010-02-12 WO PCT/KR2010/000930 patent/WO2010095837A2/en active Application Filing
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| EP0586091A2 (en) * | 1992-08-26 | 1994-03-09 | MITSUI TOATSU CHEMICALS, Inc. | High refractive index plastic lens and composition therefor |
| EP1316819A1 (en) * | 2000-09-08 | 2003-06-04 | Mitsubishi Gas Chemical Company, Inc. | Composition for optical material |
| CN1601306A (en) * | 2003-09-22 | 2005-03-30 | 保谷株式会社 | Process of producing plastic lens and plastic lens |
| WO2008047626A1 (en) * | 2006-10-16 | 2008-04-24 | Mitsui Chemicals, Inc. | Method for producing resin for optical material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010095837A3 (en) | 2010-11-25 |
| WO2010095837A2 (en) | 2010-08-26 |
| KR101142266B1 (en) | 2012-05-07 |
| KR20100094378A (en) | 2010-08-26 |
| CN101984758A (en) | 2011-03-09 |
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