WO2014035126A1 - Method for manufacturing thioepoxy-based optical material - Google Patents

Description

Manufacturing method of thioepoxy optical material

The present invention relates to a method for producing a thioepoxy clock optical material, and more particularly, to a method for producing a high-quality optical material that is colorless, transparent, and free of deformation without high occurrence of stria and turbidity due to polymerization imbalance.

Plastic optical lenses were introduced as a replacement for the high specific gravity and low impact of glass lenses. Representative examples thereof include polyethylene glycol bisallylcarbonate, polymethyl methacrylate, diallyl phthalate, and the like. However, optical lenses made of these polymers are excellent in physical properties such as moldability, dyeability, hard coat coating adhesion, impact resistance, etc., but the refractive index is about 1.50 (nD) and 1.55 (nD), resulting in a problem of thickening the lens. . Therefore, various attempts have been made to develop optical materials having high refractive indexes to reduce the thickness of lenses.

Korean Patent No. 10-0681218 proposes a thioepoxy watch plastic lens. The thioepoxy lens has a high refractive index and an excellent property of having a high Abbe number, but also has a problem that the lens is fragile and poorly dyed. In order to solve these problems, a method of copolymerizing these two kinds of resins, that is, a method of copolymerizing a thioepoxy compound, a polythiol compound, and a polyisocyanate compound, is disclosed in Korean Patent Registration No. 10-0417985, Japanese Patent Laid-Open No. 11 -352302 et al.

Both thioepoxy lenses and thioepoxy lenses copolymerizing thioepoxy and thiourethane often cause stria and turbidity due to polymerization imbalance when polymerizing the polymerizable composition, thereby degrading the quality of the lens. Since the occurrence of stria and turbidity degrade the quality of the lens, improvement has been required in the meantime. In addition, the production cost reduction has been a major concern in the recent lens field, the occurrence of striae, turbidity is a factor that increases the production cost by lowering the lens yield, the improvement is also urgently required in terms of production cost reduction.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Republic of Korea Patent Registration 10-0681218

(Patent Document 2) Republic of Korea Patent Registration 10-0417985

(Patent Document 3) JP 11-352302 A

In the thioepoxy optical material or the thioepoxy optical material in which thioepoxy and thiourethane are copolymerized, stria and turbidity may occur due to polymerization imbalance. "Stria" refers to a phenomenon that is locally different from the surrounding normal refractive index due to a difference in composition. "Cloudy" means that when the resin composition for an optical lens is cured, turbidity appears in the optical lens due to polymerization heterogeneity. McLean and turbidity adversely affect the quality and performance of optical materials.

The inventors have unexpectedly found that the temperature in the process of blending, defoaming and injecting the polymerizable composition has a significant correlation with the occurrence of striae and haze of the resulting lens. That is, when the polymerizable composition was blended, defoamed at a specific temperature, and injected into a mold to polymerize, there was almost no stria and turbidity in the finally obtained lens. The present invention has been confirmed and completed, the present invention is a method for producing a high quality thioepoxy optical material with a high yield without the occurrence of striae or turbidity using a polymerizable composition comprising a compound having at least one thioepoxy group The purpose is to provide.

In the present invention,

In the method for producing an optical material for polymerizing a polymerizable composition comprising a compound having at least one thioepoxy group, the blending, defoaming, and injection of the polymerizable composition in the temperature range of -5 ~ 20 ℃ There is provided a method for producing a thioepoxy clock optical material.

Further, in the present invention, an optical material obtained by the above manufacturing method and an optical lens composed of the optical material are provided. The optical lens in particular comprises an spectacle lens or a polarizing lens.

In the present invention, by blending, defoaming, and molding the polymerizable composition in a specific temperature range, a colorless, transparent, and high-quality lens can be manufactured without a marrow or turbidity due to polymerization imbalance. have.

In the method for producing a thioepoxy clock optical material of the present invention, in the process of compounding, defoaming, and mold injection of a polymerizable composition comprising a compound having at least one thioepoxy group, the mold polymerization is carried out by maintaining the temperature in a specific range.

In this invention, the whole process of mix | blending the polymeric composition containing the compound which has one or more thioepoxy group, and inject | pouring into a defoaming and a mold | die is performed in the temperature range of -5-20 degreeC. If the temperature is less than -5 ℃, the polymerization reaction does not occur smoothly, the reaction time is long, and partial polymerization imbalance may occur. On the other hand, when the temperature exceeds 20 ° C, the curing speed of the resin is fast, and the reaction proceeds explosively due to the overheating reaction during polymerization, resulting in a gas accompanied by a severe smell, and the resin becomes black and cannot be used. More preferably, a polymeric composition is mix | blended, defoaming, and mold injection in the temperature range of -5-15 degreeC. Conventionally, there is only recognition that the reaction should be performed at a low temperature, and the polymerization has been carried out at the lowest possible temperature. However, in the present invention, it was found for the first time that not only the temperature in the polymerization process but also the composition and defoaming temperature of the composition had a significant correlation with the striae and turbidity of the final obtained lens. , More preferably, it is confirmed that a high quality lens without striae and turbidity is obtained by a smooth polymerization reaction when maintained at -5 to 15 ° C. Conventional manufacturing methods that do not recognize this correlation do not control the temperature during blending and defoaming, while the temperature during polymerization is excessively low. In the present invention, by controlling the temperature during blending, defoaming, and mold injection process of the thioepoxy polymerizable composition in an appropriate range, it is possible to suppress striae and turbidity without changing other process conditions or raw material components, thereby providing transparent and high quality without deformation. Acrylic optical material can be manufactured easily.

Compounds having at least one thioepoxy group include, for example, bis (2,3-ethiothiopropyl) sulfide, bis (2,3-ethiothio) disulfide, 1,3-bis (β-ethiothiopropylthio) cyclo Hexane, 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3-bis (β-ethiothiopropylthiomethyl) cyclohexane, 1,4-bis (β-ethiothiopropylthiomethyl) cyclo Hexane, bis [4- (β-ethiothiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] propane, bis [4- (β-ethiothiopropyl Episulfide compounds having an alicyclic skeleton such as thio) cyclohexyl] sulfide; 1,3-bis (β-epithiopropylthiomethyl) benzene, 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2, 2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] disulfide, Episulfide compounds having an aromatic skeleton such as bis [4- (β-epithiopropylthio) phenyl] sulphine and 4,4-bis (β-epithiopropylthio) biphenyl; 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis (β-ethiothiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-ethiothiopropylthioethyl) -1,4-dithiane Sulfide compounds; 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane, 1,2-bis [(2-β-ethiothiopropylthioethyl) thio]- 3- (β-epithiopropylthio) propane, tetrakis (β-ethiothiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, bis- (β-ethiothio At least one episulfide compound having an aliphatic skeleton such as propyl) sulfide and bis- (β-ethiothiopropyl) disulfide may be used. In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-type modified compounds with polythiol may be used. The compound having at least one thioepoxy group, preferably bis (2,3-ethiothiopropyl) sulfide, bis (2,3-ethiothio) disulfide, 1,3-bis (β-ethiothiopropylthio) ) Cyclohexane, 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3-bis (β-ethiothiopropylthiomethyl) cyclohexane, 1,4-bis (β-ethiothiopropylthiomethyl ) Cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, One or more of 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane can be used.

The polymerizable composition may further include a polyisocyanate compound and a polythiol compound, and may be made of a thioepoxy clock optical material copolymerizing thioepoxy and thiourethane.

The polyisocyanate compound is not particularly limited and a compound having at least one isocyanate and / or isothiocyanate group may be used. For example, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undectriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Aliphatic isocyanate compounds such as bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether; Isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, Dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate, 2,2-dimethyldicyclohexyl methane isocyanate, 3.8-bis (isocyanatomethyl) tricyclo [5, 2,1,02,06] decane, 3.9-bis (isocyanatomethyl) tricyclo [5,2,1,02,06] decane, 4.8-bis (isocyanatomethyl) tricyclo [5,2, 1,02,06] decane, 4.9-bis (isocyanatomethyl) tricyclo [5,2,1,02,06] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2, Alicyclic isocyanate compounds such as 1] and 2,6-bis (isocyanatomethyl) bicyclo [2,2,1]; Bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl Ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine Diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3 , 3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4,4-diisocysi Aromatic diisocyanate compounds such as carbonate; Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) disulfide, Bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethyl Sulfur-containing aliphatic isocyanate compounds such as thio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyldiphenyldisulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5, Sulfur-containing aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxy diphenyldisulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) Tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanatomethyl) -1,3-dithiorane, 4,5-bis ( One or two or more sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolane can be mixed. In addition, if it is a compound having at least one isonate and / or isothiocyanate group, one or two or more kinds thereof may be mixed, and also halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents and alkoxy substituents of these isocyanate compounds. And nitro substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized products, and trimerized reaction products. As a polyisocyanate compound, Preferably, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, bis (isocyanatomethyl) tricyclo [5,2,1,02,06] decane, bis ( At least one selected from isocyanatomethyl) bicyclo [2,2,1] is used.

The said polythiol compound is not specifically limited, If it is a compound which has at least 1 or more thiol groups, 1 type (s) or 2 or more types can be mixed and used for it. For example, bis (2-mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane -1-thiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 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-propionyl Oxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethyl Thio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3 -((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14 R) -4,14-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mercapto- 2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2-((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane-1 , 2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R, 12S ) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11- Dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) , Pentaerythritol tetrakis (2-mercaptoacetate), bis pentaerythritol-ether-hexakis (3-mercaptopropionate), 1, 1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3- Dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane and the like can be used. In addition, if it is a compound which has one or more thiol groups, you may use 1 type (s) or 2 or more types in mixture. Furthermore, the polymerization modified body obtained by prepolymerization with an isocyanate, a thioepoxy compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used. As the polythiol compound, preferably, at least one other polythiol compound may be mixed with bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

The polymerizable composition may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity, etc., in order to improve optical properties of the copolymer optical resin (optical material). As an olefin compound which can be added as a reactive resin modifier, for example, benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy ethyl acrylate, phenoxy ethyl methacrylate, phenyl methacrylate, ethylene glycol Diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene Glycol Dimethacrylate, Polyethylene Glycol Diacrylate, Polyethylene Glycol Di Tacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate , 2,2-bis (4-acryoxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, 2,2-bis (4-acryoxyethoxyphenyl) propane, 2,2-bis (4-methoxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryoxyethoxyphenyl) methane, 1,1- Bis (4-methoxyethoxyphenyl) methane, 1,1-bis (4-acryldiethoxyphenyl) methane, 1,1-bis (4-methoxydiethoxyphenyl) methane, dimetholtricyclo Decanediacrylate, Trimetholpropane triacrylate, Trimetholpropane trimethacrylate, Glycerol diacryl Glycerol Dimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol Tetramethacrylate, Methylthioacrylate, Methylthiomethacrylate, Phenylthioacrylate, Benzylthiomethacrylate (Meth) acrylate compounds, such as a latex, xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate; Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallyl carbonate; And vinyl compounds such as styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobi (meth-dioxane). However, the compounds that can be used are not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

In addition, the polymerizable composition of the present invention may further include an internal mold release agent, a heat stabilizer, an ultraviolet absorber, an organic dye, an inorganic pigment, an anti-coloring agent, an antioxidant, a light stabilizer, a catalyst, and the like according to a conventional method.

As an internal mold release agent, a phosphate ester compound, a silicone type surfactant, a fluorine type surfactant, etc. can be used individually or in combination of 2 or more types, respectively. The internal mold release agent is preferably included at 0.001 to 10% by weight in the polymerizable composition. Preferably, a phosphate ester compound is used as an internal mold release agent. The phosphate ester compound is prepared by adding 2-3 moles of alcohol compound to phosphorus pentoside (P ₂ O ₅ ), where various forms of phosphate ester compounds can be obtained, depending on the type of alcohol used. Typical examples include those in which ethylene oxide or propylene oxide is added to the aliphatic alcohol, or ethylene oxide or propylene oxide is added to the nonylphenol group. In the polymerizable composition of the present invention, when the phosphate ester compound added with ethylene oxide or propylene oxide is included as an internal mold release agent, an optical material having good release property and excellent quality can be obtained. The phosphate ester compound used as the internal mold release agent is preferably polyoxyethylene nonylphenol ether phosphate (5 wt% with 5 mol of ethylene oxide added, 80 wt% with 4 mol added, 10 wt with 3 mol added). %, 1 mole added 5% by weight), polyoxyethylene nonylphenyl phosphate (9% added by 9 moles of ethylene oxide, 8 mole added by 8 moles of ethylene oxide, 7 mole added by ethylene oxide 10% by weight, 5% by weight of ethylene oxide added up to 5%), polyoxyethylenenonylphenol ether phosphate (3% by weight of 11 moles of ethylene oxide added, 80% by weight, 10 moles added, 9 moles added 5% by weight, 7% by weight 6% by weight, 6% by weight 6% by weight), polyoxyethylene nonylphenol ether phosphate (13% by weight of ethylene oxide 3% by weight, 12 moles by weight 80 Wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol Added 6% by weight), polyoxyethylene nonylphenol ether phosphate (added 17% by 17 mol of ethylene oxide, 79% by 16 mol added, 10% by weight 15 mol added, 14 mol added 4 weight%, 13 mol added 4 weight%), polyoxyethylene nonylphenol ether phosphate (5 weight% with 21 mol ethylene oxide added, 78 weight% with 20 mol added, 19 mol added 7 Weight percent, 18 mol added 6 weight percent, 17 mol added 4 weight percent), and one or more compounds selected from the group consisting of Zelec UN ™.

In the present invention, the polymerizable composition is defoamed while maintaining a constant temperature condition and injected into a mold to obtain a thioepoxy optical material through mold polymerization. First, the polymerizable composition degassed under constant temperature conditions (-5 to 20 ° C.) is injected between polymerizing molds held by gaskets or tapes under the same temperature conditions and polymerized. Polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and amount of the catalyst, the shape of the mold, and the like, but are carried out over a period of 1 to 50 hours at a temperature of about -50 to 130 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 130 ° C. and to cure in 1 to 48 hours.

The optical material obtained by hardening may process annealing etc. as needed. Treatment temperature is normally performed between 50-130 degreeC, and it is preferable to carry out at 90-100 degreeC.

Moreover, according to the objective at the time of superposition | polymerization, you may add various additives, such as a chain extender, a crosslinking agent, a light stabilizer, a ultraviolet absorber, antioxidant, a coloring inhibitor, a useful dye, a filler, and an adhesive improvement agent. The catalyst used plays an important role. As the type of catalyst, known epoxy curing agents are mainly used, but strong amines violate the isocyanate reaction, so it is necessary to pay attention to its use. In the present invention, amine salts, phosphonium salts, phosphines, tertiary amines, Lewis acids, radical initiators, etc., which do not have an electron withdrawing group, are mainly used, and the type and amount of catalysts are appropriately suited by those skilled in the art as necessary. You can choose.

The optical material of the present invention can be obtained in a molded body having various shapes by changing the mold during casting polymerization, and can be used for various optical materials such as spectacle lenses, camera lenses, and light emitting diodes (LEDs). In particular, it is suitable as optical materials, such as an eyeglass lens, a camera lens, a light emitting diode, and an optical element.

The lens made of the optical material of the present invention may be used by providing a coating layer on one or both surfaces as necessary. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, and a water repellent layer. Each of these coating layers may be performed alone, or may be performed by multilayering a plurality of coating layers. When providing a coating layer on both surfaces, you may give the same coating layer to each surface, or may give a different coating layer.

EXAMPLE

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

Example 1

89 g of bis (2,3-ethiothio) sulfide (BEPS) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, while maintaining the temperature at 5 ° C. 8-PENPP (polyoxyethylene nonylphenyl phosphate, acidic phosphoric acid ester, as an internal release agent, containing 5% by weight of 9 mol of ethylene oxide, 80% by weight of 8 mol of ethylene oxide, and 7 mol of ethylene oxide 10 wt%, 5 wt% of ethylene oxide added up to 6 mole)} 0.15 g, TBPB 0.2 g, triphenylphosphine 0.1 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5 g It mixed at 5 degreeC and set it as the homogeneous solution. Then, while maintaining the temperature in the above range, filtration with a 1μm PTFE filter was injected, while maintaining a 5 ℃ in a mold consisting of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the striae and turbidity were checked by the following method, and the results are shown in Table 1 below.

Property test and evaluation method

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

1) Refractive index and Abbe number: It was measured using an Abbe refractometer, a DR-M4 model of Atago.

2) Streaks: 100 lenses were visually observed under a Mercury Arc Lamp, which is a USHIO USH-10D, and it was determined that a lens having a whistle had a stria, and a stria occurrence rate was calculated.

3) Whitening: 100 lenses were visually observed under a Mercury Arc Lamp of USHIO USH-10D, and the lenses whose turbidity was confirmed were determined to have whitening, and the incidence of whitening was calculated.

Example 2-5

In the same manner as in Example 1, according to the composition shown in Table 1, the composition and the optical lens were prepared and tested for physical properties, respectively, and the results are shown in Table 1.

Comparative Example 1

89 g of bis (2,3-ethiothio) sulfide (BEPS-1) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound and a bis (2-mercaptoethyl) as a thiol compound while maintaining the temperature at -10 ° C. 6 g of sulfide, 8-PENPP [polyoxyethylenenonylphenol ether phosphate, acidic phosphate ester as an internal release agent (3% by weight of 9 mole of ethylene oxide, 80% by weight of 8 mole, 9 parts of mole added) %, 7 mole added 6% by weight, 6 mole added 6% by weight)] 0.15 g, TBPB 0.2 g, triphenylphosphine 0.1 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5g was mixed at -10 degreeC and it was set as the uniform solution. Then, while maintaining the temperature in the above range, the filtration was performed with a 1μm PTFE filter, and injected into the mold made of a glass mold and a tape while maintaining -10 ℃. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the stria and the turbidity were checked in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 2

The composition and the optical lens were prepared according to the composition shown in Table 1 in the same manner as in Comparative Example 1, and the physical properties were tested, and the results are shown in Table 1.

Table 1

[Abbreviation]

BEPS: bis (2,3-epithiopropyl) sulfide

ETPDS: 2,3-epoxypropyl (2,3-epoxypropyl (2,3-epithiopropyl) disulfide)

IPDI: isophorone diisocyanate

BMES: bis (2-mercaptoethyl) sulfide (bis (2-mercaptoethyl) sulfide)

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

TBPB: tetrabutylphosphonium bromide

HTQA: 1-hydroxy-4- (p-tolludine) -entroquinone (1-hydroxy-4- (p-toluidine) anthraquinone)

PRD: perinone dye

According to the present invention, it is possible to easily manufacture a thioepoxy optical material having excellent quality without striae and turbidity, and the thioepoxy optical material prepared according to the present invention can be widely used in various fields in place of existing optical materials. have. Specifically, it can be used as a plastic glasses lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, a camera lens, etc. In addition to a variety of optical, such as recording media substrates, color filters and ultraviolet absorption filters used in prisms, optical fibers, optical disks, etc. Can be used in the product.

Claims (10)

In the method for producing an optical material for polymerizing a polymerizable composition comprising a compound having at least one thioepoxy group, the blending, defoaming, and injection of the polymerizable composition in the temperature range of -5 ~ 20 ℃ Method for producing a thioepoxy clock optical material, characterized in that. The compound according to claim 1, wherein the compound having a thioepoxy group includes bis (2,3-ethiothiopropyl) sulfide, bis (2,3-ethiothiopropyl) disulfide, and 1,3-bis (β-ethiothiopropylthio). ) Cyclohexane, 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3-bis (β-ethiothiopropylthiomethyl) cyclohexane, 1,4-bis (β-ethiothiopropylthiomethyl ) Cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane and A method for producing a thioepoxy clock optical material, characterized in that at least one member selected from the group consisting of 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane. The method of manufacturing a thioepoxy optical material according to claim 1, wherein the polymerizable composition further comprises a polyisocyanate compound and a polythiol compound. The method for producing a thioepoxy clock optical material according to any one of claims 1 to 3, wherein the blending, defoaming, and injection into the mold are carried out at a temperature range of -5 to 15 ° C. . The method for producing a thioepoxy optical material according to any one of claims 1 to 3, wherein the polymerizable composition further comprises an olefin compound as a reactive resin modifier. The method for producing a thioepoxy optical material according to any one of claims 1 to 3, wherein the polymerizable composition further comprises a phosphate ester compound as an internal mold release agent. The method of claim 6, wherein the phosphate ester compound, polyoxyethylene nonyl phenol ether phosphate (5% by weight 5 mol ethylene oxide added, 80% by weight 4 mol added, 10% by weight 3 mol added, 1 mole added 5% by weight), polyoxyethylene nonylphenyl phosphate (9 mole added by 9 moles of ethylene oxide, 8 mole added by 8 moles of ethylene oxide, 7 mole added by ethylene oxide 10 % By weight, up to 6 moles of ethylene oxide added 5% by weight), polyoxyethylene nonylphenol ether phosphate (with 11 moles of ethylene oxide added 3% by weight, 10 moles added 80% by weight, 9 moles added) 5 weight%, 7 mol added 6 weight%, 6 mol added 6 weight%), polyoxyethylene nonyl phenol ether phosphate (13 mol added ethylene oxide 3 weight%, 12 mol added 80 weight% , 11 mole added 8% by weight, 9 mole added 3% by weight, 4 mole added 6% by weight) , Polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 mole added ethylene oxide, 79% by weight added 16 mole, 10% by weight added 15 mole, 4% by weight 14 mole added, 13 moles 4 weight% added), polyoxyethylene nonylphenol ether phosphate (5 weight% with 21 mol of ethylene oxide added, 20 weight added 78 weight percent, 19 weight added 7 weight percent, 18 mol added 6% by weight, 17% by weight added 4% by weight) and Zelec UN ™ (Zelec UN ™) is a method for producing a thioepoxy optical material, characterized in that one or two or more compounds selected from the group consisting of. An optical material produced by the manufacturing method of any one of claims 1 to 3. An optical lens made of the optical material of claim 8. The optical lens of claim 9, wherein the optical lens is an eyeglass lens or a polarizing lens.