Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof

Definitions

• the present invention relates to an antiviral composition containing photocatalyst particles and silver nanoparticles as active ingredients, and a member having the composition on its surface.
• the present invention relates to a highly transparent antiviral composition whose antiviral properties are further improved by doing so, and a member having the composition on its surface.
• composition having antiviral properties can be formed on the surfaces of various members, it will be possible to apply it to a wide range of areas, so there is a need for a technology that imparts antiviral properties to members.
• the object to be imparted with antiviral properties is a member that requires visibility, such as an operation touch panel, or a member with design, it is desirable that the antiviral composition formed on its surface has excellent transparency. .
• Patent Document 1 It is known that copper monoxide compounds such as cuprous oxide have antiviral properties (Patent Document 1).
• monovalent copper is easily oxidized to divalent copper by air or water, and there is a problem in that the high antiviral properties of monovalent copper cannot be maintained.
• Patent Document 2 discloses an antibacterial agent that utilizes the antibacterial effect of silver ions.
• Patent Document 1 discloses an antibacterial agent that utilizes the antibacterial effect of silver ions.
• Non-Patent Document 2 discloses an antibacterial agent that utilizes the antibacterial effect of silver ions.
• Non-Patent Document 2 discloses an antibacterial agent that utilizes the antibacterial effect of silver ions.
• silver is said to have low antiviral properties against non-enveloped viruses.
• Patent Document 3 reports the antiviral properties of silver particles against influenza viruses. However, there is no mention of antiviral properties against non-enveloped viruses, nor is there any mention of the effect of light irradiation.
• Patent Document 4 reports that metal particles containing silver particles and platinum particles exhibit antiviral properties against non-enveloped viruses. However, it is stated that silver particles alone cannot inactivate viruses such as adenovirus. Further, Patent Document 4 evaluates the antiviral properties of an antiviral agent dispersion, but does not mention imparting antiviral properties to members.
• Patent Document 5 The antiviral properties of molybdenum oxide and zinc oxide have been reported (Patent Document 5, Patent Document 6).
• Patent Document 6 The antiviral properties of molybdenum oxide and zinc oxide have been reported (Patent Document 5, Patent Document 6).
• these metal oxides tend to aggregate, making it difficult to obtain a composition with the transparency required for practical use.
• Photocatalytic materials are widely effective in cleaning the surface of substrates, such as antibacterial, antifungal, antiviral, and deodorizing properties, through photocatalytic reactions that occur when exposed to light such as sunlight or artificial lighting. It is attracting attention.
• a photocatalytic reaction is a reaction caused by excited electrons and holes generated when a photocatalyst, typically titanium oxide, absorbs light. Excited electrons and holes generated on the titanium oxide surface by the photocatalytic reaction undergo a redox reaction with oxygen and water adsorbed on the titanium oxide surface to generate active species. Since microorganisms, viruses, odors, and dirt made of organic substances are decomposed by these active species, it is thought that the above-mentioned effect of cleaning the substrate surface can be obtained.
• the photocatalytic reaction caused by titanium oxide which is a typical photocatalyst, is caused by irradiation with light in the ultraviolet region (wavelength 10 to 420 nm), so it should not be used in a dark place where there is no natural light or artificial lighting or with wavelengths below 420 nm. In principle, this effect cannot be obtained under white LED lighting or fluorescent lighting, which contains almost no light. Furthermore, research is underway to make titanium oxide responsive to visible light and to use tungsten oxide, which has a wide usable light wavelength range, but irradiation with light is essential for the generation of excited electrons.
• Patent Documents 7 and 8 disclose adding an antiviral agent such as a silver compound or a copper compound to a photocatalyst to obtain antiviral properties in the dark.
• photocatalysts are used by dispersing photocatalyst particles in a solvent, mixing film-forming components to form a paint, and applying it to a substrate.
• metal components such as silver, copper, and zinc Addition of , often caused practical problems.
• metals such as silver, copper, zinc, etc. or their compounds by reacting metal raw materials with photocatalyst particle powder, a great deal of effort is required to disperse the metals into a solvent afterwards.
• the present invention provides an antivirus that has a photocatalytic function and exhibits high antiviral properties against non-enveloped viruses that have been difficult to inactivate with silver compounds in a dark place without sunlight.
• An object of the present invention is to provide a sexual composition and a member having the composition on its surface.
• the present invention provides the following antiviral composition and a member having the composition on its surface.
• [1] Containing two types of particles: i) photocatalyst particles and ii) silver nanoparticles with a dispersed particle size of 1000 nm or less and a primary particle size of 500 nm or less, on which a protective agent is adsorbed,
• An antiviral composition having an antiviral activity value higher than 0.3 in the dark based on JISR1756:2020, and whose antiviral activity value further improves by 0.3 or more upon irradiation with light.
• the antiviral composition according to [1] further comprising a binder.
• an antiviral composition that exhibits high antiviral properties in the dark and has the characteristics that the antiviral properties are further improved by light irradiation.
• the antiviral composition of the present invention which exhibits high antiviral properties in the dark and whose antiviral properties are further improved by light irradiation, will be described in detail below.
• antiviral property is used to include the meaning of inactivating a virus (reducing the infectivity of the virus or inactivating it). Antiviral properties were measured using the "antiviral activity value" calculated in accordance with JIS R1756:2020 "Fine ceramics - Antiviral test method for visible light responsive photocatalytic materials - Method using bacteriophage Q ⁇ " Evaluation was made using the criteria described in the example. Viruses are broadly classified into viruses with an envelope (lipid double membrane) and viruses without an envelope, based on their structure, and bacteriophage Q ⁇ is a virus without an envelope. In general, non-enveloped viruses are said to have higher resistance to disinfectants, etc. than enveloped viruses, and test methods are well established and have high accuracy and reproducibility. Bacteriophage Q ⁇ was used to evaluate virality.
• the virus for which the antiviral composition of the present invention exhibits antiviral properties may be enveloped or not.
• Enveloped viruses include bacteriophage ⁇ 6, human influenza virus, avian influenza virus, rubella virus, herpes simplex virus, AIDS virus, dengue virus, Mimi virus, rabies virus, Ebola virus, Lassa virus, Empox virus, and SARS coronavirus. , MERS coronavirus, Ebola virus, Fucerovirus, West Nile virus, Zika virus, etc.
• non-enveloped viruses examples include bacteriophage Q ⁇ , adenovirus, norovirus, feline calicivirus, rotavirus, sapovirus, poliovirus, astrovirus, enterovirus, human papillomavirus, hepatitis E virus, tobacco mosaic virus, and the like.
• the antiviral composition of the present invention contains two types of particles: i) photocatalyst particles and ii) silver nanoparticles with a dispersed particle size of 1000 nm or less and a primary particle size of 500 nm or less, on the surface of which a protective agent is adsorbed. It is something.
• the photocatalyst particles contained in the antiviral composition of the present invention include titanium oxide-based, tungsten oxide-based, zinc oxide-based, and niobium oxide-based particles that are currently on the market, as well as metal oxides that are n-type semiconductors. Crystal fine particles can be used.
• anatase type titanium dioxide ( TiO2 ), rutile type titanium dioxide ( TiO2 ), tungsten trioxide ( WO3 ), zinc oxide (ZnO), Ga-doped zinc oxide (GZO), niobium oxide ( Nb2O ). 5 ) etc. can be used.
• anatase-type titanium dioxide TiO 2
• rutile-type titanium dioxide TiO 2
• tungsten trioxide WO 3
• materials with high visible light activity such as rutile-type titanium oxide supporting platinum, rutile-type titanium oxide supporting iron, rutile-type titanium oxide supporting copper, and copper hydroxide.
• rutile-type titanium oxide gold-supported anatase-type titanium oxide, and platinum-supported tungsten trioxide.
• the photocatalyst particles preferably have a fine primary particle diameter, that is, 500 nm or less, more preferably 1 to 100 nm, and even more preferably 1 to 50 nm. used for. If the primary particle size is larger than 100 nm, the transparency of the composition may decrease, or the dispersion stability in the dispersion liquid may decrease when formed into a dispersion liquid.
• the term "primary particle diameter” refers to the diameter of particles obtained from multiple particle images taken using a transmission electron microscope (for example, H-9500 manufactured by Hitachi High-Technologies, Ltd.), unless otherwise specified. It refers to the arithmetic mean value of the projected area circle equivalent diameter (Heywood diameter) of about 1000 randomly selected particles that do not overlap with each other.
• the silver nanoparticles contained in the antiviral composition of the present invention contain at least silver, and may contain other components.
• Components other than silver include, but are not limited to, copper, zinc, platinum, palladium, nickel, aluminum, titanium, cobalt, zirconium, molybdenum, tungsten, gold, antimony, tin, sodium, magnesium, silicon, phosphorus, and sulfur.
• potassium calcium, scandium, vanadium, chromium, manganese, iron, gallium, germanium, arsenic, selenium, yttrium, niobium, ruthenium, rhodium, indium, tellurium, barium, hafnium, tantalum, rhenium, osmium, iridium, mercury, thallium , lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, thorium, etc., or a mixture or alloy of two or more thereof.
• metal components other than silver are preferable, and iron, palladium, gold, platinum, copper, zinc, tin, molybdenum, titanium, and tungsten are more preferable.
• the content is preferably 0.01 to 49% by mass, and 0.1 to 40% by mass based on the mass of the metal component in the silver nanoparticles. % is more preferable, and 1 to 30% by mass is even more preferable. This is because if the content of metal components other than silver exceeds 50% by mass with respect to the mass of the metal components in the silver nanoparticles, antiviral properties may not be sufficiently exhibited. Further, when the content of metal components other than silver is less than 0.01% by mass, it hardly affects the properties of silver nanoparticles such as antiviral properties and dispersion stability.
• the silver nanoparticles contained in the antiviral composition of the present invention have a protective agent adsorbed on their surfaces.
• the term "protective agent” refers to surfactants that have the property of gathering at the interface between two phases, and low-molecular metal ligands that interact strongly with metal particles, such as alkylthiols, amine groups, silane groups, and phosphine groups. This refers to compounds with a large number of adsorption segments and polymers that easily adsorb to the particle surface. When these substances adsorb and coordinate on the surface of silver nanoparticles, electrostatic repulsion and steric repulsion occur between silver nanoparticles.
• the protective agent include surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, Water-soluble polymer compounds such as polyacrylic acid and methylcellulose; Amino acids such as cysteine, arginine, asparagine, and aspartic acid; Aliphatic amine compounds such as ethanolamine, diethanolamine, triethanolamine, and propanolamine; Tannic acid, gallocatechin, and gallic acid , pyrogallol, 4-benzylpyrogallol (2,3,4-trihydroxydiphenylmethane), ellagitannin and other polyphenols; butylamine, dibutylamine, hexylamine, cyclohexylamine, hepty
• surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric sur
• the protective agent may be one type of the above-mentioned compound or a combination of two or more types.
• the protective agent adsorbed on the surface of the silver nanoparticles preferably has a mass ratio of 0.001 to 10, more preferably 0.005 to 5, relative to the metal component in the silver nanoparticles. More preferably, the range is from 0.01 to 1.
• the dispersed particle diameter of the silver nanoparticles is such that the number-based 50% cumulative distribution diameter (D50) measured by a dynamic light scattering method using laser light is 1000 nm or less, preferably 1 to 1000 nm, and 1. It is more preferably 200 nm, and even more preferably 1 to 70 nm. Regarding the lower limit of the dispersed particle size, theoretically it is possible to use the smallest particle size that can have antiviral properties, but in practice it is preferably 1 nm or more. Further, if the dispersed particle diameter exceeds 1000 nm, it is not preferable because when an antiviral composition is prepared, not only the haze value may deteriorate but also the antiviral property may decrease.
• D50 cumulative distribution diameter measured by a dynamic light scattering method using laser light
• Examples of devices for measuring the dispersed particle size include ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.), Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and LA-910 (manufactured by Horiba Ltd.). etc. can be used.
• the primary particle diameter of the silver nanoparticles is 500 nm or less, preferably from 1 to 500 nm, more preferably from 1 to 100 nm, even more preferably from 1 to 50 nm.
• the lower limit of the primary particle diameter theoretically it is possible to use the smallest particle diameter that can have antiviral properties, but in practice it is preferably 1 nm or more.
• the primary particle diameter exceeds 500 nm, it is not preferable because when an antiviral composition is prepared, not only the haze value may deteriorate but also the antiviral property may decrease.
• the quantity ratio of photocatalyst particles to silver nanoparticles in the antiviral composition is preferably 1:0.0001 to 1:0.1, and 1:0.0005 to 1:0.05 on a mass basis. It is more preferable.
• the antiviral composition may also contain additives such as a binder and a surfactant within a range that does not impair the effects of the present invention.
• the antiviral composition of the present invention may further include a binder.
• a binder By containing a binder, the antiviral composition of the present invention further improves the antiviral effect caused by light irradiation.
• the binder include metal compound binders containing silicon, aluminum, titanium, zirconium, etc., and organic resin binders containing fluorine resins, acrylic resins, urethane resins, etc. Among these, in order to obtain an excellent composition with high antiviral properties, it is preferable to use a silicon compound binder.
• a silicon compound-based binder is a colloidal dispersion, solution, or emulsion of a silicon compound containing a solid or liquid silicon compound in an aqueous dispersion medium, and specifically includes colloidal silica (preferably particles). 1 to 150 nm in diameter); silicate solutions such as silicates; silane, siloxane hydrolyzate emulsions; silicone resin emulsions; silicone resins such as silicone-acrylic resin copolymers, silicone-urethane resin copolymers, etc. and other resins Examples include emulsions of copolymers of.
• the content of photocatalyst particles in the antiviral composition is preferably 20 to 99.99% by mass, more preferably 30 to 99.95% by mass. Further, the content of silver nanoparticles in the antiviral composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass. Further, the content of the binder in the antiviral composition is preferably 0 to 79.99% by mass, more preferably 10 to 69.99% by mass. Furthermore, the antiviral composition may contain additives such as surfactants in addition to the photocatalyst particles, silver nanoparticles, and binder, as long as the effects of the present invention are not impaired.
• One embodiment of the antiviral composition of the present invention also includes an antiviral composition (dispersion) further containing an aqueous dispersion medium.
• an aqueous dispersion medium an aqueous solvent is usually used, and it is preferable to use water, a water-soluble organic solvent that is miscible with water, or a mixed solvent of water and a water-soluble organic solvent.
• water for example, deionized water, distilled water, pure water, etc. are preferable.
• water-soluble organic solvents examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, polyethylene glycol, and ethylene glycol monomethyl.
• Glycol ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether, acetone, ketones such as methyl ethyl ketone, 2-pyrrolidone , water-soluble nitrogen-containing compounds such as N-methylpyrrolidone, ethyl acetate, etc., and these may be used alone or in combination of two or more.
• the concentration of silver nanoparticles in the dispersion is not particularly limited, but generally the thinner the concentration, the better the dispersion stability, so the silver component is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass. , more preferably 0.001 to 1% by mass. It is preferable that the concentration of silver nanoparticles is 0.0001% by mass or more because antiviral properties are exhibited in the dark.
• the concentration of photocatalyst particles in the dispersion liquid is not particularly limited, but generally the thinner the concentration, the better the dispersion stability, so the photocatalyst component is preferably 0.0001 to 80% by mass, more preferably 0.001 to 50% by mass, More preferably, it is 0.01 to 20% by mass. It is preferable that the concentration of the photocatalyst particles is 0.0001% by mass or more because the virus inactivation effect by the photocatalyst particles can be obtained.
• the concentration of the binder in the dispersion is not particularly limited, but generally the lower the concentration, the better the dispersion stability, so it is preferably 0.0001 to 90% by mass, more preferably 0.001 to 50% by mass, and even more preferably 0. .01 to 20% by mass. It is preferable that the concentration of the binder is 0.0001% by mass or more because the effect of light irradiation is further improved and it becomes easier to apply to the surfaces of various members.
• the antiviral composition of the present invention exhibits high antiviral properties in the dark and has the characteristics that the antiviral properties are further improved by light irradiation. It is characterized by having an activity value of greater than 0.3, and an antiviral activity value of 0.3 or greater when irradiated with light as specified in JIS R1756:2020.
• the antiviral composition containing a binder has a large effect of improving the antiviral activity value by light irradiation, and the antiviral activity value by light irradiation specified in JIS R1756:2020 is preferably 0.5 or more, more preferably 1. It improves by .0 or more, more preferably by 1.5 or more.
• the light that improves antiviral properties may include light with a wavelength that is absorbed by photocatalyst particles and silver nanoparticles, and the wavelength is 200 to 800 nm, more preferably 300 to 700 nm. If the wavelength is less than 200 nm, the light itself may exhibit antiviral properties, which is not practical, and if it exceeds 800 nm, it may be difficult to improve the antiviral properties by light irradiation, which is not preferred.
• the light source may be anything that includes light of these wavelengths, such as fluorescent lamps, LEDs, incandescent lamps, low-pressure sodium lamps, high-pressure sodium lamps, metal halide lamps, mercury lamps, xenon lamps, organic EL lamps, krypton lamps, and halogen lamps.
• the light irradiation intensity is 5 to 500,000 lx, more preferably 10 to 200,000 lx. If it is less than 5 lx, the effect of light irradiation may not be confirmed, and conditions exceeding 500,000 lx are difficult to imagine in a real environment.
• a device for measuring illuminance for example, LX-105 (manufactured by Custom Co., Ltd.), CHF-LT1 (manufactured by Sanwa Supply Co., Ltd.), T-10A (manufactured by Konica Minolta Japan Co., Ltd.), etc. may be used. I can do it.
• the irradiation time is preferably about 1 minute to 48 hours.
• the method for producing the antiviral composition, particularly the dispersion, of the present invention includes, for example, the following steps (1) to (6).
• (2) Producing a solution containing a raw material silver compound and a solution in which a reducing agent and a protective agent are dissolved in an aqueous dispersion medium
• Step (3) Step (4) Step (3) of mixing the solution containing the raw material silver compound produced in step (2) above with a solution containing a reducing agent and a protective agent to produce a silver nanoparticle dispersion.
• photocatalyst particles are dispersed in an aqueous dispersion medium to produce a photocatalyst particle dispersion.
• photocatalyst particles titanium oxide-based, tungsten oxide-based, zinc oxide-based, niobium oxide-based particles, etc., as well as crystal fine particles of metal oxides that are n-type semiconductors, etc. can be used.
• the various photocatalyst particles described above can be used.
• the photocatalyst particles may be used alone or in combination of two or more.
• Methods for producing photocatalyst particles are not particularly limited, but include gas phase methods (CVD method, PVD method, etc.), liquid phase methods (hydrothermal method, sol-gel method, etc.), solid phase methods (high temperature calcination method, etc.). etc.), and the photocatalyst particles may be reduced in size or classified using a crusher or a classifier.
• a mixed solvent of water and a hydrophilic organic solvent that can be mixed with water in any proportion may also be used.
• water for example, purified water such as filtered water, deionized water, distilled water, pure water, etc. is preferable.
• hydrophilic organic solvents include alcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol-n-propyl ether.
• the proportion of the hydrophilic organic solvent in the mixed solvent is preferably more than 0% by mass and 50% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. It is.
• the method of dispersing photocatalyst particles in an aqueous dispersion medium is not particularly limited, and may be a method of stirring with a stirrer or a method of dispersing with an ultrasonic disperser.
• the temperature during mixing is 20 to 100°C, preferably 20 to 80°C, more preferably 20 to 40°C, and the time is preferably 1 minute to 3 hours.
• the concentration of the photocatalyst in the photocatalyst particle dispersion is not particularly limited, but generally the lower the concentration, the better the dispersion stability, so it is preferably 0.0001 to 80% by mass, more preferably 0.001 to 50% by mass.
• the obtained photocatalyst particle dispersion may contain a basic substance or an acidic substance for pH adjustment etc.
• Basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate. , alkali metal carbonates such as potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal alkoxides such as tert-butoxypotassium, sodium methoxide, sodium ethoxide; aliphatic carbons such as butyl lithium.
• the acidic substance examples include inorganic acids such as aqua regia, hydrochloric acid, nitric acid, and sulfuric acid; organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, and trichloroacetic acid. Further, ion exchange treatment or filtration cleaning treatment may be performed to adjust the ionic component concentration, or solvent replacement treatment may be performed to change the solvent component.
• the pH of the photocatalyst particle dispersion is preferably 3 to 13, more preferably 4 to 12.
• the mass of the photocatalyst particles contained in the photocatalyst particle dispersion can be calculated from the mass and concentration of the photocatalyst particle dispersion.
• Step (2) two types of solutions are prepared: (2-1) a solution in which a raw material silver compound is dissolved in an aqueous dispersion medium, and (2-2) a solution in which a reducing agent and a protective agent are dissolved in an aqueous dispersion medium.
• a solution of The reducing agent in the solution (2-2) has the effect of reducing the raw material silver compound in the solution (2-1).
• the protective agent in the solution (2-2) is added to the surface of the silver compound when the solution (2-1) and the solution (2-2) are mixed in the subsequent step (3) and the silver compound is reduced. It has the effect of improving dispersion stability in an aqueous dispersion medium.
• These solutions may be produced by adding the raw material silver compound, reducing agent, and protective agent separately to an aqueous dispersion medium, and dissolving them by stirring.
• the stirring method is not particularly limited as long as it can be uniformly dissolved in the aqueous dispersion medium, and commonly available stirrers can be used.
• Various silver compounds can be used as the raw material silver compound, including inorganic acid salts such as silver chloride, nitrate, and sulfate; organic acids such as formic acid, citric acid, oxalic acid, lactic acid, and glycolic acid.
• Salt Complex salts such as ammine complexes, cyano complexes, halogeno complexes, and hydroxy complexes can be mentioned, and one or more of these may be used in combination.
• inorganic acid salts such as silver chloride, nitrate, and sulfate.
• the content of the raw material silver compound is such that the concentration as Ag in the solution (2-1) containing the raw material silver compound is 0.5 to 200 mmol/L, preferably 5 to 100 mmol/L.
• the silver nanoparticles contain a metal component other than silver
• raw material compounds for metal components other than silver include zinc, platinum, palladium, nickel, aluminum, titanium, cobalt, zirconium, molybdenum, tungsten, gold, antimony, tin, sodium, magnesium, silicon, phosphorus, sulfur, and potassium.
• an aqueous solvent is usually used, and water, a water-soluble organic solvent that is miscible with water, or a mixed solvent of water and a water-soluble organic solvent may be used. is preferred.
• water for example, deionized water, distilled water, pure water, etc. are preferable.
• water-soluble organic solvents include alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, and polyethylene glycol; ethylene glycol monomethyl Glycol ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether; Ketones such as acetone and methyl ethyl ketone; 2-pyrrolidone , N-methylpyrrolidone, and other water-soluble nitrogen-containing compounds; ethyl acetate, and the like, and one or more of these may be used in combination.
• the reducing agent is not particularly limited, but any of various reducing agents capable of reducing silver ions constituting the raw material silver compound can be used.
• hydrazines such as hydrazine, hydrazine monohydrate, phenylhydrazine, and hydrazinium sulfate
• amines such as dimethylaminoethanol, triethylamine, octylamine, dimethylaminoborane, and benzotriazole
• oxalic acid citric acid, ascorbic acid, and tartaric acid.
• organic acids such as malic acid, malonic acid, and formic acid
• polyphenols such as gallic acid, chlorogenic acid, catechin, cyanidin, epigallocatechin, delphinidin, tannic acid, and saponin
• aldehydes such as formaldehyde, acetaldehyde, and glycolaldehyde
• hydrides such as zinc borohydride, sodium acetoxyborohydride
• pyrrolidones such as polyvinylpyrrolidone (PVP), 1-vinylpyrrolidone, N-vinylpyrrolidone, methylpyrrolidone
• glucose galactose,
• hydrazines such as hydrazine monohydrate, organic acid salts such as sodium citrate, and gallic acid have excellent silver ion reduction ability and have small molecular weights and can be easily filtered out in the washing process of silver nanoparticles with aqueous solvents.
• polyphenols such as tannic acid, hydrides such as sodium borohydride, and aldehydes such as formaldehyde and glycolaldehyde are more preferred.
• the aqueous dispersion medium for dissolving the reducing agent the same aqueous dispersion medium as used for the above metal compound can be used.
• the content of the reducing agent can be 0.001 to 50% by mass, preferably 0.01 to 40% by mass, based on the total mass of the solution (2-2) containing the reducing agent and the protective agent. This is because when the content of the reducing agent exceeds 50% by mass, the content of the protective agent and aqueous solvent becomes relatively small, and a sufficient amount of the protective agent cannot be adsorbed on the surface of the silver nanoparticles, resulting in high dispersion stability. Silver nanoparticles may not be formed, and if the reducing agent content is less than 0.001% by mass, it is necessary to add a large amount of a solution containing a reducing agent and a protective agent to the solution containing the raw material silver compound. This is because it is not practical.
• the protective agent is not particularly limited, but any of various protective agents that can be adsorbed onto the surface of the reduced raw material silver compound and improve the dispersion stability in the aqueous dispersion medium can be used.
• surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants
• PVP polyethylene glycol, polyvinyl alcohol, polyethylene imine, polyethylene oxide, polyacrylic acid
• Water-soluble polymer compounds such as , methylcellulose, and gelatin
• Amino acids such as cysteine, arginine, asparagine, and aspartic acid
• Aliphatic amine compounds such as ethanolamine, diethanolamine, triethanolamine, and propanolamine
• Tannic acid gallocatechin, gallic acid
• Polyphenols such as pyrogallol, 4-benzylpyrogallol (2,3,4-trihydroxydiphenylmethane), ellagitannin; butylamine, dibutyl
• silicic acid compounds such as oleic acid and citric acid and their salts; light stabilizers such as hindered amines; and the like.
• organic acid salts such as sodium citrate, polyphenols such as gallic acid and tannic acid, and oleic acid, which have excellent stability of silver nanoparticles and have a small molecular weight and can be easily filtered out in the washing process of silver nanoparticles with aqueous solvents.
• carboxylic acid compounds such as sodium chloride.
• the combination is not particularly limited, but for example, in addition to PVP and sodium citrate, which have excellent dispersion stability for silver nanoparticles, using sodium silicate, gelatin, an aliphatic amine compound, hindered amine, etc. as a protective agent at the same time will improve durability. This is preferable as it may improve the results. Furthermore, it is preferable to use a surfactant, polyphenols, or the like as a protective agent since the antiviral properties may be improved.
• the content of the protective agent is preferably 0.001 to 60% by mass, more preferably 0.01 to 50% by mass, based on the total mass of the solution (2-2) containing the reducing agent and the protective agent.
• aqueous dispersion medium (aqueous solvent) for the solution (2-2) containing a reducing agent and a protecting agent it is preferable to use water, a water-soluble organic solvent miscible with water, or a mixed solvent of water and a water-soluble organic solvent.
• water for example, deionized water, distilled water, pure water, etc. are preferable.
• water-soluble organic solvents include alcohols such as methanol, ethanol, isopropanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, and ethylene glycol monomethyl ether.
• glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether, acetone, ketones such as methyl ethyl ketone, 2-pyrrolidone
• water-soluble nitrogen-containing compounds such as N-methylpyrrolidone, ethyl acetate, and the like, and the water-soluble organic solvent may be used alone or in combination of two or more thereof.
• the content of the aqueous solvent is 0.1 to 99.99% by mass, preferably 1.0 to 99.9% by mass, based on the total mass of the solution (2-2) containing the reducing agent and the protecting agent. .
• the above basic substance or acidic substance may be added to the solution (2-2) containing a reducing agent and a protecting agent.
• Examples of basic substances that can be added to the solution (2-2) include those similar to those exemplified above as basic substances that can be added to the photocatalyst particle dispersion.
• Examples of the acidic substance to be obtained include those similar to those exemplified above as acidic substances that can be added to the photocatalyst particle dispersion.
• the content is 0.0001 to 30% by mass, preferably 0.001 to 20% by mass, based on the total mass of the solution (2-2) containing a reducing agent and a protective agent. It can be expressed as % by mass.
• concentrations of these two solutions are not particularly limited, but in general, the lower the concentration, the smaller the primary particle size of each silver nanoparticle formed, so it depends on the target primary particle size range. It is preferable to set a suitable concentration range.
• the pH when these two solutions are mixed may be such that silver is reduced.
• the appropriate pH range varies depending on the reducing agent used, but for example, when using divalent iron, which undergoes a reduction reaction in an acidic aqueous solution, as the reducing agent, the pH when the two solutions are mixed is 0 to 0. It is preferable to adjust it so that it is within the range of 7. If the pH exceeds 7, the reduction reaction of silver may not proceed, and if it is less than 0, it is not preferable because the subsequent filtration step requires a lot of labor and productivity decreases.
• the pH of the two solutions should be adjusted to be within the range of 7 to 16. preferable. If the pH is less than 7, the reduction reaction of silver may not proceed, and if it exceeds 15, it is not preferable because the subsequent filtration step requires a lot of labor and productivity decreases.
• step (3) the solution prepared in step (2) in which the raw material silver compound is dissolved in an aqueous dispersion medium and the solution in which a reducing agent and a protective agent are dissolved in an aqueous dispersion medium are mixed, and the silver Produce a nanoparticle dispersion.
• the method of mixing these two solutions is not particularly limited as long as the two solutions can be mixed uniformly, but for example, the silver compound solution and the reducing agent and protectant solution are placed in a reaction container and stirred.
• the temperature during mixing is not particularly limited, and is preferably adjusted to a suitable temperature depending on the molar ratio of silver and metal components other than silver in the target silver nanoparticles, primary particle diameter, reaction time, etc.
• step (4) the silver nanoparticle dispersion produced in step (3) is washed with an aqueous dispersion medium by membrane filtration.
• aqueous dispersion medium it is preferable to use water, a water-soluble organic solvent that is miscible with water, and a mixed solvent of water and a water-soluble organic solvent.
• water for example, deionized water, distilled water, pure water, etc. are preferable.
• water-soluble organic solvents include alcohols such as methanol, ethanol, isopropanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, and ethylene glycol monomethyl ether.
• glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether, acetone, ketones such as methyl ethyl ketone, 2-pyrrolidone
• water-soluble nitrogen-containing compounds such as N-methylpyrrolidone, ethyl acetate, and the like, and the water-soluble organic solvent may be used alone or in combination of two or more thereof.
• non-volatile impurities other than silver nanoparticles such as components other than silver in raw material silver compounds, reducing agents, and protective agents not adsorbed to silver nanoparticles, are removed from the silver nanoparticle dispersion. ⁇ To separate. It is preferable to wash until the amount of the protective agent adsorbed on the surface of the silver nanoparticles becomes a mass ratio of 0.001 to 10 with respect to the total metal component in the silver nanoparticles in the silver nanoparticle dispersion. , 0.001 to 5, and even more preferably 0.001 to 1.
• the mass ratio is less than 0.001, the dispersion stability of the silver nanoparticles may decrease, and if it exceeds 10, the amount of protective agent adsorbed on the surface of the silver nanoparticles is large, resulting in poor antiviral properties. It may not be fully demonstrated.
• the metal component concentration in the silver nanoparticle dispersion was determined by appropriately diluting the silver nanoparticle dispersion with pure water and using an inductively coupled plasma optical emission spectrometer (trade name "Agilent 5110 ICP-OES", Agilent Technologies, Inc.). can be introduced and measured.
• the concentration of protective agent adsorbed on the surface of silver nanoparticles in silver nanoparticle dispersion is determined by Calculated from the mass of the nonvolatile content (metal component + protective agent adsorbed on the surface of silver nanoparticles) after sampling and heating at 105°C for 3 hours to volatilize the solvent and the mass of the sampled silver nanoparticle dispersion. It can be calculated by subtracting the metal component concentration determined by the above ICP-OES from the nonvolatile concentration.
• the membrane used in the membrane filtration method is not particularly limited as long as it can separate silver nanoparticles and non-volatile impurities other than silver nanoparticles from the silver nanoparticle dispersion.
• Examples include filtration membranes and nanofiltration membranes, and among these, a membrane having an appropriate pore size can be used.
• any method such as centrifugal filtration, pressure filtration, or cross-flow filtration can be adopted.
• any appropriate shape can be used, such as a hollow fiber type, spiral type, tubular type, or flat membrane type.
• the material of the filtration membrane is not particularly limited as long as it is durable against the silver nanoparticle dispersion, and examples include polyethylene, tetrafluoroethylene, polypropylene, cellulose acetate, polyacrylonitrile, polyimide, polysulfone, and polyethersulfone. It can be appropriately selected and used from organic films such as, inorganic films such as silica, alumina, zirconia, titania, etc.
• the above-mentioned filtration membranes include Microza (manufactured by Asahi Kasei Chemicals Co., Ltd.), Amicon Ultra (manufactured by Merck Millipore Co., Ltd.), MOLSEP (Daisen Membrane Systems Co., Ltd.), and Ultrafilter (manufactured by Merck Millipore Co., Ltd.).
• Microza manufactured by Asahi Kasei Chemicals Co., Ltd.
• Amicon Ultra manufactured by Merck Millipore Co., Ltd.
• MOLSEP Denst Configuration Membrane Systems Co., Ltd.
• Ultrafilter manufactured by Merck Millipore Co., Ltd.
• Examples include Advantech Toyo Co., Ltd.) and MEMBRALOX (Nippon Pole Co., Ltd.).
• Step (5) the photocatalyst particle dispersion produced in step (1) and the silver nanoparticle dispersion produced in step (4) are mixed to obtain a photocatalyst/silver nanoparticle dispersion.
• the mixing method is not particularly limited as long as the two dispersions can be mixed uniformly, and for example, mixing can be performed by stirring using a commonly available stirrer.
• the mixing ratio of the photocatalyst particle dispersion liquid and the silver nanoparticle dispersion liquid is the mass ratio of particles in each dispersion liquid of photocatalyst particles and silver nanoparticles (photocatalyst particles/silver nanoparticles), and is preferably 1 to 100,000. 10 to 10,000, more preferably 20 to 1,000. If the mass ratio is less than 1, the photocatalytic performance will not be sufficiently exhibited, which is undesirable, and if it exceeds 100,000, the antiviral properties in the dark will not be sufficiently exhibited, which is undesirable.
• Step (6) the purpose is to further improve the antiviral effect of light irradiation, and to make it easier to apply the photocatalyst/silver nanoparticle dispersion liquid to the surfaces of various components described below, and to make it easier to adhere the particles.
• a photocatalyst/silver nanoparticle/binder dispersion can be obtained.
• the mixing method is not particularly limited as long as it can be mixed uniformly, and for example, mixing can be performed by stirring using a commonly available stirrer.
• the mixing ratio of the binder preferably satisfies both the mass ratio of the photocatalyst particles to the binder component and the mass ratio of the silver nanoparticles to the binder component shown below.
• the mixing ratio of the photocatalyst particle dispersion and the binder is 0.01 to 50, preferably 0.05 to 30, more preferably 0.1 to 10 in mass ratio of photocatalyst particles to binder component (photocatalyst/binder). . If it is less than 0.01, the photocatalytic function may not be fully exhibited, which is not preferable, and if it exceeds 50, the effect of improving antiviral properties by light irradiation may not be confirmed, which is not preferable.
• the mixing ratio of the silver nanoparticle dispersion and the binder is the mass ratio of the silver nanoparticles and the binder component (silver nanoparticles/binder), which is 0.00001 to 10, preferably 0.0001 to 1, and more preferably 0.001. ⁇ 0.5. If it is less than 0.00001, the antiviral effect in a dark place may decrease, which is not preferable, and if it exceeds 10, the effect of improving antiviral property by light irradiation may not be confirmed, which is not preferable.
• the photocatalyst/silver nanoparticle dispersion can be used to form an antiviral composition on the surfaces of various members.
• the various members are not particularly limited, but examples of the material of the members include organic materials and inorganic materials. These can have various shapes depending on their respective purposes and uses.
• organic materials examples include vinyl chloride resin (PVC), polyethylene (PE), polypropylene (PP), polycarbonate (PC), acrylic resin, polyacetal, fluororesin, silicone resin, and ethylene-vinyl acetate copolymer (EVA).
• PVC vinyl chloride resin
• PE polyethylene
• PP polypropylene
• PC polycarbonate
• acrylic resin acrylic resin
• polyacetal polyacetal
• fluororesin silicone resin
• silicone resin ethylene-vinyl acetate copolymer
• EVA ethylene-vinyl acetate copolymer
• acrylonitrile-butadiene rubber NBR
• polyethylene terephthalate PET
• polyethylene naphthalate PEN
• polyvinyl butyral PVB
• ethylene-vinyl alcohol copolymer EVOH
• polyimide resin polyphenylene sulfide (PPS)
• polyether Synthetic resin materials such as imide (PEI), polyether ether imide (PEEI), polyether ether ketone (PEEK), melamine resin, phenol resin, acrylonitrile-butadiene-styrene (ABS) resin, natural materials such as natural rubber, or Semi-synthetic materials of the above-mentioned synthetic resin materials and natural materials can be mentioned.
• PPS polyphenylene sulfide
• inorganic materials include non-metallic inorganic materials and metallic inorganic materials.
• nonmetallic inorganic materials include glass, ceramics, and stone. These may be manufactured into various shapes such as tiles, glass, mirrors, walls, and decorative materials.
• the metal inorganic material include cast iron, steel, iron, iron alloy, aluminum, aluminum alloy, nickel, nickel alloy, zinc die casting, and the like. These may be plated with the above metal inorganic material, may be coated with the above organic material, or may be plated on the surface of the above organic material or non-metal inorganic material.
• a photocatalyst/silver nanoparticle dispersion is applied to the surface of the above member by a known coating method such as spray coating or dip coating, and then the photocatalyst/silver nanoparticle dispersion is applied at a distance. It may be dried by a known drying method such as infrared drying, IH drying, hot air drying, etc., and the thickness of the dried photocatalyst/silver nanoparticle composition can be selected in various ways, but it is usually preferably in the range of 10 nm to 10 ⁇ m. As a result, the photocatalyst/silver nanoparticle composition described above is formed on the surface of the member.
• the photocatalyst/silver nanoparticle composition formed on the member in this way exhibits antiviral activity in the dark, and furthermore, high antiviral activity can be obtained by light irradiation.
• Various members having the particle composition on the upper surface can exhibit an antiviral effect on the surface.
• the antiviral activity value was calculated in accordance with JIS R1756:2020 "Fine ceramics - Antiviral test method for visible light responsive photocatalytic material - Method using bacteriophage Q ⁇ ", and the antiviral property of the composition was evaluated as follows: It was evaluated based on the criteria.
• a 50 mm x 50 mm x 2 mm glass piece (hereinafter referred to as a test piece) was used as a member on which the composition was formed.
• ⁇ Measurement of antiviral properties based on JIS R1756:2020> A glass rod was placed in a moisturized petri dish, and a test piece was placed on top of the glass rod.
• bacteriophage solution 200 ⁇ L was placed on the test piece, the bacteriophage solution was covered with a cover film, and then the petri dish was covered with a moisturizing glass.
• the prepared petri dish was left standing for 4 hours in a dark place (0 lx) or a bright place (visible light from a white fluorescent lamp that cuts wavelengths of 380 nm or less: 500 lx).
• a digital illumination meter LX-105 manufactured by Custom Co., Ltd. was used to measure the illuminance. After standing still, the test piece and cover film were transferred to a sterilized stomach bag, washed out with 5 mL of physiological saline containing a surfactant, and the bacteriophage solution was collected.
• the collected bacteriophage solution was diluted, and 100 ⁇ L each of the solution and Escherichia coli solution were mixed, further mixed with a soft agar medium, and then plated on the medium.
• the infectious titer of the virus was determined by incubating at 37° C. overnight and counting the number of killed coliform bacteria (plaques).
• the antiviral activity value based on JIS R1756:2020 is obtained by performing the above operation using an antiviral-treated test piece and an untreated test piece, and finding it as the difference in the average value of the common logarithm of the infectious titer of both. It is a value.
• the effect of light irradiation was calculated from the antiviral activity value in the dark and the antiviral activity value in the light, and evaluated based on the following criteria.
• Preparation example 1-1 ⁇ Preparation of rutile titanium oxide dispersion>
• rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
• MPT-623 rutile titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.
• the photocatalyst particles in the obtained photocatalyst dispersion were observed using a transmission electron microscope using the method described above, and it was confirmed that the primary particle diameter was 18 nm.
• the photocatalyst dispersions obtained in Preparation Examples 1-1 to 1-3 are summarized in Table 1 below.
• Preparation example 1-2 ⁇ Preparation of anatase-type titanium oxide dispersion: Synthesis of titanium oxide by liquid phase method> After diluting a 36% by mass titanium (IV) chloride aqueous solution 10 times with pure water, a precipitate of titanium hydroxide was obtained by gradually adding 10% by mass ammonia water to neutralize and hydrolyze it. Ta. The pH at this time was 8.5. The obtained precipitate was deionized by repeating the addition of pure water and decantation.
• tungsten oxide dispersion As a photocatalyst material, commercially available tungsten trioxide nanoparticles, 99.95%, orthorhombic (manufactured by EM Japan Co., Ltd.) were dispersed in pure water, and a photocatalyst dispersion (3A) (tungsten oxide concentration 1.2% by mass) was prepared. ) was used as a photocatalyst material.
• tungsten trioxide nanoparticles 99.95%, orthorhombic (manufactured by EM Japan Co., Ltd.) were dispersed in pure water, and a photocatalyst dispersion (3A) (tungsten oxide concentration 1.2% by mass) was prepared. ) was used as
• a solution (pH 4.6) obtained by mixing 1500 mL of solution (I) containing a reducing agent and a protecting agent at 25 °C with 300 mL of solution (I) containing a raw material silver compound at 25 °C in a reactor, A silver nanoparticle dispersion ( ⁇ ) was obtained by concentrating and washing with pure water using an ultrafiltration membrane with a molecular weight cutoff of 50,000 (MOLSEP, Daisen Membrane Systems, Inc.). A desktop pH meter F-71 (manufactured by Horiba Advanced Techno Co., Ltd.) was used to measure the pH.
• the metal concentration of the obtained silver nanoparticle dispersion was measured using ICP-OES (Agilent Technologies, Inc.), and the mass ratio of the protective agent to the metal component was calculated from the nonvolatile content concentration and the metal concentration. Furthermore, the silver nanoparticle dispersion liquid was diluted to a predetermined concentration, and the dispersed particle diameter was measured using ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.).
• the obtained silver nanoparticle dispersion was photographed using a transmission electron microscope (H-9500 manufactured by Hitachi High-Technologies, Ltd.), and randomly selected particles were The projected area circle equivalent diameter (Heywood diameter) of 1000 selected particles that do not overlap with each other was measured, and the primary particle diameter of the silver nanoparticles was calculated from the arithmetic mean value.
• Table 2 The compositions and physical properties of the silver nanoparticle dispersions obtained in Preparation Examples 2-1 to 2-6 are summarized in Table 2 below.
• Preparation example 2-2 ⁇ Preparation of silver nanoparticle dispersion protected with tannic acid> Using pure water as a solvent, silver nitrate was dissolved so that the concentration of Ag was 6.0 mmol/L to obtain a solution (II) containing a raw material silver compound.
• a solution (pH 12.6) obtained by mixing 1000 mL of solution (II) containing a raw material silver compound at 90 ° C. with 100 mL of solution (ii) containing a reducing agent and a protecting agent at 60 ° C. in a reactor.
• a silver nanoparticle dispersion ( ⁇ ) was obtained by concentrating and washing with pure water in the same manner as in Preparation Example 2-1.
• a solution (III) containing a raw material silver compound is used instead of the solution (II) containing a raw material silver compound, and a solution (iii) containing a reducing agent and a protective agent is used instead of the solution (ii) containing a reducing agent and a protective agent.
• a silver-iron nanoparticle dispersion ( ⁇ ) was obtained in the same manner as in Preparation Example 2-2 except that . Note that the pH of the liquid before being concentrated using an ultrafiltration membrane and washed with pure water was 12.7. Further, the content of the silver component was 90% by mass with respect to the mass of the metal component of the silver-iron nanoparticles in the silver-iron nanoparticle dispersion ( ⁇ ), and the content of the iron component was 10% by mass.
• a solution (iv) containing a reducing agent and a protecting agent was obtained by mixing 10% by mass of polyvinylpyrrolidone K30 (PVP, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a reducing agent and a protecting agent.
• a solution (IV) containing a raw material silver compound is used instead of the solution (II) containing a raw material silver compound, and a solution (iv) containing a reducing agent and a protective agent is used instead of the solution (ii) containing a reducing agent and a protective agent.
• a silver palladium nanoparticle dispersion ( ⁇ ) was obtained in the same manner as in Preparation Example 2-2 except that . Note that the pH of the liquid before being concentrated using an ultrafiltration membrane and washed with pure water was 13.2.
• the content of the silver component was 98% by mass with respect to the mass of the metal component of the silver-palladium nanoparticles in the silver-palladium nanoparticle dispersion ( ⁇ ), and the content of the palladium component was 2% by mass.
• Preparation example 2-6 ⁇ Preparation of coarse silver particle dispersion> Mix 55% by mass of ethylene glycol and 18% by mass of pure water as a solvent, 2% by mass of potassium hydroxide as a basic substance, 20% by mass of hydrazine monohydrate as a reducing agent, and 5% by mass of dimethylaminoethanol. In this way, a solution (v) containing a reducing agent was obtained.
• a silver particle dispersion ( ⁇ ) was obtained in the same manner as in Preparation Example 2-2, except that the solution (v) containing a reducing agent was used instead of the solution (ii) containing a reducing agent and a protecting agent. Note that the pH of the liquid before being concentrated using an ultrafiltration membrane and washed with pure water was 13.2.
• Example 1 Photocatalyst particle dispersion (1A) and silver nanoparticle dispersion ( ⁇ ) were mixed so that the photocatalyst component was 4200 ppm and the silver component was 33 ppm on a mass basis to obtain a photocatalyst/silver nanoparticle dispersion (a). .
• a photocatalyst/silver nanoparticle dispersion was applied to a glass substrate at a concentration of 10 g/m 2 and dried to form a photocatalyst/silver nanoparticle composition (A) on the glass substrate, and antiviral properties were measured. I did it.
• Example 2 Except that the photocatalyst particle dispersion (2A) and the silver nanoparticle dispersion ( ⁇ ) were mixed so that the photocatalyst component was 2400 ppm and the silver component was 33 ppm to obtain a photocatalyst/silver nanoparticle dispersion (b).
• a photocatalyst/silver nanoparticle composition (B) was prepared in the same manner as in Example 1, and its antiviral properties were measured.
• Example 3 The procedure was carried out except that the photocatalyst particle dispersion (3A) and the silver nanoparticle dispersion ( ⁇ ) were mixed so that the photocatalyst component was 4200 ppm and the silver component was 13 ppm to obtain a photocatalyst/silver nanoparticle dispersion (c).
• a photocatalyst/silver nanoparticle composition (C) was prepared in the same manner as in Example 1, and its antiviral properties were measured.
• Example 4 Except that the photocatalyst particle dispersion (1A) and the silver nanoparticle dispersion ( ⁇ ) were mixed so that the photocatalyst component was 4200 ppm and the silver component was 33 ppm to obtain a photocatalyst/silver nanoparticle dispersion (d).
• a photocatalyst/silver nanoparticle composition (D) was prepared in the same manner as in Example 1, and its antiviral properties were measured.
• Example 5 A photocatalyst particle dispersion (1A) and a silver nanoparticle dispersion ( ⁇ ) were mixed so that the photocatalyst component was 7000 ppm, the silver component was 33 ppm, and the binder concentration was 4200 ppm to obtain a photocatalyst/silver nanoparticle dispersion (e).
• a photocatalyst/silver nanoparticle composition (E) was prepared in the same manner as in Example 1 except for the above, and the antiviral properties were measured.
• Example 6 A photocatalyst particle dispersion (1A), a silver nanoparticle dispersion ( ⁇ ), and colloidal silica (product name: Snowtex 20, Nissan Chemical Industries, Ltd.
• a photocatalyst/silver nanoparticle/binder composition (F) was prepared in the same manner as in Example 1, except that the photocatalyst/silver nanoparticle/binder dispersion (f) was obtained by mixing the photocatalyst/silver nanoparticle/binder dispersion (f). Viral activity was measured.
• Example 7 A photocatalyst particle dispersion (1A), a silver nanoparticle dispersion ( ⁇ ), and an aqueous silicate solution (product name: Scutum S, Shin-Etsu Chemical Co., Ltd.) were prepared so that the photocatalyst component was 4200 ppm, the silver component was 33 ppm, and the binder concentration was 6200 ppm.
• a photocatalyst/silver nanoparticle/binder composition (G) was prepared in the same manner as in Example 1, except that the photocatalyst/silver nanoparticle/binder dispersion (g) was obtained by mixing the photocatalyst/silver nanoparticle/binder dispersion (g). The sex was measured.
• Example 8 A photocatalyst particle dispersion (1A), a silver nanoparticle dispersion ( ⁇ ), and JIS No. 3 sodium silicate (manufactured by Fuji Chemical Co., Ltd.) were added so that the photocatalyst component was 4200 ppm, the silver component was 33 ppm, and the binder concentration was 2200 ppm. Except that a photocatalyst/silver nanoparticle/binder dispersion (h) was obtained by mixing a cation exchange resin (trade name: Amberlite HPR1024H, manufactured by Organo Co., Ltd.) whose pH was adjusted to 4.0. A photocatalyst/silver nanoparticle/binder composition (H) was prepared in the same manner as in Example 1, and its antiviral properties were measured.
• a photocatalyst/silver nanoparticle/binder composition (H) was prepared in the same manner as in Example 1, and its antiviral properties were measured.
• Example 1 Example 1 except that the photocatalyst/silver particle dispersion (i) was obtained by mixing the photocatalyst particle dispersion (1A) and the silver particle dispersion ( ⁇ ) so that the photocatalyst component was 4200 ppm and the silver component was 33 ppm.
• a photocatalyst/silver nanoparticle composition (I) was prepared in the same manner as above, and its antiviral properties were measured.
• a photocatalyst/silver particle/binder composition (J) was prepared in the same manner as in Example 1, except that the photocatalyst/silver particle/binder dispersion (J) was obtained by mixing the photocatalyst/silver particle/binder dispersion (J). Measurements were taken.
• a photocatalyst composition (K) was prepared in the same manner as in Example 1, except that the photocatalyst particle dispersion (1A) was diluted with pure water so that the photocatalyst component was 4200 ppm to obtain a photocatalyst dispersion (k). The antiviral properties were then measured.
• a photocatalyst particle dispersion (1A) and a silicate aqueous solution (trade name: Scutum S, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed so that the photocatalyst component was 4200 ppm and the binder concentration was 4200 ppm, and a photocatalyst/binder dispersion liquid (1) was prepared.
• a photocatalyst/binder composition (L) was prepared in the same manner as in Example 1 except that the antiviral properties were measured.
• a silver nanoparticle composition (M) was prepared in the same manner as in Example 1, except that the silver nanoparticle dispersion ( ⁇ ) was mixed so that the silver component was 33 ppm to obtain a silver nanoparticle dispersion (m). were prepared and their antiviral properties were measured.
• the antiviral composition of the present invention containing silver nanoparticles and photocatalyst particles with a dispersed particle size of 1000 nm or less and a primary particle size of 500 nm or less has an antiviral activity value of 1 in the dark. .0 (about 90% of viruses inactivated) and the effect of light irradiation exceeded 0.3, confirming that the antiviral properties of the composition and the antiviral properties were improved by light irradiation.
• the antiviral activity value in the dark was 2.0 or more (approximately 99% of viruses were inactivated), confirming the high antiviral properties of the compositions in the dark.
• Comparative Examples 1 and 2 Although the compositions containing coarse silver particles exhibit antiviral properties in the dark, the effect of light irradiation is better in Comparative Examples 3 and 4 in which the photocatalyst alone is used; It was confirmed that silver particles inhibited the photocatalytic function. Furthermore, the addition of the binder reduced the antiviral properties in the dark and the effects of light irradiation.

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