KR20200013560A - Composition for episulfide based optical material having high refractive index and method of preparing the optical material - Google Patents

Abstract

The purpose of the present invention is to solve problems of striae and transparency deterioration caused by imbalanced polymerization exhibited in an episulfide-based optical material having a refractive index of 1.67 or more or a sulfur-containing episulfide-based optical material having a ultrahigh refractive index of 1.71 or more. To this end, a composition for episulfide-based optical material according to the present invention comprises 0.01 to 5 wt% of a polymerization controlling agent having a mass ratio of dimethyltin dichloride and monomethyltin trichloride of 96.5/3.5-99.9/0.1 to control polymerization rate in a composition for optical material comprising an episulfide compound, a polythiol compound, and a polymerization catalyst. The composition for episulfide-based optical material according to the present invention can obtain a high quality episulfide-based optical material having a high refractive index free from striae or transparency deterioration, and can increase productivity by solving the imbalanced polymerization.

Description

Composition for episulfide based optical material and high refractive index and method of preparing the optical material

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to episulfide-based high refractive optical materials, and in particular to the preparation of the composition for episulfide-based optical materials and optical materials which solves the polymerization imbalance problem in episulfide-based ultra high refractive optical materials containing 1.67 or more or 1.71 or more. It is about a method.

Plastic lenses are light, impact resistant and easy to color, and in recent years, plastic lenses have been used in most eyeglass lenses. Plastic eyeglass lenses have been developed in the direction of increasing light weight, high transparency, low yellowness, heat resistance, light resistance and strength.

Korean Patent No. 10-0681218 proposes an episulfide plastic lens. Episulfide-based lenses have excellent refractive index and high Abbe number, but have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, and productivity. In order to solve this problem, a method of copolymerizing two kinds of resins having different properties, that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound together is disclosed in Korean Patent Registration No. 10-0417985 Proposed 11-352302 or the like.

Recently, in order to further increase the refractive index in the episulfide-based lens containing the episulfide compound to achieve ultra-high refractive index and high Abbe number of 1.71 or more, an optical material composition comprising an inorganic compound such as sulfur atom or selenium atom in the episulfide compound This has been proposed (Japanese Laid-Open Patent Publication 2001-2783).

However, episulfide-based high refractive lenses of 1.67 or more have a problem in that heat resistance and light resistance are poor and polymerization imbalance often appears.

Republic of Korea Patent Registration 10-0417985 Japanese Laid-Open Patent Publication No. 11-352302 Japanese Laid-Open Patent Publication 2001-2783 Republic of Korea Patent Application Publication No. 10-2014-0122721

Episulfide-based ultra-high refractive optical lenses containing 1.67 or more or 1.71 or more often exhibit problems such as striae and reduced transparency, which are caused by polymerization imbalance, which greatly reduces lens quality and reduces productivity. .

The present invention is to solve this problem by controlling the polymerization rate, in the present invention, the mass ratio of dimethyltin dichloride and monomethyltin trichloride is 96.5 / 3.5 ~ 99.9 / 0.1 polymerization regulators of episulfide-based high refractive optical lens By using together with a polymerization catalyst during polymerization, it is intended to solve the problem of striae and transparency caused by polymerization imbalance.

In order to achieve the above object, in the present invention,

In an optical material composition comprising an episulfide compound, a polythiol compound, and a polymerization catalyst, a polymerization regulator having a mass ratio of 96.5 / 3.5 to 99.9 / 0.1 of dimethyltin dichloride and monomethyltin trichloride in order to control the polymerization rate is prepared. It provides a composition for episulfide-based optical material containing 0.01 to 5% by weight in weight.

The polymerization catalyst is preferably one or more selected from amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, the polymerization catalyst is at least one selected from quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds. More preferably, the polymerization catalyst is a quaternary phosphonium salt and includes any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide.

The episulfide optical material composition may further include sulfur.

The episulfide optical material composition may further include a polyisocyanate compound.

The present invention also provides a method for producing an episulfide-based high refractive optical material having a refractive index of 1.67 or higher, comprising polymerizing the composition for an episulfide-based optical material, and an episulfide-based high refractive optical material having a refractive index of 1.67 or more obtained by polymerization in this way. . Further, the method for producing an episulfide-based ultrahigh refractive optical material having a refractive index of 1.71 to 1.77, comprising polymerizing the composition for an episulfide optical material containing sulfur further, and an episulfide having a refractive index of 1.71 to 1.77 obtained by polymerization in this manner. Provides ultra-high refractive optical materials.

In the present invention, by using a polymerization regulator having a mass ratio of 96.5 / 3.5 to 99.9 / 0.1 of dimethyltin dichloride and monomethyltin trichloride together with a polymerization catalyst in the polymerization of episulfide-based high refractive optical lens, 1.71 or more including 1.71 containing sulfur Polymerization imbalance and the resulting striae and transparency deterioration in the episulfide-based high refractive optical lens can be solved. According to the present invention, it is possible to obtain a high quality episulfide-based high refractive optical material without striae or transparency deterioration, and to improve productivity by eliminating polymerization imbalance.

In the present invention, "high refractive index" is meant to include up to 1.71 or more ultra-high refractive index unless otherwise specified.

The composition for episulfide-based optical materials of the present invention, dimethyl tin dichloride (Me ₂ SnCl ₂ ) and monomethyl tin trichloride (MeSnCl ₃ ) for controlling the polymerization rate during the polymerization together with the episulfide compound, polythiol compound and polymerization catalyst ) And a polymerization regulator having a mass ratio of 96.5 / 3.5 to 99.9 / 0.1.

The episulfide compound is a compound having an episulfide group, for example, bis (2,3-ethiothio) sulfide, bis (2,3-ethiothio) disulfide, 2,3-epidithiopropyl (2 , 3-epithiopropyl) disulfide, 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1, 3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-ethiothiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropyl Episulfide compounds having an alicyclic skeleton such as thio) cyclohexyl] propane and bis [4- (β-epithiopropylthio) cyclohexyl] sulfide; 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropyl Thio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] sulphine, 4,4-bis (β-ethiothiopropylthio) Episulfide compounds having an aromatic skeleton such as 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-epithiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, bis- (β-ethiothio And an episulfide compound having an aliphatic skeleton such as propyl) sulfide. In addition, as the episulfide compound, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-modified compounds with polythiol may be used.

As said episulfide compound, Preferably, bis (2, 3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epithiopropyl) ) Sulfide, 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1,4- Bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl One or more kinds of) -1,4-dithiane, 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane can be used.

The said polythiol compound is not specifically limited, If it is a compound which has at least 1 or more thiol groups, 1 type (s) or 2 or more types can be mixed and used for it. Preferably, bis (2-mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane -1-thiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (2- (2- Mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, bis (2- (2-mercaptoethylthio) -3 Mercaptopropyl) disulfide, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio- Propane-1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mer Capto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9 , 12-tetratiatetradecane-1,14-di Ol, (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-trithiaundane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -Trithiaundane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Vis Taerythritol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl One selected from thio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane The above can be used. In addition, if it is a compound which has one or more thiol groups, it can use 1 type or in mixture of 2 or more types. Moreover, the polymerization modified body obtained by prepolymerization with an isocyanate, an episulfide compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used.

As the polythiol compound, particularly preferably, at least one other polythiol compound may be mixed with bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

The polymerization catalyst is preferably one or more selected from amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, at least one selected from quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds can be used. As the quaternary ammonium salt, for example, tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzyl ammonium chloride, 1-n-dodecylpyridinium chloride or the like can be used. . As the quaternary phosphonium salt, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide or the like can be used, for example. Triphenylphosphine etc. can be used as a phosphine compound. Especially preferably, the polymerization catalyst is a quaternary phosphonium salt and contains any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. These polymerization catalysts can be used individually or in mixture of 2 or more types.

When the composition comprising the episulfide compound and the polythiol compound is polymerized and cured using the polymerization catalyst, the reaction proceeds rapidly and the viscosity of the composition rapidly increases. In the present invention, in order to solve this problem, a polymerization regulator having a mass ratio of dimethyltin dichloride and monomethyltin trichloride of 96.5 / 3.5 to 99.9 / 0.1 is used. This polymerization regulator can suppress the sudden rise in viscosity by adjusting the reaction rate. The mass ratio of dimethyltin dichloride and monomethyltin trichloride can be controlled by distilling the raw material containing dimethyltin dichloride and monomethyltin trichloride at a constant mass ratio at 0.01 to 40torr and 30 to 150 ° C for a certain time. have. Thus, the polymerization regulator adjusted in the mass ratio of 96.5 / 3.5 to 99.9 / 0.1 is preferably used in 0.01 to 5% by weight of the total weight of the composition for an optical material. By using this polymerization regulator, the polymerization rate can be adjusted to suppress a sudden increase in viscosity, and as a result, the polymerization yield is increased and bubbles are also eliminated.

The composition for an optical material of the present invention may further include sulfur. If more sulfur is included, the refractive index may be set to ultra high refractive index of 1.71 or more. The sulfur contained in the composition is preferably at least 98% pure. If less than 98%, the transparency of the optical material may be degraded due to the influence of impurities. The purity of sulfur is more preferably 99.0% or more, particularly preferably 99.5% or more. Commercially available sulfur is classified by the difference in shape or purification method, and there are fine powder sulfur, colloidal sulfur, precipitated sulfur, crystal sulfur, sublimed sulfur and the like. In the present invention, any sulfur can be used as long as the purity is 98% or higher. Preferably, fine powder of fine particles that can be easily dissolved may be used in preparing the composition for an optical material. The content of sulfur in the composition is preferably 1 to 40% by weight in the total weight of the composition for the optical material, more preferably 2 to 30% by weight, most preferably 3 to 22% by weight.

The composition for an optical material of the present invention may further include a polyisocyanate compound. The polyisocyanate compound is not particularly limited and a compound having at least one isocyanate group and / or isothiocyanate group can be used. For example, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, hexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocy Aliphatic isocyanate compounds such as anatoethyl) 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, diphenyl diisocyanate, toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate , Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, hexahydrobenzenediisocyanate, Aromatic isocyanate compounds such as hexahydrodiphenylmethane-4,4'-diisocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, 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-isocy Anatomethylbenzene) 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 Sulfur-containing aromatics such as -5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate Isocyanate compounds; 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 compounds selected from 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 isonate group and / or isothiocyanate group, one kind or two or more kinds may be used. In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer-type modified compounds with polyhydric alcohols or thiols, carbodiimide modified products, urea modified products, biuret modified compounds or the like Dimerization, trimerization reaction products, etc. can also be used. As polyisocyanate compound, Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI), xylylene diisocyanate (XDI), 3,8-bis (iso Cyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (Isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (iso One or more selected from cyanatomethyl) bicyclo [2,2,1] heptane can be used.

The composition for an optical material of the present invention may further include an internal release agent. Preferably, the internal mold release agent may include a phosphate ester compound. The phosphate ester compound is prepared by adding 2-3 moles of an alcohol compound to phosphorus pentoside (P ₂ O ₅ ), and various types of phosphate ester compounds can be obtained according to 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 composition of the present invention is an internal mold release agent, preferably 4-PENPP [polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mol ethylene oxide, 80% by weight 4 mol added, 3 mol addition 10% by weight, 1 mole added 5% by weight)], 8-PENPP (polyoxyethylenenonylphenol ether phosphate (3% by weight 9 mole ethylene oxide added, 80% by weight 8 mole added 9) Mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight) , 12 mole added 80%, 11 mole added 8%, 9 mole added 3%, 4 mole added 6% by weight)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 mole added with ethylene oxide, 79% by weight with 16 mole added, 10% by weight with 15 mole added, 4% by weight with 14 mole added, 4% by weight with 13 mole added)] , 20-PENPP [polyoxyethylenenonylphenolether phosphate (21% addition of 6% by weight of ethylene oxide, 20% addition of 76% by weight, 19% addition by 7% by weight, 18 parts by weight added by 6% %, 17 mole added 5% by weight)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 mole% with 5 mole of propylene oxide, 80 mole% with 4 mole added, 3 mole added) 10 weight%, 1 mol added 5 weight%)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 weight% added 9 mol propylene oxide, 80 weight% added 8 mol, 9 mol added 5 wt% added, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 wt% propylene oxide added, 12 mole added 80% by weight, 11 mole added 8% by weight, 9 mole added 3% by weight, 4 mole added 6% by weight)], 16-PPNPP [polyoxypropylene nonylphenol Ether phosphate (3% by weight of 17 moles of propylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 4% by weight of 14 moles added, 4% by weight 13 moles added) ], 20-PPNPP [Polyoxypropylenenonylphenol ether phosphate (6% by weight of 21 mol propylene oxide, 76% by weight 20 mol added, 7% by weight 19 mol added, 18 mol added 6 Wt%, 17 mol added 5 wt%)] and Zelec UN ^™ are used. Various substituents including the halogen compound substituents of such phosphate ester compounds can be used for the same purpose.

The composition for an optical material of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of adjusting 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 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 di Acrylate, 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 Dimethac Latex, neopentylglycol diacrylate, neopentylglycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2 , 2-bis (4- hydroxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2, 2-bis (4-methoxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-hydroxyethoxyphenyl) methane, 1,1-bis ( 4-Methoxyethoxyphenyl) methane, 1,1-bis (4-acryoxydiethoxyphenyl) methane, 1,1-bis (4-methoxydiethoxyphenyl) methane, dimetholtricyclodecane Acrylate, trimetholpropane triacrylate, trimetholpropane trimethacrylate, glycerol diacrylate, Liserol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meth) acrylate compounds, such as xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether and di Allyl compounds such as allyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallylcarbonate, and styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, divinylbenzene, 3 And vinyl compounds such as 9-divinylspirobi (m-dioxane); It is not limited to these exemplified compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

The composition for an optical material of this invention may further contain a ultraviolet absorber as needed. The ultraviolet absorber is used to improve the light resistance of the optical material and to block ultraviolet rays, and known ultraviolet absorbers used in the optical material may be used without limitation. For example, ethyl-2-cyano-3,3-diphenylacrylate, 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-3'-t-butyl-5'-methylphenyl) -5 having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -Chloro-2H-benzotriazole and 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole and the like can be used. Such an ultraviolet absorber can block 400 nm or more when used in an amount of 0.6 g or more with respect to 100 g of the composition for an optical material.

In addition, the composition for an optical material of the present invention may further include various additives such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a coloring inhibitor, an organic dye, a filler, and an adhesion improving agent, as necessary.

The composition for an optical material of the present invention having the above composition preferably has a liquid viscosity of 500 cps or less (20 ° C.) or less and 1.67 to 1.70 when the solid phase refractive index (Ne) after polymerization does not include sulfur. 1.71-1.77

An episulfide optical material is obtained by casting a polymerized composition. In more detail, First, the polymeric composition of this invention is inject | poured between the shaping | molding mold hold | maintained with the gasket or the tape. Under the present circumstances, it is preferable to perform the defoaming process under reduced pressure, the filtration process of pressurization, reduced pressure, etc. according to the physical property calculated | required at the time of the obtained optical material in many cases. The polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and the amount of the catalyst used, the shape of the mold, and the like, but are carried out over a period of 1 to 50 hours at a temperature of about -50 to 130 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 130 ° C. and to cure in 1 to 48 hours.

The episulfide compound optical material obtained by curing may be subjected to annealing or the like as necessary. Treatment temperature is normally performed between 50-130 degreeC, and it is preferable to carry out at 90-120 degreeC.

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, and 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 spectacle lenses, camera lenses, light emitting diodes, and optical elements.

The episulfide optical material obtained according to the present invention has excellent hard adhesion unlike general episulfide optical materials, and enables hard coating without a primer, very easy coating, and excellent coating stability. The plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides as necessary. As the coating layer, a primer layer, a hard coating layer, an antireflection film layer, an antifogging coat layer, an antifouling layer, a water repellent layer, and the like can all be used. These coating layers may be used alone or in a plurality of coating layers. In addition, when forming a coating layer on both surfaces, it is possible to form the same coating layer in each surface, or to form a different coating layer.

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 more specifically, and the scope of the present invention is not limited by these examples.

Synthesis Example 1

A polymerization regulator having a content of dimethyltin dichloride of 94% by mass and a content of monomethyltintrichloride of 6% by mass was distilled at 0.01 to 40torr for 30 minutes at 30 to 150 ° C. for 2 days to monomethyl to dimethyltin dichloride. The polymerization regulator whose content of tin trichloride is 0.3 mass%, 0.9 mass%, 1.5 mass%, 2.0 mass%, 2.6 mass%, 3.3 mass%, 3.3%, 5.0 mass% was obtained. The content% of the polymerization regulator was measured by gas chromatography.

Synthesis Example 2

Bis (3-chloro-2-hydroxy-propyl) sulfide (1070.48 g, 4.88 mol), 1,300 g of toluene and 800 g of methanol were added to a 10 liter reaction vessel, and the reaction temperature was adjusted to 30 ° C while stirring. When it reached 25 ℃ NaOH (50% (aq), 783.08g, 9.78 mol) was slowly added dropwise and the reaction temperature was added while the reaction was maintained at 35 ~ 37 ℃. The dropwise addition was within 1 hour, and the ripening was carried out at 37 ° C. for 30 minutes. After ripening, 2,000 g of toluene was added, stirred for about 10 minutes, the layers were separated, the water layer was removed, and the supernatant organic solution was washed twice with water. After removing water to the maximum, 400 g of methanol was further added to the resulting solution, followed by stirring. Thiourea (1117.65 g, 14.68 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8 DEG C, and the reaction was carried out at 18 DEG C for 18 hours. Termination of the reaction was confirmed by HPLC and the starting material disappeared. When the 2,3-epoxypropyl (2,3-epiopropyl) sulfide compound is present in the GC analysis with an integral content of 5% or less, the reaction is terminated and stirring is stopped. It stopped. The organic layer obtained by layer separation was washed five times with water, and the organic solvent was removed under reduced pressure to obtain 608 g of a bis (2,3-ethiothio) sulfide compound.

Example 1

The reactor was decompressed to 1.0 torr or lower and the external temperature was adjusted to 54 ° C. While stirring the reactor, 80 g of bis (2,3-ethiothiopropyl) sulfide compound was added, 15.5 g of sulfur, 0.8 g of UV 31 UV filter, organic dyes HTAQ (88 ppm), and PRD (30 ppm) were added thereto for 30 minutes. After defoaming under reduced pressure, 0.75 g of 2-mercapto-1-methylimidazole was added and stirred for 1 hour. After cooling to 30 ° C. of 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 3.92 g of bis (2-mercaptoethyl) sulfide, 1.0 g of dimethyltin dichloride and monomethyltin trichloride 0.5 g of a polymerization regulator having a mass ratio of 99.7 / 0.3, 0.2 g of tetrabutylphosphonium bromide, and 8-PENPP [polyoxyethylenenonyl phenol ester phosphate (9% by weight of 9 mol of ethylene oxide added) which is a phosphate ester as an internal release agent. Mole added 80% by weight, 9 mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight) 0.08 g of a mixed solution is placed in a reactor and the resin composition for an optical lens After making the optical lens was prepared in the following manner and measured the physical properties of the optical lens.

(1) the resin composition for optical lenses prepared as described above was degassed under stirring at 43 ° C. for 1 hour under reduced pressure, cooled to 30 ° C., filtered, and further subjected to reduced pressure defoaming for 5 minutes, and then assembled with a polyester adhesive tape. Into a glass mold.

(2) The glass mold into which the resin composition for spectacle lens was injected was cured by heating in a forced circulation oven from 30 ° C to 110 ° C over 20 hours, and then cooled to 70 ° C to remove the glass mold to obtain a lens. The resulting lens was processed to a diameter of 72 mm and then ultrasonically washed with an alkaline aqueous washing solution, followed by annealing at 100 ° C. for 2 hours. The physical properties of the lens thus obtained were measured in the following manner, and the results are shown in Table 1 .

Property test method

The physical properties of the optical lens manufactured in Example were measured by the following experimental method, and the results are shown in Table 1 .

1. Streaking (polymerization imbalance): 100 lenses of 80 mm in diameter and +11 D in degrees are prepared, and the Schlieren method is used under the Mercury Arc Lamp of USHIO USH-10D. Observed. If no stria is observed among 100 lenses, mark '◎'. If stria is observed from 1 to 5 lenses out of 100, mark '○'. When observed, it is indicated by 'Δ', and when striae are observed in 10 or more lenses out of 100 lenses, it is indicated by '×'.

2. Transparency: 100 lenses were visually observed under the Mercury Arc Lamp, a USHIO USH-10D. If one or more of the lenses were found to be hazy, marked with ◎, and two or three were found. If it is displayed as '○', and if four or more are found, it is indicated as '×'.

Examples 2-6

In the same manner as in Example 1 , an optical lens was manufactured according to the mass ratio of the polymerization regulator dimethyltin chloride and monomethyltin trichloride described in Table 1 , and the physical properties thereof were tested. The results are shown in Table 1 .

Comparative Examples 1 and 2

Of Example 1, but in the same way, using a polymerization regulator such as the mass ratio of dimethyl tin dichloride as monomethyl tin trichloride as described in Table 1 to prepare an optical lens, was a test of the physical properties, the results in Table 1 It is described in.

division Content of Dimethyl Tin Dichloride in Polymerization Regulator (%) Content of Monomethyltin Trichloride in Polymerization Regulators (%) Me ₂ SnCl ₂ / MeSnCl ₃ (mass% ratio) McLee Transparency Example 1 99.7 0.3 99.7 / 0.3 ◎ ◎ Example 2 99.1 0.9 99.1 / 0.9 ◎ ◎ Example 3 98.5 1.5 98.5 / 1.5 ○ ○ Example 4 98.0 2 98.0 / 2.0 ○ ○ Example 5 97.4 2.6 97.4 / 2.6 ○ ○ Example 6 96.7 3.3 96.7 / 3.3 Δ ○ Comparative Example 1 95.0 5.0 95.0 / 5.0 × × Comparative Example 2 94.0 6.0 94.0 / 6.0 × ×

The episulfide-based high and ultra-high refractive optical materials obtained according to the present invention are high quality lenses without striae and have good transparency, and can be usefully used for lenses for corrective sunglasses, fashion lenses, discoloration lenses, camera lenses, and optical devices. have.

Claims (8)

In the composition for an optical material comprising an episulfide compound, a polythiol compound and a polymerization catalyst, a polymerization regulator having a mass ratio of 96.5 / 3.5 to 99.9 / 0.1 of dimethyltin dichloride and monomethyltin trichloride in order to control the polymerization rate is used. An episulfide optical composition comprising 0.01 to 5% by weight in weight. The method of claim 1,
The polymerization catalyst is an episulfide optical composition, characterized in that at least one selected from amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. . The method of claim 1,
The polymerization catalyst is an episulfide optical composition, characterized in that at least one selected from quaternary ammonium salts, quaternary phosphonium salts, phosphine compounds. The method of claim 3,
The polymerization catalyst is a quaternary phosphonium salt, and comprises any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. The method according to any one of claims 1 to 4,
Composition for optical materials further comprising sulfur. The method according to any one of claims 1 to 4,
An optical material composition further comprising a polyisocyanate compound. A method for producing an episulfide-based high refractive optical material having a refractive index of 1.67 or more, comprising polymerizing the composition of any one of claims 1 to 4. A method for producing an episulfide-based ultrahigh refractive optical material having a refractive index of 1.71 to 1.77, comprising polymerizing the composition of claim 5.