KR20210105221A - Heat stabilizer for episulfide-based optical material, composition for optical material and manufacturing method of optical material - Google Patents

Abstract

The present invention relates to a heat stabilizer for an episulfide-based optical material which can solve the heat stability problem occurring in an episulfide-based highly refractive optical material, a composition for an episulfide-based optical material including the same, and a method for manufacturing an optical material. The present invention provides a heat stabilizer for an episulfide-based optical material, including an epislufide compound represented by chemical formula 1 as an active ingredient. The heat stabilizer according to the present invention can solve the problem of degradation of heat stability occurring in the episulfide-based highly refractive optical lens and can improve the transparency of the lens. In addition, according to the present invention, it is possible to obtain an episulfide-based optical material having high heat stability and good color through a simple method of incorporating a small amount of the heat stabilizer to the composition for an episulfide-based optical material before polymerization.

Description

Heat stabilizer for episulfide-based optical material, composition for optical material using same, and method of manufacturing optical material {Heat stabilizer for episulfide-based optical material, composition for optical material and manufacturing method of optical material}

The present invention relates to an episulfide-based high refractive optical material, and in particular, a thermal stabilizer for an episulfide-based optical material that can solve the thermal stability problem appearing in an episulfide-based high refractive optical material, and a composition and optical for an episulfide-based optical material comprising the same It relates to a method of manufacturing the material.

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

Korean Patent No. 10-0681218 proposes an episulfide-based plastic lens. Episulfide-based lenses have a high refractive index and high Abbe's number, but have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, productivity, and the like. In order to solve this problem, a method of copolymerizing two types of resins having different properties, that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound therewith, is disclosed in Korean Patent No. 10-0417985, Japanese Patent Laid-Open Patent Publication No. It was proposed in Hei 11-352302, etc.

In recent years, in order to further increase the refractive index in an episulfide-based lens containing an episulfide compound to achieve an ultra-high refractive index of 1.71 or more and a high Abbe's number, a composition for an optical material containing an inorganic compound such as a sulfur atom or a selenium atom in the episulfide compound has been proposed (Japanese Patent Application Laid-Open No. 2001-2783).

However, the episulfide-based high refractive index lens has a problem of poor thermal stability, and often a problem of color (transparency).

Republic of Korea Patent Publication No. 10-0681218 Republic of Korea Patent Publication No. 10-0417985 Japanese Unexamined Patent Publication (Kokai) Hei 11-352302 Japanese Patent Laid-Open No. 2001-2783

An object of the present invention is to provide a thermal stabilizer capable of solving the thermal stability degradation problem that appears in an episulfide-based high refractive optical lens.

In addition, an object of the present invention is to provide a composition for an optical material and an optical material having improved transparency and solving the thermal stability problem by including the thermal stabilizer in the composition for an optical material for episulfide.

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

Provided is a thermal stabilizer for an episulfide-based optical material comprising an episulfide compound represented by Formula 1 below as an active ingredient.

In addition, in the present invention,

An episulfide compound represented by Formula 2 below;

An episulfide compound represented by Formula 1 below, and

Provided is a composition for an episulfide-based optical material comprising a polymerization catalyst.

[Formula 1]

[Formula 2]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.)

The composition for an episulfide-based optical material may further include any one or more of sulfur, a polythiol compound, and a polyisocyanate compound.

The polymerization catalyst is preferably at least one selected from an amine, a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, a secondary iodonium salt, and a phosphine compound. More preferably, it is at least one selected from a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound.

The episulfide compound represented by Formula 1 is preferably included in an amount of 0.001 to 5% by weight in the Singgi composition.

In addition, the present invention provides a method for producing an episulfide-based high refractive optical material, comprising polymerizing the composition for an episulfide-based optical material.

The thermal stabilizer containing the episulfide compound of Formula 1 provided in the present invention can improve the transparency of the lens while solving the thermal stability degradation problem that occurs in the episulfide-based high refractive optical lens. In the present invention, a high-quality episulfide-based optical material having good thermal stability and color can be obtained by a simple method of polymerization by including a small amount of this thermal stabilizer in the composition for an episulfide-based optical material.

In the present invention, unless specifically limited, 'high refractive index' includes all of 1.67 or more to 1.71 or more, commonly referred to as ultra-high refractive index. Although not limited, the refractive index is usually in the range of 1.67 to 1.77.

The thermal stabilizer for an episulfide-based optical material of the present invention includes an episulfide compound represented by the following Chemical Formula 1 as an active ingredient.

By using the episulfide compound represented by Formula 1 in a small amount in the composition for an episulfide-based optical material, thermal stability of the composition and the optical material obtained by polymerization thereof can be improved, and transparency can also be improved. The episulfide compound represented by Formula 1 is sometimes generated during the synthesis of the episulfide compound represented by Formula 2, and as a result of further research, there is a large difference in thermal stability during polymerization when this compound is included and when it is not. found out that there is When the compound of Formula 1 was included in a certain range, thermal stability was significantly better and the color was also better than when it was not included at all or included in a certain range or more.

The episulfide compound represented by Formula 1 is synthesized separately and added in a small amount to the composition for optical materials prior to polymerization, or by controlling the amount generated and incorporated in the synthesis process of the episulfide compound represented by Formula 2, in the composition for optical materials. It can be included in an appropriate amount. Preferably, the compound of Formula 1 may be used in an amount of 0.001 to 5% by weight in the composition for an episulfide-based optical material, more preferably 0.005 to 3% by weight, and particularly preferably 0.01 to 1.2 It can be used by including it in weight %.

The composition for an episulfide-based optical material of the present invention,

It includes an episulfide compound represented by Formula 2 below, an episulfide compound represented by Formula 1 above, and a polymerization catalyst.

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.)

The episulfide compound represented by Formula 2 is a main component of the composition for an episulfide-based optical material. The episulfide compound of Formula 2 is, for example, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis(β-epithio). Propylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[ episulfide compounds having an alicyclic skeleton such as 4-(β-epithiopropylthio)cyclohexyl]propane and bis[4-(β-epithiopropylthio)cyclohexyl]sulfide; 1,3 and 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropyl) Thio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfine, 4,4-bis(β-epithiopropylthio) ) episulfide compounds having an aromatic skeleton such as biphenyl; 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis(β-epithiopropylthioethyl)-1,4-dithiane and 2,3,5-tri(β-epithiopropylthioethyl)-1,4-dithiane sulfide compounds; 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, 1,2-bis[(2-β-epithiopropylthioethyl)thio]- 3-(β-epithiopropylthio)propane, tetrakis(β-epithiopropylthiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, bis-(β-epithio and an episulfide compound having an aliphatic skeleton such as propyl) sulfide. In addition, the episulfide compound may be 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, or a prepolymer-type modified product with polythiol.

The episulfide compound represented by the formula (2) is preferably bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis(β-epi). thiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropyl thio) propane.

The episulfide compound represented by Formula 2 may further include a 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound. The 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound may be incorporated in particular during the preparation of the episulfide compound. The 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound increases the polymerizability of the composition to facilitate polymerization. Preferably, in the episulfide compound, the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is included in an amount of 0.3 to 15% by weight, more preferably 0.5 to 13% by weight. When the composition for an episulfide-based optical material of the present invention contains sulfur, the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is particularly preferably used in an amount of 0.5 to 5% by weight in the episulfide compound. Included.

The polythiol compound is not particularly limited, and as long as it is a compound having at least one thiol group, one type or a mixture of two or more types may be used. 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 Propanyl)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-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-pentathiaheptane-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-dimer Capto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol Ethritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hex Sakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4, At least one selected from 6-bis(mercaptomethylthio)-1,3-dithiane and 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane may be used. In addition, as long as it is a compound having one or more thiol groups, one type or a mixture of two or more types may be used. In addition, a polymerization modified product obtained by prepolymerization of the polythiol compound with an isocyanate, an episulfide compound, a thietane compound, or a compound having an unsaturated bond as a resin modifier may also be used.

As the polythiol compound, particularly preferably, bis(2-mercaptoethyl)sulfide or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or another polythiol compound is added thereto to 1 It can be used by mixing more than one species.

The polythiol compound may preferably be included in 1 to 15% by weight of the composition for an optical material, more preferably 3 to 13% by weight, and still more preferably 5 to 11% by weight.

The polyisocyanate compound is not particularly limited, and a compound having at least one isocyanate group and/or an isothiocyanate group may 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 dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane 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, trimethylbenzene triisocyanate, benzene tri 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, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, etc. aromatic isocyanate compounds; 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-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-bis( One or two or more compounds selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl)-2-methyl-1,3-dithiorane may be used. In addition, as long as it is a compound having at least one isocyanate group and/or isothiocyanate group, one type or a mixture of two or more types may be used. In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, polyhydric alcohols or thiols of these isocyanate compounds, carbodiimide modified products, urea modified products, and biuret modified products Alternatively, dimerization or trimerization reaction products may also be used.

As an isocyanate compound, Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), norborane diisocyanate (NBDI), 3 ,8-bis(isocyanatomethyl)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 At least one selected from among ,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane may be used.

The isocyanate compound is included in an amount of 0.01 to 20% by weight of the composition for an optical material, and more preferably, may be included in an amount of 0.05 to 10% by weight.

The composition for an episulfide-based optical material may further include sulfur. When sulfur is included, the refractive index may be increased to an ultra-high refractive index of 1.71 or more. The sulfur included in the composition is preferably 98% or more pure. In the case of less than 98%, the transparency of the optical material may be deteriorated due to the influence of impurities. The purity of the sulfur is more preferably 99.0% or more, and particularly preferably 99.5% or more. Generally, commercially available sulfur is classified by differences in shape or refining method, and there are fine powder, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur, and the like. In the present invention, any sulfur can be used as long as the purity is 98% or more. Preferably, fine powder of fine particles that are easily dissolved may be used in the preparation of the composition for an optical material. In the composition for an optical material, sulfur is preferably contained in an amount of 1 to 40 wt%, more preferably 2 to 30 wt%, and most preferably 3 to 22 wt%.

The polymerization catalyst is preferably at least one selected from among amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, at least one selected from a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound may be used. As the quaternary ammonium salt, for example, tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, etc. can be used. . As a quaternary phosphonium salt, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, etc. can be used, for example. As the phosphine compound, triphenylphosphine or the like can be used. Particularly preferably, the polymerization catalyst is a quaternary phosphonium salt, and includes 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.

The composition for an episulfide-based optical material may further include a tin halogen compound as a polymerization regulator. The tin halogen compound is preferably any one of dibutyl tin dichloride and dimethyl tin dichloride, or one in which monomethyl tin trichloride is included in a small amount may be used. More preferably, monomethyl tin trichloride may be included in an amount of 0.1 to 3.5 wt%. When the composition for an episulfide-based optical material is polymerized and cured, the reaction proceeds rapidly, so that the viscosity of the composition may be rapidly increased. Since the polymerization regulator can suppress a sudden increase in viscosity by controlling the reaction rate, the use of the polymerization regulator can solve this problem. The polymerization regulator is preferably used in an amount of 0.01 to 5% by weight based on the total weight of the composition for an optical material. By using this polymerization regulator, the polymerization rate can be controlled to suppress a sudden increase in viscosity, and as a result, the polymerization yield can be increased, and the occurrence of bubbles can also be suppressed.

When sulfur is included in the composition for an episulfide-based optical material, it is preferable to polymerize after forming the prepolymer. have. Said alkylimidazole particularly preferably comprises 2-mercapto-1-methylimidazole. 2-Mercapto-1-methylimidazole is preferably used with a purity of 98% or more. The alkylimidazole may be included in the composition for an optical material, preferably in an amount of 0.01 to 5% by weight, more preferably in an amount of 0.1 to 3% by weight, and still more preferably in an amount of 0.15 to 2% by weight.

The composition for an optical material of the present invention may further include an internal release agent. Preferably, it may include a phosphate ester compound as an internal mold release agent. Phosphoric acid ester compound is _{prepared by adding 2 to 3 moles of an alcohol compound to phosphorus pentoxide (P 2} O ₅ ). At this time, various types of phosphoric acid ester compounds can be obtained depending on the type of alcohol used. Representative examples are types 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 phosphoric acid ester compound to which ethylene oxide or propylene oxide is added is included in the polymerizable composition of the present invention as an internal mold release agent, it is preferable to obtain an optical material having good mold release properties and excellent quality. The composition of the present invention is an internal mold release agent, preferably 4-PENPP [polyoxyethylene nonylphenol ether phosphate (5 wt% of ethylene oxide added by 5 moles, 80 wt% of 4 moles added, 3 moles added) 10 wt% of ethylene oxide, 5 wt% of added 1 mole)], 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added), 9 5 wt% of molar addition, 6 wt% of 7 molar addition, 6 wt% of 6 molar addition)], 12-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 13 moles) , 80 wt% of 12 moles added, 8 wt% of 11 moles added, 3 wt% of 9 moles added, 6 wt% of 4 moles added)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 17 moles, 79 wt% of added 16 moles, 10 wt% of 15 moles added, 4 wt% of 14 moles added, 4 wt% of 13 moles added)] , 20-PENPP [polyoxyethylene nonylphenol ether phosphate (6 wt% of ethylene oxide added by 21 moles, 76 wt% of 20 moles added, 7 wt% of 19 moles added, 6 wt% of 18 moles added) %, 17 mol added 5 wt %)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 mol propylene oxide added 5 wt %, 4 mol added 80 wt %, 3 mol added 10% by weight, 5% by weight added by 1 mole)], 8-PPNPP [Polyoxypropylene nonylphenol ether phosphate (3% by weight of propylene oxide added by 9 moles, 80% by weight added by 8 moles) 5% by weight added, 6% by weight added by 7 moles, 6% by weight added by 6 moles)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 weight% by adding 13 moles of propylene oxide) 80 wt% of 12 moles added, 8 wt% of 11 moles added, 3 wt% of 9 moles added, 6 wt% of 4 moles added)], 16-PPNPP [polyoxypropylene nonylphenol ether phosphate ( 3 wt% of propylene oxide added by 17 moles , 16 mol added 79 wt %, 15 mol added 10 wt %, 14 mol added 4 wt %, 13 mol added 4 wt %)], 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (6 wt% of propylene oxide added by 21 moles, 76% by weight of 20 moles added, 7 wt% of 19 moles added, 6 wt% of 18 moles added, 5 wt% of 17 moles added)] and Zelec UN ^TM Use at least one selected from among. Various substituents including halogen compound substituents of the phosphoric acid ester compound can also 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 controlling impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties of the optical material. Examples of the olefin compound that can be added as the resin modifier include 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 dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylic Late, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis(4-methoxyethoxyphenyl)propane, 2, 2-bis(4-acroxydiethoxyphenyl)propane, 2,2-bis(4-methoxydiethoxyphenyl)propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis( 4-Acrythoxyphenyl)methane, 1,1-bis(4-methacrythoxyphenyl)methane, 1,1-bis(4-hydroxydiethoxyphenyl)methane, 1,1-bis(4 -Methoxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithioldiacrylate, (meth)acrylate compounds such as silylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl Allyl compounds such as tere, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate and diethylene glycol bisallyl carbonate and styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinyl and vinyl compounds such as benzene and 3,9-divinyl spirobi (m-dioxane). However, usable compounds are not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

The composition for an optical material of the present invention may further include an ultraviolet absorber, if necessary. The ultraviolet absorber is used for improving the light resistance of the optical material and blocking ultraviolet rays, and a known ultraviolet absorber used for 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'-dimethoxybenzophenone and the like may be used alone or in combination of two or more.

Preferably, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5 which has good ultraviolet absorption ability in the wavelength range of 400 nm or less and has good solubility in the composition of this invention -Chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, etc. can be used. Such a UV 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 optical materials.

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 color inhibitor, an organic dye, a filler, and an adhesion improver, if necessary.

The composition for an optical material of the present invention composed as described above preferably has a liquidus viscosity of 500 cps (20° C.) or less, and a solid state refractive index (Ne) after polymerization of 1.67 to 1.70 when sulfur is not included, and sulfur is included. It ranges from 1.71 to 1.77.

An episulfide-based optical material can be obtained by subjecting the composition composition as above to casting polymerization. A more detailed description is as follows. First, the polymerizable composition of the present invention is injected between the molding molds held by gaskets or tapes. At this time, in many cases, it is preferable to perform a degassing treatment under reduced pressure or a filtration treatment such as pressurization or reduced pressure depending on the physical properties required for the obtained optical material and if necessary. The polymerization conditions are not limited because conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, and the like, but it is carried out at a temperature of about -50 to 130° C. for 1 to 50 hours. In some cases, it is preferable to maintain or gradually increase the temperature in a temperature range of 10 to 130° C. and harden in 1 to 48 hours.

The episulfide-based optical material obtained by curing may be subjected to treatment such as annealing if necessary. The treatment temperature is usually 50 to 130°C, and preferably 90 to 120°C.

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

The episulfide-based optical material obtained according to the present invention has excellent hard adhesion and can be hard coated without a primer, can be easily coated, and has excellent coating stability. In addition, the plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides, if necessary. As the coating layer, a primer layer, a hard coating layer, an anti-reflection film layer, an anti-fogging coating film layer, an anti-fouling layer, a water-repellent layer, etc. are all possible. In addition, when the coating layer is formed on both surfaces, it is possible to form the same coating layer on each surface or to form different coating layers.

Hereinafter, the present invention will be described in more detail through specific examples. However, these examples are only for explaining the present invention in more detail, and the scope of the present invention is not limited by these examples.

[ Synthesis example One]

1-amino-3-(thiirane-2- Lylmethylthio ) propane-2- thiol synthesis

In a 1 liter reaction vessel, 100 g (1.27 mol) of bis (2,3-epithiopropyl) sulfide and 1000 g of chloroform are put, and the internal temperature of the reactor is adjusted to 5°C while stirring. When the internal temperature of the reactor reaches around 5°C, 435.2 g of 25% aqueous ammonia is adjusted to the external temperature of 30°C, and the ammonia gas flowing over while blowing nitrogen is dried with a desiccant (Molecular Sieve 4A) and slowly bis(2,3-epitio) Propyl) was passed through the sulfide solution and reacted. The reaction was terminated when the reaction of the product did not proceed any further in HPLC analysis. After removing the solvent, the obtained product was developed with a solvent of chloroform and cyclohexane, and purified by a silica gel column to obtain 52 g of 1-amino-3-(thiiran-2-ylmethylthio)propane-2-thiol.

¹ H NMR (CDCl ₃ ): 1.4 ppm (2H), 1.5 ppm (1H), 2.0-2.3 ppm (2H), 2.4-2.6 ppm (3H), 2.7-2.9 ppm (4H), 3.0 ppm (1H)

¹³ C NMR (CDCl ₃ ): 26 ppm (1C), 33 ppm (1C), 39 ppm (1C), 41 ppm (1C), 43 ppm (1C), 50 ppm (1C)

MS (EI-MS method): 195.02 (m/z)

[Example 1]

The reactor was pressure-reduced to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring the reactor, 79.99 g of bis(2,3-epithiopropyl)sulfide compound and 15.5 g of sulfur, UV31 (2-(2H-benzotriazol-2-yl-4-(1,1,3, 3-tetramethylbutyl)phenol) 0.8 g, organic dye HTAQ (88 ppm) and PRD (30 ppm) were added, and after degassing under reduced pressure for 30 minutes, 0.75 g of 2-mercapto-1-methylimidazole was added, After stirring for 1 hour, it was cooled to 30° C., 2,3-bis(2-mercaptoethylthio)propane-1-thiol 3.92g, bis(2-mercaptoethyl)sulfide 1g, dibutyltindichloride 0.5g , 0.3 g of tetrabutylphosphonium bromide and 8-PENPP [polyoxyethyrennonyl phenol ester phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added, 5 wt% of added, 6 wt% of added 7 moles, 6 wt% of added 6 moles) 0.08 g of the mixed solution was put into the reactor to make a resin composition for optical lenses, and then the optical lenses were prepared as follows. was prepared and the physical properties of the optical lens were measured.

Optical lens manufacturing

(1) The resin composition for optical lenses prepared as above was defoamed at 43° C. under 400pa reduced pressure while stirring for 1 hour, cooled to 30° C., and 1-amino-3-(thiiran-2-ylmethylthio)propane 0.005 g of -2-thiol (1-amino-3-(thiran-2-ylmethyl thio)propane-2-thiol) was added, stirred for 15 minutes to make a homogeneous solution, filtered through a 1㎛ PTFE filter, and then reduced pressure Defoaming was further performed for 5 minutes, and it was injected into a glass mold assembled with a polyester adhesive tape.

(2) The glass mold in which the resin composition for spectacle lenses was injected was heat-hardened in a forced circulation oven from 30° C. to 110° C. over 20 hours, cooled to 70° C., and detached from the glass mold to obtain a lens. The obtained lens was processed to have a diameter of 72 mm, ultrasonically washed in an alkaline aqueous cleaning solution, and then annealed at 100° C. for 2 hours. The physical properties were measured in the following way, and the results are shown in Table 1.

Physical property test method

The physical properties of the optical lenses prepared in Examples were measured by the following experimental method, and the results are shown in Table 1 .

(1) thermal stability

After maintaining the cured optical lens at 100°C for 3 hours, if the APHA value does not change by 2 or more in the measurement of color change, it is indicated by “◎”, and when the APHA value changes to 3 to 6, it is indicated by “○”, and APHA When the value changed to 7 or more, it was indicated by "x".

(2) Transparency: 100 lenses having a diameter of 80 mm and a dot of +11 D were manufactured, and observed under a Mercury Arc Lamp of USHIO USH-10D. Those in which no haze was observed among 100 lenses were marked with "○", and those in which haze was observed in at least one of 100 lenses were marked with "x".

Examples 2-8

An optical lens was manufactured according to the composition shown in Table 1 in the same manner as in Example 1 , and physical properties were tested, and the results are shown in Table 1 .

comparative example 1-2

An optical lens was manufactured according to the composition shown in Table 1 in the same manner as in Example 1 , and physical properties were tested, and the results are shown in Table 1 .

division A B A/B mass ratio Transparency thermal stability Example One 79.995 0.005 79.995/0.005 ○ ○ Example 2 79.98 0.02 79.98/0.02 ○ ◎ Example 3 79.9 0.1 79.9/0.1 ○ ◎ Example 4 79.4 0.6 79.4/0.6 ○ ◎ Example 5 79.0 1.0 79.0/1.0 ○ ◎ Example 6 78.5 1.5 78.5/1.5 ○ ○ Example 7 77.9 2.1 77.9/2.1 ○ ○ Example 8 77.2 2.8 77.2/2.8 ○ ○ comparative example One 80 0 80/0 ○ × comparative example 2 76.5 3.5 76.5/3.5 × ×

A: Bis (2,3-epithiopropyl) sulfide (Bis (2,3-epithiopropyl) sulfide)

B: 1-amino-3-(thiiran-2-ylmethylthio)propane-2-thiol (1-Amino-3-(thiiran-2-ylmethylthio)propane-2-thiol)

The thermal stabilizer of the present invention can be widely used to increase thermal stability and transparency of episulfide-based optical materials used in various fields. In addition, the episulfide-based optical material obtained according to the present invention is a high-quality, high-refractive lens with excellent thermal stability and good color, and is usefully used for corrective sunglasses, fashion lenses, color-changing lenses, camera lenses, lenses for optical devices, etc. can be

Claims (7)

A thermal stabilizer for an episulfide-based optical material comprising an episulfide compound represented by the following formula (1) as an active ingredient.
[Formula 1]

An episulfide compound represented by Formula 2 below;
An episulfide compound represented by Formula 1 below, and
A composition for an episulfide-based optical material comprising a polymerization catalyst.
[Formula 1]

[Formula 2]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) 3. The method of claim 2,
A composition for an episulfide-based optical material further comprising at least one of sulfur, a polythiol compound, and a polyisocyanate compound. 3. The method of claim 2,
The polymerization catalyst is an amine, a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, a secondary iodonium salt, a composition for an episulfide-based optical material, characterized in that at least one selected from a phosphine compound . 5. The method of claim 4,
The polymerization catalyst is a quaternary phosphonium salt, and the composition for an episulfide-based optical material comprises any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. 6. The method according to any one of claims 2 to 5,
A composition for an episulfide-based optical material comprising the episulfide compound represented by Formula 1 in an amount of 0.001 to 5% by weight. A method for producing an episulfide-based high refractive optical material, comprising polymerizing the composition of any one of claims 2 to 5.