WO1999032907A1 - Lentille en resine synthetique et procede de fabrication - Google Patents

Lentille en resine synthetique et procede de fabrication Download PDF

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Publication number
WO1999032907A1
WO1999032907A1 PCT/JP1998/005767 JP9805767W WO9932907A1 WO 1999032907 A1 WO1999032907 A1 WO 1999032907A1 JP 9805767 W JP9805767 W JP 9805767W WO 9932907 A1 WO9932907 A1 WO 9932907A1
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Prior art keywords
meth
acrylate
molecule
polyfunctional
urethane bond
Prior art date
Application number
PCT/JP1998/005767
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English (en)
Japanese (ja)
Inventor
Katsuichi Machida
Masuhiro Shouji
Original Assignee
Kureha Kagaku Kogyo Kabushiki Kaisha
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Application filed by Kureha Kagaku Kogyo Kabushiki Kaisha filed Critical Kureha Kagaku Kogyo Kabushiki Kaisha
Publication of WO1999032907A1 publication Critical patent/WO1999032907A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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

Definitions

  • the present invention relates to a synthetic resin lens and a method for producing the same, and more particularly, to a lens for spectacles having a high refractive index (for example, 1.57 or more) and low light dispersion (for example, an Abbe number of 30 or more).
  • the present invention relates to a synthetic resin lens having excellent characteristics, and a method for producing such a synthetic resin lens. Background technology
  • the thickness of the peripheral portion of the lens for correcting myopia and the thickness of the central portion of the lens for correcting hyperopia and the lens for presbyopia can be reduced, thereby reducing the weight of the lens. And ⁇ can be improved.
  • polydiethylene dalichol bisaryl carbonate which is widely used as a constituent material for spectacle lenses, has a low refractive index of about 1.50, so that the thickness of the lens can be sufficiently increased. The size cannot be reduced, and the appearance is not favorable.
  • the following methods (1) to (3) are known as methods for introducing a sulfur atom into a synthetic resin.
  • the operation of synthesizing and purifying a monomer containing a sulfur atom is complicated.
  • the monomer is reacted by reacting a (meth) atalylic acid derivative with a mercaptan compound to convert the monomer.
  • the mercaptan compound is added to the double bond of the (meth) acrylic acid derivative, and the yield of the target monomer is significantly reduced.
  • the method (2) also has a problem in that the glass constituting the mold and the isocyanate compound react with each other, so that the releasability is impaired.
  • a release agent to the monomer composition.
  • the release agent may remain in the polymer (lens material) and adversely affect the processability of the lens material. is there.
  • the sealing material of the mold elutes into the monomer composition.
  • the present invention has been made based on the above circumstances.
  • a first object of the present invention is to provide a synthetic resin lens having a high refractive index and low light dispersibility, and a method for producing the same.
  • a second object of the present invention is to provide a synthetic resin lens having low specific gravity and excellent transparency, and a method for producing the same.
  • a third object of the present invention is to provide a synthetic resin lens and a method for producing the same, which can be easily molded without dissolving or breaking a sealing material when molded by a casting polymerization method. Is to do.
  • the synthetic resin lens of the present invention comprises a radical polymerization initiator comprising a monomer mixture containing [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, and [C] a polythiol compound. Characterized by being obtained by polymerization using
  • a polyfunctional (meth) acrylate having a urethane bond includes a (meth) acrylate (a 1 ) having a hydroxyl group in a molecule and a polyisocyanate (a) having two or more isocyanate groups in a molecule.
  • a 2 ) is preferably obtained by reacting
  • a polyfunctional (meth) acrylate having a urethane bond has a hydroxyl group-containing (meth) acrylate (a ') and a molecule having an isocyanate group.
  • the number of moles is [NCO]
  • it is preferably obtained by reacting at a ratio of [OH] / [NCO] of 1 or more, especially 1 to 1.3.
  • polyisobutylene Xia sulfonates having two or more Isoshianeto groups in the molecule ( a 2 ) is preferably obtained in the presence of a highly active organotin-based catalyst.
  • a polyfunctional (meth) acrylate having a urethane bond includes a (meth) acrylate (a 1 ) having a hydroxyl group in a molecule and a polyisocyanate (a) having two or more isocyanate groups in a molecule. It is preferably obtained by reacting a 2 ) with a compound (a 3 ) having two or more hydroxyl groups in the molecule.
  • a polyfunctional (meth) acrylate having a urethane bond includes a (meth) acrylate (a 1 ) having a hydroxyl group in a molecule and a polyisocyanate (a) having two or more isocyanate groups in a molecule.
  • the number of moles of the hydroxyl groups of the (meth) acrylate (a 1 ) and the compound (a 3 ) is represented by [OH
  • the reaction is carried out at a ratio of [OH] / [NCO] of 1 or more, especially 1 to 1.3. It is preferably obtained by the following method.
  • a polyfunctional (meth) acrylate having a urethane bond includes a (meth) acrylate (a 1 ) having a hydroxyl group in the molecule and a polyisocyanate (a) having two or more isocyanate groups in the molecule. It is preferably obtained by reacting 2 ) with a compound (a 3 ) having two or more hydroxyl groups in the molecule in the presence of a highly active organotin catalyst.
  • the synthetic resin lens of the present invention comprises [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] It is obtained by polymerizing a monomer mixture containing an aromatic compound having two or more (meth) acrylic groups using a radical polymerization initiator.
  • the synthetic resin lens of the present invention comprises [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] two or more (meth) acrylinyl groups.
  • the synthetic resin lens of the present invention comprises [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] two or more (meth) acryl groups.
  • the method for producing a synthetic resin lens of the present invention comprises the steps of: preparing a monomer mixture containing [A] a polyfunctional (meth) atalylate having a urethane bond, [B] divininolebenzene, and [C] a polythiol compound, It is characterized in that polymerization is carried out using a polymerization initiator.
  • the urethane bond can be obtained by reacting (meth) acrylate (a 1 ) having a hydroxyl group in the molecule with polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule.
  • a polyfunctional (meth) acrylate having a polyfunctional (meth) acrylate having a urethane bond is prepared.
  • the monomer mixture is polymerized.
  • a (meth) acrylate (a ′) having a hydroxyl group in the molecule and a polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule can be obtained by mixing the (meth) acrylate (a 1 ) ) Is [ ⁇ H], and the number of moles of isocyanate groups in the polyisocyanate (a 2 ) is [NCO], the value of [OH] / [NCO] is 1 or more,
  • [A] a polyfunctional (meth) acrylate having a urethane bond is prepared by reacting at a ratio of 1 to 1.3, and the obtained [A] polyfunctional (meth) acrylate having a urethane bond is obtained. It is preferable to polymerize a monomer mixture containing
  • a (meth) atalylate (a 1 ) having a hydroxyl group in a molecule and a polyisocyanate (a 2 ) having two or more isocyanate groups in a molecule are combined in the presence of a highly active organotin catalyst.
  • a polyfunctional (meth) acrylate having a urethane bond is prepared by reacting the obtained monomer mixture with the obtained monomer mixture containing the [A] polyfunctional (meth) acrylate which has a urethane bond. Polymerization is preferred.
  • (meth) acrylate (a 1 ) having a hydroxyl group in the molecule polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule, and two or more hydroxyl groups in the molecule [A] a polyfunctional (meth) acrylate having a urethane bond is prepared by reacting the compound (a 3 ) with the compound (a 3 ), and the resulting polyfunctional (meth) acrylate having a [A] urethane bond is contained. It is preferable to polymerize the resulting monomer mixture.
  • (meth) acrylate (a 1 ) having a hydroxyl group in the molecule polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule, and two or more hydroxyl groups in the molecule
  • the reaction is performed at a ratio of [OH] / [NCO] of 1 or more, particularly 1 to 1.3, so that [A] a polyfunctional (meth) atali having a urethane bond is obtained.
  • (A) a simple composition containing the obtained polyfunctional (meth) acrylate having a urethane bond It is preferred to polymerize the monomer mixture.
  • Polyfunctional (meth) atalylate having a urethane bond was prepared by reacting the compound (a 3 ) with the compound (a 3 ) in the presence of a highly active organotin catalyst, and the obtained [A] urethane bond It is preferable to polymerize a monomer mixture containing a polyfunctional (meth) acrylate which has
  • a (meth) acrylate having a hydroxyl group in the molecule (a 1 ) and a polyisocyanate having two or more isocyanate groups in the molecule (a 2 ) are subjected to a urethanation reaction in [B] divinyl benzene.
  • a mixed system of [A] a polyfunctional (meth) acrylate having a urethane bond and [B] dibutylbenzene is prepared, and [C] a polythiol compound is added to the mixed system and mixed. It is preferable to prepare a monomer mixture and polymerize this monomer mixture using a radical polymerization initiator.
  • (meth) acrylate (a 1 ) having a hydroxyl group in the molecule polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule, and two or more hydroxyl groups in the molecule Urethanation reaction of the compound (a 3 ) with the compound (a 3 ) in [B] dibutylbenzene to form a mixed system of [A] a polyfunctional (meth) acrylate having a urethane bond and [B] dibibenzenebenzene. It is preferable to prepare a monomer mixture by adding and mixing the (C) polythiol compound into the mixed system, and then polymerize the monomer mixture using a radical polymerization initiator. .
  • the method for producing a synthetic resin lens of the present invention comprises: [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] (meth) acrylic group.
  • a monomer mixture containing two or more aromatic compounds is polymerized using a radical polymerization initiator.
  • the method for producing a synthetic resin lens of the present invention comprises: [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] an (meth) acryl group.
  • Aromatic compounds having two or more by mass ratio of 10 to It is characterized in that a monomer mixture containing 70: 10 to 60: 5 to 50: 0 to 30 is polymerized by using a radical polymerization initiator.
  • the method for producing a synthetic resin lens of the present invention comprises: [A] a polyfunctional (meth) acrylate having a urethane bond, [B] dibutylbenzene, [C] a polythiol compound, and [D] a (meth) acryl group. It is characterized in that a monomer mixture containing at least one aromatic compound having a ratio satisfying the following formula (i) is polymerized using a radical polymerization initiator.
  • (B) urethanation reaction in (B) divinyl benzene is carried out with (meth) acrylate (a ′) having a hydroxyl group in the molecule and polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule.
  • a mixed system of [A] a polyfunctional (meth) atalylate having a urethane bond and [B] dibutylbenzene is prepared, and [C] a polythiol compound and [D] (meta) are added to the mixed system. It is preferable to prepare a monomer mixture by adding and mixing with an aromatic compound having two or more acrylic groups, and polymerize this monomer mixture using a radical polymerization initiator.
  • (meth) acrylate (a ′) having a hydroxyl group in the molecule polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule, and two or more hydroxyl groups in the molecule
  • the compound (a 3 ) has a urethanation reaction in [B] dibutylbenzene to form a mixed system of [A] a polyfunctional (meth) acrylate having a urethane bond and [B] divinylbenzene.
  • the mixture is prepared as follows: [C] a polythiol compound and [D] an aromatic compound having two or more (meth) acryl groups. It is preferable that a monomer mixture is prepared by adding and mixing the monomer mixture, and the monomer mixture is polymerized using a radical polymerization initiator.
  • the copolymer (lens material) obtained by polymerizing the monomer mixture has a crosslinked structure. be introduced.
  • the copolymer having a urethane bond has a small thermal deformation in a low temperature range.
  • the urethane bond introduced into the copolymer imparts toughness to the copolymer, makes the synthetic resin lens finally obtained hard to crack, and further improves the dyeability of the synthetic resin lens and the hard coat. Adhesion can also be improved.
  • a polythiol compound is added (addition reaction of a thiol group to an unsaturated double bond proceeds simultaneously).
  • the copolymer (lens material) into which the sulfur atom is introduced in this way has both high refractive index and low dispersibility.
  • (meta) acrylate means “acrylate”
  • (Meth) acrylic group means both “acrylic group” and “methacrylic group”.
  • the monomer mixture used to obtain the synthetic resin lens of the present invention is ( A ) urethane A polyfunctional (meth) acrylate having a tan bond, [B] divinylbenzene,
  • [C] It may contain a polythiol compound as an essential component, and [D] may contain an aromatic compound having two or more (meth) acryl groups.
  • the [A] polyfunctional (meth) acrylate having a urethane bond (hereinafter, also referred to as “[A] component”) constituting the monomer mixture is as follows:
  • (meth) acrylate (a 1 ) having a hydroxyl group in the molecule [hereinafter, simply referred to as “(meth) acrylate (a 1 )”.
  • These can be used alone or in combination of two or more.
  • Polyisocyanate (a 2 ) having two or more isocyanate groups in the molecule [hereinafter, simply referred to as “polyisocyanate (a 2 )”.
  • Polyisocyanate (a 2 ) Hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethinolehexamethylene diisocyanate, dicyclohexynolemethane-1,4,4-diisocyanate, Tetramethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tolylene diisocyanate, 4,4-diphenyl methane diisocyanate, naphthalene diisocyanate , 3,3-Dimethyl-4,4-bisphenylenediisocyanate, m-xylylenediisocyanate, hexamethylenediisocyanate buretation reaction product, is
  • hydroxyl-containing compound (a 3 ) a compound having two or more hydroxyl groups in the molecule used in the reaction (2) (a 3 ) [hereinafter referred to as “hydroxyl-containing compound (a 3 )”.
  • 2,2'-thiojetanol ethylenebis (2-hydroxyshetyl sulfide), 4,4'-thio (6-tert-butyl-meth-cresol), 4,4-thiodiphenol
  • 1 Sulfur-containing alcohols such as 1,2′-thiobis (2-naphthol), 2,2-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxypropyl) propane, 2, Hydroxy group-containing aromatic compounds such as 2'-bis (hydroxymethyl) diphene oleate ⁇ , bis (hydroxymethinole) duran, bis (2-hydroxyxenotinole) terephthalate, 2,2—bis (4—hydroxy ethoxy-3
  • halogen-containing compounds such as 2,5-bis (brom
  • the reaction catalyst used in the urethanization reaction of the above (1) and (2) is not particularly limited, such as an amine catalyst, a metal salt catalyst, and an organometallic catalyst. It is preferable to use a highly active organotin catalyst such as acetate or dibutyltin dilaurate.
  • the polythiol compound constituting the monomer mixture is a compound having two or more thiol groups in the molecule.
  • Such [C] polythiol compounds include 1,4-bismercaptomethylbenzene, ethanedithiol, 1,4-butanedithiol, ethylene glycol dithioglycolate, 1,2-propanedithiol, bismercaptoethyl sulfide, Bis (mercaptoethylthio) ethane, trimethylolpropanetris (thioglycolate), trimethylolpropanetris (thiopropionate), pentaerythritol tetrakis (thiodalicholate), pentaerythritol tetrakis (thiopropionate), etc. These can be exemplified, and these can be used alone or in combination of two or more.
  • the aromatic compound having two or more [D] (meth) acrylic groups (hereinafter also referred to as “[D] component”) constituting the monomer mixture as an optional component includes 2,2-bis (4) —Bisphenol A derivative such as methacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dichloro-4-propmethacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4) -Methacryloxyethoxyphenyl) Derivatives of halogen-substituted bisphenol A such as propane, and diphenylfluorene derivatives such as 9,9-bis (4-methacrylic xylethoxyphenyl) fluorene.
  • 2,2-bis (4) —Bisphenol A derivative such as methacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dichloro-4-propmethacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4) -
  • the moldability (moldability) of the lens can be improved, and the heat resistance and dyeing of the finally obtained lens can be improved. Color properties can be improved.
  • the content ratio of [A] component, [B] dibutylbenzene, [C] polythiol compound and [D] component in the monomer mixture is as follows: [[A] component: [B] divinylbenzene: [C] Polythiol compound: [D] component (mass ratio) force is preferably from 10 to 70:10 to 60: 5 to 50: 0 to 30, more preferably a ratio that satisfies the following formula (i). You.
  • the content of the component (D) is 30% by mass. /. If it exceeds, the effect of introducing a sulfur atom is impaired, the dispersibility is low (abbe number is high), and it is difficult to obtain a lens with a low specific gravity.
  • Various additives may be contained in the monomer mixture in order to improve the weather resistance, thermal characteristics, and the like of the synthetic resin lens of the present invention.
  • additives examples include p-tert-butylphenyl salicylate and the like.
  • Benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, and 2,4-dihydroxybenzophenone; 2- (2,2-hydroxy-3,1-tert.) —Butyl-5,1-methylphenyl) 1-5 monobenzobenzotriazole, 2- (2, -hydroxy-15′-octylphenyl) benzotriazole-based UV absorber such as benzotriazole, etc.
  • 2-ethyl-cyano— UV absorbers based on cyanoacrylates such as 3,3-diphenylacrylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) 4-piperidyl) sebacate, di (1,2,2,6,6-pentamethyl-4-piperidyl) -butyl (3,, 5'-di-tert-butyl-4-hydroxy- Jill) malonate, 1- (2- (3- (3-3)
  • the method of preparing the monomer mixture is not particularly limited, but a preferred method is (B) dibutylbenzene in the medium, (meth) and Atari rate (a 1), polyisobutylene Xia sulfonate (a 2) and by urethanization reaction, or (meth) Atari rate and (a 1), polyisobutylene Xia sulfonate (a 2 ) And a hydroxyl group-containing compound (a 3 ), followed by a urethanation reaction.
  • [B] dibutylbenzene is used as a reaction solvent in the urethanization reaction for producing the [A] component.
  • [B] divinylbenzene used as a reaction solvent in the urethanization reaction is preferably of high purity, specifically, preferably 80 mass%.
  • the reaction temperature of the urethanization reaction is usually 20 to 120 ° C, and preferably 30 to 80 ° C. If the reaction temperature is lower than 20 ° C., the reaction time is undesirably too long, or unreacted isocyanate groups remain. On the other hand, when the reaction temperature exceeds 120 ° C., a polymerization reaction of [B] dibutylbenzene used as a reaction solvent may occur. From the viewpoint of preventing the polymerization of [B] dibutylbenzene during the urethanization reaction, it is preferable to add a polymerization inhibitor to the reaction system.
  • the polymerization inhibitor include dihydroxybenzene and methoxyphenol-phenol-based antioxidants.
  • the synthetic resin lens of the present invention comprises the above monomer mixture comprising (A) component, (B) dibutylbenzene and (C) polythiol compound as essential components, and (D) component and various additives as optional components.
  • a monomer composition can be obtained by adding a radical polymerization initiator, and the monomer composition can be produced by subjecting the monomer composition to a polymerization treatment by a cast polymerization method.
  • the casting polymerization method involves injecting the monomer composition into a mold or mold (mold) made of glass, plastic, or metal designed to obtain a lens having a desired shape and power. Is polymerized by raising the temperature.
  • the viscosity of the monomer mixture containing the component (A) is 35 to 200 cp (2 (5 ° C), the sealing material elutes or breaks during casting polymerization of a monomer composition obtained by adding a radical polymerization initiator to this monomer mixture. It can be easily molded (molded) without rubbing.
  • examples of the radical polymerization initiator include ordinary organic peroxide-based polymerization initiators. Specifically, tert-butyl peroxy neodecanoate, tert-butylvaloxyvivalate, and tert Peroxyesters such as butyl peroxybenzoate, tert-butynolepoxy-1-2-ethynolehexanoate, tert-butyl benzoyl laurate, tert-butyl peroxy-1,3,5,5-trimethylenolehexanoate Oxides, 3,5,5-trimethylhexanoyl peroxide, and other disilver oxides; 1,1-bis (tert-butyl-butoxy) -1,3,5,5-trimethylcyclo Preferred are peroxy ketals such as hexane. Also, 2,2, -azobis (isobutyronitrile), 2,2, -azobis (2,4-dimethylpareronitrile), 1,1, -azobis
  • the monomer composition to be subjected to the polymerization treatment may further contain a polymerization regulator such as 2,4-diphenyl-4-methyl-1-pentene.
  • the synthetic resin lens obtained as described above can be subjected to a force grinding process, a polishing process, a dyeing process, a forming process of a hard coat layer, a forming process of an anti-reflection layer, or the like, which can be used as it is.
  • the synthetic resin lens of the present invention has a high refractive index (for example, 1.57 or more, further 1.58 or more, especially 1.59 or more), and low light dispersion (for example, an Abbe number of 30 or more). , Especially over 31). Further, the synthetic resin lens of the present invention has a low specific gravity (for example, 1.3 or less) and is excellent in transparency.
  • Mol of the content of component [A] in the monomer mixture is 35 weight 0/0, the number of moles of (meth) acrylic groups of the component [A] a, vinyl Le group of the [B] di Bulle benzene
  • the value of (a + b) / c was 1.77.
  • the joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acryl resin adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold.
  • the temperature was raised to 80 ° C over 4 hours, and further raised to 120 ° C over 2 hours. 120 ° C , And cooled to 70 ° C, and the glass mold was peeled off to obtain a colorless and transparent lens (the synthetic resin lens of the present invention).
  • the refractive index of this lens was as high as 1.596, and the Abbe number was 37 with low light dispersion.
  • the specific gravity was 1.27, which was light.
  • the content of the component [A] is 20% by mass
  • [a] is the number of moles of the (meth) acrylic group of the component A3
  • [B] is the number of moles of the vinyl group of dibutylbenzene.
  • [C] the number of moles of the thiol group of the polythiol compound is c
  • the joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acryl resin adhesive layer, and the monomer obtained as described above is placed in the cavity of the glass mold.
  • the temperature was raised to 95 ° C over 4 hours, and further raised to 130 ° C over 2 hours.
  • the temperature was cooled to 70 ° C and the glass mold was peeled off to obtain a colorless and transparent lens (the synthetic resin lens of the present invention).
  • the refractive index of this lens was as high as 1.597, and the Abbe number was 36 with low light dispersion.
  • the specific gravity was as light as 1.25.
  • the light transmittance decreased from 87% to 35%.
  • the number of moles of the content of component [A] in the monomer mixture has a 45 mass 0 I component [A] (meth) acryl group a, the number of moles of vinyl Le groups of (B) di Bulle benzene b, [C]
  • the value of (a + b) / c was 2.23, where c is the number of moles of the thiol group in the polythiol compound.
  • the joint between the male and female molds constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold.
  • the temperature was raised to 80 ° C over 4 hours, and further raised to 120 ° C over 2 hours.
  • the temperature was cooled to 70 ° C and the glass mold was peeled off to obtain a colorless and transparent lens (the synthetic resin lens of the present invention).
  • the refractive index of this lens was as high as 1.598, and the Abbe number was 35 with low light dispersion.
  • the specific gravity was as light as 1.21.
  • This monomer mixture does not contain the component (A), and the number of moles of the butyl group of dibutylbenzene is b, and the number of moles of the thiol group of pentaerythritol tetrakis (thiopropionate) is c.
  • the value of b / c was 2.03.
  • the joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acryl resin adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold.
  • the temperature was raised to 80 ° C over 4 hours, and then raised to 120 ° C over 2 hours.
  • the monomer composition leaked out of the glass mold.
  • the temperature was raised to 120 ° C, held at 120 ° C for one hour, cooled to 70 ° C, the glass mold was peeled off, and the lens was removed. Obtained. When the obtained lenses were observed, cloudiness was observed at each peripheral portion.
  • Dibutyltin dilaurate (catalyst for urethanization reaction) 0.02 0.02 0.02
  • 2,4--diph j 2-ru 4-methyl-1-pentene (polymerization regulator) 0.3
  • Ratio of component [A] in monomer mixture [% by mass] 35 20 450
  • component [A] in the monomer mixture has a 38 mass 0 I component [A] (meth) a number of moles of acrylic group, the number of moles of vinyl Le groups of (B) di Bulle benzene b, [C] When the number of moles of the thiol group in the polythiol compound is c, the value of (a + b) Zc was 1.96.
  • the joint between the male mold and the female mold making up the glass mold is sealed with an adhesive tape having an ataryl resin-based adhesive layer.
  • an adhesive tape having an ataryl resin-based adhesive layer.
  • the temperature is raised to 75 ° C over 4 hours, and further raised to 120 ° C over 2 hours.
  • the temperature was cooled to 70 ° C and the glass mold was peeled off to obtain a colorless and transparent lens (the synthetic resin lens of the present invention).
  • the refractive index of this lens was as high as 1.597, and the Abbe number was 33 with low light dispersion.
  • the specific gravity was as light as 1.22.
  • the content of the component [A] in the monomer mixture is 30% by mass, and the content of the component [A]
  • (A) The number of moles of the (meth) acrylic group is a
  • [B] The number of moles of the vinyl group of dibutylbenzene is b
  • [C] The number of moles of the thiol group of the polythiol compound is c.
  • the joint between the male mold and the female mold that constitute the glass monoredo is sealed with an adhesive tape having an acryl resin adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold.
  • This lens had a high refractive index of 1.57, an Abbe number of 36, and low light dispersion.
  • the specific gravity was 1.22, which was light.
  • the lens according to the present invention has a high refractive index and low power, light and light dispersion. Further, the lens according to the present invention has a low specific gravity and is excellent in transparency.
  • the sealing material can be easily molded without being eluted or damaged.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une lentille en résine synthétique présentant un indice de réfraction élevé, une faible densité, une excellente transparence, une dispersion de lumière réduite, et qui peut facilement être moulée par polymérisation du produit de coulée sans que le matériau de scellement se dissolve ou s'abîme. La lentille en résine synthétique de la présente invention est caractérisée en ce qu'on l'obtient en polymérisant, à l'aide d'un radical initiateur de polymérisation, un mélange monomère comprenant (a) un (méth)acrylate polyfonctionnel à liaison uréthane, (b) un divinylbenzène, et (c) un composé polythiol.
PCT/JP1998/005767 1997-12-22 1998-12-21 Lentille en resine synthetique et procede de fabrication WO1999032907A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35300097 1997-12-22
JP9/353000 1997-12-22

Publications (1)

Publication Number Publication Date
WO1999032907A1 true WO1999032907A1 (fr) 1999-07-01

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Application Number Title Priority Date Filing Date
PCT/JP1998/005767 WO1999032907A1 (fr) 1997-12-22 1998-12-21 Lentille en resine synthetique et procede de fabrication

Country Status (1)

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WO (1) WO1999032907A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111225933A (zh) * 2017-11-28 2020-06-02 三井化学株式会社 (甲基)丙烯酸酯及其用途

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63207805A (ja) * 1987-02-23 1988-08-29 Mitsubishi Rayon Co Ltd プラスチツクレンズ材料の製造方法
JPS63309509A (ja) * 1987-06-12 1988-12-16 Showa Denko Kk 高屈折率樹脂用組成物
JPH01103616A (ja) * 1987-07-06 1989-04-20 Mitsubishi Rayon Co Ltd プラスチックレンズ材料
JPH01163702A (ja) * 1987-12-21 1989-06-28 Kureha Chem Ind Co Ltd プラスチックレンズ材料
JPH01182314A (ja) * 1988-01-14 1989-07-20 Mitsubishi Gas Chem Co Inc 高アッベ数レンズ用組成物
JPH01197528A (ja) * 1988-02-01 1989-08-09 Mitsubishi Gas Chem Co Inc 高屈折率レンズ用組成物
JPH01209401A (ja) * 1988-02-17 1989-08-23 Mitsubishi Rayon Co Ltd プラスチツクレンズ
JPH02141792A (ja) * 1988-11-22 1990-05-31 Mitsubishi Rayon Co Ltd 面光源装置
JPH02283731A (ja) * 1989-04-24 1990-11-21 Toray Ind Inc 光学用樹脂
JPH02289622A (ja) * 1989-01-20 1990-11-29 Toray Ind Inc 光学用樹脂の製造方法
JPH02308201A (ja) * 1989-05-24 1990-12-21 Kureha Chem Ind Co Ltd プラスチックレンズ材料およびその製造方法
JPH0379614A (ja) * 1989-08-22 1991-04-04 Kureha Chem Ind Co Ltd プラスチックレンズ
JPH0457831A (ja) * 1990-06-27 1992-02-25 Toray Ind Inc 光学用樹脂
JPH04108816A (ja) * 1990-08-29 1992-04-09 Mitsubishi Petrochem Co Ltd 高屈折率レンズ用モノマー組成物
JPH0532724A (ja) * 1991-08-01 1993-02-09 Kureha Chem Ind Co Ltd 高屈折率合成樹脂光学材料

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63207805A (ja) * 1987-02-23 1988-08-29 Mitsubishi Rayon Co Ltd プラスチツクレンズ材料の製造方法
JPS63309509A (ja) * 1987-06-12 1988-12-16 Showa Denko Kk 高屈折率樹脂用組成物
JPH01103616A (ja) * 1987-07-06 1989-04-20 Mitsubishi Rayon Co Ltd プラスチックレンズ材料
JPH01163702A (ja) * 1987-12-21 1989-06-28 Kureha Chem Ind Co Ltd プラスチックレンズ材料
JPH01182314A (ja) * 1988-01-14 1989-07-20 Mitsubishi Gas Chem Co Inc 高アッベ数レンズ用組成物
JPH01197528A (ja) * 1988-02-01 1989-08-09 Mitsubishi Gas Chem Co Inc 高屈折率レンズ用組成物
JPH01209401A (ja) * 1988-02-17 1989-08-23 Mitsubishi Rayon Co Ltd プラスチツクレンズ
JPH02141792A (ja) * 1988-11-22 1990-05-31 Mitsubishi Rayon Co Ltd 面光源装置
JPH02289622A (ja) * 1989-01-20 1990-11-29 Toray Ind Inc 光学用樹脂の製造方法
JPH02283731A (ja) * 1989-04-24 1990-11-21 Toray Ind Inc 光学用樹脂
JPH02308201A (ja) * 1989-05-24 1990-12-21 Kureha Chem Ind Co Ltd プラスチックレンズ材料およびその製造方法
JPH0379614A (ja) * 1989-08-22 1991-04-04 Kureha Chem Ind Co Ltd プラスチックレンズ
JPH0457831A (ja) * 1990-06-27 1992-02-25 Toray Ind Inc 光学用樹脂
JPH04108816A (ja) * 1990-08-29 1992-04-09 Mitsubishi Petrochem Co Ltd 高屈折率レンズ用モノマー組成物
JPH0532724A (ja) * 1991-08-01 1993-02-09 Kureha Chem Ind Co Ltd 高屈折率合成樹脂光学材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111225933A (zh) * 2017-11-28 2020-06-02 三井化学株式会社 (甲基)丙烯酸酯及其用途
CN111225933B (zh) * 2017-11-28 2022-10-04 三井化学株式会社 (甲基)丙烯酸酯及其用途

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