WO2016190599A1 - Thioepoxy-based ultra-high-refraction optical resin composition, and production method for thioepoxy-based optical material - Google Patents

Abstract

The present invention relates to a thioepoxy-based ultra-high-refraction optical resin. And more particularly relates to: a thioepoxy-based optical resin composition which has good light resistance and initial colour and hard adhesive strength and allows an increased thiourethane content; and a production method for a thioepoxy-based optical material. The present invention concerns an optical resin composition comprising a thioepoxy compound in the form of bis(2,3-epithiopropyl)sulphide and comprising a thiourethane component in the form of xylylene diisocyanate (XDI) and 2,3-bis(2-mercaptoethylthio) propane-1-thiol (GST), the composition incorporating (2,3-epithiopropyl) (2,3-epoxypropyl)sulphide in an amount of between 2.46 and 12.75 wt.% with respect to the composition as a whole, thereby increasing the content of the thiourethane component to at least 15 wt.% and consequently providing a thioepoxy-based optical material which has outstanding tensile strength, compression strength, colourability, initial colour, hard adhesive strength and the like.

Description

Thioepoxy Ultra High Refractive Optical Resin Composition and Method for Manufacturing Thioepoxy Optical Materials

The present invention relates to a thioepoxy clock ultra-high refractive optical resin, and more particularly, to a thioepoxy optical resin composition and a method for producing a thioepoxy clock optical material, which have good light resistance, an initial color and a hard adhesion, and which can increase the thiourethane content.

Plastic lenses are light, impact resistant and easy to color, and plastic lenses have been applied to most spectacle lenses in recent years. Among them, a typical diethylene glycol bisallylcarbonate (CR-39) lens has been applied to a common spectacle lens. This lens is useful for providing a comfortable field of view due to its low chromatic aberration, but a high refractive index has been required due to its low refractive index. Korean Patent Publication Nos. 1993-0006918, 1992-0005708 and the like propose a thiourethane lens in which a polythiol compound and a polyisocyanate compound are reacted. The thiourethane-based lens has advantages of high refractive index and excellent impact strength, but there are disadvantages such as a soft surface of the lens and problems of center depression, and also a problem in that Abbe's number decreases rapidly when the refractive index is increased.

Korean Patent No. 10-0681218 proposes a thioepoxy plastic lens. Although thioepoxy lenses have excellent refractive index and high Abbe's number, they have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, and productivity. In order to solve this problem, a method of copolymerizing two kinds of resins having different properties, that is, a method of copolymerizing a thioepoxy compound and a polythiol compound or a polyisocyanate compound together is disclosed in Korean Patent Registration No. 10-0417985 and Japanese Patent Publication. Suggested in US Pat. The problem with the thioepoxy lens of 1.70 or more can be greatly improved by increasing the content of the thiourethane component, that is, the polythiol compound and the polyisocyanate compound, and the physical properties of the lens can be improved in many aspects. However, until now, the composition for thioepoxide 1.70 optical materials was difficult to contain the thiourethane component in 10 weight% or more.

[Preceding technical literature]

[Patent Documents]

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

(Patent Document 2) JP 11-352302 A

(Patent Document 3) Republic of Korea Patent Registration 10-0681218

The present invention is to solve a number of problems appearing in a thioepoxy 1.70 lens containing a thioepoxy compound as the main monomer component, in the present invention, in particular by increasing the content of the thiourethane component in the composition tensile strength, compressive strength, colorability, initial An object of the present invention is to provide a high quality thioepoxy optical material having excellent color, hard adhesion, and the like.

The inventors of the present invention include bis (2,3-ethiothio) sulfide as a thioepoxy compound and xylylene diisocyanate (XDI) and 2,3-bis (2-mercaptoethylthio) propane- as thiouurethane components. When the optical resin composition containing 1-thiol (GST) contains (2,3-epiopropyl) (2,3-epoxypropyl) sulfide in 2.46 to 12.75% by weight of the total composition, The content can be increased to 15% by weight or more, and as a result, it was confirmed that a thioepoxy optical material having excellent tensile strength, compressive strength, colorability, initial color, hard adhesion, and the like can be obtained.

In the present invention,

(a) bis (2,3-epithiopropyl) sulfide as a thioepoxy compound; (b) xylylenediisocyanate as the polyisocyanate compound in the thiourethane component; (c) 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 as a polythiol compound in the thiourethane component , 9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 5,7-dimercaptomethyl-1,11-di At least one of mercapto-3,6,9-trithiaoundecan,

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

Provided is a thioepoxy optical resin composition comprising at least 15% by weight of the thiourethane component combined with (b) and (c).

The thioepoxy compound may further contain other thioepoxy compounds in addition to bis (2,3-epithiopropyl) sulfide as necessary. In addition, the polyisocyanate compound and the polythiol compound may further include different polyisocyanate compounds and different polythiol compounds, respectively, as necessary.

The thioepoxy optical resin composition of the present invention may further include an olefin compound as a reactive resin modifier as necessary.

The thioepoxy optical resin composition of the present invention may further include an internal mold release agent as necessary.

The thioepoxy optical resin composition of the present invention may further include an ultraviolet absorber as necessary.

In the present invention,

(a) bis (2,3-epithiopropyl) sulfide as a thioepoxy compound; (b) xylylenediisocyanate as the polyisocyanate compound in the thiourethane component; (c) 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 as a polythiol compound in the thiourethane component , 9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 5,7-dimercaptomethyl-1,11-di At least one of mercapto-3,6,9-trithiaoundecan,

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

It provides a method for producing a thioepoxy clock optical material comprising the step of polymerizing a polymerizable composition comprising at least 15% by weight of the thiourethane component combined with (b) and (c).

Moreover, in this invention, the thio epoxy clock optical material which consists of the said thio epoxy clock optical resin composition is provided. The optical material of the present invention particularly includes optical lenses such as spectacle lenses.

The present invention provides a thioepoxy optical resin composition having a content of the thiourethane component increased to 15% by weight or more. The thioepoxy optical resin composition of the present invention is excellent in tensile strength, compressive strength, colorability, initial color, hard adhesion, and the like. The thioepoxy watch optical material obtained according to the present invention can be usefully used as a high quality vision correction lens, sunglasses lens, fashion lens, discoloration lens, camera lens, lens for optical devices and the like.

The thioepoxy optical resin composition of this invention contains bis (2, 3- epithiopropyl) sulfide as a thio epoxy compound. Further, if necessary, other thioepoxy compounds may be further included in addition to the bis (2,3-epiopropyl) sulfide.

The other thioepoxy compound is, for example, bis (2,3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epithiopropyl) disulfide, 2, 3- epidithione Opropyl (2,3-ethiothiopropyl) sulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-ethiothiopropylthio Methyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] propane, bis [4- (β- Episulfide compounds having an alicyclic skeleton such as epithiopropylthio) cyclohexyl] sulfide; 1,3 and 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropyl Thio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] sulphine, 4,4-bis (β-ethiothiopropyl Episulfide compounds having an aromatic skeleton such as thio) biphenyl; 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis (β-ethiothiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-ethiothiopropylthioethyl) -1,4-dithiane Sulfide compounds; 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane, 1,2-bis [(2-β-ethiothiopropylthioethyl) thio]- 3- (β-epithiopropylthio) propane, tetrakis (β-ethiothiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, bis- (β-ethiothio Episulfide compounds having an aliphatic skeleton such as propyl) sulfide. In addition to the other thioepoxy compounds, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-type modified compounds with polythiol may be used.

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

The other polyisocyanate compound is not particularly limited and compounds having at least one isocyanate and / or isothiocyanate group may be used. For example, 2,2-dimethylpentane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undectriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyane Aliphatic isocyanate compounds such as itoethyl) carbonate and bis (isocyanatoethyl) ether; Isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, Alicyclic isocyanate compounds such as dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate and 2,2-dimethyldicyclohexyl methane isocyanate; Bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl Ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl 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-diisocysi Aromatic diisocyanate compounds such as carbonate; 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 ( Sulfur-containing 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-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5, Sulfur-containing aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxy diphenyldisulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) Tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanatomethyl) -1,3-dithiorane, 4,5-bis ( One or two or more selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolan can be used. In addition, as long as it is a compound having at least one isocyanate and / or isothiocyanate group, one kind or two or more kinds can be used, and also halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents and nitros of these isocyanate compounds. Substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized, trimerized reaction products, and the like can also be used.

The thioepoxy optical resin composition of the present invention is a polythiol compound in the thiourethane component as 2,3-bis (2-mercaptoethylthio) propane-1-thiol (GST), 4,8-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaoundecan (FSH), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan ( FSH), 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan (FSH). In addition, other polythiol compounds may be further included as needed.

The said other polythiol compound is not specifically limited, If it is a compound which has at least 1 or more thiol groups, it can use 1 type (s) or 2 or more types in mixture. Preferably, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, tetrakis (mercapto Methyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (2- ( 2-mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, bis (2- (2-mercaptoethylthio) ) -3-mercaptopropyl) disulfide, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio ] Propylthio-propane-1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-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 Pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mercapto-2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2- ((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane-1,2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13, 16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaery Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) At least one selected from ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane Can be used. In addition, if it is a compound which has one or more thiol groups, it can use 1 type or in mixture of 2 or more types. Furthermore, the polymerization modified body obtained by prepolymerization with an isocyanate, a thioepoxy compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used.

The optical resin composition of the present invention comprises at least 15% by weight of the thiourethane component, i.e., the component in which the polyisocyanate compound and the polythiol compound included in the composition are combined. In the optical resin composition of the present invention, the thiourethane component may be more preferably included in an amount of 15 to 40% by weight. When the thiourethane content is less than 15%, the dyeability, tensile strength, compressive strength is lowered, when 41% or more there is a problem that 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 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 optical resin composition of the present invention contains (2,3-epiopropyl) (2,3-epoxypropyl) sulfide which can be represented by the following formula (1). (2,3-Epithiopropyl) (2,3-epoxypropyl) sulfide is preferably included at 2.46-12.75% by weight of the total composition. When (2,3-epiopropyl) (2,3-epoxypropyl) sulfide was included in the optical resin composition at the above content, the content of thiourethane component in the composition could be greatly increased to 15% or more without polymerization imbalance, As a result, there was an unexpected effect that the tensile strength, dyeability and hard adhesive strength are greatly improved. The present invention has confirmed and completed this point, and the present invention is based on the entirety of (2,3-epithiopropyl) (2,3-epoxypropyl) sulfide, which was considered only an impurity for bis (2,3-ethiothio) sulfide. Intentionally included in the composition at 2.46-12.75% by weight. In the present invention, (2,3-epiopropyl) (2,3-epoxypropyl) sulfide is preferably obtained by intentionally controlling the degree of reaction in the preparation of bis (2,3-epiopropyl) sulfide. It can be used by mixing in about 4,1 to 15% of the compound to become. However, the method of including (2,3-epiopropyl) (2,3-epoxypropyl) sulfide in the optical resin composition of the present invention is not limited thereto, and may be added in whole or in part from the outside as necessary. have. When the content of (2,3-epiopropyl) (2,3-epoxypropyl) sulfide in the composition was less than 2.46% by weight, there was a problem in that the initial color deviation of the lens was large and the hard adhesion was reduced, and 12.75% by weight was used. If exceeded, there was a problem that the lens was not easily released from the mold after casting.

[Equation 1]

The thioepoxy optical resin composition of the present invention prepared as above preferably has a liquidus viscosity of 500 cps (20 ° C.) or less.

The optical resin composition of the present invention may further include an internal release agent as necessary. Preferably, the internal mold release agent may include a phosphate ester compound. Phosphate ester is prepared by adding 2-3 moles of alcohol compound to phosphorus pentoside (P ₂ O ₅ ). There may be various types of phosphate ester compounds depending on the type of alcohol used. Typical examples include those in which ethylene oxide or propylene oxide is added to the aliphatic alcohol, or ethylene oxide or propylene oxide is added to the nonylphenyl group. When the phosphate ester compound added with ethylene oxide or propylene oxide is included in the composition of the present invention as an internal mold release agent, an optical material having good release property and excellent quality can be obtained. The composition of the present invention is an internal mold release agent, preferably 4-PENPP (5% by weight of 5 mole of ethylene oxide added, 80% by weight of 4 mole added, 10% by weight of 3 mole added, 1 mole) Polyoxyethylenenonylphenyletherphosphate consisting of 5% by weight of addition, 8-PENPP (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, Polyoxyethylenenonylphenyletherphosphate) consisting of 7 mole added 6% by weight, 6 mole added 6% by weight), 12-PENPP (13 mole added by 13 mole ethylene oxide, 12 mole added 80) Polyoxyethylenenonylphenyletherphosphate consisting of 8% by weight, 11% by weight added, 8% by weight added, 9% by weight added and 6% by weight added, 16-PENPP (17 moles added by ethylene oxide) Consisting of 3% by weight, 16% by weight added 79% by weight, 15% by weight added 10% by weight, 14% by weight added 4% by weight, 13 parts by weight added 4% by weight Polyoxyethylene nonylphenyl ether phosphate), 20-PENPP (21% addition of ethylene oxide 5% by weight, 20% addition by 78% by weight, 19% addition by 7% by weight, 18 moles by addition 6% by weight %, 17 mol added 4% by weight of polyoxyethylene nonylphenyl ether phosphate), 4-PPNPP (5 mol added with 5 mol of propylene oxide, 80 mol% with 4 mol added, 3 mol added Polyoxypropylene nonylphenyl ether phosphate consisting of 10% by weight, 5% by weight of 1 mole added, 8-PPNPP (3% by weight of 9 moles of propylene oxide added, 80% by weight of 8 moles added, 9 moles Polyoxypropylenenonylphenyletherphosphate consisting of 5% by weight added, 6% by weight added by 7 mol, 6% by weight added, 12-PPNPP (3% by weight added by 13 moles of propylene oxide), 12 mole added 80% by weight, 11 mole added 8% by weight, 9 mole added by 3% by weight, 4 mole added by 6% by weight Polyoxypropylene nonylphenyl ether phosphate), 16-PPNPP (17 moles of propylene oxide added 3% by weight, 16 moles added 79% by weight, 15 moles added 10% by weight, 14 moles added 4 Polyoxypropylene nonylphenyl ether phosphate consisting of 4% by weight of 13% by weight, 20-PPNPP (5% by weight of 21 moles of propylene oxide, 78% by weight of 20 moles, 19 parts of mole added Polyoxypropylenenonylphenyletherphosphate) consisting of 7% by weight, 18% by weight added 6% by weight, 17% by weight added 4% by weight and Zelec UN ^TM Use at least one selected from. Various substituents including the halogen compound substituents of such phosphate ester compounds may be used for the same purpose.

The optical resin composition of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity, etc., in order to improve optical properties of the copolymer optical resin (optical material). have. As an olefin compound which can be added as a resin modifier, for example, benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2 Hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy ethyl acrylate, phenoxy ethyl methacrylate, phenyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate, Polyethylene Glycol Diacrylate, Polyethylene Glycol Dimethac Latex, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2 , 2-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2, 2-bis (4-methoxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-hydroxyethoxyphenyl) methane, 1,1-bis ( 4-Methoxyethoxyphenyl) methane, 1,1-bis (4-acryoxydiethoxyphenyl) methane, 1,1-bis (4-methoxydiethoxyphenyl) methane, dimethyloltricyclodecane Acrylate, trimetholpropane triacrylate, trimetholpropane trimethacrylate, glycerol diacrylate, Liserol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meth) acrylate compounds, such as xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether , Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallylcarbonate, and styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, and divinylbenzene , Vinyl compounds such as 3,9-divinylspirobi (m-dioxane), and the like, It is not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

The optical resin composition of the present invention may further include an ultraviolet absorbent as necessary. As the ultraviolet absorber is used for improving the light resistance of the optical material and blocking the ultraviolet ray, 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'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types.

Preferably, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -Chloro-2H-benzotriazole and 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole and the like can be used. Such an ultraviolet absorber can block 400 nm or more when used in an amount of 0.6 g or more with respect to 100 g of the optical resin composition.

In addition, 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 improving agent, as necessary.

As the polymerization initiator, an amine-based or tin-based compound can be used. As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Oxalic acid stannous; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; triphenyltin chloride; Dibutyltin sulfide; Di (2-ethylsecyl) tin oxide and the like may be used alone or in combination of two or more thereof. Especially preferably, tetrabutyl phosphonium bromide and dibutyl tin chloride can be used together.

When such a tin compound was used, the polymerization yield was high and there was no bubble generation. It is preferable to use the usage-amount in 0.001-4 weight% of the whole composition.

The optical resin composition of the present invention having the above composition, preferably has a liquid viscosity of 500 cps or less (20 ° C.) or less, and the solid phase refractive index (Ne) after polymerization is 1.691 to 1.709. As used herein, the term "refractive index 1.70" or "1.70 lens" means an optical material (lens) in which the solid state refractive index Ne falls in the range of 1.691 to 1.709.

The composition prepared as described above is subjected to mold polymerization to obtain a thioepoxy optical material. In more detail, First, the polymeric composition of this invention is inject | poured between the shaping | molding mold hold | maintained with the gasket or the tape. Under the present circumstances, it is preferable to perform the defoaming process under reduced pressure, the filtration process, such as pressurization and reduced pressure, etc. according to the physical property calculated | required at the time of the obtained optical material in many cases. The polymerization conditions are not limited because the conditions largely vary depending on the polymerizable composition, the type and amount of the catalyst, the shape of the mold, and the like, but are carried out over a period of 1 to 50 hours at a temperature of about -50 to 150 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 150 ° C. and to cure in 1 to 48 hours.

The thioepoxy compound, isocyanate compound, and thiol compound copolymer obtained by hardening may perform annealing etc. as needed. Treatment temperature is normally performed between 50-150 degreeC, and it is preferable to carry out at 90-140 degreeC.

During the polymerization, various additives such as an internal mold release agent may be added to the composition, and the description thereof is the same as that of the above composition. In the polymerization, the catalyst used in particular plays an important role. As the catalyst, epoxy curing agents are mainly used. Strong amines can also be used, but they require caution because they intensify the isocyanate reaction. In the present invention, preferably, amine salts, phosphonium salts, phosphines and tertiary amines having no electron withdrawing groups, Lewis acids, radical initiators and the like are mainly used. The type and amount of catalyst may vary from case to case.

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

Unlike conventional thioepoxy optical materials, the thioepoxy optical material obtained in accordance with the present invention has excellent hard adhesion, and enables hard coating without a primer, very easy coating, and excellent coating stability. The plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides as necessary. As the coating layer, a primer layer, a hard coating layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, a water repellent layer, and the like can all be used. These coating layers may be used alone or in a plurality of coating layers. In addition, when forming a coating layer in both surfaces, it is possible to form the same coating layer in 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 examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.

Test and evaluation method

1) refractive index (nE) and Abbe's number

Measurements were made at 20 ° C. using an Abe refractometer, an Atago IT and DR-M4 model.

2) dysplasia

The number of damaged molds and lenses generated by injecting a thioepoxy optical material composition containing an additive into the glass mold for lens frequency -4.00 and thermosetting and separating the optical lens and the mold at 40 ° C. It is expressed as the sum total.

3) Initial color (APHA)

Hunterlab's ColorQuest XE instrument was used to measure the APHA value of a 2 mm thick plastic optical lens.

4) dyeability

After dipping for 2 minutes in a thickness of 2 mm and a 0.00 degree lens in BPI gray colored dye solution heated to 98 ° C. for 40 minutes, the resultant was washed and dried in clear water, and then the light blocking rate was measured using a Shimadzu UV 2450 spectrophotometer.

5) Hard film adhesive

After dipping and coating the lens in Itosa hard liquid for 1.67 (ITOH, Z-118), the film was heat-cured at 1 mm intervals in 1 mm intervals on a transparent coating film obtained by thermal curing at 85 ° C. for 4 minutes at 1 ° C and 110 ° C. for 120 minutes at 1 ° C. The dogs were cut with a knife, and 100 cells of 1 mm x 1 mm were made, and an adhesive tape (Kwanggwang Tape Co. K-5) having excellent adhesive strength was attached thereto, and they were sharply removed to be close to an angle of 180 ° C. This was repeated five times at the same location. The number of spaces in which the hard curtain fell off at least was recorded.

6) tensile strength

10 eyeglass lenses with a diameter of 75 mm (frequency -2.00, center thickness of 1.20 mm) were punched on both ends (8 mm from the edge of the lens to the center of drilling, 8 mm diameter 2.9 mm) with a punch The measured parts were measured by Lloyd Instruments Ltd. (USA) LR5K Plus model universal tester at room temperature of 20 ℃ and expressed as the average value of the maximum load on the universal tester. The unit is N.

7) compressive strength

Lloyd Instruments Ltd at room temperature 20 ℃ based on the measuring method of ISO 14889 (JIS T7331, Korea Institute of Food and Drug Safety Evaluation (Mechanical Strength Test)) of 10 spectacle lenses with a diameter of 75 mm (frequency -2.00, center thickness of 1.20 mm) It was measured by the universal testing machine of LR5K Plus model of USA and expressed as the average value of the maximum load on the universal testing machine. The unit is N.

8) transmittance

The measurement was carried out using a shimadzu UV 2450 spectrophotometer.

9) Polymerization heterogeneity

-2.00, -4.00, -6.00, -8.00, -10.00 20 eyeglass lenses of 20 degrees each are prepared and visually observed. If there is no polymerization unevenness, ◎, there is a trace of polymerization unevenness of 5 mm or more outside 40 mm from the center of the lens. If you see ~ 5, 6 ~ 30 polymerization nonuniformity traces over 5mm from the center of the lens are visible. When the trace of polymerization nonuniformity was seen within 40 mm from the center, it represented by x.

10) thermal stability

Measure the initial light transmittance using a Shimadzu UV 2450 spectrophotometer after preparing a lens having a center thickness of 2 mm and a tap water, and then leaving it for 12 hours in an oven at 120 ° C. and measuring the light transmittance again to display the difference value (△). It was.

Example 1

64.40 g of bis (2,3-epiopropyl) sulfide (BEPS), 5.60 g of (2,3-epiopropyl) (2,3-epoxypropyl) sulfide (EPTES), 2,3-bis (2 16.60 g of mercaptoethylthio) propane-1-thiol (GST), 13.40 g of xylene diisocyanate (XDI); 0.07 g of polyoxyethylenenonylphenyletherphosphate) consisting of 80% by weight added, 5% by weight added by 9 moles, 6% by weight added by 7 moles, and 6% by weight added by 6 moles 0.07 g of phonium bromide, 0.03 g of dibutyltin chloride, organic dye HTAQ (0.2 ppm) and PRD (0.1 ppm), and 0.6 g of an ultraviolet absorber HOPBT were uniformly mixed at 10 ° C. The mixed solution was degassed at 3 torr for 1 hour, filtered through a 1 μm PTFE filter, and poured into a mold made 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 the completion of the polymerization, the oven was gradually cooled to 70 ° C. for 1 hour, and then the mold was taken out and released from the mold to obtain a lens. The obtained lens was further annealed at 100 ° C for 4 hours. The physical properties of the obtained lens were evaluated according to the above test method, and the results are shown in Table 1 below.

Examples 2-7

A lens was obtained in the same manner as in Example 1 except that the monomer composition was described in Table 1, and the physical 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 showed good results in terms of initial color, thermal stability, dyeing, hard film adhesion, tensile strength, and compressive strength. In particular, the more the thiourethane component contained, the better the initial color, dyeing property, hard film adhesion, tensile strength, and compressive strength. There was no.

Comparative Example 1

81.24 g of bis (2,3-epithiopropyl) sulfide (BEPS), (2,3-epiopropyl) (2,3-epoxypropyl) sulfide (EPTES) 7.06 g, 2,3-bis (2 Mercaptoethylthio) propane-1-thiol (GST) 6.46 g, xylene diisocyanate (XDI) 5.24 g, 8-PENPP is an acidic phosphate ester (3% by weight of 9 mole of ethylene oxide, 80% by weight of 8 mole added, 5% by weight of 9 mole added, 6% by weight of 7 mole added, 6) 0.07 g of polyoxyethylenenonylphenyl ether phosphate consisting of 6% by weight of a molar addition, 0.07 g of tetrabutylphosphonium bromide, 0.03 g of dibutyltin chloride, Organic dyes HTAQ (0.2ppm) and PRD (0.1ppm), 0.6g of UV absorber HOPBT at 10 ℃ Mix uniformly. This mixed solution After degassing at 3 torr for 1 hour, filtration was carried out with a 1 μm PTFE filter and injected into a mold made 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 the completion of the polymerization, the oven was gradually cooled to 70 ° C. for 1 hour, and then the mold was taken out and released from the mold to obtain a lens. The obtained lens was further annealed at 100 ° C for 4 hours. Physical properties of the obtained lens were evaluated according to the above test method, and the results are shown in Tables 2 to 3 below.

Comparative Examples 2-9

A lens was obtained in the same manner as in Example 1 except that the monomer composition was set forth in Tables 2 and 9, and the physical properties of the lens obtained in the same manner as in Example 1 were evaluated, and the results are shown in Tables 2 to 3 below. Shown in

Comparative Example 1 was to contain less than the thiourethane component of 11.7% compared to the Example, all compared with the Example, the initial color, dyeing, hard film adhesion, tensile strength, thermal stability was significantly lower than the Example. Comparative Example 2 contains 50% of the thiourethane component, and Comparative Example 7 uses another compound instead of GST or FSH as a polythiol component. The initial color and thermal stability are poor, and polymerization nonuniformity appears to be used as a lens. Not suitable Polyisocyanates and / or polythiols use other compounds instead of XDI, GST, or FSH, or the EPTES content is less than 2.46 or too little or more than 12.75 and Comparative Examples 3 to 5 and 7 to 9 are polymerizable in uneven enough to be difficult to measure physical properties. It appeared very badly.

TABLE 1

TABLE 2

TABLE 3

<Abbreviation>

BEPS: bis (2,3-epithiopropyl) sulfide

EPTES: (2,3-epoxypropyl) (2,3-epoxypropyl) sulfide ((2,3-epithiopropyl) (2,3-ep oxypropyl) 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-trithiaoundecan

PETMP: pentaerythritol tetrakis (3-mercaptopropionate)

BMES: bis (2-mercaptoethyl) sulfide

XDI: Zylene 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'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole)

HTQA: 1-hydroxy-4- (p-tolludine) -entroquinone (1-hydroxy-4- (p-toluidine) anthraquinone)

PRD: perinone dye

Claims (17)

1. (a) bis (2,3-epithiopropyl) sulfide as a thioepoxy compound; (b) xylylenediisocyanate as the polyisocyanate compound in the thiourethane component; (c) 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 as a polythiol compound in the thiourethane component , 9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 5,7-dimercaptomethyl-1,11-di At least one of mercapto-3,6,9-trithiaoundecan,

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

   A thioepoxy optical resin composition comprising at least 15% by weight of a thiourethane component of the above (b) and (c) in the total composition.
2. The method of claim 1,

   A thioepoxy optical resin composition having a liquidus viscosity of 500 cps or less and a solid phase refractive index (Ne) of 1.691 to 1.709 after polymerization.
3. The method of claim 1,

   The thioepoxy optical resin composition whose ratio of NCO group / SH group of the said polyisocyanate compound and a polythiol compound is 0.3-3.0.
4. The method of claim 1,

   A thioepoxy optical resin composition, further comprising a thioepoxy compound in addition to the thioepoxy compound.
5. The thioepoxy optical resin composition according to claim 1, further comprising a polyisocyanate compound in addition to the polyisocyanate compound.
6. The thioepoxy optical resin composition according to claim 1, further comprising another polythiol compound in addition to the polythiol compound.
7. The thioepoxy optical resin composition according to any one of claims 1 to 6, further comprising an olefin compound as a reactive resin modifier.
8. The thioepoxy optical resin composition according to any one of claims 1 to 6, further comprising an internal release agent.
9. The thioepoxy optical resin composition according to any one of claims 1 to 6, further comprising an ultraviolet absorber.
10. The thioepoxy optical resin composition according to any one of claims 1 to 6, further comprising tetrabutylphosphonium bromide and dibutyl tin chloride as a polymerization initiator.
11. (a) bis (2,3-epithiopropyl) sulfide as a thioepoxy compound; (b) xylylenediisocyanate as the polyisocyanate compound in the thiourethane component; (c) 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 as a polythiol compound in the thiourethane component , 9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 5,7-dimercaptomethyl-1,11-di At least one of mercapto-3,6,9-trithiaoundecan,

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

    A method for producing a thioepoxy optical material comprising the step of polymerizing a polymerizable composition comprising at least 15% by weight of the thiourethane component combined with (b) and (c).
12. The method of claim 11,

    The polymerizable composition has a liquid phase viscosity of 500 cps (20 ° C.) or less, and has a solid phase refractive index (Ne) of 1.691 to 1.709 of the optical material obtained after the polymerization.
13. 12. The method of claim 11, wherein the polymerizable composition further comprises an internal release agent.
14. 12. The method of claim 11, wherein the polymerizable composition further comprises an ultraviolet absorber.
15. 12. The method of claim 11, wherein the polymerizable composition further comprises tetrabutylphosphonium bromide and dibutyl tin chloride as a polymerization initiator.
16. A thioepoxy clock optical material comprising the thioepoxy clock optical resin composition according to any one of claims 1 to 6.
17. The thioepoxy optical material according to claim 16, wherein the thioepoxy optical material is any one of an optical lens for vision correction lens, sunglasses lens, fashion lens, discoloration lens, camera lens, lens for optical device.