WO2015040989A1 - Anti-viral composition, method for producing the composition, and virus inactivation method - Google Patents

Anti-viral composition, method for producing the composition, and virus inactivation method Download PDF

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Publication number
WO2015040989A1
WO2015040989A1 PCT/JP2014/071458 JP2014071458W WO2015040989A1 WO 2015040989 A1 WO2015040989 A1 WO 2015040989A1 JP 2014071458 W JP2014071458 W JP 2014071458W WO 2015040989 A1 WO2015040989 A1 WO 2015040989A1
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WIPO (PCT)
Prior art keywords
copper
viral
viral composition
divalent copper
copper compound
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Application number
PCT/JP2014/071458
Other languages
French (fr)
Inventor
Sou MIYAISHI
Yasuhiro Hosogi
Yasushi Kuroda
Original Assignee
Showa Denko K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to KR1020167002448A priority Critical patent/KR20160025608A/en
Priority to CN201480050249.1A priority patent/CN105530816A/en
Publication of WO2015040989A1 publication Critical patent/WO2015040989A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/24Heavy metals; Compounds thereof
    • A61K33/245Bismuth; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/24Heavy metals; Compounds thereof
    • A61K33/34Copper; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12Antivirals

Definitions

  • the present invention relates to an anti-viral
  • composition for inactivating a virus to an anti-viral agent containing the anti-viral composition, to a photocatalyst containing the anti-viral composition, to a method for producing the anti-viral composition—hereinafter referred to as a "anti-viral composition production method, "—and to a method for inactivating a virus—hereinafter referred to as a "virus inactivation method.”
  • Patent Document 1 discloses a phage/virus inactivating agent consisting of anatase-type titanium oxide containing copper at a CuO/Ti02 (mass% ratio) of 1.0 to 3.5.
  • Patent Document 1 relating to a virus inactivating agent was accomplished with respect to the finding that copper-containing titanium oxide can inactivate phages/viruses .
  • Patent Document 2 discloses that platinum- deposited tungsten oxide particles exhibit anti-viral activity under irradiation with visible light.
  • BiV0 4 Bismuth vanadate
  • the bandgap of BiV0 4 is about 2.3 eV, which is smaller than the band gap of titanium oxide; i.e., 3.0 to 3.2 eV.
  • BiVC serves as a photocatalyst which can more effectively utilize red-side light (visible light), as compared with titanium oxide well known as a photocatalyst material.
  • Patent Document 3 discloses that BiV04 powder bearing silver microparticles or copper oxide microparticles exhibits high photocatalytic activity in photodecomposition of endocrine disruptors.
  • Patent Document 1 Japanese Patent Application Laid-Open (koaki) No. 2006-232729
  • Patent Document 2 Japanese Patent Application Laid-Open (koaki) No. 2011-136984
  • Patent Document 3 Japanese Patent Application Laid-Open ⁇ koaki) No. 2004-330047
  • Non-Patent Document 1 J. Phys . Chem. B2006, 110, p.p. 11352- 11360
  • Non-Patent Document 2 J. Am. Chem. Soc. 1999, 121, p.p.
  • Non-Patent Document 3 Bulletin of Photofunctional Material Research Association "Photocatalysis, " vol. 37, p. 31-32 (2012)
  • Patent Document 1 anti-viral performance of CuO/TiC>2 samples was assessed under irradiation with UV light
  • Patent Document 1 which exhibits no anti-viral activity, in the dark and under light, is thought to exhibit no anti-viral activity under a white LED fluorescent lamp. Therefore, application of the phage/virus inactivating agent disclosed in Patent Document 1 to an interior material is considerably restricted.
  • the platinum-deposited tungsten oxide particles disclosed in Patent Document 2 exhibit anti-viral property under irradiation with visible light.
  • platinum is a rare and expensive metal, thereby impeding industrial use of platinum-deposited tungsten oxide particles.
  • Patent Document 2 requires light irradiation as long as 1 to 6 hours so as to attain virus inactivation, which impedes application thereof to members which people frequently touch.
  • Patent Document 3 discloses that BiV0 powder bearing silver microparticles or copper oxide microparticles exhibits high photocatalytic activity in photodecomposition of
  • Patent Document 3 is silent to anti-viral activity. Meanwhile, photocatalyst materials exhibiting excellent organic substance decomposition activity do not necessarily have excellent anti-viral activity (see, for example, Non-Patent Document 3) . That is, the two effects are attained through different action mechanisms, and thus, there is no relationship between excellent organic substance decomposition activity and excellent anti-viral activity. Consequently, those skilled in the art have never conceived use of BiV0 powder bearing silver microparticles or copper oxide microparticles as an anti-viral agent.
  • an object of the invention is to provide an anti-viral composition, an antiviral agent, and a photocatalyst , which exhibit excellent anti-viral property under light and in the dark. Another object is to provide a method for producing the anti-viral composition. Still another object is to provide a virus inactivation method.
  • the present inventors have found that a composition containing BiVC> 4 and a divalent copper compound exhibits excellent anti-viral activity under irradiation with light and in the dark.
  • the present invention has been accomplished on the basis of this finding. Accordingly, the present invention provides the following [1] to [19].
  • An anti-viral composition comprising BiVC and a divalent copper compound.
  • X in formula (1) is a species selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of an inorganic acid, and OH.
  • divalent copper inorganic acid salt (c) is composed of one or more species selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate.
  • a method for producing an anti-viral composition comprising:
  • the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance is 3 to 25 mass%.
  • a virus inactivation method comprising inactivating a virus by use of an anti-viral composition as recited in any one of [1] to [10] above, an anti-viral agent as recited in [11] above, or a photocatalyst as recited in [12] above.
  • an anti-viral composition an anti-viral agent, and a photocatalyst , which exhibit excellent anti-viral property under light and in the dark, a method for producing the antiviral composition, and a virus inactivation method.
  • the present inventors have conducted extensive studies, and have found that use of a composition containing BiVCu and a divalent copper compound realizes production of an antiviral composition, an anti-viral agent, and a photocatalyst, which exhibit excellent anti-viral property under light including no UV light and in the dark, a method for producing the anti-viral composition, and a virus inactivation method.
  • the present invention has been accomplished.
  • the present invention will next be described in detail. The following embodiments should not be construed as limiting the invention thereto.
  • the term "under light” refers to an environment where visible light having a
  • the anti-viral composition of the present invention contains BiV0 4 and a divalent copper compound. Through combining BiV0 with a divalent copper compound, the antiviral composition can exhibit excellent anti-viral property under light and in the dark.
  • B1VO4 employed in the present invention exhibits high photocatalytic activity under visible light.
  • B1VO4 is generally produced through a solid-phase method or a liquid- phase method.
  • BiVC>4 produced through any of the production methods may be used in the anti-viral composition.
  • Examples of the BiVC production method include a production method disclosed in Japanese Patent Application Laid-Open (koaki) No. 2001-2419 and that disclosed in Japanese Patent Application Laid-Open (koaki) No. 2004-24936.
  • B1VO4 preferably has a specific surface area of 1 to 200 m 2 /g, more preferably 3 to 100 m 2 /g, still more preferably 4 to 70 m 2 /g, particularly preferably 8 to 50 m 2 /g.
  • the specific surface area of BiVC>4 is 1 m 2 /g or more, occurrence of virus contact on the surface of the anti-viral composition increases, whereby the anti-viral property of the anti-viral composition under light and in the dark can be further enhanced.
  • the specific surface area of BiV0 4 is 200 m 2 /g or less, handling of the anti-viral composition can be further facilitated.
  • the specific surface area is measured through the BET technique based on nitrogen adsorption.
  • the divalent copper compound employed in the present invention is a compound of a divalent copper.
  • the divalent copper compound exhibits no antiviral property under light and in the dark.
  • the divalent copper compound when used in combination with BiV0 , the divalent copper compound exhibits an anti-viral property under light and in the dark. No particular limitation is imposed on the divalent copper compound, so long as the copper is divalent.
  • the divalent copper is divalent.
  • X in formula (1) is more preferably any species
  • a halogen such as CI, Br, or I
  • a conjugate base of a carboxylic acid such as
  • X in formula (1) is still more preferably one or more species selected from the group consisting of CI, CH3COO, N0 3 , (S0 4 )i/2, and OH.
  • X in formula (1) is yet more preferably one species selected from the group consisting of
  • the divalent copper halide (b) is composed of one or more species selected from the group consisting of copper chloride, copper fluoride, and copper bromide .
  • the divalent copper inorganic acid salt (c) is composed of one or more species selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper
  • the divalent copper organic acid salt (d) is a divalent copper carboxylic acid salt.
  • preferred divalent copper carboxylic acid salts include one or more species selected from the group consisting of copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper
  • Examples of other preferred divalent copper compounds include one or more species selected from the group
  • ethylacetoacetonatocopper copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, and copper dimethyldithiocarbamate .
  • the divalent copper compound of the present invention is preferably one or more species selected from group
  • the divalent copper compound of the present invention is a hydroxide- group-containing divalent copper compound represented by formula (1), by virtue of low impurity level and low cost.
  • the hydroxide-group-containing divalent copper compound represented by formula (1) may be anhydrate or a hydrate.
  • the divalent copper compound contained in the antiviral composition of the present invention preferably has a copper element content by mass of 0.01 to 20 parts by mass with respect to 100 parts by mass of BiV0 4 , more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 15 parts by mass, particularly preferably 0.3 to 10 parts by mass.
  • the divalent copper compound has a copper element content by mass of 0.01 parts by mass or more with respect to 100 parts by mass of BiV0 4 , favorable anti-viral property and antibiotic property can be attained under light and in the dark.
  • the divalent copper compound has a copper element content by mass of 20 parts by mass or less with respect to 100 parts by mass of BiVO 4 , complete coverage of the surface of the divalent copper compound with BiV04 is prevented, whereby the anti-viral composition exhibits higher photocatalytic activity.
  • viruses can be
  • the mass-basis copper element content of the divalent copper compound with respect to 100 parts by mass of BiV0 4 may be calculated from the amount of the supplied divalent copper compound raw material and the amount of supplied
  • the mass-basis copper element content of the divalent copper compound with respect to 100 parts by mass of BiV0 4 may be determined from each component content of the anti-viral composition, which has been measured through the below-mentioned ICP (inductively coupled plasma) emission spectroscopic analysis.
  • ICP inductively coupled plasma
  • the divalent copper compound may be supported by BiVC>4 .
  • the divalent copper compound may be dispersed in BiVCU, instead of being supported by BiVC>4 .
  • the anti-viral composition of the present invention contains, as essential components, BiV0 and a divalent copper compound.
  • the antiviral composition may further contain another optional component. From the viewpoint of improvement in anti-viral property, the total amount of BiVC>4 and the divalent copper compound contained in the anti-viral composition is
  • the anti-viral composition of the present invention can be suitably produced through the anti-viral composition production method of the present invention.
  • Examples . of the anti-viral composition production method of the present invention includes the following first to third embodiments of the anti-viral composition production method.
  • production method of the present invention includes a mixing step of mixing BiV0 4 , a divalent copper compound or a
  • BiVC>4 is the same BiVC>4 as mentioned in relation to the anti-viral composition.
  • the mass-basis BiV0 4 content of the mixture i.e., the percent ratio of the mass of BiV0 4 to the total mass of BiV0 4 , the divalent copper compound or the divalent copper compound raw material, water, and the
  • alkaline substance is preferably 3 to 25 ma.ss%, more
  • the anti ⁇ viral composition productivity increases, which is
  • the divalent copper compound is the same as described in relation to the anti-viral composition.
  • Examples of the divalent copper compound raw material include one or more species of the divalent copper compound raw material
  • X has the same meaning as defined in the aforementioned formula (1). That is, X represents an anion, which is preferably a halogen such as CI, Br, or I; a carboxylic acid conjugate base such as CH3COO; an inorganic acid conjugate base such as NO3 or (S04)i/2 , or OH. X is more preferably one or more species selected from among CI,
  • CH3COO , NO3 , and (S04)i/2 still more preferably one species selected from among CI, CH3COO , NO3 , and (S0 4 )i/2 .
  • divalent copper compound raw material is hydrolyzed to form a corresponding divalent copper compound, which is then
  • the divalent copper compound raw material represented by formula (2) may be a single divalent copper compound raw material (i.e., a single divalent copper compound raw
  • divalent copper compound raw material in which X is a specific single species or a mixture of divalent copper compound raw materials in which X is two or more different species, for example, a mixture of Cu(N0 3 )2 and Cu(OH) 2 .
  • the divalent copper compound raw material represented by formula (2) may be
  • divalent copper compound raw material represented by formula (2) may be anhydrate or a hydrate.
  • the divalent copper compound raw material preferably has a copper element content of 0.01 to 20 parts by mass with respect to 100 parts by mass of BiV04, more preferably 0.1 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass.
  • the divalent copper compound raw material has a copper element content by mass of 0.01 parts by mass or more with respect to 100 parts by mass of B1VO 4
  • the produced anti-viral composition exhibits excellent anti-viral property under light and in the dark.
  • the divalent copper compound raw material has a copper element content by mass of 20 parts by mass or less with respect to 100 parts by mass of BiVC ⁇ , complete coverage of the surface of the divalent copper compound raw material with BiVCu is prevented, whereby the produced anti-viral composition exhibits higher
  • viruses can be any virus that can be used to catalytic activity.
  • viruses can be any virus that can be used to catalytic activity.
  • viruses can be any virus that can be used to catalytic activity.
  • the copper element content by mass of the divalent copper compound raw material is the same as the copper element content by mass of the divalent copper compound described in relation to the anti-viral composition.
  • Water is used as a solvent for preparing the
  • the solvent may further contain a polar solvent other than water. So long as the divalent copper compound or the divalent copper compound raw material, the alkaline substance, and water can be dissolved therein, no particular limitation is imposed on the polar solvent optionally contained in water.
  • the polar solvent include an alcohol, a ketone, and a mixture thereof.
  • Specific examples of the polar solvent include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol,
  • dimethylformamide dimethylformamide
  • tetrahydrofuran tetrahydrofuran
  • alkaline compounds examples include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, and a basic surfactant (e.g., BYK- 9077, product of BYK Japan K.K.).
  • sodium hydroxide is a particularly preferred alkaline substance.
  • the alkaline compound is preferably added in the solution form.
  • the alkaline compound concentration of the solution to be added is preferably 0.1 to 5 mol/L, more preferably 0.3 to 4 mol/L, still more preferably 0.5 to 3. mol/L. When the alkaline substance concentration of the alkali solution is 5 mol/L or less, failure to uniform deposition of the copper divalent compound occur upon addition of the alkaline solution can be prevented.
  • BiVC is mixed with water optionally under stirring, and then the divalent copper compound or the divalent copper compound raw material is added to the mixture under stirring.
  • the divalent copper compound or the divalent copper compound raw material is mixed with water optionally under stirring, and then BiVC is is added to the mixture under stirring.
  • the divalent copper compound or the divalent copper compound raw material and B1VO4 are simultaneously added to water, and the mixture is stirred .
  • the alkaline substance is added before, during, or after mixing of B1VO4 and/or the divalent copper compound or the divalent copper compound raw material with water.
  • the alkaline substance may be added at least one of the three timings of addition.
  • BiV0 4 and the divalent copper compound or the divalent copper compound raw material are mixed with water under sufficient stirring, and then the alkaline substance is added to the mixture.
  • the stirring time is preferably, for example, about 5 to about 120 minutes, more preferably about 10 to about 60 minutes, still more preferably about 15 to about 45 minutes.
  • No particular limitation is imposed on the temperature of the mixture during at stirring, and the temperature is, for example, room temperature to about 70°C.
  • the pH of the mixture of BiV0 4 , the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance may be modified.
  • the pH of the mixture may be modified.
  • the pH of the mixture of BiVC , the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance is preferably 8 to 12, more preferably 9 to 11.5, still more preferably 9.5 to 11.
  • the pH of the mixture is determined by means of a pH meter (D-51, product of HORIBA, Ltd.). Upon heating the mixture, the pH of the mixture is measured by means of the above pH meter at 25°C, and then the mixture is heated.
  • an anti-viral composition can be isolated from the . thus-obtained mixture as, for example, a solid component.
  • the anti-viral composition may be separated from the mixture through filtration, sedimentation, centrifugation, evaporation to dryness, or the like.
  • the anti-viral composition may be separated from the mixture through filtration. If required, the thus- isolated anti-viral composition is subjected to washing with water, drying, pulverization, classification, etc. [0042]
  • the anti-viral composition isolated from the mixture through the separation step may be further subjected to a thermal treatment. Through the thermal treatment, the divalent copper compound is more firmly deposited on BiVC>4 .
  • the temperature of the thermal treatment step is preferably 150 to 600°C, more preferably 200 to 500°C, still more preferably 250 to 450°C.
  • the thermal treatment temperature is 150°C or higher, the divalent copper compound is more strongly bound to BiV04, whereas when the thermal treatment temperature is 600°C or lower, grain growth and reduction in specific surface area, which would otherwise be caused by sintering, are suppressed. In this case, the produced anti-viral composition exhibits more excellent antiviral property under light and in the dark.
  • the time of the thermal treatment step is preferably 1 to 10 hours, more preferably 2 to 8 hours, still more
  • the thermal treatment time is 1 hour or longer, the divalent copper compound is strongly bound to BiVC , whereas when the thermal treatment time is 10 hours or shorter, grain growth and reduction in specific surface area, which would otherwise be caused by sintering, are suppressed. In this case, the produced anti-viral composition exhibits more excellent anti-viral property under light and in the dark.
  • the thermal treatment is preferably performed in an oxygen-containing atmosphere such as air.
  • a second embodiment of the anti-viral composition production method of the present invention includes a mixing step of mixing BiVC and a divalent copper compound.
  • the mixing step may be performed through dry mixing or wet mixing and may be performed through a widely known mixing technique.
  • B1VO4 and the divalent copper compound employed in the second embodiment are the same as those described in relation to the anti-viral composition.
  • solvent employed in the mixing include water, an alcohol, a ketone, and a mixture thereof.
  • the alcohol include methanol, ethanol, 1- propanol, 2-propanol, 1-butanol, and a mixture thereof.
  • ketone examples include acetone, acetylacetone, methyl ethyl ketone, and a mixture thereof.
  • the anti-viral composition produced through the second embodiment of the production method of the present invention is a simple mixture of BiVCU and the divalent copper
  • the anti-viral composition produced through the method also exhibits antiviral property under light and in the dark.
  • the anti-viral composition produced through mixing BiV04 and the divalent copper compound may be further subjected to a thermal treatment.
  • the thermal treatment is performed through, for example, the same procedure as employed in the aforementioned thermal treatment step.
  • the production method of the present invention includes a mixing step of mixing BiVC with an aqueous solution of a divalent copper compound, to thereby form a mixture, a heating step of heating the mixture, and a separation step of separating an anti-viral composition from the heated mixture.
  • the aqueous divalent copper compound solution has a divalent copper compound concentration of some g/100 mL to some tens og g/100 mL. No particular limitation is imposed on the separation technique employed in the separation step, and the anti-viral composition may be separated from the mixture through
  • BiVC>4 and the divalent copper compound employed in the third embodiment are the same as those described in relation to the anti-viral composition.
  • the third embodiment of the production method of the present invention is carried out in the following manner. Specifically, an aqueous divalent copper compound solution is added to a specific container in such an amount that the copper content of the aqueous
  • divalent copper compound solution with respect to the mass of BiVC>4 to be added is adjusted to 0.01 to 20 parts by mass.
  • BiV0 4 is added to the container and mixed with the aqueous divalent copper compound solution, to thereby suspend BiVC>4 in the aqueous copper compound solution, whereby a mixture is produced.
  • the mixture is heated at about 50 to about 90°C, and then filtered, to thereby yield an anti-viral composition.
  • the anti-viral composition recovered through filtration is subjected to washing with water, drying, pulverization, classification, etc .
  • the anti-viral composition isolated from the mixture through the separation step may be further subjected to a thermal treatment.
  • the thermal treatment is performed through, for example, the same procedure as employed in the aforementioned thermal treatment step in the first
  • the anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention.
  • the anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention.
  • photocatalyst of the present invention exhibit excellent anti-viral property under light and in the dark.
  • the anti-viral composition or the like of the present invention may be used in a solid form, such as micropowder or granules. In this case, the anti-viral composition or the like of the present invention is directly charged into an appropriate container for use. In an alternative mode of use, the anti-viral composition or the like of the present invention may be incorporated into the surface and/or the inside of a
  • the substrate includes a single-member substrate formed of a general material such as fiber, metal, ceramic material, glass, etc., and a composite substrate formed of two or more members.
  • the anti-viral composition or the like of the present invention may be incorporated into a coating agent such as a floor polish, which is removable by
  • composition or the like of the present invention is
  • the anti-viral composition or the like of the present invention immobilized on a membrane, to thereby realize a continuous membrane on which the anti-viral composition or the like of the present invention is exposed to the atmosphere.
  • a thin film of the anti-viral composition or the like of the present invention is formed through sputtering on a BiV04 thin film formed on a glass by sputtering.
  • the anti-viral composition or the like of the present invention may be dispersed in a solvent, to thereby provide a paint material.
  • Examples of the material for immobilizing the antiviral composition or the like of the present invention immobilized on the substrate include a material for
  • immobilizing anti-viral composition or the like of the present invention by generally employed immobilizing means such as means by using a binder.
  • an organic binder or an inorganic binder may be used for immobilizing the antiviral composition or the like of the present invention.
  • an inorganic binder is preferably used, for the purpose of preventing decomposition of the binder induced by a photocatalytic substance. No particular limitation is imposed on the type of the binder.
  • the inorganic binder include a silica-based binder, which is generally used for immobilizing a photocatalytic substance onto a substrate.
  • the organic binder include a polymer binder, which can form thin film through polymerization or
  • the substrate containing the material is a material produced by dispersing the anti-viral composition or the like of the present invention in a resin, to thereby form a dispersion, and hardening the dispersion.
  • Either natural resin or synthetic . resin may be used for dispersing the antiviral composition or the like of the present invention.
  • the synthetic resin include acrylic resin, phenolic resin, polyurethane resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polyester resin, and epoxy resin.
  • the anti-viral composition or the like of the present invention which exhibits high virus- inactivating performance in the presence of water (e.g., water or sea water), under dry conditions (e.g., low-humidity conditions in, for example, winter) , under high humidity conditions, or in the co-presence of organic substance, can continuously inactivate viruses.
  • the anti-viral composition or the like of the present invention may be applied to any object such as a wall, floor, or ceiling; buildings such as hospitals and factories; machine tools and measuring
  • Non-limitative examples of preferred dark places include the inside of a machine, a storage compartment of a refrigerator, and a hospital
  • a UV light source may be omitted, thereby enhancing safety of the air purifier without elevating cost thereof.
  • the present invention provides a virus inactivation method for inactivating a virus by use of the anti-viral composition, the anti-viral agent or photocatalyst of the present invention.
  • the anti-viral composition of the present invention can inactivate a target virus.
  • the anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention, the anti-viral agent or photocatalyst of the present invention can inactivate a target virus.
  • the antiviral composition, anti-viral agent, and photocatalyst of the present invention preferably exhibit a virus inactivation performance of 99.0% or higher, more preferably 99.9% or higher, after irradiation with visible light at an
  • the virus inactivation performance can be calculated by the formula, LOG(N/No).
  • No represents a phage concentration before visible light irradiation
  • N represents a phage
  • NH4VO3 (99.0%) was dissolved in 2-mol/L nitric acid, and Bi (N0 3 ) 3-5H 2 0 (product of Kanto Chemical Co., Inc., 99.9%) was dissolved in water, to thereby form a 0.12-mol/L aqueous solution thereof.
  • aqueous solutions 100 mL were mixed together, and 3 g of urea was dissolved in the mixed solution.
  • the resultant solution was heated at 90°C by a hot stirrer and maintained for 24 hours. The thus-formed
  • Example 1 The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl 2 -2H 2 0, 0.1179 g (0.5 parts by mass of copper with respect to 100 parts by mass of BiVC ) of
  • Example 3 The procedure of Example 1 was repeated, except that the amount of CuC ⁇ 2 -2H20 added to the suspension was changed from 0.0805 g to 0.1610 g (1 part by mass of copper with respect to 100 parts by mass of BiVOi) , to thereby yield an anti-viral composition of Example 3.
  • Example 2 The procedure of Example 1 was repeated, except that the amount of CuCl2-2H20 added to the suspension was changed from 0.0805 g to 0.4829 g (3 part by mass of copper with respect to 100 parts by mass of BIVC ), to thereby yield an anti-viral composition of Example 4.
  • a BIVC material was used as the composition of
  • Example 3 The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl 2 -2H 2 0, 0.0625 g (0.5 parts by mass of zinc with respect to 100 parts by mass of B1VO4) of ZnCl2 (product of Kanto Chemical Co., Inc.) was added to the suspension, to thereby yield a composition of Comparative Example 3.
  • Example 1 The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl 2 -2H 2 0, 0.1452 g (0.5 parts by mass of iron with respect to 100 parts by mass of BiV04) of
  • Example 1 The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl 2 -2H 2 0, 0.1215 g (0.5 parts by mass of iron with respect to 100 parts by mass of BiVO-j) of
  • NiCl 2 -6H 2 0 product of Kanto Chemical Co., Inc. was added to the suspension, to thereby yield a composition of Comparative Example 5.
  • Example 2 The procedure of Example 1 was repeated, except that BiV0 was changed to rutile-type titanium oxide Fl-R (product of SHOWA TITANIUM CO., LTD), to thereby yield a composition of Comparative Example 6.
  • each of the compositions of Examples 1 to 4 and Comparative Examples 3 to 5 were determined through the ICP emission spectroscopic analysis. Specifically, each of the compositions of Examples 1 to 4 and Comparative Examples 3 to 5 was heated in a hydrofluoric acid solution until the composition was
  • the anti-viral performance of the compositions of the Examples 1 to 4 and the Comparative Examples 1 to 7 was assessed through the following model experiment employing bacteriophage. Notably, assessment of anti-viral performance with respect to inactivation performance with respect to bacteriophage is disclosed in, for example, Appl . Microbiol. Biotechnol., 79, pp. 127-133, (2008). The document discloses that the bacteriophage inactivation performance is known as a reliable model for the assessment. The measurement is based on JIS R 1706.
  • a piece of filter paper was placed on the bottom of a deep Petri dish, and a small amount of sterilized water was added to the Petri dish.
  • the aforementioned measurement units were placed under the light source at a position where the illuminance (measured by means of an illuminometer : TOPCON IM-5) was 800 lx. After the elapse of 3 minutes, 10 minutes, and 60 minutes from the start of light irradiation, the phage concentration of each sample present on the glass plate was measured. During the measurement, the illuminance in the room was adjusted to 200 lx or lower. The elapse of time after the start of light irradiation was measured by means of a commercial stopwatch.
  • a phage recovery liquid SCDLP medium
  • the phage-recovered liquid was appropriately diluted with physiological saline containing peptone.
  • 1 mL of each dilution was mixed with a separately prepared E. coli (NBRC 106373) culture liquid having a concentration of 5.0 x 10 8 to 2.0 x 10 9 cells/mL) and a calcium-added LB soft agar medium under stirring.
  • the mixture was inoculated to a calcium-added LB agar medium and cultured at 37°C for 15 hours.
  • the number of plaques of the phage was visually counted.
  • the phage concentration N was derived through multiplication of the count by the dilution factor of the phage recovered liquid.
  • the relative phage concentration (LOG (N/No) ) was determined.
  • the smaller the LOG(N/No) i.e., the larger the absolute value of the minus value
  • the stronger the antiviral property the smaller the LOG(N/No) (i.e., the larger the absolute value of the minus value) , the stronger the antiviral property.
  • Example 1 (ICP emission spectroscopic analysis) The composition of Example 1 was found to have a copper ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC> 4 .
  • the composition of Example 2 was found to have a copper ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC .
  • the composition of Example 3 was found to have a copper ion content of 1 part by mass with respect to 100 parts by mass of BiV04.
  • the composition of Example 4 was found to have a copper ion content of 3 parts by mass with respect to 100 parts by mass of BIVC .
  • the composition of Comparative Example 3 was found to have a zinc ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied zinc ions was found to be supported on the surface of B1VO4.
  • the composition of Comparative Example 4 was found to have an iron ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied iron ions was found to be supported on the surface of BiV04.
  • the composition of Comparative Example 5 was found to have a nickel ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied nickel ions was found to be supported on the surface of BiVC>4.
  • compositions of Examples 1 to 4 were found to exhibit excellent anti-viral performance under light and in the dark. Particularly, under light, the compositions of Examples 1 to 4 were found to inactivate about 99.9% of phages through irradiation with light for a period as short as 3 minutes. The performance can be attained very quickly, as compared with a conventional photocatalyst . In particular, the compositions of Examples 2 to 4 were found to exhibit a virus inactivating performance of 99.9% or higher through irradiation with visible light 800 lx for 3 minutes.

Abstract

To provide an anti-viral composition, an anti-viral agent, and a photocatalyst, which exhibit excellent anti-viral property under light and in the dark; a method for producing the anti-viral composition; and a virus inactivation method. The anti-viral composition of the present invention contains BiVO4 and a divalent copper compound. The anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention. The anti-viral composition production method includes a mixing step of mixing BiVO4, a divalent copper compound or a divalent copper compound raw material, water, and an alkaline substance, to thereby form a mixture; and a separation step of separating an anti-viral composition from the mixture. The virus inactivation method of the present invention inactivates a virus by use of the anti-viral composition of the present invention, the anti-viral agent of the present invention, or the photocatalyst of the present invention.

Description

DESCRIPTION
ANTI-VIRAL COMPOSITION, METHOD FOR PRODUCING THE COMPOSITION, AND VIRUS INACTIVATION METHOD
Technical Field
[0001]
The present invention relates to an anti-viral
composition for inactivating a virus, to an anti-viral agent containing the anti-viral composition, to a photocatalyst containing the anti-viral composition, to a method for producing the anti-viral composition—hereinafter referred to as a "anti-viral composition production method, "—and to a method for inactivating a virus—hereinafter referred to as a "virus inactivation method."
Background Art
[0002]
In recent years, new viruses which are harmful for human health have been found, and people are considerably concerned about spread of infection with such viruses. One candidate material for preventing viral infections is a photocatalyst (see, for example, Patent Documents 1 and 2).
[0003]
Patent Document 1 discloses a phage/virus inactivating agent consisting of anatase-type titanium oxide containing copper at a CuO/Ti02 (mass% ratio) of 1.0 to 3.5. The
invention of Patent Document 1 relating to a virus inactivating agent was accomplished with respect to the finding that copper-containing titanium oxide can inactivate phages/viruses . Patent Document 2 discloses that platinum- deposited tungsten oxide particles exhibit anti-viral activity under irradiation with visible light.
[0004]
Bismuth vanadate (hereinafter referred to as BiV04) is widely known as a visible light-response water-decomposition catalyst having excellent decomposition activity (see Non- Patent Documents 1 to 3) . The bandgap of BiV04 is about 2.3 eV, which is smaller than the band gap of titanium oxide; i.e., 3.0 to 3.2 eV. In other words, BiVC serves as a photocatalyst which can more effectively utilize red-side light (visible light), as compared with titanium oxide well known as a photocatalyst material. Some documents report that BiV04 serves as an organic substance decomposition photocatalyst. For example, Patent Document 3 discloses that BiV04 powder bearing silver microparticles or copper oxide microparticles exhibits high photocatalytic activity in photodecomposition of endocrine disruptors.
Prior Art Documents
Patent Documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open (koaki) No. 2006-232729
Patent Document 2: Japanese Patent Application Laid-Open (koaki) No. 2011-136984 Patent Document 3: Japanese Patent Application Laid-Open {koaki) No. 2004-330047
Non-Patent Documents
[0006]
Non-Patent Document 1: J. Phys . Chem. B2006, 110, p.p. 11352- 11360
Non-Patent Document 2: J. Am. Chem. Soc. 1999, 121, p.p.
11459-11467
Non-Patent Document 3: Bulletin of Photofunctional Material Research Association "Photocatalysis, " vol. 37, p. 31-32 (2012)
Summary of the Invention
Problems to be Solved by the invention
[0007]
In Patent Document 1, anti-viral performance of CuO/TiC>2 samples was assessed under irradiation with UV light
(Examples 1 to 4, and Comparative Examples 3 and 4), under irradiation with visible light (Comparative Example 2), and in the dark (Comparative Example 1) . No phage/virus
inactivating effect was observed under irradiation with visible light (Comparative Example 2), and in the dark
(Comparative Example 1) . Meanwhile, recently popular white LED fluorescent lamps provide light including no UV light. The phage/virus inactivating agent disclosed in Patent
Document 1, which exhibits no anti-viral activity, in the dark and under light, is thought to exhibit no anti-viral activity under a white LED fluorescent lamp. Therefore, application of the phage/virus inactivating agent disclosed in Patent Document 1 to an interior material is considerably restricted. The platinum-deposited tungsten oxide particles disclosed in Patent Document 2 exhibit anti-viral property under irradiation with visible light. However, platinum is a rare and expensive metal, thereby impeding industrial use of platinum-deposited tungsten oxide particles. In addition, both the phage/virus inactivating agent disclosed in Patent Document 1 and the platinum-deposited tungsten oxide
particles disclosed in Patent Document 2 require light irradiation as long as 1 to 6 hours so as to attain virus inactivation, which impedes application thereof to members which people frequently touch.
[0008]
Patent Document 3 discloses that BiV0 powder bearing silver microparticles or copper oxide microparticles exhibits high photocatalytic activity in photodecomposition of
endocrine disruptors. However, Patent Document 3 is silent to anti-viral activity. Meanwhile, photocatalyst materials exhibiting excellent organic substance decomposition activity do not necessarily have excellent anti-viral activity (see, for example, Non-Patent Document 3) . That is, the two effects are attained through different action mechanisms, and thus, there is no relationship between excellent organic substance decomposition activity and excellent anti-viral activity. Consequently, those skilled in the art have never conceived use of BiV0 powder bearing silver microparticles or copper oxide microparticles as an anti-viral agent.
[0009]
The present invention has been conceived in order to solve the aforementioned problems. Thus, an object of the invention is to provide an anti-viral composition, an antiviral agent, and a photocatalyst , which exhibit excellent anti-viral property under light and in the dark. Another object is to provide a method for producing the anti-viral composition. Still another object is to provide a virus inactivation method.
Means for Solving the Problems
[0010]
The present inventors have found that a composition containing BiVC> 4 and a divalent copper compound exhibits excellent anti-viral activity under irradiation with light and in the dark. The present invention has been accomplished on the basis of this finding. Accordingly, the present invention provides the following [1] to [19].
[0011]
[1] An anti-viral composition comprising BiVC and a divalent copper compound.
[2] An anti-viral composition as described in [1] above, wherein the divalent copper compound has a copper element content by mass of 0.01 to 20 parts by mass with respect to 100 parts by mass of BiV0 .
[3] An anti-viral composition as described in [1] or [2] above, wherein the divalent copper compound is composed of one or more species selected from the group consisting of (a) a hydroxide-group-containing divalent copper compound
represented by the following formula (1):
Cu2(OH)3X (1)
(wherein X represents an anion) , (b) a divalent copper halide, (c) a divalent copper inorganic acid salt, (d) a divalent copper organic acid salt, (e) cupric oxide, (f) copper sulfide, (g) copper (II) azide, and (h) copper
silicate.
[4] An anti-viral composition as described in [3] above, wherein X in formula (1) is a species selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of an inorganic acid, and OH.
[5] An anti-viral composition as described in [3] above, wherein the divalent copper halide (b) is composed of one or more species selected from the group consisting of copper chloride, copper fluoride, and copper bromide.
[6] An anti-viral composition as described in [3] above, wherein the divalent copper inorganic acid salt (c) is composed of one or more species selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate.
[7] An anti-viral composition as described in [3] above, wherein the divalent copper organic acid salt (d) is a divalent copper carboxylic acid salt. [8] An anti-viral composition as described in [3] or [4] above, wherein the divalent copper compound is a hydroxide- group-containing divalent copper compound represented by formula ( 1 ) .
[9] An anti-viral composition as described in any of [3] to [8] above, wherein X is one species selected from the groups consisting of CI, CH3COO, NO3, and (S04)i/2.
[10] An anti-viral composition as described in any of [1] to [9] above, which has a virus inactivating performance of 99.9% or higher after irradiation with visible light at 800 lx for 3 minutes.
[11] An anti-viral agent containing an anti-viral composition as recited in any of [1] to [10] above.
[12] A photocatalyst containing an anti-viral composition as recited in any of [1] to [10] above.
[13] A method for producing an anti-viral composition,, the method comprising:
a mixing step of mixing BiVCU, a divalent copper
compound or a divalent copper compound raw material, water, and an alkaline substance, to thereby form a mixture; and a separation step of separating an anti-viral composition from the mixture.
[14] An anti-viral composition production method as described in [13] above, which further includes a thermal treatment step of subjecting to a thermal treatment step the anti-viral composition separated by the separation step.
[15] An anti-viral composition production method as described in [13] or [14] above, wherein, in the mixing step, the pH of the mixture is adjusted to 8 to 12.
[16] An anti-viral composition production method as described in any of [13] to [15] above, wherein the divalent copper compound raw material includes at least one divalent copper compound represented by the following formula (2):
CuX2 (2)
(wherein X represents an anion) .
[17] An anti-viral composition production method as described in any of [13] to [16] above, wherein in the mixing step, the percent ratio of the mass of BiVC to the total mass of
BiVC>4 , the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance is 3 to 25 mass%.
[18] An anti-viral composition production method as described in any of [13] to [17] above, wherein, in the mixing step, BiV04 and the divalent copper compound or the divalent copper compound raw material are mixed in water with stirring, and then the alkaline substance is added to the mixture.
[19] A virus inactivation method comprising inactivating a virus by use of an anti-viral composition as recited in any one of [1] to [10] above, an anti-viral agent as recited in [11] above, or a photocatalyst as recited in [12] above.
Effects of the Invention
[0012]
According to the present invention, there can be
provided an anti-viral composition, an anti-viral agent, and a photocatalyst , which exhibit excellent anti-viral property under light and in the dark, a method for producing the antiviral composition, and a virus inactivation method.
Modes for Carrying Out the Invention
[0013]
The present inventors have conducted extensive studies, and have found that use of a composition containing BiVCu and a divalent copper compound realizes production of an antiviral composition, an anti-viral agent, and a photocatalyst, which exhibit excellent anti-viral property under light including no UV light and in the dark, a method for producing the anti-viral composition, and a virus inactivation method. Thus, the present invention has been accomplished. The present invention will next be described in detail. The following embodiments should not be construed as limiting the invention thereto. As used herein, the term "under light" refers to an environment where visible light having a
wavelength of 400 nm or longer is present but no UV light is present, and the term "in the dark" refers to an environment where neither UV light nor light other than UV light is present .
[0014]
[Anti-viral composition]
The anti-viral composition of the present invention contains BiV04 and a divalent copper compound. Through combining BiV0 with a divalent copper compound, the antiviral composition can exhibit excellent anti-viral property under light and in the dark.
[0015]
<BiV04>
B1VO4 employed in the present invention exhibits high photocatalytic activity under visible light. B1VO4 is generally produced through a solid-phase method or a liquid- phase method. In the present invention, BiVC>4 produced through any of the production methods may be used in the anti-viral composition. Examples of the BiVC production method include a production method disclosed in Japanese Patent Application Laid-Open (koaki) No. 2001-2419 and that disclosed in Japanese Patent Application Laid-Open (koaki) No. 2004-24936.
[0016]
B1VO4 preferably has a specific surface area of 1 to 200 m2/g, more preferably 3 to 100 m2/g, still more preferably 4 to 70 m2/g, particularly preferably 8 to 50 m2/g. When the specific surface area of BiVC>4 is 1 m2/g or more, occurrence of virus contact on the surface of the anti-viral composition increases, whereby the anti-viral property of the anti-viral composition under light and in the dark can be further enhanced. When the specific surface area of BiV04 is 200 m2/g or less, handling of the anti-viral composition can be further facilitated. In the present invention, the specific surface area is measured through the BET technique based on nitrogen adsorption.
[0017] <Divalent copper compound>
The divalent copper compound employed in the present invention is a compound of a divalent copper. When a single component, the divalent copper compound exhibits no antiviral property under light and in the dark. However, quite surprisingly, when used in combination with BiV0 , the divalent copper compound exhibits an anti-viral property under light and in the dark. No particular limitation is imposed on the divalent copper compound, so long as the copper is divalent. For example, the divalent copper
compound is composed of one or more species selected from the group consisting of (a) a hydroxide-group-containing divalent copper compound represented by the following formula (1):
Cu2(OH)3X (1)
(wherein X represents an anion), (b) a divalent copper halide, (c) a divalent copper inorganic acid salt, (d) a divalent copper organic acid salt, (e) cupric oxide, (f) copper sulfide, (g) copper (II) azide, and (h) copper
silicate.
[0018]
X in formula (1) is more preferably any species
selected from the group consisting of a halogen such as CI, Br, or I; a conjugate base of a carboxylic acid such as
CH3COO; a conjugate base of an inorganic acid such as NO3 or (S04)i/2; and OH. X in formula (1) is still more preferably one or more species selected from the group consisting of CI, CH3COO, N03, (S04)i/2, and OH. X in formula (1) is yet more preferably one species selected from the group consisting of
CI, CH3COO, N03, (S04)i/2, and OH.
[0019]
More preferably, the divalent copper halide (b) is composed of one or more species selected from the group consisting of copper chloride, copper fluoride, and copper bromide .
[0020]
More preferably, the divalent copper inorganic acid salt (c) is composed of one or more species selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper
tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate .
[0021]
More preferably, the divalent copper organic acid salt (d) is a divalent copper carboxylic acid salt. Examples of preferred divalent copper carboxylic acid salts include one or more species selected from the group consisting of copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper
myristate, copper palmitate, copper margarate, copper
stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper mellitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper
tartrate, acetylacetonatocopper, ethylacetoacetonatocopper, copper isovalerate, copper β-resorcinate, copper
diacetoacetate , copper formylsuccinate, copper
aminosalicylate, copper bis ( 2-ethylhexanoate ) , copper
sebacate, and copper naphthenate.
[0022]
Examples of other preferred divalent copper compounds include one or more species selected from the group
consisting of oxine-copper , acetylacetonatocopper,
ethylacetoacetonatocopper, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, and copper dimethyldithiocarbamate .
[0023]
The divalent copper compound of the present invention is preferably one or more species selected from group
consisting of a hydroxide-group-containing divalent copper compound represented by formula (1), a dilavent copper halide, a divalent copper inorganic acid salt, and a divalent copper organic acid salt. More preferably, the divalent copper compound of the present invention is a hydroxide- group-containing divalent copper compound represented by formula (1), by virtue of low impurity level and low cost. The hydroxide-group-containing divalent copper compound represented by formula (1) may be anhydrate or a hydrate. [0024]
The divalent copper compound contained in the antiviral composition of the present invention preferably has a copper element content by mass of 0.01 to 20 parts by mass with respect to 100 parts by mass of BiV04, more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 15 parts by mass, particularly preferably 0.3 to 10 parts by mass. When the divalent copper compound has a copper element content by mass of 0.01 parts by mass or more with respect to 100 parts by mass of BiV04, favorable anti-viral property and antibiotic property can be attained under light and in the dark. Also, when the divalent copper compound has a copper element content by mass of 20 parts by mass or less with respect to 100 parts by mass of BiVO4, complete coverage of the surface of the divalent copper compound with BiV04 is prevented, whereby the anti-viral composition exhibits higher photocatalytic activity. In addition, viruses can be
inactivated by a small amount of the anti-viral composition, which is economically advantageous.
[0025]
The mass-basis copper element content of the divalent copper compound with respect to 100 parts by mass of BiV04 may be calculated from the amount of the supplied divalent copper compound raw material and the amount of supplied
BiV04. Alternatively, the mass-basis copper element content of the divalent copper compound with respect to 100 parts by mass of BiV04 may be determined from each component content of the anti-viral composition, which has been measured through the below-mentioned ICP (inductively coupled plasma) emission spectroscopic analysis.
[0026]
In the anti-viral composition, the divalent copper compound may be supported by BiVC>4 . Alternatively, in the anti-viral composition, the divalent copper compound may be dispersed in BiVCU, instead of being supported by BiVC>4 .
[0027]
As described above, the anti-viral composition of the present invention contains, as essential components, BiV0 and a divalent copper compound. However, so long as the objects of the present invention are not impeded, the antiviral composition may further contain another optional component. From the viewpoint of improvement in anti-viral property, the total amount of BiVC>4 and the divalent copper compound contained in the anti-viral composition is
preferably 90 massl or more, more preferably 95 mass% or more, still more preferably 99 mass% or more, particularly preferably 100 mass%.
[0028]
[Anti-viral composition production method]
The anti-viral composition of the present invention can be suitably produced through the anti-viral composition production method of the present invention. Examples . of the anti-viral composition production method of the present invention includes the following first to third embodiments of the anti-viral composition production method.
[0029]
[First embodiment of the anti-viral composition production method of the present invention]
A first embodiment of the anti-viral composition
production method of the present invention includes a mixing step of mixing BiV04, a divalent copper compound or a
divalent copper compound raw material, water, and an alkaline substance, to thereby form a mixture; and a separation step of separating an anti-viral composition from the mixture. The first embodiment of the anti-viral composition production method of the present invention will next be described in detail.
[0030]
<Mixing step>
(BiV04)
BiVC>4 is the same BiVC>4 as mentioned in relation to the anti-viral composition. The mass-basis BiV04 content of the mixture; i.e., the percent ratio of the mass of BiV04 to the total mass of BiV04, the divalent copper compound or the divalent copper compound raw material, water, and the
alkaline substance is preferably 3 to 25 ma.ss%, more
preferably 5 to 22.5 mass%, still more preferably 7 to 20 mass%. When the BiV04 content is 3 massl or more, the anti¬ viral composition productivity increases, which is
economically advantageous, whereas when the BiV04 content is 25 massl or less, difficulty in handling, which would otherwise be caused by an increase in viscosity of the mixture, can be prevented.
[0031]
(Divalent copper compound or divalent copper compound raw material )
The divalent copper compound is the same as described in relation to the anti-viral composition. Examples of the divalent copper compound raw material include one or more species of the divalent copper compound raw material
represented by the following formula (2):
CuX2 (2) .
In formula (2), X has the same meaning as defined in the aforementioned formula (1). That is, X represents an anion, which is preferably a halogen such as CI, Br, or I; a carboxylic acid conjugate base such as CH3COO; an inorganic acid conjugate base such as NO3 or (S04)i/2 , or OH. X is more preferably one or more species selected from among CI,
CH3COO , NO3 , and (S04)i/2 , still more preferably one species selected from among CI, CH3COO , NO3 , and (S04)i/2 .
[0032]
Through the below-described reaction scheme, the
divalent copper compound raw material is hydrolyzed to form a corresponding divalent copper compound, which is then
deposited on the surfaces of BIVC , whereby the anti-viral composition is produced. HX in the reaction scheme is removed from the anti-viral composition through, for example, washing with water and drying. 2CuX2 + BiV04 + 3H20 → CU2 (OH) 3X/B1VO4 + 3HX In the reaction, "Cu2 (OH) 3X/BiV04" refers to a state in which Cu2(OH)3X is deposited on B1VO4.
[0033]
The divalent copper compound raw material represented by formula (2) may be a single divalent copper compound raw material (i.e., a single divalent copper compound raw
material in which X is a specific single species), or a mixture of divalent copper compound raw materials in which X is two or more different species, for example, a mixture of Cu(N03)2 and Cu(OH)2. Alternatively, the divalent copper compound raw material represented by formula (2) may be
CuX1X2 (wherein X1 and X2 are anions different from each other). Furthermore, divalent copper compound raw material represented by formula (2) may be anhydrate or a hydrate.
[0034]
The divalent copper compound raw material preferably has a copper element content of 0.01 to 20 parts by mass with respect to 100 parts by mass of BiV04, more preferably 0.1 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass. When the divalent copper compound raw material has a copper element content by mass of 0.01 parts by mass or more with respect to 100 parts by mass of B1VO4, the produced anti-viral composition exhibits excellent anti-viral property under light and in the dark. Also, when the divalent copper compound raw material has a copper element content by mass of 20 parts by mass or less with respect to 100 parts by mass of BiVC^, complete coverage of the surface of the divalent copper compound raw material with BiVCu is prevented, whereby the produced anti-viral composition exhibits higher
photocatalytic activity. In addition, viruses can be
inactivated by a small amount of the produced anti-viral composition, which is economically advantageous. The copper element content by mass of the divalent copper compound raw material is the same as the copper element content by mass of the divalent copper compound described in relation to the anti-viral composition.
[0035]
(Water)
Water is used as a solvent for preparing the
aforementioned mixture. However, the solvent may further contain a polar solvent other than water. So long as the divalent copper compound or the divalent copper compound raw material, the alkaline substance, and water can be dissolved therein, no particular limitation is imposed on the polar solvent optionally contained in water. Examples of the polar solvent include an alcohol, a ketone, and a mixture thereof. Specific examples of the polar solvent include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol,
dimethylformamide , and tetrahydrofuran . These solvents may be used singly or in combination of two or more species.
[0036]
(Alkaline substance)
Examples of preferred alkaline compounds include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, and a basic surfactant (e.g., BYK- 9077, product of BYK Japan K.K.). Of these, sodium hydroxide is a particularly preferred alkaline substance. The alkaline compound is preferably added in the solution form. The alkaline compound concentration of the solution to be added is preferably 0.1 to 5 mol/L, more preferably 0.3 to 4 mol/L, still more preferably 0.5 to 3. mol/L. When the alkaline substance concentration of the alkali solution is 5 mol/L or less, failure to uniform deposition of the copper divalent compound occur upon addition of the alkaline solution can be prevented.
[0037]
(Mixing)
No particular limitation is imposed on the order of mixing BiVCU, the divalent copper compound or the divalent copper compound raw material, water, and the alkaline
substance. However, in one preferred mode, BiVC is mixed with water optionally under stirring, and then the divalent copper compound or the divalent copper compound raw material is added to the mixture under stirring. In an alternative mode, the divalent copper compound or the divalent copper compound raw material is mixed with water optionally under stirring, and then BiVC is is added to the mixture under stirring. In another alternative mode, the divalent copper compound or the divalent copper compound raw material and B1VO4 are simultaneously added to water, and the mixture is stirred .
[0038]
The alkaline substance is added before, during, or after mixing of B1VO4 and/or the divalent copper compound or the divalent copper compound raw material with water. The alkaline substance may be added at least one of the three timings of addition. However, in a preferred mode, BiV04 and the divalent copper compound or the divalent copper compound raw material are mixed with water under sufficient stirring, and then the alkaline substance is added to the mixture.
[0039]
No particular limitation is imposed on the time of stirring BiVC>4 , the divalent copper compound or the divalent copper compound raw material, water, and the alkaline
substance, so long as BiV04, the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance can be uniformly mixed. The stirring time is preferably, for example, about 5 to about 120 minutes, more preferably about 10 to about 60 minutes, still more preferably about 15 to about 45 minutes. No particular limitation is imposed on the temperature of the mixture during at stirring, and the temperature is, for example, room temperature to about 70°C.
[0040]
The pH of the mixture of BiV04, the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance may be modified. For example, through modifying the amount of the alkaline substance contained in the mixture, the pH of the mixture may be modified. The pH of the mixture of BiVC , the divalent copper compound or the divalent copper compound raw material, water, and the alkaline substance is preferably 8 to 12, more preferably 9 to 11.5, still more preferably 9.5 to 11. When the pH of the mixture is 8 to 12, the divalent copper
compound raw material is effectively hydrolyzed and deposited on the surface of BiVC . In this case, the amount of the alkaline substance can be reduced, and waste water treatment is facilitated. The pH of the mixture is determined by means of a pH meter (D-51, product of HORIBA, Ltd.). Upon heating the mixture, the pH of the mixture is measured by means of the above pH meter at 25°C, and then the mixture is heated.
[0041]
<Separation step>
In the separation step, an anti-viral composition can be isolated from the . thus-obtained mixture as, for example, a solid component. No particular limitation is imposed on the separation method, and the anti-viral composition may be separated from the mixture through filtration, sedimentation, centrifugation, evaporation to dryness, or the like.
Preferably, the anti-viral composition may be separated from the mixture through filtration. If required, the thus- isolated anti-viral composition is subjected to washing with water, drying, pulverization, classification, etc. [0042]
<Thermal treatment step >
The anti-viral composition isolated from the mixture through the separation step may be further subjected to a thermal treatment. Through the thermal treatment, the divalent copper compound is more firmly deposited on BiVC>4 .
[0043]
The temperature of the thermal treatment step is preferably 150 to 600°C, more preferably 200 to 500°C, still more preferably 250 to 450°C. When the thermal treatment temperature is 150°C or higher, the divalent copper compound is more strongly bound to BiV04, whereas when the thermal treatment temperature is 600°C or lower, grain growth and reduction in specific surface area, which would otherwise be caused by sintering, are suppressed. In this case, the produced anti-viral composition exhibits more excellent antiviral property under light and in the dark.
[0044]
The time of the thermal treatment step is preferably 1 to 10 hours, more preferably 2 to 8 hours, still more
preferably 3 to 5 hours. When the thermal treatment time is 1 hour or longer, the divalent copper compound is strongly bound to BiVC , whereas when the thermal treatment time is 10 hours or shorter, grain growth and reduction in specific surface area, which would otherwise be caused by sintering, are suppressed. In this case, the produced anti-viral composition exhibits more excellent anti-viral property under light and in the dark. Notably, the thermal treatment is preferably performed in an oxygen-containing atmosphere such as air.
[0045]
[Second embodiment of the anti-viral composition production method of the present invention]
A second embodiment of the anti-viral composition production method of the present invention includes a mixing step of mixing BiVC and a divalent copper compound. The mixing step may be performed through dry mixing or wet mixing and may be performed through a widely known mixing technique. B1VO4 and the divalent copper compound employed in the second embodiment are the same as those described in relation to the anti-viral composition.
[0046]
In the case where BiV04 and the divalent copper compound are mixed through wet mixing, no particular limitation is imposed solvent employed in the mixing, so long as the solvent does not dissolve BiV04 or the divalent copper compound. Examples of the solvent employed in wet mixing include water, an alcohol, a ketone, and a mixture thereof. Examples of the alcohol include methanol, ethanol, 1- propanol, 2-propanol, 1-butanol, and a mixture thereof.
Examples of the ketone include acetone, acetylacetone, methyl ethyl ketone, and a mixture thereof.
[0047]
The anti-viral composition produced through the second embodiment of the production method of the present invention is a simple mixture of BiVCU and the divalent copper
compound, in which the divalent copper compound is not satisfactorily deposited on BiVC>4 . However, the anti-viral composition produced through the method also exhibits antiviral property under light and in the dark.
[0048]
The anti-viral composition produced through mixing BiV04 and the divalent copper compound may be further subjected to a thermal treatment. The thermal treatment is performed through, for example, the same procedure as employed in the aforementioned thermal treatment step.
[0049]
[Third embodiment of the anti-viral composition production method of the present invention]
A third embodiment of the anti-viral composition
production method of the present invention includes a mixing step of mixing BiVC with an aqueous solution of a divalent copper compound, to thereby form a mixture, a heating step of heating the mixture, and a separation step of separating an anti-viral composition from the heated mixture. The aqueous divalent copper compound solution has a divalent copper compound concentration of some g/100 mL to some tens og g/100 mL. No particular limitation is imposed on the separation technique employed in the separation step, and the anti-viral composition may be separated from the mixture through
filtration, sedimentation, centrifugation, evaporation to dryness, or the like. BiVC>4 and the divalent copper compound employed in the third embodiment are the same as those described in relation to the anti-viral composition.
[0050]
In one specific mode, the third embodiment of the production method of the present invention is carried out in the following manner. Specifically, an aqueous divalent copper compound solution is added to a specific container in such an amount that the copper content of the aqueous
divalent copper compound solution with respect to the mass of BiVC>4 to be added is adjusted to 0.01 to 20 parts by mass. Subsequently, BiV04 is added to the container and mixed with the aqueous divalent copper compound solution, to thereby suspend BiVC>4 in the aqueous copper compound solution, whereby a mixture is produced. The mixture is heated at about 50 to about 90°C, and then filtered, to thereby yield an anti-viral composition. Notably, the copper component concentration of the aqueous divalent copper compound
solution and the temperature of the mixture are not limited to the aforementioned values. If required, the anti-viral composition recovered through filtration is subjected to washing with water, drying, pulverization, classification, etc .
[0051]
The anti-viral composition isolated from the mixture through the separation step may be further subjected to a thermal treatment. The thermal treatment is performed through, for example, the same procedure as employed in the aforementioned thermal treatment step in the first
embodiment .
[0052]
[Anti-viral agent and photocatalyst]
The anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention. Thus, the anti-viral agent and
photocatalyst of the present invention exhibit excellent anti-viral property under light and in the dark.
[0053]
[Modes of use of anti-viral composition, anti-viral agent, and photocatalyst]
No particular limitation is imposed on the mode of use of the anti-viral composition, anti-viral agent, and
photocatalyst of the present invention (hereinafter these may be referred to as "the anti-viral composition or the like of the present invention"). In one mode thereof, the anti-viral composition or the like of the present invention may be used in a solid form, such as micropowder or granules. In this case, the anti-viral composition or the like of the present invention is directly charged into an appropriate container for use. In an alternative mode of use, the anti-viral composition or the like of the present invention may be incorporated into the surface and/or the inside of a
substrate. Generally, the latter mode is preferred. No particular limitation is imposed on the substrate, and examples of the substrate include a single-member substrate formed of a general material such as fiber, metal, ceramic material, glass, etc., and a composite substrate formed of two or more members.
[0054]
Alternatively, the anti-viral composition or the like of the present invention may be incorporated into a coating agent such as a floor polish, which is removable by
appropriate means. Yet alternatively, the anti-viral
composition or the like of the present invention is
immobilized on a membrane, to thereby realize a continuous membrane on which the anti-viral composition or the like of the present invention is exposed to the atmosphere. In a still alternative mode of use of the anti-viral composition or the like of the present invention, a thin film of the anti-viral composition or the like of the present invention is formed through sputtering on a BiV04 thin film formed on a glass by sputtering. In a further alternative mode of use thereof, the anti-viral composition or the like of the present invention may be dispersed in a solvent, to thereby provide a paint material.
[0055]
Examples of the material for immobilizing the antiviral composition or the like of the present invention immobilized on the substrate include a material for
immobilizing anti-viral composition or the like of the present invention by generally employed immobilizing means such as means by using a binder. Either an organic binder or an inorganic binder may be used for immobilizing the antiviral composition or the like of the present invention. Of these, an inorganic binder is preferably used, for the purpose of preventing decomposition of the binder induced by a photocatalytic substance. No particular limitation is imposed on the type of the binder. Examples of the inorganic binder include a silica-based binder, which is generally used for immobilizing a photocatalytic substance onto a substrate. Examples of the organic binder include a polymer binder, which can form thin film through polymerization or
vaporization of solvent.
[0056]
One example of a material containing the anti-viral composition or the like of the present invention for
producing the substrate containing the material is a material produced by dispersing the anti-viral composition or the like of the present invention in a resin, to thereby form a dispersion, and hardening the dispersion. Either natural resin or synthetic . resin may be used for dispersing the antiviral composition or the like of the present invention. No particular limitation is imposed on the type of resin, and examples of the synthetic resin include acrylic resin, phenolic resin, polyurethane resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polyester resin, and epoxy resin.
[0057] No particular limitation is imposed on the place where the anti-viral composition or the like of the present
invention is employed, and it may be used in the presence of any light beam or in the dark. The anti-viral composition or the like of the present invention, which exhibits high virus- inactivating performance in the presence of water (e.g., water or sea water), under dry conditions (e.g., low-humidity conditions in, for example, winter) , under high humidity conditions, or in the co-presence of organic substance, can continuously inactivate viruses. The anti-viral composition or the like of the present invention may be applied to any object such as a wall, floor, or ceiling; buildings such as hospitals and factories; machine tools and measuring
apparatuses; inside and parts of electric appliances (inside of a refrigerator, a clothes washer, a dish washer, etc., and a filter of an air purifier) . Non-limitative examples of preferred dark places include the inside of a machine, a storage compartment of a refrigerator, and a hospital
facility (e.g., waiting room or surgical operation room), which is dark at night or when in a stand-by state.
[0058]
There has been proposed a device having a BiV04-coated ceramic or non-woven fabric filter employed in an air
purifier, in combination with a light source for UV
radiation, as one countermeasure against influenza. When the anti-viral composition or the like of the present invention is applied to such a filter of an air purifier, a UV light source may be omitted, thereby enhancing safety of the air purifier without elevating cost thereof.
[0059]
[Virus inactivation method]
The present invention provides a virus inactivation method for inactivating a virus by use of the anti-viral composition, the anti-viral agent or photocatalyst of the present invention. As described above, by virtue of antiviral property, the anti-viral composition of the present invention can inactivate a target virus. Also, since the anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention, the anti-viral agent or photocatalyst of the present invention can inactivate a target virus. The antiviral composition, anti-viral agent, and photocatalyst of the present invention preferably exhibit a virus inactivation performance of 99.0% or higher, more preferably 99.9% or higher, after irradiation with visible light at an
illuminance of 800 lx for 3 minutes. The virus inactivation performance can be calculated by the formula, LOG(N/No). In the formula, No represents a phage concentration before visible light irradiation, and N represents a phage
concentration after visible light irradiation. The virus inactivation performance will be described in detail in the below-described Examples.
Examples
[0060] The present invention will next be described in detail by way of examples, which should not be construed as limiting the invention thereto.
[0061]
In the below-described Examples 1 to 4 and Comparative Examples 1 to 6, the following BiVC material was used.
[0062]
<BiV04 material>
NH4VO3 (99.0%) was dissolved in 2-mol/L nitric acid, and Bi (N03) 3-5H20 (product of Kanto Chemical Co., Inc., 99.9%) was dissolved in water, to thereby form a 0.12-mol/L aqueous solution thereof. These aqueous solutions (100 mL) were mixed together, and 3 g of urea was dissolved in the mixed solution. The resultant solution was heated at 90°C by a hot stirrer and maintained for 24 hours. The thus-formed
suspension was filtered, and the recovered solid was dried, to thereby yield a BiVCU powder. The crystal structure of the thus-dried BiV04 powder was determined by means of a powder X-ray diffractometer (X'pertPRO, product of
PANalytical ) . The measurement was performed with a copper target for generating the Cu-Kal line under conditions including a tube voltage of 45 kV, a tube current of 40 mA, a measurement range 2Θ = 20 to 100°, a sampling width of
0.0167°, and a scanning speed of 3.3°/min. The X-ray analysis has revealed that the BiV04 material assumes a BiV04 single phase.
[0063] Next, the production procedures of Examples 1 to 4 and Comparative Examples 1 to 7 will be described.
[0064]
<Example 1>
6 g of BiVC was suspended in 100 mL of distilled water, to thereby form a suspension. To the suspension, 0.0805 g (0.5 parts by mass of copper with respect to 100 parts by mass of BiV04) of CuCl2-2H20 (product of Kanto Chemical Co., Inc.) was added, and the mixture was stirred for 10 minutes. The pH of the suspension was adjusted to 10 by adding 1-mol/L aqueous sodium hydroxide (product of Kanto Chemical Co., Inc.) thereto, and the suspension was stirred for 30 minutes. The resultant suspension was filtered, and the recovered powder was washed with pure water, dried at 80°C, and crushed by means of a mixer, to thereby yield an anti-viral
composition of Example 1.
[0065]
<Example 2>
The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl2-2H20, 0.1179 g (0.5 parts by mass of copper with respect to 100 parts by mass of BiVC ) of
CuS04-5H20 (product of Kanto Chemical Co., Inc.) was added to the suspension, to thereby yield an anti-viral composition of Example 2.
[0066]
<Example 3>
The procedure of Example 1 was repeated, except that the amount of CuC±2-2H20 added to the suspension was changed from 0.0805 g to 0.1610 g (1 part by mass of copper with respect to 100 parts by mass of BiVOi) , to thereby yield an anti-viral composition of Example 3.
[0067]
<Example 4>
The procedure of Example 1 was repeated, except that the amount of CuCl2-2H20 added to the suspension was changed from 0.0805 g to 0.4829 g (3 part by mass of copper with respect to 100 parts by mass of BIVC ), to thereby yield an anti-viral composition of Example 4.
[0068]
<Comparative Example 1>
A BIVC material was used as the composition of
Comparative Example 1.
[0069]
<Comparative Example 2>
5 g (100 parts by mass) of BiVC>4 material and 0.025 g
(0.5 parts by mass) of copper (product of Kanto Chemical Co., Inc., powder form, <45 μιτι, 325 mesh) were placed in an agate mortar and mixed with crushing for 30 minutes, to thereby yield a composition of Comparative Example 2.
[0070]
<Comparative Example 3>
The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl2-2H20, 0.0625 g (0.5 parts by mass of zinc with respect to 100 parts by mass of B1VO4) of ZnCl2 (product of Kanto Chemical Co., Inc.) was added to the suspension, to thereby yield a composition of Comparative Example 3.
[0071]
<Comparative Example 4>
The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl2-2H20, 0.1452 g (0.5 parts by mass of iron with respect to 100 parts by mass of BiV04) of
FeCl3-6H20 (product of Kanto Chemical Co., Inc.) was added to the suspension, to thereby yield a composition of Comparative Example 4.
[0072]
<Comparative Example 5>
The procedure of Example 1 was repeated, except that, instead of 0.0805 g of CuCl2-2H20, 0.1215 g (0.5 parts by mass of iron with respect to 100 parts by mass of BiVO-j) of
NiCl2-6H20 (product of Kanto Chemical Co., Inc.) was added to the suspension, to thereby yield a composition of Comparative Example 5.
[0073]
<Comparative Example 6>
The procedure of Example 1 was repeated, except that BiV0 was changed to rutile-type titanium oxide Fl-R (product of SHOWA TITANIUM CO., LTD), to thereby yield a composition of Comparative Example 6.
[0074]
<Comparative Example 7> 3 g of CuC±2-2H20 (product of Kanto Chemical Co., Inc.) was suspended in 100 mL of distilled water, and the mixture was stirred for 10 minutes. The pH of the suspension was adjusted to 10 by adding 1-mol/L aqueous sodium hydroxide (product of Kanto Chemical Co., Inc.) thereto, and the suspension was stirred for 30 minutes, to thereby prepare a mixture. The mixture was filtered, and the recovered powder was washed with pure water, dried at 80°C, and crushed by means of a mixer, to thereby yield a composition of
Comparative Example 7 assuming a Cu2(OH)3Cl single phase.
[0075]
<Measurements>
The thus-produced compositions of Examples 1 to 4 and Comparative Examples 1 to 7 were subjected to the following measurements .
[0076]
(ICP emission spectroscopic analysis)
The copper ion content and the like of each of the compositions of Examples 1 to 4 and Comparative Examples 3 to 5 were determined through the ICP emission spectroscopic analysis. Specifically, each of the compositions of Examples 1 to 4 and Comparative Examples 3 to 5 was heated in a hydrofluoric acid solution until the composition was
completely dissolved, to thereby prepare a solution. A sample was extracted from the solution and analyzed by means of an ICP emission spectroscopic analyzer (product of
Shimadzu Corporation, model: ICPS-7500), to thereby determine copper ion content and the like.
[0077]
(Evaluation of anti-viral performance under irradiation with visible light: determination of LOG(N/No))
The anti-viral performance of the compositions of the Examples 1 to 4 and the Comparative Examples 1 to 7 was assessed through the following model experiment employing bacteriophage. Notably, assessment of anti-viral performance with respect to inactivation performance with respect to bacteriophage is disclosed in, for example, Appl . Microbiol. Biotechnol., 79, pp. 127-133, (2008). The document discloses that the bacteriophage inactivation performance is known as a reliable model for the assessment. The measurement is based on JIS R 1706.
[0078]
A piece of filter paper was placed on the bottom of a deep Petri dish, and a small amount of sterilized water was added to the Petri dish. A glass base plate having a
thickness of about 5 mm was placed on the filter paper piece. On the glass base plate, there was placed a glass plate (50 mm x 50 mm x 1 mm) onto which each of the samples of the Examples and the Comparative Examples in an amount of 0.25 mg had been applied. 100 μΐ, of QPphage (NBRC20012) suspension whose bacteriophage infection value had been adjusted to about 6.7 x 106 to about 2.6 x 107 pfu/mL by use of 1/500 NB was added dropwise to the glass plate. In order to bring the sample surface into contact with the phage, the glass plate was covered with a film made of PET (polyethylene terephthalate ) . A glass lid was put on the deep Petri dish, to thereby provide a measurement unit. Regarding each sample, a plurality of measurement units were provided.
[0079]
Also, a 15W white fluorescent lamp (Full white
fluorescent lamp, FL15N, product of Panasonic Corporation) equipped with a UV-cutting filter (N-113, product of Nitto Jushi Kogyo Co., Ltd.) was employed as a light source. The aforementioned measurement units were placed under the light source at a position where the illuminance (measured by means of an illuminometer : TOPCON IM-5) was 800 lx. After the elapse of 3 minutes, 10 minutes, and 60 minutes from the start of light irradiation, the phage concentration of each sample present on the glass plate was measured. During the measurement, the illuminance in the room was adjusted to 200 lx or lower. The elapse of time after the start of light irradiation was measured by means of a commercial stopwatch.
[0080]
Phage concentration was determined through the
following procedure. Specifically, the sample present on the glass plate was immersed in 9.9 mL of a phage recovery liquid (SCDLP medium) , and the liquid was shaken by means of a shaker for 10 minutes. The phage-recovered liquid was appropriately diluted with physiological saline containing peptone. 1 mL of each dilution was mixed with a separately prepared E. coli (NBRC 106373) culture liquid having a concentration of 5.0 x 108 to 2.0 x 109 cells/mL) and a calcium-added LB soft agar medium under stirring.
Thereafter, the mixture was inoculated to a calcium-added LB agar medium and cultured at 37°C for 15 hours. The number of plaques of the phage was visually counted. The phage concentration N was derived through multiplication of the count by the dilution factor of the phage recovered liquid.
[0081]
From the initial phage concentration No and phage concentrations N after the elapse of a predetermined time, the relative phage concentration (LOG (N/No) ) was determined. Notably, the smaller the LOG(N/No) (i.e., the larger the absolute value of the minus value) , the stronger the antiviral property.
[0082]
(Evaluation of anti-viral performance in the dark:
determination of LOG(N/No))
The above procedure ("Evaluation of anti-viral
performance under light: determination of LOG(N/No)") was repeated, except that measurement units were placed in the dark without irradiation with light from the light source. Notably, the smaller the LOG(N/No) (i.e., the larger the absolute value of the minus value) , the stronger the antiviral property.
[0083]
<Results>
(ICP emission spectroscopic analysis) The composition of Example 1 was found to have a copper ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. The composition of Example 2 was found to have a copper ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC . The composition of Example 3 was found to have a copper ion content of 1 part by mass with respect to 100 parts by mass of BiV04. The composition of Example 4 was found to have a copper ion content of 3 parts by mass with respect to 100 parts by mass of BIVC . Thus, in Examples 1 to 4, the entire amount of supplied copper ions
(originating from CuCl2-2H20) was found to be supported on the surface of BIVC .
[0084]
The composition of Comparative Example 3 was found to have a zinc ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied zinc ions was found to be supported on the surface of B1VO4. The composition of Comparative Example 4 was found to have an iron ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied iron ions was found to be supported on the surface of BiV04. The composition of Comparative Example 5 was found to have a nickel ion content of 0.5 parts by mass with respect to 100 parts by mass of BiVC>4. Thus, the entire amount of supplied nickel ions was found to be supported on the surface of BiVC>4.
[0085] (Evaluation of anti-viral performance under irradiation with visible light: determination of LOG(N/No) )
Table 1 shows the results.
[Table 1]
Table 1 Evaluation of anti-viral performance under light
Figure imgf000042_0001
[0086]
(Evaluation of. anti-viral performance in the dark:
determination of LOG(N/No) )
Table 2 shows the results.
[Table 2]
Table 2 Evaluation of anti-viral performance in the
Figure imgf000043_0001
[0087]
Through comparison the results of Examples 1 to 4 with, those of Comparative Examples 1 to 7, the compositions of Examples 1 to 4 were found to exhibit excellent anti-viral performance under light and in the dark. Particularly, under light, the compositions of Examples 1 to 4 were found to inactivate about 99.9% of phages through irradiation with light for a period as short as 3 minutes. The performance can be attained very quickly, as compared with a conventional photocatalyst . In particular, the compositions of Examples 2 to 4 were found to exhibit a virus inactivating performance of 99.9% or higher through irradiation with visible light 800 lx for 3 minutes.

Claims

Claims
1. An anti-viral composition comprising B1VO4 and a divalent copper compound.
2. An anti-viral composition according to claim 1, wherein the divalent copper compound has a copper element content by mass of 0.01 to 20 parts by mass with respect to 100 parts by mass of BIVC .
3. An anti-viral composition according to claim 1 or 2, wherein the divalent copper compound is composed of one or more species selected from. the group consisting of (a) a hydroxide-group-containing divalent copper compound
represented by the following formula (1):
Cu2(OH)3X (1)
(wherein X represents an anion) , (b) a divalent copper halide, (c) a divalent copper inorganic acid salt, (d) a divalent copper organic acid salt, (e) cupric oxide, (f) copper sulfide, (g) copper (II) azide, and (h) copper
silicate.
4. An anti-viral composition according to claim 3, wherein X in formula (1) is a species selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of an inorganic acid, and OH.
5. An anti-viral composition according to claim 3, wherein the divalent copper halide (b) is composed of one or more species selected from the group consisting of copper chloride, copper fluoride, and copper bromide.
6. An anti-viral composition according to claim 3, wherein the divalent copper inorganic acid salt (c) is composed of one or more species selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate , copper ammonium chloride, copper pyrophosphate, and copper carbonate.
7. An anti-viral composition according to claim 3, wherein the divalent copper organic acid salt (d) is a divalent copper carboxylic acid salt.
8. An anti-viral composition according to claim 3 or 4, wherein the divalent copper compound is a hydroxide-group- containing divalent copper compound represented by formula (1) ·
9. An anti-viral composition according to any one of claims 3 to 8, wherein X is one species selected from the groups consisting of CI, CH3COO, NO3, and (S04)i/2.
10. An anti-viral composition according to any one of claims 1 to 9, which has a virus inactivating performance of 99.9% or higher after irradiation with visible light at 800 lx for 3 minutes.
11. An anti-viral agent containing an anti-viral composition as recited in any one of claims 1 to 10.
12. A photocatalyst containing an anti-viral
composition as recited in any one of claims 1 to 10.
13. A method for producing an anti-viral composition, the method comprising: a mixing step of mixing BiVC , a divalent copper
compound or a divalent copper compound raw material, water, and an alkaline substance, to thereby form a mixture; and a separation step of separating an anti-viral composition from the mixture .
14. An anti-viral composition production method
according to claim 13, which further includes a thermal treatment step of subjecting to a thermal treatment the antiviral composition separated by the separation step.
15. An anti-viral composition production method
according to claim 13 or 14, wherein, in the mixing step, the pH of the mixture is adjusted to 8 to 12.
16. An anti-viral composition production method as described in any one of claims 13 to 15, wherein the divalent copper compound raw material includes at least one divalent copper compound represented by the following formula (2):
CuX2 (2)
(wherein X represents an anion) .
17. An anti-viral composition production method
according to any one of claims 13 to 16, wherein in the mixing step, the percent ratio of the mass of BiVC to the total mass of BiVC>4 , the divalent copper compound or the divalent copper compound raw material, water, and the
alkaline substance is 3 to 25 mass%.
18. An anti-viral composition production method
according to any one of claims 13 to 17, wherein, in the mixing step, BiVCU and the divalent copper compound or the divalent copper compound raw material are mixed in water with stirring, and then the alkaline substance is added to the mixture .
19. A virus inactivation method comprising inactivating a virus by use of an anti-viral composition as recited in any one of claims 1 to 10, an anti-viral agent as recited in claim 11, or a photocatalyst as recited in claim 12.
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