WO2020046005A1 - Agent stabilisant de matériau optique à base d'épisulfure hautement réfractif, composition de matériau optique utilisant celui-ci, et procédé de production de matériau optique - Google Patents

Agent stabilisant de matériau optique à base d'épisulfure hautement réfractif, composition de matériau optique utilisant celui-ci, et procédé de production de matériau optique Download PDF

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WO2020046005A1
WO2020046005A1 PCT/KR2019/011042 KR2019011042W WO2020046005A1 WO 2020046005 A1 WO2020046005 A1 WO 2020046005A1 KR 2019011042 W KR2019011042 W KR 2019011042W WO 2020046005 A1 WO2020046005 A1 WO 2020046005A1
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episulfide
optical material
bis
composition
formula
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PCT/KR2019/011042
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Korean (ko)
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장동규
노수균
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주식회사 케이오씨솔루션
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Publication of WO2020046005A1 publication Critical patent/WO2020046005A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures

Definitions

  • the present invention relates to an episulfide-based high refractive optical material, in particular a stabilizer for episulfide-based high refractive optical material that can solve the problems of striae, color and thermal stability in episulfide-based high refractive optical material and episulfide-based optical material comprising the same It relates to a method for producing a composition for optical and optical materials.
  • Plastic lenses are light, impact resistant and easy to color, and in recent years, plastic lenses have been used in most eyeglass lenses.
  • Plastic eyeglass lenses have been developed in the direction of increasing light weight, high transparency, low yellowness, heat resistance, light resistance and strength.
  • Korean Patent No. 10-0681218 proposes an episulfide plastic lens.
  • Episulfide-based lenses have excellent refractive index and high Abbe number, but have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, and productivity.
  • a method of copolymerizing two kinds of resins having different properties that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound together is disclosed in Korean Patent Registration No. 10-0417985 Proposed 11-352302 or the like.
  • episulfide-based high refractive lenses of 1.67 or more often have a problem of appearing stria and inferior color and thermal stability.
  • Patent Document 1 Republic of Korea Registered Patent Publication 10-0417985
  • Patent Document 2 JP 11-352302 A
  • Patent Document 3 Japanese Unexamined Patent Publication 2001-2783
  • Patent Document 4 Republic of Korea Patent Publication 10-2014-0122721
  • Episulfide-based high refractive optical lenses often present striae, color and thermal stability issues, which degrade lens quality, reduce productivity and disrupt commercialization.
  • An object of the present invention is to provide a stabilizer that can solve the problems of striae, color and thermal stability that are often found in episulfide-based high refractive optical lenses, and by using this, episulfide-based optical materials having good quality and thermal stability can be obtained with high productivity. It is to provide a composition for an optical material and a method for producing the optical material.
  • composition for episulfide-based optical material containing a polymerization catalyst.
  • the episulfide optical material composition may further include sulfur.
  • the episulfide optical material composition may further include a polyisocyanate compound.
  • the episulfide optical material composition may further include a tin halogen compound as a polymerization regulator.
  • the present invention provides a method for producing an episulfide high refractive optical material comprising polymerizing the composition for episulfide optical material.
  • Stabilizers comprising an episulfide compound of formula (1) provided by the present invention can solve the problems of striae, color, and thermal stability often found in episulfide-based high refractive optical lenses.
  • this stabilizer in the composition for episulfide-based optical materials, it solves the problems of striae, color and thermal stability often found in episulfide-based high refractive optical lenses in a relatively simple method, and has high lens quality and thermal stability with high productivity.
  • a sulfide optical material can be obtained.
  • 'high refractive index' is not particularly limited, meaning that it includes all from 1.67 or more to 1.71 or more commonly referred to as ultrahigh refractive index. Typically, but not limited to, the refractive index ranges from 1.67 to 1.77.
  • an episulfide compound represented by the following Chemical Formula 1 is provided as a stabilizer for an episulfide optical material.
  • the episulfide compound represented by Chemical Formula 1 may be produced and synthesized in a small amount during the synthesis process of the episulfide compound represented by Chemical Formula 2, and as a result of the research, when the compound is included or not It was found that there is a difference in the stability of the polymerization reaction.
  • the compound of Formula 1 significantly affected the generation of stria and the color and thermal stability of the manufactured lens during the polymerization of the composition for an optical material containing the compound of Formula 2.
  • the compound of Formula 1 Compared with the case where the compound of Formula 1 is not included at all in a certain range or more than a certain range, the compound of Formula 1 has no stria and color and thermal stability are good.
  • the compound of Formula 1 may be used in an amount of 0.01 to 5.5% by weight in the composition for episulfide optical materials, more preferably 0.1 to 5% by weight, and more preferably 0.5 to 3.3% by weight. Can be.
  • composition for episulfide optical materials of the present invention includes an episulfide compound represented by Formula 2 below, an episulfide compound represented by Formula 1, a polythiol compound, and a polymerization catalyst.
  • the episulfide compound represented by the formula (2) is a main component of the composition for episulfide optical materials.
  • Formula 2 episulfide compound is, for example, bis (2,3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epoxypropyl (2, 3- epithiopropyl Disulfide, 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, 1,3 and 1,4-bis ( ⁇ -epithiopropylthio) cyclohexane, 1,3 and 1,4-bis ⁇ -epithiopropylthiomethyl) cyclohexane, bis [4- ( ⁇ -epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- ( ⁇ -ethiothiothio) cyclohexyl] propane, bis Episulfide compounds having an alicycl
  • halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-modified compounds with polythiol may be used.
  • 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-epiopropyl) disulfide, 1,3 and 1,4-bis ( ⁇ -epithiopropylthio) cyclohexane, 1,3 and 1,4-bis ( ⁇ - Epithiopropylthiomethyl) cyclohexane, 2,5-bis ( ⁇ -ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis ( ⁇ -ethiothiopropylthioethylthiomethyl) -1, One or more of 4-dithiane, 2- (2- ⁇ -epithiopropylthioethylthio) -1,3-bis ( ⁇ -ethiothiothio
  • the episulfide compound represented by the formula (1) may be included in the composition by adding it separately or by adjusting the amount generated and synthesized in the synthesis process of the episulfide compound represented by the formula (2).
  • the episulfide compound of Formula 1 is included in the composition for optical materials 0.01 to 5.5% by weight. More preferably, it is included in 0.1 to 5% by weight, and more preferably in 0.5 to 3.3% by weight.
  • the said polythiol compound is not specifically limited, If it is a compound which has at least 1 or more thiol groups, 1 type (s) or 2 or more types can be mixed and used for it.
  • 1 type (s) or 2 or more types can be mixed and used for it.
  • the polymerization modified body obtained by prepolymerization with an isocyanate, an episulfide compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used.
  • polythiol compound particularly preferably, bis (2-mercaptoethyl) sulfide or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or other polythiol compound It can mix and use species.
  • the polythiol may preferably be included in the composition for the optical material 1 to 15% by weight, more preferably 4 to 13% by weight, still more preferably 5 to 11% by weight.
  • the polymerization catalyst is preferably one or more selected from amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, at least one selected from quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds can be used.
  • quaternary ammonium salt for example, tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride or the like can be used.
  • quaternary phosphonium salt tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide or the like can be used, for example.
  • Triphenylphosphine etc. can be used as a phosphine compound.
  • the polymerization catalyst is a quaternary phosphonium salt and contains any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. These polymerization catalysts can be used individually or in mixture of 2 or more types.
  • the episulfide optical material composition may further include sulfur.
  • the sulfur When the sulfur is further included, the refractive index can be increased to ultra high refractive index of 1.71 or more.
  • the sulfur contained in the composition is preferably at least 98% pure. If less than 98%, the transparency of the optical material may be degraded due to the influence of impurities.
  • the purity of sulfur is more preferably 99.0% or more, particularly preferably 99.5% or more. Commercially available sulfur is classified by the difference in shape or purification method, and there are fine powder sulfur, colloidal sulfur, precipitated sulfur, crystal sulfur, sublimed sulfur and the like. In the present invention, any sulfur can be used as long as the purity is 98% or higher.
  • fine powder of fine particles that can be easily dissolved may be used in preparing the composition for an optical material.
  • the content of sulfur in the composition is preferably 1 to 40% by weight in the total weight of the composition for the optical material, more preferably 2 to 30% by weight, most preferably 3 to 22% by weight.
  • the episulfide optical material composition may further include a polyisocyanate compound.
  • the polyisocyanate compound is not particularly limited and a compound having at least one isocyanate group and / or isothiocyanate group can be used.
  • the compound has at least one isocyanate group and / or isothiocyanate group, one kind or two or more kinds can be used.
  • halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer-type modified compounds with polyhydric alcohols or thiols, carbodiimide modified products, urea modified products and biuret modified compounds of these isocyanate compounds.
  • dimerization, trimerization reaction products and the like can also be used.
  • isophorone diisocyanate IPDI
  • hexamethylene diisocyanate HDI
  • dicyclohexyl methane diisocyanate H12MDI
  • xylylene diisocyanate XDI
  • 3,8-bis (iso Cyanatomethyl) tricyclo [5,2,1,02,6] decane 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane
  • 4,8-bis (Isocyanatomethyl) tricyclo [5,2,1,02,6] decane 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane
  • 2,6-bis iso One or more selected from cyanatomethyl) bicyclo [2,2,1] heptane can be used.
  • the episulfide optical material composition may further include a tin halogen compound as a polymerization regulator.
  • the tin halide compound may be preferably any one of dibutyltin dichloride and dimethyltin dichloride or a small amount of monomethyltin trichloride contained therein. More preferably monomethyltin trichloride may be included in 0.1 to 3.5% by weight.
  • the polymerization regulator is preferably used in 0.01 to 5% by weight of the total weight of the composition for an optical material.
  • the polymerization rate can be adjusted to suppress a sudden increase in viscosity, and as a result, the polymerization yield is increased and bubbles are also eliminated.
  • alkylimidazole When sulfur is included in the composition for episulfide optical materials, it is preferable to form a prepolymer and then polymerize.
  • alkylimidazole may be further included as a polymerization regulator.
  • the alkylimidazole particularly preferably comprises 2-mercapto-1-methylimidazole. 2-mercapto-1-methylimidazole is preferably used with a purity of 98% or more.
  • Preferably in the composition for an optical material may be included 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, 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.
  • the internal mold release agent may include a phosphate ester compound.
  • the phosphate ester compound is prepared by adding 2-3 moles of an alcohol compound to phosphorus pentoside (P 2 O 5 ), and various types of phosphate ester compounds can be obtained according to 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 nonylphenol group.
  • P 2 O 5 phosphorus pentoside
  • 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 nonylphenol group.
  • the phosphate ester compound added with ethylene oxide or propylene oxide is included 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 [polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mol ethylene oxide, 80% by weight 4 mol added, 3 mol addition 10% by weight, 1 mole added 5% by weight)], 8-PENPP (polyoxyethylenenonylphenol ether phosphate (3% by weight 9 mole ethylene oxide added, 80% by weight 8 mole added 9) Mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight) , 12 mole added 80%, 11 mole added 8%, 9 mole added 3%, 4 mole added 6% by weight)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 mole added with ethylene oxide, 79% by weight with 16 mole added, 10% by weight with 15 mole
  • the composition for an optical material of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of adjusting impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties of the optical material.
  • 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, tri
  • the composition for an optical material of this invention may further contain a ultraviolet absorber as needed.
  • the ultraviolet absorber is used to improve the light resistance of the optical material and to block ultraviolet rays, and known ultraviolet absorbers used in the optical material may be used without limitation.
  • 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'
  • 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 composition for an optical material.
  • composition for an optical material of the present invention may further include various additives such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a coloring inhibitor, an organic dye, a filler, and an adhesion improving agent, as necessary.
  • 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.
  • composition for an optical material of the present invention having the above composition preferably has a liquid viscosity of 500 cps or less (20 ° C.) or less and 1.67 to 1.70 when the solid phase refractive index (Ne) after polymerization does not include sulfur. 1.71-1.77
  • the polymeric composition of this invention is inject
  • the polymerization conditions are not limited because the conditions vary greatly depending on the polymerizable composition, the type and the amount of the catalyst used, 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 130 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 130 ° C. and to cure in 1 to 48 hours.
  • the episulfide compound optical material obtained by curing may be subjected to annealing or the like as necessary.
  • Treatment temperature is normally performed between 50-130 degreeC, and it is preferable to carry out at 90-120 degreeC.
  • the optical material of this invention can be obtained by the molded object of various shapes by changing the mold at the time of casting polymerization, it can be used with various optical materials, such as an eyeglass lens, a camera lens, and a light emitting diode (LED).
  • various optical materials such as an eyeglass lens, a camera lens, and a light emitting diode (LED).
  • LED light emitting diode
  • it is suitable as optical materials, such as an eyeglass lens, a camera lens, a light emitting diode, and an optical element.
  • the episulfide optical material obtained according to the present invention is excellent in hard adhesion, and can be hard-coated without a primer, coating is very easy, and coating stability is also excellent.
  • the plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides as necessary.
  • a primer layer, a hard coating layer, an antireflection film layer, an antifogging coat 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.
  • Epichlorohydrin (5563 g, 60.12 mol) and methanol (3500 g) were added to a 10 liter reactor, caustic soda (50% (aq), 5 g) when the reaction temperature was set at 6 ° C. and the reaction temperature reached 6 ° C. Was added.
  • methanol (1000 g) and water (500 g) were added and stirred to dissolve completely.
  • the layers are separated and the organic layer, the supernatant, is washed three times with water and the water is removed as much as possible.
  • 400 g of methanol was further added to the organic layer solution, followed by stirring.
  • the reaction temperature was 372.23 g (4.89 mol) of thiourea and acetic anhydride (35 g) at 8 ° C., and the reaction temperature was reacted at 18 ° C. for 24 hours.
  • stirring was stopped and the layers were separated, the lower layer was removed, the organic layer was washed three times with water, the toluene layer was removed, and developed with a dichloromethane and a cyclohexane solvent to purify the silica gel column.
  • the temperature of the obtained organic layer solution was adjusted to 25 ° C, and 196.8 g of 25% NaOH (aq) was slowly added dropwise to maintain the internal temperature at 30 to 35 ° C.
  • the internal temperature was aged at 35 ° C. for 1 hour, the layers were separated to remove the water layer, the organic layer was washed with water, and 1 g of triethylamine and 44.3 g of water were added to the obtained organic layer and reacted at 60 ° C. for 48 hours.
  • the obtained organic solution was removed under reduced pressure, developed with chloromethane and cyclohexane solvent, and purified by silica gel column. After purification, 3- (2-hydroxy-3- (thiran-2-ylmethylthio) propylthio) 153.85 g of propane-1,2-diol were obtained.
  • the reactor was decompressed to 1.0 torr or lower and the external temperature was adjusted to 54 ° C. While stirring the reactor, 79.9 g of bis (2,3-ethiothiopropyl) sulfide compound and 3- (2-hydroxy-3- (thiran-2-ylmethylthio) propylthio) propane-1,2-diol 0.1 g was added, sulfur 15.5 g, sunscreen UV 31 0.8 g, organic dyes HTAQ (88 ppm) and PRD (30 ppm) were added, followed by degassing under reduced pressure for 30 minutes, followed by 2-mercapto-1-methylimidazole. 0.75 g was added and stirred for 1 hour.
  • the resin composition for optical lenses prepared as described above was degassed under stirring at 43 ° C. for 1 hour under reduced pressure, cooled to 30 ° C., filtered, and further subjected to reduced pressure defoaming for 5 minutes, and then assembled with a polyester adhesive tape. Into a glass mold.
  • Streaking (polymerization imbalance): 100 lenses with a diameter of 80 mm and a +11 D degree were prepared and observed by the Schlieren method under Mercury Arc Lamp of USHIO USH-10D. It was. If no stria of 100 lenses is observed at all, mark ⁇ , and if no stria is observed at 1 to 5 lenses out of 100, mark ' ⁇ '. The fact that no stria is observed is indicated by ' ⁇ ', and the fact that stria is observed in 10 or more lenses out of 100 lenses is indicated by ' ⁇ '.
  • the cured optical lens is kept at 100 ° C for 3 hours, and when the APHA value changes from 0 to less than 2 in the measurement of color change, it is indicated by ' ⁇ ', and when the APHA value changes from 2 to less than 7, ⁇ ', and when the APHA value changes to 7 or more,' ⁇ '.
  • An optical lens was manufactured according to the mass ratio of the episulfide compound (Formula 1) and the episulfide compound (Formula 2) shown in Table 1 in the same manner as in Example 1, and the physical properties thereof were tested. The results are shown in Table 1 . It was.
  • the episulfide optical material obtained according to the present invention is a high quality lens having no striae and good color and thermal stability, and can be usefully used for lenses for corrective sunglasses, fashion lenses, discoloration lenses, camera lenses, and optical devices. .

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Abstract

La présente invention concerne un agent stabilisant de matériau optique à base d'épisulfure hautement réfractif qui peut résoudre des problèmes de stries, de couleur et de stabilité thermique qui surviennent dans un matériau optique à base d'épisulfure hautement réfractif, une composition de matériau optique comprenant l'agent stabilisant de matériau optique à base d'épisulfure hautement réfractif, et un procédé de production du matériau optique. La présente invention concerne un agent stabilisant de matériau optique à base d'épisulfure comprenant le composé épisulfure exprimé par la formule chimique 1. De plus, l'invention concerne une composition de matériau optique à base d'épisulfure comprenant le composé épisulfure exprimé par la formule chimique 2, l'agent stabilisant et analogues. En incluant l'agent stabilisant dans la composition de matériau optique à base d'épisulfure, la présente invention peut résoudre, au moyen d'un procédé relativement simple, les problèmes de stries, de couleur et de stabilité thermique qui surviennent occasionnellement dans des lentilles optiques à base d'épisulfure hautement réfractives.
PCT/KR2019/011042 2018-08-31 2019-08-29 Agent stabilisant de matériau optique à base d'épisulfure hautement réfractif, composition de matériau optique utilisant celui-ci, et procédé de production de matériau optique WO2020046005A1 (fr)

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KR10-2018-0103954 2018-08-31
KR1020180103954A KR20200025927A (ko) 2018-08-31 2018-08-31 에피설파이드계 고굴절 광학재료용 안정제와 이를 이용한 광학재료용 조성물 및 광학재료의 제조방법

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KR20170066660A (ko) * 2015-03-31 2017-06-14 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 신규한 에피설파이드 화합물 및 이것을 포함하는 광학재료용 조성물
KR101827334B1 (ko) * 2015-03-31 2018-02-08 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 신규 에피설파이드 화합물 및 이것을 포함하는 광학재료 조성물

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JP4161411B2 (ja) 1998-06-10 2008-10-08 セイコーエプソン株式会社 プラスチックレンズの製造方法及びプラスチックレンズ
JP3738817B2 (ja) 1999-04-23 2006-01-25 三菱瓦斯化学株式会社 光学材料用組成物
CA2337955C (fr) 2000-03-15 2006-07-25 Hoya Corporation Lentilles en plastique pour lunettes
TWI568775B (zh) 2012-02-14 2017-02-01 Mitsubishi Gas Chemical Co A polymerizable composition for optical materials, a method for producing the same, and a method for producing an optical material

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KR20080053958A (ko) * 2001-04-06 2008-06-16 미츠비시 가스 가가쿠 가부시키가이샤 중합 조정제 및 수지용 조성물
JP2005272418A (ja) * 2004-03-26 2005-10-06 Mitsui Chemicals Inc エピスルフィド化合物の安定剤
KR20150053826A (ko) * 2013-03-14 2015-05-18 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 신규 에피설파이드 화합물 및 광학재료용 조성물
KR20170066660A (ko) * 2015-03-31 2017-06-14 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 신규한 에피설파이드 화합물 및 이것을 포함하는 광학재료용 조성물
KR101827334B1 (ko) * 2015-03-31 2018-02-08 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 신규 에피설파이드 화합물 및 이것을 포함하는 광학재료 조성물

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