WO2020197156A1 - Composition for episulfide-based high refractive optical material, and method for manufacturing optical material using same - Google Patents

Abstract

The present invention relates to a composition for an episulfide-based high refractive optical material and a method for manufacturing an optical material using same and, in particular, to a composition for an episulfide-based high refractive optical material having a refractive index in the range of 1.71 to 1.77 that contains sulfur without using a polymerization regulator, such as tin halide, but does not have color deterioration or a polymerization imbalance, and does not have deterioration of thermal stability, light resistance, and releasability, and a method for manufacturing an optical material using same. The present invention provides a composition for an episulfide-based high refractive optical material having a refractive index in the range of 1.71 to 1.77 comprising: 70- 92% by weight of an episulfide compound represented by chemical formula 1; 4-20% by weight of a polythiol compound; 2-9% by weight of solid sulfur; 0.01-5% by weight of an isocyanate compound; and 0.05-2% by weight of one or more polymerization catalysts selected from quaternary phosphonium salt and a tertiary amine compound.

Description

Composition for episulfide-based high refractive optical material and manufacturing method of optical material using same

The present invention relates to an episulfide-based high-refractive optical material, and in particular, the refractive index ranges from 1.71 to 1.77 without the use of a polymerization modifier such as tin halide and without a decrease in color deterioration or polymerization imbalance, and no decrease in thermal stability, light resistance, and releasability while containing sulfur. The present invention relates to a composition for an episulfide-based high refractive optical material and a method of manufacturing an optical material using the same.

Plastic lenses are lightweight, 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 light weight, high transparency, low yellowness, heat resistance, light resistance, and strength.

Korean Patent Registration No. 10-0681218 proposes an episulfide-based plastic lens. The episulfide-based lens has an excellent property of having a high refractive index and high Abbe number. In addition, in order to improve tensile strength, compressive strength, colorability, hard adhesion, productivity, etc., a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound therewith is disclosed in Korean Patent Registration No. 10-0417985, Japanese Patent Application Publication No. It was proposed in No. 11-352302, etc.

Recently, in order to achieve an ultra-high refractive index of 1.71 or higher and a high Abbe number by further increasing the refractive index in an episulfide-based lens containing an episulfide compound, a composition for optical materials in which an inorganic compound such as sulfur atom or selenium atom is mixed with an episulfide compound. Was proposed (Japanese Patent Laid-Open Patent 2001-2783). However, when the inorganic compounds are mixed in this way, problems often arise in color, transparency, polymerization imbalance, thermal stability, light resistance, and releasability. In particular, if inorganic compounds such as sulfur remain as unreacted substances, the color of the lens, polymerization imbalance, and thermal stability are affected.In order to increase the refractive index, sulfur is used in a large amount of about 10% or more, usually 15%. As the sulfur content in the resin increases in this way, the possibility that sulfur remains as an unreacted material increases.

[Prior technical literature]

[Patent Literature]

(Patent Document 1) Republic of Korea Patent Publication 10-0417985

(Patent Document 2) Japanese Unexamined Patent Application Publication No. Hei 11-352302

(Patent Document 3) Japanese Laid-Open Patent Publication 2001-2783

(Patent Document 4) Republic of Korea Patent Publication 10-2014-0122721

An object of the present invention is to provide a composition for an episulfide-based high refractive optical material having a refractive index of 1.71 to 1.77, which contains sulfur and does not have problems of lowering color, polymerization imbalance, thermal stability, light resistance, and releasability due to sulfur.

In particular, in the present invention, a certain amount of sulfur and a small amount of isocyanate compound, and a quaternary phosphonium salt as a polymerization catalyst are included in the episulfide resin composition including the episulfide compound and the polythiol compound. , To provide a composition for an episulfide-based high refractive optical material in the range of 1.71 to 1.77, which does not have problems of polymerization imbalance, thermal stability, light resistance, and deterioration of releasability.

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

Episulfide compound represented by Formula 1 below 70 to 92% by weight, polythiol compound 4 to 20% by weight, solid sulfur 2 to 9% by weight, isocyanate compound 0.01 to 5% by weight, and quaternary phosphonium salt and tertiary It provides a composition for an episulfide-based high refractive optical material having a refractive index of 1.71 to 1.77, comprising 0.05 to 2% by weight of one or more polymerization catalysts selected from grade amine compounds.

[Formula 1]

(In the formula, X is O or S, m is an integer of 0 to 4, and n is an integer of 0 to 2.)

In the composition, the quaternary phosphonium salt preferably contains one of tetra-butylphosphonium bromide and tetraphenylphosphonium bromide.

The tertiary amine compound in the composition is N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N-methyldicyclohexyl It is preferred to include one of the amines.

In the composition, the episulfide compound is bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 2,3-epoxypropyl(2,3-epithiopropyl)sulfide, 2 ,3-epoxypropyl (2,3-epithiopropyl) disulfide, bis (2,3-ethiopropylthio) methane, 2,3-epoxypropylthio (2', 3'-epithiopropylthio) methane, 1,3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epi Thiopropylthiomethyl)-1,4-dithian, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-ditian, 2-(2-β-epithiopropylthioethylthio It is preferred to include one of )-1,3-bis(β-epithiopropylthio)propane.

In the composition, the polythiol compound is bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane-1 -It is preferred to include one of thiols.

The isocyanate compounds in the composition are isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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, It is preferred to include one of 6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

In addition, the present invention provides a method for producing an episulfide-based high refractive optical material having a refractive index of 1.71 to 1.77, comprising polymerizing the composition.

The composition for an episulfide-based high refractive optical material having a refractive index of 1.71 to 1.77 provided by the present invention contains sulfur, but does not have color deterioration or polymerization imbalance such as haze due to sulfur, and has excellent thermal stability, light resistance, and releasability.

The composition for an episulfide-based high refractive optical material of the present invention exhibits a high refractive index of 1.71 to 1.77, and an episulfide compound represented by Formula 1, a polythiol compound, solid sulfur, a small amount of an isocyanate compound, and a fourth-class polymerization catalyst Phosphonium salts and/or tertiary amine compounds.

[Formula 1]

(In the formula, X is O or S, m is an integer of 0 to 4, and n is an integer of 0 to 2.)

The episulfide compound represented by Formula 1 is a main component of an episulfide-based optical material. As the episulfide compound, preferably, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, 2,3-epoxypropyl (2,3-epithiopropyl) sulfide , 2,3-epoxypropyl (2,3-epithiopropyl) disulfide, bis (2,3-ethiopropylthio) methane, 2,3-epoxypropylthio (2', 3'-epithiopropylthio) Methane, 1,3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β -Epithiopropylthiomethyl)-1,4-dithian, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithian, 2-(2-β-epithiopropylthio Ethylthio)-1,3-bis(β-epithiopropylthio)propane may be used.

Particularly preferably, the episulfide compound is at least one of bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl) disulfide and bis(2,3-epithiopropylthio)methane. The selected A compound and at least one selected B compound from 2,3-epoxypropyl (2,3-epithiopropyl) sulfide and 2,3-epoxypropyl (2,3-epithiopropyl) disulfide are included together. At this time, preferably, 0.1 to 20 parts by weight of the B compound is included with respect to 100 parts by weight of the A compound, more preferably 0.3 to 10 parts by weight of the B compound, and particularly preferably 0.5 to 5 parts by weight of the B compound.

The episulfide compound may be included in the composition in an amount of 70 to 92% by weight, more preferably, in an amount of 75 to 90% by weight.

The polythiol compound is not particularly limited, and a 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-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), penta 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-ditian and 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-ditian 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 a polythiol compound with an isocyanate, episulfide compound, thiethane compound, or a compound having an unsaturated bond as a resin modifier may be used.

The polythiol compound is particularly preferably bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane. One or more of -1-thiol may be included, or one or more of other polythiol compounds may be mixed thereto.

Polythiol may be included in 4 to 20% by weight in the composition, more preferably 5 to 15% by weight.

The solid sulfur is preferably at least 98% pure. In the case of less than 98%, the transparency of the optical material may decrease due to the influence of impurities. The purity of sulfur is more preferably 99.0% or more, and particularly preferably 99.5% or more. Commercially available sulfur is classified by the difference in shape or purification method, and includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, and sublimated sulfur. In the present invention, any sulfur can be used with a purity of 98% or more. Preferably, when preparing the composition for an optical material, a fine dispersion of fine particles that are easily dissolved may be used.

Sulfur plays a role in increasing the refractive index of the composition.If sulfur is used as much as 10% by weight to 15% by weight, it is preferable in terms of increasing the refractive index, but it is difficult to control the polymerization rate, so that polymerization imbalance is likely to occur, and dibutyltin dichloride is used to control the polymerization rate. , Tin halogen compounds such as dimethyl tin dichloride should be used separately. In addition, unreacted sulfur is likely to remain, and as a result, it is easy to cause a decrease in transparency such as haze on the lens. In order to solve this problem, in the present invention, the sulfur content in the composition is 9% by weight or less, and a small amount of isocyanate compound is used together as described below, and as a polymerization catalyst, a quaternary phosphonium salt and/or a third Only grade amine compounds are used, and tin halogen compounds are not used separately.

Sulfur in the composition is included in 2 to 9% by weight, more preferably 3 to 7% by weight.

Since the isocyanate compound is contained in a small amount in the composition, the problem of lowering the transparency of the optical material caused by unreacted sulfur can be solved. The polyisocyanate compound is not particularly limited, and a compound having at least one or more isocyanate groups and/or isothiocyanate groups 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-trimethylhexamethylenediisocyanate, 1,6,11-undecan triisocyanate, 1,3,6-hexamethylene triisocyanate, 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, ethyl phenylene 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, hexahydrobenzenediisocyanate, 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'-diisocyanatedibenzylthioether, 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 -5,5'-diisocyanate, 3,3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyl disulfide-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-ditian, 2,5-bis(isocyanatomethyl) -1,4-dithiolane, 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-dithiolane 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 two or more types may be used in combination. In addition, halogen substituents such as chlorine substituents and bromine substituents of these isocyanate compounds, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer-type modified products with polyhydric alcohols or thiols, carbodiimide modified products, urea modified products, and biuret modified products Alternatively, dimerization, trimerization reaction products, and the like can also be used.

As an isocyanate compound, preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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. Particularly preferably, as the isocyanate compound, at least one selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), and noborane diisocyanate (NBDI) may be used.

The isocyanate compound is included in 0.01 to 5% by weight of the composition, more preferably 0.05 to 3.5% by weight.

In the composition, the polymerization catalyst is at least one selected from a quaternary phosphonium salt and a tertiary amine compound. It is preferable to use the tertiary amine compound at the same time as a co-catalyst for the quaternary phosphonium salt, especially when heat hardening is difficult to occur. By including 2 to 9% by weight of sulfur in the composition, only a quaternary phosphonium salt and/or a tertiary amine compound may be used as a catalyst, and a tin halogen compound may not be separately used for controlling the polymerization rate. Since the tin halogen compound is not used, an isocyanate compound may be included in the composition as described above.

The quaternary phosphonium salt preferably contains any one of tetra-butylphosphonium bromide and tetraphenylphosphonium bromide.

Tertiary amine compounds are trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n -Butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine ， Tridodecylamine, trilaurylamine, dicyclohexylethylamine, cyclohexyldiethylamine, tricyclohexylamine, N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexyl Amine, N,N-diethylcyclohexylamine, N-methyldicyclohexylamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine ， N,N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N,N-dimethylamino-p-cresol, N,N-dimethylaminomethylphenol, 2-(N,N-dimethylaminomethyl)phenol ， N, N-dimethylaniline, N,N-diethylaniline, N-methylmorpholine, N-methylpiperidine, 2-(2-dimethylaminoethoxy)-4-methyl-1, 3, 2- One or two or more compounds selected from tertiary amine compounds such as dioxabornane may be mixed and used. The tertiary amine compound is preferably N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N-methyldicyclohexyl Contains any one of amines.

The polymerization catalyst is included in the composition in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1.5% by weight. When using a tertiary amine compound as a cocatalyst for a quaternary phosphonium salt, it is preferable to use it within the total content range of the polymerization catalyst, and at this time, the tertiary amine compound is contained in the composition in an amount of 0.05 to 1% by weight. More preferable.

The composition is preferably polymerized after first forming a prepolymer during polymerization. In this case, it is preferable to further include alkylimidazole as a polymerization regulator in order to facilitate the formation of the prepolymer. The alkylimidazole particularly preferably comprises 2-mercapto-1-methylimidazole. 2-mercapto-1-methylimidazole is preferably used with a purity of 98% or more. In the composition for an optical material, preferably 0.01 to 5% by weight may be included, more preferably 0.1 to 3% by weight, and even more preferably 0.15 to 1% by weight may be included.

The composition for an optical material of the present invention may further include an internal release agent. Preferably, a phosphate ester compound may be included as an internal release agent. The phosphoric acid ester compound is prepared by adding 2 to 3 mol of an alcohol compound to phosphorus pentoxide (P ₂ O ₅ ), and 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 phosphate ester compound to which ethylene oxide or propylene oxide is added to the polymerizable composition of the present invention is included as an internal release agent, it is preferable because an optical material having good releasability and excellent quality can be obtained. The composition of the present invention is an internal release agent, preferably, 4-PENPP [polyoxyethylene nonylphenyl ether phosphate (5% by weight of 5 mol of ethylene oxide, 80% by weight of 4 mol of added, 3 mol) 10% by weight of 1 mol, 5% by weight of added 1 mol)], 8-PENPP [polyoxyethylene nonylphenyl ether phosphate (3 wt% of 9 mol of ethylene oxide, 80 wt% of 8 mol added), 9 Molar added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PENPP [polyoxyethylene nonylphenyl ether phosphate (ethylene oxide 13 mol added 3 wt% , 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP [polyoxyethylene nonylphenyl ether phosphate (3 wt% of ethylene oxide added by 17 mol, 79 wt% of added 16 mol, 10 wt% of 15 mol added, 4 wt% of 14 mol added, 4 wt% of 13 mol added)] , 20-PENPP [polyoxyethylene nonylphenyl ether phosphate (6 wt% of ethylene oxide added by 21 mol, 76 wt% of added 20 mol, 7 wt% of 19 mol added, and 6 wt. %, 17 mol added 5 wt%)], 4-PPNPP [polyoxypropylene nonylphenyl ether phosphate (5 wt% propylene oxide added 5 mol, 4 mol added 80 wt%, 3 mol added 10 wt%, 1 mol added 5 wt%)], 8-PPNPP [polyoxypropylene nonylphenyl ether phosphate (9 mol propylene oxide added 3 wt%, 8 mol added 80 wt%, 9 mol Added 5% by weight, 7 mol added 6% by weight, 6 mol added 6% by weight)], 12-PPNPP [polyoxypropylene nonylphenyl ether phosphate (3 wt% propylene oxide added 13 mol, 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PPNPP [polyoxypropylene nonylphenyl ether phosphate ( 3% by weight of propylene oxide added by 17 mol , 16 mol added 79 wt%, 15 mol added 10 wt%, 14 mol added 4 wt%, 13 mol added 4 wt%)], 20-PPNPP [polyoxypropylene nonylphenyl ether phosphate (6 wt% of propylene oxide added by 21 mol, 76 wt% of added 20 mol, 7 wt% of added 19 mol, 6 wt% of added 18 mol, 5 wt% of 17 mol added)] And Zelec UN ^TM Use at least one selected from among the. Various substituents including halogen compound substituents of the phosphoric acid ester compounds 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, and monomer viscosity in order to improve the optical properties of the optical material. As an olefin compound that 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 dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate Rate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis(4-acoxyethoxyphenyl)propane, 2,2-bis(4-methoxyethoxyphenyl)propane, 2, 2-bis(4-acoxydiethoxyphenyl)propane, 2,2-bis(4-methacoxydiethoxyphenyl)propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis( 4-acoxyethoxyphenyl)methane, 1,1-bis(4-methacoxyethoxyphenyl)methane, 1,1-bis(4-acoxydiethoxyphenyl)methane, 1,1-bis(4 -Methoxydiethoxyphenyl)methane, dimethyroltricyclodecane diacrylate, trimethyrolpropane triacrylate, trimethyrolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithioldiacrylate, c (Meth)acrylate compounds such as silylenedithioldimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethylsulfidedimethacrylate, and allylglycidyl Allyl compounds such as ter, diallylphthalate, diallyl terephthalate, diallyisophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, and styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinyl Vinyl compounds such as benzene and 3,9-divinylspirobi (m-dioxane), and the like, and the compounds usable are not limited to these exemplary compounds. These olefin compounds may be used alone or in combination of two or more.

The composition for an optical material of the present invention may further include an ultraviolet absorber if necessary. The ultraviolet absorber is used to improve the light resistance of the optical material and to block 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 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, etc. can be used. When used in an amount of 0.6 g or more with respect to 100 g of the composition for an optical material, such an ultraviolet absorber can 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 improving agent, if necessary.

The composition for an optical material of the present invention composed as above preferably has a liquidus viscosity of 500 cps (20° C.) or less, and a solid refractive index (Ne) of 1.71 to 1.77 after polymerization.

When the composition prepared as above is subjected to mold polymerization, an episulfide-based optical material can be obtained. In more detail, it is as follows. First, the polymerizable composition of the present invention is injected between molding molds held by a gasket or tape. At this time, depending on the required physical properties of the optical material to be obtained, or as necessary, it is often preferable to perform a degassing treatment under reduced pressure or a filtration treatment such as pressurization or reduced pressure. The polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst, and the shape of the mold, but are carried out at a temperature of about -50 to 130°C over 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 cure in 1 to 48 hours.

The episulfide-based optical material obtained by curing may be subjected to a treatment such as annealing, if necessary. The treatment temperature is usually performed between 50 and 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 material or 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 good hard adhesion and can be hard coated without a primer, it is very easy to coat, and the stability of the coating is also very excellent. The plastic optical lens obtained according to the present invention may 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 layer, an anti-fogging coating layer, an antifouling layer, a water repellent layer, and the like can all be used, and these coating layers may be used individually or may be used in a multilayered form of a plurality of coating layers. In addition, in the case of forming the coating layer on both sides, it is possible to form the same coating layer on each side or to form a different coating layer.

[ Example ]

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

< Example 1>

The reactor was decompressed to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring this reactor, 86 g of bis(2,3-epithiopropyl)sulfide compound and 2 g of 2,3-epoxypropyl (2,3-epithiopropyl) sulfide were added, followed by 4 g of sulfur and 0.8 g of UV-blocking agent UV 31. Was added, and after degassing under reduced pressure for 30 minutes, 0.15 g of 2-mercapto-1-methylimidazole was added, followed by stirring for 1 hour. After cooling to 30 ℃ bis (2-mercaptoethyl) sulfide 2g, 2,3-bis (2-mercaptoethylthio) propane-1-thiol 6g, tetrabutylphosphonium bromide 0.3g and phosphate ester as an internal release agent 8-PENPP [polyoxyethylene nonylphenol ester phosphate (9 mol of ethylene oxide added 3 wt%, 8 mol added 80 wt%, 9 mol added 5 wt%, 7 mol added 6 Weight%, 6% by weight added 6%) 0.08g was put into a reactor, and after making a resin composition for an optical lens, an optical lens was prepared by the following method, and the physical properties of the optical lens were measured.

(1) Degassing the resin composition for an optical lens prepared as above under reduced pressure at 43° C. for 1 hour, cooled to 30° C., and a mixed solution of 0.1 g of IPDI and organic dye HTAQ (88 ppm) and PRD (30 ppm) It was added, stirred for 15 minutes, filtered, and degassed under reduced pressure for 5 minutes, and then poured into a glass mold assembled with polyester adhesive tape.

(2) The glass mold into which the resin composition for spectacle lenses was injected was heat-cured 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 obtained lens was processed to a diameter of 72 mm, ultrasonically washed in an alkaline aqueous cleaning solution, and then annealed at 100° C. for 2 hours. Physical properties were measured by the following method and the results are shown in Table 1 .

Physical property test method

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

1) Refractive index and Abbe number: It was measured using an Abbe refractometer, a DR-M4 model manufactured by Atago.

2) Transparency: Observe 100 lenses with the naked eye under the USHIO USH-10D Mercury Arc Lamp, and if less than 1 lens turbidity is found, mark "◎" and 2~3 are found. If it is, it is marked with "○", and if four or more are found, it is marked with "x".

3) Polymerization imbalance: 100 spectacle lenses are visually observed under the Mercury Arc Lamp of USHIO USH-10D, and the lens with confirmed arc image is judged to have polymerization imbalance, and no arc image is "◎ "", those with 1 to 2 arc images are indicated by "○", and those with 3 or more arc images are indicated by "x".

4) Light resistance: Q-Lab.'s QUV/SE model Accelerated Weathering Tester was used. The QUV test was conducted on a flat lens with a thickness of 1.2mm under UVA-340 (340nm), light intensity 0.76W/㎡, 4 hours BPT (Black Panel Temperature) (60℃), and 4 hours condensation (50℃) for 24 hours. After irradiation, in the measurement of color change, if the APHA value changes from 0 to 2, it is marked as "◎", if the APHA value changes to 3 to 4, it is marked as "○", and if the APHA value changes to 4 to 6, it is displayed as "Δ". When the APHA value is changed to 7 or more, "x" is indicated.

5) Thermal stability: The cured optical lens is maintained at 100°C for 3 hours, and when the APHA value changes to 2 or less in the measurement of color change, "◎" is displayed, and when the APHA value changes to 3~5, "○" When the APHA value changes from 6 to 8, it is indicated by "Δ", and when the APHA value is changed to 9 or more, it is indicated by "x".

6) Releasability: When the resin composition for optical lenses is thermally cured and demolded at 70°C, if one of the 100 glass molds is not broken because the plastic lens and the mold are easily separated, "◎" is indicated, and 1~2 of 100 glass molds When a dog breaks, it is marked with "○", and when 3 or more of 100 glass molds are broken because it is not easily separated, it is marked with "x". (For uniform evaluation, a mold of -0.00 diopters was used.).

< Example 2~4>

Example 1, producing an optical lens according to the proportion described in Table 1 in the same way and their properties were measured, the results shown in Table 1.

< Example 5>

The reactor was decompressed to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring this reactor, 80 g of bis (2,3-epithiopropylthio) methane compound and 2 g of 2,3-epoxypropyl (2,3-epithiopropyl) sulfide were added, followed by 5 g of sulfur and 0.8 of UV blocker UV 31. g was added, and after degassing under reduced pressure for 30 minutes, 0.15 g of 2-mercapto-1-methylimidazole was added, followed by stirring for 1 hour. After cooling to 30 ℃ bis (mercaptomethyl) sulfide 4g, 2,3-bis (2-mercaptoethylthio) propane-1-thiol 9g, tetrabutylphosphonium bromide 0.3g and phosphate ester 8 -PENPP [polyoxyethylene nonylphenol ester phosphate (3 wt% of ethylene oxide 9 mol added, 8 mol added 80 wt%, 9 mol added 5 wt%, 7 mol added 6 wt% , 6 mol added 6% by weight) 0.08g was added to the reactor, and after making the resin composition for optical lenses, degassed while stirring at 43°C for 1 hour under reduced pressure, cooled to 30°C, XDI 0.1g, organic dye HTAQ A mixed solution of (88ppm) and PRD (30ppm) was added. The resin composition was stirred for 15 minutes, cooled to 20°C, 0.2 g of N,N-dimethylcyclohexylamine was slowly added, stirred for 15 minutes, filtered, and degassed under reduced pressure for 5 minutes, and polyester adhesive tape The optical lens was manufactured in the same manner as in Example 1 by injecting it into a glass mold assembled with, and its physical properties were measured. The results are shown in Table 1.

< Example 6~8>

Example 1, producing an optical lens according to the proportion described in Table 1 in the same way and their properties were measured, the results shown in Table 1.

< Comparative example 1>

The reactor was reduced to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring this reactor, 86 g of bis(2,3-epithiopropyl) episulfide compound and 2 g of 2,3-epoxypropyl (2,3-epithiopropyl) sulfide were added, followed by 4 g of sulfur and 0.8 of UV-blocking agent UV 31. g was added, and after degassing under reduced pressure for 30 minutes, 0.15 g of 2-mercapto-1-methylimidazole was added, followed by stirring for 1 hour. After cooling to 30 ℃ bis (mercaptomethyl) sulfide 2g, 2,3-bis (2-mercaptoethylthio) propane-1-thiol 6g, tetrabutylphosphonium bromide 0.3g and phosphate ester 8 as an internal release agent -PENPP [polyoxyethylene nonylphenol ester phosphate (3 wt% of ethylene oxide 9 mol added, 8 mol added 80 wt%, 9 mol added 5 wt%, 7 mol added 6 wt% , 6 mol of added 6% by weight) 0.08g was added to the reactor, and after making the resin composition for optical lenses, the mixture was stirred and degassed under reduced pressure at 43°C for 1 hour, cooled to 30°C, and organic dye HTAQ (88ppm) and A mixed solution of PRD (30ppm) was added. The resin composition was stirred for 15 minutes, filtered, and then degassed under reduced pressure for 5 minutes, and injected into a glass mold assembled with polyester adhesive tape to prepare an optical lens in the same manner as in Example 1, and its physical properties were measured. And the results are shown in Table 2 .

< Comparative example 2~4>

An optical lens was manufactured according to the composition shown in Table 2 in the same manner as in Example 1, and its physical properties were measured, and the results are shown in Table 2 .

< Comparative example 5-6>

An optical lens was manufactured according to the resin described in Table 2 in the same manner as in Example 5, and its physical properties were measured, and the results are shown in Table 2 .

< Comparative example 7>

An optical lens was manufactured according to the composition shown in Table 2 in the same manner as in Comparative Example 1, and its physical properties were measured, and the results are shown in Table 2 .

division	Example One	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8
EPS(g)	86	86	86	86		2
EPDS(g)					2		10
EPTM(g)					80	80	66	80
EPETS(g)	2	2	2	2		2	2	2
Sulfur (g)	4	4	5	5	5	6	6	6
BMMS(g)					4		4	4
MMTM(g)						5
BMS(g)	2	2	2	2			2
GST(g)	6	6	6	6	9	5	10	8
IPDI(g)	0.1	2.5	3.5	4.8
XDI(g)					4.0
NBDI(g)						0.1	3.0	4.8
Refractive index (Ne, 20℃)	1.7213	1.7208	1.7200	1.7187	1.7356	1.7366	1.7601	1.7610
Abbesu	34	34	34	34	32	32	30	29
Transparency	◎	◎	◎	○	◎	◎	◎	○
Polymerization imbalance	◎	◎	◎	◎	◎	◎	◎	◎
Light resistance	◎	◎	◎	◎	○	◎	◎	◎
Thermal stability	◎	◎	◎	◎	○	◎	◎	◎
Dysplasia	◎	◎	◎	○	◎	◎	◎	○

division	Comparative example One	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7
EPS(g)	86	86	86	86	80
EPDS(g)					3	3
EPTM(g)						80	80
EPETS(g)	2	2	2	2			2
Sulfur (g)	4	4	4	4	3	3	3
BMMS(g)					4		6
MMTM(g)						4
BMS(g)	2	2	2				2
GST(g)	6	6	6	6	10	10	7
IPDI(g)		6				8
XDI(g)			6
NBDI(g)				8
Refractive index (Ne, 20℃)	1.7215	1.7170	1.7176	1.7173	1.7312	1.7570	1.7370
Abbesu	34	34	34	34	33	30	32
Transparency	○	○	○	×	○	×	○
Polymerization imbalance	○	×	×	×	○	×	×
Light resistance	Δ	◎	◎	◎	×	○	Δ
Thermal stability	×	◎	◎	◎	×	○	Δ
Dysplasia	◎	×	×	×	◎	×	◎

Abbreviation

EPS: bis(2,3-epithiopropyl)sulfide

EPDS: bis(2,3-epithiopropyl) disulfide

EPTM: bis(2,3-epithiopropylthio) methane

EPETS: 2,3-epoxypropyl (2,3-epithiopropyl) sulfide (2,3-epoxypropyl (2,3-epithiopropyl) sulfide)

BMS: bis(2-mercaptoethyl)sulfide

BMMS: bis(mercaptomethyl)sulfide

MMTM: bis (mercaptomethylthio) methane (bis (mercaptomethylthio) methane)

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

IPDI: isophorone diisocyanate

XDI: m-xylylenediisocyanate (m-xylylenediisocyanate)

NBDI: norbornane diisocyanate

The episulfide-based optical material obtained according to the present invention has a high refractive index, including sulfur, of 1.71 to 1.77, and has no color deterioration or polymerization imbalance due to sulfur, and has excellent thermal stability, light resistance, and releasability, so it is corrected as a high-quality lens. It can be usefully used for lenses for lenses, lenses for sunglasses, fashion lenses, color-changing lenses, camera lenses, lenses for optical devices, and the like.

Claims (7)

1. Episulfide compound represented by Formula 1 below 70 to 92% by weight, polythiol compound 4 to 20% by weight, solid sulfur 2 to 9% by weight, isocyanate compound 0.01 to 5% by weight, and quaternary phosphonium salt and tertiary A composition for an episulfide-based high refractive optical material having a refractive index of 1.71-1.77, comprising 0.05-2% by weight of one or more polymerization catalysts selected from grade amine compounds.

   [Formula 1]

   

   (In the formula, X is O or S, m is an integer of 0 to 4, and n is an integer of 0 to 2.)
2. The method of claim 1,

   The quaternary phosphonium salt is a composition for optical materials comprising one of tetra-butylphosphonium bromide and tetraphenylphosphonium bromide.
3. The method of claim 1,

   The tertiary amine compound is among N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, and N-methyldicyclohexylamine. An optical material composition comprising one.
4. The method of claim 1,

   The episulfide compound is bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, 2,3 -Epoxypropyl (2,3-epithiopropyl) disulfide, bis (2,3-ethiopropylthio) methane, 2,3-epoxypropylthio (2', 3'-epithiopropylthio) methane, 1, 3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropyl) Thiomethyl)-1,4-dithian, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithian, 2-(2-β-epithiopropylthioethylthio)- A composition for an optical material comprising one of 1,3-bis(β-epithiopropylthio)propane.
5. The method of claim 1,

   The polythiol compound is bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane-1-thiol An optical material composition comprising one of.
6. The method of claim 1,

   The isocyanate compound is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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, 2,6- A composition for an optical material comprising one of bis(isocyanatomethyl)bicyclo[2,2,1]heptane.
7. A method for producing an episulfide-based high refractive optical material, comprising polymerizing the composition of any one of claims 1 to 6.