WO2020202320A1 - Catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, et procédé de fabrication d'un catalyseur de décomposition - Google Patents

Catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, et procédé de fabrication d'un catalyseur de décomposition Download PDF

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Publication number
WO2020202320A1
WO2020202320A1 PCT/JP2019/014194 JP2019014194W WO2020202320A1 WO 2020202320 A1 WO2020202320 A1 WO 2020202320A1 JP 2019014194 W JP2019014194 W JP 2019014194W WO 2020202320 A1 WO2020202320 A1 WO 2020202320A1
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Prior art keywords
carrier
hydrogen peroxide
catalyst
solution
coating layer
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PCT/JP2019/014194
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English (en)
Japanese (ja)
Inventor
雄司 大久保
智史 清野
和也 山村
理 森
Original Assignee
株式会社メニコン
国立大学法人大阪大学
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Application filed by 株式会社メニコン, 国立大学法人大阪大学 filed Critical 株式会社メニコン
Priority to JP2020555529A priority Critical patent/JP6829857B1/ja
Priority to PCT/JP2019/014194 priority patent/WO2020202320A1/fr
Publication of WO2020202320A1 publication Critical patent/WO2020202320A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C13/00—Assembling; Repairing; Cleaning

Definitions

  • the present invention relates to a catalyst for decomposing hydrogen peroxide for disinfecting contact lenses, a method for producing the same, and the like.
  • Patent Document 1 As the decomposition treatment of hydrogen peroxide, it is known that the decomposition of hydrogen peroxide is promoted by using a catalyst supporting an active metal having hydrogen peroxide decomposition activity such as platinum.
  • a catalyst supporting an active metal having hydrogen peroxide decomposition activity such as platinum.
  • Patent Document 1 by using platinum fine particles immobilized on a carrier, hydrogen peroxide is decomposed to a sufficiently low concentration after a lapse of a predetermined time while effectively disinfecting contact lenses with hydrogen peroxide. It is disclosed to do.
  • the hydrogen peroxide decomposition catalyst of Patent Document 1 has room for further improvement in terms of durability.
  • the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to provide a decomposition catalyst for hydrogen peroxide having improved durability.
  • a decomposition catalyst of hydrogen peroxide for disinfecting contact lenses which comprises a carrier and fine particles containing platinum immobilized on the carrier, wherein the carrier is a base material. And a coating layer provided on the surface of the substrate, the coating layer containing a repeating unit having an aromatic ring substituted with two or more hydroxyl groups and a heteroatom having a lone electron pair.
  • a catalyst is provided, including.
  • the aromatic ring substituted with the two or more hydroxyl groups is the ortho-dihydroxybenzene ring.
  • the coating layer comprises polycatecholamines obtained by polymerizing catecholamines.
  • the coating layer comprises polydopamine.
  • the average particle size of the fine particles is 1000 nm or less.
  • a carrier in which a coating layer containing polycatecholamine is formed on the surface of the base material by polymerizing the catecholamines in a state where the solution containing the catecholamines is in contact with the base material to obtain, to attach an irradiation solution containing platinum ions to the carrier, and to irradiate the carrier to which the irradiation solution is attached with radiation to immobilize fine particles containing platinum on the surface of the carrier.
  • a method for producing a decomposition catalyst for the above-mentioned hydrogen peroxide for disinfecting contact lenses which comprises the above.
  • the substrate is subjected to a hydrophilization treatment prior to contact with the solution containing the catecholamines.
  • the carrier on which the coating layer is formed is subjected to an ultrasonic cleaning treatment before the irradiation solution is attached.
  • FIG. 1 is a schematic cross-sectional view of a catalyst according to one embodiment of the present invention.
  • the decomposition catalyst 100 of hydrogen peroxide for contact lens disinfection includes a carrier 10 and platinum-containing fine particles (hereinafter, platinum-containing fine particles) 20 immobilized on the carrier 10.
  • the carrier 10 has a base material 12 and a coating layer 14 provided on the surface thereof.
  • the coating layer 14 is provided on the entire surface of the base material 12 and the platinum-containing fine particles 20 are immobilized.
  • the formation of the coating layer 14 and / or the immobilization of the platinum-containing fine particles 20 is performed. It may be applied to only a part of the surface of the base material 12 (for example, only one side).
  • the hydrogen peroxide concentration before immersion is preferably 1% or less, more preferably 0, over a 6-hour immersion period.
  • a hydrogen peroxide solution up to a concentration of .5% or less, more preferably 0.2% or less (for example, 3.5% by weight (35000 ppm) of hydrogen peroxide solution, preferably 350 ppm or less, more preferably 175 ppm or less, More preferably, it can decompose hydrogen peroxide (to a concentration of 70 ppm or less).
  • the total weight of platinum immobilized on the carrier (hereinafter, may be referred to as "platinum-supported weight of catalyst”) is preferably 1 ⁇ g to 300 ⁇ g, and more preferably 1 ⁇ g to 100 ⁇ g. Further, in the catalyst of the present invention, the weight of the immobilized platinum per geometric surface area of the carrier is preferably 0.01 ⁇ g / cm 2 to 300 ⁇ g / cm 2 , more preferably 0.01 ⁇ g / cm 2 to 100 ⁇ g. / Cm 2 .
  • any suitable material can be used as the material for forming the base material.
  • the material for forming the base material include inorganic materials such as metal, glass and ceramic, and organic materials such as synthetic resin.
  • Organic materials such as synthetic resins can be more advantageous than inorganic materials in terms of moldability, operability, price and the like. Another advantage is that it does not require firing at a high temperature.
  • synthetic resins include acrylonitrile-butadiene-styrene (ABS) resin, polyethylene (PE) resin, polypropylene (PP) resin, polyurethane (PU) resin, modified polyphenylene ether (PPE) resin, and polystyrene (PS) resin.
  • ABS acrylonitrile-butadiene-styrene
  • PE polyethylene
  • PP polypropylene
  • PU polyurethane
  • PPE modified polyphenylene ether
  • PS polystyrene
  • PC Polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PVC polyvinyl chloride
  • PEI polyetherimide
  • PSU polysulfone
  • PMMA polymethylmethacrylate
  • ABS acrylonitrile, butadiene, styrene (ABS) resin, polyethylene (PE) resin, polypropylene (PP) resin, and their copolymers, from the viewpoints of moldability, price, durability against hydrogen peroxide, adhesion of platinum-containing fine particles, etc.
  • Polyethylene resin is preferable.
  • the above materials may be used alone or in combination of two or more.
  • the shape of the base material can be appropriately set according to the purpose and the like.
  • the base material may be, for example, a square plate, a disk, a prism, a column, or the like. Further, from the viewpoint of increasing the geometric surface area, it may be formed so as to have a wave shape such as a sine wave, a rectangular wave, or a triangular wave.
  • the surface of the base material may be roughened. By roughening the surface, the specific surface area can be increased, and as a result, the surface area of the obtained carrier can be increased. Further, the platinum-containing fine particles can be firmly immobilized by the carrier.
  • the specific surface area of the carrier can be, for example, 3 cm 2 / g to 200 cm 2 / g, preferably 10 cm 2 / g to 100 cm 2 / g.
  • the base material preferably has high surface hydrophilicity.
  • a hydrophilic group such as an -OH group or a -COOH group
  • a coating layer can be suitably formed and a strong bond can be formed with the coating layer.
  • the surface hydrophilicity of the base material may be improved by hydrophilizing the base material.
  • the hydrophilization treatment include a dry process such as plasma treatment, corona treatment, and frame treatment, and a wet process of immersing in a chemical such as potassium permanganate or chromic acid.
  • the coating layer contains a repeating unit having an aromatic ring substituted with two or more hydroxyl groups and a heteroatom having an isolated electron pair (excluding the oxygen atom present in the hydroxyl group as a substituent of the aromatic ring). Contains polymers. The presence of heteroatoms and aromatic rings with lone electron pairs in the repeating units of the polymer forming the coating layer allows platinum ions and platinum particles to be contained with the coating layer (more specifically, the polymer contained in the coating layer). Since the coordination bond can be achieved, the effect of improving the carrying amount and / or durability of the platinum-containing fine particles can be achieved.
  • the coating layer when an aromatic ring substituted with two or more hydroxyl groups is present in the repeating unit of the polymer forming the coating layer, even if the material for forming the base material is an organic substance, it contains a metal or a metal oxide. Even if the coating layer can be formed well.
  • hetero atom having the above lone electron pair examples include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a chlorine atom, an iodine atom, and a bromine atom.
  • a nitrogen atom and an oxygen atom are preferable, and a nitrogen atom is more preferable.
  • Heteroatoms can be used alone or in combination of two or more.
  • the repeating unit is typically derived from an aromatic compound having an aromatic ring substituted with two or more hydroxyl groups.
  • the polymer may contain repeating units derived from one type of aromatic compound, or may contain repeating units derived from two or more types of aromatic compounds.
  • the aromatic compound comprises drawable hydrogen, and in one embodiment, the coating layer can be formed by self-polymerization of the aromatic compound.
  • a benzene ring is preferable.
  • the benzene ring substituted with two or more hydroxyl groups include a dihydroxybenzene ring or a trihydroxybenzene ring. It is preferably a dihydroxybenzene ring, more preferably an ortho- or para-dihydroxybenzene ring, and even more preferably an ortho-dihydroxybenzene ring.
  • the aromatic ring (preferably a benzene ring) has an alkyl group, an amino group (for example, a primary or secondary amino group), a carboxyl group, and an alkoxysilyl group (for example, trimethoxy) in addition to two or more hydroxyl groups. It may be substituted with a silyl group or a triethoxysilyl group) or the like.
  • the aromatic compound has two or more hydroxyl groups and an alkyl group, an amino group (eg, a primary or secondary amino group), a carboxyl group, and an alkoxysilyl group (eg, an alkoxysilyl group) having a hetero atom.
  • aromatic compound examples include ortho-dihydroxybenzene (hereinafter, also referred to as catecholamines) into which an alkylamine has been introduced.
  • Catecholamines can preferably form a coating layer containing polycatecholamines by polymerization (eg, self-polymerization).
  • catecholamines that can be preferably used in the present invention are shown in the following formula (I).
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.
  • the above X is preferably a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and more preferably a substituted or unsubstituted ethylene group.
  • substituents include -OH, -COOH, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, and the like.
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group, respectively.
  • the catecholamines represented by the formula (I) can be preferably used.
  • dopamine represented by the formula (II) can be preferably used.
  • the coating layer comprises polydopamine.
  • Polydopamine can be produced by polymerization of dopamine (eg, self-polymerization).
  • dopamine eg, self-polymerization
  • the exact structure of polydopamine is unclear, but is typically thought to include the following repeating units:
  • the thickness of the coating layer is preferably 3 nm or more, more preferably 5 nm to 1000 nm (for example, 10 nm to 300 nm, and for example, 15 nm to 200 nm).
  • the average particle size of the platinum-containing fine particles is, for example, 1000 nm or less, preferably 300 nm or less, more preferably 20 nm or less, still more preferably 15 nm or less, and even more preferably 10 nm or less.
  • the average particle size is preferably 1 nm or more, more preferably 1.5 nm or more, still more preferably 2 nm or more, and even more preferably 2.5 nm or more.
  • the average particle size of the platinum-containing fine particles can be adjusted, for example, by changing the concentration of active metal ions in the irradiation solution in the production method described later. Specifically, the average particle size can be increased by increasing the concentration of active metal ions in the irradiation solution, and the average particle size can be decreased by decreasing the concentration.
  • the average particle size of the fine particles can be determined by, for example, the following method. ⁇ Measurement of average particle size ⁇ The flakes of the catalyst to be measured are observed and imaged with a transmission electron microscope (for example, manufactured by JEOL Ltd., product number "JEM-2100"). The primary particle size of any 50 fine particles in the obtained image is measured, and the average value (geometric mean) of these is calculated as the average particle size. If the fine particles are not spherical, the major axis is measured.
  • the platinum-containing fine particles may further contain components other than platinum, if necessary.
  • the content of platinum in the platinum-containing fine particles can be preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight, still more preferably 95% by weight to 100% by weight.
  • platinum fine particles examples include active metals having hydrogen peroxide decomposition activity such as palladium (Pd), iridium (Ir), ruthenium (Ru), rhodium (Rh), and osmium (Os). .. These components may be used alone or in combination of two or more.
  • the platinum-containing fine particles may be immobilized in a state of being scattered on the surface of the carrier, or several fine particles may be connected to each other and immobilized like a string of beads.
  • the specific surface area of the active metal can be increased and the adhesion of oxygen bubbles can be more preferably suppressed as compared with the case where the active metal is formed in layers. Further, when some fine particles are connected and fixed, high durability can be obtained.
  • the catalyst according to item A can be produced by any suitable method.
  • a coating layer containing polycatecholamine is formed on the surface of the base material by polymerizing the catecholamines in a state where the solution containing the catecholamines is in contact with the base material.
  • Obtaining a carrier step of forming a coating layer
  • attaching an irradiation solution containing platinum ions to the carrier adheresion step of the irradiation solution
  • irradiating the carrier to which the irradiation solution is attached with radiation.
  • the present invention comprises immobilizing the platinum-containing fine particles on the surface of the carrier (immobilization step of the platinum-containing fine particles).
  • the substrate it is preferable to subject the substrate to a hydrophilization treatment before contacting it with a solution containing catecholamines. Further, it is preferable that the carrier on which the coating layer is formed is subjected to an ultrasonic cleaning treatment before the irradiation solution is attached.
  • a coating layer containing polycatecholamines is formed on the surface of the base material by polymerizing the catecholamines in a state where the solution containing the catecholamines is in contact with the base material.
  • a carrier having a structure in which a coating layer containing polycatecholamine is provided on the surface of the base material can be obtained.
  • the catecholamines can be self-polymerized with the substrate immersed in a solution containing the catecholamines.
  • the catecholamines can be polymerized by using a conductive base material and immersing the base material in a solution containing catecholamines to carry out electrolytic polymerization.
  • the polymerization reaction can be promoted by coexisting an enzyme such as tyrosinase or laccase.
  • the above solution containing catecholamines is a solution in which catecholamines or salts thereof are dissolved in a solvent.
  • catecholamines are as described in Item A.
  • the solvent include water, ethanol, propanol and the like.
  • the solvent only one kind may be used alone, or two or more kinds may be used in combination.
  • the solvent is water.
  • the concentration of catecholamines in the above solution can be, for example, 0.1 mg / mL to 10 mg / mL, preferably 1 mg / mL to 8 mg / mL, and more preferably 2 mg / mL to 6 mg / mL.
  • the above solution may contain any suitable additive, if desired.
  • the additive include a pH buffer (tris hydrochloride, etc.), an enzyme (laccase secreted by the white-rot fungus Trametes versicolor, etc.) and the like.
  • the pH of the above solution is preferably 4 to 12, more preferably 7 to 9.
  • the liquid temperature (at the time of contact) of the above solution is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of improving the reaction rate.
  • the upper limit of the liquid temperature can be, for example, below the boiling point of the solvent.
  • the contact time with the above solution can be appropriately selected depending on the purpose and the like.
  • the contact time can be, for example, 1 hour or longer, preferably 3 hours or longer, more preferably 6 hours or longer, still more preferably 12 hours or longer, still more preferably 18 hours or longer.
  • the upper limit of the contact time is not particularly limited, but may be, for example, 72 hours, or 48 hours, for example, from the viewpoint of manufacturing efficiency.
  • a coating layer can be preferably formed on the surface of the base material by polymerization of catecholamines (for example, self-polymerization).
  • a carrier having a coating layer containing polycatecholamine formed on the surface of the base material can be obtained.
  • the resulting carrier is washed.
  • the cleaning liquid water, alcohol, a mixed liquid thereof and the like can be used, and water can be preferably used.
  • cleaning can be performed by immersing the carrier in a cleaning solution and subjecting it to sonication.
  • a cleaning solution By subjecting the carrier to an ultrasonic cleaning treatment after forming the coating layer, catecholamines or polymers thereof that are not bonded to the substrate or have a weak bonding force are desorbed, and a coating layer having a strong bond to the substrate remains. Therefore, a catalyst having excellent durability can be obtained.
  • the frequency in ultrasonic processing is, for example, 20 kHz to 100 kHz, and it is desirable to alternately oscillate three waves with different frequencies by a timer to eliminate uneven cleaning.
  • the ultrasonic output can be, for example, 50 W to 1500 W, preferably 100 W to 1000 W.
  • the temperature of the cleaning liquid can be, for example, 5 ° C to 90 ° C, preferably 20 ° C to 80 ° C.
  • the washing time can be, for example, 20 seconds or more, preferably 1 minute to 30 minutes.
  • the irradiation solution containing platinum ions is brought into contact with the carrier, and the irradiation solution is adhered to the carrier.
  • the contact method include a method of immersing the carrier in the irradiation solution, a method of applying the carrier to the irradiation solution, a method of spraying the irradiation solution onto the carrier, and the like.
  • a method of immersing the carrier in the irradiation solution is preferable. This is because the irradiation solution can adhere well to the carrier.
  • the irradiation solution containing platinum ions is prepared by dissolving a soluble compound of platinum such as hexachloroplatinum (IV) acid, potassium hexachloroplatinate (IV), acetylacetonate platinum (II) or a salt thereof in water. Can be done.
  • concentration of platinum ions in the irradiation solution is preferably 1 mM to 200 mM, more preferably 1 mM to 100 mM, and even more preferably 1 mM to 10 mM.
  • the irradiation solution may contain ions of an active metal having hydrogen peroxide decomposing activity other than platinum. The active metal is as described in Item A.
  • the total concentration of the active metal ions (including platinum ions) in the irradiation solution is preferably 1 mM to 200 mM, more preferably 1 mM to 150 mM, still more preferably 1 mM to 100 mM. Within this range, fine particles having a desired particle size can be preferably obtained.
  • the irradiation solution containing platinum ions typically further contains an alcohol having 1 to 3 carbon atoms such as methanol, ethanol, and isopropyl alcohol. Platinum ions can be suitably reduced by the function of the alcohol as a reduction aid.
  • the content of alcohol in the irradiation solution is preferably 0.1% by volume to 30% by volume, more preferably 0.5% by volume to 10% by volume.
  • the irradiation solution containing platinum ions preferably further contains a particle size control agent.
  • a particle size control agent a compound that can form an energetically more stable bond between an active metal such as platinum and the metal (for example, a compound that gives a mixing heat smaller than the mixing heat between the active metals such as platinum).
  • Specific examples thereof include phosphorus compounds such as sodium phosphinate (NaPH 2 O 2 ) and sodium phosphonate (NaPHO 3 ), and nitrogen such as sodium nitrite (NaNO 2 ) and sodium thiosulfate (Na 2 S 2 O 3 ).
  • examples include compounds and sulfur compounds such as sodium sulfite (Na 2 SO 3 ).
  • the concentration of the particle size control agent in the irradiation solution is preferably 0.05 mM to 50 mM, more preferably 0.1 mM to 10 mM.
  • the irradiation solution containing platinum ions may further contain any constituent components such as a pH adjuster and a chelating agent, if necessary.
  • a pH adjuster and a chelating agent
  • Specific examples of the arbitrary constituents include sodium hydroxide, ammonia, tartaric acid, citric acid and the like.
  • the carrier to which the irradiation solution containing platinum ions is attached is irradiated with radiation.
  • platinum ions are reduced on the surface of the carrier, and platinum-containing fine particles are immobilized on the surface of the carrier.
  • Irradiation may be performed on the carrier immersed in the irradiation solution, or may be performed on the carrier whose surface is wet with the irradiation solution by immersion, coating, spraying, or the like. (Dip EB method), or may be performed on a carrier in an apparently dry state after the irradiation solution is attached (dry EB method). When the dip EB method is used, there is an advantage that the cost of the irradiation solution can be suppressed.
  • electron beam As the radiation to be irradiated, electron beam, ⁇ ray, X-ray or the like can be used. Among them, an electron beam is preferable because continuous irradiation is possible in an open atmosphere and an electron beam having a high dose rate has an advantage that nanoparticles can be generated and supported in 10 seconds or less.
  • the acceleration energy of the electron beam is preferably 0.5 MeV to 10 MeV, more preferably 1 MeV to 8 MeV.
  • the absorbed dose to the carrier in electron beam irradiation is preferably 1 kGy to 100 kGy, and more preferably 10 kGy to 50 kGy.
  • the electron beam irradiation conditions can be appropriately set according to the purpose and the like.
  • electron beam irradiation can be performed under atmospheric pressure and room temperature conditions.
  • the irradiation time can be appropriately set according to the active metal ion concentration, the dose of the electron beam, and the like.
  • the irradiation time may be, for example, 1 second to 1 minute, preferably 2 seconds to 30 seconds, and more preferably 3 seconds to 10 seconds.
  • the electron beam may be continuously irradiated or intermittently irradiated. When irradiated intermittently, the irradiation time is the total.
  • the carrier immersed in the irradiation solution When the carrier immersed in the irradiation solution is irradiated with an electron beam, it is more preferable to replace the dissolved oxygen in the irradiation solution with an inert gas such as nitrogen gas or argon gas prior to the electron beam irradiation. ..
  • the production method of the present invention is very suitable for mass production of the catalyst according to item A.
  • the hydrophilization treatment is applied to the substrate before contact with a solution containing catecholamines.
  • the hydrophilization treatment removes contaminants such as oils and dusts existing on the surface when the base material is an inorganic material, and when the base material is an organic material, hydrophilic groups such as hydroxyl groups and carboxyl groups are removed on the surface of the base material.
  • hydrophilization treatment Any suitable method can be used as the hydrophilization treatment.
  • Specific examples include a dry process such as plasma treatment, corona treatment, and frame treatment, and a wet process of immersing in a chemical such as potassium permanganate or chromic acid. Since these surface treatments are well known to those skilled in the art, detailed description thereof will be omitted.
  • the method for disinfecting a contact lens of the present invention includes immersing the contact lens and the catalyst according to item A in a contact lens disinfectant solution containing hydrogen peroxide.
  • the concentration of hydrogen peroxide in the contact lens disinfectant is, for example, 1.0% by weight to 5.0% by weight, preferably 2.5% by weight to 4.0% by weight.
  • the contact lens disinfectant may contain any suitable additive, if desired.
  • the additive component include a chelating agent, a surfactant, an isotonic agent, a buffering agent, a thickener, a preservative and the like. These additive components may be used alone or in combination of two or more. The concentration of each additive component in the disinfectant solution can be appropriately set according to the purpose and the like.
  • the chelating agent improves the stability of the disinfectant solution and is effective in terms of its long-term storage.
  • the chelating agent include EDTA (ethylenediaminetetraacetic acid) or a salt thereof, etidronic acid or a salt thereof, DTPMP [diethylenetriaminepenta (methylenephosphonic acid)], sodium tinate and the like.
  • the concentration of the chelating agent in the disinfectant solution is generally about 0.01% by weight to 0.5% by weight.
  • Surfactants can impart effective contact lens cleaning effects such as lipid removing action to contact lens disinfectants.
  • known anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants generally used for liquids for contact lenses and the like can be used.
  • Specific examples include polyethylene glycol ether of higher alcohol, polyethylene glycol ester of higher fatty acid, polyglycerin ester of higher fatty acid, polyethylene glycol ether of alkylphenol, polyethylene glycol sorbitan alkyl ester, polyoxyethylene-polyoxypropylene glycol (poroxummer), and so on.
  • examples thereof include ethylenediamine tetrapolyoxyethylene polyoxypropylene (poroxamine).
  • a block copolymer of polyoxyethylene and polyoxypropylene or a derivative thereof is preferably used.
  • the tonicity agent is added for the purpose of adjusting the osmotic pressure of the contact lens disinfectant solution (before and after disinfection).
  • a known tonicity agent generally used for a liquid agent for contact lenses or the like can be used.
  • the contact lens disinfectant solution can be prepared by dissolving or dispersing each component in an aqueous medium.
  • the aqueous medium include water, physiological saline and the like.
  • the order of addition is not limited, and the desired disinfectant can be easily obtained by adding each component sequentially or simultaneously and dispersing or dissolving them, respectively.
  • the amount of the contact lens disinfectant used may be an amount that allows the contact lens and the catalyst to be immersed.
  • the amount used is, for example, 5.0 mL to 20 mL.
  • the amount of contact lens disinfectant used is, for example, 0.01 mL to 20 mL, preferably 0.05 mL to 10 mL, more preferably 0.1 mL to 5 mL, per 1 ⁇ g of platinum supported on the catalyst. obtain.
  • contact lenses to be disinfected all types of contact lenses can be applied regardless of water-containing or non-water-containing, so-called soft or hard materials.
  • the disinfection method of the present invention is particularly suitable for soft contact lenses.
  • soft contact lenses those made of water-containing hydrogels are known, and for example, hydrophilic monomers such as 2-hydroxyethyl methacrylate, N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, and methacrylate.
  • hydrophilic monomers such as 2-hydroxyethyl methacrylate, N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, and methacrylate.
  • those formed from the polymer or copolymer of the above those formed from a copolymer produced by copolymerizing the hydrophilic monomer with a hydrophobic monomer containing silicone, etc. Can be mentioned.
  • disinfection of contact lenses with hydrogen peroxide and decomposition of hydrogen peroxide with a catalyst can be suitably compatible.
  • the catalyst and the contact lens may coexist in the disinfectant solution from the beginning, or the catalyst may be added after the contact lens is immersed and both may coexist.
  • the immersion temperature is preferably 5 ° C. to 40 ° C., more preferably 10 ° C. to 30 ° C.
  • the concentration of hydrogen peroxide in the disinfectant solution after disinfection is, for example, 150 ppm or less, preferably 100 ppm or less. With the residual concentration of hydrogen peroxide, it is possible to avoid the occurrence of pain, irritation, etc. even if the contact lens after disinfection is worn as it is.
  • a titanium sulfate solution (30%, Wako Pure Chemical Industries, Ltd.) was diluted to 5%, mixed with a sample containing hydrogen peroxide, and the hydrogen peroxide concentration was measured by measuring the absorbance at 407 nm.
  • the catalyst having the PDA coating layer has an increased amount of platinum fine particles supported as compared with the catalyst having no PDA coating layer (immersion time 0h), and the initial stage The catalytic activity of (1st time) was improved. Further, the catalyst having no PDA coating layer has a large increase in the residual H 2 O 2 concentration during repeated use, but the catalyst having a PDA coating layer suppresses the increase and has a large increase in the PDA coating amount. In the catalyst (immersion time 3h, 24h), the increase amount is remarkably suppressed.
  • the base material taken out from the DA solution was immersed in pure water at room temperature and ultrasonically cleaned for 5 minutes (manufactured by AS-ONE, model number "USK-1R", frequency: 40 kHz, output: 100 W). Then, nitrogen gas was blown with an air gun to dry it, whereby a carrier (PDA-coated ABS resin plate) was obtained.
  • the catalyst obtained by ultrasonically cleaning the carrier taken out from the DA solution and then immobilizing the platinum fine particles is a residual H 2 O after repeated use. 2 It can be seen that the increase in concentration is suppressed and the durability is improved.
  • the slide glass taken out from the DA solution was immersed in pure water at room temperature and ultrasonically cleaned for 5 minutes (manufactured by AS-ONE, model number "USK-1R", frequency: 40 kHz, output: 100 W). Then, nitrogen gas was blown with an air gun to dry it, whereby a carrier (PDA-coated slide glass) was obtained.
  • the obtained carrier was analyzed by X-ray photoelectron spectroscopy to obtain a Si2p-XPS spectrum. Further, as a comparison target, a Si2p-XPS spectrum of a carrier having an immersion time of 1 or 24 hours, which was rinsed instead of the ultrasonic cleaning treatment, was obtained.
  • the spectra obtained for each carrier are shown in FIGS. 7 (a) or 7 (b).
  • the peak intensity derived from the base material is increased by ultrasonic cleaning. From this, the PDA that is not bonded to the base material is desorbed by ultrasonic cleaning, and as a result, a catalyst having a PDA coating layer that is firmly bonded to the base material (as a result, a catalyst having excellent durability). Is presumed to have been obtained.
  • FIG. 7B no peak derived from the base material was confirmed for the carrier having an immersion time of 24 hours regardless of the presence or absence of ultrasonic cleaning. It is presumed that this is because the thickness of the PDA coating layer is increased due to the long immersion time, and as a result, the surface of the substrate is not exposed even when the PDA that is not bonded to the substrate is detached. To.
  • the base material was immersed for 24 hours.
  • the base material taken out from the DA solution was immersed in pure water at room temperature and ultrasonically cleaned for 5 minutes (manufactured by AS-ONE, model number "USK-1R", frequency: 40 kHz, output: 100 W). Then, nitrogen gas was blown with an air gun to dry it, whereby a carrier (a PDA-coated ABS resin plate after plasma treatment) was obtained.
  • FIG. 8 shows an SEM photograph of an ABS resin plate (base material) before plasma treatment, a carrier coated with PDA after plasma treatment, and a catalyst obtained by immobilizing platinum-containing fine particles on the carrier.
  • the amount of platinum supported is increased by subjecting the substrate to plasma treatment before immersion in the DA solution.
  • the initial catalytic activity is improved and the increase in the residual H 2 O 2 concentration during repeated use is suppressed. , Durability is improved.
  • the reason why such an effect is exhibited is that as a result of the formation of hydrophilic groups by the plasma treatment, the formation of the PDA coating layer is promoted and the bond between the PDA coating layer and the base material is strengthened. Guess.
  • the base material taken out from the DA solution was immersed in pure water at room temperature and ultrasonically cleaned for 5 minutes (AS-ONE, model number "USK-1R", frequency: 40 kHz, output: 100 W). Then, nitrogen gas was blown with an air gun to dry it, whereby a carrier (a PDA-coated ABS resin plate after plasma treatment) was obtained.
  • the solution was prepared. Under the condition of room temperature (22 ⁇ 2 ° C.), the plasma-treated substrate was immersed in this KBM-803 solution for 10 minutes. Next, the base material was taken out from the KBM-803 solution, washed with water, and then heat-treated at 80 ° C. for 10 minutes using a vacuum dryer (AVO-200NS-D manufactured by AS-ONE).
  • the product was immersed in pure water, ultrasonically cleaned with an ultrasonic cleaner (USK-1R manufactured by AS-ONE) for 5 minutes, and blown with nitrogen gas with an air gun to dry.
  • a carrier ABS resin plate treated with KBM-803 after plasma treatment
  • TMS tetramethyl orthosilicate
  • the base material was taken out from the TMOS solution, washed with water, and then vacuum dried (manufactured by AS-ONE).
  • AVO-200NS-D was heat-treated at 80 ° C. for 10 minutes, then immersed in pure water and used in an ultrasonic cleaner (USK-1R, manufactured by AS-ONE) for more than 5 minutes. It was sonicated and dried by blowing nitrogen gas with an air gun.
  • the TMOS-coated ABS resin plate was immersed in the KBM-803 solution having the same volume percent concentration as the TMOS solution for 10 minutes, and similarly.
  • the carrier (ABS resin treated with TMOS and KBM-803 after plasma treatment) was obtained by pulling up, washing, heat-treating, and ultrasonically washing.
  • the catalyst using the carrier treated with the silane coupling agent has an increase in the residual H 2 O 2 concentration during repeated use as compared with the catalyst using the carrier not subjected to the treatment. It was increasing, and the effect of improving durability could not be obtained.
  • the catalyst of the present invention can be suitably used in disinfecting contact lenses.

Abstract

La présente invention concerne un catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, le catalyseur de décomposition ayant une excellente durabilité. Ce catalyseur est un catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, le catalyseur de décomposition contenant un support et des microparticules contenant du platine fixées sur le support, le support ayant un substrat et une couche d'enrobage disposée sur la surface de la base; et la couche d'enrobage comprend un polymère qui comprend des unités de répétition ayant un cycle aromatique substitué par deux groupes hydroxyle ou plus, et un hétéroatome ayant une paire d'électrons célibataires.
PCT/JP2019/014194 2019-03-29 2019-03-29 Catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, et procédé de fabrication d'un catalyseur de décomposition WO2020202320A1 (fr)

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JP2020555529A JP6829857B1 (ja) 2019-03-29 2019-03-29 コンタクトレンズ消毒用過酸化水素の分解触媒およびその製造方法
PCT/JP2019/014194 WO2020202320A1 (fr) 2019-03-29 2019-03-29 Catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, et procédé de fabrication d'un catalyseur de décomposition

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PCT/JP2019/014194 WO2020202320A1 (fr) 2019-03-29 2019-03-29 Catalyseur de décomposition pour peroxyde d'hydrogène pour désinfecter des lentilles de contact, et procédé de fabrication d'un catalyseur de décomposition

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WO2023042666A1 (fr) * 2021-09-15 2023-03-23 日東電工株式会社 Matériau de base composite et son procédé de production
CN116063653A (zh) * 2023-03-06 2023-05-05 开贝科技(苏州)有限公司 一种改性聚氨酯及其制备方法和应用

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WO2023042666A1 (fr) * 2021-09-15 2023-03-23 日東電工株式会社 Matériau de base composite et son procédé de production
CN116063653A (zh) * 2023-03-06 2023-05-05 开贝科技(苏州)有限公司 一种改性聚氨酯及其制备方法和应用

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