KR20180120650A - Mold polymerization method for thioepoxy based optical material and the polymerizable composition - Google Patents

Abstract

The present invention relates to a mold polymerization method of a thioepoxy-based optical material and a polymeric composition, and more particularly, to a mold polymerization method of a thioepoxy-based optical material with excellent de-formation from a mold and excellent surface precision, and a polymeric composition. According to the present invention, the polymeric composition containing a thioepoxy compound is placed in a mold to be polymerized, wherein water content of the polymeric composition is 100 to 2,500 ppm and an internal mold release agent is added in the polymeric composition before polymerizing the polymeric composition. Therefore, the thioepoxy-based optical material with excellent surface precision can be replaced an existing optical material to be used in various fields.

Description

[0001] The present invention relates to a method for polymerizing a template of a thioepoxy-based optical material and a polymerizable composition for the same,

TECHNICAL FIELD The present invention relates to a method for casting a thioepoxy-based optical material and a polymerizable composition thereof, and more particularly, to a method for polymerizing a thioepoxy-based optical material and a polymerizable composition.

The thiourethane-based lens has a high refractive index and an excellent impact strength, but it has disadvantages such as a lens surface roughness and a center depression, and also has a problem that abbe number is rapidly lowered as the refractive index increases. Korean Patent No. 10-0681218 proposes a thioepoxy-based plastic lens. Thioepoxy-based lenses have the advantage of having a high refractive index and a high Abbe number, but the lens is fragile. In order to solve these problems, a method of copolymerizing two kinds of resins having different properties has been proposed in Korean Patent Registration No. 10-0417985 and Japanese Patent Laid-Open No. 11-352302. However, the composition containing the thioepoxy compound is not easily separated from the mold after polymerization, in particular, after copolymerization, and there is a problem that the precision of the surface is not good even when the lens is broken and separated during the separation.

Korean Patent Publication No. 10-0681218 Korean Patent Publication No. 10-0417985 Japanese Patent Application Laid-Open No. 11-352302

The present inventors have studied and tried various methods to solve the problem of low releasability from a mold that appears when a polymerizable composition comprising a thioepoxy compound is prepared by molding together a lens. As a result, the inventors of the present invention have discovered that when the polymerizable composition contains an appropriate amount of water, the internal defoaming agent such as a silicone surfactant or a phosphoric acid ester compound is used, and when the separator is separated from the mold after polymerization, . If the water content of the polymerizable composition deviates from the proper range even if the inner mold agent is not used or used, the mold is poorly releasable, so that the lens is broken during the separation from the mold, and the accuracy of the separated lens is not good.

It is an object of the present invention to provide a casting polymerization method of a thioepoxy-based optical material which is easily demolded from a mold and has excellent surface precision, and a polymerizable composition therefor.

In the present invention, a "thioepoxy compound" is defined as a compound having at least one thioepoxy group.

In the present invention, the term "thioepoxy-based optical material" is defined to include both an optical material obtained by polymerizing a thioepoxy compound and an optical material obtained by copolymerizing thioepoxy and thiourethane, unless otherwise specified.

In the present invention,

A method for casting an optical material in which a polymerizable composition comprising a thioepoxy compound is put into a mold and polymerized,

Wherein the polymerizable composition has a water content of 100 to 2,500 ppm and an internal mold release agent is added to the polymerizable composition before polymerization in advance.

In the present invention,

There is provided a polymerizable composition comprising a thioepoxy compound, wherein the polymerizable composition has a water content of 100 to 2,500 ppm and contains an internal defoaming agent.

Further, in the present invention, there is provided an optical material obtained by polymerization by the casting polymerization method and an optical lens made of this optical material. The optical lens particularly includes a spectacle lens or a polarizing lens.

According to the present invention, it is possible to obtain a thioepoxy-based optical material which is easy to release from a mold (glass mold type) after polymerization and has excellent surface precision. Since the casting polymerization method of the present invention improves the productivity of the lens and improves the yield of the lens due to the lowered fracture rate, the production cost can be greatly reduced while obtaining a high-quality lens.

In the casting polymerization method of the thioepoxy-based optical material of the present invention, the water content of the polymerizable composition containing a thioepoxy compound is adjusted to 100 to 2,500 ppm, and the inner mold agent is previously added to the polymerizable composition before polymerization.

The thioepoxy compound may be, for example, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, 1,3- and 1,4- ([Beta] -epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- ( episopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, and other episulfide compounds having an alicyclic skeleton; Bis [4- (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2- (Β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- ) Phenyl] sulfine, and 4,4-bis (? - epithiopropylthio) biphenyl; 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthiomethyl) Epithiocene skeleton such as bis (β-epithiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-epithiopropylthioethyl) -1,4- Sulfide compounds; Bis [(2 -? - epithiopropylthioethyl) thio] -1,3-bis (? - epithiopropylthio) propane, (Β-epithiopropylthiomethyl) propane, bis- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1- Propyl) sulfide, and bis- (β-epithiopropyl) disulfide, and the like. In addition, a chlorine substituent of a compound having an episulfide group, a halogen substituent such as a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent, and a prepolymer type modified form with a polythiol can also be used. As the thioepoxy compound, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, 1,3- and 1,4- Cyclohexane, 1,3- and 1,4-bis (? - epithiopropylthiomethyl) cyclohexane, 2,5-bis (? -Epithiopropylthiomethyl) -1,4-dithiane, 2,5 Bis (? - epithiopropylthioethyl) -1,4-dithiane, 2- (2-β-epithiopropylthioethylthio) -1,3-bis May be used.

In the casting polymerization method of the thioepoxy-based optical material of the present invention, the water content of the polymerizable composition containing the thioepoxy compound is set to 100 to 2,500 ppm. The moisture content of the composition is measured to remove moisture to have a water content in the above range or to add a small amount of water to adjust the water content. Removal can be done, for example, by high vacuum. When the water content of the polymerizable composition is less than 100 ppm, the de-molding is not good even if the internal defoaming agent is used, and the cotton precision is bad even when the de-molding is performed. Likewise, despite the use of internal blowing agents, moldability and surface accuracy were poor even when the water content of the polymerizable composition exceeded 2,500 ppm. In addition, the excessive water content of the polymerizable composition also has other negative effects such as bubbling and whitening in the optical material obtained by polymerization.

The polymerizable composition may further comprise a polythiol compound or a polyisocyanate compound or both.

The polythiol compound is not particularly limited, and any compound having at least one thiol group may be used alone or in combination of two or more. For example, there may be mentioned bis (2-mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3- 1-thiol, 1,3- and 1,4-benzenedimethanol thiol (1,3- and 1,4-xylylenedithiol), 2,2-bis (mercaptomethyl) Dithiol, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) (2,3-dimercaptopropanyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane , 2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) (2-mercaptoethylthio) propylthio-propane-1-thiol, 2,2-mercaptoethyl-3- - bis- (3-mercapto-propionylox Methyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) ) Propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15 (R-3-mercapto-2 - ((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2- (7R, 11S) -7,11-bis (mercaptomethyl) propane-1-thiol, Dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13-pentafluoroheptadecane- Dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl 1,1-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11- Mercapto-3,6,9-trithiandecane, 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 (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, compounds having one or more thiol groups may be used alone or in combination of two or more. It is also possible to use a modified polymer obtained by prepolymerization of a polythiol compound with an isocyanate, a thioepoxy compound, a thiotane compound or a compound having an unsaturated bond as a resin modifier. As the polythiol compound, one or more other polythiol compounds may be preferably used in combination with bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

The polyisocyanate compound contained in the polymerizable composition is not particularly limited and a compound having at least one isocyanate and / or isothiocyanate group may be used. For example, there may be mentioned 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, butene diisocyanate, 1,3-butadiene- , 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Aliphatic isocyanate compounds such as bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether; (Isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, Alicyclic isocyanate compounds such as dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane isocyanate; (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatoethyl) Isocyanatomethyl) diphenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, benzene tri Isocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis Cyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexa Aromatic isocyanate compounds such as hydroiodiphenylmethane-4,4-diisocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, Bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) Aliphatic isocyanate compounds such as thio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenyl sulfide 2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzyl thioether, bis (4- Isomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyl diphenyl disulfide-5,5 Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- Sulfided aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxy diphenyl disulfide-4,4-diisocyanate, and 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate; 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) (Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) Dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis Isocyanatomethyl) -2-methyl-1,3-dithiolane can be used singly or in combination of two or more. In addition, at least one compound having at least one isocyanate and / or isothiocyanate group may be used alone or in combination of two or more. In addition, halogen substituents such as chlorine substituents and bromine substituents of these isocyanate compounds, alkyl substituents, A prepolymer-type modified product of a nitro substituent, a polyhydric alcohol or a thiol, a carbodiimide-modified product, a urea-modified product, a biuret-modified product, or a dimerized or trimarized product may be used. As the polyisocyanate compound, at least one selected from isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate is preferably used.

As the internal release agent, a phosphoric acid ester compound, a silicone surfactant, a fluorinated surfactant, etc. may be used either singly or in combination. The internal blowing agent is preferably contained in an amount of 0.001 to 10% by weight in the polymerizable composition. A silicone surfactant or a phosphoric acid ester compound is preferably used as the inner mold release agent. The phosphoric acid ester compound is prepared by adding 2 to 3 moles of alcohol compound to phosphorus pentoxide (P ₂ O ₅ ). Depending on the type of alcohol used, various types of phosphoric acid ester compound may be present. Representative examples are those in which ethylene oxide or propylene oxide is added to an aliphatic alcohol, or ethylene oxide or propylene oxide is added to a nonylphenol group or the like. When the polymerizable composition of the present invention contains a phosphoric acid ester compound to which ethylene oxide or propylene oxide has been added as an internal mold release agent, an optical material having good releasability and excellent quality can be obtained. The phosphoric acid ester compound may be, for example, a compound selected from the group consisting of methyl acid phosphate, dimethyl acid phosphate, ethyl acid phosphate, diethyl acid phosphate, propyl acid phosphate, dipropyl acid phosphate, isopropyl acid phosphate, diisopropyl acid phosphate, Diisodecylic acid phosphate, tridecanolic acid phosphate, bistridecanedioic acid phosphate, etc., and ethylene oxide or propylene oxide is added to the aliphatic alcohol, or ethylene oxide or propylene oxide is added to the nonylphenol group and the like, There is a kind added. Particularly, in the present invention, polyoxyethylene nonylphenol ether phosphate (5 mol% of ethylene oxide, 5 mol% of ethylene oxide, 80 mol% of 4 mol%, 10 mol% of 3 mol%, and 5 mol% ), Polyoxyethylenenonylphenol ether phosphate (3 mol% of ethylene oxide, 9 mol%, 8 mol% of 80 mol%, 9 mol of 5 mol%, 7 mol of 6 mol%, 6 mol of ethylene oxide, 6% by weight of a molar part), polyoxyethylene nonylphenol ether phosphate (3 mol% of ethylene oxide 13 mol%, 80 mol% of 12 mol%, 8 mol% of 11 mol% 3 parts by weight of ethylene oxide, 3 parts by weight of 4 parts by weight of ethylene oxide, 6 parts by weight of 4 parts by weight of ethylene oxide), polyoxyethylene nonylphenol ether phosphate (17 parts by weight of ethylene oxide, 3 parts by weight, 16 parts by mol of 79 parts by weight, By weight, 4% by weight of 14 mol% and 4% by weight of 13 mol%), polyoxyethylene nonylphenol ether phosphate (ethylene oxide 5 parts by weight of 21 molar parts, 78 parts by weight of 20 parts by weight, 7 parts by weight of 19 parts by weight, 6 parts by weight of 18 parts by weight, and 4 parts by weight of 17 parts by weight of ethylene oxide) One or two or more kinds of phosphoric acid ester compounds to which propylene oxide is added can be selected and used.

The polymerizable composition of the present invention may further contain a reactive resin modifier for the purpose of adjusting impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties. Examples of the olefin compound which can be added as the reactive resin modifier include benzyl acrylate, benzyl methacrylate, butoxy ethyl acrylate, butoxy methyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol Diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene 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 But are not limited to, acrylate, acrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate (4-alkoxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, Bis (4-methoxyethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acroxyethoxyphenyl) Bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxy diethoxyphenyl) methane, 1,1- Decane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate Acrylates such as methyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, butyl methacrylate, (Meth) acrylate compounds such as xylylene dithiol diacrylate, xylylene dithiol diacrylate, xylyl dithiol dimethacrylate, mercaptoethylsulfide diacrylate, and mercaptoethylsulfide dimethacrylate, and allyl glycidyl ether , Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate and diethylene glycol bisallylcarbonate, and allyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinyl Benzene, and 3,9-divinyl spirobi (meta-dioxane). Possible, but is not limited to the compounds exemplified compounds. These olefin compounds may be used alone or in combination of two or more.

In addition, the polymerizable composition of the present invention may further contain additives such as a chain extender, a crosslinking agent, a polymerization initiator, a light stabilizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring inhibitor, an organic dye, Etc. may be further added.

The ultraviolet absorber is added in an amount of 0.005 to 6 wt% (50 to 60,000 ppm), preferably 0.01 to 3 wt% (100 to 30,000 ppm) based on the total monomer weight. When the addition amount of the ultraviolet absorber is less than 0.005% by weight, effective ultraviolet absorbing ability can not be obtained, so that when the lens is exposed to the ultraviolet ray, yellowing may be severe. In addition, when it is 6% by weight or more, it is difficult to dissolve in the composition, and a polymerization failure may be caused at the time of curing. As the ultraviolet ray absorbing agent, any known ultraviolet ray absorbing agent usable in 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'-dimethoxybenzophenone, and the like, or a mixture of two or more thereof. (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole or 2 (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole having a good ultraviolet ray absorbing ability in a wavelength region 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 organic dyes, known organic dyes can be used. In one embodiment of the present invention, the present inventors have conducted extensive studies in order to investigate the effects of 1-hydroxy-4- (p-toluidine) anthraquinone and perinone dye ) Were used. By adding such an organic dye in an amount of 0.5 to 10,000 ppm, preferably 5 to 1000 ppm, per 1 kg of the monomer, it is possible to prevent the optical lens from being yellowed by adding the ultraviolet absorbent.

Polymerization initiators (catalysts) play an important role in curing. Epoxy hardeners are mainly used as catalysts, but strong amines cause intense isocyanate reaction, so use caution. In the present invention, mainly amine salts, phosphonium salts, phosphines and tertiary amines having no electron attracting group, Lewis acids, radical initiators and the like are mainly used, and the kind and amount of the catalyst are suitably adjusted by a person skilled in the art You can choose.

Examples of the amine-based amine include triethylamine, tripropylamine, dipropylethylamine, tributylamine, trihexylamine, dimethylcyclohexylamine, dicyclohexylamine, tricyclohexylamine, diethylcyclohexylamine, dicyclohexyl N, N-diethylbenzylamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, dibutylcyclohexylamine, dicyclohexylbutylamine, N, N-dibutylbenzylamine, N-methylbenzylamine, 2-dimethylaminomethylphenol, 2,4,6-tris (N, N- dimethylaminomethyl) phenol, triethylenediamine, tetramethyl But are not limited to, ethylenediamine, tetraethylethylenediamine, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, tetrapropylethylenediamine, tetrabutylethylenediamine, pentamethyldiethylenetriamine, , Pentapropyl diethylene triamine, pent Butyl piperidine, N, N-dimethylpiperazine, N, N-diethylpiperazine, N, N-dimethylpiperazine, N, , N, N-dipropylpyrazine, N, N-dibutylphepazine, hexamethylenetetramine, dimethylaminoethyl acetate, diethylaminoethyl acetate, dimethylaminopropionitrile, diethylaminopropionitrile, N- Methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-cyclohexylmorpholine, N-methylpiperidone, N-ethylpiperidone, But are not limited to, piperidone, piperidone, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpyrrolidone, And N-butylpyrrolidone. Examples of aromatic tertiary amines include N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropyl aniline, N, N-dibutyl aniline, N, N-cyclohexylmethylaniline, N, N Dicyclohexyl aniline, diphenylmethylamine, diphenylethylamine, triphenylamine, N, N-dimethyltoluidine, N, N-diethyltoluidine, N-cyclohexyl- N'-dimethylnaphthylamine, N, N-diethylnaphthylamine, N, N-dimethyl anisidine, N, N-diethylanisidine and N, Tetramethylphenylenediamine, and the like. Pyridine, picoline, dimethylpyridine, 2,2'-bipyridine, 4,4'-bipyridine, pyridine, N-methylpyrazole, N-ethylpyrazole, N-propylpyrazole, , N-cyclohexyl pyrazole, N-cyclohexyl pyrazole, N-cyclohexyl pyrazole, pyridazine, pyrimidine, pyrinoline, oxazole, thiazole, Ethyl-4-methylimidazole, 1-ethyl-2-ethyl-4-methylol, N-methylpyrrole, N-ethylpyrrole, N- Pyrroline, N-ethylpyrroline, N-butylpyrroline, pyrimidine, purine, quinoline, isoquinoline, N-methylcarbazole, N-ethylcarbazole and N-butylcarbazole. As the tin compound, butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octoate; Dibutyl tin dilaurate; Tetrafluoro-tin; Tetrachlorotin; Tetrabromoquite; Tetraiodide tin; Methyl tin trichloride; Butyltin trichloride; Dimethyl tin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; triphenyltin chloride; Dibutyltin sulfide; Di (2-ethyl sec-butyl) tin oxide, etc. may be used alone or in combination of two or more.

Examples of Lewis acids include zinc-based compounds such as zinc chloride, zinc acetyl acetone and zinc dibutyldithiocarbamate; Iron-based compounds such as iron chloride and acetylacetone iron; aluminum compounds such as alumina, aluminum fluoride, aluminum chloride and triphenyl aluminum; and the like. The amount to be used is preferably 0.001 to 5% by weight based on the total weight of the monomers.

After the polymerizable composition is prepared as described above, the optical material is obtained through the template polymerization. The polymerizable composition is injected between the molds held by a gasket or a tape and polymerized. Polymerization conditions are not limited, but are carried out at a temperature of about -50 to 150 캜 for 1 to 50 hours, because the conditions largely vary depending on the polymerizable composition, type and amount of catalyst used, shape of the mold, In some cases, it is preferable to maintain or slowly raise the temperature in the range of 10 to 150 占 폚 and cure in 1 to 48 hours. The optical material obtained by the curing may be subjected to treatment such as annealing if necessary. The treatment temperature is usually from 50 to 150 캜, preferably from 90 to 140 캜.

The optical material of the present invention can be obtained as a molded article of various shapes by changing the mold at the time of casting polymerization, and thus can be used as various optical materials such as spectacle lenses, camera lenses, and light emitting diodes (LED). In particular, it is suitable as an optical material such as a spectacle lens, a camera lens, a light emitting diode, and an optical element.

In the optical lens obtained according to the present invention, a coating layer may be formed on one surface or both surfaces thereof, if 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 formed singly or a plurality of coating layers may be formed in a multi-layered structure. When a coating layer is applied to both surfaces, the same coating layer may be formed on each surface or a different coating layer may be formed. The optical lens obtained according to the present invention may be used after coloring 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 embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

Physical properties test method

The physical properties of the optical lens prepared in the examples were measured by the following physical property test method, and the results are shown in Table 1 below.

1) Moisture content: Moisture content (ppm) was measured by Karl Fischer solution by an automatic moisture measurement in which a water vaporizer of 860 KF thermoprep was installed in a moisture meter of Metrohm.

2) Surface accuracy: It was judged whether there was any noticeable damage by irradiating USHIO USH-102D Mercury Arc Lamp with no breakage during separation. (Good surface accuracy), good separation of the mold release, or surface damage (poor surface accuracy).

3) Refractive index (nE) and Abbe number: Measured at 20 캜 using an Abbe refractometer which is a model of IT and DR-M4 of Atago.

[Example 1]

60 parts by weight of bis (2,3-epithiopropyl) sulfide as a thioepoxy compound, 20 parts by weight of isophorone diisocyanate as an isocyanate compound, 1,2-bis [(2-mercaptoethyl) 20 parts by weight of 3-mercaptopropane, 8 parts by weight of 8-PENPP [polyoxyethylene nylon phenol ethephosphate (3 parts by weight of ethylene oxide and 9 parts by weight of ethylene oxide, 80 parts by weight of 8 parts by weight of ethylene oxide, 5 parts by weight of 9 molar parts, 6 parts by weight of 7 parts by weight and 6 parts by weight of 6 parts by weight)], 0.1 part by weight of tetrabutylphosphonium bromide, 0.1 part by weight of triphenylphosphine, Dye HTAQ (20 ppm), PRD (10 ppm), and ultraviolet absorber HOPBT (1.5 g) were mixed and dissolved at 20 캜 to prepare a homogeneous solution. The moisture content of the resin composition was 145 ppm, and the mixed solution was deaerated at 400 Pa for 1 hour. Thereafter, filtration was performed with a 1 mu m PTFE filter, and the solution was injected into a mold of a glass mold and a tape. The mold was placed in a polymerization oven, and the temperature was gradually elevated to 25 ° C to 130 ° C over 21 hours to polymerize. After completion of the polymerization, the mold was taken out of the oven. The releasability from the mold type was good. The obtained resin was further annealed at 130 캜 for 4 hours. The physical properties of the obtained resin were 1.664 in refractive index (nE) and 36 in Abbe number. The state of dissolution before injection into the mold was visually observed, and after confirming whether or not the surface was precise after demoulding, no abnormality was observed, whitening was not observed, and it was confirmed that a stable quality resin was obtained. The evaluation results are shown in Table 1 below.

[Examples 2 to 12]

The composition and the lens were prepared in the same manner as in Example 1, respectively, according to the composition shown in Table 1 below, and the evaluation results are shown in Table 1.

[Comparative Example 1]

Except that 8-PENPP, which is a phosphoric acid ester, was not added as an internal blowing agent. The results are shown in Table 1 below. ≪ tb > < TABLE > Even after cooling after the polymerization, the copolymer lens of the thioepoxy compound and the isocyanate compound and the thiol compound remained as they were not separated and separated from the glass lens model.

[Comparative Examples 2 to 9]

The composition and the lens were prepared in the same manner as in Example 1, respectively, according to the composition shown in Table 1 below, and the evaluation results are shown in Table 1. In Table 1, parts means parts by weight.

As shown in Table 1, the lens of the present invention obtained in Examples 1 to 12 had good decal formation, excellent surface accuracy, and good yield.

<Abbreviation>

EDPS: bis (2,3-epithiopropyl) sulfide

EDPDS: bis (2,3-epithiopropyl) disulfide

IPDI: isophorone diisocyanate

HDI: 1,6-hexamethylene diisocyanate

DMTMP: 2,3-bis (2-mercaptoethylthio) propane-1-thiol

PETMP: pentaerythritol tetrakis (3-mercapto) propionate

8-PENPP: Polyoxyethylenenonylphenol ethephosphate (9 wt% of ethylene oxide, 3 wt% of ethylene oxide, 80 wt% of 8 mol of ethylene oxide, 5 wt% of 9 mol of ethylene oxide, 7 mol of ethylene oxide of 6 wt% 6% by weight, 6% by weight)

12-PENPP: polyoxyethylene nonylphenol ether phosphate (3 mol% of ethylene oxide 13 mol, 80 mol% of 12 mol, 8 mol% of 11 mol, and 3 mol% of 9 mol of ethylene oxide, 6 mol% of 4 moles)

20-PENPP: polyoxyethylene nonylphenol ether phosphate (containing 21 mol of ethylene oxide, 5 wt%, 20 mol of 78 wt%, 19 mol of 7 wt%, 18 mol of 6 wt% , 4 parts by weight of 17 parts by mol)

KF-353A: a product name of Shin-Etsu Silicones syrup-silicone surfactant

DOP: dioctyl acid phosphate

IDP: isodecylic acid phosphate

According to the present invention, it is possible to produce a thioepoxy-based optical material which is easily demoulded and has excellent surface precision. The thioepoxy-based optical material produced according to the present invention having excellent surface precision can be widely used in various fields in place of conventional optical materials. Specifically, it can be used as a plastic spectacle lens, a 3D polarized lens in which a polarizing film is attached to a spectacle lens, a camera lens, etc. In addition, a recording medium substrate used for a prism, an optical fiber, Products.

Claims (8)

A method for casting an optical material in which a polymerizable composition comprising a thioepoxy compound is put into a mold and polymerized,
The thioepoxy compound may be at least one compound selected from the group consisting of bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, 1,3- and 1,4-bis (β-epithiopropylthio) , 1,3- and 1,4-bis (? -Epithiopropylthiomethyl) cyclohexane, 2,5-bis (? -Epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane and 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) And at least one compound selected from the group consisting of
The water content of the polymerizable composition before polymerization is measured by Karl Fischer method to have a water content in the range of 100 to 2,500 ppm;
And adding a phosphoric acid ester compound as an inner mold agent to the polymerizable composition having a water content in the range of 100 to 2,500 ppm and then polymerizing the monomer. The method according to claim 1, wherein the polymerizable composition further comprises a polythiol compound. The method according to claim 2, wherein the polymerizable composition further comprises a polyisocyanate compound. The phosphoric acid ester compound according to claim 1, wherein the phosphoric acid ester compound is polyoxyethylene nonylphenol ether phosphate (5 mol% of ethylene oxide, 5 mol% of ethylene oxide, 80 mol% of 4 mol%, 10 mol% 5 mol% of polyoxyethylenenonylphenol), 10 wt% of polyoxyethylenenonylphenol, 3 wt% of ethylene oxide 9 mol, 80 wt% of 8 mol of ethylene oxide, 5 wt% of 9 mol of ethylene oxide, 6 mol% of 7 mol%, 6 wt% of 6 mol%), polyoxyethylene nonylphenol ether phosphate (3 mol% of ethylene oxide 13 mol, 12 mol% of 80 mol% 8 parts by weight of ethylene oxide, 3 parts by weight of 9 parts by weight, and 6 parts by weight of 4 parts by weight), polyoxyethylene nonylphenol ether phosphate (containing 3 parts by weight of ethylene oxide and 17 parts by weight of ethylene oxide, 79% by weight, 15% by mol, 10% by weight, 14% by mol and 4% by weight, respectively) and polyoxyethylene nonylphenol (5 parts by weight of ethylene oxide, 21 parts by weight of ethylene oxide, 78 parts by weight of 20 parts by weight, 7 parts by weight of 19 parts by weight, 6 parts by weight of 18 parts by weight and 4 parts by weight of 17 parts by weight, ). &Lt; / RTI &gt; The method according to claim 1,   The method according to any one of claims 1, 2, and 3, wherein the polymerizable composition further comprises an olefin compound as a reactive resin modifier.  A thioepoxy-based optical material obtained by casting polymerization according to any one of claims 1, 2 and 3. An optical lens made of the optical material of claim 6. The optical lens according to claim 7, wherein the optical lens is a spectacle lens or a polarizing lens.