WO2017150063A1 - 抗ウイルス剤、コーティング組成物、樹脂組成物及び抗ウイルス製品 - Google Patents
抗ウイルス剤、コーティング組成物、樹脂組成物及び抗ウイルス製品 Download PDFInfo
- Publication number
- WO2017150063A1 WO2017150063A1 PCT/JP2017/003686 JP2017003686W WO2017150063A1 WO 2017150063 A1 WO2017150063 A1 WO 2017150063A1 JP 2017003686 W JP2017003686 W JP 2017003686W WO 2017150063 A1 WO2017150063 A1 WO 2017150063A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antiviral
- acid
- antiviral agent
- resin
- coating composition
- Prior art date
Links
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
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- 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
- 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
- A01N59/20—Copper
-
- 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
- A01N59/26—Phosphorus; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/12—Antivirals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Definitions
- the present invention relates to an antiviral agent containing an inorganic solid acid, a coating composition containing the antiviral agent, a resin composition, and an antiviral product.
- the antiviral agent of the present invention is applied to textile products such as clothing, bedding and masks, filters used for air purifiers and air conditioners, interior products such as curtains, carpets and furniture, spraying and coating processing on automobile interior materials, Or the effect which reduces viral activity is provided by carrying out the spreading process to the surface layer of building materials, such as a wallpaper and a flooring material.
- ethanol For coronavirus, ethanol, sodium hypochlorite, iodophor, peracetic acid, formaldehyde, glutaraldehyde and ethylene oxide gas have been reported to be effective as disinfectants.
- 1-adamantanamine hydrochloride, thiosemicarbazide, arabinosyl nucleoside, nucleoside, 2,3-dideoxy nucleoside, pyrophosphate derivative and the like are known as antiviral agents.
- these antiviral drugs have only a temporary effect, and there is a problem with heat resistance, and therefore a sustained effect cannot be expected for antiviral products.
- Patent Document 1 discloses an inorganic antiviral agent composition containing an inorganic peroxide, tetraacetylethylenediamine, and an alkali metal salt of an inorganic acid and / or an alkaline earth metal salt of an inorganic acid. .
- this inorganic antiviral agent is an inorganic peroxide type, there are still problems in sustainability and processability. When these products containing conventional antiviral agents come into direct contact with the human body, there is also a problem that the skin is irritated.
- Patent Document 2 discloses inorganic oxide fine particles having a specific metal component and an average particle diameter of 500 nm or less
- Patent Document 3 includes a copper and titanium-containing composition
- Patent Document 4 includes a BET specific surface area.
- An antibacterial and antiviral composition containing 5 to 100 m 2 / g of cuprous oxide particles and a saccharide having an aldehyde group is disclosed.
- the present invention is an antiviral agent containing an inorganic solid acid having an acid point concentration exceeding 0.005 mmol / g, a coating composition containing the antiviral agent, a resin composition, and an antiviral product.
- the antiviral agent of the present invention not only exhibits high antiviral activity compared to existing antiviral agents, but also has heat resistance because it is an inorganic substance.
- it can be a light-colored substance, it is suitable for the production of a coating composition, a resin composition, etc. that are less colored and discolored, have excellent processability, and give a film that does not desorb by contact with water or the like. is there.
- an antiviral product of the present invention containing the antiviral agent of the present invention for example, a resin molded article, an article provided with a film containing an antiviral agent, etc. not only exhibit high antiviral activity but also include an antiviral product. Since the virus agent does not detach or flow out with water, it is excellent in durability.
- the present invention is as follows. (1) An antiviral agent containing an inorganic solid acid having an acid point concentration exceeding 0.005 mmol / g. (2) The antiviral agent according to (1) above, wherein the acid strength (pKa) at an acid point in the inorganic solid acid is 3.3 or less. (3) The antiviral agent according to (1) or (2), wherein the inorganic solid acid contains an inorganic phosphoric acid compound, an inorganic silicic acid compound or an inorganic oxide. (4) The antiviral agent according to any one of (1) to (3) above, comprising at least one selected from the group consisting of silver, copper, and compounds thereof. (5) A coating composition comprising the antiviral agent according to any one of (1) to (4) above. (6) A resin composition comprising the antiviral agent according to any one of (1) to (4) above. (7) An antiviral product comprising the antiviral agent according to any one of (1) to (4) above.
- the inorganic solid acid is a substance having an acid point on the surface of the inorganic solid.
- An acid point is a location showing the property of giving a proton to a base or the property of receiving an electron pair from a base.
- the number of acid points can be represented by the acid point concentration, and is usually expressed as the number of acid points or acidic centers on the surface of the solid, as the number per unit weight of the solid or the number per unit surface area or the number of moles.
- the concentration of acid points on the surface of the inorganic solid suitably expresses the effect of inactivating viruses (hereinafter referred to as “antiviral effect”). Therefore, it should exceed 0.005 mmol / g.
- antiviral effect since an antiviral effect will increase, so that an acid point concentration is high, there is no upper limit in the acid point concentration of an inorganic solid acid.
- the upper limit is usually 10 mmol / g.
- the preferred acid point concentration in the present invention is 0.008 mmol / g or more, more preferably 0.01 mmol / g or more.
- the antiviral effect of an inorganic solid acid having an acid point concentration of 0.01 mmol / g or more is excellent, and exhibits a high effect on various viruses.
- the antiviral agent of the present invention exhibits an antiviral effect at the acid point on the surface of an inorganic solid acid having an acid point concentration exceeding 0.005 mmol / g.
- viruses are (1) adsorbed on the cell surface, (2) invaded into cells, (3) unshelled, (4) synthesized components, (5) assembled components, and (6) from infected cells. It propagates through the stage of release.
- the inorganic solid acid is presumed to exhibit an antiviral effect by inactivating the adsorption of the virus in contact with the acid sites on the surface of the inorganic solid to the cell surface.
- the acid point concentration can be determined by measuring the amount of base that reacts with the powder (inorganic solid acid).
- the acid point concentration can be measured in a liquid phase or a gas phase.
- a titration method is known as a method for measuring in a liquid phase.
- a gas chemical adsorption method for measuring the difference between the adsorption / desorption amount of He gas or hydrogen gas and the adsorption / desorption amount of basic gas is known. Since the reaction between the antiviral agent and the virus in the present invention is a liquid-mediated reaction, titration in the liquid phase is suitable for measuring the acid point concentration.
- a specific method for measuring the acid point concentration of an inorganic solid acid by a titration method in a liquid phase is as follows.
- the inorganic solid acid dispersed in the nonpolar solvent is titrated with n-butylamine, and the end point of the titration is confirmed by discoloration of the acid-base conversion indicator.
- the indicator before the reaction exhibits a base type color, but when adsorbed on an inorganic solid acid, exhibits a conjugate acid type color.
- the acid point concentration is determined from the titration amount of n-butylamine required to return from the conjugate acid type color to the base type color.
- One solid acid point corresponds to one n-butylamine molecule.
- the titrating base Since the titrating base must replace the indicator that has reacted with the solid acid sites, its basicity is stronger than the basicity of the indicator.
- the indicator shows an acidic color due to solid acidity, but it is preferable to allow sufficient time until the reaction is completed.
- n-butylamine is dropped, and the acid point concentration is calculated from the amount of n-butylamine when the indicator color returns to the basic color, which is the original color.
- the specific procedure for measuring the acid point concentration of the inorganic solid acid is as follows. (1) 10 mL of benzene and 0.5 g of inorganic solid acid are placed in a 20 mL sample bottle and stirred to disperse the inorganic solid acid. For example, 20 mixed dispersions are prepared. (2) Change the amount added to each sample bottle, add n-butylamine with a normality of 0.1 N, and stir with a shaker to prepare 20 types of liquid mixture. (3) After 24 hours, add 0.5 mL of 0.1% indicator methyl red solution to each mixture and observe the discoloration of the indicator.
- the amount of n-butylamine added in the system with the largest amount of n-butylamine in which no indicator discoloration is confirmed is defined as the amount of base reacted with the acid point and expressed as acid point concentration (mmol / g).
- the inorganic solid acid is preferably an inorganic compound having a structure in which a proton donating or proton accepting substituent is arranged on the surface in contact with the virus.
- the inorganic solid acid include phosphoric compounds of titanium group elements such as zirconium phosphate, hafnium phosphate and titanium phosphate, inorganic phosphate compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral); Inorganic silicate compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), zeolite (aluminosilicate); alumina, titania, hydrous titanium oxide, etc.
- inorganic oxides having an acid point concentration of 0.005 mmol / g or more.
- ⁇ -type or ⁇ -type zirconium phosphate, ⁇ -type or ⁇ -type titanium phosphate, amorphous magnesium silicate, active titanium oxide, and the like have an acid point concentration exceeding 0.005 mmol / g. It is preferable as an inorganic solid acid contained in an antiviral agent.
- the acid point on the surface of the inorganic solid has strength. That is, in addition to the high acid point concentration of the inorganic solid acid itself, a higher antiviral effect can be obtained if the strength of each acid point is high. Therefore, the inorganic solid acid contained in the antiviral agent of the present invention preferably has a high acid point strength.
- the acid point strength can be expressed as pKa as acid strength.
- pKa is preferably 3.3 or less, more preferably pKa 1.5 or less, and further preferably 0.8 or less.
- the acid strength at the acid point is small, that is, when the pKa is high, the ability to inactivate the virus tends to decrease, and when the pKa is 0.8 or less, particularly excellent antiviral performance is obtained.
- the acid strength of the inorganic solid acid in the present invention is the ability of the acid point on the surface of the inorganic solid acid to give a proton to the base or to accept an electron pair from the base.
- the acid strength (pKa) of the inorganic solid acid can be measured as the ability to change the base form to its conjugate acid form using various acid-base conversion indicators whose pKa is known. When the base type is changed to the conjugated acid type, the acid-base conversion indicator is discolored and can be distinguished.
- acid-base conversion indicators examples include methyl red (+4.8), 4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3), 2 -Amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5), 4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8), p-nitrobenzeneazo -P'-nitro-diphenylamine (+0.43), dicinnamylacetone (-3.0), benzalacetophenone (-5.6), anthraquinone (-8.2) and the like can be exemplified.
- the example of the method of measuring the acid strength (pKa) of an inorganic solid acid using said acid-base conversion indicator is shown below.
- the acid strength (pKa) of the inorganic solid acid is equal to or less than the strongest acid strength (that is, the lowest pKa value) at which indicator discoloration is confirmed, and the weakest acid strength (that is, no indicator discoloration is confirmed) The highest pKa value). Therefore, the pKa value of the inorganic solid acid is expressed as (the highest pKa value where no discoloration is confirmed) to (the lowest pKa value where discoloration is confirmed). When there is no appropriate indicator indicating the lower limit, “less than the lowest pKa value in which discoloration is confirmed” is set. .
- the antiviral agent of the present invention can contain silver or copper, or both.
- the antiviral agent of the present invention may contain an inorganic solid acid having a silver ion (silver atom) or a copper ion (copper atom) in the structure, and silver or copper, or a compound thereof, and silver And a mixture with an inorganic solid acid not containing copper.
- An antiviral agent containing silver or copper has an excellent antiviral effect.
- the total content of silver or copper in these antiviral agents or their compounds is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 1% by mass or more. is there.
- inorganic solid acid which has a silver ion (silver atom) or a copper ion (copper atom) in a structure
- silver ion (silver atom) or a copper ion (copper atom) in a structure silver zirconium phosphate, copper zirconium phosphate, etc. are illustrated, for example.
- the antiviral agent of the present invention is preferably in a powder form in order to be applied to processing into various materials and forms.
- the powdered antiviral agent contains this antiviral agent and a binder, prepares a coating composition with excellent dispersibility, contains an antiviral agent and a molding resin, and gives a resin molded product with excellent dispersibility It is suitable for preparing a resin composition.
- the average particle size of the powdered antiviral agent is preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m.
- a powder having an average particle size of 0.01 ⁇ m or more has an advantage of being easy to handle because it is difficult to agglomerate.
- the coating composition containing a powder having an average particle size of 50 ⁇ m or less has good dispersibility, so that when coated on the surface of the fiber, the texture of the coated fiber is not impaired, and the resin composition It is possible to make yarn breakage less likely to occur when a fiber is produced by spinning from a fiber.
- the average particle diameter can be measured with a laser diffraction particle size distribution analyzer or the like, and is a median diameter analyzed on a volume basis.
- the color tone of the antiviral agent of the present invention is not limited, but white color or light color with high brightness is preferable in order to apply it to various materials and forms.
- the lightness is preferably 80 or more, more preferably 85 or more, and still more preferably 95 or more as an L value when measured with a color difference meter.
- the antiviral agent of the present invention easily develops an antiviral effect by having a certain amount of water.
- the water content in the antiviral agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
- the inorganic solid acid having hygroscopicity can keep moisture in the inorganic solid acid even when mixed with other materials or the humidity of the atmosphere changes. It is excellent in that the antiviral agent itself has the necessary moisture.
- the antiviral effect for the measurement of the antiviral effect, a method of measuring the amount of virus (infectious titer) using the phenomenon of cytopathic change in which the shape of cells infected with the virus changes is used.
- the method for measuring the infectious titer include a plaque number measuring method, a 50% tissue culture infectious dose (TCID 50 ) measuring method, and a 50% virus titer (EID 50 ) measuring method.
- the antiviral effect can be evaluated as an antiviral activity value obtained by the following formula (1).
- the initial virus infectivity titer means the virus amount of the virus solution immediately after inoculation used for the evaluation
- the residual virus infectivity titer is the amount of virus after a certain period of time after contact with the antiviral sample. means. The higher the value of the antiviral activity, the higher the antiviral effect, preferably 2 or more, more preferably 3 or more.
- Antiviral activity value Log (initial virus infectivity titer) ⁇ Log (residual virus infectivity titer) (1)
- the usage form of the antiviral agent of the present invention is not particularly limited, and the antiviral agent can be used alone. Depending on the application, it can be appropriately mixed with other components or combined with other materials. Can be.
- the powdered antiviral agent has various usage forms such as powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, and powder-containing aerosol. be able to. Furthermore, if necessary, it can be used in combination with various additives such as deodorants, antibacterial agents, antifungal agents, flameproofing agents, anticorrosion, and fertilizers; materials such as building materials.
- the antiviral agent of the present invention is added to resin, paper, plastic, rubber, glass, metal, concrete, wood, paint, fiber, leather, stone, etc., which are materials that humans may come into contact with. It is possible to inactivate viruses in the living space.
- the coating composition of the present invention is a composition containing the antiviral agent of the present invention and, if necessary, a binder, a dispersant and the like.
- the coating composition of the present invention may further contain an additive.
- it can also be diluted with a solvent or water before apply
- the concentration of the antiviral agent in the coating composition is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, because it is easy to disperse and has good storage stability.
- the antiviral effect is manifested by the contact of the antiviral agent with the virus on the surface of the antiviral product of various shapes, so that the antiviral agent is immobilized on the surface of the antiviral product with the coating composition of the present invention. This is preferable because a large effect can be obtained with a smaller amount of the antiviral agent.
- Dispersant that can be used in the coating composition of the present invention is not particularly limited as long as the antiviral agent of the present invention can be uniformly dispersed in the coating composition.
- Dispersants include polymer-type dispersants such as polycarboxylic acids, polyethylene glycols, polyethers, polyalkylene polyamines; alkylsulfonic acids, quaternary ammoniums, higher alcohol alkylene oxides, polyhydric alcohol esters And surfactant type dispersants such as alkyl polyamines; inorganic type dispersants such as polyphosphates; water, alcohol solutions, lime, soda ash, sodium silicate, starch, glue, gelatin, tannin and the like.
- pigments such as zinc oxide and titanium oxide
- dyes such as antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact strengthening agents
- glass Lubricants such as fibers and metal soaps, thickeners, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifung
- the coating composition of the present invention is useful for forming a film having an antiviral effect on the surface of an article containing an inorganic material or an organic material.
- the main use of the coating composition of the present invention is to process fibers or fiber products (woven fabric, non-woven fabric, knitted fabric, etc.).
- Examples of the method of applying to the fiber or the fiber product include a method of applying, dipping or spraying the fiber or the fiber product with the coating composition as it is or with a liquid diluted with a solvent or the like.
- fibers there are no restrictions on the above fibers, natural fibers such as cotton, silk, wool, etc .; synthetic fibers such as polyester, nylon (polyamide synthetic fiber), acrylonitrile; semisynthetic fibers such as triacetate and diacetate; viscose rayon, etc. Examples include recycled fibers.
- the composite fiber containing 2 or more types of these fibers may be sufficient. In the case of a nonwoven fabric, it can contain polyethylene fiber, polypropylene fiber, and the like.
- the manufacturing method of the antiviral product by a coating composition is not specifically limited, Even if it is a case where any application methods, such as a dipping process, a printing process, and a spraying process, are employ
- adopted a coating composition After coating, the coating film needs to be dried.
- the drying method any of natural drying, hot air drying, vacuum drying, and the like can be used, but a method using heat is preferable.
- the drying conditions are preferably 40 ° C. to 250 ° C., more preferably 50 ° C. to 180 ° C., preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours. Thereby, the antiviral agent can be fixed to the fiber or the fiber product.
- the spread amount of the antiviral agent on the fiber or the fiber product is preferably 0 with respect to the surface area of 1 m 2 of the fiber or the fiber product from the viewpoint that the antiviral effect can be suitably expressed. .05g or more. From the viewpoint of suppressing the deterioration of physical properties and texture of the obtained antiviral product, the spreading amount is preferably 10 g / m 2 or less, more preferably 0.3 to 5 g / m 2 .
- the coating composition of the present invention When the coating composition of the present invention is applied to articles such as fibers and textile products, if the coating composition is strongly acidic, the metal of the production machine may be corroded, the processing solution may be deteriorated, and the stability may be reduced. there's a possibility that. On the other hand, if it is strongly alkaline, the inorganic solid acid may be neutralized to reduce the antiviral effect. Therefore, the pH of the coating composition of the present invention is preferably 3 or more and 9 or less, more preferably 5 or more and 8 or less.
- Factors that determine the pH of the coating composition are greatly affected by the pKa of the inorganic solid acid, but are also affected by the acid point concentration, the solubility when the antiviral agent is dissolved in the medium, the hydrophilicity, and the like.
- the coating composition of the present invention can also be used as a paint.
- oils and fats such as soybean oil, linseed oil, safflower oil, castor oil, natural resins such as rosin, copal, shellac, chroman resin, processed resin such as petroleum resin, alkyd resin, acrylic resin,
- resin components for paints oils and fats such as soybean oil, linseed oil, safflower oil, castor oil, natural resins such as rosin, copal, shellac, chroman resin, processed resin such as petroleum resin, alkyd resin, acrylic resin, Examples include epoxy resins, polyurethane resins, vinyl chloride resins, silicone resins, synthetic resins such as fluororesins, rubber derivatives such as chlorinated rubber and cyclized rubber, and cellulose derivatives such as nitrified cotton (lacquer) and acetylcellulose.
- the paints described above are pigments, UV curing agents, plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, and anti-skinning agents that are conventionally contained in known paints.
- Additives such as agents, desiccants, anti-sagging agents, matting agents, antistatic agents, conductive agents, flame retardants, graffiti inhibitors, etc .; may contain solvents.
- the pigments include (white) titanium, (black) carbon, (brown) bengara, (red) chrome vermilion, (blue) bitumen, (yellow) yellow lead, (red) iron oxide, etc., calcium carbonate,
- extender pigments such as talc and barite powder, rust preventive pigments such as red lead, lead oxide, and thiamidlead, and functional pigments such as aluminum powder and zinc sulfide (fluorescent pigment).
- the solvent include water, alcohol, paint thinner, lacquer thinner, polyurethane resin thinner, and the like.
- the coating material is used as it is, or a liquid coating material diluted with a solvent or the like is applied to a substrate or the like with a brush coating method, a roller method, or a spraying method. Apply by (spray) method, iron coating method, etc., and dry if necessary.
- the content of the antiviral agent contained in the coating film is preferably 0.05 g or more with respect to the surface area of 1 m 2 of the substrate. Further, after coating, the obtained coating film may be cured by irradiation with radiation such as UV.
- Base materials include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyester, polycarbonate, acrylic resin, polystyrene, polyacrylonitrile, ABS resin, MBS resin, polyamide resin, cellophane and other plastic molded products, modified silicone And joint agents such as metal and urethane, metal, alloy, ceramic siding, porcelain, stoneware, pottery, glazed tile, marble, granite, and glass.
- the lower limit of the content ratio of the antiviral agent is that the antiviral agent and the resin component can be suitably expressed from the viewpoint that the antiviral effect by the film containing the antiviral agent can be suitably expressed.
- the total solid content such as is 100% by mass, it is preferably 10% by mass.
- the upper limit is preferably 50% by mass in terms of economical reasons, physical properties of the substrate to be coated, the point of not damaging the texture of the resulting antiviral product, and the point that the physical properties and functions of the coating are not significantly impaired.
- a particularly preferable content ratio of the antiviral agent is 20 to 40% by mass.
- the resin composition of the present invention contains a resin and the antiviral agent of the present invention.
- a resin and the antiviral agent of the present invention There is no restriction
- Specific resins include, for example, olefin resin (polyethylene, polypropylene, etc.), vinyl chloride, ABS resin, AS resin, MBS resin, nylon resin (polyamide synthetic resin), polyester (PET, PBT, etc.), polyvinylidene chloride , Polystyrene, polyacetal, polycarbonate, acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, melamine, urea resin, tetrafluoroethylene resin, unsaturated polyester resin, rayon, acetate, polyvinyl alcohol, cupra, triacetate, vinylidene, etc.
- the resin composition of this invention can also contain an additive.
- Additives include pigments such as zinc oxide and titanium oxide, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact resistance enhancers, glass fibers, metal soaps and other lubricants, moisture-proofing agents , Bulking agent, coupling agent, nucleating agent, fluidity improver, deodorant, wood powder, antifungal agent, antifouling agent, rust preventive agent, metal powder, ultraviolet absorber, ultraviolet shielding agent and the like. Any of these can be preferably used.
- the method for producing the resin composition of the present invention is not particularly limited, and conventionally known methods can be employed.
- a raw material mixture containing a resin and an antiviral agent is kneaded. Can be manufactured.
- a modified resin or an antiviral agent having a special functional group on the surface for example, (1) dispersion of an additive or an antiviral agent for facilitating adhesion between the antiviral agent and the resin A method for directly mixing pellet-like resin or powder-like resin with a mixer using a dispersant for improving the properties, (2) Mixing as in (1) above, and making it into a pellet with an extruder A method of blending the molded product into a pellet-shaped resin after molding, (3) Dispersing and mixing the antiviral agent in wax or the like, molding into a pellet shape, and then blending the pellet-shaped molded product into the pellet-shaped resin And (4) a method in which an antiviral agent is dispersed and mixed in a high-viscosity liquid such as polyol to prepare a paste-like composition, and then the paste-like composition is blended into a pellet-like resin.
- a high-viscosity liquid such as polyol
- the antiviral product of the present invention is an article containing the antiviral agent of the present invention.
- the antiviral product of the present invention is obtained, for example, by molding the resin composition of the present invention into a predetermined shape. After coating the coating composition of the present invention on a predetermined portion of the substrate, the coating film is dried. And the like and the like.
- the shape of the molded product can be a lump, sponge, film, sheet, thread, pipe, or a composite thereof.
- the antiviral product obtained by applying the coating composition of the present invention is a film containing an antiviral agent on at least a part of the surface of a substrate such as a fiber, fiber product (woven fabric, non-woven fabric, knitted fabric, etc.), film, etc.
- a substrate such as a fiber, fiber product (woven fabric, non-woven fabric, knitted fabric, etc.), film, etc.
- anti-virus products examples include indoor products, bedding, filters, furniture, in-car products, textile products, residential building products, paper products, toys, leather products, toiletry products, etc. Is done. More specifically, carpets, curtains, wallpaper, tatami mats, shoji paper, floor wax, calendars and other indoor products, futons, beds, sheets, pillows, pillow covers and other beddings, air purifiers, air conditioner filters, etc. Furniture such as sofas, chairs, in-car items such as child seats and seats, vacuum cleaner dust bags, clothing, masks, stuffed animals, kitchen utensils, etc., but are not limited to this. .
- the antiviral agent of the present invention When the antiviral agent of the present invention is contained in a non-aqueous coating composition, resin composition or the like to produce an antiviral product, the antiviral agent contained in the antiviral product comes into contact with other articles and other The metal part in the article may be corroded or the resin part may be discolored.
- the present inventors have confirmed by a water dispersion test that such problems can be suppressed by setting the pH of the coating composition within a predetermined range.
- aqueous dispersion test a simple method is to disperse an antiviral agent in water and measure its pH. For example, the pH after dispersing in deionized water so that the antiviral agent is 5% by mass and stirring with a stirrer at 25 ° C.
- the pH at that time is preferably 3 or more and 9 or less, more preferably 5 or more and 8 or less.
- An antiviral product containing an antiviral agent having a pH of the aqueous dispersion in the above range is preferable for use in coating compositions, paints, resin compositions and the like because it hardly causes metal corrosion or resin discoloration.
- % Is mass%.
- physical properties of antiviral agents were measured and heat resistance was evaluated, coating compositions containing antiviral agents were manufactured and evaluated, and resin compositions containing antiviral agents were manufactured and evaluated. It was.
- the method for measuring the acid point concentration of the inorganic solid acid powder constituting the antiviral agent is as follows. Add 0.5 g of inorganic solid acid powder to each of 20 20 mL sample bottles, add 10 mL of benzene to them and shake gently. Next, the amount of addition is changed to each sample bottle, and 0.1N of n-butylamine is added to obtain 20 kinds of mixed solutions, which are then stirred with a shaker. After 24 hours, 0.5 mL of 0.1% methyl red solution diluted with benzene is added to each mixture, and the color change of methyl red is visually observed.
- the addition amount of n-butylamine with the largest addition amount of n-butylamine, in which no discoloration of methyl red is confirmed is defined as the amount of base reacted with the acid point, and the acid point concentration (mmol / g).
- the method for measuring the acid strength of the inorganic solid acid powder constituting the antiviral agent is as follows. 0.1 g of a sample is taken into a test tube, 2 mL of benzene and 2 drops of a 0.1% benzene solution of the following indicator are added, gently shaken, and the color change is observed. In the case of crystal violet, a 0.1% ethanol solution is used. The acid strength is less than or equal to the strongest acid strength (lowest pKa value) at which discoloration of the indicator was confirmed, and is considered to be greater than the weakest acid strength (highest pKa) at which the indicator did not discolor, so the range is pKa. Record as a value.
- the average particle diameter of the inorganic solid acid powder constituting the antiviral agent is a volume-based median diameter ( ⁇ m) obtained by measurement with a laser diffraction particle size distribution analyzer.
- the method for measuring the moisture content of the inorganic solid acid powder constituting the antiviral agent is as follows. About 5 g of sample was weighed in an aluminum cup that had been weighed at 250 ° C. for 1 hour in a drier, dried at 250 ° C. for 2 hours, weighed again, and the amount obtained by dividing the loss on drying by the mass before drying was expressed in%. The water content of the acid powder was used.
- the evaluation method of the antiviral effect of the antiviral agent is as follows. Purified water is added to the antiviral agent to adjust the concentration of the inorganic solid acid powder to 0.5 mg / mL, and the influenza A virus having a viral infectivity of 2 ⁇ 10 4 PFU / mL with respect to 900 ⁇ L of this liquid Add 100 ⁇ L of the solution and let stand at 25 ° C. for 2 hours. Thereafter, the mixed solution is recovered, and this recovered solution is subjected to the plaque number measurement method to measure the virus infectivity titer. Moreover, the virus infectivity titer is also measured for the mixed solution before standing for 2 hours. The antiviral effect is determined by these virus infectivity titers.
- the evaluation of 1 of the coating composition was performed by evaluating the antiviral effect of an antiviral product (antiviral processed fabric) obtained by dip coating this composition onto a polyester fabric.
- antiviral processed fabric obtained by dip coating this composition onto a polyester fabric.
- 0.4 g of antiviral processed fabric before or after washing is inoculated with 0.2 mL of influenza A virus solution having a virus infection titer of 2 ⁇ 10 4 PFU / mL and allowed to stand at 25 ° C. for 2 hours. Thereafter, the virus solution is collected, and this collected solution is subjected to a plaque number measurement method to measure the virus infectivity. Moreover, a virus infectivity titer is measured also with respect to the contact liquid before leaving still for 2 hours.
- the antiviral effect was evaluated by the antiviral activity value obtained by the following formula.
- Antiviral activity value Log (virus infectivity immediately after inoculation) ⁇ Log (virus infectivity after 2 hours)
- Another evaluation of the coating composition was performed by evaluating the antiviral effect of an antiviral product (antiviral processed film) obtained by applying this composition to a polyester film.
- 0.4 mL of influenza A virus solution having a virus infection titer of 2 ⁇ 10 4 PFU / mL is dropped on the surface of the antiviral processed film having a size of 5 cm ⁇ 5 cm, and then the liquid portion is made of polyethylene having a size of 4 cm ⁇ 4 cm. Cover with film.
- the virus solution dropped on the surface of the antiviral processed film is recovered, and this recovered solution is subjected to a plaque number measurement method to measure the virus infectivity titer.
- Antiviral activity value Log (virus infectivity immediately after inoculation) ⁇ Log (virus infectivity after 2 hours)
- Evaluation of the resin composition containing an antiviral agent was performed by evaluating the antiviral effect of the antiviral fiber obtained by spinning the composition.
- 0.4 g of antiviral fiber is infiltrated with 0.2 mL of an influenza A virus solution having a virus infection titer of 2 ⁇ 10 4 PFU / mL and allowed to stand at 25 ° C. for 2 hours. Thereafter, the virus solution is collected, and this collected solution is subjected to a plaque number measurement method to measure the virus infectivity. Moreover, a virus infectivity titer is measured also with respect to the contact liquid before leaving still for 2 hours.
- the antiviral effect was evaluated by the antiviral activity value obtained by the following formula.
- Antiviral activity value Log (virus infectivity immediately after inoculation) ⁇ Log (virus infectivity after 2 hours)
- Example 2 ( ⁇ -type zirconium phosphate) A 15% zirconium oxychloride aqueous solution was added to a 75% phosphoric acid aqueous solution and aged at 100 ° C. for 12 hours. Thereafter, the obtained precipitate was filtered, washed with water, dried and pulverized to obtain a white ⁇ -type zirconium phosphate powder. Using the obtained ⁇ -type zirconium phosphate powder as an antiviral agent (V2), the color L value, average particle diameter, water content, acid strength and acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Example 3 ( ⁇ -type silver zirconium phosphate) A 15% zirconium oxychloride aqueous solution was added to a 75% phosphoric acid aqueous solution and aged at 100 ° C. for 12 hours. Thereafter, the obtained precipitate was washed with water and collected. The precipitate was then stirred at 100 ° C. for 2 hours in an aqueous silver nitrate solution. Thereafter, the obtained precipitate was filtered, washed with water, dried and crushed to obtain a white ⁇ -type silver zirconium phosphate powder containing 4.2% of silver. Using the obtained ⁇ -type silver zirconium phosphate powder as an antiviral agent (V3), the color L value, average particle size, water content, acid strength and acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Example 4 ( ⁇ -type copper zirconium phosphate) A 15% zirconium oxychloride aqueous solution was added to a 75% phosphoric acid aqueous solution and aged at 100 ° C. for 12 hours. Thereafter, the obtained precipitate was washed with water and collected. Next, this precipitate was stirred in an aqueous copper sulfate solution at 100 ° C. for 2 hours. Thereafter, the obtained precipitate was filtered, washed with water, dried and crushed to obtain a light blue ⁇ -type copper zirconium phosphate powder containing 2.8% copper. Using the obtained ⁇ -type copper zirconium phosphate powder as an antiviral agent (V4), the color L value, average particle size, water content, acid strength and acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Example 5 ( ⁇ -type zirconium phosphate) A zirconium carbonate aqueous solution was added to a 75% phosphoric acid aqueous solution and heated to reflux at 98 ° C. for 24 hours. Thereafter, the obtained precipitate was filtered, washed with water, dried and crushed to obtain a white ⁇ -type zirconium phosphate powder. Using the obtained ⁇ -type zirconium phosphate powder as an antiviral agent (V5), the color L value, average particle size, water content, acid strength and acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Example 6 (activated titanium oxide) As raw materials, titanyl sulfate and oxalic acid were mixed and reacted. Next, the obtained precipitate was filtered and dried, and baked at 500 ° C. Then, the white active titanium oxide powder was obtained by grind
- Comparative Example 2 (crystalline silver copper aluminum silicate) Sodium hydroxide and sodium silicate were added to aluminum hydroxide and aged at 100 ° C. for 6 hours. Thereafter, the obtained precipitate was washed with water and collected. The precipitate was then placed in an aqueous solution of silver nitrate and copper nitrate and stirred at 100 ° C. for 2 hours. Thereafter, the obtained precipitate was filtered, washed with water, dried and crushed to obtain a crystalline silver copper aluminum silicate powder containing 2.2% silver and 6.2% copper. Using the obtained crystalline silver copper aluminum silicate powder as an antiviral agent (V8), the average particle size, water content, acid strength and acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Comparative Example 4 (titanium oxide) A powder of titanium oxide “MC-50” (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used as an antiviral agent (V10). The average particle size and acid strength of this powder were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Comparative Example 5 (activated alumina) A powder of activated alumina “GNDY-2” (trade name) manufactured by Mizusawa Chemical Co., Ltd. was used as an antiviral agent (V11). The average particle size and acid strength of this powder were measured to evaluate the antiviral effect. The results are shown in Table 1.
- Examples 1 to 6 using the antiviral agents (V1) to (V6) comprising an inorganic solid acid having an acid point concentration exceeding 0.005 mmol / g showed excellent antiviral activity.
- Comparative Examples 1 to 5 using an antiviral agent comprising an inorganic solid acid having an acid point concentration of 0.005 mmol / g or less did not show antiviral activity. From the above, it was shown that an antiviral agent containing an inorganic solid acid having an acid point concentration exceeding 0.005 mmol / g is useful.
- Example 7 The antiviral agent (V1) comprising the amorphous magnesium silicate of Example 1 and the urethane emulsion binder having a nonvolatile content of 30% (hereinafter referred to as “NV30”) are 1: 1 in the solid content mass ratio.
- NV30 urethane emulsion binder having a nonvolatile content of 30%
- Example 8 A coating composition (C2) was produced in the same manner as in Example 7, except that the antiviral agent (V2) composed of ⁇ -type zirconium phosphate of Example 2 was used instead of the antiviral agent (V1). Thereafter, an antiviral processed dough was produced using the coating composition (C2), and the antiviral effect was evaluated. The results are shown in Table 2.
- Example 9 A coating composition (C3) was produced in the same manner as in Example 7, except that the antiviral agent (V3) comprising ⁇ -type silver zirconium phosphate of Example 3 was used instead of the antiviral agent (V1). . Thereafter, an antiviral processed dough was produced using the coating composition (C3), and the antiviral effect was evaluated. The results are shown in Table 2.
- Example 10 A coating composition (C4) was produced in the same manner as in Example 7 except that the antiviral agent (V4) comprising ⁇ -type copper zirconium phosphate of Example 4 was used instead of the antiviral agent (V1). . Thereafter, an antiviral processed dough was produced using the coating composition (C4), and the antiviral effect was evaluated. The results are shown in Table 2.
- Example 11 A coating composition (C5) was produced in the same manner as in Example 7, except that the antiviral agent (V5) comprising ⁇ -type zirconium phosphate of Example 5 was used instead of the antiviral agent (V1). Thereafter, an antiviral processed dough was produced using the coating composition (C5), and the antiviral effect was evaluated. The results are shown in Table 2.
- Example 12 A coating composition (C6) was produced in the same manner as in Example 7, except that the antiviral agent (V6) comprising active titanium oxide of Example 6 was used instead of the antiviral agent (V1). Thereafter, an antiviral processed dough was produced using the coating composition (C6), and the antiviral effect was evaluated. The results are shown in Table 2.
- Comparative Example 6 A coating composition (C7) was produced in the same manner as in Example 7 except that the antiviral agent (V7) composed of crystalline magnesium silicate of Comparative Example 1 was used instead of the antiviral agent (V1). Thereafter, an antiviral processed dough was produced using the coating composition (C7), and the antiviral effect was evaluated. The results are shown in Table 2.
- Comparative Example 7 A coating composition (C8) is produced in the same manner as in Example 7 except that the antiviral agent (V8) comprising the crystalline silver copper aluminum silicate of Comparative Example 2 is used instead of the antiviral agent (V1). did. Thereafter, an antiviral processed dough was produced using the coating composition (C8), and the antiviral effect was evaluated. The results are shown in Table 2.
- Comparative Example 8 A coating composition (C9) was produced in the same manner as in Example 7, except that dodecylbenzyldimethylammonium chloride (quaternary ammonium salt) was used instead of the antiviral agent (V1). Thereafter, an antiviral processed dough was produced using the coating composition (C9), and the antiviral effect was evaluated. The results are shown in Table 2.
- the antiviral processed fabrics of Examples 7 to 12 have higher antiviral activity values than the polyester fabric of Comparative Example 9, and thus the coating composition is useful. Moreover, since the antiviral processed fabric after washing these fabrics three times also showed a high antiviral activity value, it was shown that the antiviral agent in the film was difficult to flow out with water. On the other hand, the antiviral processed fabrics of Comparative Examples 6 and 7 had low antiviral activity values both in the unwashed state and after 3 times of washing, and the formed film did not exhibit the antiviral effect. Moreover, since the comparative example 8 showed the antiviral activity value in non-washing, although the formed film expresses the antiviral effect, the antiviral activity value after washing 3 times becomes very small. The antiviral agent in the coating composition seems to have flowed out with water.
- Example 13 The antiviral agent (V3) composed of ⁇ -type silver zirconium phosphate of Example 3 and the above-mentioned urethane emulsion binder of NV30 were mixed at a solid content mass ratio of 1: 1, and the coating composition (C11) was mixed. Manufactured. Next, this coating composition (C11) was applied to a polyester film so that the spread amount of the antiviral agent (V3) was 0.5 g / m 2 and air-dried to obtain an antiviral processed film. It was. And the antiviral activity value of this antiviral processed film was measured. The results are shown in Table 3.
- Comparative Example 10 instead of the antiviral agent (V3), the coating composition (C12) was prepared in the same manner as in Example 13 except that the antiviral agent (V8) composed of crystalline silver copper aluminum silicate of Comparative Example 2 was used. Obtained. Next, an antiviral processed film was produced using this coating composition (C12). And the antiviral activity value of this antiviral processed film was measured. The results are shown in Table 3.
- Comparative Example 11 A coating composition (C13) was obtained in the same manner as in Example 13, except that the antiviral agent (V10) comprising titanium oxide of Comparative Example 4 was used instead of the antiviral agent (V3). Next, an antiviral processed film was produced using this coating composition (C13). And the antiviral activity value of this antiviral processed film was measured. The results are shown in Table 3.
- Comparative Example 12 A coating composition (C14) was obtained in the same manner as in Example 13, except that the antiviral agent (V11) made of activated alumina of Comparative Example 5 was used instead of the antiviral agent (V3). Next, an antiviral processed film was produced using this coating composition (C14). And the antiviral activity value of this antiviral processed film was measured. The results are shown in Table 3.
- Comparative Example 13 The urethane emulsion binder was applied to a polyester film such that the spread amount of the urethane resin was 1 g / m 2 and air-dried to produce a film having a film made of the urethane resin. And the antiviral activity value was measured. The results are shown in Table 3.
- the antiviral processed film of Example 13 has an antiviral activity value exceeding 4.4, and the coating composition containing the antiviral agent of the present invention exhibits an antiviral effect. It has been found that the film is suitably formed. On the other hand, the antiviral activity values of the antiviral processed films of Comparative Examples 10 to 12 were less than 0.3, indicating that the antiviral effect was insufficient.
- Example 15 A masterbatch was produced in the same manner as in Example 14 except that the antiviral agent (V3) comprising ⁇ -type silver zirconium phosphate of Example 3 was used instead of the antiviral agent (V2). Subsequently, similarly, similarly, similarly, similarly, similarly, a resin composition (R2) containing 2% of the antiviral agent (V3) was obtained. Then, using this resin composition (R2), a 2 denier antiviral processed fiber was produced as an antiviral product. And the antiviral activity value of this antiviral processed fiber was measured. The results are shown in Table 4.
- Comparative Example 14 A masterbatch was produced in the same manner as in Example 14 except that the antiviral agent (V9) comprising NASICON type silver zirconium phosphate of Comparative Example 3 was used instead of the antiviral agent (V2). Subsequently, similarly, similarly, similarly, similarly, similarly, similarly, a resin composition (R3) containing 3% of an antiviral agent (V9) was obtained. Thereafter, a 2-denier processed fiber was produced using the resin composition (R3). And the antiviral activity value of this processed fiber was measured. The results are shown in Table 4.
- the resin composition of the present invention exhibits an antiviral effect. You can see that the product gives. Moreover, since the resin composition is melt-spun, it can be seen that the antiviral agent of the present invention is excellent in heat resistance and processability.
- Example 16 Heat Resistance Test of Antiviral Agent
- V2 comprising the ⁇ -type zirconium phosphate powder of Example 2 was heated to 350 ° C. for 1 hour using an electric furnace and then cooled to room temperature.
- the color L value, the average particle diameter, the water content, the acid strength, and the acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 5.
- Example 17 The antiviral agent (V3) comprising the ⁇ -type silver zirconium phosphate powder of Example 3 was heated to 350 ° C. for 1 hour using an electric furnace and then cooled to room temperature. About this heat-processed material, the color L value, the average particle diameter, the water content, the acid strength, and the acid point concentration were measured to evaluate the antiviral effect. The results are shown in Table 5.
- ⁇ -type zirconium phosphate and ⁇ -type silver zirconium phosphate are excellent in heat resistance because they have almost no change in physical properties other than water content even when heated at 350 ° C. and have antiviral activity. I understand that.
- the antiviral agent, coating composition and resin composition of the present invention exhibit an excellent antiviral effect. Moreover, it was shown that the antiviral agent of this invention is excellent in workability and has heat resistance.
- Influenza virus and the like can be inactivated by using the antiviral agent of the present invention as a material related to human living space such as textile products and housing building materials.
- the coating composition or resin composition containing the antiviral agent of the present invention is used for textile products such as clothing, bedding, and masks; filters used in air cleaners, air conditioners, etc .; wallpaper, curtains, carpets, furniture, etc. It is suitable for the production of anti-viral products such as interior products; automobile interior materials; building materials.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Virology (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
特許文献1には、無機過酸化物と、テトラアセチルエチレンジアミンと、無機酸のアルカリ金属塩及び/又は無機酸のアルカリ土類金属塩とを含有する無機系抗ウイルス剤組成物が開示されている。しかし、この無機系抗ウイルス剤は無機過酸化物系であるため、やはり持続性、加工性等に問題があった。
これら従来の抗ウイルス剤を含む製品が直接人体に接触すると、皮膚が刺激されるという問題もある。
更に、本発明の抗ウイルス剤を含有する本発明の抗ウイルス製品として、例えば、樹脂成形品、抗ウイルス剤を含む皮膜を備える物品等は、高い抗ウイルス活性を示すだけでなく、含まれる抗ウイルス剤が水で脱離又は流出することがないため、耐久性にも優れるものである。
(1)酸点濃度が0.005mmol/gを超える無機固体酸を含む抗ウイルス剤。
(2)上記無機固体酸における酸点の酸強度(pKa)が3.3以下である上記(1)に記載の抗ウイルス剤。
(3)無機固体酸が、無機リン酸化合物、無機ケイ酸化合物又は無機酸化物を含む(1)又は(2)に記載の抗ウイルス剤。
(4)銀、銅、及びそれらの化合物からなる群から選択される少なくとも1つを含む上記(1)~(3)のいずれかに記載の抗ウイルス剤。
(5)上記(1)~(4)のいずれかに記載の抗ウイルス剤を含むコーティング組成物。
(6)上記(1)~(4)のいずれかに記載の抗ウイルス剤を含む樹脂組成物。
(7)上記(1)~(4)のいずれかに記載の抗ウイルス剤を含む抗ウイルス製品。
尚、酸点濃度が高いほど、抗ウイルス効果も高まるため、無機固体酸の酸点濃度に上限はない。但し、酸点濃度が10mmol/gを超えるものは一般的に知られていないので、上限は、通常、10mmol/gである。
本発明における好ましい酸点濃度は0.008mmol/g以上、より好ましくは0.01mmol/g以上である。特に酸点濃度が0.01mmol/g以上の無機固体酸による抗ウイルス効果は優れており、様々なウイルスに対して高い効果を示す。
本発明の抗ウイルス剤は、上記のように、0.005mmol/gを超える酸点濃度を有する無機固体酸の表面の酸点において、抗ウイルス効果を発現させる。
通常、ウイルスは、(1)細胞表面への吸着、(2)細胞内への侵入、(3)脱殻、(4)部品の合成、(5)部品の集合、及び(6)感染細胞からの放出、という段階を経て増殖を行う。上記無機固体酸は、無機固体表面の酸点に接触したウイルスの細胞表面への吸着を不活性化することにより、抗ウイルス効果を発現させると推察される。
酸点濃度は、液相又は気相で測定することができる。液相で測定する方法としては、滴定法が知られている。また、気相で測定する方法としては、Heガスや水素ガスの吸脱着量と塩基性ガスの吸脱着量との差を測定する気体化学吸着法が知られている。
本発明における抗ウイルス剤とウイルスとの反応は、液体を媒介とした反応であるため、酸点濃度の測定は、液相での滴定法が適している。
無極性溶媒中に分散した無機固体酸をn-ブチルアミンで滴定し、滴定の終点を酸塩基変換指示薬の変色で確認する。反応前の指示薬は塩基型の色を呈しているが、無機固体酸に吸着するとその共役酸型の色を呈する。共役酸型の色から塩基型の色に戻るまでに要したn-ブチルアミンの滴定量よりその酸点濃度を決定する。固体の酸点一個とn-ブチルアミン一分子とが対応する。滴定用塩基は、固体の酸点と反応した指示薬を置換しなければならないため、その塩基性は指示薬の塩基性よりも強いものとなる。
通常の滴定方法は、無機固体酸/ベンゼン分散液に指示薬を加えると、固体酸性により指示薬は酸性色を示すが、反応が完結するまで十分な時間をおくことが好ましい。次に、n-ブチルアミンを滴下していき、指示薬の色が元の色である塩基性色に戻ったときのn-ブチルアミンの量から酸点濃度を計算する。
(1)ベンゼン10mL及び無機固体酸0.5gを20mLのサンプル瓶に入れて撹拌し、無機固体酸を分散させる。この混合分散液を、例えば、20個準備する。
(2)各サンプル瓶に添加量を変えて規定度0.1Nのn-ブチルアミンを加え、振とう機で攪拌し、20種の混合液を調製する。
(3)24時間後、各混合液に0.1%指示薬メチルレッド溶液を0.5mL加え、指示薬の変色を観察する。
(4)指示薬の変色が確認されないn-ブチルアミンの添加量が最も多い系のn-ブチルアミンの添加量を酸点と反応した塩基量とし、酸点濃度(mmol/g)として表す。
酸点の酸強度が小さい、即ち、pKaが高い場合には、ウイルスを不活性化する能力が低下する傾向にあり、pKaが0.8以下の場合に特に優れた抗ウイルス性能が得られる。
尚、pKaが低いほど塩基にプロトンを与える性質、又は、塩基から電子対を受け取る性質の強さ、即ち、酸強度が強くなり、酸強度が強いほどウイルスを不活性化する能力が高くなる。
酸強度の測定に用いることができる酸塩基変換指示薬(pKa値)としては、メチルレッド(+4.8)、4-フェニルアゾ-1-ナフチルアミン(+4.0)、ジメチルイエロー(+3.3)、2-アミノ-5-アゾトルエン(+2.0)、4-フェニルアゾ-ジフェニルアミン(+1.5)、4-ジメチルアミノアゾ-1-ナフタレン(+1.2)、クリスタルバイオレット(+0.8)、p-ニトロベンゼンアゾ-p’-ニトロ-ジフェニルアミン(+0.43)、ジシンナミルアセトン(-3.0)、ベンザルアセトフェノン(-5.6)、アントラキノン(-8.2)等が例示できる。
(1)ベンゼン2mL及び無機固体酸0.1gを試験管に入れて撹拌し、無機固体酸を分散させる。この分散液を、試験する酸塩基変換指示薬の種類の分だけ用意する。
(2)各種酸塩基変換指示薬の0.1%ベンゼン溶液(クリスタルバイオレットはベンゼン溶液でなく、0.1%エタノール溶液とする)の約2滴を、分散液に添加し軽く振り混ぜ、色の変化を観察する。
(3)無機固体酸の酸強度(pKa)は、指示薬の変色が確認された最も強い酸強度(即ち、最も低いpKa値)以下であり、指示薬の変色が確認されない最も弱い酸強度(即ち、最も高いpKa値)より大きいことになる。従って、無機固体酸のpKa値は(変色の確認されない最も高いpKa値)~(変色の確認された最も低いpKa値)として表記する。また、下限を示す適当な指示薬がない場合は「変色の確認された最も低いpKa値以下」とし、上限を示す適当な指示薬がない場合は「変色の確認されない最も高いpKa値より大きい」とする。
粉末状の抗ウイルス剤の平均粒径は、好ましくは0.01~50μmであり、より好ましくは0.1~20μmである。平均粒径が0.01μm以上の粉末は凝集し難いため取り扱い易いという長所がある。また、平均粒径が50μm以下の粉末を含有するコーティング組成物は、分散性が良好であるために繊維の表面に塗布した場合、皮膜付き繊維の風合いを損ねることがなく、また、樹脂組成物から紡糸して繊維を作製した場合に糸切れを起こし難くすることができる。
上記平均粒径は、レーザー回折式粒度分布測定器等で測定することができ、体積基準で解析したメジアン径である。
抗ウイルス剤中の含水率は、好ましくは0.5質量%以上、より好ましくは1質量%以上、更に好ましくは3質量%以上である。また、吸湿性を有する上記無機固体酸は、他の材料と混合しても、あるいは大気の湿度が変化しても、水分を無機固体酸中に保つことができるから、ウイルスの不活性化に必要な水分を抗ウイルス剤自体が有している点で優れている。
感染価の測定方法としては、プラック数測定法、50%組織培養感染量(TCID50)測定法及び50%ウイルス力価(EID50)測定法が挙げられる。
抗ウイルス効果は、下記式(1)により得られる抗ウイルス活性値として評価することが可能である。式(1)中で初期ウイルス感染価とは、評価に用いた接種直後のウイルス液のウイルス量を意味し、残存ウイルス感染価とは、抗ウイルス試料と接触し一定時間経過後のウイルス量を意味する。抗ウイルス活性値は、数値が高いほど抗ウイルス効果が高く、好ましくは2以上、より好ましくは3以上である。
抗ウイルス活性値=Log(初期ウイルス感染価)-Log(残存ウイルス感染価) (1)
粉末状の抗ウイルス剤は、例えば、粉末含有分散液、粉末含有粒子、粉末含有塗料、粉末含有繊維、粉末含有紙、粉末含有プラスチック、粉末含有フィルム、粉末含有エアゾール等の種々の使用形態とすることができる。更に、必要に応じて、消臭剤、抗菌剤、抗カビ剤、防炎剤、防食、肥料等の各種の添加剤;建材等の材料等と併用することもできる。
また、本発明の抗ウイルス剤を、人が接触する可能性のある材料である、樹脂、紙、プラスチック、ゴム、ガラス、金属、コンクリート、木材、塗料、繊維、革、石等に添加することによって生活空間におけるウイルスを不活性化させることが可能である。
コーティング組成物中における抗ウイルス剤の濃度は、分散が容易で保存性が良いことから、好ましくは0.5~50質量%、更に好ましくは1~30質量%である。通常、抗ウイルス効果は、各種形状の抗ウイルス製品の表面で抗ウイルス剤とウイルスとが接触することによって発現するので、本発明のコーティング組成物で抗ウイルス製品の表面に抗ウイルス剤を固定することは、より少ない量の抗ウイルス剤で大きな効果を得ることができるので好ましい。
本発明のコーティング組成物の主な使用用途は、繊維又は繊維製品(織布、不織布、編物等)への加工である。
繊維又は繊維製品に塗布する方法としては、コーティング組成物をそのまま、あるいは、溶剤等で希釈した液体を、繊維又は繊維製品に塗布、浸漬又は吹き付ける方法が例示される。上記繊維には制限はなく、綿、絹、羊毛等の天然繊維;ポリエステル、ナイロン(ポリアミド系合成繊維)、アクリルニトリル等の合成繊維;トリアセテート、ジアセテート等の半合成繊維;ビスコースレーヨン等の再生繊維等が挙げられる。また、これらの繊維を2種類以上含む複合繊維でもよい。不織布の場合、ポリエチレン繊維、ポリプロピレン繊維等を含むものとすることが可能である。
尚、コーティング組成物による抗ウイルス製品の製造方法は、特に限定されるものではないが、浸漬処理、プリント処理、吹き付け処理等の何れの塗布方法を採用した場合であっても、コーティング組成物の塗布後には、塗膜の乾燥を要する。乾燥方法は、自然乾燥、熱風乾燥、真空乾燥等いずれも用いることができるが、好ましくは熱による方法である。乾燥条件は、好ましくは40℃~250℃、より好ましくは50℃~180℃で好ましくは1分~5時間、より好ましくは5分~3時間である。これによって抗ウイルス剤を繊維又は繊維製品に定着させることができる。
コーティング組成物のpHを決める要因は、無機固体酸のpKaが大きく効くが、その他にも酸点濃度や、抗ウイルス剤が媒体に溶解する場合の溶解性、親水性等が影響を与える。
塗料用樹脂成分としては、大豆油、あまに油、サフラワー油、ひまし油等の油脂類、ロジン、コパール、セラック等の天然樹脂、クロマン樹脂、石油樹脂等の加工樹脂、アルキド樹脂、アクリル樹脂、エポキシ樹脂、ポリウレタン樹脂、塩化ビニル樹脂、シリコーン樹脂、フッ素樹脂等の合成樹脂、塩素化ゴム、環化ゴム等のゴム誘導体、硝化綿(ラッカー)、アセチルセルロース等のセルロース誘導体等が例示される。
上記塗料は、従来、公知の塗料に含有されている顔料、UV硬化剤、可塑剤、分散剤、沈降防止剤、乳化剤、増粘剤、消泡剤、防カビ剤、防腐剤、皮張り防止剤、乾燥剤、たれ防止剤、つや消し剤、帯電防止剤、導電剤、難燃剤、落書き防止剤等の添加剤;溶剤を含有してもよい。
顔料としては、(白)チタン、(黒)カーボン、(茶)べんがら、(朱)クロムバーミリオン、(青)紺青、(黄)黄鉛、(赤)酸化鉄等の着色含量、炭酸カルシウム、タルク、バライト粉等の体質顔料、鉛丹、亜酸化鉛、シアミド鉛等の防錆顔料、アルミニウム粉、硫化亜鉛(蛍光顔料)等の機能性顔料等が例示される。
また、溶剤としては、水、アルコール、塗料用シンナー、ラッカーシンナー、ポリウレタン樹脂用シンナー等のシンナー等が例示される。
基材としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリエステル、ポリカーボネート、アクリル樹脂、ポリスチレン、ポリアクリロニトリル、ABS樹脂、MBS樹脂、ポリアミド樹脂、セロファン等のプラスチック成形品、変性シリコーンやウレタン等の目地剤、金属、合金、窯業サイディング、磁器、石器、陶器、施釉タイル、大理石、御影石、ガラス等である。
樹脂組成物に用いることができる樹脂の種類に制限はなく、天然樹脂、合成樹脂及び半合成樹脂のいずれであってもよく、また、熱可塑性樹脂、熱硬化性樹脂のいずれであってもよい。
具体的な樹脂としては、例えば、オレフィン樹脂(ポリエチレン、ポリプロピレン等)、塩化ビニル、ABS樹脂、AS樹脂、MBS樹脂、ナイロン樹脂(ポリアミド系合成樹脂)、ポリエステル(PET、PBT等)、ポリ塩化ビニリデン、ポリスチレン、ポリアセタール、ポリカーボネート、アクリル樹脂、フッ素樹脂、ポリウレタンエラストマー、ポリエステルエラストマー、メラミン、ユリア樹脂、四フッ化エチレン樹脂、不飽和ポリエステル樹脂、レーヨン、アセテート、ポリビニルアルコール、キュプラ、トリアセテート、ビニリデン等の成形用又は繊維用樹脂、天然ゴム、シリコーンゴム、スチレンブタジエンゴム、エチレンプロピレンゴム、フッ素ゴム、ニトリルゴム、クロルスルホン化ポリエチレンゴム、ブタジエンゴム、合成天然ゴム、ブチルゴム、ウレタンゴム、アクリルゴム等のゴム状樹脂が挙げられる。
また、本発明の樹脂組成物は、添加剤を含有することもできる。添加剤としては、酸化亜鉛や酸化チタン等の顔料、染料、酸化防止剤、耐光安定剤、難燃剤、帯電防止剤、発泡剤、耐衝撃強化剤、ガラス繊維、金属石鹸等の滑剤、防湿剤、増量剤、カップリング剤、核剤、流動性改良剤、消臭剤、木粉、防黴剤、防汚剤、防錆剤、金属粉、紫外線吸収剤、紫外線遮蔽剤等が挙げられる。これらは、いずれも好ましく用いることができる。
本発明の抗ウイルス製品は、例えば、本発明の樹脂組成物を所定の形状に成形して得られたもの、本発明のコーティング組成物を基材の所定部分に塗布した後、塗膜を乾燥して皮膜化させたもの等が挙げられる。
水分散系の試験としては、抗ウイルス剤を水分散してそのpHを測定するのが簡易な方法である。例えば、抗ウイルス剤が5質量%となるように脱イオン交換水中に分散させ、25℃で攪拌機により5分間攪拌した後のpHを、ガラス電極式pHメーターを用いて測定する。その時のpHは、好ましくは3以上9以下であり、更に好ましくは5以上8以下である。水分散液のpHが上記範囲にある抗ウイルス剤を含む抗ウイルス製品は、金属の腐食や樹脂の変色を起こしにくいので、コーティング組成物、塗料、樹脂組成物等に用いるものとして好ましい。
実施例及び比較例では、抗ウイルス剤の物性測定及び耐熱性評価と、抗ウイルス剤を含むコーティング組成物の製造及びその評価と、抗ウイルス剤を含む樹脂組成物の製造及びその評価とを行った。
抗ウイルス効果は、これらのウイルス感染価で判定し、2時間静置後のウイルス感染価が検出限界以下であった場合を「++」、2時間静置後の抗ウイルス活性値、即ち、Log(接種直後のウイルス感染価)-Log(2時間後のウイルス感染価)の計算値が1以上低下していた場合を「+」、2時間静置後に「++」及び「+」以外の場合を「-」とした。
抗ウイルス効果は、下記式で得られる抗ウイルス活性値で評価した。
抗ウイルス活性値=Log(接種直後のウイルス感染価)-Log(2時間後のウイルス感染価)
抗ウイルス効果は、下記式で得られる抗ウイルス活性値で評価した。
抗ウイルス活性値=Log(接種直後のウイルス感染価)-Log(2時間後のウイルス感染価)
抗ウイルス効果は、下記式で得られる抗ウイルス活性値で評価した。
抗ウイルス活性値=Log(接種直後のウイルス感染価)-Log(2時間後のウイルス感染価)
実施例1(非晶質ケイ酸マグネシウム)
原料として、硫酸、硫酸マグネシウム及び水ガラスを用い、これらを混合・反応させた。次いで、得られた沈殿物をろ過、水洗、乾燥及び粉砕することで、白色の、非晶質ケイ酸マグネシウム(SiO2/MgO=1.3)粉末を得た。得られた非晶質ケイ酸マグネシウム粉末を抗ウイルス剤(V1)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
75%リン酸水溶液に15%オキシ塩化ジルコニウム水溶液を添加し、100℃で12時間熟成させた。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、白色のα型リン酸ジルコニウム粉末を得た。得られたα型リン酸ジルコニウム粉末を抗ウイルス剤(V2)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
75%リン酸水溶液に15%オキシ塩化ジルコニウム水溶液を添加し、100℃で12時間熟成させた。その後、得られた沈殿物を水洗し、回収した。次いで、この沈殿物を硝酸銀水溶液中にて100℃で2時間撹拌した。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、白色の、銀を4.2%含有するα型銀リン酸ジルコニウム粉末を得た。得られたα型銀リン酸ジルコニウム粉末を抗ウイルス剤(V3)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
75%リン酸水溶液に15%オキシ塩化ジルコニウム水溶液を添加し、100℃で12時間熟成させた。その後、得られた沈殿物を水洗し、回収した。次いで、この沈殿物を硫酸銅水溶液中にて100℃で2時間撹拌した。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、水色の、銅を2.8%含有するα型銅リン酸ジルコニウム粉末を得た。得られたα型銅リン酸ジルコニウム粉末を抗ウイルス剤(V4)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
75%リン酸水溶液に炭酸ジルコニウム水溶液を添加し、98℃で24時間加熱還流させた。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、白色のγ型リン酸ジルコニウム粉末を得た。得られたγ型リン酸ジルコニウム粉末を抗ウイルス剤(V5)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
原料として、硫酸チタニル及びシュウ酸を用い、これらを混合・反応させた。次いで、得られた沈殿物をろ過及び乾燥し、500℃で焼成処理した。その後、粉砕することで、白色の活性酸化チタン粉末を得た。得られた酸化チタン粉末を抗ウイルス剤(V6)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
原料として、硫酸、硫酸マグネシウム及び水ガラスを用い、これらを混合・反応させた。次いで、得られた沈殿物をろ過、水洗、水熱処理、乾燥及び粉砕することで、結晶質ケイ酸マグネシウム(SiO2/MgO=1.3)粉末を得た。得られた結晶質ケイ酸マグネシウム粉末を抗ウイルス剤(V7)として、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
水酸化アルミニウムに、水酸化ナトリウム及び珪酸ソーダを加えて、100℃で6時間熟成した。その後、得られた沈殿物を水洗し、回収した。次いで、この沈殿物を、硝酸銀及び硝酸銅の水溶液に入れ、100℃で2時間撹拌した。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、銀を2.2%、銅を6.2%含有する結晶質銀銅ケイ酸アルミニウム粉末を得た。得られた結晶質銀銅ケイ酸アルミニウム粉末を抗ウイルス剤(V8)として、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
オキシ塩化ジルコニウム水溶液にシュウ酸及び75%リン酸水溶液を添加した。次いで、苛性ソーダで混合液のpHを2.7に調整し、98℃で12時間加熱還流した。その後、得られた沈殿物をろ過、水洗、乾燥及び解砕することで、NASICON型リン酸ジルコニウム粉末を得た。得られたNASICON型リン酸ジルコニウム粉末を抗ウイルス剤(V9)として、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
石原産業社製酸化チタン「MC-50」(商品名)の粉末を抗ウイルス剤(V10)として用いた。この粉末の平均粒径及び酸強度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
水澤化学工業社製活性アルミナ「GNDY-2」(商品名)の粉末を抗ウイルス剤(V11)として用いた。この粉末の平均粒径及び酸強度を測定し、抗ウイルス効果を評価した。その結果を表1に示した。
一方、酸点濃度が0.005mmol/g以下の無機固体酸からなる抗ウイルス剤を用いた比較例1~5は、抗ウイルス活性を示さなかった。
以上から、酸点濃度が0.005mmol/gを超える無機固体酸を含む抗ウイルス剤が有用であることが示された。
実施例7
実施例1の非晶質ケイ酸マグネシウムからなる抗ウイルス剤(V1)と、不揮発分が30%(以下、「NV30」という)のウレタンエマルションバインダーとを、固形分質量比で1:1になるように混合し、コーティング組成物(C1)を製造した。
次いで、このコーティング組成物(C1)に、185g/m2のポリエステル生地を、抗ウイルス剤(V1)の展着量が3g/m2となるように浸漬し、105℃で乾燥して、抗ウイルス加工生地を製造した。
この抗ウイルス加工生地、及び、JIS L0217 103法による洗濯3回後の抗ウイルス加工生地について、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、実施例2のα型リン酸ジルコニウムからなる抗ウイルス剤(V2)を用いた以外は、実施例7と同様にしてコーティング組成物(C2)を製造した。その後、コーティング組成物(C2)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、実施例3のα型銀リン酸ジルコニウムからなる抗ウイルス剤(V3)を用いた以外は、実施例7と同様にしてコーティング組成物(C3)を製造した。その後、コーティング組成物(C3)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、実施例4のα型銅リン酸ジルコニウムからなる抗ウイルス剤(V4)を用いた以外は、実施例7と同様にしてコーティング組成物(C4)を製造した。その後、コーティング組成物(C4)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、実施例5のγ型リン酸ジルコニウムからなる抗ウイルス剤(V5)を用いた以外は、実施例7と同様にしてコーティング組成物(C5)を製造した。その後、コーティング組成物(C5)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、実施例6の活性酸化チタンからなる抗ウイルス剤(V6)を用いた以外は、実施例7と同様にしてコーティング組成物(C6)を製造した。その後、コーティング組成物(C6)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、比較例1の結晶質ケイ酸マグネシウムからなる抗ウイルス剤(V7)を用いた以外は、実施例7と同様にしてコーティング組成物(C7)を製造した。その後、コーティング組成物(C7)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、比較例2の結晶質銀銅ケイ酸アルミニウムからなる抗ウイルス剤(V8)を用いた以外は、実施例7と同様にしてコーティング組成物(C8)を製造した。その後、コーティング組成物(C8)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
抗ウイルス剤(V1)に代えて、ドデシルベンジルジメチルアンモニウムクロライド(第4アンモニウム塩)を用いた以外は、実施例7と同様にしてコーティング組成物(C9)を製造した。その後、コーティング組成物(C9)を用いて抗ウイルス加工生地を製造し、抗ウイルス効果を評価した。その結果を表2に示した。
未加工のポリエステル生地に対し、抗ウイルス効果を評価した。その結果を表2に示した。
一方、比較例6及び7の抗ウイルス加工生地は、未洗濯及び洗濯3回後の双方で抗ウイルス活性値が低く、形成された皮膜が抗ウイルス効果を発現していなかった。また、比較例8は、未洗濯で抗ウイルス活性値を示したので、形成された皮膜が抗ウイルス効果を発現しているものの、洗濯3回後の抗ウイルス活性値が非常に小さくなることから、コーティング組成物中の抗ウイルス剤が水で流出したものと思われる。
実施例13
実施例3のα型銀リン酸ジルコニウムからなる抗ウイルス剤(V3)と、NV30の上記ウレタンエマルションバインダーとを固形分質量比で1:1になるように混合し、コーティング組成物(C11)を製造した。次いで、このコーティング組成物(C11)を、ポリエステルフィルムに、抗ウイルス剤(V3)の展着量が0.5g/m2となるように塗工し、風乾することで抗ウイルス加工フィルムを得た。そして、この抗ウイルス加工フィルムの抗ウイルス活性値を測定した。その結果を表3に示した。
抗ウイルス剤(V3)に代えて、比較例2の結晶質銀銅ケイ酸アルミニウムからなる抗ウイルス剤(V8)を用いた以外は、実施例13と同様にして、コーティング組成物(C12)を得た。次いで、このコーティング組成物(C12)を用いて抗ウイルス加工フィルムを製造した。そして、この抗ウイルス加工フィルムの抗ウイルス活性値を測定した。その結果を表3に示した。
抗ウイルス剤(V3)に代えて、比較例4の酸化チタンからなる抗ウイルス剤(V10)を用いた以外は、実施例13と同様にして、コーティング組成物(C13)を得た。次いで、このコーティング組成物(C13)を用いて抗ウイルス加工フィルムを製造した。そして、この抗ウイルス加工フィルムの抗ウイルス活性値を測定した。その結果を表3に示した。
抗ウイルス剤(V3)に代えて、比較例5の活性アルミナからなる抗ウイルス剤(V11)を用いた以外は、実施例13と同様にして、コーティング組成物(C14)を得た。次いで、このコーティング組成物(C14)を用いて抗ウイルス加工フィルムを製造した。そして、この抗ウイルス加工フィルムの抗ウイルス活性値を測定した。その結果を表3に示した。
上記ウレタンエマルションバインダーを、ウレタン樹脂の展着量が1g/m2となるようにポリエステルフィルムに塗工し、風乾することで、ウレタン樹脂からなる皮膜を有するフィルムを製造した。そして、抗ウイルス活性値を測定した。その結果を表3に示した。
一方、比較例10~12の抗ウイルス加工フィルムの抗ウイルス活性値は0.3未満であり、抗ウイルス効果が不十分であることが分かった。
実施例14
実施例2のα型リン酸ジルコニウムからなる抗ウイルス剤(V2)を、三菱レイヨン社製ポリエステル樹脂「MA2101」に20%の割合で配合し、2軸押出成形機を用いて、温度290℃で混練し、ペレット状のマスターバッチを作製した。次いで、このマスターバッチと、上記ポリエステル樹脂とを混合し、α型リン酸ジルコニウムを3%含有する樹脂組成物(R1)を製造した。その後、得られた樹脂組成物(R1)を溶融紡糸して、290℃で36fマルチフィラメントを製造した。更に、このフィラメントを延伸し、抗ウイルス製品として、2デニールの抗ウイルス加工繊維を製造した。そして、この抗ウイルス加工繊維の抗ウイルス活性値を測定した。その結果を表4に示した。
抗ウイルス剤(V2)に代えて、実施例3のα型銀リン酸ジルコニウムからなる抗ウイルス剤(V3)を用いた以外は、実施例14と同様にして、マスターバッチを製造した。次いで、同様にして、抗ウイルス剤(V3)を2%含有する樹脂組成物(R2)を得た。その後、この樹脂組成物(R2)を用いて、抗ウイルス製品として、2デニールの抗ウイルス加工繊維を製造した。そして、この抗ウイルス加工繊維の抗ウイルス活性値を測定した。その結果を表4に示した。
抗ウイルス剤(V2)に代えて、比較例3のNASICON型銀リン酸ジルコニウムからなる抗ウイルス剤(V9)を用いた以外は、実施例14と同様にしてマスターバッチを製造した。次いで、同様にして、抗ウイルス剤(V9)を3%含有する樹脂組成物(R3)を得た。その後、この樹脂組成物(R3)を用いて、2デニールの加工繊維を製造した。そして、この加工繊維の抗ウイルス活性値を測定した。その結果を表4に示した。
上記ポリエステル樹脂のみを用いて紡糸し2デニールの繊維を得た。その後、この繊維の抗ウイルス活性値を測定した。その結果を表4に示した。
実施例16
実施例2のα型リン酸ジルコニウム粉末からなる抗ウイルス剤(V2)を、電気炉を用いて350℃で1時間加熱後に室温まで冷却した。この熱処理物について、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表5に示した。
実施例3のα型銀リン酸ジルコニウム粉末からなる抗ウイルス剤(V3)を、電気炉を用いて350℃で1時間加熱後に室温まで冷却した。この熱処理物について、色彩L値、平均粒径、含水率、酸強度及び酸点濃度を測定し、抗ウイルス効果を評価した。その結果を表5に示した。
Claims (7)
- 酸点濃度が0.005mmol/gを超える無機固体酸を含むことを特徴とする抗ウイルス剤。
- 上記無機固体酸における酸点の酸強度(pKa)が3.3以下である請求項1に記載の抗ウイルス剤。
- 上記無機固体酸が、無機リン酸化合物、無機ケイ酸化合物又は無機酸化物を含む請求項1又は2に記載の抗ウイルス剤。
- 銀、銅、及びそれらの化合物からなる群から選択される少なくとも1つを含む請求項1乃至3のいずれか一項に記載の抗ウイルス剤。
- 請求項1乃至4のいずれか一項に記載の抗ウイルス剤を含むことを特徴とするコーティング組成物。
- 請求項1乃至4のいずれか一項に記載の抗ウイルス剤を含むことを特徴とする樹脂組成物。
- 請求項1乃至4のいずれか一項に記載の抗ウイルス剤を含むことを特徴とする抗ウイルス製品。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17759534.5A EP3424326A4 (en) | 2016-03-01 | 2017-02-02 | ANTIVIRAL, COATING COMPOSITION, RESIN COMPOSITION, AND ANTIVIRAL PRODUCT |
US16/078,534 US20190045793A1 (en) | 2016-03-01 | 2017-02-02 | Antiviral agent, coating composition, resin composition and antiviral product |
JP2018502963A JP6721035B2 (ja) | 2016-03-01 | 2017-02-02 | 抗ウイルス剤、コーティング組成物、樹脂組成物及び抗ウイルス製品 |
KR1020187026980A KR20180117644A (ko) | 2016-03-01 | 2017-02-02 | 항바이러스제, 코팅 조성물, 수지 조성물 및 항바이러스 제품 |
CN201780013766.5A CN108697094A (zh) | 2016-03-01 | 2017-02-02 | 抗病毒剂、涂料组合物、树脂组合物及抗病毒制品 |
US17/238,281 US20210235702A1 (en) | 2016-03-01 | 2021-04-23 | Antiviral agent, coating composition, resin composition and antiviral product |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-039362 | 2016-03-01 | ||
JP2016039362 | 2016-03-01 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/078,534 A-371-Of-International US20190045793A1 (en) | 2016-03-01 | 2017-02-02 | Antiviral agent, coating composition, resin composition and antiviral product |
US17/238,281 Division US20210235702A1 (en) | 2016-03-01 | 2021-04-23 | Antiviral agent, coating composition, resin composition and antiviral product |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017150063A1 true WO2017150063A1 (ja) | 2017-09-08 |
Family
ID=59743750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/003686 WO2017150063A1 (ja) | 2016-03-01 | 2017-02-02 | 抗ウイルス剤、コーティング組成物、樹脂組成物及び抗ウイルス製品 |
Country Status (7)
Country | Link |
---|---|
US (2) | US20190045793A1 (ja) |
EP (1) | EP3424326A4 (ja) |
JP (1) | JP6721035B2 (ja) |
KR (1) | KR20180117644A (ja) |
CN (1) | CN108697094A (ja) |
TW (1) | TWI801335B (ja) |
WO (1) | WO2017150063A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020203069A1 (ja) * | 2019-04-04 | 2020-10-08 | リケンテクノス株式会社 | 抗ウイルス性塗膜形成用塗料、塗膜、及び積層フィルム |
JP6973835B1 (ja) * | 2021-03-19 | 2021-12-01 | 株式会社Yooコーポレーション | 抗ウイルス剤 |
WO2022075438A1 (ja) * | 2020-10-08 | 2022-04-14 | ミドリオートレザー株式会社 | 皮革、皮革コーティング剤、及び皮革の製造方法 |
JP2022093249A (ja) * | 2020-12-11 | 2022-06-23 | 東亞合成株式会社 | 活性エネルギー線硬化型抗ウイルス用組成物 |
JP7283710B1 (ja) * | 2021-07-16 | 2023-05-30 | 国立研究開発法人物質・材料研究機構 | 抗ウイルス性コーティング剤、積層体、及び、包装体又は容器 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110934153B (zh) * | 2019-12-04 | 2021-06-15 | 上海朗亿功能材料有限公司 | 磷酸锆载体、磷酸锆载铜抗菌剂、磷酸锆抗菌剂及其制备方法和应用 |
CN112878037B (zh) * | 2020-04-21 | 2023-06-06 | 中国科学院大连化学物理研究所 | 一种吸附灭活病毒聚丙烯熔喷布及其生产方法与应用 |
CN112890322B (zh) * | 2020-04-21 | 2023-04-07 | 中国科学院大连化学物理研究所 | 一种吸附灭活病毒口罩产品 |
CN112871133A (zh) * | 2020-04-21 | 2021-06-01 | 中国科学院大连化学物理研究所 | 一种吸附灭活病毒大孔无机功能材料的制备方法与应用 |
CN111500140A (zh) * | 2020-06-19 | 2020-08-07 | 广东润立新材科技有限公司 | 一种新型抗菌抗病毒多功能涂料及其制备方法 |
KR102335588B1 (ko) * | 2021-03-23 | 2021-12-06 | 주식회사 케미슈티칼 | 구연산동을 유효성분으로 포함하는 항균성 수분산 조성물 |
JP2022171189A (ja) * | 2021-04-30 | 2022-11-11 | 株式会社コトブキ | 人工再生木材 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001233719A (ja) * | 1999-12-13 | 2001-08-28 | Natl Inst Of Advanced Industrial Science & Technology Meti | 殺菌材および殺菌方法 |
WO2005037296A1 (ja) * | 2003-10-16 | 2005-04-28 | Toagosei Co., Ltd. | 抗コロナウイルス剤 |
JP2006232729A (ja) * | 2005-02-24 | 2006-09-07 | Taki Chem Co Ltd | ファージ・ウイルスの不活性化剤及び水溶性塗料 |
WO2012050156A1 (ja) * | 2010-10-14 | 2012-04-19 | 東亞合成株式会社 | 抗アレルゲン剤 |
JP2014503201A (ja) * | 2010-12-06 | 2014-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | 微生物濃縮プロセス及び装置 |
WO2016157942A1 (ja) * | 2015-03-31 | 2016-10-06 | 本田技研工業株式会社 | 繊維製品および繊維加工剤 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03190806A (ja) * | 1989-12-21 | 1991-08-20 | Rasa Kogyo Kk | 脱臭性能を有する抗菌剤 |
US5919422A (en) * | 1995-07-28 | 1999-07-06 | Toyoda Gosei Co., Ltd. | Titanium dioxide photo-catalyzer |
CN1085709C (zh) * | 1997-09-09 | 2002-05-29 | 赵全玺 | 无机涂料 |
CN1128188C (zh) * | 1999-07-21 | 2003-11-19 | 赵全玺 | 改性无机磷酸盐涂料 |
JP2003221304A (ja) * | 2002-01-28 | 2003-08-05 | Catalysts & Chem Ind Co Ltd | 抗ウイルス剤、これを含有する塗料および基材 |
EP1635771A2 (en) * | 2003-04-18 | 2006-03-22 | MERCK PATENT GmbH | Cosmetic formulations comprising antimicrobial pigments |
AU2005322839B2 (en) * | 2003-06-03 | 2012-03-29 | American Silver, Llc | Silver/water, silver gels and silver-based compositions; and methods for making and using the same |
BRPI0610153A2 (pt) * | 2005-04-28 | 2010-06-01 | Toagosei Co Ltd | agente antimicrobiano inorgánico com base em prata, e, produto antimicrobiano. |
BRPI0619010B8 (pt) * | 2006-04-24 | 2021-05-25 | Nm Tech Ltd Nanomaterials And Microdevices Tech | compostos nanocristalinos antivirais e antibacterianos, composição, uso dos compostos, uso não-médico de compostos e método para regeneração de compostos nanocristalinos |
JP2007307540A (ja) * | 2006-05-22 | 2007-11-29 | Ichiro Moriya | 白色蛍光灯の照射により高活性を示す光触媒 |
CN101453888A (zh) * | 2006-05-30 | 2009-06-10 | 日晷公司 | 具有高抗病毒功效组合物 |
JP2009539891A (ja) * | 2006-06-16 | 2009-11-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 抗菌性炭素 |
WO2008105542A1 (ja) * | 2007-03-01 | 2008-09-04 | Sharp Kabushiki Kaisha | 生物活性制御方法及びこの方法を適用した各種装置 |
JP2009267338A (ja) * | 2007-09-28 | 2009-11-12 | Nippon Chemicon Corp | 電極体および電気二重層キャパシタ |
CN101883490B (zh) * | 2007-10-05 | 2013-06-26 | 东亚合成株式会社 | 含银无机抗菌剂 |
JP4265685B2 (ja) * | 2007-11-26 | 2009-05-20 | 住友化学株式会社 | 光触媒体、その製造方法およびそれを用いてなる光触媒体コーティング剤 |
JP5354012B2 (ja) * | 2009-05-21 | 2013-11-27 | 東亞合成株式会社 | 銀系無機抗菌剤およびその製造方法、ならびに抗菌加工製品 |
US9210939B2 (en) * | 2011-12-22 | 2015-12-15 | Showa Denko K.K. | Copper-and-titanium-containing composition and production method therefor |
JP5194185B1 (ja) * | 2012-06-20 | 2013-05-08 | 株式会社Nbcメッシュテック | 抗ウイルス組成物 |
KR101764516B1 (ko) * | 2013-03-13 | 2017-08-02 | 파나소닉 아이피 매니지먼트 가부시키가이샤 | 구리 복합 산화티탄 분산액, 코팅제 조성물 및 항균·항바이러스성 부재 |
CN105008049A (zh) * | 2013-03-15 | 2015-10-28 | 昭和电工株式会社 | 抗菌抗病毒性光催化剂氧化钛、在中性区域分散而得的抗菌抗病毒性光催化剂氧化钛浆料以及它们的制造方法 |
JP2015059089A (ja) * | 2013-09-17 | 2015-03-30 | 昭和電工株式会社 | 抗ウイルス性組成物、その製造方法およびウイルス不活性化方法 |
KR20160086906A (ko) * | 2014-02-20 | 2016-07-20 | 쇼와 덴코 가부시키가이샤 | 항바이러스성 조성물, 항바이러스제, 광촉매 및 바이러스 불활성화 방법 |
-
2017
- 2017-02-02 US US16/078,534 patent/US20190045793A1/en not_active Abandoned
- 2017-02-02 WO PCT/JP2017/003686 patent/WO2017150063A1/ja active Application Filing
- 2017-02-02 EP EP17759534.5A patent/EP3424326A4/en active Pending
- 2017-02-02 JP JP2018502963A patent/JP6721035B2/ja active Active
- 2017-02-02 CN CN201780013766.5A patent/CN108697094A/zh active Pending
- 2017-02-02 KR KR1020187026980A patent/KR20180117644A/ko not_active Application Discontinuation
- 2017-02-16 TW TW106105115A patent/TWI801335B/zh active
-
2021
- 2021-04-23 US US17/238,281 patent/US20210235702A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001233719A (ja) * | 1999-12-13 | 2001-08-28 | Natl Inst Of Advanced Industrial Science & Technology Meti | 殺菌材および殺菌方法 |
WO2005037296A1 (ja) * | 2003-10-16 | 2005-04-28 | Toagosei Co., Ltd. | 抗コロナウイルス剤 |
JP2006232729A (ja) * | 2005-02-24 | 2006-09-07 | Taki Chem Co Ltd | ファージ・ウイルスの不活性化剤及び水溶性塗料 |
WO2012050156A1 (ja) * | 2010-10-14 | 2012-04-19 | 東亞合成株式会社 | 抗アレルゲン剤 |
JP2014503201A (ja) * | 2010-12-06 | 2014-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | 微生物濃縮プロセス及び装置 |
WO2016157942A1 (ja) * | 2015-03-31 | 2016-10-06 | 本田技研工業株式会社 | 繊維製品および繊維加工剤 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3424326A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020203069A1 (ja) * | 2019-04-04 | 2020-10-08 | リケンテクノス株式会社 | 抗ウイルス性塗膜形成用塗料、塗膜、及び積層フィルム |
JP6799200B1 (ja) * | 2019-04-04 | 2020-12-09 | リケンテクノス株式会社 | 抗ウイルス性塗膜形成用塗料、塗膜、及び積層フィルム |
WO2022075438A1 (ja) * | 2020-10-08 | 2022-04-14 | ミドリオートレザー株式会社 | 皮革、皮革コーティング剤、及び皮革の製造方法 |
JP2022093249A (ja) * | 2020-12-11 | 2022-06-23 | 東亞合成株式会社 | 活性エネルギー線硬化型抗ウイルス用組成物 |
JP6973835B1 (ja) * | 2021-03-19 | 2021-12-01 | 株式会社Yooコーポレーション | 抗ウイルス剤 |
WO2022196226A1 (ja) * | 2021-03-19 | 2022-09-22 | 株式会社Yooコーポレーション | 抗ウイルス剤 |
JP2022144998A (ja) * | 2021-03-19 | 2022-10-03 | 株式会社Yooコーポレーション | 抗ウイルス剤 |
JP7283710B1 (ja) * | 2021-07-16 | 2023-05-30 | 国立研究開発法人物質・材料研究機構 | 抗ウイルス性コーティング剤、積層体、及び、包装体又は容器 |
Also Published As
Publication number | Publication date |
---|---|
JP6721035B2 (ja) | 2020-07-08 |
US20210235702A1 (en) | 2021-08-05 |
US20190045793A1 (en) | 2019-02-14 |
JPWO2017150063A1 (ja) | 2019-01-24 |
EP3424326A4 (en) | 2019-08-14 |
CN108697094A (zh) | 2018-10-23 |
TWI801335B (zh) | 2023-05-11 |
CN113647408A (zh) | 2021-11-16 |
TW201736526A (zh) | 2017-10-16 |
EP3424326A1 (en) | 2019-01-09 |
KR20180117644A (ko) | 2018-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6721035B2 (ja) | 抗ウイルス剤、コーティング組成物、樹脂組成物及び抗ウイルス製品 | |
JP5099380B2 (ja) | 抗アレルゲン剤 | |
JP5434192B2 (ja) | 抗アレルゲン性組成物および抗アレルゲン性製品 | |
JP5067168B2 (ja) | アルデヒド消臭分散液および消臭加工製品 | |
KR20090097600A (ko) | 환경친화형 수성 도료 조성물 및 그 제조 방법 | |
JP5594367B2 (ja) | 抗アレルゲン剤 | |
JP3956973B2 (ja) | 耐水性に優れる消臭剤 | |
KR20120028913A (ko) | 은계 무기 항균제 및 그 제조 방법, 및 항균 가공제품 | |
CN106238036A (zh) | 水系分散液、 使用水系分散液的涂料、 光催化膜及制品 | |
JP3846369B2 (ja) | ペースト状消臭剤および該消臭剤を用いて製造した消臭製品 | |
CN107474598A (zh) | 一种高效分解甲醛的耐擦洗贝壳粉涂料 | |
KR100951757B1 (ko) | 제올라이트를 함유하는 섬유 코팅용 조성물 및 섬유제품 | |
JP2007320977A (ja) | キトサンパウダーおよび水性コーティング剤 | |
JP4980204B2 (ja) | 酸化チタン系消臭剤の製造方法 | |
JP4534454B2 (ja) | 硫黄系悪臭の消臭に適した消臭剤 | |
CN113647408B (zh) | 抗病毒剂、涂料组合物、树脂组合物及抗病毒制品 | |
JP2005132724A (ja) | 抗菌性無機酸化物微粒子およびその製造方法 | |
JP6667866B2 (ja) | 水性組成物および粉体組成物 | |
JPWO2005044447A1 (ja) | 複合酸化型チタニア系光触媒及びその用途 | |
US20070116783A1 (en) | Silver-based inorganic antibacterial agent dispersion | |
KR20050087633A (ko) | 다기능성 바이오 코트의 제조방법 | |
CN107840601A (zh) | 一种纳米颗粒复合型抗菌防霉硅藻泥 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2018502963 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20187026980 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017759534 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2017759534 Country of ref document: EP Effective date: 20181001 |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17759534 Country of ref document: EP Kind code of ref document: A1 |