WO2010128770A2 - Composition de résine pour lentille optique en uréthanne, présentant une résistance thermique et une réactivité élevées - Google Patents

Composition de résine pour lentille optique en uréthanne, présentant une résistance thermique et une réactivité élevées Download PDF

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Publication number
WO2010128770A2
WO2010128770A2 PCT/KR2010/002664 KR2010002664W WO2010128770A2 WO 2010128770 A2 WO2010128770 A2 WO 2010128770A2 KR 2010002664 W KR2010002664 W KR 2010002664W WO 2010128770 A2 WO2010128770 A2 WO 2010128770A2
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WIPO (PCT)
Prior art keywords
diisocyanate
resin composition
bis
isocyanatomethyl
optical lens
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PCT/KR2010/002664
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English (en)
Korean (ko)
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WO2010128770A3 (fr
Inventor
장동규
노수균
김종효
김문일
서진무
Original Assignee
주식회사 케이오씨솔루션
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Priority claimed from KR1020100038562A external-priority patent/KR101157497B1/ko
Application filed by 주식회사 케이오씨솔루션 filed Critical 주식회사 케이오씨솔루션
Priority to CN201080000845.0A priority Critical patent/CN102112548B/zh
Publication of WO2010128770A2 publication Critical patent/WO2010128770A2/fr
Publication of WO2010128770A3 publication Critical patent/WO2010128770A3/fr

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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • G02B1/043—Contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a plastic optical resin composition, and more particularly, to a resin composition for urethane-based optical lenses having high heat resistance and good reactivity.
  • Urethane-based plastic optical lenses manufactured by using mercapto compounds and isocyanates have been widely used as optical lens materials because of excellent optical properties, that is, transparency, Abbe number, and tensile strength.
  • urethane-based plastic optical lenses have a low heat distortion temperature, which causes problems with the center deformation of the lens during hard and multi-coating (anti-reflective coating) on the lens surface after casting, and is also exposed to high temperature and high humidity or heat in a sauna. In this case, the thermal deformation of the lens is severe and the multi-film is severely cracked. This causes a problem of deterioration of the transparency of the lens sharply by forming a cloudy film on the lens surface.
  • a urethane-based high refractive plastic optical lens having excellent transparency, Abbe number, and tensile strength is manufactured by thermally curing 0.05 moles of xylene diisocyanate and 0.025 moles of pentaerythritol tetrakis (mercaptopropionate).
  • the urethane-based high refractive plastic optical lens manufactured as described above has a problem in that thermal deformation is severe when exposed to high temperature, so that the multi-film is easily cracked, and the lens center portion is deformed during hard and multi-coating on the lens surface.
  • xylene diisocyanate and 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane are thermally cured to obtain a urethane-based ultrahigh refractive plastic optical lens.
  • This lens has a high refractive index of 1.655, There is a problem in that the lens center portion is deformed during hard and multi-coating on the lens surface, and when the film is exposed to high temperature, the thermal deformation is severe and the multi-film easily breaks.
  • Korean Patent Publication No. 1993-0006918 describes bis (isocyanatomethyl) triscyclo [5,2,1,0 2 , 6] decane and bis (isocyanato) in urethane optical lens manufacturing.
  • a urethane system is obtained by thermosetting methyl) bicyclo [2,2,2] heptane compound and pentaerythritol tetrakismercaptopropionate or 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane.
  • Plastic optical lenses are manufactured.
  • the urethane-based plastic optical lens thus manufactured has a bis (isocyanatomethyl) triscyclo [5,2,1,0 2 , 6] decane, bis (isocyanatomethyl) bicyclo [2 , 2,2] has a problem that is expensive to prepare heptane.
  • a method of preparing a resin composition for an optical lens by prepolymerizing a mercapto compound and an isocyanate compound is introduced in Korean Patent No. 10-0472837, which adds a dihydric alcohol to a polyisocyanate to increase lens impact resistance.
  • a resin composition for an optical lens and an optical lens having a high Abbe number and high impact resistance could not be produced.
  • the resin composition for an optical lens introduced in this patent has a high viscosity, which is difficult to inject, and there is a problem that a large amount of polymerization defect occurs during curing of the resin composition.
  • the manufactured lens has a refractive index of 1.545 to 1.556, which has a problem that the edge of the lens becomes thick due to its low refractive index.
  • Korean Patent Registration Nos. 10-0237664 and 10-0241989 disclose that a component obtained by prepolymerizing a polythiol compound having a characteristic structure with a polyisocyanate compound is composed of a component consisting of a (meth) acrylate compound and a compound copolymerizable with them.
  • the composition was polymerized and cured to provide an optical lens resin and an optical lens excellent in both physical properties and productivity of the lens.
  • the prepolymer obtained by reacting the resin composition for the optical lens with a molar ratio of -SH / -NCO in the range of 3.0 to 7.0 can be blended with acryl, but the viscosity is so high that it is directly blended with polyisocyanate, a urethane curing agent, and injected into the mold. Injecting is difficult, and there is a problem that a lot of polymerization failure occurs.
  • the prepolymer having a -SH / -NCO molar ratio of 0.5 to 2.0 shown in Japanese Patent Application Laid-Open No. 5-25240 has a higher viscosity and thus has the above problems in manufacturing a urethane-based optical lens.
  • the inventors of the present invention by using a low-cost general purpose isocyanate compound prior to the present invention while increasing the heat resistance of the lens, by mixing isophorone diisocyanate or dicyclohexyl methane diisocyanate with 1,6-hexamethylene diisocyanate He has developed and filed a method of use.
  • this method can achieve good heat resistance when the content of isophorone diisocyanate or dicyclohexyl methane diisocyanate in the isocyanate content is 40% by weight or more, in which case the reactivity with the mercapto compound decreases, resulting in high temperature.
  • the present invention aims to solve such problems of the prior art. That is, in the present invention, in order to increase the heat resistance of the lens, the low-cost general purpose isophorone diisocyanate or dicyclohexyl methane diisocyanate is mixed with 40% or more of the isocyanate compound to reduce the reactivity and the resulting reaction at high temperature. It is intended to solve the problem that the pressure-sensitive adhesive of the pressure-sensitive adhesive tape is eluted causing whitening at the edge of the lens. In addition, in the present invention, it is intended to solve the problem that bubbles are generated at the edge of the lens by the leakage of liquid caused by the expansion of the liquid composition with the increase of the reaction temperature.
  • the optical resin prepolymer obtained by the addition reaction in the range where the mercapto compound and isophorone diisocyanate or dicyclohexyl methane diisocyanate is in the range of less than 0.50 or more than 7.00 is added.
  • the optical resin prepolymer obtained by the addition reaction in the range where the mercapto compound and isophorone diisocyanate or dicyclohexyl methane diisocyanate is in the range of less than 0.50 or more than 7.00 is added.
  • a resin composition for an optical lens comprising the diisocyanate and another isocyanate compound in an amount of 3 to 60% by weight based on the total weight of the resin composition for an optical lens.
  • the resin composition for an optical lens of the present invention using the prepolymer reduces the content of isophorone diisocyanate or dicyclohexyl methane diisocyanate having low reactivity with the mercapto compound in the monomer composition and has good reactivity with the mercapto compound.
  • isocyanate eg, 1,6-hexamethylene diisocyanate
  • the optical resin prepolymer is a mixture obtained by pre-adding some isocyanate to the mercapto compound in advance or pre-adding a part of the mercapto compound to the isocyanate.
  • the optical resin prepolymer includes some mercapto compound or isocyanate that does not react with the reacted prepolymer.
  • the resin composition for an optical lens of the present invention is a mixture obtained by mixing the remaining mercapto compound and isocyanate in an optical resin prepolymer, and may be used for spectacle lenses by including other additives such as a release agent.
  • optical resin prepolymer obtained by the addition of the mercapto compound and isophorone diisocyanate or dicyclohexyl methane diisocyanate in advance by appropriately controlling the -SH / -NCO molar ratio.
  • an optical resin prepolymer is prepared by pre-adding some isophorone diisocyanate or dicyclohexyl methane diisocyanate to a mercapto compound.
  • Said 'some' is preferably one with a molar ratio of -SH / -NCO greater than 7 and less than 50, more preferably greater than 7 and less than 20.
  • the desired effect that is, the effect of increasing the reactivity is inferior
  • the viscosity of the resin composition for the spectacle lens is too high, which makes it difficult to inject the resin composition into the fixed mold.
  • the viscosity of the resin composition for the spectacle lens is about 40 to 150 cps in this range, the phenomenon of the leakage of the liquid composition and the resulting bubble problem is solved.
  • some of the mercapto compounds are previously added to isophorone diisocyanate or dicyclohexyl methane diisocyanate to obtain an optical resin prepolymer.
  • the 'parts' are -SH / -NCO molar ratio of less than 0.50, and more preferably 0.05 to 0.20. If it is smaller than 0.05, the desired effect, that is, the effect of increasing the reactivity is inferior, and when larger than 0.20 and smaller than 0.50, the viscosity of the resin composition for the spectacle lens is too high, which makes it difficult to inject the resin composition into the fixed mold. Similarly, when the -SH / -NCO molar ratio is 0.05 to 0.20, the viscosity of the resin composition for the spectacle lens becomes about 40 to 150 cps, which also solves the problem of leakage of liquid resin composition and air bubbles at the edge thereof. do.
  • polymerization of the resin composition for ophthalmic lenses is generally a rubber
  • Chem's JS-100, JS-200, LB-100; Tapes 810A, 6255, 6233, 815; Bestech 505; MR-2 from Comet Tape Co .; 8860, 870 from 3M; SLIONTEC's 6263 tape is useful. That is, a glass mold is assembled using such an adhesive tape, and a resin composition for spectacle lenses mixed with additives is put therein, followed by heat curing to prepare a lens.
  • the resin composition for the spectacle lens was prepared by including the optical resin prepolymer in which the mercapto compound and isophorone diisocyanate or dicyclohexyl methane diisocyanate were previously reacted to prepare the spectacle lens. .
  • the mercapto compound is a compound having at least one sulfur atom in the molecule.
  • the mercapto compound comprises a thiol ester compound.
  • the thiol ester compound is a trivalent thiol ester compound having three thiol groups in one molecule, trimethylolpropane tris (mercaptopropionate), trimethylolethane tris (mercaptopropionate), glycerol tris ( Mercaptopropionate), trimethylolchlorotris (mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), and the like.
  • PETMP pentaerythritol tetrakis (mercaptopropionate)
  • PETMA pentaerythritol tetrakis
  • BPEHMP bispentaerythritol-ether-hexakis (mercaptopropionate)
  • BPEHMA Bispentaerythritol-ether-hexakis (2-mercaptoacetate)
  • BPEMA bispentaerythritol hexa (2-mercapto Cetate)
  • BTMPMP bistrimethylolpropane tetrakis (3-mercaptopropionate)
  • BTMPMA bistrimethylolpropane tetrakis (2-mercaptoacetate)
  • 'isocyanates' except mercapto compounds, isophorone diisocyanates and dicyclohexyl methane diisocyanates include alkylene diisocyanate compounds, cycloaliphatic diisocyanate compounds, heterocyclic diisocyanate compounds, and sulfur-containing aliphatic diisocyanate compounds. Can be used.
  • alkylene diisocyanate compound for example, Ethylene diisocyanate; Trimethylene diisocyanate; Tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; Octamethylene diisocyanate; Nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexanediisocyanate; Decamethylene diisocyanate; Butene diisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecanetriisocyanate; 1,3,6-hexamethylenetriisocyanate; 1,8-diisocyanato-4-isocyanatomethyloctane; 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane; Bis (isocyanatoethyl) carbonate
  • alicyclic diisocyanate compound for example, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,0 2 , 6] decane; 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,0 2 , 6] decane; 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,0 2 , 6] decane; 4,9-bis (isocyanatomethyl) tricyclo [5,2,1,0 2 , 6] decane; 2,5 - Bis (isocyanatomethyl) bicyclo [2,2,1] heptane; 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane; Bis (isocyanatomethyl) cyclohexane; Dicyclohexyl methane diisocyanate; Cyclohexanediisocyanate; Methylcyclohexanediisocyanate; Dicyclohexyl
  • Heterocyclic diisocyanate compounds include, for example, thiophene-2,5-diisocyanate; Methyl thiophene-2,5-diisocyanate; 1,4-dithiane-2,5-diisocyanate; Methyl 1,4-dithiane-2,5-diisocyanate; 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate; Ethyl 1,3-dithiolane-2,2-diisocyanate; Tetrahydrothiophene-2,5-diisocyanate; Methyltetrahydrothiophene-2,5-diisocyanate; Ethyl tetrahydrothiophene-2,5-diisocyanate; Methyl te
  • Sulfur-containing aliphatic diisocyanate compounds include, for example, 4-isocyanato-4'-isothiocyanatodiphenylsulfide; 2-isocyanato-2'-isothiocyanatodiethyl disulfide; Thiodiethyl diisocyanate; Thiodipropyl diisocyanate; Thiodihexyl diisocyanate; Dimethyl sulfon diisocyanate; Dithiodimethyl diisocyanate; Dithiodiethyl diisocyanate; Dithiodipropyl diisocyanate; Dicyclohexylsulfur-4,4'- diisocyanate; 1-isocyanatomethylthia-2,3-bis (2-isocyanatoethylthia) propane and the like.
  • 1,6-hexamethylene diisocyanate, 2,4-trimethyl-1,6-diisocyanate hexane, or the like may be used alone or in combination of two or more as 'other isocyanates' which are highly reactive with the mercapto compound. .
  • the resin composition for lenses is used, a urethane-based high refractive optical lens having good heat resistance can be obtained.
  • the resin composition for optical lenses obtained by mixing the remaining dicyclohexyl methane diisocyanate or mercapto compound with the optical resin prepolymer in which the dicyclohexyl methane diisocyanate and the mercapto compound are partially reacted in advance is used, the heat resistance and impact resistance This good urethane-based high refractive optical lens can be obtained.
  • the resin composition for an optical lens of the present invention may further contain a known additive such as an ultraviolet absorber, a release agent, a polymerization initiator, and the like, and may be used as a resin composition for spectacle lenses.
  • a known additive such as an ultraviolet absorber, a release agent, a polymerization initiator, and the like
  • the total weight of the resin composition for the spectacle lens may include 0.001 to 10% by weight of the ultraviolet absorber, 0.0001 to 10% by weight of the release agent, and 0.001 to 10% by weight of the polymerization initiator.
  • any known ultraviolet absorber that can be used in the resin composition for the spectacle lens can 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-t-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-5-t-butyl
  • 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole 2-hydroxy- having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention.
  • 4-methoxybenzophenone, ethyl-2-cyano-3,3-diphenylacrylate, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole or 2,2-di Hydroxy-4,4-dimethoxybenzophenone, 2- (2-hydroxy-3,5-di-t-amylphenyl) -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 -Dihydroxy-4,4-dimethoxybenzophenone and the like can be used
  • the resin composition for spectacle lenses of the present invention may further include an organic dye.
  • an organic dye In the embodiment of the present invention, 1-hydroxy-4- (p-toluidine) anthraquinone [1-hydroxy-4- (p-toluidino) anthraquinone], perinone dye, and the like were used.
  • the organic dye is added in an amount of 0.001 to 50,000 ppm, preferably 0.005 to 1000 ppm per kg of the resin composition for spectacle lenses, thereby preventing the lens from becoming yellow by the addition of an ultraviolet absorber.
  • the releasing agent is a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group, a silicone-based nonionic surfactant having a dimethylpolysiloxane group or a hydroxyalkyl group or a phosphate ester group, an alkyl quaternary ammonium salt, that is, Trimethylcetyl ammonium salt, trimethyl stearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt, phosphate ester, phosphonic acid ester may be used alone or in combination of two or more thereof.
  • phosphate ester or phosphonic acid ester is used.
  • phosphate ester Isopropyl acid four state; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl acid phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof.
  • ZELEC UN DuPont Co., Ltd.
  • the addition amount of the release agent may be used in 0.0001 to 3% by weight in the composition, but preferably used at 0.001 to 2% by weight was good in the mold deformability and high polymerization yield in the lens. If the addition amount of the release agent is less than 0.0001% by weight, a phenomenon occurs that the glass mold surface adheres to the lens when the molded spectacle lens is separated from the glass mold. If the amount is more than 2% by weight, the lens is separated from the glass mold during polymerization of the lens. There is a problem that a stain occurs on the surface.
  • the polymerization initiator used in the present invention may be an amine-based or tin-based compound.
  • 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-ethylhexyl) tin oxide and the like may be used alone or in combination of two or more thereof. When such a tin compound was used, the polymerization yield was high and there was no bubble generation.
  • the resin composition for an optical lens of the present invention uses isophorone diisocyanate or dicyclohexyl methane diisocyanate in an amount of 40% by weight or more in the total isocyanate compound, but the reactivity of the resin composition for the optical lens is good and the edges of the adhesive tape due to the adhesive dissolution of the adhesive tape No whitening phenomenon occurs, and by maintaining an appropriate viscosity, bubbles of lens edges due to leakage do not appear.
  • the present invention can be utilized as a method of improving the heat resistance of the lens while being inexpensive, in particular, it is inexpensive and heat-resistant using a urethane high refractive lens and dicyclohexyl methane diisocyanate which are inexpensive and have good heat resistance using isophorone diisocyanate which is widely used. It can be utilized as a method of obtaining a urethane high refractive lens with good impact resistance.
  • the resin composition for an optical lens of the present invention can be used for various optical products in addition to the plastic spectacle lens.
  • the resin composition for urethane-based optical lenses of the present invention is thermally cured to obtain a urethane-based plastic optical lens, particularly an spectacle lens.
  • a preferred embodiment thereof is as follows. First, after the polymerization initiator is finally added to the composition of the present invention, it is replaced with nitrogen to remove air in the mixing vessel, and the stirring is carried out for 1 to 2 hours, the stirring is stopped, and the pressure is then degassed and injected into the mold. .
  • the mold preferably uses a plastic gasket or glass mold fixed with polyester or polypropylene adhesive tape. The glass mold into which the resin composition for optical lens was injected was placed in a forced circulation oven, and maintained at 33 to 37 ° C. for 2 hours, heated to 38 to 42 ° C.
  • the optical lens thus obtained is annealed at about 120 ° C. for about 2 hours to obtain a final desired plastic spectacle lens (dough).
  • the optical lens obtained by the above method was subjected to hard coating and multi-coating treatment in order to increase the optical characteristics.
  • Formation of the hard coating layer comprises at least one silane compound having functional groups such as epoxy group, alkoxy group and vinyl group and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, aluminum oxide, etc.
  • the coating composition was coated with a thickness of 0.5 to 10 ⁇ m on the surface of the optical lens by impregnation or spin coating, followed by heating or UV curing to complete the coating film.
  • the multi-coating layer that is, the anti-reflective coating layer may be formed by vacuum deposition or sputtering of metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide and yttrium oxide.
  • metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide and yttrium oxide.
  • the silicon oxide film and the zirconium oxide film are repeatedly vacuum-deposited three or more times on both surfaces of the lens, and then the silicon oxide film is finally vacuum deposited.
  • a water film (fluorine resin) layer may be provided at the end, or an ITO layer may be provided between the silicon oxide and the zirconium oxide film.
  • the optical lens of the present invention may be used after coloring treatment using a disperse dye or a photochromic dye.
  • the resin composition for optical lens prepared as described above was placed in a mixing vessel capable of vacuum defoaming stirring and maintained at 15 ° C. while ZELEC UN 0.1 g, 2- (2-hydroxy-5-t-octylphenyl)- 1.5 g of 2H-benzotriazole, 20 ppm of HTAQ, 10 ppm of PRD, and 0.1 g of dibutyltin dichloride were added and stirred for 20 minutes under a nitrogen stream to obtain a resin composition for spectacle lenses, followed by vacuum defoaming under 0.1 tor for 1 hour and 30 minutes. After the vacuum was removed, the resultant was injected into a glass mold fixed with a polyester adhesive tape [Elbichem Co., Ltd. JS-100] using nitrogen pressure (diopta -5.00).
  • the lens obtained in (3) was surface-etched in a KOH 5% solution, then impregnated in Harden Co., Ltd., followed by thermosetting, and silicon oxide, zirconium oxide, silicon oxide, ITO, zirconium oxide, Silicon oxide, zirconium oxide, and water film (fluorine resin) were vacuum deposited to obtain a hard coated and multi-coated optical lens.
  • Refractive index and Abbe number Measured using an Abbe refractometer of Atago Co., 1T and DR-M4.
  • Edge bubble 100 lenses obtained in the process (2) were visually observed, and if bubbles due to leakage appeared on the edges of three or more lenses, they were marked as 'X'.
  • Example 2 In the same manner as in Example 1, according to the composition shown in Tables 1-3, the compositions and the lenses were prepared, respectively, and physical properties were tested. The results are shown in Tables 1-3.
  • IPDI isophorone diisocyanate
  • 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane in 4.2 g of 1,6-hexamethylene diisocyanate, pentaerythritol tetrakis (3 -Mercaptopropionate) 9.2 g was mixed to prepare a resin composition for an optical lens, except that the same procedure as in Example 1 was carried out, and the properties thereof are shown in Table 4.
  • IPDI isophorone diisocyanate
  • HDI 1,6-hexamethylene diisocyanate (hexamethylene-1,6-diisocyanate)
  • TMPMP trimethylolpropane tris (3-mercaptopropionate)
  • PETMP pentaerythritol tetrakis (3-mercaptopropionate)
  • PETMA pentaerythritol tetrakis (2-mercaptoacetate)
  • GSTIPDI0.1 Compound added by the equivalent ratio of GST / IPDI to 0.1
  • GSTIPDI0.15 Compound added by the equivalent ratio of GST / IPDI to 0.15
  • GSTH 12 MDI0.1 Compound having the equivalent ratio of GST / H 12 MDI added at 0.1
  • ETS4IPDI0.1 Compound added by ETS4 / IPDI with an equivalent ratio of 0.1
  • ETS4H 12 MDI0.1 Compound having an equivalent ratio of ETS4 / H 12 MDI added at 0.1
  • GSTIPDI10 Compound to which the equivalent ratio of GST / IPDI was added at 10
  • GSTIPDI17 Compound to which the equivalent ratio of GST / IPDI was 17
  • GSTH 12 MDI10 Compound having the equivalent ratio of GST / H 12 MDI added at 10
  • GSTH 12 MDI10 Compound having the equivalent ratio of GST / H 12 MDI added at 15
  • ETS4IPDI10 A compound to which the equivalent ratio of ETS4 / IPDI was added at 10
  • ETS4H 12 MDI10 Compound having an equivalent ratio of ETS4 / H 12 MDI added at 10
  • TMPMPIPDI0.1 A compound to which the equivalent ratio of TMPMP / IPDI was added at 0.1.
  • TMPMPH 12 MDI0.1 Compound having an equivalent ratio of TMPMP / H 12 MDI added at 0.1
  • PETMPIPDI0.1 A compound in which the equivalent ratio of PETMP / IPDI is 0.1
  • PETMPH 12 MDI0.1 A compound in which the equivalent ratio of PETMP / H 12 MDI was added at 0.1
  • PETMAIPDI0.1 A compound in which the equivalent ratio of PETMA / IPDI is 0.1
  • PETMAH 12 MDI0.1 A compound in which the equivalent ratio of PETMA / H 12 MDI was added at 0.1
  • BPEHMPIPDI0.1 A compound in which the equivalent ratio of BPEHMP / IPDI was added at 0.1
  • BPEHMPH 12 MDI0.1 Compound having an equivalent ratio of BPEHMP / H 12 MDI added at 0.1
  • ZELEC UN an acidic phosphate ester manufactured by DuPont trade name ZELEC UN TM
  • HOPBT 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole
  • a urethane-based plastic optical lens made of a resin composition for a urethane-based optical lens having high heat resistance and high reactivity is excellent in impact resistance and less heat deformation after multi-coating.
  • the optical lens according to the present invention can be applied to the spectacle lens, in particular, used for 3D polarized lenses equipped with a polarizing film on the spectacle lens, recording medium substrate, coloring filter, used for prism, optical fiber, optical disk, magnetic disk, etc. It can be used as various optical products such as ultraviolet absorbing filter.

Abstract

L'invention concerne une composition de résine destinée à une lentille optique en matière plastique, et en particulier une composition de résine destinée à une lentille optique en uréthanne, présentant une résistance thermique et une réactivité élevées. La composition de résine destinée à une lentille optique selon l'invention, contient un prépolymère de résine optique obtenu lors d'une réaction secondaire précédente entre un composé mercapto et un –SH/-NCO de diisocyanate d'isophorone ou de dicyclohexylméthanediisocyanate dans des rapports molaires appropriés. L'utilisation de diisocyanate d'isophorone ou de dicyclohexylméthanediisocyanate permet d'augmenter la résistance thermique de la lentille optique, et l'utilisation de prépolymère de résine optique, à raison de 20 à 70 % pds du poids total de la composition de résine destinée à la lentille optique, permet d'éluer l'adhésif de la bande adhésive en raison d'une réactivité diminuée qui résulte d'une réaction à température élevée, ce qui permet de résoudre les problèmes de blanchiment et de formation de mousse apparaissant sur le bord de la lentille en raison d'une fuite de la composition liquide se produisant lorsque la température de réaction augmente.
PCT/KR2010/002664 2009-05-04 2010-04-28 Composition de résine pour lentille optique en uréthanne, présentant une résistance thermique et une réactivité élevées WO2010128770A2 (fr)

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CN201080000845.0A CN102112548B (zh) 2009-05-04 2010-04-28 具备优秀耐热性及反应性的氨基甲酸酯类光学透镜用树脂组合物

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KR10-2009-0038929 2009-05-04
KR20090038929 2009-05-04
KR1020100038562A KR101157497B1 (ko) 2009-05-04 2010-04-26 내열성 및 반응성이 우수한 우레탄계 광학 렌즈용 수지조성물
KR10-2010-0038562 2010-04-26

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WO2013160227A1 (fr) 2012-04-23 2013-10-31 Bayer Materialscience Ag Compositions polyuréthane photostables
EP3061780A4 (fr) * 2013-10-21 2017-06-21 Mitsui Chemicals, Inc. Composition polymérisable pour matériau optique et matériau optique
US20180319924A1 (en) * 2015-12-08 2018-11-08 Jiangsu Qianyuan New Material Technology Co. Ltd. Optical resin composition having high impact resistance, heat resistance and refractivity and obtained by applying organic-inorganic hybrid, and preparation method thereof
AU2018200984B2 (en) * 2013-09-30 2020-02-27 Hoya Lens Thailand Ltd Transparent plastic substrate and plastic lens
CN112142940A (zh) * 2020-08-18 2020-12-29 江苏乾元新材料科技有限公司 一种光学透镜树脂组合物和光学镜片
CN115181219A (zh) * 2022-08-09 2022-10-14 江苏可奥熙光学材料科技有限公司 一种高折射率镜片的制备方法

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WO2013160227A1 (fr) 2012-04-23 2013-10-31 Bayer Materialscience Ag Compositions polyuréthane photostables
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AU2018200984B2 (en) * 2013-09-30 2020-02-27 Hoya Lens Thailand Ltd Transparent plastic substrate and plastic lens
US10745539B2 (en) 2013-09-30 2020-08-18 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
US10947365B2 (en) 2013-09-30 2021-03-16 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
US11001699B2 (en) 2013-09-30 2021-05-11 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
EP3061780A4 (fr) * 2013-10-21 2017-06-21 Mitsui Chemicals, Inc. Composition polymérisable pour matériau optique et matériau optique
US20180319924A1 (en) * 2015-12-08 2018-11-08 Jiangsu Qianyuan New Material Technology Co. Ltd. Optical resin composition having high impact resistance, heat resistance and refractivity and obtained by applying organic-inorganic hybrid, and preparation method thereof
CN112142940A (zh) * 2020-08-18 2020-12-29 江苏乾元新材料科技有限公司 一种光学透镜树脂组合物和光学镜片
CN115181219A (zh) * 2022-08-09 2022-10-14 江苏可奥熙光学材料科技有限公司 一种高折射率镜片的制备方法

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