WO2023068316A1 - Matériau pour lentille de contact souple ayant une fonction d'amélioration du contraste - Google Patents

Matériau pour lentille de contact souple ayant une fonction d'amélioration du contraste Download PDF

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WO2023068316A1
WO2023068316A1 PCT/JP2022/039021 JP2022039021W WO2023068316A1 WO 2023068316 A1 WO2023068316 A1 WO 2023068316A1 JP 2022039021 W JP2022039021 W JP 2022039021W WO 2023068316 A1 WO2023068316 A1 WO 2023068316A1
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meth
group
polymer
acrylate
carbon atoms
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隆英 尾下
宏典 鈴木
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興和株式会社
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • 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
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • 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
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses

Definitions

  • the present invention relates to polymers suitable for soft contact lenses and capable of improving the contrast of visually recognized objects.
  • Patent No. 5778109 Japanese Patent Application Laid-Open No. 2019-66501
  • Soft contact lenses are also required to have improved antiglare properties and contrast properties.
  • soft contact lens materials are required to have softness suitable for wearing and water retention necessary for placing the lens directly on the cornea.
  • an object of the present invention is to provide a polymer suitable for a soft contact lens material that can improve antiglare properties and contrast properties.
  • the present invention is as follows.
  • a polymer obtained by copolymerizing an organic dye having a yellow region light absorption ability and one or more polymerizable monomers A polymer, wherein the polymerizable monomer contains one or more selected from acrylamide-based monomers and vinyl-based monomers.
  • a 1 to A 8 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a linear chain, branched or cyclic alkyl group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, monoalkylamino group having 1 to 20 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, carbon a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms; , may form a ring other than an aromatic ring via a linking group, M is two
  • Cu represents a divalent copper atom
  • tBu represents a tertiary butyl group
  • the four tertiary butyl groups represent four pyrrole rings present in the porphyrin skeleton in formula (2). It means that each one is bound to one carbon atom of .
  • the total amount of one or more selected from acrylamide-based monomers and vinyl-based monomers is 30 parts by weight or more when the total amount of polymerizable monomers is 100 parts by weight, [1] to [6] ]
  • the present invention it is possible to obtain a polymer suitable for soft contact lens materials that can improve antiglare properties and contrast properties. Since dyes are less likely to elute from such polymers, antiglare properties and contrast properties are maintained, and safety is excellent even when worn repeatedly on a daily basis.
  • 1 is a graph showing UV-visible absorption spectra of the polymer of Example 1 before and after an elution test.
  • 2 is a graph showing UV-visible absorption spectra of the polymer of Example 2 before and after the elution test.
  • 4 is a graph showing UV-visible absorption spectra of the polymer of Example 3 before and after the elution test.
  • 4 is a graph showing UV-visible absorption spectra for each polymer of Examples 1-3 after repeating the dissolution test four times.
  • 4 is a graph showing UV-visible absorption spectra of the polymer of Example 4 before and after the elution test.
  • 10 is a graph showing UV-visible absorption spectra of the polymer of Example 5 before and after the elution test.
  • 10 is a graph showing UV-visible absorption spectra of the polymer of Example 6 before and after the elution test.
  • 4 is a graph showing the UV-visible absorption spectra for each polymer of Examples 4-6 after repeating the dissolution test four times.
  • 4 is a graph showing UV-visible absorption spectra of the polymer of Comparative Example 1 before and after the elution test.
  • 4 is a graph showing UV-visible absorption spectra of the polymer of Comparative Example 3 before and after the elution test.
  • 4 is a graph showing ultraviolet-visible absorption spectra of the polymers of Comparative Examples 1 and 3 after repeating the dissolution test four times.
  • FIG. 10 is a graph showing UV-visible absorption spectra of the polymer of Example 7 before and after the elution test.
  • 10 is a graph showing UV-visible absorption spectra of the polymer of Example 8 before and after the elution test.
  • 10 is a graph showing the UV-visible absorption spectra of the polymer of Example 9 before and after the elution test.
  • 10 is a graph showing the UV-visible absorption spectra of the polymer of Example 10 before and after the elution test.
  • 11 is a graph showing UV-visible absorption spectra of the polymer of Example 11 before and after the elution test.
  • FIG. 10 is a graph showing UV-visible absorption spectra of the polymer of Example 12 before and after the elution test; FIG.
  • FIG. 4 is a graph showing UV-visible absorption spectra for each polymer of Examples 7-12 after repeating the dissolution test four times.
  • FIG. 10 is a graph showing the relationship between the amount of dye added and the amount remaining after dissolution treatment in Test Example 3.
  • FIG. 4 is a graph showing UV-visible absorption spectra for each polymer of Examples 7-12 after repeating the dissolution test four times.
  • FIG. 10 is a graph showing the relationship between the amount of dye added and the amount remaining after dissolution treatment in Test Example 3.
  • FIG. 10 is a graph showing the relationship between the amount of dye added and the amount remaining after dissolution treatment in Test Example 3.
  • the polymer of the present invention is a polymer obtained by copolymerizing an organic dye having a light absorption ability in the yellow region and one or more polymerizable monomers.
  • the polymerizable monomer is characterized by containing one or more selected from acrylamide-based monomers and vinyl-based monomers.
  • acrylamide-based monomer refers to an amide compound having an acryloyl group as a polymerizable group
  • vinyl-based monomer refers to a compound having a vinyl group as a polymerizable group.
  • the total content of one or more selected from acrylamide-based monomers and vinyl-based monomers is preferably 30 parts by weight or more, more preferably 40 parts by weight or more when the total polymerizable monomer is 100 parts by weight. More preferably, 50 parts by weight or more is acrylamide-based monomer and/or vinyl-based monomer.
  • the upper limit of the content of the acrylamide-based monomer and/or the vinyl-based monomer is not particularly limited. contains 35 parts by weight or less of acrylamide-based monomers and/or vinyl-based monomers.
  • the polymer tends to have the softness (Young's modulus) and water retention (moisture content) suitable for soft contact lenses, and the polymer tends to retain the organic pigment having the ability to absorb light in the yellow region.
  • the acrylamide-based monomer is not particularly limited, but acrylamide, N-methylacrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-ethyl-N-amino Ethylacrylamide and the like can be mentioned, and among these, N,N-dimethylacrylamide is particularly preferred.
  • vinyl-based monomers include, but are not limited to, N-vinyl-2-pyrrolidone, ⁇ -methylene-N-methylpyrrolidone, N-acryloylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-methyl-N-vinylacetamide.
  • Polymerizable monomers in the present invention may include monomers other than acrylamide-based monomers and vinyl-based monomers.
  • Other polymerizable monomers are not particularly limited as long as they are commonly used, and examples thereof include the following.
  • (meth)acryl is a term including "methacryl” and "acryl”.
  • methacrylamide N-methylmethacrylamide, N-ethylmethacrylamide, N-hydroxyethylmethacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N-ethyl-N-aminoethylmethacrylamide, etc. methacrylamides;
  • Styrene pentafluorostyrene, methylstyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl-3,3-bis(trimethylsiloxy)trisiloxanyl)styrene, (hexamethyl-3-trimethylsiloxytrisiloxanyl)styrene, dimethylaminostyrene styrene derivatives such as;
  • aminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate;
  • Alkoxy group-containing (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate;
  • Benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, tribromophenyl (meth)acrylate Acrylates, 2-(meth)acryloyloxyethyl-phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol-( Meth)acrylic acid-benzoate, EO-modified phenol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, EO-modified orthophenylphenol (meth)acrylate, EO-modified tribromophenyl (meth)acrylate, EO-modified bisphenol A di (meth)acrylates,
  • glycidyl (meth)acrylate Tetrahydrofurfuryl (meth)acrylate; N-(meth)acryloylpiperidine; N-(meth)acryloylmorpholine.
  • Alkyl esters optionally substituted with alkyl groups such as itaconic acid, crotonic acid, maleic acid, fumaric acid, fluorine-containing alkyl groups, or siloxanylalkyl groups; glycidyl (meth)acrylate; Tetrahydrofurfuryl (meth)acrylate; N-(meth)acryloylpiperidine; N-(meth)acryloylmorpholine.
  • one or more of the above polymerizable monomers may be selected and polymerized to form a macromonomer, which may be used as one of the polymerizable monomers for polymer production.
  • polymerizable ultraviolet absorbers mainly those that absorb ultraviolet rays
  • polymerizable dyes things that do not absorb ultraviolet rays and absorb mainly blue light
  • polymerizable ultraviolet rays Absorbing dyes can also be used.
  • the polymer of the present invention is used as a soft contact lens material as described later, it is useful because it can adjust the color tone of the soft contact lens, and can impart ultraviolet absorption ability and blue region light absorption ability.
  • polymerizable UV absorber for example, a benzophenone-based polymerizable UV absorber disclosed in JP-A-2003-253248 or a benzotriazole-based polymerizable UV absorber disclosed in Japanese Patent No. 2685980 can be used.
  • UV absorbers such as benzophenone; 2-(2'-hydroxy -5′-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2′-hydroxy-5′-(meth)acryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-( 2′-Hydroxy-5′-(meth)acryloyloxypropylphenyl)-2H-benzotriazole, 2-(2′-hydroxy-5′-(meth)acryloyloxypropyl-3
  • Salicylic acid derivative-based polymerizable UV absorber such as phenyl 2-hydroxy-4-methacryloyloxymethylbenzoate; 2-cyano-3-phenyl-3-(3′-(meth)acryloyloxyphenyl) propenyl acid methyl ester, etc. These can be used alone or in combination of two or more.
  • polymerizable dye for example, azo-based, anthraquinone-based, nitro-based, and phthalocyanine-based polymerizable dyes disclosed in JP-A-10-148797 can be used. These can be used alone or in combination of two or more.
  • polymerizable azo dyes examples include 1-phenylazo-4-(meth)acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (Meth)acryloyloxynaphthalene, 1-( ⁇ -anthriazo)-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-((4'-(phenylazo)-phenyl)azo)-2-hydroxy-3- (Meth) acryloyloxynaphthalene, 1-(2′,4′-xylylazo)-2-(meth)acryloyloxynaphthalene, 1-(o-tolylazo)-2-(meth)acryloyloxynaphthalene, 2-(m- (meth)acryloylamido-anilino)-4,6-bis(1′-(o-tolylazo)-2′-n
  • polymerizable anthraquinone dyes include 1,5-bis((meth)acryloylamino)-9,10-anthraquinone, 1-(4'-vinylbenzoylamido)-9,10-anthraquinone, 4 -amino-1-(4'-vinylbenzoylamido)-9,10-anthraquinone, 5-amino-1-(4'-vinylbenzoylamido)-9,10-anthraquinone, 8-amino-1-(4' -vinylbenzoylamido)-9,10-anthraquinone, 4-nitro-1-(4'-vinylbenzoylamido)-9,10-anthraquinone, 4-hydroxy-1-(4'-vinylbenzoylamido)-9, 10-anthraquinone, 1-(3′-vinylbenzoylamide)-9,10-anthraquinone, 1-
  • polymerizable nitro dyes include o-nitroanilinomethyl (meth)acrylate and the like.
  • polymerizable phthalocyanine dyes include (meth)acryloylated tetraaminocopper phthalocyanine and (meth)acryloylated (dodecanoylated tetraaminocopper phthalocyanine).
  • polymerizable UV-absorbing dyes include 2,4-dihydroxy-3(p-stylenoazo)benzophenone, 2,4-dihydroxy-5-(p-stylenoazo)benzophenone, 2,4-dihydroxy-3 -(p-(meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(meth) ) acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(meth)acryloyloxypropylphenylazo) ) benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxypropylphenylazo)benzophenone, 2,
  • the organic dye having the ability to absorb light in the yellow region in the present invention exhibits a specific absorption behavior.
  • the organic dye has a main absorption peak (P) between 565 nm and 605 nm in a visible light absorption spectrum measured with a chloroform or toluene solution.
  • the organic dye has an absorption coefficient (ml/g ⁇ cm) of 0.5 ⁇ 10 5 or more at the apex of the main absorption peak (P) (Pmax: the point showing the maximum absorption coefficient in the peak).
  • the peak width at the absorbance of 1/4 of the absorbance of (Pmax) of the peak (P) is 50 nm or less, and the peak width at the absorbance of 1/2 of the absorbance of (Pmax) of the peak (P) is 30 nm or less, and the peak width at the absorbance of 2/3 of the absorbance of (Pmax) of the peak (P) is in the range of 20 nm or less.
  • the organic dye has a peak apex (Pmax) of the main absorption peak (P) between 580 nm and 590 nm.
  • the peak width at the absorbance of 1/4 of the absorbance of the peak apex (Pmax) of the main absorption peak (P) is 40 nm or less, and 1 of the absorbance of the peak apex (Pmax) of the main absorption peak (P)
  • the peak width at the absorbance of /2 may be 25 nm or less, and the peak width at the absorbance of 2/3 of the absorbance of the peak peak (Pmax) of the main absorption peak (P) may be 20 nm or less.
  • organic dyes exhibiting such absorption behavior include tetraazaporphyrin compounds represented by the following general formula (1).
  • a 1 to A 8 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, or a linear chain having 1 to 20 carbon atoms.
  • a branched or cyclic alkyl group an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carbon number a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, A ring other than an aromatic ring may be formed via a linking group.
  • M represents two hydrogen atoms, a divalent metal atom, a divalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, preferably a divalent metal Atom, more preferably a divalent copper atom.
  • M is a divalent copper atom, and one of A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 is tertiary butyl is a group and the other is a hydrogen atom.
  • a tetra-t-butyl-tetraazaporphyrin/copper complex represented by the following chemical formula (2) is particularly preferable.
  • Cu represents a divalent copper atom.
  • tBu represents a tertiary butyl group, and the four tertiary butyl groups are each one for one carbon atom of four pyrrole rings present in the porphyrin skeleton in formula (2). It means that they are connected one by one.
  • the tetra-t-butyl-tetraazaporphyrin/copper complex represented by the chemical formula (2) is available from Mitsui Chemicals, Inc. under the product number “PD-311S”.
  • the polymer of the present invention is obtained by blending an organic dye and a polymerizable monomer having an ability to absorb light in the yellow region in arbitrary amounts, mixing them uniformly, and then copolymerizing the polymerizable monomer mixture. can be done.
  • the amount of the organic dye having the ability to absorb light in the yellow region is preferably 0.00001 to 0.02 parts by weight, preferably 0.0001 to 0.02 parts by weight, when the total amount of all polymerizable monomers is 100 parts by weight. 0.01 parts by weight is more preferred, and 0.001 to 0.005 parts by weight is even more preferred. If the amount is less than 0.00001 parts by weight, sufficient antiglare properties and contrast properties may not be obtained.
  • the amount of components other than the polymerizable monomer used for copolymerization that is, the organic dye, the polymerization initiator described later, the cross-linking agent, the diluent, etc., when the mixture is included in the polymerizable monomer mixture is , is the amount when the entire polymerizable monomer is 100 parts by weight. Therefore, the total compounding amount of the entire polymerizable monomer mixture is expressed as exceeding 100 parts by weight.
  • the polymer of the present invention can be synthesized by a method commonly practiced in the technical field. For example, an organic dye having a yellow region light absorption ability and a polymerizable monomer are uniformly mixed, and if necessary, a polymerization initiator is added and gradually heated in a temperature range of room temperature to about 130 ° C.
  • the polymer can be polymerized by irradiation with electromagnetic waves such as microwaves, ultraviolet rays, and radiation (gamma rays).
  • electromagnetic waves such as microwaves, ultraviolet rays, and radiation (gamma rays).
  • various methods widely and commonly used by those skilled in the art such as radical polymerization, bulk polymerization or solvent polymerization can be employed. You may let
  • the polymerizable monomer mixture may contain a polymerization initiator.
  • polymerization initiators include lauryl peroxide, benzoyl peroxide, isopropyl carbonate, azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2′-azobis(2 ,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and other compounds. .
  • Photoinitiators such as aromatic ⁇ -hydroxyketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides and tertiary amines plus diketones can also be used.
  • photoinitiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4- 4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzoin methyl Examples include esters, camphoquinone and ethyl 4-(N,N-dimethylamino)benzoate. One or more of these polymerization initiators can be used.
  • the amount of the polymerization initiator used is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 2.5 parts by weight, more preferably 0.1 to 1 part by weight, when the total polymerizable monomer is 100 parts by weight. Parts by weight are more preferred.
  • the polymerizable monomer mixture may contain a diluent.
  • the diluent has the role of increasing the reaction rate of copolymerization and also increasing the releasability of the copolymer.
  • the diluent is preferably water-soluble, such as 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol.
  • tertiary amyl alcohol tertiary butyl alcohol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-propanol, 2-propanol, ethanol, methanol , 3,3-dimethyl-2-butanol, decanoic acid, octanoic acid, dodecanoic acid, 1-ethoxy-2-propanol, 1-tert-butoxy-2-propanol, EH-5, 2,3,6,7- Tetrahydroxy-2,3,6,7-tetramethyloctane, 9-(1-methylethyl)-2,5,8,10,13,16-hexaoxaheptadecane, 3,5,7,9,11 , 13-hexamethoxy-1-tetradecanol, tripropylene glycol methyl ether, water and the like are preferable, and these may be used singly or in combination
  • the amount of the diluent used is preferably 0 to 75 parts by weight, more preferably 10 to 70 parts by weight, and even more preferably 30 to 65 parts by weight, when the total polymerizable monomer is 100 parts by weight.
  • the polymer of the present invention when the polymer of the present invention is produced by copolymerization, a three-dimensional crosslinked structure can be formed in the resulting polymer by adding a cross-linking agent to the polymerizable monomer mixture. As a result, the mechanical strength and hardness of the polymer can be improved, and the elution of monomers and dyes (including organic dyes having yellow region light absorption ability) from the polymer can be suppressed.
  • the polymer of the present invention when the polymer of the present invention is used as a soft contact lens material as described later, it is possible to obtain a uniform, transparent, distortion-free soft contact lens with excellent optical properties, and the soft contact lens has durability ( Chemical resistance, heat resistance, solvent resistance) can also be imparted.
  • the blending ratio is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of all the polymerizable monomers. If it is less than 0.01 part by weight, it is difficult to obtain the effect, and if it exceeds 10 parts by weight, the resulting polymer tends to be brittle.
  • cross-linking agents examples include butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ) acrylate, dipropylene glycol di(meth)acrylate, diallyl fumarate, allyl (meth)acrylate, vinyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, methacryloyloxyethyl (meth)acrylate, divinylbenzene, diallyl phthalate , diallyl adipate, triallyl diisocyanate, ⁇ -methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth)acrylate, 3-vinylbenzyl (meth)acrylate, 2,2-bis((meth)acryloyloxyphenyl)hexa Fluoride, ethylene glycol
  • a suitable polymerizable monomer can be selected to impart various functionalities to the polymer of the present invention.
  • the polymer of the present invention is preferably applied as a soft contact lens material, it is required to have a certain level of oxygen permeability.
  • silicon-containing monomers such as the above-mentioned silicon-containing (meth)acrylates and silicon-containing styrene derivatives, fluorine-containing alkyl (meth)acrylates, and the like are used as polymerizable monomers. should be selected.
  • silicones having a polymerizable group may be used as polymerizable monomers. These include mono-(meth)acryloyl-terminated polysiloxanes, monoalkyl-terminated polysiloxanes, and more specifically ⁇ -(meth)acryloxypropyl terminated ⁇ -butyl (or ⁇ -methyl) Terminated polydimethylsiloxane, ⁇ -(meth)acryloxy-2-hydroxypropyloxypropyl terminated ⁇ -butyl (or ⁇ -methyl) terminated polydimethylsiloxane, ⁇ -(2-hydroxyl-methacryloxypropyloxypropyl)- ⁇ - Butyl-decamethylpentasiloxane, ⁇ -[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ⁇ -butyl (or ⁇ -methyl) terminated polydi
  • alkyl (meth)acrylates, styrene derivatives including styrene, or (meth)acrylic acid may be selected as polymerizable monomers.
  • the polymer of the present invention can be used as a material for soft contact lenses as described later.
  • a contamination function may be added.
  • the polymer of the present invention contains structural units of acrylamide-based monomers and/or vinyl-based monomers, it is highly hydrophilic and can be used as a soft, water-absorbing material for soft contact lenses.
  • a monomer having a hydrophilic group such as hydroxyacrylates, aminoalkyl acrylates, and acrylates may be selected.
  • the polymer of the present invention can be used as a lens material with a high refractive index. .
  • polymerizable monomers for imparting various functionalities to the polymer of the present invention it is preferably 0.01 weight part when the total of all polymerizable monomers is 100 parts by weight. parts or more, more preferably 0.05 parts by weight or more, and preferably 5 parts by weight or less, more preferably 3 parts by weight or less when all the polymerizable monomers are 100 parts by weight. .
  • the polymer of the present invention retains an organic dye capable of absorbing light in the yellow region inside the polymer. As a result, the contrast becomes clear when viewed when applied to a soft contact lens material. In addition, the anti-glare property is also excellent due to the organic dye having the ability to absorb light in the yellow region. Specifically, the polymer of the present invention has excellent absorption of light in the yellow region, and specifically, the light transmittance at 590 nm is preferably 90% or less, more preferably 80% or less, and still more preferably 70% or less. .
  • the polymer of the present invention is also excellent in retention of the organic dye that is retained inside and has the ability to absorb light in the yellow region. Since the dye hardly elutes from such a polymer, the antiglare property and contrast property are maintained, and the soft contact lens is excellent in safety even when worn repeatedly on a daily basis.
  • the polymer of the present invention is a hydrogel containing structural units of hydrophilic monomers such as acrylamide-based monomers and/or vinyl-based monomers, it has high water retention.
  • the water content ratio of water contained in the polymer to the weight of the polymer
  • the oxygen permeability tends to be high, the eyes are less likely to dry out, and it is useful in that it provides an excellent feel when worn.
  • the polymer of the present invention has excellent softness.
  • the Young's modulus at 25° C. is preferably 0.9 MPa or less, and usually 0.2 MPa or more. Due to such softness, when used as a soft contact lens material, it is useful because it can be worn smoothly and has an excellent feel during wearing.
  • the polymer of the present invention has excellent oxygen permeability.
  • the oxygen permeability coefficient is preferably 9 to 34 ⁇ 10 ⁇ 11 (cm 2 /sec) ⁇ (mLO 2 /(mL ⁇ mmHg)) when silicon is included in the polymer structure (Si system), and does not contain silicon.
  • the case (non-Si system) is preferably 80 to 140 ⁇ 10 ⁇ 11 (cm 2 /sec) ⁇ (mLO 2 /(mL ⁇ mmHg)). Owing to such oxygen permeability, when used as a material for a soft contact lens, the supply of oxygen to the cornea during wearing is less likely to be hindered, which is useful.
  • the polymer of the present invention is suitable for application when it is used as a soft contact lens material because it has transparency without becoming cloudy.
  • the transparency means that the transmittance of visible light (average transmittance of 400 to 700 nm) is preferably 60% or more, more preferably 70% or more.
  • the polymer of the present invention is suitable as a soft contact lens material.
  • a soft contact lens material When used as a soft contact lens material, it can be molded by a known method. For example, after a polymerization reaction is carried out in an appropriate mold or container to obtain a rod-shaped, block-shaped, or plate-shaped polymer, it is processed into a desired shape by mechanical processing such as cutting, polishing, or the like. After the polymerization reaction is carried out in a mold corresponding to the above to obtain a polymer molded article, mechanical finish processing is performed as necessary.
  • the surface of the lens may be subjected, if necessary, to a surface modification treatment in order to make the surface hydrophilic.
  • a surface modification treatment in order to make the surface hydrophilic.
  • Plasma treatment or ultraviolet treatment is preferred, and corona Discharge treatment, glow discharge treatment or ultraviolet/ozone treatment is more preferable.
  • a processing device and a processing method in that case conventionally known normal devices and methods can be used.
  • Example 1 The components shown in Table 1 are uniformly mixed, placed in a polymerization mold (length 30 mm, width 30 mm, thickness 1 mm), polymerized at 65 ° C. for 60 minutes to prepare a polymer sheet with a thickness of 1 mm, and the polymer sheet is released from the mold. bottom.
  • the obtained polymer sheet was cut into a size of 10 mm ⁇ 10 mm ⁇ 1 mm, and after being immersed in water at 23° C. for 24 hours, the light transmittance was measured (before the elution test; 0th time). After that, the polymer sheet was immersed in 10 mL of ethanol at 50° C. for 16 hours, and the light transmittance of the eluate was measured. After wiping off ethanol adhering to the surface of the polymer sheet taken out from the eluate, it was subjected to the next ethanol immersion. Elution was carried out four times per polymer sheet, and the light transmittance of the eluate was measured each time. The polymer sheet taken out after the fourth elution was dried at 50° C.
  • the light transmittance of the hydrated polymer sheet was measured (after the elution test; 4th time).
  • the light transmittance of the polymer sheet was measured using an integrating sphere ultraviolet-visible absorption spectrophotometer (U-4100, Hitachi High-Tech Science), and the eluate was measured using an ultraviolet-visible absorption altimeter (UV-2700, Shimadzu Corporation) in the range of 250 to 800 nm. bottom.
  • the dye retention rate of the polymer sheet was calculated by the following formula from the measured absorbance at the maximum absorption wavelength near 590 nm of the polymer sheet after the 0th and 4th elutions.
  • Dye retention rate (%) ⁇ 1-(4th absorbance) ⁇ (0th absorbance) ⁇ ⁇ 100
  • Example 2 The components shown in Table 2 are uniformly mixed, placed in a polymerization mold (length 30 mm, width 30 mm, thickness 1 mm), polymerized at 65 ° C. for 60 minutes to prepare a polymer sheet with a thickness of 1 mm, and the polymer sheet is released from the mold. bottom. Each polymer sheet thus obtained was subjected to the following tests for evaluation. (1) Dissolution test It was carried out in the same manner as in Test Example 1.
  • Moisture content (Weight of hydrated polymer sheet/Weight of dried polymer sheet - 1) x 100
  • ⁇ Test Example 3> A polymer was prepared in the same manner as in Test Example 1 using the components and formulations shown in Table 4, and an elution test was performed to evaluate the dye retention rate.

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention a pour objet un polymère qui est approprié pour être utilisé en tant que matériau pour une lentille de contact souple qui permet d'améliorer les propriétés antireflet et le contraste. Le polymère selon l'invention est obtenu par copolymérisation d'un colorant organique ayant le pouvoir d'absorber la lumière dans la région du jaune et d'un ou plusieurs monomères polymérisables. Les monomères polymérisables comprennent un ou plusieurs types choisis parmi les monomères à base d'acrylamide et les monomères à base de vinyle. Les monomères polymérisables comprennent également un monomère contenant du silicium.
PCT/JP2022/039021 2021-10-20 2022-10-20 Matériau pour lentille de contact souple ayant une fonction d'amélioration du contraste WO2023068316A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH095682A (ja) * 1995-02-07 1997-01-10 Seiko Epson Corp 着色コンタクトレンズおよびその製造法
JP2013533518A (ja) * 2010-07-30 2013-08-22 ノバルティス アーゲー 架橋親水性コーティングを備えるシリコーンヒドロゲルレンズ
JP2014523542A (ja) * 2011-06-09 2014-09-11 ノバルティス アーゲー ナノテクスチャー表面を持つシリコーンヒドロゲルレンズ
JP2017165941A (ja) * 2015-12-25 2017-09-21 日東電工株式会社 有機ｅｌ表示装置用粘着剤組成物、有機ｅｌ表示装置用粘着剤層、有機ｅｌ表示装置用粘着剤層付き偏光フィルム、及び有機ｅｌ表示装置
JP6290170B2 (ja) * 2013-02-28 2018-03-07 山本化成株式会社 自動車用合わせガラス
JP6307209B1 (ja) * 2016-09-30 2018-04-04 三井化学株式会社 フォトクロミックレンズおよび重合性組成物
WO2019111969A1 (fr) * 2017-12-06 2019-06-13 三井化学株式会社 Composition polymérisable pour matériau optique et article moulé
JP2022071514A (ja) * 2020-10-28 2022-05-16 興和株式会社 コントラスト改善機能を有する眼科用材料

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH095682A (ja) * 1995-02-07 1997-01-10 Seiko Epson Corp 着色コンタクトレンズおよびその製造法
JP2013533518A (ja) * 2010-07-30 2013-08-22 ノバルティス アーゲー 架橋親水性コーティングを備えるシリコーンヒドロゲルレンズ
JP2014523542A (ja) * 2011-06-09 2014-09-11 ノバルティス アーゲー ナノテクスチャー表面を持つシリコーンヒドロゲルレンズ
JP6290170B2 (ja) * 2013-02-28 2018-03-07 山本化成株式会社 自動車用合わせガラス
JP2017165941A (ja) * 2015-12-25 2017-09-21 日東電工株式会社 有機ｅｌ表示装置用粘着剤組成物、有機ｅｌ表示装置用粘着剤層、有機ｅｌ表示装置用粘着剤層付き偏光フィルム、及び有機ｅｌ表示装置
JP6307209B1 (ja) * 2016-09-30 2018-04-04 三井化学株式会社 フォトクロミックレンズおよび重合性組成物
WO2019111969A1 (fr) * 2017-12-06 2019-06-13 三井化学株式会社 Composition polymérisable pour matériau optique et article moulé
JP2022071514A (ja) * 2020-10-28 2022-05-16 興和株式会社 コントラスト改善機能を有する眼科用材料

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