KR20160139798A - Composition for thioepoxy based optical material having superhigh refractive index and method of preparing the optical material - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a thioepoxy-based ultrahigh refractive optical resin, and more particularly, to a thioepoxy-based optical resin composition and a method for producing a thioepoxy-based optical material capable of increasing the thiourethane content with good light fastness, initial color and hard adhesion. In the present invention, xylylene diisocyanate (XDI) and 2,3-bis (2-mercaptoethylthio) propane-1 (2-mercaptoethylthio) (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the total composition in an amount of 2.46 to 12.75% by weight in the total composition in an optical resin composition containing a thiol (GST) To 15% by weight or more, and as a result, provides a thioepoxy-based optical material excellent in tensile strength, compressive strength, colorability, initial color, hard adhesion and the like.

Description

TECHNICAL FIELD The present invention relates to a thioepoxy-based ultrahigh refractive optical resin composition and a method for producing a thioepoxy-based optical material,

TECHNICAL FIELD The present invention relates to a thioepoxy-based ultrahigh refractive optical resin, and more particularly, to a thioepoxy-based optical resin composition and a method for producing a thioepoxy-based optical material capable of increasing the thiourethane content with good light fastness, initial color and hard adhesion.

Plastic lenses are lightweight, have good impact resistance and are easy to color. Recently, plastic lenses have been applied to most spectacle lenses. Among them, diethylene glycol bisallyl carbonate (CR-39) lenses have been applied to general spectacle lenses. This lens is useful in terms of providing a comfortable field of view because the chromatic aberration is small, but the refractive index is low and a high refractive index has been required. Korean Patent Publication Nos. 1993-0006918 and 1992-0005708 propose a thiourethane-based lens in which a polythiol compound is reacted with a polyisocyanate compound. The thiourethane-based lens has a high refractive index and an excellent impact strength, but it has a disadvantage that the surface of the lens is hollow and has a problem such as a central depression, and the Abbe number is drastically lowered when the refractive index is increased.

Korean Patent No. 10-0681218 proposes a thioepoxy-based plastic lens. Thioepoxy-based lenses have excellent properties with a high refractive index and a high Abbe number, but they are problematic in terms of tensile strength, compressive strength, colorability, hard adhesion, productivity and the like. In order to solve these problems, a method of copolymerizing two kinds of resins having different properties, that is, a method of copolymerizing a thioepoxy compound and a polythiol compound or a polyisocyanate compound together therewith is disclosed in Korean Patent Registration No. 10-0417985, 11-352302. The problem with the thioepoxy-based lens of 1.70 or more is that the content of the thiourethane component, that is, the polythiol compound and the polyisocyanate compound, can be greatly improved and the physical properties of the lens can be improved in many aspects. However, the composition for the 1.70 optical material of the thioepoxy system so far has been difficult to contain the thiourethane component in an amount of 10 wt% or more.

Korean Patent Publication No. 10-0417985 Japanese Patent Application Laid-Open No. 11-352302 Korean Patent Publication No. 10-0681218

The present invention aims at solving various problems in a thioepoxy-based 1.70 lens containing a thioepoxy compound as a main monomer component. In the present invention, the content of a thiourethane component in a composition is increased and tensile strength, compressive strength, Color, hard adherence, and the like, and to provide a high quality thioepoxy-based optical material.

The present inventors have found that when a thioepoxy compound contains bis (2,3-epithiopropyl) sulfide and xylylene diisocyanate (XDI) and 2,3-bis (2-mercaptoethylthio) When 2,3-epithiopropyl (2,3-epoxypropyl) sulfide is contained in the total composition in an amount of 2.46 to 12.75% by weight in an optical resin composition comprising 1-thiol (GST) It is possible to increase the content to 15 wt% or more, and as a result, a thioepoxy-based optical material excellent in tensile strength, compressive strength, coloring property, initial color, hard adhesion and the like can be obtained.

In the present invention,

(a) bis (2,3-epithiopropyl) sulfide with a thioepoxy compound; (b) xylylene diisocyanate as the polyisocyanate compound in the thiourethane component; (c) a polythiol compound selected from the group consisting of 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto- , 9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-di Mercapto-3,6,9-trithiane undecane,

(2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the total composition in an amount of 2.46 to 12.75% by weight,

The present invention provides a thioepoxy-based optical resin composition comprising at least 15% by weight of a thiourethane component which is a combination of the components (b) and (c).

The thioepoxy compound may further contain a thioepoxy compound other than bis (2,3-epithiopropyl) sulfide, if necessary. In addition, the polyisocyanate compound and the polythiol compound may further include polythiol compounds different from polyisocyanate compounds that are different from each other as needed.

The thioepoxy-based optical resin composition of the present invention may further contain an olefin compound as a reactive resin modifier, if necessary.

The thioepoxy-based optical resin composition of the present invention may further contain an internal release agent, if necessary.

The thioepoxy-based optical resin composition of the present invention may further contain an ultraviolet absorber as required.

Further, in the present invention,

(a) bis (2,3-epithiopropyl) sulfide with a thioepoxy compound; (b) xylylene diisocyanate as the polyisocyanate compound in the thiourethane component; (c) a polythiol compound selected from the group consisting of 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto- , 9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-di Mercapto-3,6,9-trithiane undecane,

(2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the total composition in an amount of 2.46 to 12.75% by weight,

And polymerizing the polymerizable composition comprising at least 15% by weight of the total composition of the thiourethane compound (b) and (c).

Further, in the present invention, a thioepoxy-based optical material comprising the thioepoxy-based optical resin composition is provided. The optical material of the present invention particularly includes an optical lens such as a spectacle lens.

The present invention provides a thioepoxy-based optical resin composition in which the content of thiourethane component is increased to 15 wt% or more. The thioepoxy-based optical resin composition of the present invention is excellent in tensile strength, compressive strength, coloring property, initial color, hard adhesive force and the like. The thioepoxy-based optical material obtained according to the present invention can be usefully used as a high-quality lens for vision correction, a lens for sunglasses, a fashion lens, a discoloration lens, a camera lens, a lens for an optical device and the like.

The thioepoxy-based optical resin composition of the present invention contains bis (2,3-epithiopropyl) sulfide as a thioepoxy compound. In addition, if necessary, other thioepoxy compounds besides bis (2,3-epithiopropyl) sulfide may be further included.

Examples of other thioepoxy compounds include bis (2,3-epithiopropyl) disulfide, 2,3-epithiopropyl (2,3-epithiopropyl) disulfide, 2,3- (2,3-epithiopropyl) sulfide, 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthio (Β-epithiopropylthio) cyclohexane] propane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2- Epithiopropylthio) cyclohexyl] sulfide; an episulfide compound having an alicyclic skeleton; 1,3- and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2- (Β-epithiopropylthio) phenyl] sulfone, bis [4- (β-epithiopropylthio) Thio) biphenyl, and the like; 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthiomethyl) Epithiocene skeleton such as bis (β-epithiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-epithiopropylthioethyl) -1,4- Sulfide compounds; Bis [(2 -? - epithiopropylthioethyl) thio] -1,3-bis (? - epithiopropylthio) propane, (Β-epithiopropylthiomethyl) propane, bis- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1- Propyl sulfide and the like) having an aliphatic skeleton. Other thioepoxy compounds may also be used, such as chlorine substituents of compounds having episulfide groups, halogen substituents such as bromine substituents, alkyl substituents, alkoxy substituents, and prepolymer type modifications with nitro substituents or polythiols.

The thioepoxy-based optical resin composition of the present invention contains xylylene diisocyanate (XDI) as a polyisocyanate compound in the thiourethane component. In addition, if necessary, other polyisocyanate compounds other than xylylenediisocyanate (XDI) may be further included.

The other polyisocyanate compound is not particularly limited and a compound having at least one isocyanate and / or isothiocyanate group may be used. Examples of the diisocyanate compound include 2,2-dimethylpentane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene- 1,6-hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyanate), 1,6-hexamethylene diisocyanate, Iso-ethyl) carbonate, bis (isocyanatoethyl) ether, and the like; (Isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, Alicyclic isocyanate compounds such as dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane isocyanate; Bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) There may be mentioned ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine Diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) , 3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4-diisocyanate Aromatic diisocyanate compounds such as carbonate; Bis (isocyanatoethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis Bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatoethylthio) Aliphatic isocyanate compounds such as isocyanatomethylthio) 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- Diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyl diphenyldisulfide-5,5 Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- A sulfided aromatic isocyanate compound such as 5-diisocyanate, 3,3-dimethoxy diphenyl disulfide-4,4-diisocyanate and 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate; 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) (Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) Dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis Isocyanatomethyl) -2-methyl-1,3-dithiolane, and the like can be used. In addition, at least one compound having at least one isocyanate group and / or an isothiocyanate group may be used alone or two or more of them may be used. Further, halogen substituents such as chlorine substituents and bromine substituents of the isocyanate compounds, alkyl substituents, alkoxy substituents, A prepolymer-type modified product of a substituent, a polyhydric alcohol or a thiol, a carbodiimide-modified product, a urea-modified product, a buret-modified product, a dimerization product or a trimarized product may be used.

The thioepoxy-based optical resin composition of the present invention is characterized in that the polythiol compound among the thiourethane compounds is 2,3-bis (2-mercaptoethylthio) propane-1-thiol (GST), 4,8- 1,1-dimercapto-3,6,9-trithiaundecane (FSH), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane ( FSH), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH). In addition, if necessary, the polythiol compound may further include a polythiol compound.

The other 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. Preferred examples thereof include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis Methyl) methane; (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Bis (2-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (2,3-dimercaptopropanel) disulfide, (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, bis (2- (2-mercaptoethylthio) ) -3-mercaptopropyl) disulfide, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- Propyl-1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (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 (R-3-mercapto-2 - ((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2- (7R, 11S) -7,11-bis (mercaptomethyl) propane-1-thiol, Dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13-pentafluoroheptadecane- Dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl 1,1-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, pentaerythritol (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol Tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) propane, 1,1,2,3-tetrakis Ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) Can be used. In addition, compounds having one or more thiol groups may be used alone or in combination of two or more. It is also possible to use a modified polymer obtained by prepolymerization of a polythiol compound with an isocyanate, a thioepoxy compound, a thiotane compound or a compound having an unsaturated bond as a resin modifier.

The thioepoxy-based optical resin composition of the present invention includes (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide which can be represented by the following Formula 1. (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide is preferably included in the composition in an amount of 2.46 to 12.75% by weight. When the (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide is contained in the optical resin composition in the above-mentioned content, the content of the thiourethane component in the composition can be increased to 15% or more without polymerization imbalance, There was an unexpected effect that greatly improved tensile strength, dyeability and hard adhesion. The present invention confirms and completes this point and discloses that the (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide which is considered to be only an impurity for bis (2,3- Is intentionally included in the composition from 2.46 to 12.75% by weight. In the present invention, (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide is preferably obtained by intentionally controlling the degree of reaction during the production of bis (2,3-epithiopropyl) And about 4 to about 15% of the compound to be used. However, the method of incorporating (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide into the optical resin composition of the present invention is not limited to this, and if necessary, have. When the content of (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the composition is less than 2.46% by weight, there is a problem that the initial color deviation of the lens is large and the hard adherence is degraded. There is a problem that the lens is not easily released from the mold after casting.

[Formula 1]

The optical resin composition of the present invention contains a thiourethane component, that is, a component containing a polyisocyanate compound and a polythiol compound contained in the composition in an amount of 15% by weight or more based on the total composition. The thiourethane component in the optical resin composition of the present invention is more preferably contained in an amount of 15 to 40% by weight. When the thiourethane content is less than 15%, the dyeability, the tensile strength and the compressive strength are lowered, and when the thiourethane content is more than 41%, the refractive index is lowered.

The NCO group / SH group ratio of the polyisocyanate compound and the polythiol compound in the optical resin composition of the present invention is preferably in the range of 0.3 to 3.0, more preferably 0.7 to 1.3. If the ratio of NCO group / SH group is out of this ratio, polymerization imbalance appears in the lens.

The thioepoxy-based optical resin composition of the present invention formed as described above preferably has a liquid viscosity of 500 cps (20 캜) or less.

The optical resin composition of the present invention may further contain an internal mold release agent as required. Preferably, the phosphoric acid ester compound may be contained as an inner mold release agent. Phosphoric esters are prepared by adding 2 to 3 moles of alcohol compound to phosphorus pentoxide (P ₂ O ₅ ). Depending on the type of alcohol used, various types of phosphoric acid ester compounds may be present. Representative 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 or the like. When a phosphoric acid ester compound to which ethylene oxide or propylene oxide is added is included in the composition of the present invention as an internal mold release agent, an optical material having good releasability and excellent quality can be obtained. The composition of the present invention preferably contains 4-PENPP [polyoxyethylene nonylphenol ether phosphate (5 mol% of ethylene oxide, 5 mol%, 4 mol of 80 wt%, 3 mol of ethylene oxide, 10 parts by weight of ethylene oxide, 5 parts by weight of 1 part by weight of ethylene oxide), 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 parts by weight of ethylene oxide, 3 parts by weight, 8 parts by mol of 80 parts by weight, 5% by weight of a molar part, 6% by weight of a 7-mol part, and 6% by weight of a 6-mol part), 12-PENPP [polyoxyethylene nonylphenol ether phosphate (3 mol% , 8 parts by weight of 12 parts by mol, 8 parts by weight of 11 parts by weight, 3 parts by weight of 9 parts by weight and 6 parts by weight of 4 parts by weight), 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3 parts by weight of ethylene oxide, 17 parts by weight of ethylene oxide, 79 parts by weight of 16 parts by weight, 10 parts by weight of 15 parts by weight, 4 parts by weight of 14 parts by weight and 4 parts by weight of 13 parts by weight) , 20-PENPP [polyoxyethylene nonylphenol ether phosphate (21 mol of ethylene oxide, 5 wt%, 20 mol of 76 wt%, 19 mol of 7 wt%, 18 mol of 6 wt% of ethylene oxide 4 mol% of 4-PPNPP [polypropylene nonylphenol ether phosphate (5 mol% of propylene oxide added, 4 mol% of 80 mol% of propylene oxide, 3 mol% 8 mol% of polyoxypropylene nonylphenol ether phosphate (9 mol of propylene oxide, 3 mol% of propylene oxide, 9 mol of propylene oxide) 5% by weight of an addition product, 6% by weight of a 7-mole addition product and 6% by weight of a 6-mole addition product), 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 mol% 8 parts by weight of 12 molar parts, 8 parts by weight of 11 parts by mol, 3 parts by weight of 9 parts by mol and 6 parts by weight of 4 parts by mol), 16-PPNPP [polyoxypropylene nonylphenol Ether phosphate (3 mol% of propylene oxide, 3 mol% of propylene oxide, 16 mol% of propylene oxide, 9 mol% of propylene oxide, 4 mol% of propylene oxide and 4 mol% of propylene oxide) ], 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 mol% of propylene oxide 21 mol%, 76 wt% of 20 mol addition, 7 wt% of 19 mol addition, 18 mol of addition 6 By weight, 17% by mole, 4% by weight)] and Zelec UN ^TM At least one of them is used. Various substituents including halogen compound substituents of such phosphoric acid ester compounds can also be used for the same purpose.

The optical resin composition of the present invention may further comprise an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity and the like in order to improve the optical properties of the copolymer optical resin (optical material) have. Examples of the olefin compound which can be added as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2 -Hydroxy ethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl 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 dimethacrylate Diethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol A dimethacrylate, 2-ethylhexyl glycidyl methacrylate, 2-bis (4-alkoxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, Bis (4-methacryloxyethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acroxyethoxyphenyl) methane, 1,1-bis (4-methoxyethoxyphenyl) methane, 1,1-bis (4-acryloxy diethoxyphenyl) methane, 1,1- Acrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, But are not limited to, cyclopentyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, (Meth) acrylate compounds such as xylyl dithiol diacrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether , Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate and diethylene glycol bisallylcarbonate, and allyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene , And 3,9-divinyl spiro (m-dioxane), and the like. But are not limited to these exemplified compounds. These olefin compounds may be used alone or in combination of two or more.

The optical resin composition of the present invention may further contain an ultraviolet absorber as required. The ultraviolet absorber is used for improving the light resistance of the optical material and for ultraviolet shielding. Any known ultraviolet absorber used in the optical material may be used without limitation. For example, ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and the like, or a mixture of two or more thereof.

(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 (4'-hydroxyphenyl) propionic acid having good ultraviolet ray absorbing ability in a wavelength range of 400 nm or less and having good solubility in the composition of the present invention -Chloro-2H-benzotriazole and 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole. When such an ultraviolet absorber is used in an amount of 0.6 g or more per 100 g of the optical resin composition, blocking of 400 nm or more is possible.

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

As the polymerization initiator, an amine-based or tin-based compound can be used. As the tin compound, butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octoate; Dibutyl tin dilaurate; Tetrafluoro-tin; Tetrachlorotin; Tetrabromoquite; Tetraiodide tin; Methyl tin trichloride; Butyltin trichloride; Dimethyl tin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; triphenyltin chloride; Dibutyltin sulfide; Di (2-ethyl sec-butyl) tin oxide, etc. may be used alone or in combination of two or more. Particularly preferably, tetrabutylphosphonium bromide and dibutyltin chloride can be used together.

When such a tin compound was used, the polymerization yield was high and bubbles were not generated. The amount to be used is preferably 0.001 to 4% by weight of the total composition.

The optical resin composition of the present invention thus formed preferably has a liquid viscosity of 500 cps (20 캜) or less and a solid-phase refractive index (Ne) after polymerization of 1.691 to 1.709. In the present specification, "refractive index 1.70" or "1.70 lens" means an optical material (lens) having a solid-state refractive index (Ne) in the range of 1.691 to 1.709.

The composition thus formed is subjected to template polymerization to obtain a thioepoxy-based optical material. A more detailed explanation is as follows. First, the polymerizable composition of the present invention is injected between molding molds held by a gasket or a tape or the like. At this time, depending on the physical properties required for the resulting optical material, it is often desirable to carry out a defoaming treatment under reduced pressure, a filtration treatment such as pressurization and depressurization, and the like. Polymerization conditions are not limited, but are carried out at a temperature of about -50 to 150 캜 for 1 to 50 hours, because the conditions largely vary depending on the polymerizable composition, type and amount of catalyst used, shape of the mold, In some cases, it is preferable to maintain or slowly raise the temperature in the range of 10 to 150 占 폚 and cure in 1 to 48 hours.

The thioepoxy compound obtained by the curing and the isocyanate compound or the thiol compound copolymer may be subjected to a treatment such as annealing if necessary. The treatment temperature is usually from 50 to 150 캜, preferably from 90 to 140 캜.

Various additives such as internal mold release agents may be added to the composition during the polymerization, and the description thereof is the same as that for the above composition. Particularly, the catalysts used in polymerization play an important role, and epoxy curing agents are mainly used as catalysts. Strong amines can also be used, but the use of caution should be used as they make the isocyanate reaction vigorous. In the present invention, tertiary amines, Lewis acids, radical initiators and the like which do not have amine salts, phosphonium salts, phosphines and electron attracting groups are mainly used. The type and amount of catalyst may vary.

The copolymer resin of the present invention can be obtained as a molded article of various shapes by changing a mold at the time of casting polymerization, and can be used as various optical materials such as a spectacle lens, a camera lens, and a light emitting diode (LED). In particular, it is suitable as an optical material such as a spectacle lens, a camera lens, a light emitting diode, and an optical element.

The thioepoxy-based optical material obtained in accordance with the present invention has hard adherence unlike ordinary thioepoxy-based optical materials, which enables hard coating without a primer, coating is very easy, and coating stability is also excellent. The plastic optical lens obtained according to the present invention may be formed by forming various coating layers on one side or both sides as required. As the coating layer, a primer layer, a hard coat layer, an antireflective film layer, an antifogging coat film layer, an antifouling layer, a water repellent layer, or the like can be used, and these coating layers may be used alone or in multiple layers of a plurality of coating layers. Further, when a coating layer is formed on both surfaces, it is possible to form the same coating layer on each surface or to form a different coating layer.

[ Example ]

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

Test and evaluation methods

1) The refractive index (nE) and Abbe number

It was measured at 20 캜 using an Abbe refractometer, which is a model of IT and DR-M4 manufactured by Atago.

2) Dysplasia

A composition for a thioepoxy-based optical material containing an additive in the production of an optical lens was injected into 50 sets of a glass mold for a lens frequency of -4.00 and thermally cured, and then the number of broken molds and lenses As shown in Fig.

3) Initial color (APHA)

Using a ColorQuest XE instrument from Hunterlab, the APHA value of a plastic optical lens with a thickness of 2 mm (0.001) was measured.

4) Dyeability

A thickness of 2 mm and a diopter of 0.00 was immersed in a BPI grays colored dye solution heated to 98 DEG C for 40 minutes, washed in clear water and dried, and then the light blocking rate was measured using a UV 2450 spectrophotometer by shimadzu.

5) Hard film adhesion

1.67 The lens was coated on ITOH and Z-118 by immersion and then thermally cured at 85 ° C for 4 minutes and then at 110 ° C for 120 minutes. The strings were drawn with a knife, and 100 squares of 1 mm x 1 mm were made. Adhesive tapes (Seo Kwang Tape Co., Ltd. K-5) having excellent adhesive strength were stuck thereon and abruptly peeled off at an angle of 180 ° C. This was repeated 5 times at the same position. The hard film recorded the number of squares that fell even a little.

6) Tensile strength

10 glasses with a diameter of 75 mm (frequency of -2.00, center thickness of 1.20 mm) were perforated with a perforator in 8 mm from the edge to the both ends (8 mm from the edge of the lens to the perforation center and 2.9 mm in perforation diameter) And measured with an universal testing machine, LR5K Plus model manufactured by Lloyd Instruments Ltd. (USA) at room temperature of 20 ° C, and the result is expressed as an average value of the maximum load applied to the universal testing machine.

7) Compressive strength

10 spectacle lenses (frequency -2.00, center thickness 1.20 mm) having a diameter of 75 mm were measured at a room temperature of 20 캜 according to the method of ISO 14889 (JIS T7331, Korea Food and Drug Safety Evaluation Institute (mechanical strength test)) by Lloyd Instruments Ltd (Unit: N), which is the average value of the maximum load applied to the universal testing machine as measured by a universal testing machine (LR5K Plus, USA).

8) Transmittance

were measured using a shimadzu UV 2450 spectrophotometer.

9) Polymerization unevenness

-2.00, -4.00, -6.00, -8.00, and -10.00 degrees, respectively, and observed with the naked eye to see if the polymerization was uneven. ≪ EMI ID = If 5 ~ 5 images can be seen, if there are 6 ~ 30 images of polymerization nonuniformity of 5 mm or more on the outer side of 40 mm from the center of the lens, 31 or more marks of polymerization nonuniformity of 5 mm or more on the outer side of 40 mm from the center of the lens, And when there is a sign of polymerization non-uniformity within 40 mm from the surface of the substrate,

10) Thermal stability

A lens having a center thickness of 2 mm and a water count of 0.00 was prepared, and the initial light transmittance was measured using a UV 2450 spectrophotometer manufactured by Shimadzu Co., then left in an oven at 120 ° C for 12 hours and the light transmittance was measured again, Respectively.

Example  One

Bis (2,3-epithiopropyl) sulfide (BEPS), 5.60 g of (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide (EPTES) 16.60 g of propylene-1-thiol (GST), 13.40 g of xylene diisocyanate (XDI), 8-PENPP (polyoxyethylenenonylphenol ether phosphate (9 mol of ethylene oxide 3 parts by weight of the additive, 80 parts by weight of 8 parts by weight, 5 parts by weight of 9 parts by weight, 6 parts by weight of 7 parts by weight and 6 parts by weight of 6 parts by weight)], 0.07 g of tetrabutylphosphine 0.07 g of dibutyltin chloride, 0.03 g of dibutyltin chloride, 0.6 g of organic dye HTAQ (0.2 ppm) and PRD (0.1 ppm), and ultraviolet absorber HOPBT were uniformly mixed at 10 캜. The mixed solution was degassed at 3 torr for 1 hour, filtered through a 1 μm PTFE filter, and then injected into a mold of a glass mold and a tape. The mold was placed in a polymerization oven and gradually heated to 25 ° C to 100 ° C over 21 hours to polymerize. After completion of the polymerization, the oven was gradually cooled to 70 deg. C for 1 hour, and then the mold was taken out, and the lens was released from the mold. The resulting lens was further annealed at 100 DEG C for 4 hours. The physical properties of the resulting lens were evaluated according to the above test method, and the results are shown in Table 1 below.

Example  2 to 7

The lens was obtained in the same manner as in Example 1 except that the monomer composition was changed as shown in Table 1. The properties of the lens obtained in the same manner as in Example 1 were evaluated and the results are shown in Table 1 below.

All of the examples gave good results in terms of initial color, thermal stability, dyeability, hard film adhesion, tensile strength and compressive strength. In particular, as the content of the thiourethane component was increased, the initial color, the dyeability, the hard film adhesion, the tensile strength and the compressive strength were found to be good. In Example 2 including the Example 2 containing 38% There was no.

Comparative Example  One

Bis (2,3-epithiopropyl) sulfide (BEPS), 7.06 g of (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide (EPTES) -Mercaptoethylthio) propane-1-thiol (GST), 5.24 g of xylene diisocyanate (XDI) 8-PENPP (polyoxyethylenenonylphenol ether phosphate (3 mol% of ethylene oxide, 9 mol% of ethylene oxide, 80 wt% of 8 mol%, 5 wt% of 9 mol% of ethylene oxide, 7 6 weight% of the molar content and 6 weight% of the 6 mole content)], 0.07 g of tetrabutylphosphonium bromide, 0.03 g of dibutyltin chloride, Organic dyes HTAQ (0.2 ppm) and PRD (0.1 ppm), 0.6 g of ultraviolet absorber HOPBT at 10 캜 And uniformly mixed. The mixed solution After defoaming at 3 torr for 1 hour, filtration was performed with a 1 탆 PTFE filter, and the solution was injected into a mold of a glass mold and a tape. The mold was placed in a polymerization oven, and the temperature was gradually elevated to 25 ° C to 100 ° C over 21 hours to polymerize. After completion of the polymerization, the oven was gradually cooled to 70 deg. C for 1 hour, and then the mold was taken out, and the lens was released from the mold. The resulting lens was further annealed at 100 DEG C for 4 hours. The physical properties of the resultant lens were evaluated according to the above test methods, and the results are shown in Tables 2 to 3 below.

Comparative Example  2 to 9

The lenses were obtained in the same manner as in Example 1 except that the monomer composition was changed as shown in Tables 2 and 9. The properties of the lenses obtained in the same manner as in Example 1 were evaluated, Respectively.

In Comparative Example 1, the content of the thiourethane component was as low as 11.7% as compared with the Examples. However, the initial color, dyeability, hard film adhesion, tensile strength and thermal stability were significantly lower than those of Examples. Comparative Example 2 contained 50% of the thiourethane component and Comparative Example 7 was obtained by using other compound instead of GST or FSH as the polythiol component. However, the initial color and thermal stability were poor and the polymerization was uneven, Did not do it. In Comparative Examples 3 to 5 and 7 to 9, in which the polyisocyanate and / or the polythiol were used in place of XDI, GST and FSH, or the EPTES content was less than 2.46 but too little or more than 12.75, polymerization unevenness Very severe.

[Table 1]

[Table 2]

[표 3]

[Table 3]

<Abbreviation>

BEPS: bis (2,3-epithiopropyl) sulfide

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

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

FSH: 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianedecane

PETMP: pentaerythritol tetrakis (3-mercaptopropionate)

BMES: bis (2-mercaptoethyl) sulfide

XDI: Xylene diisocyanate

NBDI: 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2,2,1] heptane

IPDI: isophorone diisocyanate

HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole) 2- (2'-

HTQA: 1-hydroxy-4- (p-toluidine) anthraquinone.

PRD: Perinone dye

Claims (17)

(a) bis (2,3-epithiopropyl) sulfide with a thioepoxy compound; (b) xylylene diisocyanate as the polyisocyanate compound in the thiourethane component; (c) a polythiol compound selected from the group consisting of 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto- , 9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-di Mercapto-3,6,9-trithiane undecane,
(2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the total composition in an amount of 2.46 to 12.75% by weight,
A thioepoxy-based optical resin composition comprising at least 15% by weight of a thiourethane component (b) and (c) combined in the total composition. The method according to claim 1,
Wherein the liquid phase viscosity is 500 cps (20 캜) or less and the solid-phase refractive index (Ne) after polymerization is 1.691 to 1.709. The method according to claim 1,
Wherein the ratio of the NCO group / SH group of the polyisocyanate compound and the polythiol compound is 0.3 to 3.0. The method according to claim 1,
Wherein the thioepoxy compound further comprises another thioepoxy compound. The thioepoxy-based optical resin composition according to claim 1, wherein the polyisocyanate compound further comprises another polyisocyanate compound. The thioepoxy-based optical resin composition according to claim 1, wherein the polythiol compound further comprises another polythiol compound. The thioepoxy-based optical resin composition according to any one of claims 1 to 6, further comprising an olefin compound as a reactive resin modifier. The thioepoxy-based optical resin composition according to any one of claims 1 to 6, further comprising an internal mold release agent. The thioepoxy-based optical resin composition according to any one of claims 1 to 6, further comprising an ultraviolet absorber. The thioepoxy-based optical resin composition according to any one of claims 1 to 6, further comprising tetrabutylphosphonium bromide and dibutyltin chloride as polymerization initiators. (a) bis (2,3-epithiopropyl) sulfide with a thioepoxy compound; (b) xylylene diisocyanate as the polyisocyanate compound in the thiourethane component; (c) a polythiol compound selected from the group consisting of 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto- , 9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-di Mercapto-3,6,9-trithiane undecane,
(2,3-epithiopropyl) (2,3-epoxypropyl) sulfide in the total composition in an amount of 2.46 to 12.75% by weight,
And polymerizing a polymerizable composition comprising at least 15% by weight of the total composition of the thiourethane compound (b) and (c). 12. The method of claim 11,
Wherein the polymerizable composition has a liquid phase viscosity of 500 cps (20 캜) or less and a solid-phase refractive index (Ne) of the optical material obtained after the polymerization is 1.691 to 1.709. 12. The method of producing a thioepoxy-based optical material according to claim 11, wherein the polymerizable composition further comprises an inner mold release agent. The method for producing a thioepoxy-based optical material according to claim 11, wherein the polymerizable composition further comprises an ultraviolet absorber. The method for producing a thioepoxy-based optical material according to claim 11, wherein the polymerizable composition further comprises tetrabutylphosphonium bromide and dibutyltin chloride as polymerization initiators. A thioepoxy-based optical material comprising the thioepoxy-based optical resin composition according to any one of claims 1 to 6. 17. The thioepoxy-based optical material according to claim 16, wherein the thioepoxy-based optical material is any optical lens selected from the group consisting of a lens for vision correction, a lens for sunglasses, a fashion lens, a color change lens, a camera lens and a lens for an optical device.