KR20130069524A - Mold polymerization method for thioepoxy based optical material and the polymerizable composition - Google Patents

Abstract

PURPOSE: A mold-polymerization method of an optical material of thioepoxy series is provided to manufacture an optical material of thioepoxy series which is easy to separate from a mold and has an excellent face precision. CONSTITUTION: A mold-polymerization method of an optical material of thioepoxy series comprises a step performing polymerization after putting a polymerizable composition including thioepoxy compound into a mold. A water content of a polymerizable composition is 100-2,500 ppm. An internal release agent is added in a polymerizable composition before polymerization in advance. Moreover, a polymerizable composition for an optical material of thioepoxy series is a polymerizable composition including thioepoxy compound, has a water content of 100-2,500 ppm, and includes an internal release agent.

Description

Mold polymerization method for thioepoxy based optical material and its polymerizable composition

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a method for polymerizing a thioepoxy clock optical material and a polymerizable composition thereof, and more particularly, to a method for polymerizing a thioepoxy optical material with a good moldability and good mold release from a mold.

The thiourethane-based lens has the advantages of high refractive index and excellent impact strength, but there are disadvantages such as softness of the lens surface and central depression, and also a problem in that Abbe's number decreases rapidly as the refractive index increases. Korean Patent No. 10-0681218 proposes a thioepoxy plastic lens. The thioepoxy lens has an advantage of having a high refractive index and a high Abbe's number, but has a disadvantage of fragile lens. In order to solve this problem, 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 easy to separate from the mold after polymerization, in particular copolymerization, there is a problem that the surface accuracy is good even when the lens is broken well when separated.

Republic of Korea Patent Registration 10-0681218 Republic of Korea Patent Publication 10-0417985 Japanese Patent Laid-Open No. 11-352302

The present inventors have studied and tried various methods to improve the low releasability problem from the mold which appears when mold-polymerizing a polymerizable composition comprising a thioepoxy compound. As a result, the present inventors found that when the polymerizable composition contains an appropriate release agent such as a silicone-based surfactant or a phosphate ester compound, and the polymerizable composition contains adequate moisture, there is no damage during separation from the mold after polymerization and the surface precision is very good. . Even when no internal mold release agent is used or when the water content of the polymerizable composition is out of an appropriate range, the mold release property is not good, and the lens is broken when the mold is separated from the mold, and the detached lens has poor surface accuracy.

The present invention has been confirmed and completed. It is an object of the present invention to provide a mold polymerization method for a thioepoxy optical material having easy release from a mold and excellent surface precision, and a polymerizable composition therefor.

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,

In the mold polymerization method of the optical material which polymerizes the polymerizable composition containing a thioepoxy compound in a mold, and polymerizes,

The water content of the said polymerizable composition is 100-2,500 ppm, The mold polymerization method of the thioepoxy optical material characterized by the addition of the internal mold release agent before superposition | polymerization to the said polymerizable composition is provided.

In the present invention,

A polymerizable composition comprising a thioepoxy compound, which has a water content of 100 to 2500 ppm and contains an internal mold release agent, is provided with a polymerizable composition for a thioepoxy optical material.

In the present invention, there is provided an optical material obtained by polymerization by the above-described mold polymerization method and an optical lens made of the optical material. The optical lens particularly includes a spectacle lens or a polarizing lens.

According to the present invention, a thioepoxy optical material having easy releasing from a mold (glass mold type) after polymerization and excellent surface accuracy can be obtained. Since the mold polymerization method of the present invention improves the productivity of the lens due to the good deformability and the breakage rate is lowered, the yield can be improved, and the production cost can be greatly reduced while obtaining a high quality lens.

In the mold polymerization method of the thioepoxy optical material of the present invention, the water content of the polymerizable composition containing the thioepoxy compound is adjusted to 100 to 2500 ppm, and an internal mold release agent is added to the polymerizable composition before polymerization.

The thioepoxy group compounds include, for example, bis (2,3-ethiothiopropyl) sulfide, bis (2,3-ethiothio) disulfide, 1,3- and 1,4-bis (β-ethiothiopropylthio) cyclo Hexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, bis [4- (β-ethiothiopropylthio) cyclohexyl] methane, 2,2-bis [4- ( episulfide compounds having an alicyclic skeleton such as β-epithiopropylthio) cyclohexyl] propane and bis [4- (β-epithiopropylthio) 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.

In the mold polymerization method of the thioepoxy optical material of the present invention, the water content of the polymerizable composition containing the thioepoxy compound is set to 100 to 2500 ppm. The moisture content of the composition is measured to remove moisture to have a moisture content in the above range or to add a small amount of moisture to adjust the moisture content. Removal can be carried out by high vacuum, for example. When the water content of the polymerizable composition was less than 100 ppm, the demolition was not good even when the internal mold release agent was used, and the surface precision was bad even when the mold release was performed. Similarly, despite the use of an internal mold release agent, mold release property and surface precision were inferior even when the water content of the polymerizable composition exceeded 2,500 ppm. In addition, excessive moisture content of the polymerizable composition also had other negative effects such as bubble generation and whitening on the optical material obtained by polymerization.

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

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, 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 polyisocyanate compound included 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, 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, 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-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 used. In addition, as long as it is a compound having at least one isocyanate and / or isothiocyanate group, one kind or two or more kinds can be used, and in addition, 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.

As the internal mold release agent, a phosphate ester compound, a silicone-based surfactant, a fluorine-based surfactant, or the like may be used alone or in combination of two or more. The internal mold release agent is preferably included at 0.001 to 10% by weight in the polymerizable composition. As the internal mold release agent, a silicone surfactant or 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. Phosphoric acid ester compounds are, for example, methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, propyl phosphate, dipropyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, and octylic acid. Phosphate, dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, tridecanoic acid phosphate, bistridecanoic acid phosphate, etc., ethylene oxide or propylene oxide is added to aliphatic alcohol, There is a kind added. In particular, in the present invention, polyoxyethylene nonylphenol ether phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol added, 10% by weight of 3 mol added, 5% by weight of 1 mol added) ), Polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 mole of ethylene oxide, 80% by weight of 8 mole added, 5% by weight of 9 mole added, 6% by weight 7 mole added, 6 Mole added 6% by weight), polyoxyethylene nonylphenol ether phosphate (13% by weight of ethylene oxide added 3%, 12 moles added 80% by weight, 11 moles added 8% by weight, 9 moles 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 mol added 10 Weight%, 14 mol added 4 weight%, 13 mol added 4 weight%), polyoxyethylene nonylphenol ether phosphate (ethylene oxa Ethylene oxide, such as 5% by weight of 21 mole added, 76% by weight 20% added, 7% by weight 19% added, 6% by 18% added, 4% by weight added 17) One type or two types or more can be selected and used out of the phosphate ester compound which the propylene oxide added.

The polymerizable composition of the present invention may further include a reactive resin modifier for the purpose of adjusting impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties. 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, in the polymerizable composition of the present invention, 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, an inorganic pigment, a filler, and an adhesion improving agent according to a known molding method. And the like may be further added.

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 absorbent, any known ultraviolet absorbent usable 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-toluidine) anthraquinone [1-hydroxy-4- (p-toluidine) 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. You can choose.

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-dibutylperazine, 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-2methylimidazole, 1-benzyl 2-methylimidazole, 1-ethyl-4-methylimidazole, 1-ethyl-2-ethyl-4-methylol, N-methylpyrrole, N-ethylpyrrole, N-butylpyrrole, N-methyl Pyrroline, N-ethylpyrroline, N-butylpyrroline, pyrimidine, purine, quinoline, isoquinoline, N-methylcarbazole, N-ethylcarbazole and N-butylcarbazole 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. 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, 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 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 manufactured in Example by the following physical property test method are shown in Table 1 below.

1) Moisture Content: The moisture content (ppm) was measured by Karl Fischer solution by automatic moisture measurement in which the water metering device of the 860KF thermoprep was set in a Metrohm moisture meter.

2) Surface precision: The mercury arc lamp with no damage during release separation and surface condition of USHIO USH-102D was examined to determine whether there was any noticeable damage. Good release of the mold and no damage was indicated by ○ (good surface precision), and when difficult to release the mold or surface damage was indicated by × (bad surface precision).

3) Refractive index (nE) and Abbe number: It was measured at 20 ° C using an Abbe refractometer, which is an IT and DR-M4 model 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 and 1,2-bis [(2-mercaptoethyl) thio]-as a thiol compound 20 parts by weight of 3-mercaptopropane, 8-PENPP [polyoxyethylenenonylphenol ethofate (phosphate ester) added as 9% of ethylene oxide, 80% by weight of 8 mol, 9 mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight)] 0.2 part by weight, 0.1 part by weight of tetrabutylphosphonium bromide, 0.1 part by weight of triphenylphosphine, organic The dye HTAQ (20 ppm), PRD (10 ppm), and the ultraviolet absorber HOPBT 1.5g were mixed and dissolved at 20 degreeC, and it was made into a homogeneous solution. The water content of the resin composition was 145 ppm, and the mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with the 1 micrometer PTFE filter, and injected into the mold mold which consists 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 end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical property of obtained resin was refractive index (nE) 1.664 and Abbe's number 36. The state dissolved before injection into the mold was visually observed, and after confirming the surface precision after demolding, there was no abnormality, no whitening was observed, and it was confirmed that a resin of stable quality was obtained. The evaluation results are shown in Table 1 below.

EXAMPLES 2-12

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

Comparative Example 1

Except that 8-PENPP which is a phosphate ester is not added as an internal mold release agent, it was carried out according to the composition described in Table 1 below in the same manner as in Example 1. Even after cooling after the polymerization, the copolymer lens of the thioepoxy compound, the isocyanate compound, and the thiol compound remained attached without being released from the glass lens model.

[Comparative Examples 2-9]

Compositions and lenses were prepared according to the compositions shown in Table 1 below in the same manner as in Example 1, and the evaluation results are shown in Table 1 below. In Table 1, parts mean parts by weight.

As shown in Table 1, the lens of the present invention obtained in Examples 1 to 12 had good demoulding properties, excellent surface precision, and good yield.

<Abbreviation>

EDPS: bis (2,3- epithiopropyl) sulfide

EDPDS: Bis (2,3-Ethiothiopropyl) 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-Ethofate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 7 moles added) Weight%, 6 mol added 6 weight%)

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

20-PENPP: polyoxyethylene nonyl phenol ether phosphate (21% addition of 5% by weight of ethylene oxide, 20% addition of 76% by weight, 19% addition of 7% by weight, 18% addition of 6% by weight , 17 mol added 4% by weight)

KF-353A: Brand Name-Silicone Surfactant of Shin-Etsu Silicone Internal Molding Agent

DOP: Dioctylate Phosphate

IDP: Isodecyl Phosphate

According to the present invention, it is possible to manufacture a thioepoxy optical material having easy demoulding and excellent surface precision. The thioepoxy optical material having excellent surface precision 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)

In the mold polymerization method of the optical material which polymerizes the polymerizable composition containing a thioepoxy compound in a mold, and polymerizes,
The water content of the said polymerizable composition is 100-2,500 ppm, The internal mold release agent is previously added to the said polymerizable composition before superposition | polymerization, The casting polymerization method of the thioepoxy optical material characterized by the above-mentioned. The thioepoxy group compound according to claim 1, wherein the thioepoxy group compound is bis (2,3-ethiothio) 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 polymerizing a thioepoxy clock optical material, characterized in that it is one or two or more compounds selected from the group consisting of thiopropylthio) propane. The method of claim 1, wherein the polymerizable composition further comprises a polythiol compound. The method of claim 3, wherein the polymerizable composition further comprises a polyisocyanate compound. The method according to any one of claims 1 to 4, wherein the internal mold releasing agent is a silicone-based surfactant or a phosphate ester compound. The method of claim 5, wherein the phosphate ester compound, polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mol ethylene oxide added, 80% by weight 4 mol added, 10% by weight 3 mol added, 1 mole added 5% by weight), polyoxyethylenenonylphenol ethofate (3% by weight 9 mole 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), polyoxyethylene nonylphenol ether phosphate (3% by weight, 17% by weight of ethylene oxide) 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent), and polyoxyethylenenonylphenol Le phosphate (21% added ethylene oxide 5%, 20 mol added 76%, 19 mol added 7%, 18 mol added 6%, 17 mol added 4% by weight And at least one member selected from the group consisting of   The method of any one of claims 1 to 4, wherein the polymerizable composition further comprises an olefin compound as a reactive resin modifier. A polymerizable composition comprising a thioepoxy compound, wherein the polymerizable composition for a thioepoxy optical material is characterized by having a water content of 100 to 2500 ppm and containing an internal mold release agent. The polymerizable composition for a thioepoxy clock optical material according to claim 8, further comprising a polythiol compound. The polymerizable composition for a thioepoxy clock optical material according to claim 9, further comprising a polyisocyanate compound. The polymerizable composition for a thioepoxy optical material according to any one of claims 8 to 10, wherein the internal mold release agent is a silicone surfactant or a phosphate ester compound. A thioepoxy clock optical material obtained by casting polymerization by the method according to any one of claims 1 to 4. An optical lens made of the optical material of claim 12. The optical lens of claim 13, wherein the optical lens is an eyeglass lens or a polarizing lens.