WO2011068094A1 - 抗ウイルス剤およびそれを用いた抗ウイルス剤機能製品 - Google Patents
抗ウイルス剤およびそれを用いた抗ウイルス剤機能製品 Download PDFInfo
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- WO2011068094A1 WO2011068094A1 PCT/JP2010/071348 JP2010071348W WO2011068094A1 WO 2011068094 A1 WO2011068094 A1 WO 2011068094A1 JP 2010071348 W JP2010071348 W JP 2010071348W WO 2011068094 A1 WO2011068094 A1 WO 2011068094A1
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- WIPO (PCT)
- Prior art keywords
- photocatalyst
- noble metal
- virus
- antiviral agent
- dispersion
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- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012888 bovine serum Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- XCBKGJWOCHSAMS-UHFFFAOYSA-L copper;dichlorocopper Chemical compound [Cu].Cl[Cu]Cl XCBKGJWOCHSAMS-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 201000002491 encephalomyelitis Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012894 fetal calf serum Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- PMCMJPXEJUKOAO-UHFFFAOYSA-M gold(1+);bromide Chemical compound [Au]Br PMCMJPXEJUKOAO-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003292 kidney cell Anatomy 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical class [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KABWJWZACJCALW-UHFFFAOYSA-J platinum tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl.[Pt] KABWJWZACJCALW-UHFFFAOYSA-J 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 210000004926 tubular epithelial cell Anatomy 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 241001529453 unidentified herpesvirus Species 0.000 description 1
- 241001430294 unidentified retrovirus Species 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
- A61L9/20—Ultraviolet radiation
- A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/12—Antivirals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Definitions
- the present invention relates to an antiviral agent comprising a noble metal-supported photocatalyst dispersion and an antiviral functional product using the antiviral agent.
- Patent Document 1 An antiviral agent in which a photocatalyst of a bowl-shaped crystal particle and a photocatalyst of a spherical crystal particle are bonded through an OH group detoxifies avian influenza virus under irradiation of a fluorescent lamp. . (Patent Document 1).
- An object of the present invention is to provide an antiviral agent that exhibits high antiviral properties even under visible light irradiation and can render viruses harmless.
- the present inventors diligently studied to develop an antiviral agent exhibiting high activity.
- the noble metal-supported photocatalyst containing 0.01 to 1 part by weight of noble metal atoms with respect to 100 parts by weight of the photocatalyst particles.
- the present inventors have found that an antiviral agent comprising a body particle dispersion exhibits high antiviral properties, and have reached the present invention. Therefore, the antiviral agent according to the present invention is characterized by comprising a noble metal-supported photocatalyst particle dispersion containing 0.01 to 1 part by mass of noble metal atoms with respect to 100 parts by mass of the photocatalyst particles.
- the antiviral agent of the present invention is composed of a noble metal-supported photocatalyst particle dispersion in which noble metal-supported photocatalyst particles are highly stably dispersed, and can be easily applied to a substrate. Therefore, a photocatalyst layer having a uniform film quality can be formed on the substrate, and this photocatalyst layer exhibits high antiviral properties under a practical light source such as visible light contained in a fluorescent lamp. Therefore, according to the present invention, it is possible to provide an antiviral agent capable of expressing a high antiviral property even under visible light irradiation and detoxifying the virus.
- the antiviral agent of the present invention comprises a noble metal-supported photocatalyst particle dispersion in which noble metal-supported photocatalyst particles are dispersed in a solvent.
- the photocatalyst particle used in the antiviral agent of the present invention refers to a particulate photocatalyst.
- the photocatalyst include compounds of metal elements and oxygen, nitrogen, sulfur, and fluorine.
- metal elements include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and Cu.
- tungsten oxide is suitable for the present invention because it exhibits high antiviral activity when irradiated with visible light (wavelength of about 400 nm to about 800 nm).
- the photocatalyst particles usually have an average dispersed particle size of 40 nm to 250 nm.
- the tungsten oxide particles include, for example, (i) a method of adding tungstic acid as a precipitate by adding an acid to an aqueous solution of tungstate, and firing this tungstic acid, (ii) meta It can be obtained by a method of thermally decomposing by heating ammonium tungstate or ammonium paratungstate, or (iii) a method of firing metallic tungsten particles.
- the noble metal precursor used in the present invention those which can be dissolved in a dispersion medium are used.
- the noble metal element constituting the precursor usually becomes a noble metal ion having a positive charge and exists in the dispersion medium.
- the noble metal ions are reduced to zero-valent noble metal by light irradiation and are supported on the surface of the photocatalyst particles.
- the noble metal include Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh.
- the precursor include hydroxides, nitrates, sulfates, halides, organic acid salts, carbonates, and phosphates of these noble metals.
- the noble metal is preferably Cu, Pt, Au, or Pd, and among these, Pt is particularly preferable.
- Cu As a precursor of Cu, for example, copper nitrate (Cu (NO 3 ) 2 ), copper sulfate (CuSO 4 ), copper chloride (CuCl 2 , CuCl), copper bromide (CuBr 2 , CuBr), copper iodide (CuI) , Copper iodate (CuI 2 O 6 ), copper copper chloride (Cu (NH 4 ) 2 Cl 4 ), copper oxychloride (Cu 2 Cl (OH) 3 ), copper acetate (CH 3 COOCu, (CH 3 COO) 2 Cu), copper formate ((HCOO) 2 Cu), copper carbonate (CuCO 3 ), copper oxalate (CuC 2 O 4 ), copper citrate (Cu 2 C 6 H 4 O 7 ), copper phosphate (CuPO 4) ).
- Pt platinum chloride
- PtBr 2 , PtBr 4 platinum bromide
- platinum iodide PtI 2 , PtI 4
- potassium tetrachloroplatinate K 2 PtCl 4
- Potassium hexachloroplatinate K 2 PtCl 6
- hexachloroplatinic acid H 2 PtCl 6
- platinum sulfite H 3 Pt (SO 3 ) 2 OH
- tetraammineplatinum chloride Pt (NH 3 ) 4 Cl 2
- bicarbonate tetraammineplatinum C 2 H 14 N 4 O 6 Pt
- tetraammine platinum hydrogen phosphate Pt (NH 3) 4 HPO 4
- hydroxide tetraammineplatinum Pt (NH 3) 4 ( OH) 2
- nitrate tetraammineplatinum Pt (NH 3) 4 ( OH) 2
- Au precursors include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), and tetrachlorogold.
- Au precursors include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), and tetrachlorogold.
- Examples include potassium acid (KAuCl 4 ) and potassium tetrabromoaurate (KAuBr 4 ).
- Examples of the precursor of Pd include palladium acetate ((CH 3 COO) 2 Pd), palladium chloride (PdCl 2 ), palladium bromide (PdBr 2 ), palladium iodide (PdI 2 ), palladium hydroxide (Pd (OH) 2 ), palladium nitrate (Pd (NO 3 ) 2 ), palladium sulfate (PdSO 4 ), potassium tetrachloropalladate (K 2 (PdCl 4 )), potassium tetrabromopalladate (K 2 (PdBr 4 )), tetraammine Palladium chloride (Pd (NH 3 ) 4 Cl 2 ), tetraammine palladium bromide (Pd (NH 3 ) 4 Br 2 ), tetraammine palladium nitrate (Pd (NH 3 ) 4 (NO 3 ) 2 ), tetraammine palladium tetrach
- Precious metal precursors may be used alone or in combination of two or more.
- the amount used is usually 0.01 parts by mass or more, in terms of cost, in terms of sufficiently improving the photocatalytic action with respect to 100 parts by mass of the photocatalyst particles in terms of precious metal atoms. Is usually 1 part by mass or less, preferably 0.05 to 0.6 parts by mass, and more preferably 0.05 to 0.2 parts by mass.
- the noble metal-supported photocatalyst dispersion liquid used in the present invention is 4.0 ⁇ 10 17 or more, preferably 6.0 ⁇ 10 17 or more, more preferably 7.5 ⁇ 10 10 per 1 g of photocatalyst particles by irradiation with visible light. Generates 17 or more OH radicals. When the amount of OH radicals produced is less than 4.0 ⁇ 10 17 , sufficient antiviral properties cannot be obtained under visible light irradiation.
- the amount of radicals generated is measured by measuring the ESR spectrum after irradiating the noble metal-supported photocatalyst dispersion with visible light in the presence of DMPO (5,5-dimethyl-1-pyrroline-N-oxide), which is a radical scavenger. Then, the area value of the signal is obtained for the obtained spectrum and calculated from this area value.
- DMPO 5,5-dimethyl-1-pyrroline-N-oxide
- irradiation with visible light is performed at room temperature and in the atmosphere for 20 minutes using a white light emitting diode as a light source and an illuminance of 20000 lux.
- the measurement of the ESR spectrum is performed in a state in which the light from a fluorescent lamp having an illuminance of less than 500 lux is struck as room light using EMX-Plus (manufactured by BRUKER) after irradiation with visible light for 20 minutes.
- the measurement conditions of the ESR spectrum were: temperature: room temperature, pressure: atmospheric pressure, Microwave Frequncy: 9.86 GHz, Microwave Power: 3.99 mW, Center Field: 3515G, Sweep Width: 100G, Conv. Time: 20.00 mSec, Time Const. : 40.96ms, Resolution: 6000, Mod. Amplitude: 2G, Number of Scans: 1, Measurement area: 2.5cm, Temperature: Room temperature, Pressure: Atmospheric pressure, Magnetic field fair: Tesla meter used.
- the ESR spectrum of DMPO-OH which is an OH radical adduct of DMPO, is compared with the ESR spectrum of a substance having a known number of radicals.
- a relational expression between the area obtained from the ESR spectrum and the number of radical species is obtained by the following procedure.
- 4-hydroxy-TEMPO is used as a substance with a known radical number.
- 0.17621 g of 4-hydroxy-TEMPO (4-Hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl) (purity 98%) is dissolved in 100 mL of water.
- the liquid obtained is designated as A.
- B Take 1 mL of B and add water to make 100 mL.
- C be the resulting liquid.
- the concentration is 0.001 mM.
- the number y1 of OH radicals after irradiation with the white light-emitting diode is calculated from the ESR spectrum of DMPO-OH and the first-order linear approximation calculated using the known concentration of 4-hydroxy-TEMPO. Further, the number of OH radicals y2 contained in the noble metal-supported photocatalyst dispersion before light irradiation is calculated in the same manner, and the difference (y1-y2) is the number of OH radicals generated by irradiation of the white light emitting diode.
- the aqueous solvent which has water as a main component is used.
- the dispersion medium may be water alone or a mixed solvent of water and a water-soluble organic solvent.
- a mixed solvent of water and a water-soluble organic solvent is used, the content of water is preferably 50% by mass or more.
- the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, methyl ethyl ketone, ethyl cellosolve, butyl cellosolve, ethyl acetate, diethyl ether, and the like.
- a dispersion medium may be used independently and may use 2 or more types together.
- the amount of the dispersion medium used is usually 5 to 200 times by mass with respect to the photocatalyst particles. If the amount of the dispersion medium used is less than 5 mass times, the photocatalyst particles are likely to settle, and if it exceeds 200 mass times, it is disadvantageous in terms of volume efficiency.
- a sacrificial agent is added to the raw material dispersion.
- the sacrificial agent include alcohols such as ethanol, methanol, and propanol, ketones such as acetone, and carboxylic acids such as oxalic acid.
- the sacrificial agent may be used by dissolving in a suitable solvent, or may be used as a solid.
- the sacrificial agent is added to the raw material dispersion after light irradiation for a certain period of time, and further light irradiation is performed.
- the amount of the sacrificial agent is usually 0.001 to 0.3 times by mass, preferably 0.005 to 0.1 times by mass with respect to the dispersion medium. If the amount of the sacrificial agent used is less than 0.001 times by mass, the noble metal is insufficiently supported on the photocatalyst particles, and if it exceeds 0.3 times by mass, the amount of sacrificial agent is excessive and an effect commensurate with the cost cannot be obtained. .
- the raw material dispersion may be prepared by dispersing photocatalyst particles in a dispersion medium.
- a dispersion treatment with a known apparatus such as a wet medium stirring mill.
- the raw material dispersion is irradiated with light.
- You may perform irradiation of the light to a raw material dispersion liquid, stirring. Irradiation may be performed from inside or outside the tube while passing through a transparent glass or plastic tube, or this may be repeated.
- the light source is not particularly limited as long as it can irradiate light having energy greater than the band gap of the photocatalyst particles, and specific examples include germicidal lamps, mercury lamps, light emitting diodes, fluorescent lamps, halogen lamps, xenon lamps, solar Light can be used.
- the wavelength of the irradiated light is usually 180 nm to 500 nm.
- the light irradiation time is usually 20 minutes or longer, preferably 1 hour or longer, usually 24 hours or shorter, preferably 6 hours or shorter before and after the addition of the sacrificial agent.
- the time exceeds 24 hours, most of the precursors of the noble metal have been supported as noble metals by that time, and an effect commensurate with the cost of light irradiation cannot be obtained.
- the precious metal is not uniformly supported, and high antiviral activity cannot be obtained.
- PH adjustment In the present invention, light irradiation is performed while maintaining the pH of the raw material dispersion at 2.5 to 4.5, preferably 2.8 to 4.0.
- the pH of the dispersion gradually changes to acidic, so that a base is usually added to maintain the pH within the range specified in the present invention. do it. Thereby, a noble metal-supported photocatalyst dispersion with excellent dispersibility is obtained.
- Examples of the base include aqueous solutions of ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lanthanum hydroxide, etc. Among them, ammonia and sodium hydroxide are used. It is preferable to use it.
- the amount of dissolved oxygen in the raw material dispersion is adjusted to 1.0 mg / L or less, preferably 0.7 mg / L or less as necessary.
- the amount of dissolved oxygen can be adjusted by, for example, blowing a gas not containing oxygen into the raw material dispersion, and examples of the gas include nitrogen and rare gases (helium, neon, argon, krypton, etc.). .
- the amount of dissolved oxygen exceeds 1.0 mg / L, a reduction reaction of dissolved oxygen occurs in addition to the loading of the precursor of the noble metal, the loading of the noble metal becomes uneven, and high antiviral activity cannot be obtained.
- Precious metal supported photocatalyst Thus, while adjusting the pH, if necessary, the amount of dissolved oxygen is reduced to a predetermined value or less, and light irradiation is performed. After the addition of the sacrificial agent, the light is further irradiated, whereby the noble metal precursor becomes a noble metal and the photocatalyst particles.
- the target noble metal-supported photocatalyst particles are obtained by being supported on the surface.
- the noble metal-supported photocatalyst particles are dispersed in the used dispersion medium without settling.
- the dispersion in which the noble metal-supported photocatalyst particles are dispersed is easy to handle because of the excellent dispersibility of the noble metal-supported photocatalyst particles, and also exhibits high antiviral activity.
- This noble metal-supported photocatalyst particle dispersion may contain various known additives as long as the effects of the present invention are not impaired.
- additives include silicon compounds such as amorphous silica, silica sol, water glass, alkoxysilane, and organopolysiloxane, aluminum compounds such as amorphous alumina, alumina sol, and aluminum hydroxide, and aluminosilicates such as zeolite and kaolinite.
- Alkaline earth metal oxides such as salts, magnesium oxide, calcium oxide, strontium oxide, barium oxide, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, Ti, Zr , Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Os, Ir, Ag, Zn, Cd, Ga, In, Tl, Ge, Sn , Pb, Bi, La, Ce and other metal element hydroxides and oxides, zirco oxalate Um, calcium phosphate, molecular sieve, active carbon, a polycondensation product of an organopolysiloxane compound, phosphate, a fluorine-based polymer, silicone-based polymers, acrylic resins, polyester resins, melamine resins, urethane resins, alkyd resins. When these additives are added and used, they can be used alone or in
- the additive can also be used as a binder for holding the photocatalyst particles more firmly on the surface of the substrate when the photocatalyst layer is formed on the surface of the substrate using the photocatalyst (for example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658, JP-A-10-225658 JP-A-11-1620, JP-A-11-1661, JP-A-2002-80829, JP-A-2004-059686, JP-A-2004-107381, JP-A-2004-256590, JP-A-2004-. No.
- JP-A No. 2005-113028, JP-A No. 2005-230661, JP-A No. 2007-161824 See Japanese, WO 96/029375, WO 97/000134, such as International Publication No. 98/003607).
- the antiviral agent functional product of the present invention is provided with a photocatalyst layer formed on the surface using the noble metal-supported photocatalyst particle dispersion.
- the photocatalyst layer is formed by a conventionally known film formation method, for example, after the noble metal-supported photocatalyst particle dispersion of the present invention is applied to the surface of the substrate (product), and then the dispersion medium is volatilized. Can do.
- the film thickness of the photocatalyst body layer is not particularly limited, and may usually be appropriately set from several tens of nanometers to several millimeters according to the application.
- the photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product).
- the photocatalyst layer is a surface irradiated with light (visible light) and a virus It is preferably formed on a surface that is continuously or intermittently connected to an existing location.
- the material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can withstand practical use. For example, plastic, metal, ceramics, wood, concrete, paper, etc. , Products made of any material can be targeted.
- antiviral agent functional product of the present invention include, for example, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, floors, automobile interior materials (automobile instrument panels, automobile seats, automobiles).
- ceiling materials, automotive glass home appliances such as refrigerators and air conditioners, textile products such as clothes and curtains, train straps, elevator buttons, and the like, such as the surface of a substrate that an unspecified number of people come into contact with.
- the functional product of the antiviral agent of the present invention exhibits high antiviral activity by light irradiation not only outdoors but also in an indoor environment that receives only light from a visible light source such as a fluorescent lamp, a sodium lamp, and a light emitting diode. . Therefore, the noble metal-supported photocatalyst particle dispersion of the present invention is applied to, for example, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, films, floors, automobile interior materials (automobile instrument panels, automobile seats, automobiles).
- refrigerators For ceiling materials), refrigerators, air conditioners, personal computers, printers, photocopiers, fax machines, telephones, stoves, etc., furniture such as desks, chairs, tables, bags, storage shelves, textile products such as clothes and curtains And then dried, indoor lighting, turkey herpes virus, Marek's disease virus, infectious bursal disease virus, Newcastle disease virus, infectious bronchitis virus, infectious laryngotracheitis virus, chicken encephalomyelitis virus , Chicken anemia virus, fowlpox virus, avian reovirus, avian leukemia virus, reticuloendothelium Virus, avian adenovirus and hemorrhagic enteritis virus, herpes virus, smallpox virus, cowpox virus, measles virus, adenovirus, coxsackie virus, calicivirus, retrovirus, coronavirus, avian influenza virus, human influenza virus, swine influenza virus, Norovirus, foot-and-
- BET specific surface area The BET specific surface area of the photocatalyst particles was measured by a nitrogen adsorption method using a specific surface area measuring device (“Monosorb” manufactured by Yuasa Ionics).
- Average dispersed particle size (nm) The particle size distribution was measured using a submicron particle size distribution measuring device (“N4Plus” manufactured by Coulter, Inc.), and the result obtained by automatically performing the monodisperse mode analysis with the software attached to this device was used as the average dispersed particle size. .
- Crystalline X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and the crystal form was determined from the spectrum.
- Dissolved oxygen The dissolved oxygen in the raw material dispersion was measured using a dissolved oxygen meter ("OM-51" manufactured by Horiba, Ltd.).
- Antiviral properties were evaluated by measuring the virus titers of influenza virus and adenovirus by irradiation with visible light from a fluorescent lamp. That is, spin coater (manufactured by Mikasa) was applied to a glass plate (5 cm ⁇ 5 cm ⁇ 2 mm) so that the obtained noble metal-supported photocatalyst particle dispersion was 1 g / m 2 in terms of solid content conversion per unit area. “1H-D7”) was uniformly formed on one side of the glass plate. Next, this glass plate was dried by holding it in the air at 130 ° C. for 10 minutes in the air, thereby forming a photocatalyst layer on one side of the glass plate.
- the photocatalyst layer has an ultraviolet intensity of 2 mW / cm 2 (measured by attaching a UV receiver “UD-36” to Topcon's UV intensity meter “UVR-2”). This was irradiated for a period of time and used as a sample for measuring antiviral activity.
- Influenza virus A / Northern pintail / Miyagi / 1472/08 (H1N1) was used as the influenza virus. That is, inoculate the photocatalyst layer with a test solution containing a virus, put a coating film on the photocatalyst layer, and make a close contact, and store it at room temperature (25 ⁇ 5 ° C.) under visible light irradiation or shading for 6 hours.
- the virus titer per mouse was determined as a logarithmic value (LogTCID50 / ml) of 50% tissue culture infectious dose using MDCK cells (Madin-Darby canine kidney cell, a cell line derived from canine kidney tubular epithelial cells).
- a test solution containing virus and MDCK cells were prepared in the following maintenance medium (MM) or growth medium (GM).
- the medium for virus preparation or cell culture is 9.4 g of Eagle's minimum essential medium (Nissui Pharmaceutical Co., Ltd., Tokyo) and 3.0 g of Tryptose Phosphate Broth (TPB: Difco laboratories, Detroit, MI, USA) in distilled water. After dissolving in 1,000 ml and autoclaving, 7% NaHCO 3 , 200 mM L-glutamin, penicillin and streptomycin are added to a final concentration of 2%, 1%, 100 units / ml and 100 ⁇ g / ml, respectively.
- MM maintenance medium
- FCS fetal calf serum
- the collected infected chorioallantoic fluid was ultracentrifuged at 25000 rpm for 90 minutes at 4 ° C., and the resulting pellet was resuspended in phosphate buffered saline (PBS) of 1/100 of the initial chorioallantoic fluid.
- PBS phosphate buffered saline
- This virus was diluted 100 times with PBS, and 100 ⁇ l was dropped onto the photocatalyst processed product, and antiviral activity was measured by a film adhesion method. After a certain period of time, the glass plate and film were placed in a plastic bag, and 1 ml of MM was added to recover the virus.
- the recovered virus solution was transferred to a microtube, treated with a centrifuge at 15000 rpm for 3 minutes, and the residual virus titer was measured for the supernatant.
- the virus titer was measured by inoculating a 96-well tissue culture plate with 4 wells of each diluted dilution of the virus solution 10 times with MM. Prior to inoculation, MDCK cells were washed 3 times with 200 ⁇ l of PBS, trypsin was added to MM to 2 ⁇ g / ml, 100 ⁇ l was added to each well, and 100 ⁇ l of the diluted virus solution was inoculated there.
- Evaluation of antiviral property was performed simultaneously using three samples for measuring antiviral activity, and the evaluation was performed using the average value of logarithmic values of these three virus titers.
- Irradiation with visible light uses a commercially available white fluorescent lamp (20 W, 2) as a light source, and is included in the fluorescent lamp from above the photocatalyst layer on which the coating film is placed through an acrylic resin plate (“N113” manufactured by Nitto Resin Kogyo). The visible light was irradiated. At this time, irradiation in the vicinity of the coating film was set to 1000 lux (measured with a luminometer “T-10” manufactured by Minolta).
- the measurement limit of the logarithmic value of the virus titer was 1.5.
- Adenovirus Avian adenovirus was used as the adenovirus, and this standard strain, Ote strain, was distributed by the National Institute for Animal Health (Ibaraki Prefecture).
- the avian adenovirus was passaged in chicken kidney cultured cells (CK cells) described later, and the infected culture medium was dispensed and stored at ⁇ 80 ° C. until use.
- MM Inoculate the photocatalyst layer with the test solution containing the virus, put the coated film into close contact, and store it at room temperature (25 ⁇ 5 ° C.) under visible light irradiation or shading for 6 hours.
- the virus titer was determined by a plaque formation test on CK cells described later.
- 100 ⁇ L of a test solution containing a virus diluted 1000 times with double-distilled water (hereinafter referred to as “dW2”) was dropped for evaluation, and then the cell maintenance medium was adjusted so that the amount of the recovered solution became 1000 ⁇ L. (Hereinafter referred to as MM).
- CK cells Chicken kidney cultured cells
- CK cells cell concentration: 0.3%) are seeded in 4 ml each in a cell culture dish (Tissue Culture Dishes, PS, 60 ⁇ 15 mm, with vents, sterile, Greiner bio-one), 37 ° C., 5% CO 2 incubator.
- the medium used is 9.4 g of E-MEM medium, 3.0 g of Tryptose Phosphate Broth (TPB) dissolved in 1000 ml of dW2, and after high-pressure steam sterilization, 2% of 7% NaHCO 3 and 1% of 200 mM L-glutamin are used.
- Bovine serum Calf Serum: hereinafter CS
- penicillin 100 units / ml streptomycin 100 ⁇ g / ml
- amphotericin B 0.5 ⁇ g / ml
- E-MEM medium and 3.0 g of TPB are dissolved in 500 ml of dW2 as a basic medium for the multilayer agar medium for plaque formation test, and after autoclaving, 2% of 7% NaHCO 3 and 200 mM L-glutamin are used. It was added to 1%, penicillin 100 units / ml, streptomycin 100 ⁇ g / ml, amphotericin B 0.5 ⁇ g / ml, and used as primary MM. Furthermore, 10 ml of 0.5% neutral red was added to make a secondary multilayer MM.
- CK cells were inoculated with serially diluted virus (100 ⁇ l / dish, 2 dishes / sample), 1 hour after inoculation, the inoculum was removed, and the primary agar medium was further layered in 3 ml layers and 5 After 3 days, 3 ml of the secondary agar medium was overlaid, and plaque counting was performed 7 days after inoculation, and a plaque forming unit (hereinafter referred to as PFU / ml) was calculated.
- the detection limit of the virus titer of avian adenovirus was set to 10 5 PFU / ml.
- the evaluation of antiviral property was performed simultaneously using two samples for measuring antiviral activity, and the evaluation was performed by the average value of the logarithmic values of these two virus titers.
- Irradiation with visible light uses a commercially available white fluorescent lamp (20 W, 2) as a light source, and is included in the fluorescent lamp from above the photocatalyst layer on which the coating film is placed through an acrylic resin plate (“N113” manufactured by Nitto Resin Kogyo). The visible light was irradiated. At this time, irradiation in the vicinity of the coating film was set to 1000 lux (measured with a luminometer “T-10” manufactured by Minolta).
- the smaller the virus titer of the avian adenovirus 6 hours after irradiation with visible light the higher the antiviral property of the avian adenovirus, that is, the photocatalytic activity.
- the measurement limit of the logarithmic value of the virus titer was 5.2.
- Example 1 1 kg of tungsten oxide particles (manufactured by Nippon Inorganic Chemical Co., Ltd.) was added to 4 kg of ion exchange water as a dispersion medium and mixed to obtain a mixture. This mixture was dispersed using a wet medium stirring mill to obtain a tungsten oxide particle dispersion.
- the average dispersed particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 118 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 40 m 2 / g. In addition, when the mixture before the dispersion treatment was similarly vacuum-dried to obtain a solid content, and the solid content of the mixture before the dispersion treatment and the solid content after the dispersion treatment were measured and compared, The peak shape was the same, and no change in crystal form due to dispersion treatment was observed. At this time, when the obtained dispersion was kept at 20 ° C. for 24 hours, no solid-liquid separation was observed during storage.
- tungsten oxide particle dispersion To this tungsten oxide particle dispersion, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is added so that hexachloroplatinic acid is 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, A hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained as a raw material dispersion.
- the solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 17.6 parts by mass (solid content concentration 17.6% by mass). Thereafter, the pH of this dispersion was 2.0.
- This is a light irradiation device consisting of a glass tube (inner diameter: 37 mm, height: 360 mm) with an underwater sterilization lamp (manufactured by Sankyo Electric Co., Ltd., GLD15MQ), and while distributing 1200 g of the raw material dispersion at a rate of 1 liter per minute, The pH of the dispersion was adjusted to 3.0. Nitrogen was blown at a rate of 2 L / min.
- the virus titer against influenza virus which was 6.8 when the light irradiation time was 0 hour, was less than 1.5 (less than the detection limit) after 2 hours of light irradiation. Moreover, the virus titer was 4.8 when left in the dark for 2 hours without light irradiation.
- the virus titer against avian adenovirus which was 8.9 when the light irradiation time was 0 hour, became less than 5.2 (less than the detection limit) after 6 hours of light irradiation. It was.
- Example 1 Influenza which was 6.8 when the light irradiation time was 0 hours when antiviral evaluation was performed in the same manner as in Example 1 except that raw glass without a photocatalyst layer was used.
- the virus titer against the virus was 6.8 after 2 hours of light irradiation, and was 6.8 even when left in the dark for 2 hours without light irradiation.
- the virus titer against avian adenovirus which was 8.9 when the light irradiation time was 0 hour, became 7.9 after 6 hours of light irradiation.
- Example 2 By applying the antiviral agent obtained in Example 1 to a tile constructed on an indoor wall surface and drying it, a photocatalyst layer can be formed on the tile surface.
- Viruses having an envelope such as avian influenza virus, human influenza virus, and swine influenza virus in space, and viruses having no envelope such as adenovirus and foot-and-mouth disease can be rendered harmless.
- Viruses having an envelope such as avian influenza virus, human influenza virus, swine influenza virus, and viruses having no envelope such as adenovirus and foot-and-mouth disease can be rendered harmless.
- Example 5 By applying the antiviral agent obtained in Example 1 to an indoor floor surface and drying it, a photocatalyst layer can be formed on the floor surface, thereby avian influenza in an indoor space by light irradiation by indoor lighting. Viruses having envelopes such as viruses, human influenza viruses and swine influenza viruses, and viruses having no envelope such as adenoviruses and foot-and-mouth disease can be rendered harmless.
- Example 6 By applying the antiviral agent obtained in Example 1 to the surface of automobile interior materials such as an instrument panel for automobiles, an automobile seat, an automobile ceiling material, and the inside of an automobile glass, these automobile interiors are dried. A photocatalyst layer can be formed on the surface of the material. By this, light with an interior illumination can cause an envelope virus such as avian influenza virus, human influenza virus, swine influenza virus, adenovirus, foot-and-mouth disease, etc. Viruses that do not have the envelope can be detoxified.
- an envelope virus such as avian influenza virus, human influenza virus, swine influenza virus, adenovirus, foot-and-mouth disease, etc. Viruses that do not have the envelope can be detoxified.
- Viruses having envelopes such as viruses, human influenza viruses and swine influenza viruses, and viruses having no envelope such as adenoviruses and foot-and-mouth disease can be rendered harmless.
- a photocatalyst layer can be formed in the refrigerator, thereby allowing light by indoor lighting or light irradiation in the refrigerator.
- Viruses having an envelope such as avian influenza virus, human influenza virus, and swine influenza virus in a refrigerator, and viruses having no envelope such as adenovirus and foot-and-mouth disease can be rendered harmless.
- a photocatalyst layer is formed on the surface of the substrate by applying and drying the antiviral agent obtained in Example 1 on the surface of the substrate that is contacted by an unspecified number of people, such as train straps and elevator buttons.
- viruses having an envelope such as bird flu virus, human influenza virus, swine flu virus, etc. on the surface of the base material, and viruses having no envelope such as adenovirus and foot-and-mouth disease by light irradiation by indoor lighting. It can be detoxified.
- Viruses having an envelope such as avian influenza virus, human influenza virus, and swine influenza virus on the surface of the base material, and viruses having no envelope such as adenovirus and foot-and-mouth disease can be rendered harmless by light irradiation by indoor lighting.
- Example 11 By applying and drying the antiviral agent obtained in Example 1 on the surface of home appliances such as a personal computer, printer, scanner, copier, telephone, television, stereo, washing machine, stove, dryer, microwave oven, etc.
- a photocatalyst layer can be formed on the surface of the base material, and by this, light having an indoor illumination causes an enveloped virus such as avian influenza virus, human influenza virus, and swine influenza virus on the surface of the base material, adenovirus, Viruses that do not have an envelope, such as foot-and-mouth disease, can be rendered harmless.
- a photocatalyst layer By applying and drying the antiviral agent obtained in Example 1 on the surface of cocoons, tatami mats, shoji, etc., a photocatalyst layer can be formed on the surface of the base material.
- viruses having an envelope such as avian influenza virus, human influenza virus, and swine influenza virus on the surface of the substrate, and viruses having no envelope such as adenovirus and foot-and-mouth disease can be rendered harmless.
- a photocatalyst layer can be formed on the surface of the film, and this film can be used as a building material, furniture, wall, floor, ceiling, touch panel, Envelopes such as bird flu virus, human flu virus, swine flu virus etc. on the film surface by light irradiation with indoor lighting by constructing on equipment buttons, doors, door knobs, handrails of stairs, interior walls of aircraft and train cabins, etc. And viruses that do not have an envelope, such as adenovirus and foot-and-mouth disease.
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Abstract
Description
本発明は、可視光照射下でも高い抗ウイルス性を発現しウイルスを無害化することのできる抗ウイルス剤を提供することを目的とする。
したがって、本発明に係る抗ウイルス剤は、光触媒体粒子100質量部に対して、貴金属原子を0.01質量部~1質量部含有する貴金属担持光触媒体粒子分散液からなることを特徴とする。
よって、本発明によれば、可視光照射下でも高い抗ウイルス性を発現しウイルスを無害化することのできる抗ウイルス剤を提供することができる。
(光触媒体粒子)
本発明の抗ウイルス剤で用いる光触媒体粒子とは、粒子状の光触媒体をいう。光触媒体としては、金属元素と酸素、窒素、硫黄および弗素との化合物が挙げられる。金属元素としては、例えば、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Tc、Re、Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt、Cu、Ag、Au、Zn、Cd、Ga、In、Tl、Ge、Sn、Pd、Bi、La、Ceが挙げられる。その化合物としては、これら金属元素の1種類または2種類以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。なかでも、酸化タングステンは、可視光線(波長約400nm~約800nm)を照射したとき、高い抗ウイルス活性を示すことから、本発明に好適である。
本発明で使用する貴金属の前駆体としては、分散媒中に溶解し得るものが使用される。かかる前駆体が溶解すると、これを構成する貴金属元素は通常、プラスの電荷を帯びた貴金属イオンとなって、分散媒中に存在する。そして、この貴金属イオンが、光の照射により0価の貴金属に還元されて、光触媒体粒子の表面に担持される。貴金属としては、例えばCu、Pt、Au、Pd、Ag、Ru、IrおよびRhが挙げられる。その前駆体としては、これら貴金属の水酸化物、硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩などが挙げられる。これらの中でも高い抗ウイルス活性を得る点から、貴金属は、Cu、Pt、Au、Pdが好ましく、これらの中でも特にPtが好ましい。
本発明で用いる貴金属担持光触媒体分散液は、可視光照射により、光触媒体粒子1g当たり4.0×1017個以上、好ましくは6.0×1017個以上、より好ましくは7.5×1017個以上のOHラジカルを生成する。OHラジカルの生成量が4.0×1017個未満の場合、可視光照射下で十分な抗ウイルス性が得られない。
(1)4-hydroxy-TEMPO(4-Hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl)(純度98%)0.17621gを100mLの水に溶解する。得られた液をAとする。
(2)Aを1mL取り、そこに水を加えて100mLにする。得られた液をBとする。
(3)Bを1mL取り、そこに水を加えて100mLにする。得られた液をCとする。濃度は0.001mMである。
(4)Bを1mL取り、そこに水を加えて50mLにする。得られた液をDとする。濃度は0.002mMである。
(5)Bを3mL取り、そこに水を加えて100mLにする。得られた液をEとする。濃度は0.003mMである。
(6)C、D、Eの各液をフラットセルに充填し、ESRスペクトルの測定を行う。得られる3本のピーク(面積比1:1:1)の低磁場側の1本の面積を求め、これを3倍したものを4-hydroxy-TEMPOの各濃度における面積とする。尚、ピークの面積は、ESRスペクトル(微分形)を積分形に変換して求める。
(7)4-hydroxy-TEMPOは1分子当たりラジカルを1つ有することから、C~Eに含まれる4-hydroxy-TEMPOのラジカル数を算出し、これと前記ESRスペクトルから求めた面積を用いて1次線形近似式を得ることができる。
本発明では、分散媒中に前記光触媒体粒子が分散され、前記貴金属の前駆体が溶解した原料分散液を用いる。
分散媒としては、特に制限はなく、通常は、水を主成分とする水性溶媒が用いられる。具体的には、分散媒は、水単独であってもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水と水溶性有機溶媒との混合溶媒を用いる場合には、水の含有量が50質量%以上であることが好ましい。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール溶媒、アセトン、メチルエチルケトン、エチルセロソルブ、ブチルセロソルブ、酢酸エチル、ジエチルエーテル、等が挙げられる。なお、分散媒は、単独で用いてもよいし、2種以上を併用してもよい。分散媒の使用量は、光触媒体粒子に対して、通常5質量倍~200質量倍である。分散媒の使用量が5質量倍未満では光触媒体粒子が沈降し易くなり、200質量倍を超えると容積効率の点で不利である。
本発明では、犠牲剤を原料分散液に添加する。犠牲剤としては、例えばエタノール、メタノール、プロパノール等のアルコール、アセトン等のケトン、蓚酸等のカルボン酸が用いられる。犠牲剤が固体の場合、この犠牲剤を適当な溶媒に溶解して用いてもよいし、固体のまま用いてもよい。尚、犠牲剤は、原料分散液に一定時間光照射を行った後に添加し、さらに光照射を行う。犠牲剤の量は分散媒に対して、通常0.001質量倍~0.3質量倍、好ましくは0.005質量倍~0.1質量倍である。犠牲剤の使用量が0.001質量倍未満では光触媒体粒子への貴金属の担持が不十分となり、0.3質量倍を超えると犠牲剤の量が過剰量となりコストに見合う効果が得られない。
原料分散液は、分散媒中に光触媒体粒子を分散させて調製すればよい。光触媒体粒子を分散媒に分散させる際には湿式媒体撹拌ミルなどの公知の装置で分散処理を施すことが好ましい。
本発明では、かかる原料分散液に光を照射する。原料分散液への光の照射は、撹拌しながら行ってもよい。透明なガラスやプラスチック製の管内を通過させながら管の内外から照射してもよく、これを繰り返してもよい。光源としては光触媒体粒子のバンドギャップ以上のエネルギーを有する光を照射できるものであれば特に制限はなく、具体例としては、殺菌灯、水銀灯、発光ダイオード、蛍光灯、ハロゲンランプ、キセノンランプ、太陽光を用いることができる。照射する光の波長は通常、180nm~500nmである。光照射を行う時間は、十分な量の貴金属を担持できることから、犠牲剤の添加前後において、通常20分以上、好ましくは1時間以上、通常24時間以下、好ましくは6時間以下である。24時間を越える場合、それまでに貴金属の前駆体の殆どは貴金属となって担持されてしまい、光照射にかかるコストに見合う効果が得られない。また、犠牲剤の添加前に光照射を行わない場合、貴金属の担持が不均一となり、高い抗ウイルス活性が得られない。
本発明では、原料分散液のpHを2.5~4.5、好ましくは2.8~4.0に維持しながら光照射を行う。通常、光照射により貴金属が光触媒体粒子の表面に担持される際には分散液のpHが酸性に除々に変化するので、pHを本発明で規定する範囲内に維持するため、通常塩基を添加すればよい。これにより分散性に優れる貴金属担持光触媒体分散液が得られる。塩基としては、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、水酸化ランタン等の水溶液が挙げられるが、これらの中でもアンモニアおよび水酸化ナトリウムを用いるのが好ましい。
本発明では、原料分散液への光照射前もしくは光照射中に、必要に応じて原料分散液中の溶存酸素量を1.0mg/L以下、好ましくは0.7mg/L以下に調整する。溶存酸素量の調整は、例えば、原料分散液に酸素を含まないガスを吹き込むことにより行うことができ、前記ガスとしては、窒素、および希ガス(ヘリウム、ネオン、アルゴン、クリプトン等)があげられる。溶存酸素量が1.0mg/Lを越える場合、貴金属の前駆体の担持のほかに、溶存酸素の還元反応が起こり、貴金属の担持が不均一となり、高い抗ウイルス活性が得られない。
かくしてpHを調整しながら、必要に応じて溶存酸素量を所定値以下にして光照射を行い、犠牲剤添加後、さらに光を照射することにより、貴金属前駆体が貴金属となって光触媒体粒子の表面に担持されて、目的の貴金属担持光触媒体粒子を得る。この貴金属担持光触媒体粒子は用いた分散媒中に、沈降することなく分散されている。
この貴金属担持光触媒体粒子が分散された分散液は、貴金属担持光触媒体粒子の分散性に優れているため取り扱いやすく、しかも高い抗ウイルス活性を発現する。
本発明の抗ウイルス剤機能製品は、前記貴金属担持光触媒体粒子分散液を用いて形成された光触媒体層を表面に備えるものである。ここで、光触媒体層は、例えば、本発明の貴金属担持光触媒体粒子分散液を基材(製品)の表面に塗布した後に、分散媒を揮発させるなど、従来公知の成膜方法によって形成することができる。光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数十nm~数mmまで適宜設定すればよい。光触媒体層は、基材(製品)の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光(可視光線)が照射される面であって、かつウイルスが存在する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。なお、基材(製品)の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。
なお、各実施例における測定法は、以下の通りである。
光触媒体粒子のBET比表面積は、比表面積測定装置(湯浅アイオニクス社製「モノソーブ」)を用い、窒素吸着法により測定した。
サブミクロン粒度分布測定装置(コールター社製「N4Plus」)を用いて粒度分布を測定し、この装置に付属のソフトで自動的に単分散モード解析して得られた結果を平均分散粒子径とした。
X線回折装置(リガク社製「RINT2000/PC」)を用いてX線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
原料分散液の溶存酸素は、溶存酸素計(堀場製作所製「OM-51」)を用いて測定した。
サンプル管(容量:13.5mL,内径:2cm,高さ:6.5cm(内溶液充填可能部高さ:5.5cm))に、攪拌子と水で濃度0.1質量%に調整した貴金属担持光触媒体分散液2mL(貴金属担持光触媒体粒子2mg含有)を入れ、さらに濃度が100mMとなるようにDMPO(純度97%)23μLを入れた。その後、スターラーで攪拌後、上澄みをフラットセルに注入してESR測定を行った。これを光照射0分の試料とした。次に、前記サンプル管の上部から白色発光ダイオード(東芝ライテック製,LEDベッド灯、LEDA-21002W-LS1(白色相当、メイン波長:約450nm))で光照射を20分間行った。サンプル管内の液面での照度は20000ルクス(ミノルタ社製照度計「T-10」で測定)であった。その後、上澄みをフラットセルに取り、生成したDMPO-OH付加体のESR測定を行った。光照射0分と20分のDMPO-OH付加体の数から可視光照射で生成されたOHラジカルの数を算出し、これと貴金属担持光触媒体粒子の重量(2mg)から、貴金属担持光触媒体粒子1g当たりのOHラジカルの生成量を求めた。
抗ウイルス性は、蛍光灯の可視光の照射によるインフルエンザウイルス及びアデノウイルスのウイルス力価を測定することにより評価した。すなわち、ガラス板(5cm×5cm×2mm)に、得られた貴金属担持光触媒体粒子分散液を、単位面積あたりの固形分換算の塗布量が1g/m2となるように、スピンコーター(ミカサ製「1H-D7」)によりガラス板片面に均一に形成した。次いで、このガラス板を130℃の乾燥機内で大気中で10分間保持することにより乾燥させて、ガラス板の片面に光触媒体層を形成した。この光触媒体層に紫外線強度が2mW/cm2(トプコン社製紫外線強度計「UVR-2」に同社製受光部「UD-36」を取り付けて測定)となるようにブラックライトからの紫外線を16時間照射して、これに抗ウイルス性活性測定用試料とした。
インフルエンザウイルスにはA/Northern pintail/Miyagi/1472/08(H1N1)を用いた。すなわち、光触媒体層にウイルスを含む試験液を接種し、被覆フィルムをのせて密着させ、これを室温(25±5℃)、可視光照射下または遮光下で6時間保存し、試料検体1個当たりのウイルス力価を、MDCK細胞(Madin-Darby canine kidney cell,イヌ腎臓尿細管上皮細胞由来の細胞株)を用いた、50%組織培養感染量の対数値(LogTCID50/ml)で求めた。ウイルスを含む試験液やMDCK細胞は、下記に示す維持培地(MM)、あるいは増殖培地(GM)で調製した。
ウイルスを10日齢の発育鶏卵に尿膜腔内接種し、3日後に漿尿液を回収した。回収した感染漿尿液を25000rpmで90分間4℃で超遠心し、得られたペレットを初期の漿尿液の100分の1量の燐酸緩衝食塩水(PBS)に再浮遊した。このウイルスをPBSで100倍希釈し、光触媒加工製品に100μl滴下し、フィルム密着法により、抗ウイルス活性を測定した。一定時間経過後、ガラスプレートとフィルムとをビニール袋に入れ、MMを1ml加えて、ウイルスを回収した。マイクロチューブに回収ウイルス液を移し、遠心分離機にて15000rpmで3分間処理し、その上清について、残存ウイルスの力価を測定した。
ウイルス力価の測定は、MMで10倍階段希釈したウイルス液を各希釈について4ウェルずつ96穴組織培養プレートに接種した。なお、接種前に、MDCK細胞を200μlのPBSで3回洗浄し、2μg/mlになるようトリプシンをMMに添加して、各ウェルに100μlずつ加え、そこに希釈ウイルス液を100μl接種した。
アデノウイルスにはトリアデノウイルスを用い、この標準株であるOte株は、独立行政法人・動物衛生研究所(茨城県)から分与された。トリアデノウイルスは、後述する鶏腎培養細胞(CK細胞)で継代し、感染培養液をウイルスとし、分注し、使用まで-80℃で保存した。
初生鶏ひな(小岩井農場)を炭酸ガスで安楽殺後、腎臓を採取し、トリプシン液で消化することにより、鶏腎(以下、CK)細胞を得た。CK細胞(細胞濃度:0.3%)を細胞培養シャーレ(Tissue Culture Dishes,PS,60×15mm,with vents,sterile,Greiner bio‐one)に4mlずつ播種し、37℃、5%CO2インキュベーターにおいて培養した。なお使用培地はE‐MEM培地 9.4g、Tryptose Phosphate Broth (TPB) 3.0gをdW2 1000mlに溶解し、高圧蒸気滅菌後、7%NaHCO3を2%、200mM L‐glutaminを1%、仔ウシ血清(Calf Serum:以下CS)を5%、ペニシリン 100units/ml ストレプトマイシン 100μg/ml、アムホテリシンB 0.5μg/mlになるように加えCK用増殖培地とした(CK用Growth Medium:以下CK用GM)。プラック形成試験用の重層寒天培地の基礎培地として、E‐MEM培地 9.4g、TPB 3.0gをdW2 500mlに溶解し、高圧蒸気滅菌後、7%NaHCO3を2%、200mM L‐glutaminを1%、ペニシリン 100units/ml、ストレプトマイシン 100μg/ml、アムホテリシンB 0.5μg/mlとなるように加え1次重層用MMとした。さらに0.5%ニュートラルレッドを10ml加え2次重層用MMとした。Bacto Agar (Difco laboratories,Detroit,MI,USA)1.6gをdW2 100mlに溶解し、高圧蒸気滅菌を行い、2×Bacto Agarとした。1次重層用 MMと電子レンジで溶かした2×Bacto Agarとを等量混合し、1次重層用寒天培地とした。また、2次重層用MMと電子レンジで溶かした2×Bacto Agarとを等量混合し、2次重層用寒天培地とした。
トリアデノウイルスについては、階段希釈したウイルスをCK細胞に接種(100μl/dish, 2 dishes/sample)し、接種1時間後、接種液を除去し、1次重層用寒天培地を3ml重層、さらに5日後に2次重層用寒天培地を3ml重層し、接種7日後にプラックカウントを行い、プラック形成単位(plaque forming unit:以下PFU/ml)を算出した。トリアデノウイルスのウイルス力価の検出限界を105 PFU/mlとした。
分散媒としてイオン交換水4kgに、酸化タングステン粒子(日本無機化学製)1kgを加えて混合して混合物を得た。この混合物を湿式媒体撹拌ミルを用いて分散処理して酸化タングステン粒子分散液を得た。
光触媒体層を形成していない未加工のガラスを用いた以外は、実施例1と同様にして抗ウイルス性の評価を行うと、光照射時間が0時間のときに6.8であったインフルエンザウイルスに対するウイルス力価が、光照射2時間で6.8となり、光照射を行わずに暗所で2時間放置しても6.8であった。
白金担持酸化タングステン粒子分散液の代わりに酸化タングステン粒子分散液(白金無担持)の分散液の白色発光ダイオード照射下でのOHラジカル生成量を測定すると、酸化タングステン粒子1g当たり3.2×1017個であった。次に、この白金担持酸化タングステン粒子分散液を用いて形成した光触媒体層の抗ウイルス性の評価を行ったところ、光照射時間が0時間のときに7.5であったインフルエンザウイルスに対するウイルス力価が、光照射2時間で4.6となった。
実施例1で得た抗ウイルス剤を、天井を構成する天井材の表面に塗布し乾燥させることにより、天井材の表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、屋内の壁面に施工されたタイルに塗布し乾燥させることにより、タイル表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、窓ガラスの屋内側表面に塗布し乾燥させることにより、ガラス表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、壁紙に塗布し乾燥させることにより、壁紙の表面に光触媒体層を形成することができ、さらにこの壁紙を屋内の壁面に施工することによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、屋内の床面に塗布し乾燥させることにより、床面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、自動車用インストルメントパネル、自動車用シート、自動車の天井材、自動車用ガラスの車内側などの自動車内装材の表面に塗布し乾燥させることにより、これら自動車内装材の表面に光触媒体層を形成することができ、これによって、車内照明による光照射により車内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、エアコンの表面に塗布し乾燥させることにより、エアコンの表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、冷蔵庫の庫内に塗布し乾燥させることにより、冷蔵庫内に光触媒体層を形成することができ、これによって、屋内照明や冷蔵庫内の光源による光照射により冷蔵庫内における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、電車のつり革、エレベーターのボタン等、不特定多数の人が接触する基材表面に塗布し乾燥させることにより、前記基材表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により前記基材表面における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、テーブル、箪笥、収納棚、机等の家具の表面に塗布し乾燥させることにより、前記基材表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により前記基材表面における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、パソコン、プリンター、スキャナー、コピー機、電話機、テレビ、ステレオ、洗濯機、ストーブ、ドライヤー、電子レンジ等、家電製品の表面に塗布し乾燥させることにより、前記基材表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により前記基材表面における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、襖、畳、障子等の表面に塗布し乾燥させることにより、前記基材表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により前記基材表面における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
実施例1で得た抗ウイルス剤を、フィルムに塗布し乾燥させることにより、フィルムの表面に光触媒体層を形成することができ、さらにこのフィルムを建材、家具、壁、床、天井、タッチパネル、機器のボタン、ドア、ドアノブ、階段の手すり、航空機や列車の客室の内壁等に施工することによって、屋内照明による光照射により前記フィルム表面における鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス等のエンベロープを持つウイルスや、アデノウイルスや***等のエンベロープを持たないウイルスを無害化することができる。
Claims (5)
- 光触媒体粒子100質量部に対して、貴金属原子を0.01質量部~1質量部含有する貴金属担持光触媒体粒子分散液からなる抗ウイルス剤。
- 光触媒体粒子100質量部に対して、貴金属原子を0.01質量部~1質量部含有し、照度20000ルクスの白色発光ダイオードを光源とする可視光照射を20分間行うことにより、貴金属担持光触媒体粒子1g当たり4.0×1017個以上のOHラジカルを生成する貴金属担持光触媒体粒子分散液からなる請求項1に記載の抗ウイルス剤。
- 前記貴金属がCu、Pt、Au、Pd、Ag、Ru、Ir及びRhから選ばれる少なくとも1種類の貴金属である請求項1または2に記載の抗ウイルス剤。
- 光触媒体が酸化タングステンである請求項1~3のいずれか1項に記載の抗ウイルス剤。
- 基材表面に光触媒体層を備える光触媒機能製品であって、前記光触媒体層が請求項1~4のいずれか1項に記載の抗ウイルス剤を用いて形成されていることを特徴とする抗ウイルス剤機能製品。
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WO2013094572A1 (ja) * | 2011-12-22 | 2013-06-27 | 昭和電工株式会社 | 銅及びチタン含有組成物並びにその製造方法 |
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JP5837288B2 (ja) * | 2010-07-15 | 2015-12-24 | 株式会社Nbcメッシュテック | 抗ウイルス剤 |
JP2013067566A (ja) * | 2011-09-20 | 2013-04-18 | Nbc Meshtec Inc | 抗ウイルス性を有する部材 |
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CN106470550A (zh) | 2014-09-19 | 2017-03-01 | 昭和电工株式会社 | 抗菌抗病毒组合物、抗菌抗病毒剂、光催化剂以及细菌病毒灭活方法 |
JP2016113331A (ja) | 2014-12-16 | 2016-06-23 | 昭和電工株式会社 | BiVO4が担持された酸化チタンの製造方法および抗ウイルス性組成物 |
JP2016113417A (ja) | 2014-12-16 | 2016-06-23 | 昭和電工株式会社 | 抗ウイルス性組成物、抗ウイルス剤、光触媒およびウイルス不活性化方法 |
JP2016113332A (ja) | 2014-12-16 | 2016-06-23 | 昭和電工株式会社 | BiVO4が担持された酸化チタン、その製造方法および抗ウイルス性組成物 |
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WO2013008807A1 (ja) * | 2011-07-11 | 2013-01-17 | 住友化学株式会社 | ウイルスを不活性化する抗ウイルス剤及びウイルスを不活性化する方法 |
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JP5343176B1 (ja) * | 2011-12-22 | 2013-11-13 | 昭和電工株式会社 | 銅及びチタン含有組成物並びにその製造方法 |
KR101397500B1 (ko) | 2011-12-22 | 2014-05-20 | 쇼와 덴코 가부시키가이샤 | 동 및 티탄 함유 조성물과 그 제조 방법 |
TWI489946B (zh) * | 2011-12-22 | 2015-07-01 | Showa Denko Kk | A composition containing copper and titanium, and a method for producing the same |
US9210939B2 (en) | 2011-12-22 | 2015-12-15 | Showa Denko K.K. | Copper-and-titanium-containing composition and production method therefor |
US9516881B2 (en) | 2011-12-22 | 2016-12-13 | Showa Denko K.K. | Copper-and-titanium-containing composition and production method therefor |
Also Published As
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KR20120098826A (ko) | 2012-09-05 |
US20120294923A1 (en) | 2012-11-22 |
EP2508257A4 (en) | 2013-11-06 |
JP2011136984A (ja) | 2011-07-14 |
CN102762301A (zh) | 2012-10-31 |
EP2508257A1 (en) | 2012-10-10 |
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