WO2013095016A1 - Polymerizable composition for optical material containing thioepoxy compound, and preparation method of optical material - Google Patents

Abstract

The present invention relates to a polymerizable composition for an optical material, and a preparation method of an optical material for obtaining a high quality thioepoxy-based optical material without uncuring or polymer imbalance. The present invention provides a preparation method of a thioepoxy-based optical material comprising the steps of: preparing a polymerizable composition containing a thioepoxy compound with a pH of 4-8; and template polymerizing the polymerizable composition. The thioepoxy-based optical material prepared according to the present invention can be widely used in various fields by replacing conventional optical materials.

Description

Polymeric composition for optical materials containing thioepoxy compound and method for producing optical material

The present invention relates to a method for producing an optical material for polymerizing a thioepoxy compound, and more particularly, to a polymerizable composition for an optical material and a method for producing an optical material capable of obtaining a high quality thioepoxy optical material without uncuring or polymerization imbalance. will be.

Korean Patent No. 10-0681218 proposes a thioepoxy plastic lens. The thioepoxy lens has a high refractive index and an excellent property of having a high Abbe number, but has a problem in that the lens is fragile and not easily 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 No. 10-0417985, Japanese Patent Laid-Open No. 11 -352302 et al.

Both the thioepoxy lens and the thioepoxy lens copolymerizing thioepoxy and thiourethane have a problem of hardening when casting the polymerizable composition. As a result, the polymerization imbalance causes striae, whitening, bubbles, etc. Often the quality of the lens is degraded. Such uncuring and the resulting polymerization imbalance may cause the lens to lower the yield, thereby increasing the production cost. One of the major concerns in the field of lenses in recent years is the production cost reduction, and the problem of uncured and unbalanced polymerization in optical materials including thioepoxy compounds is urgently needed to improve.

The present inventors unexpectedly noticed that the degree of curing varies greatly depending on the pH of the thioepoxy compound when the lens is polymerized with the polymerizable composition containing a thioepoxy compound. When the pH of the thioepoxy compound is lower or higher than the proper range confirmed by the inventors, the composition is hardly hardened to obtain a lens, or even when cured, it is difficult to use the lens due to deterioration in quality due to polymerization imbalance. Yield was greatly lowered. However, when the pH of the thioepoxy compound is in the proper range identified in the present invention, curing of the composition occurred well, and thus a high quality optical lens without polymerization imbalance could be easily produced.

The present invention has been confirmed and completed, and the present invention uses a polymerizable composition for an optical material containing a compound having at least one thioepoxy group, and provides high-quality thioepoxy clock optics with high yield without the occurrence of uncuring or polymerization imbalance. It is an object of the present invention to provide a method for producing a material and a polymerizable composition for a thioepoxy optical material.

In the present invention, "thioepoxy compound" is defined as a compound having one or more thioepoxy groups.

In the present invention, "thioepoxy optical material" is defined as including both optical materials obtained by polymerizing a thioepoxy compound and optical materials copolymerized with thioepoxy and thiourethane, unless otherwise specified.

In the present invention,

making a polymerizable composition comprising a thioepoxy compound having a pH of 4 to 8,

Provided is a method for producing a thioepoxy optical material comprising the step of polymerizing the polymerizable composition.

In the present invention,

The polymeric composition for optical materials containing the thioepoxy compound of pH 4-8 is provided.

Moreover, in this invention, the optical material obtained by hardening | curing the said polymeric composition and the optical lens which consists of this optical material are provided. The optical lens in particular comprises an spectacle lens or a polarizing lens.

In the present invention, by setting the pH of the thioepoxy compound to a specific range, it is possible to manufacture a colorless, transparent, high-quality lens without the occurrence of striae, whitening, and bubbles due to uncured or unbalanced polymerization, and to lower the production cost by improving the yield. .

The manufacturing method of the thioepoxy clock optical material of this invention includes the step of making the polymeric composition containing the thioepoxy compound of pH 4-8, and the step of carrying out mold polymerization of this polymeric composition.

When the pH of the thioepoxy compound was lower than 4 or higher than 8, the lens could not be obtained properly due to hardening during polymerization, and even when partially cured, it was difficult to use the lens due to deterioration in quality due to polymerization imbalance. Problems due to polymerization imbalance are mainly caused by striae, whitening, and edge bubble generation. If it is out of the above range, the quality of the lens is deteriorated due to the occurrence of striae or whitening or bubbles even if it is cured to some extent, and the yield is lowered. There was a problem of elevating. On the other hand, when the polymerizable composition was prepared and polymerized in a state where the pH of the thioepoxy compound was 4 to 8, the optical material could be easily prepared without the difficulty of curing shown in the preparation of the thioepoxy optical material without changing other conditions. .

The thioepoxy group compounds include, for example, 1,3- and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, Bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] propane, bis [4- (β-ethiothiopropylthio) Episulfide compounds having an alicyclic skeleton such as cyclohexyl] sulfide; 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2,2-bis [4- (β-ethiothio Propylthio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] disulfide, bis [4- (β-ethiothiopropylthio Episulfide compounds having an aromatic skeleton such as) 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-epithiopropyl) 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. As the thioepoxy compound, preferably bis (2,3- epithiopropyl) sulfide, bis (2,3- epithiopropyl) disulfide, 1,3- and 1,4-bis (β-ethiothiopropylthio) Cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5 -Bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2- (2-β-ethiothiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane One or more of them can be used.

The polymerizable composition may further include a polythiol compound. The polythiol compound is not particularly limited and may be used alone or in combination of two or more thereof as long as it is a compound having at least one thiol group. For example, bis (2-mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane -1-thiol, 1,3- and 1,4-benzenedimethanolthiol (1,3- and 1,4-xylylenedithiol), 2,2-bis (mercaptomethyl) -1,3-propane Dithiol, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) Ethanethiol, bis (2,3-dimercaptopropanyl) 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 jade Methyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio 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, 14R) -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-dimercaptomethyl-1,11- Mercapto-3,6,9-trithiaoundecan, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-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. Moreover, the polymerization modified body obtained by the 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 a polythiol compound, Preferably, 1 or more types of other polythiol compounds can be mixed and used with bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

The polymerizable composition may further include a polyisocyanate compound. The polyisocyanate compound is not particularly limited and a compound having at least one isocyanate and / or isothiocyanate group can 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-undecanetriisocyanate, 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, Alicyclic isocyanate compounds such as dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate and 2,2-dimethyldicyclohexyl methane isocyanate; Xylylene diisocyanate (XDI), 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, benzene tree Isocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (iso Cyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzenediisocyanate, hexa Aromatic isocyanate compounds such as hydrodiphenylmethane-4,4-diisocyanate; 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-isocyanatomethyl Benzene) 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-5,5-diisocyanate, 3,3 Sulfur-containing aromatic isocyanate compounds such as dimethoxydiphenyldisulfide-4,4-diisocyanate and 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 used. In addition, as long as it is a compound having at least one or more isocyanate and / or isothiocyanate groups, one kind or two or more kinds can be used, and further, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, Nitro substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized, and trimerized reaction products can also be used. As a polyisocyanate compound, Preferably, 1 or more types chosen from isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexyl methane diisocyanate is used.

 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 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 the rate, xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether , Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallylcarbonate, and styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, and divinyl Vinyl compounds such as benzene and 3,9-divinylspirobiby (meta-dioxane); Possible, but is not limited to the compounds exemplified 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 be a chain extender, a crosslinking agent, a polymerization initiator, an internal mold release agent, an optical stabilizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, an anti-colorant, an organic dye, an inorganic pigment, a filler, according to a known molding method. Various additives, such as an adhesion promoter, may be further included.

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, and an internal mold release agent is contained in 0.001-10 weight% preferably in a polymeric composition. As the internal mold release agent, a phosphate ester compound is preferably used. The phosphate ester compound is prepared by adding 2-3 moles of an alcohol compound to phosphorus pentoside (P ₂ O ₅ ), and there may be various types of phosphate ester compounds 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), polyoxyethylenenonylphenol ether phosphate (3% by weight 9 mole of ethylene oxide added, 80% by weight 8 mole added, 5% by weight 9 mole added, 7 mole added 6% by weight, 6 mole added 6% by weight), polyoxyethylene nonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight, 12 mole added by 80% by weight, 11 mole added 8% by weight, 9% by weight, 3% by weight, 4% by weight, 6% by weight), polyoxyethylenenonylphenol ether phosphate (3% by weight, 17 parts by weight of ethylene oxide added, 16 parts by weight) 79 weight%, 15 mol added 10 weight%, 14 mol added 4 weight%, 13 mol added 4 weight%), polyoxyethyl Nonylphenol ether phosphate (21 wt% ethylene oxide added 5 wt%, 20 mol added 76 wt%, 19 mol added 7 wt%, 18 mol added 6 wt%, 17 mol added 4 1 or 2 or more types selected from the group consisting of phosphate ester compounds to which ethylene oxide or propylene oxide is added may be used.

The ultraviolet absorber is added in an amount of 0.005 to 6% by weight (50 to 60,000 ppm), preferably 0.01 to 3% by weight (100 to 30,000 ppm) based on the total monomer weight. If the amount of the ultraviolet absorber is less than 0.005% by weight, no effective ultraviolet absorbing capacity can be obtained, and yellowing may be severe when the lens is exposed to ultraviolet rays. In addition, when it is 6% by weight or more, not only it is difficult to dissolve in the composition, but also a poor polymerization may occur during curing. As the ultraviolet absorber, a known ultraviolet absorber which can be used for spectacle lenses can be used without limitation. For example, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'- dihydroxy-4,4'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole or 2 having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention; , 2'-dihydroxy-4,4'-dimethoxybenzophenone and the like can be used.

As the organic dye, known organic dyes may be used. In one embodiment of the present invention, 1-hydroxy-4- (p-toludine) enthraquinone [1-hydroxy-4- (p-toludine) anthraquinone], perinone dye ) And the like. By adding 0.5 to 10,000 ppm, preferably 5 to 1000 ppm, of such organic dye per kg of the monomer, it is possible to prevent the optical lens from becoming yellow by the addition of an ultraviolet absorber.

The polymerization initiator (catalyst) plays an important role in curing. Epoxy curing agents are mainly used as the type of catalyst, but strong amines are intensive in isocyanate reaction. 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 amount used is preferably 0.001 to 5% by weight based on the total monomer weight.

As an amine system, triethylamine, tripropylamine, dipropylethylamine, tributylamine, trihexylamine, dimethylcyclohexylamine, dicyclohexylethylamine, tricyclohexylamine, diethylcyclohexylamine, dicyclohexyl Ethylamine, dipropylcyclohexylamine, dicyclohexylpropylamine, dibutylcyclohexylamine, dicyclohexylbutynamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-di Propylbenzylamine, N, N-dibutylbenzylamine, N-methylbenzylamine, 2-dimethylaminomethylphenol, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, triethylenediamine, tetramethyl Ethylenediamine, tetraethylethylenediamine, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, tetrapropylethylenediamine, tetrabutylethylenediamine, pentamethyldiethylenetriamine, pentaethyldiethylenetriamine Pentapropyldiethylenetriamine, pen Butyldiethylenetriamine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N, N-dimethylpiperazine, N, N-diethylpiperazine , N, N-dipropylpyrazine, N, N-dibutylpiperazine, hexamethylenetetramine, dimethylaminoethyl acetate, diethylaminoethyl acetate, dimethylaminopropionitrile, diethylaminopropionitrile, N- Methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-cyclohexylmorpholine, N-methylpiperidone, N-ethylpiperidone, N-propylpiperidone, N-butyl Piperidone, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrroli Toxin and N-butylpyrrolidone. Examples of aromatic tertiary amines include N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-dibutylaniline, N, N-cyclohexylmethylaniline, N, N -Dicyclohexylaniline, diphenylmethylamine, diphenylethylamine, triphenylamine, N, N-dimethyltoluidine, N, N-diethyltoluidine, N-cyclohexyl-N-methyltoluidine, N, N-dicy Clohexyltoluidine, N, N-dimethylnaphthylamine, N, N-diethylnaphthylamine, N, N-dimethylanisidine, N, N-diethylanisidine and N, N, N`, N`- Tetramethylphenylenediamine and the like. Pyridine, picoline, dimethylpyridine, 2,2'-bipyridine, 4,4'-bipyridine, pyridine, N-methylpyrazole, N-ethylpyrazole, N-propylpyrazole, N-butylpyrazole , N-cyclosecsilpyrazole, pyridazine, pyrimidine, pyriline, oxazole, thiazole, 1-methylimidazole, 1-benzylimidazole, 1-methyl-2-methylimidazole, 1- Benzyl-2-methylimidazole, 1-ethyl-4-methylimidazole, 1-ethyl-2-ethyl-4-methylol, N-methylpyrrole, N-ethylpyrrole, N-butylpyrrole, N- Methylpyrroline, N-ethylpyrroline, N-butylpyrroline, pyrimidine, purine, quinoline, isoquinoline, N-methylcarbazole, N-ethylcarbazole and N-butylcarbazole, and the like can be used. As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Oxalic acid stannous; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; Di (2-ethylsecyl) tin oxide and the like may be used alone or in combination of two or more thereof.

Examples of Lewis acids include zinc compounds such as zinc chloride, acetylacetone zinc and zinc dibutyldithiocarbamate; Iron compounds such as iron chloride and acetylacetone iron; Aluminum compounds, such as alumina, aluminum fluoride, aluminum chloride, and triphenyl aluminum, etc. can be used.

After the polymerizable composition is prepared as described above, an optical material is obtained through mold polymerization. The polymerizable composition is polymerized by injecting it between molding molds held by a gasket or tape. The polymerization conditions are not limited because the conditions largely vary 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 150 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 150 ° 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 50-150 degreeC, and it is preferable to carry out at 90-140 degreeC.

Since the optical material of this invention can be obtained by the molded object of various shapes by changing the mold at the time of casting polymerization, it can be used with various optical materials, such as an eyeglass lens, a camera lens, and a light emitting diode (LED). 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 optical lens obtained according to the present invention may be used by forming 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. These coating layers may be formed alone, or may be formed by multilayering a plurality of coating layers. When coating layers are provided on both surfaces, the same coating layer may be formed on each surface, or different coating layers may be formed. The optical lens obtained according to the present invention may be used after being subjected to coloring treatment using a disperse dye or a photochromic dye, if necessary.

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.

Property test method

The physical properties of the optical lens manufactured in Example by the physical property test method described below are shown in Table 1 below.

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

2) Polymerization Imbalance: 100 lenses obtained in the process were visually observed and marked with 'X' if three or more striae, whitening, and edge bubbles appeared, and 'O' if not.

3) Curing state: When hardening or vigorous reaction occurs and hardening is not proper, 'X' is indicated. When curing occurs well, colorless solid resin is formed, 'O' is indicated.

4) Glass transition temperature (Tg): TMA was measured under high purity nitrogen by the Penatelay method of TMAQ400 (TA Instruments) (0.8N load, pin tip 0.5mm Φ, elevated temperature 5 ° C / min).

Synthesis Example 1 Synthesis of Bis (3-chloro-2-hydroxypropyl) sulfide

Epichlorohydrin (5563 g, 60.12 mol) and methanol (2500 g) were added to a 10 liter reactor, caustic soda (50% aq, 5 g) was added when the reaction temperature reached 6 ° C. do. In another 10 liter reactor, NaSH.xH ₂ O (70% NaSH, 3660 g, 45.75 mol), methanol (1000 g) and water (500 g) were added and stirred to dissolve completely, and hydrochloric acid was slowly added dropwise to epidemic hydrogen sulfide gas. Addition to chlorohydrin solution affords bis (3-chloro-2-hydroxypropyl) sulfide. Termination of the reaction confirmed the final product by GC, which completely eliminated epichlorohydrin and 3-chloro-2-hydroxy-propane-1-thiol compound and produced bis (3-chloro-2-hydroxypropyl) sulfide. The time point was the end of the reaction. If 3-chloro-2-hydroxy-propane-1-thiol is present, the relative content is calculated by GC to react with addition of epichlorohydrin to obtain bis (3-chloro-2-hydroxypropyl) sulfide. The product had a yield of almost 99% or higher and a purity of 95% or higher.

Synthesis Example 2 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 2.5)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1072.48 g, 4.89 mol), 1300 g of toluene and 800 g of methanol were added to a 10 liter reaction container, and the reaction temperature was adjusted to 30 degreeC, stirring. When it reaches 25 degreeC, NaOH (50% aq., 783.08g, 9.78 mol) is added dropwise, and when it is added, reaction temperature is performed at 35-37 degreeC, and it is made to react, maintaining temperature. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, the mixture is stirred for about 10 minutes, the layers are separated, the organic layer serving as a supernatant is washed twice with water, and the water is removed as much as possible. The solution was further stirred with 400 g of methanol, and thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8 ° C., and the reaction temperature was raised to 18 ° C. for 18 hours. Termination of the reaction is confirmed by HPLC, when the starting material disappears and the product no longer changes. After the reaction was completed, the stirring was stopped, the organic layer obtained in the layer separation was washed three times with water, 10% sulfuric acid was added to the organic layer obtained, and the organic solvent was removed to remove bis (2,3-ethiothiopropyl) sulfide having a pH of 2.5. Got it. The refractive index (nD, 20 ° C) was 1.614.

Synthesis Example 3 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 3.5)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1072.48 g, 4.89 mol), 1300 g of toluene, and 800 g of methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 25 degreeC, stirring. When it reaches 25 degreeC, NaOH (50% aq., 783.08g, 9.78 mol) is added dropwise, and when it is added, it reacts, maintaining reaction temperature to 35-37 degreeC. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, the mixture is stirred for about 10 minutes, the layers are separated, the organic layer serving as a supernatant is washed twice with water, and the water is removed as much as possible. The solution was further stirred with 400 g of methanol, and thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8 ° C., and the reaction temperature was raised to 18 ° C. for 18 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction was completed, the stirring was stopped and the organic layer obtained in the layer separation was washed three times with water, 5% sulfuric acid was added to the organic layer obtained, and the organic solvent was removed to remove bis (2,3-ethiothiopropyl) sulfide having a pH of 3.5. Got it. The refractive index (nD, 20 ° C) was 1.614.

Synthesis Example 4 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 5.0)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1071.48 g), 1300 g of toluene and 800 g of methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 25 degreeC, stirring. When reached at 25 ° C., NaOH (50%, aq., 783.08 g) is added dropwise and reacted while maintaining the reaction temperature at 37 ° C. upon dropping. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, stirred for about 30 minutes, and the layers are separated. The supernatant is neutralized with 1 g of hydrochloric acid solution, water is removed as much as possible, and the organic layer is removed. After further adding 400 g of methanol to the phosphorus organic solution, the mixture was stirred, and thiourea (1117.65 g) and acetic anhydride (70 g) were added at a reaction temperature of 8 ° C., and the reaction temperature was raised to 16.5 ° C. for 24 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction was completed, the stirring was stopped and the organic layer obtained in the layer separation was washed three times with water, and the organic layer obtained was washed with 0.1% sulfuric acid, and the organic solvent was removed to remove bis (2,3-ethiothiopropyl) sulfide having a pH of 5.0. Got. The refractive index (nD, 20 ° C) was 1.614.

Synthesis Example 5 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 7.0)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1071.48 g), 1300 g of toluene and 800 g of methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 25 degreeC, stirring. When reached at 25 ° C., NaOH (50%, aq., 783.08 g) is added dropwise and reacted while maintaining the reaction temperature at 37 ° C. upon dropping. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, stirred for about 30 minutes, and the layers are separated. The supernatant is neutralized with 1 g of hydrochloric acid solution, water is removed as much as possible, and the organic layer is removed. After further adding 400 g of methanol to the phosphorus organic solution, the mixture was stirred, and thiourea (1117.65 g) and acetic anhydride (70 g) were added at a reaction temperature of 8 ° C., and the reaction temperature was raised to 16.5 ° C. for 24 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction was terminated, the stirring was stopped and the organic layer obtained in the layer separation was washed several times with water, and the organic solvent was removed to obtain bis (2,3-ethiothiopropyl) sulfide having a pH of 7.0. The refractive index (nD, 20 ° C) was 1.614.

Synthesis Example 6 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 8.0)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1071.48g,), toluene 1300g, and 800g methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 25 degreeC, stirring. When reached at 25 ° C., NaOH (50%, aq., 783.08 g) is added dropwise and reacted while maintaining the reaction temperature at 37 ° C. upon dropping. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, the mixture is stirred for about 30 minutes, and the layers are separated. The phosphorus organic solution was further stirred with methanol 400g, and thiourea (1117.65g) and acetic anhydride (70g) were added at a reaction temperature of 8 ° C, and the reaction temperature was raised to 16.5 ° C for 24 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction was completed, the stirring was stopped and the organic layer obtained in the layer separation was washed three times with water, 0.1% ammonia water was added to the obtained organic layer, and the organic solvent was removed to remove bis (2,3-ethiothiopropyl) at pH 8.0. Obtained sulfide. The refractive index (nD, 20 ° C) was 1.614.

Synthesis Example 7 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (pH 10.0)

Bis (3-chloro-2-hydroxy-propyl) sulfide (1071.48g,), toluene 1300g, and 800g methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 25 degreeC, stirring. When reached at 25 ° C., NaOH (50%, aq., 783.08 g) is added dropwise and reacted while maintaining the reaction temperature at 37 ° C. upon dropping. The dropping time is within 1 hour, and the ripening is performed at 37 ° C. for about 30 minutes. After ripening, 2000 g of toluene is added, stirred for about 30 minutes, and the layers are separated. The supernatant is neutralized with 1 g of hydrochloric acid solution, water is removed as much as possible, and the organic layer is removed. The phosphorus organic solution was further stirred with methanol 400g, and thiourea (1117.65g) and acetic anhydride (70g) were added at a reaction temperature of 8 ° C, and the reaction temperature was raised to 16.5 ° C for 24 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. After the reaction was completed, the stirring was stopped, the organic layer obtained in the layer separation was washed three times with water, 5% ammonia water was added to the organic layer obtained, and the organic solvent was removed to remove bis (2,3-ethiothiopropyl) sulfide having a pH of 10.0. Got it. The refractive index (nD, 20 ° C) was 1.614.

Example 1

100 g of bis (2,3-ethiothiopropyl) sulfide at pH 7.0 obtained in Synthesis Example 5, 0.01 g of internal release agent 8-PENPP, 1.0 g of ultraviolet absorber HOPBT, 0.4 g of polymerization initiator TBPB, 20 g of organic dyes HTAQ (20 ppm) and PRD ( 10 ppm) was stirred and mixed at 20 ° C to obtain a homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold shape which consists of a glass mold and a tape. The mold was charged into a polymerization oven, gradually heated to 30 to 100 ° C for 15 hours at 30 ° C, and polymerized. After the completion of the polymerization, the mold was taken out of the oven. The releasability from the mold was good. The obtained resin was annealed at 110 degreeC for 2 hours. The obtained physical properties were 1.702, refractive index (nE), Abbe number 34.5, and heat resistance (Tg) 95 degreeC. The dissolved state injected into the mold was visually observed, and there was no abnormality as a result of checking whether there was any foreign matter after demolding, and there was no bleaching and malting.

Examples 2-3

Compositions and lenses were prepared according to the compositions shown in Table 1 in the same manner as in Example 1, and the results of the evaluation are shown in Table 1.

Comparative example One

100 g of bis (2,3-ethiothiopropyl) sulfide having a pH of Synthesis Example 2, 0.01 g of internal mold release agent 8-PENPP, 1.0 g of ultraviolet absorbent HOPBT, 0.4 g of polymerization initiator TBTB, 20 h of organic dyes HTAQ (20 ppm) and PRD (10 ppm) was stirred and mixed at 20 DEG C to obtain a homogeneous solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold shape which consists of a glass mold and a tape. The mold was charged into a polymerization oven, gradually heated to 30 to 100 ° C for 15 hours at 30 ° C, and polymerized. However, the resin composition turned yellow without curing.

Comparative Examples 2-3

Table 1 shows the data obtained by curing the resin composition in the same manner as in Comparative Example 1.

Table 1

[Abbreviation]

EPS: bis (2,3-epithiopropyl) sulfide

8-PENPP: polyoxyethylenenonylphenol ether phosphate

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, a thioepoxy optical material having excellent quality without uncuring or polymerization imbalance can be easily produced. The thioepoxy optical material manufactured according to the present invention may be widely used in various fields in place of the existing optical material. 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 (14)

1. making a polymerizable composition comprising a thioepoxy compound having a pH of 4 to 8,

   Method for producing a thioepoxy clock optical material comprising the step of polymerizing the polymerizable composition.
2. The method of claim 1, wherein the thioepoxy compound is selected from the group consisting of bis (2,3-epithiopropyl) sulfide, bis (2,3-ethiothio) disulfide, 1,3- and 1,4-bis (β-epi). Thiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane , 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, and 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epi A method for producing a thioepoxy clock optical material, characterized in that one or two or more compounds selected from the group consisting of thiopropylthio) propane.
3. The method of claim 1, wherein the polymerizable composition further comprises a polythiol compound.
4. The method for producing a thioepoxy clock optical material according to claim 3, wherein the polymerizable composition further comprises a polyisocyanate compound.
5. The method for producing a thioepoxy clock optical material according to any one of claims 1 to 4, wherein the polymerizable composition further comprises an olefin compound as a reactive resin modifier.
6. The method for producing a thioepoxy optical material according to any one of claims 1 to 4, wherein the polymerizable composition further comprises a phosphate ester compound as an internal mold release agent.
7. 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 nonylphenol ether phosphate (9% added by 9 moles of ethylene oxide, 80% added by 8 moles added, 5% by weight 9 moles added, 7 moles added 6 wt%, 6 mol added 6 wt%), polyoxyethylene nonylphenol ether phosphate (13 wt% added ethylene oxide 3 wt%, 12 wt% added 80 wt%, 11 mol added 8 Wt%, 9 mol added 3 wt%, 4 mol added 6 wt%), polyoxyethylene nonylphenol ether phosphate (17 mol added ethylene oxide 3 wt%, 16 mol added 79 wt% , 15 mole added 10% by weight, 14 mole added 4% by weight, 13 mole added 4% by weight), polyoxyethylene nonylphenol ether 5% by weight of 21 mole of ethylene oxide added, 76% by weight of 20 mole added, 7% by weight of 19 mole added, 6% by weight 18 mole added, 4% by weight 17 mole added ), And Zelec UN ™, a method for producing a thioepoxy clock optical material, characterized in that one or two or more compounds selected from the group consisting of.
8. Polymeric composition for optical materials containing the thioepoxy compound of pH 4-8.
9. The polymerizable composition for an optical material according to claim 8, further comprising a polythiol compound.
10. The polymerizable composition for an optical material according to claim 9, further comprising a polyisocyanate compound.
11. The polymerizable composition for an optical material according to any one of claims 8 to 10, further comprising a phosphate ester compound as an internal mold release agent.
12. The optical material obtained by thermosetting the polymeric composition for optical materials of any one of Claims 8-10.
13. An optical lens made of the optical material of claim 12.
14. The optical lens of claim 13, wherein the optical lens is an eyeglass lens or a polarizing lens.