WO2022230405A1 - Antibacterial/antiviral paint, method for manufacturing antibacterial/antiviral paint, and method for manufacturing antibacterial/antiviral paint coating - Google Patents

Antibacterial/antiviral paint, method for manufacturing antibacterial/antiviral paint, and method for manufacturing antibacterial/antiviral paint coating Download PDF

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Publication number
WO2022230405A1
WO2022230405A1 PCT/JP2022/011474 JP2022011474W WO2022230405A1 WO 2022230405 A1 WO2022230405 A1 WO 2022230405A1 JP 2022011474 W JP2022011474 W JP 2022011474W WO 2022230405 A1 WO2022230405 A1 WO 2022230405A1
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Prior art keywords
antibacterial
antiviral
paint
coating
component
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PCT/JP2022/011474
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French (fr)
Japanese (ja)
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克昭 団
滋彦 数原
康明 荻原
敬幸 猪飼
一 住友
克之 藤波
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三菱鉛筆株式会社
Vbジャパンテクノロジー株式会社
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Priority to JP2023517134A priority Critical patent/JPWO2022230405A1/ja
Publication of WO2022230405A1 publication Critical patent/WO2022230405A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44Guanidine; Derivatives thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular

Definitions

  • the present invention relates to an antibacterial/antiviral paint, a method for producing an antibacterial/antiviral paint, and a method for producing an antibacterial/antiviral coating film.
  • antibacterial and antiviral substances are being used to improve hygiene around the kitchen.
  • Such antibacterial and antiviral substances are used by dissolving or dispersing them in a solvent such as water, and by spraying them on daily necessities, walls, floors, etc., it is possible to remove bacteria and viruses adhering to the surfaces of daily necessities. It can be carried out.
  • Patent Document 1 discloses an antiviral coating composition using oxides and/or hydroxides of calcium and/or magnesium as an antiviral component.
  • Patent Document 1 calcium and/or magnesium oxides and/or hydroxides used as antiviral components are 2 to 40% by mass in the non-volatile component, and 50 to 500% by mass based on the solid content of the paint resin component. % should be included. That is, in Patent Document 1, it is necessary to use a large amount of an antiviral component, which is inferior in terms of cost, and the workability when forming a coating film with this coating composition is inferior. In some cases, it has been difficult to develop the desired color in the resulting coating film.
  • An object of the present invention is to provide an antibacterial/antiviral paint that can impart a high antibacterial/antiviral effect even if the amount of the antibacterial/antiviral component used is small, and a method for producing the antibacterial/antiviral paint.
  • An object of the present invention is to provide a method for producing an antibacterial/antiviral coating using an antibacterial/antiviral paint.
  • An antibacterial/antiviral paint containing an antibacterial/antiviral component containing K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] and a paint raw material (2) The antibacterial/antiviral paint according to (1), wherein the antibacterial/antiviral component further contains VOSO 4 ; (3) The antibacterial/antiviral paint according to (1) or (2), wherein the antibacterial/antiviral component further contains polyhexamethylene biguanide or a salt thereof; (4) The antibacterial/antiviral paint according to any one of (1) to (3), wherein the paint raw material uses an aqueous solvent as a liquid medium, (5) The antibacterial/antiviral paint according to any one of (1) to (3), wherein the paint raw material uses an organic solvent as a liquid medium, (6) A manufacturing method for obtaining the antibacterial/antiviral paint according to (5), comprising: a step of miniaturizing the antibacterial/antiviral component;
  • a method for producing an antibacterial/antiviral coating film comprising a step of heating and/or drying the antibacterial/antiviral paint, (8) The method for producing an antibacterial/antiviral coating film according to (7), wherein the object to be treated with antibacterial/antiviral treatment is a writing instrument; is provided.
  • an antibacterial/antiviral paint that can impart a high antibacterial/antiviral effect even if the amount of the antibacterial/antiviral component used is small, and a method for producing the antibacterial/antiviral paint.
  • the antibacterial/antiviral paint of the present invention will be described below.
  • the antibacterial/antiviral paint of the present invention comprises an antibacterial/antiviral component containing K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ], and a paint raw material. .
  • the antibacterial/antiviral paint of the present invention contains K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] as antibacterial/antiviral components.
  • K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] are compounds belonging to the metal oxide cluster called polyoxometalates (PM compounds, polyacids).
  • the PM compound is a metal oxide cluster compound having polyacid ions, and each compound belonging to the PM compound is described in Journal of Materials Chemistry, Vol. 15, pp. 4773-4782, 2005, Royal Society of Chemistry. As described, each has unique biological activities, such as antibacterial and antiviral activities.
  • Polyacid refers to a metal oxide cluster compound composed of transition metal elements (W (VI), V (V), etc.), and oxygen atoms are usually 4- or 6-coordinated to metal atoms. It has a structure in which solids or octahedrons are used as basic units and these basic units are connected via edges or vertices.
  • the polyacid used in the present invention is obtained by formulating K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] in a predetermined ratio.
  • the compounding ratio of each compound is not particularly limited, but Na 9 [SbW 9 O 33 ] is preferably 0.1 to 30 mol, more preferably 10 to 20 mol. Further, it is particularly preferable to use 17.3 mol of Na 9 [SbW 9 O 33 ] per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
  • VOSO 4 may be used as an antibacterial/antiviral component in addition to the PM compound (polyacid).
  • VOSO4 is a vanadium compound characterized by the diatomic ion VO2 + .
  • physiological activity it is described in International Publication No. 99/17782 and the like that it has a blood sugar lowering action.
  • VOSO 4 it is preferable to use 0.1 to 20 mol, and 4 to 8 mol, of VOSO 4 per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ]. It is more preferable to use Moreover, it is particularly preferable to use 5.5 mol of VOSO 4 per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
  • PHMB polyhexamethylene biguanide or a salt thereof
  • n represents an integer of 2 to 18, preferably 12.
  • PHMB is odorless and hypoallergenic, and is a safe compound granule that is used as an industrial antibacterial agent in 30 countries around the world. Furthermore, unlike hypochlorous acid, etc., it does not corrode metals and rubber, so it is a compound that can facilitate the maintenance of factory equipment in the manufacturing process.
  • PHMB can be produced by a known method. PHMB can also be used as a salt of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, or the like, and is preferably used as a hydrochloride because it is easily available.
  • the compounding ratio of PHMB is not particularly limited, but is preferably 0.1 to 30 mol, more preferably 1 to 5 mol, per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ]. Mole. Moreover, it is particularly preferable to use 2.3 mol of PHMB with respect to 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
  • the antibacterial/antiviral component used in the present invention has a broad antibacterial/antiviral spectrum. That is, the antibacterial and antiviral components used in the present invention are bacteria (for example, Gram-positive bacteria such as Staphylococcus aureus, Streptococcus aureus, and Bacillus subtilis, Gram-negative bacteria such as Escherichia coli, Proteus Vulgaris, Salmonella typhi, Shigella dysenteriae, and Salmonella choleraesuis ), fungi (e.g., Peonicillium citrinum, Candida albicans, etc., Trichophyton floccosum Epidermophyton floccosum), viruses (e.g., influenza virus, herpes virus), etc.
  • bacteria for example, Gram-positive bacteria such as Staphylococcus aureus, Streptococcus aureus, and Bacillus subtilis
  • Gram-negative bacteria such as Escherichia coli, Proteus Vulgaris
  • the antibacterial/antiviral component used in the present invention has activity against a wide range of fungal species and viruses. Furthermore, the antibacterial/antiviral component used in the present invention has activity against MRSA (methicillin-resistant Staphylococcus aureus).
  • MRSA methicillin-resistant Staphylococcus aureus
  • the antibacterial/antiviral component used in the present invention is water-soluble, and when it is made into an aqueous solution, it inhibits the growth of microorganisms such as bacteria, fungi (molds), and viruses even when the concentration is low. can be done.
  • PHMB a coating film having a bactericidal effect against spores can be formed using the antibacterial/antiviral paint of the present invention by using PHMB together with the above metal compound.
  • the antibacterial/antiviral component used in the present invention can maintain antibacterial and antiviral activity even at high temperatures (for example, the temperature at which the coating film is formed), and is relatively stable even at high temperatures.
  • the compounds constituting the antibacterial/antiviral component used in the present invention do not react with each other, and the antibacterial activity and antiviral activity of each compound are not inhibited.
  • these compounds are highly safe compounds that do not cause rough skin to the human body.
  • the antibacterial/antiviral component used in the present invention is a highly safe compound that does not accumulate in the human body.
  • each compound that constitutes the antibacterial/antiviral component used in the present invention is a compound that is not subject to environmental regulations, and the manufacturing process is not complicated, making it possible to reduce manufacturing costs.
  • the antibacterial/antiviral component used in the present invention is less effective even if the coating film formed by the antibacterial/antiviral paint of the present invention is dirty, and is nonvolatile, so the effect is reduced. hard to do.
  • a paint raw material usually contains a film-forming agent and, if necessary, a liquid medium, a pigment, and an additive.
  • the coating film-forming agent is not particularly limited, but preferably contains a resin containing a binder component as a component for hardening the paint.
  • resins include, but are not limited to, acrylic resins, urethane resins, epoxy resins, fluororesins, polyester resins, silicone resins, aqueous resins, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the liquid medium can be appropriately selected according to the type of coating film-forming agent, and is not particularly limited.
  • Water alcohols such as methanol, ethanol, isopropanol and butanol; ketones such as acetone and methyl ethyl ketone; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene; Esters of methyl acetate and ethyl acetate; Ethers such as diethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Pigments are not particularly limited, but extender pigments such as talc, clay, calcium carbonate, feldspar, mica, barium sulfate; titanium oxide, red iron oxide, yellow iron oxide, azo pigments, carbon black, phthalocyanine green, and phthalocyanine blue. and other coloring pigments. One of these may be used alone, or two or more may be used in combination, depending on the application and purpose.
  • Additives include, but are not limited to, dispersants, thickeners, antifoaming agents, lubricants, stabilizers, waxes, ultraviolet absorbers, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the antibacterial/antiviral paint of the present invention can be obtained by mixing the antibacterial/antiviral component and the paint raw material, and when it contains a liquid medium, oil-based paint, lacquer (cellulose paint), synthetic resin paint, water-based It can be obtained in the form of a paint or the like.
  • the antibacterial/antiviral paint of the present invention can be obtained in a state in which the antibacterial/antiviral component, film-forming agent, optionally used pigments, and additives are dissolved or dispersed in a liquid medium.
  • the antibacterial/antiviral paint of the present invention can be obtained in the form of a solventless paint.
  • Solvent-free paints include solvent-free epoxy resin paints, solvent-free polyurethane resin paints, solvent-free acrylic resin paints, ultraviolet curable paints, electron beam curable paints, and the like. Moreover, it can also be set as a powder coating.
  • the method of mixing the antibacterial/antiviral component and the paint raw material is not particularly limited, and a known method such as using an industrial stirrer can be adopted.
  • K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] as antibacterial and antiviral components, and VOSO 4 used as necessary are the respective hydrates. may be used.
  • the antibacterial/antiviral component dissolves in the liquid medium, but when the liquid medium is an organic solvent, the antibacterial/antiviral component is finely divided and mixed with the paint raw material. is preferred.
  • the antibacterial/antiviral component can be finely divided and mixed with the paint raw material.
  • the method of refining is not particularly limited, but includes a refining method using a grinder, bead mill, jet mill, roll mill, or the like.
  • the type of water-based solvent is not particularly limited, but water, a water-soluble organic solvent, or a mixed solvent thereof is preferable.
  • the antibacterial/antiviral component can be dispersed or dissolved according to the type of solventless paint.
  • the "aqueous solvent” dissolves the antibacterial/antiviral component and also dissolves or disperses the paint raw material.
  • the “organic solvent” dissolves or disperses antibacterial/antiviral components and paint raw materials.
  • the content of the antibacterial/antiviral component is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 5% by mass, based on the raw material for the coating material. is 0.1 to 3% by mass.
  • the viscosity of the antibacterial/antiviral paint of the present invention is preferably set according to the coating method described below.
  • An antibacterial/antiviral coating film can be obtained by applying the antibacterial/antiviral paint of the present invention to the surface of an object to be treated, followed by heating and/or drying.
  • the method of applying the antibacterial/antiviral paint to the surface of the object to be treated is not particularly limited, but may be brush coating method, spin coating method, bar coater method, roll coater method, spray method, dipping method, gravure printing method, offset printing method, Known methods such as screen printing, inkjet printing, ironing, PAD printing and silk printing can be used.
  • heating and drying conditions for the antibacterial/antiviral paint can be appropriately set according to the type of liquid medium, the type of coating film-forming agent, and the type of other components.
  • heating may be performed, or air drying may be performed at room temperature or the like.
  • the coating film formed by the antibacterial/antiviral paint of the present invention is not particularly limited, and can be formed on the surface of a wide variety of objects to be treated, such as writing instruments, other stationery, cosmetics, and touch pens. It can be formed into daily necessities, furniture, interior and exterior of buildings, and the like. When used for writing instruments, cosmetics, and touch pens, it is preferable to form a coating film on portions that come into contact with hands, such as barrels, grips, and clips.
  • the objects to be treated for the antibacterial/antiviral treatment are not particularly limited, but include writing instruments, other stationery, cosmetics, daily necessities such as touch pens, furniture, interiors and exteriors of buildings, and the like.
  • An antibacterial/antiviral paint was prepared by mixing the finely divided powder and the paint raw material in a predetermined ratio.
  • Nippe 2200 ME Clear E manufactured by Nippon Paint Industrial Coatings Co., Ltd.
  • urethane paint for water-based clear ME manufactured by Nippon Paint Industrial Coatings Co., Ltd.
  • the antibacterial/antiviral paint prepared above was applied onto the pencil shaft of a pencil (clear-coated product) by ironing, and dried to form a coating film. That is, the antibacterial/antiviral paint was applied using a coating apparatus as shown in the schematic diagram of FIG.
  • the coating device 2 is provided with a coating tank 10 containing a protruding roll 4, an antibacterial/antiviral coating 6, and provided with an ironing rubber die 8.
  • the coating process was performed as follows. As shown by the arrow in FIG. 1, the pencil shaft 12 was fed into the coating tank 10 by the shaft-extrusion roll 4, and the antibacterial/antiviral paint 6 contained in the coating tank 10 was adhered to the surface of the pencil shaft 12. Then, when projecting the pencil shaft 12 to the outlet 14 of the coating tank 10, the excessive antibacterial/antiviral paint 6 was removed by passing through a squeezing rubber die 8. - ⁇ As a result, the antibacterial/antiviral paint 6 was uniformly applied to the surface of the pencil shaft 12 . The paint was then dried.
  • Specimen 1 was a control, and an antibacterial/antiviral paint 6 was used in which the powder was not added to the oil-based paint, and the above coating and drying processes were performed twice to form a coating film.
  • sample 3 an oil-based paint with 1.0 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
  • specimen 4 1.0 wt% of the powder was added to the oil-based paint, and the antibacterial/antiviral paint 6 was used. % of the above powder was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
  • sample 6 an oil-based paint with 2.0 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
  • the thickness of the formed coating film was 5 to 20 ⁇ m for all specimens.
  • an influenza virus (Influenza virus type A H1N1) was prepared. Put 3 mL of the virus solution added to the maintenance medium (1% FBS-added culture medium) in a sterilized bag, and immerse each specimen with the above coating film in it for 24 hours (37 ° C, 5% CO 2 conditions Bottom), incubated, and after 24 hours, the virus solution was taken out. Viral activity was determined by quantitative RT-PCR.
  • the results were obtained by the ⁇ Ct method. That is, the ⁇ Ct value obtained by multiplying the difference in the number of cycles of each specimen with respect to the specimen 1 (control) by -1 was obtained as the result. Also, the relative ratio (fold) to sample 1 (control) can be determined by 2 ⁇ Ct . For undetected specimens, the number was calculated as 55 cycles. A smaller ⁇ Ct value and relative ratio indicates a higher antiviral effect.
  • Table 1 is a table showing the results of the first round. The average values of 5 samples were obtained for samples 1, 2, 4 to 6, and the average values of 4 samples were obtained for sample 3.
  • Table 2 is a table showing the above second results. The average value of 5 samples was obtained for samples 1, 3 to 6, and the average value of 4 samples was obtained for sample 2.
  • samples 1, 3, 5 and 6 were also evaluated 60 minutes after the start of incubation. That is, the virus was prepared. Put 3 mL of virus solution of influenza virus (Influenza virus type A H1N1) added to the maintenance medium (1% FBS-added culture medium) in a sterile bag, and put the specimens 1, 3, 5, and 6 with the coating film thereon. Each was soaked and incubated for 24 hours (under 37°C, 5% CO 2 conditions), and after 60 minutes the virus solution was taken out. Viral activity was determined by quantitative RT-PCR as described above. Table 3 shows the results. In addition, the result was calculated
  • influenza virus Influenza virus type A H1N1
  • maintenance medium 1% FBS-added culture medium
  • a coating film formed using an antiviral paint was shown to have an antiviral effect against influenza virus.
  • the antiviral effect was confirmed not only after 24 hours from the start of incubation, but also after 60 minutes.

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Abstract

Provided is an antibacterial/antiviral paint comprising: a paint raw material; and an antibacterial/antiviral component including K11H[(VO)3(SbW9O33)2] and Na9[SbW9O33].

Description

抗菌・抗ウイルス塗料、抗菌・抗ウイルス塗料の製造方法および抗菌・抗ウイルス塗膜の製造方法Antibacterial/antiviral paint, method for producing antibacterial/antiviral paint, and method for producing antibacterial/antiviral coating
 本発明は、抗菌・抗ウイルス塗料、抗菌・抗ウイルス塗料の製造方法および抗菌・抗ウイルス塗膜の製造方法に関するものである。 The present invention relates to an antibacterial/antiviral paint, a method for producing an antibacterial/antiviral paint, and a method for producing an antibacterial/antiviral coating film.
 近年、衛生意識の高まりにより、台所回り等の衛生状態を向上させるために抗菌・抗ウイルス性物質が用いられている。このような抗菌・抗ウイルス性物質は、水などの溶媒に溶解または分散させて用いられ、日用品、壁または床等に噴霧等することにより、日用品等の表面に付着した細菌やウイルスの除去を行うことができる。 In recent years, due to the heightened awareness of hygiene, antibacterial and antiviral substances are being used to improve hygiene around the kitchen. Such antibacterial and antiviral substances are used by dissolving or dispersing them in a solvent such as water, and by spraying them on daily necessities, walls, floors, etc., it is possible to remove bacteria and viruses adhering to the surfaces of daily necessities. It can be carried out.
 また、抗菌・抗ウイルス性物質を日用品や、家具、建物の内装や外装に含ませることが検討されている。特許文献1では、カルシウムおよび/またはマグネシウムの酸化物および/または水酸化物を抗ウイルス成分として用いた抗ウイルス性塗料組成物が開示されている。 In addition, consideration is being given to including antibacterial and antiviral substances in daily necessities, furniture, and the interior and exterior of buildings. Patent Document 1 discloses an antiviral coating composition using oxides and/or hydroxides of calcium and/or magnesium as an antiviral component.
特開2007-106876号公報JP 2007-106876 A
 しかし、特許文献1においては、抗ウイルス成分として用いるカルシウムおよび/またはマグネシウムの酸化物および/または水酸化物を不揮発成分中2~40質量%、塗料樹脂成分の固形分に対して50~500質量%含有させる必要があった。即ち、特許文献1では抗ウイルス成分を多量に用いる必要があり、コスト面に劣り、また、この塗料組成物による塗膜形成時の作業性に劣るほか、多量に抗ウイルス成分が含まれるため、形成される塗膜において所望の色を発現させることが困難な場合があった。 However, in Patent Document 1, calcium and/or magnesium oxides and/or hydroxides used as antiviral components are 2 to 40% by mass in the non-volatile component, and 50 to 500% by mass based on the solid content of the paint resin component. % should be included. That is, in Patent Document 1, it is necessary to use a large amount of an antiviral component, which is inferior in terms of cost, and the workability when forming a coating film with this coating composition is inferior. In some cases, it has been difficult to develop the desired color in the resulting coating film.
 本発明の目的は、抗菌・抗ウイルス成分の使用量が少量であっても高い抗菌・抗ウイルス効果を付与することができる抗菌・抗ウイルス塗料および抗菌・抗ウイルス塗料の製造方法、また、この抗菌・抗ウイルス塗料を用いたおよび抗菌・抗ウイルス塗膜の製造方法を提供することである。 An object of the present invention is to provide an antibacterial/antiviral paint that can impart a high antibacterial/antiviral effect even if the amount of the antibacterial/antiviral component used is small, and a method for producing the antibacterial/antiviral paint. An object of the present invention is to provide a method for producing an antibacterial/antiviral coating using an antibacterial/antiviral paint.
 本発明者らは鋭意検討の結果、所定のクラスター化合物を用いることにより上記目的が達成されることを見出し、本発明の完成に至った。 As a result of extensive studies, the present inventors have found that the above object can be achieved by using a predetermined cluster compound, and have completed the present invention.
 即ち、本発明によれば、
(1) K11H[(VO)(SbW33]およびNa[SbW33]を含む抗菌・抗ウイルス成分と、塗料原料と、を含む抗菌・抗ウイルス塗料、
(2) 前記抗菌・抗ウイルス成分は、さらにVOSOを含む(1)記載の抗菌・抗ウイルス塗料、
(3) 前記抗菌・抗ウイルス成分は、さらにポリヘキサメチレンビグアナイドまたはその塩を含む(1)または(2)記載の抗菌・抗ウイルス塗料、
(4) 前記塗料原料は、液媒体として水系溶媒を用いる(1)~(3)の何れかに記載の抗菌・抗ウイルス塗料、
(5) 前記塗料原料は、液媒体として有機溶媒を用いる(1)~(3)の何れかに記載の抗菌・抗ウイルス塗料、
(6) (5)記載の抗菌・抗ウイルス塗料を得るための製造方法であって、前記抗菌・抗ウイルス成分を微細化する工程と、前記塗料原料と、微細化された前記抗菌・抗ウイルス成分とを混合する工程とを含む抗菌・抗ウイルス塗料の製造方法、
(7) (1)~(5)の何れかに記載の抗菌・抗ウイルス塗料を抗菌・抗ウイルス処理対象物の表面に塗布する工程と、前記抗菌・抗ウイルス処理対象物の表面に塗布した抗菌・抗ウイルス塗料を加熱および/または乾燥させる工程とを含む抗菌・抗ウイルス塗膜の製造方法、
(8) 前記抗菌・抗ウイルス処理対象物は、筆記具である(7)記載の抗菌・抗ウイルス塗膜の製造方法、
が提供される。
That is, according to the present invention,
(1) An antibacterial/antiviral paint containing an antibacterial/antiviral component containing K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] and a paint raw material,
(2) The antibacterial/antiviral paint according to (1), wherein the antibacterial/antiviral component further contains VOSO 4 ;
(3) The antibacterial/antiviral paint according to (1) or (2), wherein the antibacterial/antiviral component further contains polyhexamethylene biguanide or a salt thereof;
(4) The antibacterial/antiviral paint according to any one of (1) to (3), wherein the paint raw material uses an aqueous solvent as a liquid medium,
(5) The antibacterial/antiviral paint according to any one of (1) to (3), wherein the paint raw material uses an organic solvent as a liquid medium,
(6) A manufacturing method for obtaining the antibacterial/antiviral paint according to (5), comprising: a step of miniaturizing the antibacterial/antiviral component; A method for producing an antibacterial/antiviral paint, comprising the step of mixing the ingredients,
(7) A step of applying the antibacterial/antiviral paint according to any one of (1) to (5) to the surface of the antibacterial/antiviral treatment target, and applying the antibacterial/antiviral coating to the surface of the antibacterial/antiviral treatment target. A method for producing an antibacterial/antiviral coating film, comprising a step of heating and/or drying the antibacterial/antiviral paint,
(8) The method for producing an antibacterial/antiviral coating film according to (7), wherein the object to be treated with antibacterial/antiviral treatment is a writing instrument;
is provided.
 本発明によれば、抗菌・抗ウイルス成分の使用量が少量であっても高い抗菌・抗ウイルス効果を付与することができる抗菌・抗ウイルス塗料および抗菌・抗ウイルス塗料の製造方法、また、この抗菌・抗ウイルス塗料を用いたおよび抗菌・抗ウイルス塗膜の製造方法が提供される。 According to the present invention, an antibacterial/antiviral paint that can impart a high antibacterial/antiviral effect even if the amount of the antibacterial/antiviral component used is small, and a method for producing the antibacterial/antiviral paint. Provided are methods of using antimicrobial and antiviral paints and of making antimicrobial and antiviral coatings.
実施例にて用いた塗布装置を示す概略図である。It is a schematic diagram showing a coating device used in an example.
 以下、本発明の抗菌・抗ウイルス塗料について説明する。本発明の抗菌・抗ウイルス塗料は、K11H[(VO)(SbW33]およびNa[SbW33]を含む抗菌・抗ウイルス成分と、塗料原料と、を含む。 The antibacterial/antiviral paint of the present invention will be described below. The antibacterial/antiviral paint of the present invention comprises an antibacterial/antiviral component containing K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ], and a paint raw material. .
 (抗菌・抗ウイルス成分)
 本発明の抗菌・抗ウイルス塗料は、抗菌・抗ウイルス成分として、K11H[(VO)(SbW33]およびNa[SbW33]を含む。
(Antibacterial and antiviral ingredients)
The antibacterial/antiviral paint of the present invention contains K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] as antibacterial/antiviral components.
 K11H[(VO)(SbW33]およびNa[SbW33]は、polyoxometalates(PM化合物、ポリ酸)と呼ばれる金属酸化物クラスターに属する化合物である。ここで、PM化合物は、ポリ酸イオンを有する金属酸化物クラスター化合物であり、PM化合物に属する各化合物は、Journal of Materials Chemistry、15巻、4773-4782ページ、2005年、英国王立化学会に記載されているように抗菌活性や抗ウイルス活性など、それぞれに特有の生物活性を有する。なお、ポリ酸とは、遷移金属元素(W(VI)、V(V)など)によって構成される金属酸化物クラスター化合物をいい、金属原子などに酸素原子が、通常4又は6配位した四面体又は八面体を基本単位として、この基本単位が稜又は頂点を介して結合した構造を有するものである。 K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] are compounds belonging to the metal oxide cluster called polyoxometalates (PM compounds, polyacids). Here, the PM compound is a metal oxide cluster compound having polyacid ions, and each compound belonging to the PM compound is described in Journal of Materials Chemistry, Vol. 15, pp. 4773-4782, 2005, Royal Society of Chemistry. As described, each has unique biological activities, such as antibacterial and antiviral activities. Polyacid refers to a metal oxide cluster compound composed of transition metal elements (W (VI), V (V), etc.), and oxygen atoms are usually 4- or 6-coordinated to metal atoms. It has a structure in which solids or octahedrons are used as basic units and these basic units are connected via edges or vertices.
 ここで、本発明において用いるポリ酸は、K11H[(VO)(SbW33]およびNa[SbW33]を所定の割合で処方したものである。各化合物の配合比は、特に制限されないが、Na[SbW33]は好ましくは0.1~30モル、より好ましくは10~20モルである。また、K11H[(VO)(SbW33] 1モルに対し、Na[SbW33]を17.3モル用いることが特に好ましい。 Here, the polyacid used in the present invention is obtained by formulating K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] in a predetermined ratio. The compounding ratio of each compound is not particularly limited, but Na 9 [SbW 9 O 33 ] is preferably 0.1 to 30 mol, more preferably 10 to 20 mol. Further, it is particularly preferable to use 17.3 mol of Na 9 [SbW 9 O 33 ] per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
 また、本発明において、抗菌・抗ウイルス成分として、上記PM化合物(ポリ酸)に加えて、VOSOを用いてもよい。VOSOは、二原子イオンVO2+を特徴とするバナジウム化合物である。なお、生理活性としては、国際公開第99/17782号等に血糖値降下作用を有する旨が記載されている。ここで、VOSOを用いる場合には、K11H[(VO)(SbW33] 1モルに対し、VOSOを0.1~20モル用いることが好ましく、4~8モル用いることがより好ましい。また、K11H[(VO)(SbW33] 1モルに対し、VOSOを5.5モル用いることが特に好ましい。 Further, in the present invention, VOSO 4 may be used as an antibacterial/antiviral component in addition to the PM compound (polyacid). VOSO4 is a vanadium compound characterized by the diatomic ion VO2 + . As for physiological activity, it is described in International Publication No. 99/17782 and the like that it has a blood sugar lowering action. Here, when VOSO 4 is used, it is preferable to use 0.1 to 20 mol, and 4 to 8 mol, of VOSO 4 per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ]. It is more preferable to use Moreover, it is particularly preferable to use 5.5 mol of VOSO 4 per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
 また、本発明において、抗菌・抗ウイルス成分として、上記ポリ酸および必要に応じて用いられるVOSOに加えて、ポリヘキサメチレンビグアナイドまたはその塩(以下、「PHMB」ということがある。)を用いてもよい。PHMBは、式(1)
Figure JPOXMLDOC01-appb-C000001
で表される化合物である。ここで、上記式(1)中、nは2~18の整数を示し、nは12であることが好ましい。
In addition, in the present invention, polyhexamethylene biguanide or a salt thereof (hereinafter sometimes referred to as "PHMB") is used in addition to the above polyacid and VOSO 4 used as necessary as an antibacterial/antiviral component. may PHMB is represented by formula (1)
Figure JPOXMLDOC01-appb-C000001
It is a compound represented by Here, in the above formula (1), n represents an integer of 2 to 18, preferably 12.
 また、PHMBは無臭・低刺激であり、世界30か国で工業用抗菌剤として利用されている安全な化合粒であり、また、不揮発性のため効果が落ちにくい化合物である。さらに、次亜塩素酸等とは異なり、金属・ゴムを腐蝕させないため、製造工程における工場の設備のメンテナンスを容易なものとすることができる化合物である。 In addition, PHMB is odorless and hypoallergenic, and is a safe compound granule that is used as an industrial antibacterial agent in 30 countries around the world. Furthermore, unlike hypochlorous acid, etc., it does not corrode metals and rubber, so it is a compound that can facilitate the maintenance of factory equipment in the manufacturing process.
 なお、PHMBは公知の方法により製造することができる。また、PHMBは、塩酸、硝酸、硫酸、酢酸等の塩として用いることもでき、入手が容易である点で塩酸塩として用いることが好ましい。 PHMB can be produced by a known method. PHMB can also be used as a salt of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, or the like, and is preferably used as a hydrochloride because it is easily available.
 本発明において、PHMBの配合比は特に限定されないが、K11H[(VO)(SbW33] 1モルに対し、好ましくは0.1~30モル、より好ましくは1~5モルである。また、K11H[(VO)(SbW33] 1モルに対し、PHMBを2.3モル用いることが特に好ましい。 In the present invention, the compounding ratio of PHMB is not particularly limited, but is preferably 0.1 to 30 mol, more preferably 1 to 5 mol, per 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ]. Mole. Moreover, it is particularly preferable to use 2.3 mol of PHMB with respect to 1 mol of K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ].
 ここで、本発明に用いる抗菌・抗ウイルス成分は、広い抗菌・抗ウイルススペクトルを有する。即ち、本発明に用いる抗菌・抗ウイルス成分は、細菌(例えば、Staphylococcus aureus、Streptococcus aureus、Bacillus subtilis等のグラム陽性菌、Escherichia coli、Proteus Vulgaris、Salmonella typhi、Shigella dysenteriae、Salmonella choleraesuis等のグラム陰性菌)・真菌(カビ)(例えば、Peonicillium citrinum、Candida albicans等のカビ、Trichophyton floccosum Epidermophyton floccosum)・ウイルス(例えば、インフルエンザウイルス、ヘルペスウイルス)等の幅広い菌種・ウイルスに対して活性を有する。さらに、本発明に用いる抗菌・抗ウイルス成分はMRSA(メチシリン耐性黄色ブドウ球菌)に対しても活性を有する。なお、本発明に用いる抗菌・抗ウイルス成分は、水溶性であり、水溶液とした場合には、濃度が低い場合であっても細菌・真菌(カビ)・ウイルス等の微生物の発育を阻止することができる。また、PHMBを用いる場合、上記の金属化合物と共に用いることにより、芽胞に対しても殺菌効果を有する塗膜を、本発明の抗菌・抗ウイルス塗料を用いて形成することができる。 Here, the antibacterial/antiviral component used in the present invention has a broad antibacterial/antiviral spectrum. That is, the antibacterial and antiviral components used in the present invention are bacteria (for example, Gram-positive bacteria such as Staphylococcus aureus, Streptococcus aureus, and Bacillus subtilis, Gram-negative bacteria such as Escherichia coli, Proteus Vulgaris, Salmonella typhi, Shigella dysenteriae, and Salmonella choleraesuis ), fungi (e.g., Peonicillium citrinum, Candida albicans, etc., Trichophyton floccosum Epidermophyton floccosum), viruses (e.g., influenza virus, herpes virus), etc. It has activity against a wide range of fungal species and viruses. Furthermore, the antibacterial/antiviral component used in the present invention has activity against MRSA (methicillin-resistant Staphylococcus aureus). The antibacterial/antiviral component used in the present invention is water-soluble, and when it is made into an aqueous solution, it inhibits the growth of microorganisms such as bacteria, fungi (molds), and viruses even when the concentration is low. can be done. When PHMB is used, a coating film having a bactericidal effect against spores can be formed using the antibacterial/antiviral paint of the present invention by using PHMB together with the above metal compound.
 また、本発明に用いる抗菌・抗ウイルス成分は、高温(例えば、塗膜の形成温度)に対しても抗菌、抗ウイルス活性を保持することができ、高温となった場合でも比較的安定である。また、本発明に用いる抗菌・抗ウイルス成分を構成する各化合物は、化合物同士が反応せず、かつ、各化合物が有する抗菌活性や抗ウイルス活性が阻害されない。また、これらは人体に対して肌荒れ等を起こさない安全性の高い化合物である。さらに、本発明に用いる抗菌・抗ウイルス成分は、人体に蓄積しない安全性の高い化合物である。 In addition, the antibacterial/antiviral component used in the present invention can maintain antibacterial and antiviral activity even at high temperatures (for example, the temperature at which the coating film is formed), and is relatively stable even at high temperatures. . In addition, the compounds constituting the antibacterial/antiviral component used in the present invention do not react with each other, and the antibacterial activity and antiviral activity of each compound are not inhibited. In addition, these compounds are highly safe compounds that do not cause rough skin to the human body. Furthermore, the antibacterial/antiviral component used in the present invention is a highly safe compound that does not accumulate in the human body.
 また、本発明に用いる抗菌・抗ウイルス成分を構成する各化合物は、環境規制の対象外である化合物であり、また、製造工程が煩雑ではなく、製造にかかるコストを抑制することができる。また、本発明に用いる抗菌・抗ウイルス成分は、本発明の抗菌・抗ウイルス塗料により形成される塗膜に汚れが付着していても効果が低減しにくく、さらに不揮発性であるため効果が低減しにくい。 In addition, each compound that constitutes the antibacterial/antiviral component used in the present invention is a compound that is not subject to environmental regulations, and the manufacturing process is not complicated, making it possible to reduce manufacturing costs. In addition, the antibacterial/antiviral component used in the present invention is less effective even if the coating film formed by the antibacterial/antiviral paint of the present invention is dirty, and is nonvolatile, so the effect is reduced. hard to do.
 (塗料原料)
 塗料原料は、通常、塗膜形成剤を含み、必要に応じてさらに液媒体、顔料、添加剤を含む。
(raw material for paint)
A paint raw material usually contains a film-forming agent and, if necessary, a liquid medium, a pigment, and an additive.
 塗膜形成剤としては、特に限定されないが、塗料を固めるための成分としてのバインダー成分を含有した樹脂を含むことが好ましい。このような樹脂としては、特に限定されないが、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、フッ素樹脂、ポリエステル樹脂、シリコーン樹脂、水性樹脂等が挙げられる。これらは、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The coating film-forming agent is not particularly limited, but preferably contains a resin containing a binder component as a component for hardening the paint. Examples of such resins include, but are not limited to, acrylic resins, urethane resins, epoxy resins, fluororesins, polyester resins, silicone resins, aqueous resins, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
 また、液媒体としては、塗膜形成剤の種類に応じて適宜選択することでき、特に限定はされないが、水;メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、n-ヘキサン、n-ヘプタン等の脂肪族炭化水素類;トルエン、キシレン等の芳香族炭化水素類;酢酸メチル、酢酸エチルのエステル類;ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のエーテル類等が挙げられる。これらは、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The liquid medium can be appropriately selected according to the type of coating film-forming agent, and is not particularly limited. Water; alcohols such as methanol, ethanol, isopropanol and butanol; ketones such as acetone and methyl ethyl ketone; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene; Esters of methyl acetate and ethyl acetate; Ethers such as diethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
 また、顔料としては、特に限定はされないが、タルク、クレー、炭酸カルシウム、長石、マイカ、硫酸バリウム等の体質顔料;酸化チタン、ベンガラ、黄色酸化鉄、アゾ顔料、カーボンブラック、フタロシアニングリーン、フタロシアニンブルー等の着色顔料等が挙げられる。これらは、用途、目的に応じて1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 Pigments are not particularly limited, but extender pigments such as talc, clay, calcium carbonate, feldspar, mica, barium sulfate; titanium oxide, red iron oxide, yellow iron oxide, azo pigments, carbon black, phthalocyanine green, and phthalocyanine blue. and other coloring pigments. One of these may be used alone, or two or more may be used in combination, depending on the application and purpose.
 また、添加剤としては、特に限定はされないが、分散剤、増粘剤、消泡剤、潤滑剤、安定剤、ワックス類、紫外線吸収剤等が挙げられる。これらは、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 Additives include, but are not limited to, dispersants, thickeners, antifoaming agents, lubricants, stabilizers, waxes, ultraviolet absorbers, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
 (塗料)
 本発明の抗菌・抗ウイルス塗料は、上記抗菌・抗ウイルス成分と、上記塗料原料とを混合することにより、液媒体を含む場合には、油性塗料、ラッカー(セルロース塗料)、合成樹脂塗料、水性塗料等の形態として得ることができる。なお、通常、液媒体に抗菌・抗ウイルス成分、塗膜形成剤、必要に応じて用いられる顔料、添加剤が溶解または分散した状態で本発明の抗菌・抗ウイルス塗料を得ることができる。
(paint)
The antibacterial/antiviral paint of the present invention can be obtained by mixing the antibacterial/antiviral component and the paint raw material, and when it contains a liquid medium, oil-based paint, lacquer (cellulose paint), synthetic resin paint, water-based It can be obtained in the form of a paint or the like. In general, the antibacterial/antiviral paint of the present invention can be obtained in a state in which the antibacterial/antiviral component, film-forming agent, optionally used pigments, and additives are dissolved or dispersed in a liquid medium.
 また、塗料原料が液媒体を含まない場合には、本発明の抗菌・抗ウイルス塗料は、無溶剤系塗料との形態として得ることができる。することもできる。無溶剤系塗料としては、無溶剤エポキシ樹脂系塗料、無溶剤ポリウレタン樹脂系塗料、無溶剤アクリル樹脂系塗料、紫外線硬化塗料、電子線硬化塗料等が挙げられる。また、粉体塗料とすることもできる。 In addition, when the paint raw material does not contain a liquid medium, the antibacterial/antiviral paint of the present invention can be obtained in the form of a solventless paint. You can also Solvent-free paints include solvent-free epoxy resin paints, solvent-free polyurethane resin paints, solvent-free acrylic resin paints, ultraviolet curable paints, electron beam curable paints, and the like. Moreover, it can also be set as a powder coating.
 抗菌・抗ウイルス成分と、塗料原料とを混合する方法は、特に限定されず、工業用撹拌機を用いる等、公知の方法を採用し得る。なお、抗菌・抗ウイルス成分としてのK11H[(VO)(SbW33]、Na[SbW33]および必要に応じて用いられるVOSOは、それぞれの水和物を用いてもよい。 The method of mixing the antibacterial/antiviral component and the paint raw material is not particularly limited, and a known method such as using an industrial stirrer can be adopted. K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] as antibacterial and antiviral components, and VOSO 4 used as necessary are the respective hydrates. may be used.
 また、液媒体が水系溶媒の場合には、抗菌・抗ウイルス成分は液媒体に溶解するが、液媒体が有機溶媒の場合には、抗菌・抗ウイルス成分を微細化して、塗料原料と混合することが好ましい。なお、液媒体が水系溶媒の場合に抗菌・抗ウイルス成分を微細化して、塗料原料と混合することも可能である。微細化の方法としては、特に限定されないが、摩砕機、ビーズミル、ジェットミル、ロールミル等を用いた微細化方法が挙げられる。
 また、水系溶媒としては、種類は特に限定されないが、水、水溶性有機溶媒、あるいはこれらの混合溶媒であることが好ましい。
 また、無溶剤系塗料とする場合、抗菌・抗ウイルス成分は無溶剤系塗料の種類に応じて、分散または溶解させることができる。
In addition, when the liquid medium is an aqueous solvent, the antibacterial/antiviral component dissolves in the liquid medium, but when the liquid medium is an organic solvent, the antibacterial/antiviral component is finely divided and mixed with the paint raw material. is preferred. When the liquid medium is an aqueous solvent, the antibacterial/antiviral component can be finely divided and mixed with the paint raw material. The method of refining is not particularly limited, but includes a refining method using a grinder, bead mill, jet mill, roll mill, or the like.
The type of water-based solvent is not particularly limited, but water, a water-soluble organic solvent, or a mixed solvent thereof is preferable.
In the case of a solventless paint, the antibacterial/antiviral component can be dispersed or dissolved according to the type of solventless paint.
 なお、本発明において、「水系溶媒」は、抗菌・抗ウイルス成分を溶解させ、また、塗料原料を溶解または分散させる。また、「有機溶媒」は、抗菌・抗ウイルス成分および塗料原料を溶解または分散させる。 In the present invention, the "aqueous solvent" dissolves the antibacterial/antiviral component and also dissolves or disperses the paint raw material. In addition, the "organic solvent" dissolves or disperses antibacterial/antiviral components and paint raw materials.
 本発明の抗菌・抗ウイルス塗料において、抗菌・抗ウイルス成分の含有量は、上記塗料原料に対して、好ましくは0.001~10質量%、より好ましくは0.01~5質量%、さらに好ましくは0.1~3質量%である。
 また、塗膜形成のし易さの観点から、本発明の抗菌・抗ウイルス塗料の粘度は、後述する塗布方法に応じた粘度とすることが好ましい。
In the antibacterial/antiviral paint of the present invention, the content of the antibacterial/antiviral component is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 5% by mass, based on the raw material for the coating material. is 0.1 to 3% by mass.
From the viewpoint of ease of coating film formation, the viscosity of the antibacterial/antiviral paint of the present invention is preferably set according to the coating method described below.
 (塗膜)
 本発明の抗菌・抗ウイルス塗料を抗菌・抗ウイルス処理を行う処理対象物の表面に塗布して、加熱および/または乾燥させることにより、抗菌・抗ウイルス塗膜を得ることができる。
(Coating film)
An antibacterial/antiviral coating film can be obtained by applying the antibacterial/antiviral paint of the present invention to the surface of an object to be treated, followed by heating and/or drying.
 処理対象物表面に対する抗菌・抗ウイルス塗料の塗布方法は、特に限定されないが、刷毛塗り法、スピンコート法、バーコーター法、ロールコーター法、スプレー法、浸漬法、グラビア印刷法、オフセット印刷法、スクリーン印刷法、インクジェット印刷法、しごき塗装、PAD印刷およびシルク印刷等の公知の方法を用いることができる。 The method of applying the antibacterial/antiviral paint to the surface of the object to be treated is not particularly limited, but may be brush coating method, spin coating method, bar coater method, roll coater method, spray method, dipping method, gravure printing method, offset printing method, Known methods such as screen printing, inkjet printing, ironing, PAD printing and silk printing can be used.
 また、抗菌・抗ウイルス塗料の加熱・乾燥条件は、液媒体の種類、塗膜形成剤の種類やその他の成分の種類に応じて適宜設定することができる。また、乾燥を行う際には、加熱を行ってもよいし、室温等で自然乾燥させてもよい。 In addition, the heating and drying conditions for the antibacterial/antiviral paint can be appropriately set according to the type of liquid medium, the type of coating film-forming agent, and the type of other components. Moreover, when performing drying, heating may be performed, or air drying may be performed at room temperature or the like.
 (用途)
 本発明の抗菌・抗ウイルス塗料により形成される塗膜は、特に限定はされず、広汎な処理対象物の表面に形成することができ、例えば、筆記具、その他の文房具、化粧具、タッチペン等の日用品、家具、建物の内装、外装等に形成することができる。筆記具、化粧具、タッチペンに用いる場合には、軸筒、把持部、クリップ等、手が触れる部分に塗膜を形成することが好ましい。
(Application)
The coating film formed by the antibacterial/antiviral paint of the present invention is not particularly limited, and can be formed on the surface of a wide variety of objects to be treated, such as writing instruments, other stationery, cosmetics, and touch pens. It can be formed into daily necessities, furniture, interior and exterior of buildings, and the like. When used for writing instruments, cosmetics, and touch pens, it is preferable to form a coating film on portions that come into contact with hands, such as barrels, grips, and clips.
 即ち、上記抗菌・抗ウイルス処理を行う処理対象物としては、特に限定はされないが、筆記具、その他の文房具、化粧具、タッチペン等の日用品、家具、建物の内装、外装等が挙げられる。 That is, the objects to be treated for the antibacterial/antiviral treatment are not particularly limited, but include writing instruments, other stationery, cosmetics, daily necessities such as touch pens, furniture, interiors and exteriors of buildings, and the like.
 以下、実施例を示して本発明について具体的に説明するが、本発明は以下の実施例に限定されるものではなく、本発明の要旨及び均等の範囲を逸脱しない範囲において任意に変更して実施することができる。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples, and can be arbitrarily changed within the scope of the spirit and equivalents of the present invention. can be implemented.
 (抗菌・抗ウイルス成分を含む粉体の調製)
 K11H[(VO)(SbW33]の原末として89.1mgのK11H[(VO)(SbW33]・27HOと、Na[SbW33]の原末として9.9mgのNa[SbW33]・19HOとを混合し、混合溶液を得た。得られた混合溶液を粉体化し、抗菌・抗ウイルス成分を含む粉体を得た。
 (粉体の微細化)
 得られた粉体を平均粒子径7μmとなるまで微細化した。
(Preparation of powder containing antibacterial and antiviral ingredients)
89.1 mg of K 11 H[(VO) 3 ( SbW 9 O 33 ) 227H 2 O and Na 9 [ SbW 9 9.9 mg of Na 9 [SbW 9 O 33 ].19H 2 O as a bulk powder of O 33 ] was mixed to obtain a mixed solution. The obtained mixed solution was pulverized to obtain a powder containing an antibacterial/antiviral component.
(Refinement of powder)
The obtained powder was pulverized to an average particle size of 7 μm.
 (抗菌・抗ウイルス塗料の調製)
 微細化した粉体と、塗料原料とを所定の割合で混合し、抗菌・抗ウイルス塗料を調製した。なお、塗料原料としては油性の塗料原料としてニッペ 2200 ME クリアーE(日本ペイント・インダストリアルコーティングス株式会社製)、水性の塗料原料として、水性クリアー ME用 ウレタン塗料(日本ペイント・インダストリアルコーティングス株式会社製)を用いた。
(Preparation of antibacterial/antiviral paint)
An antibacterial/antiviral paint was prepared by mixing the finely divided powder and the paint raw material in a predetermined ratio. In addition, Nippe 2200 ME Clear E (manufactured by Nippon Paint Industrial Coatings Co., Ltd.) is used as a raw material for oil-based paints, and urethane paint for water-based clear ME (manufactured by Nippon Paint Industrial Coatings Co., Ltd.) is used as a raw material for water-based paints. ) was used.
 (塗膜の形成)
 上記にて調製した抗菌・抗ウイルス塗料をしごき塗装にて鉛筆(クリア塗装品)の鉛筆軸上に塗布し、乾燥することにより塗膜を形成した。即ち、図1の概略図に示すような塗布装置により抗菌・抗ウイルス塗料を塗布した。
(Formation of coating film)
The antibacterial/antiviral paint prepared above was applied onto the pencil shaft of a pencil (clear-coated product) by ironing, and dried to form a coating film. That is, the antibacterial/antiviral paint was applied using a coating apparatus as shown in the schematic diagram of FIG.
 図1に示すように、塗布装置2は、軸突き出しロール4、抗菌・抗ウイルス塗料6を収容し、しごきゴムダイス8が設けられた塗装タンク10を備えている。この塗布装置2を用いて、次のように塗布工程を行った。図1の矢印で示すように軸突き出しロール4により鉛筆軸12を塗装タンク10に送り込み、塗装タンク10に収容された抗菌・抗ウイルス塗料6を鉛筆軸12の表面に付着させた。そして、鉛筆軸12を塗装タンク10の出口14へ突き出す際に、しごきゴムダイス8を通過させることにより、余分な抗菌・抗ウイルス塗料6を除去した。これにより、鉛筆軸12の表面に抗菌・抗ウイルス塗料6が均一に塗布された。その後、塗料を乾燥させた。 As shown in FIG. 1, the coating device 2 is provided with a coating tank 10 containing a protruding roll 4, an antibacterial/antiviral coating 6, and provided with an ironing rubber die 8. Using this coating device 2, the coating process was performed as follows. As shown by the arrow in FIG. 1, the pencil shaft 12 was fed into the coating tank 10 by the shaft-extrusion roll 4, and the antibacterial/antiviral paint 6 contained in the coating tank 10 was adhered to the surface of the pencil shaft 12. Then, when projecting the pencil shaft 12 to the outlet 14 of the coating tank 10, the excessive antibacterial/antiviral paint 6 was removed by passing through a squeezing rubber die 8. - 特許庁As a result, the antibacterial/antiviral paint 6 was uniformly applied to the surface of the pencil shaft 12 . The paint was then dried.
 検体1はコントロールであり、油性塗料に上記粉体を加えないものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、塗膜を形成した。 Specimen 1 was a control, and an antibacterial/antiviral paint 6 was used in which the powder was not added to the oil-based paint, and the above coating and drying processes were performed twice to form a coating film.
 また、検体2では、油性塗料に0.5wt%の上記粉体を加えたものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、塗膜を形成した。 In addition, for sample 2, an oil-based paint with 0.5 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
 また、検体3では、油性塗料に1.0wt%の上記粉体を加えたものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、塗膜を形成した。 In addition, for sample 3, an oil-based paint with 1.0 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
 また、検体4では、油性塗料に1.0wt%の上記粉体を加えたものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、さらに、水性塗料に1.0wt%の上記粉体を加えたもの抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、塗膜を形成した。 In specimen 4, 1.0 wt% of the powder was added to the oil-based paint, and the antibacterial/antiviral paint 6 was used. % of the above powder was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film.
 また、検体5では、油性塗料に1.0wt%の上記粉体を加えたものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を4回行い、塗膜を形成した。 In addition, for sample 5, an oil-based paint with 1.0 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed four times to form a coating film.
 また、検体6では、油性塗料に2.0wt%の上記粉体を加えたものを抗菌・抗ウイルス塗料6として用い、上記の塗布、乾燥工程を2回行い、塗膜を形成した。形成された塗膜の厚さは、いずれの検体も5~20μmであった。 In addition, for sample 6, an oil-based paint with 2.0 wt% of the powder added was used as the antibacterial/antiviral paint 6, and the above coating and drying steps were performed twice to form a coating film. The thickness of the formed coating film was 5 to 20 μm for all specimens.
 (抗ウイルス活性の評価)
 ウイルスとしては、インフルエンザウイルス(Influenza virus A型 H1N1)を用意した。維持培地(1%FBS添加培養液)に添加したウイルス液3mLを滅菌袋に入れ、そこに上記の塗膜を形成した各検体をそれぞれ浸した状態で24時間(37℃、5%CO条件下)、インキュベーションし、24時間経過後ウイルス液を取り出した。ウイルス活性は、定量RT-PCRにより判定した。
(Evaluation of antiviral activity)
As a virus, an influenza virus (Influenza virus type A H1N1) was prepared. Put 3 mL of the virus solution added to the maintenance medium (1% FBS-added culture medium) in a sterilized bag, and immerse each specimen with the above coating film in it for 24 hours (37 ° C, 5% CO 2 conditions Bottom), incubated, and after 24 hours, the virus solution was taken out. Viral activity was determined by quantitative RT-PCR.
 定量RT-PCR法の具体的な手順としては以下のように行った。各検体から取り出したウイルス液をTrizol試薬(ambion)を用いてTotal RNAの抽出を行った。抽出したRNAからPrimeScript RT Master Mix (Takara)の方法に準じてcDNAに逆転写し、SYBR Premix EX Taq II (Takara)により増幅を行った。なお、50μL(25μL SYBR Green Mix (2x), 1μL cDNA, 2μL primer pair mix (5pmol/μL each primer), 22μL HO)のPCR反応液を用い、反応は95℃にて30秒を1サイクル、さらに95℃にて5秒および60℃にて30秒のサイクルを55サイクルの条件にて行った。結果はΔCt法により求めた。即ち、検体1(コントロール)に対する各検体のサイクル数の差に-1を乗じたΔCt値を求め結果とした。また、検体1(コントロール)に対する相対比(倍数)を、2ΔCtにより求めることができる。なお、検出されない検体については、55サイクルとして算出した。ΔCt値及び相対比が小さいほど、抗ウイルス効果が高いことを示す。 A specific procedure of the quantitative RT-PCR method was performed as follows. Total RNA was extracted from the virus solution taken from each sample using Trizol reagent (ambion). The extracted RNA was reverse transcribed into cDNA according to the PrimeScript RT Master Mix (Takara) method, and amplified with SYBR Premix EX Taq II (Takara). A PCR reaction solution of 50 μL (25 μL SYBR Green Mix (2x), 1 μL cDNA, 2 μL primer pair mix (5 pmol/μL each primer), 22 μL H 2 O) was used, and the reaction was carried out at 95° C. for 30 seconds for one cycle. Furthermore, 55 cycles of 95° C. for 5 seconds and 60° C. for 30 seconds were performed. The results were obtained by the ΔCt method. That is, the ΔCt value obtained by multiplying the difference in the number of cycles of each specimen with respect to the specimen 1 (control) by -1 was obtained as the result. Also, the relative ratio (fold) to sample 1 (control) can be determined by 2 ΔCt . For undetected specimens, the number was calculated as 55 cycles. A smaller ΔCt value and relative ratio indicates a higher antiviral effect.
 上記の評価は2回行った。表1は、上記の1回目の結果を示す表である。なお、検体1,2,4~6については、5つのサンプルの平均値について結果を求め、検体3については、4つのサンプルの平均値について結果を求めた。 The above evaluation was performed twice. Table 1 is a table showing the results of the first round. The average values of 5 samples were obtained for samples 1, 2, 4 to 6, and the average values of 4 samples were obtained for sample 3.
 また、表2は上記の2回目の結果を示す表である。なお、検体1,3~6については、5つのサンプルの平均値について結果を求め、検体2については、4つのサンプルの平均値について結果を求めた。 In addition, Table 2 is a table showing the above second results. The average value of 5 samples was obtained for samples 1, 3 to 6, and the average value of 4 samples was obtained for sample 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 さらに、上記に加えて検体1,3,5,6については、インキュベーション開始60分後についても評価を行った。即ち、ウイルスとしては、用意した。維持培地(1%FBS添加培養液)に添加したインフルエンザウイルス(Influenza virus A型 H1N1)のウイルス液3mLを滅菌袋に入れ、そこに上記の塗膜を形成した検体1,3,5,6をそれぞれ浸した状態で24時間(37℃、5%CO条件下)、インキュベーションし、60分経過後ウイルス液を取り出した。ウイルス活性は、上記と同様に定量RT-PCRにより判定した。
表3に結果を示す。なお、各検体について10個のサンプルの平均値について結果を求めた。
Furthermore, in addition to the above, samples 1, 3, 5 and 6 were also evaluated 60 minutes after the start of incubation. That is, the virus was prepared. Put 3 mL of virus solution of influenza virus (Influenza virus type A H1N1) added to the maintenance medium (1% FBS-added culture medium) in a sterile bag, and put the specimens 1, 3, 5, and 6 with the coating film thereon. Each was soaked and incubated for 24 hours (under 37°C, 5% CO 2 conditions), and after 60 minutes the virus solution was taken out. Viral activity was determined by quantitative RT-PCR as described above.
Table 3 shows the results. In addition, the result was calculated|required about the average value of 10 samples about each specimen.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表1~3に示すようにK11H[(VO)(SbW33]およびNa[SbW33]を含む抗菌・抗ウイルス成分と、塗料原料と、を含む抗菌・抗ウイルス塗料を用いて形成された塗膜は、インフルエンザウイルスに対して抗ウイルス効果を有することが示された。また、インキュベーション開始24時間経過後だけでなく、60分経過後であっても抗ウイルス効果が確認された。 Antibacterial/antiviral ingredients containing K 11 H[(VO) 3 (SbW 9 O 33 ) 2 ] and Na 9 [SbW 9 O 33 ] as shown in Tables 1 to 3, and paint raw materials. A coating film formed using an antiviral paint was shown to have an antiviral effect against influenza virus. In addition, the antiviral effect was confirmed not only after 24 hours from the start of incubation, but also after 60 minutes.
2…塗布装置、4…軸突き出しロール、6…抗菌・抗ウイルス塗料、8…しごきゴムダイス、10…塗装タンク、12…鉛筆軸、14…出口
 
 
2... coating device, 4... axis projecting roll, 6... antibacterial/antiviral paint, 8... ironing rubber die, 10... coating tank, 12... pencil shaft, 14... exit

Claims (8)

  1.  K11H[(VO)(SbW33]およびNa[SbW33]を含む抗菌・抗ウイルス成分と、
     塗料原料と、
    を含む抗菌・抗ウイルス塗料。
    an antibacterial and antiviral component comprising K11H [( VO ) 3 ( SbW9O33 ) 2 ] and Na9 [ SbW9O33 ] ;
    raw materials for paint,
    Antibacterial and antiviral paint containing.
  2.  前記抗菌・抗ウイルス成分は、さらにVOSOを含む請求項1記載の抗菌・抗ウイルス塗料。 The antibacterial/antiviral paint according to claim 1, wherein the antibacterial/antiviral component further comprises VOSO4 .
  3.  前記抗菌・抗ウイルス成分は、さらにポリヘキサメチレンビグアナイドまたはその塩を含む請求項1または2記載の抗菌・抗ウイルス塗料。 The antibacterial/antiviral paint according to claim 1 or 2, wherein the antibacterial/antiviral component further contains polyhexamethylene biguanide or a salt thereof.
  4.  前記塗料原料は、液媒体として水系溶媒を用いる請求項1~3の何れかに記載の抗菌・抗ウイルス塗料。 The antibacterial/antiviral paint according to any one of claims 1 to 3, wherein the paint raw material uses an aqueous solvent as a liquid medium.
  5.  前記塗料原料は、液媒体として有機溶媒を用いる請求項1~3の何れかに記載の抗菌・抗ウイルス塗料。 The antibacterial/antiviral paint according to any one of claims 1 to 3, wherein the paint raw material uses an organic solvent as a liquid medium.
  6.  請求項5記載の抗菌・抗ウイルス塗料を得るための製造方法であって、
     前記抗菌・抗ウイルス成分を微細化する工程と、
     前記塗料原料と、微細化された前記抗菌・抗ウイルス成分とを混合する工程と
    を含む抗菌・抗ウイルス塗料の製造方法。
    A manufacturing method for obtaining the antibacterial/antiviral paint according to claim 5,
    A step of miniaturizing the antibacterial/antiviral component;
    A method for producing an antibacterial/antiviral paint, comprising a step of mixing the paint raw material and the micronized antibacterial/antiviral component.
  7.  請求項1~5の何れかに記載の抗菌・抗ウイルス塗料を抗菌・抗ウイルス処理対象物の表面に塗布する工程と、
     前記抗菌・抗ウイルス処理対象物の表面に塗布した抗菌・抗ウイルス塗料を加熱および/または乾燥させる工程と
    を含む抗菌・抗ウイルス塗膜の製造方法。
    A step of applying the antibacterial/antiviral paint according to any one of claims 1 to 5 to the surface of an object to be treated with antibacterial/antiviral treatment;
    A method for producing an antibacterial/antiviral coating film, comprising heating and/or drying the antibacterial/antiviral paint applied to the surface of the antibacterial/antiviral treated object.
  8.  前記抗菌・抗ウイルス処理対象物は、筆記具である請求項7記載の抗菌・抗ウイルス塗膜の製造方法。
     
    8. The method for producing an antibacterial/antiviral coating film according to claim 7, wherein the object to be treated with antibacterial/antiviral treatment is a writing instrument.
PCT/JP2022/011474 2021-04-28 2022-03-15 Antibacterial/antiviral paint, method for manufacturing antibacterial/antiviral paint, and method for manufacturing antibacterial/antiviral paint coating WO2022230405A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51124126A (en) * 1975-04-22 1976-10-29 Dainippon Toryo Co Ltd Pigment composition for paint use
JP2005281299A (en) * 2004-03-01 2005-10-13 Paratex Japan:Kk Antibacterial/mildewproofing agent and coating material composition using the same
WO2013115062A1 (en) * 2012-01-31 2013-08-08 Vbジャパンテクノロジー株式会社 Aqueous solution
WO2018021106A1 (en) * 2016-07-26 2018-02-01 ニッポン高度紙工業株式会社 Antimicrobial, antiviral and/or algae-proofing material comprising inorganic-organic hybrid compound, and production method therefor
WO2019230211A1 (en) * 2018-06-01 2019-12-05 京セラドキュメントソリューションズ株式会社 Display control device and electronic device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51124126A (en) * 1975-04-22 1976-10-29 Dainippon Toryo Co Ltd Pigment composition for paint use
JP2005281299A (en) * 2004-03-01 2005-10-13 Paratex Japan:Kk Antibacterial/mildewproofing agent and coating material composition using the same
WO2013115062A1 (en) * 2012-01-31 2013-08-08 Vbジャパンテクノロジー株式会社 Aqueous solution
WO2018021106A1 (en) * 2016-07-26 2018-02-01 ニッポン高度紙工業株式会社 Antimicrobial, antiviral and/or algae-proofing material comprising inorganic-organic hybrid compound, and production method therefor
WO2019230211A1 (en) * 2018-06-01 2019-12-05 京セラドキュメントソリューションズ株式会社 Display control device and electronic device

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