KR20200033423A - Composition for episulfide based optical material having high refractive index and method of preparing the optical material - Google Patents

Abstract

The present invention relates to a composition for an episulfide-based high-refractive-index optical material, which is capable of addressing striae formation, and transparency and color reduction that arise in an episulfide-based high-refractive-index optical material; and a method of producing the same. In the present invention, provided is a composition for an episulfide-based optical material, comprising an episulfide compound represented by chemical formula 1, a polythiol compound, and a polymerization catalyst, wherein the total content of toluene remaining in the compound is 3-5,000 ppm. In the present invention, by controlling the total content of toluene remaining in the compound, the problems associated with striae formation, and color and transparency reduction can be addressed by a relatively simple method, and a good-quality episulfide-based high-refractive-index optical material can be produced. In the chemical formula 1, m is an integer of 0-4, and n is an integer of 0-2.

Description

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

The present invention relates to an episulfide-based high-refractive optical material, and more particularly, to a composition for an episulfide-based high-refractive optical material and a method for manufacturing the optical material capable of improving the occurrence of pulsation, transparency and color deterioration in the episulfide-based high refractive optical material will be.

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

Korean Patent Registration No. 10-0681218 proposes an episulfide plastic lens. Episulfide-based lenses have high refractive index and excellent properties with high Abbe's number, but there are 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 of different properties, that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound together, Korean Patent Registration No. 10-0417985, Japanese Patent Publication It was proposed in Hei 11-352302.

Recently, in order to further increase the refractive index of the episulfide-based lens containing an episulfide compound to achieve an ultra-high refractive index of 1.71 or more and a high Abbe number, an optical material composition containing an inorganic compound such as a sulfur atom or selenium atom in the episulfide compound This was proposed (Japanese Patent Publication No. 2001-2783).

However, in episulfide-based high-refractive lenses of 1.67 or more, there is a problem that often shows a streak and poor color and transparency.

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

In episulfide-based high-refractive-optical lenses, there is often a problem of pulse generation, transparency, and color deterioration, which degrades the quality of the lens, reduces productivity, and interferes with commercialization.

In the process of synthesizing the episulfide compound, toluene is used in a large amount for layer separation into an organic layer. In addition, toluene is also used in the synthesis of other compounds included in the composition for episulfide-based optical materials such as polythiol compounds. The toluene used in this way is removed through washing and vacuum removal. The present inventors believe that toluene, which was thought to have been sufficiently removed through such a conventional removal process, can actually be contained in a composition for an optical material by retaining a significant portion of the compound, and toluene contained in this process produces a streak and degrades color and transparency when manufacturing the optical material. It was found to affect the. In the present invention, the total content of toluene contained in the composition for an optical material remaining in the synthesis process of an episulfide compound, etc., is a cause of unintended pulsation or a decrease in color and transparency, which is often unknown in episulfide-based high refractive optical lenses. It aims to clarify and solve this problem.

The ultimate object of the present invention is to solve the problem of deterioration of McLina, color and transparency often seen in episulfide-based high refractive optical lenses, and to provide a high-quality composition for episulfide-based high refractive optical materials and a method of manufacturing the optical material.

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

Provided as a composition comprising an episulfide compound represented by Formula 1 below, a polythiol compound, and a polymerization catalyst, the total content of toluene remaining in the compound is 3 to 5,000 ppm, providing a composition for an episulfide-based optical material do.

[Formula 1]

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

In addition, in the present invention,

In the method for producing an optical material, comprising the step of polymerizing the composition for an optical material comprising an episulfide compound, a polythiol compound and a polymerization catalyst represented by Formula 1 below,

Further comprising the step of adjusting the total content of toluene in the range of 3 ~ 5,000ppm by checking the content of toluene remaining in the compound, in order to prevent the occurrence of pulsation and color and transparency of the optical material, episulfide-based high refractive optical Provides a method of manufacturing a material.

[Formula 1]

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

According to the present invention, by controlling the total content of toluene contained in the composition for an optical material remaining in the synthesis process of an episulfide compound or the like, it is possible to solve the problem of deterioration of McLina, color and transparency often seen in episulfide-based high refractive optical lenses. In a relatively simple way, it is possible to provide a high-quality episulfide-based high refractive optical material without increasing production costs.

In the present invention, 'high refraction' is meant to include everything from 1.67 or higher to 1.71 or higher, commonly referred to as ultra high refraction, unless otherwise specified. Without being limited, the refractive index ranges from 1.67 to 1.77.

The composition for an episulfide-based optical material of the present invention includes an episulfide compound represented by Formula 1 below, a polythiol compound, and a polymerization catalyst, and the total amount of toluene remaining in all the compounds including the episulfide compound and the polythiol compound The content is 3 ~ 5,000ppm.

(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 1 is a main component of the composition for episulfide-based optical materials of the present invention. The episulfide compound represented by Chemical Formula 1 is, for example, bis (2,3-ethiothio) sulfide, bis (2,3-ethiothiopropyl) disulfide, 2,3-epoxypropyl (2,3- Epithiopropyl) disulfide, 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 and 1,4 -Bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] Episulfide compounds having an alicyclic skeleton such as propane and bis [4- (β-ethiothiopropylthio) cyclohexyl] sulfide; 1,3 and 1,4-bis (β-ethiothiothiothio) benzene, bis [4- (β-ethiothiothio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropyl) Thio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] sulfin, 4,4-bis (β-ethiothiopropylthio ) 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, 2,3,5-tri (β-epithiopropylthioethyl) -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-epithiopropylthiomethyl) propane, bis- (β-epithio Profile) It may be an episulfide compound having an aliphatic skeleton such as sulfide. In addition, a halogen substituent such as a chlorine substituent or a bromine substituent of a compound having an episulfide group as an episulfide compound, an alkyl substituent, an alkoxy substituent, a prepolymer modified with a nitro substituent or polythiol, and the like can also be used.

The episulfide compound, preferably, bis (2,3-ethiothio) sulphide, bis (2,3-ethiothiopropyl) disulfide, 2,3-epoxypropyl (2,3-ethiothiopropyl) sulfide , 2,3-epoxypropyl (2,3-ethiothiopropyl) disulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1,4-bis (β- Epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1, One or more of 4-dithiane and 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane can be used.

In the process of synthesizing the episulfide compound, toluene is used in a large amount for layer separation into an organic layer, and the toluene used in this way may not be sufficiently removed even through a conventional removal process such as washing and vacuum decompression. In the present invention, the total content of toluene remaining in all compounds included in the composition including the episulfide compound is limited to a certain range. The content of toluene remaining in the episulfide compound is preferably 1 to 4,000 ppm, more preferably 1 to 2,400 ppm, and even more preferably 1 to 1,900 ppm.

The polythiol compound is not particularly limited, and any compound having at least one thiol group may be used alone or in combination of two or more. 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-di All, (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-dimercapto-3,6,9-trithiaundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -Trithiaundecan, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Bis Taerythritol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl 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, any compound having one or more thiol groups may be used alone or in combination of two or more. Also, it is possible to use a polymerization modified product obtained by prepolymerization with an isocyanate or episulfide compound, a thiethane compound, or a compound having an unsaturated bond as a resin modifier in a polythiol compound.

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

The polythiol may preferably be contained in 1 to 15% by weight in the composition for the optical material, more preferably 4 to 13% by weight, even more preferably 5 to 11% by weight.

In the process of synthesizing the polythiol compound, toluene is used in a large amount for layer separation into an organic layer, etc. The toluene used in this way may not be sufficiently removed even through a general removal process such as washing and vacuum decompression. The content of toluene remaining in the polythiol compound is preferably 0 to 500 ppm, and more preferably 0 to 100 ppm.

As described above, in the composition of the present invention, the content of toluene remaining in all the compounds including the episulfide compound and the polythiol compound is controlled. The total content of toluene remaining in the compound is preferably 3 to 5,000 ppm, more preferably 3 to 2,500 ppm, and even more preferably 3 to 2,000 ppm.

In the process of synthesizing episulfide compounds and polythiol compounds, toluene is used in a large amount for layer separation into an organic layer, and the toluene used in this way is a significant amount of the compound obtained even through a general removal process such as washing and vacuum decompression. May remain. The residual toluene is included in the composition for an optical material of the present invention together with a compound, and when the content of toluene exceeds a certain range, it causes a streak and a decrease in color and transparency when manufacturing the optical material. In the present invention, the total content of toluene contained in the composition is controlled within the above range by controlling the content of toluene remaining in each compound, thereby eliminating the cause of bleeding and deterioration in color and transparency.

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, one or more selected from quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds 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 the quaternary phosphonium salt, for example, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, or the like can be used. As the phosphine compound, triphenylphosphine or the like can be used. Particularly preferably, the polymerization catalyst is a quaternary phosphonium salt, and includes any of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. These polymerization catalysts may be used alone or in combination of two or more.

The episulfide-based optical material composition may further include sulfur. When sulfur is further included, the refractive index can be increased to an ultra-high refractive index of 1.71 or more. The sulfur contained in the composition is preferably 98% or more in purity. In the case of less than 98%, the transparency of the optical material may be reduced due to impurities. The purity of sulfur is more preferably 99.0% or more, and particularly preferably 99.5% or more. Generally, commercially available sulfur is classified according to a difference in shape or purification method, and there are finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, and sublimation sulfur. In the present invention, any sulfur can be used as long as the purity is 98% or more. Preferably, when preparing a composition for an optical material, it is possible to use fine powder of fine particles that are easily soluble. The content of sulfur in the composition is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, and most preferably 3 to 22% by weight of the total weight of the composition for optical materials.

The episulfide-based optical material composition 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 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-undecantriisocyanate, 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, cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane isocyanate; Xylylenediisocyanate (XDI), bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis ( Isocyanatomethyl) diphenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, 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 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-dithioran, 4,5-bis (isocyanatomethyl) -1,3-dithiolan, 4,5-bis ( One or two or more compounds selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolan can be used. In addition, if the compound has at least one isocyanate group and / or isothiocyanate group, one or two or more of them may be used in combination. In addition, these isocyanate compounds include halogen substituents such as chlorine and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, and burette-modified products. Alternatively, dimerization or trimerization reaction products may also be used. As a polyisocyanate compound, preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane 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 episulfide-based optical materials may further include a tin-halogen compound as a polymerization regulator. The tin halogen compound may be preferably one of dibutyl tin dichloride and dimethyl tin dichloride, or a small amount of monomethyl tin trichloride contained therein. More preferably, monomethyl tin trichloride may be included in an amount of 0.1 to 3.5% by weight. When the composition for episulfide-based optical materials is polymerized and cured, the reaction proceeds rapidly, so that the viscosity of the composition may rapidly increase. Since the polymerization regulator can suppress a rapid 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 of the total weight of the composition for an optical material. With the use of this polymerization regulator, not only the rapid increase in viscosity can be suppressed by controlling the polymerization rate, but as a result, the polymerization yield is increased, and the generation of bubbles is also eliminated.

When sulfur is included in the composition for the episulfide-based optical material, it is preferable to form a prepolymer and then polymerize. At this time, in order to facilitate the formation of the prepolymer, an alkylimidazole may be further included as a polymerization regulator. have. The alkylimidazole particularly preferably includes 2-mercapto-1-methylimidazole. 2-Mercapto-1-methylimidazole is preferably used having a purity of 98% or more. The optical material composition may preferably contain 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, and even more preferably 0.15 to 1% by weight.

The composition for an optical material of the present invention may further include an internal release agent. Preferably, a phosphoric acid ester compound may be included as the internal release agent. Phosphoric acid ester compounds are prepared by adding 2 to 3 mol of alcohol compounds 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. Typical examples are those in which ethylene oxide or propylene oxide is added to an aliphatic alcohol or ethylene oxide or propylene oxide is added to a nonylphenol group. When the phosphoric acid ester compound to which the ethylene oxide or propylene oxide is added is included in the polymerizable composition of the present invention as an internal release agent, it is preferable because an optical material having good mold release properties and excellent quality can be obtained. The composition of the present invention is an internal release agent, preferably 4-PENPP [polyoxyethylenenonylphenol ether phosphate (5% by weight of 5 moles of ethylene oxide added, 80% by weight of 4 moles added, 80% by weight added) 10% by weight, 5% by weight of 1 mole added), 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 9) 5% by weight of molar addition, 6% by weight of 7 mole addition, 6% by weight of 6 mole addition)], 12-PENPP [polyoxyethylenenonylphenol 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, 6% by weight of 4 moles added)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate] (Ethylene oxide added 17 mol 3 wt%, 16 mol added 79 wt%, 15 mol added 10 wt%, 14 mol added 4 wt%, 13 mol added 4 wt%)] , 20-PENPP [Polyoxyethylene Nonylphenol Ether Phosphate (6% by weight of 21 moles of ethylene oxide added, 76% by weight of 20 moles added, 7% by weight of 19 moles added, 6% of 18 moles added) %, 17 mol added 5 wt%)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 wt% propylene oxide added 5 mol, 4 wt% added 80 wt%, 3 mol added) 10% by weight, 5% by weight of 1 mol added), 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3% by weight of 9 mol of propylene oxide added, 80% by weight of 8 mol added, 9 mol) 5 wt% added, 7 mol added 6 wt%, 6 mol added 6 wt%), 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 mol% propylene oxide 13 mol added), 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%), 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 of 13 moles added) ], 20-PPNPP [Polyoxypropylene nonylphenol ether phosphate (6 weight% of 21 mol of propylene oxide added, 76 weight% of 20 mol added, 7 weight% of 19 mol added, 18 mol added 6) Weight percent, 17 mol added 5 weight percent)] and Zelec UN ^TM One or more selected from among them is used. Various substituents such as 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 adjusting the impact resistance, specific gravity and monomer viscosity, etc. in order to improve the 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, phenoxyethyl 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 Rate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2 , 2-bis (4-acoxyethoxyphenyl) propane, 2,2-bis (4-methacoxyethoxyphenyl) propane, 2,2-bis (4-acoxydiethoxyphenyl) propane, 2, 2-bis (4-methacryloxyethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acoxyethoxyphenyl) methane, 1,1-bis ( 4-methoxyethoxyphenyl) methane, 1,1-bis (4-acoxydiethoxyphenyl) methane, 1,1-bis (4-methacryoxyethoxyphenyl) methane, dimethyroltricyclodecanedi Acrylate, trimethyrolpropane triacrylate, trimethyrolpropane trimethacrylate, glycerol diacrylate, Riserol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meth) acrylate compounds such as xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether, di Allyl compounds such as allyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallyl carbonate, and styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3 , 9-divinyl spiro ratio (m-dioxane), and other vinyl compounds. 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 the present invention may further include an ultraviolet absorber as needed. The ultraviolet absorber is used to improve light resistance of the optical material and block ultraviolet light, and a known ultraviolet absorber used in the optical material can 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 having good ultraviolet absorbing ability in a wavelength range of 400 nm or less and good solubility in the composition of the present invention. -Chloro-2H-benzotriazole and 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole can be used. When such an ultraviolet absorber is used in an amount of 0.6 g or more with respect to 100 g of an optical material composition, it is possible to block 400 nm or more.

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, an anti-coloring agent, an organic dye, a filler, and an adhesion improver, if necessary.

For the compounds further included in the composition of the present invention as described above, by controlling the content of toluene remaining in each compound, the total content of toluene contained in the composition is controlled within the above range.

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

Method of manufacturing an episulfide-based high refractive optical material of the present invention,

Comprising the step of polymerizing the composition for an optical material comprising an episulfide compound, a polythiol compound and a polymerization catalyst represented by Formula 1 below,

In order to prevent the occurrence of pulsation and color and transparency of the optical material, further comprising the step of adjusting the total content of toluene in the range of 3 to 5,000 ppm by checking the content of toluene remaining in the compound.

Redundant description of each configuration is omitted.

When the composition composed as above is mold-polymerized, an episulfide-based optical material can be obtained. The details are as follows. First, the polymerizable composition of the present invention is injected between a molding mold held with a gasket or a tape. At this time, it is often desirable to perform defoaming under reduced pressure, filtration treatment such as pressurization or reduced pressure, etc., depending on the physical properties required for the obtained optical material and, if necessary. The polymerization conditions are not limited since the conditions vary greatly depending on the polymerizable composition, the type and amount of the catalyst, the shape of the mold, and the like, but are 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 raise the temperature in the temperature range of 10 to 130 ° C, and to cure in 1 to 48 hours.

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

Since the optical material of the present invention can be obtained as a molded body of various shapes by changing the mold during mold 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 element such as a spectacle lens, a camera lens, a light emitting diode, and an optical element.

The episulfide-based optical material obtained according to the present invention is excellent in hard adhesion, and thus a hard coating is possible without a primer, coating is very easy, and stability of the coating is also excellent. 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 antireflection coating layer, an anti-fog coating layer, an anti-pollution layer, a water repellent layer, and the like can all be used, and these coating layers may be used alone or in multiple layers. In addition, when forming a coating layer on both sides, it is possible to form the same coating layer on each side, or to form different coating layers.

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

[Synthesis Example 1]

Bis (3-chloro-2-hydroxy-propyl) sulfide (1070.48g, 4.88 mol), toluene 1300g, and methanol 800g were placed in a 10 liter reaction vessel, and the reaction temperature was adjusted to 30 ° C while stirring. When reaching 25 ℃ NaOH (50% (aq), 783.08g, 9.78 mol) was slowly added dropwise and reacted while dropping while maintaining the reaction temperature at 35-37 ℃. The dropwise addition was within 1 hour, aging was performed at 37 ° C. for 30 minutes, and after aging, 2000 g of toluene was added and stirred for about 10 minutes, and the layer was separated to remove the water layer, and the organic solution, which is the supernatant, was washed twice with water. After removing water as much as possible, 400 g of methanol was further added to the obtained solution and stirred. Thiourea (1117.65 g, 14.68 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8 ° C, and the reaction was reacted at 18 ° C for 18 hours. Termination of the reaction was confirmed by HPLC, the starting material disappeared, and when the 2,3-epoxypropyl (2,3-ethiothiopropyl) sulfide compound had an integral content of 5% or less in GC analysis, the reaction was terminated and stirred. Stopped. The organic layer obtained by layer separation was washed 5 times with water, and the organic solvent was removed under high vacuum pressure to obtain 610 g of bis (2,3-ethiothiopropyl) sulfide compound having a toluene balance of 3 ppm.

[ Synthetic example  2]

Toluene content shown in Table 1 was added to the bis (2,3-ethiothio) sulfide compound having a toluene content of 3 ppm obtained in Synthesis Example 1 toluene content of 100 ppm, 500 ppm, 890 ppm, 1700 ppm, 2500 ppm, 3600 ppm, 4800 ppm, 6000 ppm , 10000pmm episulfide compound was prepared. The toluene content was obtained by measuring GC chromatography.

[Example 1]

The reactor was decompressed to 1.0 torr or less, and the external temperature was adjusted to 54 ° C. While stirring the reactor, 80 g of bis (2,3-ethiothio) sulfide compound having a toluene content of 3 ppm was added, 15.5 g of sulfur, 0.8 31 of UV blocking agent, HTAQ (88 ppm) and PRD (30 ppm) of organic dye were added. After defoaming under reduced pressure for 30 minutes, 0.75 g of 2-mercapto-1-methylimidazole was added and stirred for 1 hour. Subsequently, the mixture was cooled to 30 ° C., and 3.92 g of 2,3-bis (2-mercaptoethylthio) propane-1-thiol with a toluene content of 0.1 ppm, and bis (2-mercaptoethyl) with a toluene content of 0.1 ppm. ) 1 g of sulfide, 0.5 g of dibutyltin dichloride, 0.2 g of tetrabutylphosphonium bromide, and 8-PENPP [polyoxyethrenonyl phenol ester phosphate (3% by weight with 9 mol of ethylene oxide added), 8 as phosphoric acid ester as an internal release agent. 80% by weight of the molar addition, 5% by weight of the 9 mole addition, 6% by weight of the 7 mole addition, 6% by weight of the 6 mole addition) 0.08 g of a mixed solution was added to the reactor, and the resin composition for optical lenses was added. After making and manufacturing an optical lens in the following manner, the physical properties of the optical lens were measured.

(1) The resin composition for optical lenses prepared as above was defoamed while stirring at 43 ° C. under reduced pressure for 1 hour, cooled to 30 ° C. and filtered, and then degassed under reduced pressure for 5 minutes, and assembled with polyester adhesive tape. The molded glass mold.

(2) The glass mold in which the resin composition for spectacle lenses was injected was heated and cured in a forced circulation oven over 30 hours from 30 ° C to 110 ° C, and then cooled to 70 ° C to detach the glass mold to obtain a lens. The obtained lens was processed to a diameter of 72 mm and then ultrasonically washed in an alkaline aqueous washing solution, followed by annealing at 100 ° C. for 2 hours. Table 1 shows the results of measuring the physical properties in the following manner.

Property test method

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

1. McLee (Polymerization Imbalance): 100 lenses with 80mm diameter and +11 D in diameter are manufactured, and observed by the Schlieren method under the Mercury Arc Lamp of USHIO USH-10D. Did. Of the 100 lenses, no pulsation was observed at all, indicated by '◎', and in 1 to 5 lenses of 100 lenses, no stalk was observed by '○', and of the 100 lenses, 6 to 9 lenses It is indicated by 'Δ' that no pulsation is observed, and 'x' is one where pulsation is observed in 10 or more lenses out of 100 lenses.

2. Transparency: 100 lenses are visually observed under the Mercury Arc Lamp, which is USHIO USH-10D, and marked as "◎" when less than one lens is found, and when 2-3 are found. "○", and if more than 4 are found, "X".

3. Color: In the color measurement of the lens, if the APHA value changes from 2 to less than 2 on the basis of 18, it is displayed as '◎'. It was denoted by '×'.

Example  2 ~ 8

Except for the content of toluene remaining in the episulfide compound as shown in Table 1 An optical lens was prepared in the same manner as in Example 1, and the physical properties were tested. Table 1 shows the results.

Comparative example  1-2

Except for the content of toluene remaining in the episulfide compound as shown in Table 1 An optical lens was prepared in the same manner as in Example 1, and the physical properties were tested. Table 1 shows the results.

division  A B C McLee Transparency color Example 1 3 0.1 0.1 ◎ ◎ ◎ Example 2 100 0.1 0.1 ◎ ◎ ◎ Example 3 500 0.1 0.1 ◎ ◎ ◎ Example 4 890 0.1 0.1 ◎ ◎ ◎ Example 5 1700 0.1 0.1 ◎ ○ ○ Example 6 2500 0.1 0.1 ○ ○ ○ Example 7 3600 0.1 0.1 ○ ○ ○ Example 8 4800 0.1 0.1 Δ ○ ○ Comparative Example 1 6000 0.1 0.1 × × × Comparative Example 2 10000 0.1 0.1 × × ×

A: Residual amount of toluene (ppm) in the episulfide compound

B: Residual amount of toluene (ppm) in 2,3-bis (2-mercaptoethylthio) propane-1-thiol

C: Residual amount of toluene (ppm) in bis (2-mercaptoethyl) sulfide

The episulfide-based optical material obtained according to the present invention is a high-quality high-refractive lens having no pulsation and good transparency and color, and can be usefully used for corrective sunglasses lenses, fashion lenses, discoloration lenses, camera lenses, lenses for optical devices, and the like. .

Claims (10)

A composition for an episulfide-based optical material, characterized in that the total content of toluene remaining in the compound is 3 to 5,000 ppm, as a composition comprising an episulfide compound represented by Formula 1 below, a polythiol compound, and a polymerization catalyst.
[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) According to claim 1,
The composition for an episulfide-based optical material, characterized in that the total content of the toluene is 3 to 2,500 ppm. According to claim 1,
Episulfide-based optical material composition further comprising sulfur. The method according to any one of claims 1 to 3,
A composition for an episulfide-based optical material further comprising a polyisocyanate compound. The method according to any one of claims 1 to 3,
A composition for an episulfide-based optical material further comprising a tin-halogen compound as a polymerization regulator. The method of claim 5,
The tin halide compound is a composition for episulfide-based optical materials, characterized in that a small amount of dimethyl tin dichloride or dimethyl tin dichloride or monomethyl tin trichloride is contained therein in an amount of 0.1 to 3.5% by weight. The method according to any one of claims 1 to 3,
The polymerization catalyst, episulfide-based optical material composition, characterized in that at least one selected from amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, phosphine compounds . In the method for producing an optical material, comprising the step of polymerizing the composition for an optical material comprising an episulfide compound, a polythiol compound and a polymerization catalyst represented by Formula 1 below,
Further comprising the step of adjusting the total content of toluene in the range of 3 ~ 5,000ppm by checking the content of toluene remaining in the compound, in order to prevent the occurrence of pulsation and color and transparency of the optical material, episulfide-based high refractive optical Method of manufacturing the material.
[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) The method of claim 8,
Method of manufacturing an episulfide-based high refractive optical material, characterized in that the total content of the toluene is adjusted to 3 to 2,500 ppm. The method of claim 8,
The composition for an optical material further comprises sulfur, a method for producing an episulfide-based high refractive optical material.