JP5723097B2 - Antiviral paint and parts coated with antiviral paint and dried - Google Patents

Description

  The present invention relates to an antiviral paint containing a monovalent copper compound that exhibits a high effect on various viruses regardless of the presence or absence of an envelope as an active ingredient, and a member coated and dried with the antiviral paint. .

  Conventionally, antibacterial agents, disinfectants, and antiviral agents are used in hospitals, nursing homes, and other buildings, fixtures, and medical devices in order to prevent infection with bacteria and viruses. In recent years, deaths due to viral infections such as SARS (Severe Acute Respiratory Syndrome), Norovirus, and avian influenza have been reported. Currently, we are facing a “pandemic” crisis that spreads around the world due to traffic development and virus mutation. Therefore, it is desired to provide antiviral performance to various members as well as general public facilities.

  Here, viruses can be classified into viruses encapsulated in a membrane called lipid-containing envelope and viruses without an envelope. Since the envelope consists mostly of lipids, it can be easily destroyed when treated with ethanol, organic solvents, soaps, and the like. For this reason, viruses with envelopes such as influenza viruses are easy to inactivate (decrease or inactivate viruses), whereas viruses without envelopes such as norovirus are resistant to the above treatment agents. It is said to be strong.

As a solution to these problems, organic antiviral agents are effective only against specific viruses, and there are also problems with the durability of the effects. It has been reported. For example, paints containing antiviral components including calcium or magnesium oxides or hydroxides (Patent Document 1) and paints containing fine particles carrying inorganic ions on inorganic oxides (Patent Document 2) have been reported. ing.
JP 2007-106876 A JP 2003-221304 A

  However, in the method using calcium or magnesium oxide or hydroxide, it is difficult to develop antiviral properties unless the content of the antiviral component is 50% by mass or more with respect to the coating resin component. Thus, when it is made to contain in a large amount of oxides or hydroxides of calcium and magnesium, the coating film formed by coating and drying of the paint becomes hard, and the use application is limited. In addition, in the case of a coating containing fine particles carrying metal ions on an inorganic oxide, it is necessary to stabilize the metal ions by mixing with other substances, so the ratio of copper ions contained in the composition Will be limited. That is, since it is essential to include a metal ion stabilizer, the degree of freedom in designing the composition is small. In addition, with either method of paint, only the influenza with the envelope has been shown to be effective.

  Therefore, in order to solve the above-described problems, the present invention provides a paint having antiviral properties that can inactivate viruses in a shorter time than before and with or without an envelope, and the paint is applied and dried. A member is provided.

  That is, the first invention is an antiviral paint characterized in that it contains a monovalent copper compound as an active ingredient that inactivates viruses.

  Furthermore, the second invention is the same as the first invention, wherein the monovalent copper compound is chloride, acetate, sulfide, iodide, bromide, peroxide, oxide, hydroxide, cyanide, thiocyanate. It is an antiviral paint characterized by being an acid salt or a mixture thereof.

Further, according to a third aspect, in the second aspect, the monovalent copper compound is made of CuCl, Cu (CH ₃ COO), CuI, CuBr, Cu ₂ O, CuOH, Cu ₂ S, CuCN, and CuSCN. At least one kind selected from the group is an antiviral paint.

  According to a fourth invention, in any one of the first to third inventions, the content of the monovalent copper compound with respect to the total amount of the non-volatile components in the paint is 0.1% by mass to 60% by mass. It is a characteristic antiviral paint.

  A fifth invention is a fiber structure obtained by applying and drying the antiviral paint of any one of the first to fourth inventions. A well-known thing can be used for a fiber structure, For example, it can be set as the filter for an air conditioning, a net | network, the net for screen doors, bedding, clothing, and a mask. Moreover, the antiviral coating material of this invention can also be apply | coated to a film or a sheet, for example. Furthermore, it can apply | coat to molded objects, such as a panel, a building material, and an interior material.

  The monovalent copper compound contained in the paint of the present invention is a virus that comes into contact with various viruses such as a virus encapsulated in a membrane called a lipid-containing envelope or a virus that does not have an envelope. Can be inactivated. Therefore, according to the present invention, there are provided an antiviral paint capable of imparting high antiviral performance to various products simply by coating and drying, and a product imparted with antiviral properties by applying and drying the antiviral paint. can do.

  The antiviral paint of the present invention comprises a monovalent copper compound as an active ingredient that inactivates viruses.

The type of monovalent copper compound that is an active ingredient is not particularly limited, but chloride, acetate, sulfide, iodide, bromide, peroxide, oxide, hydroxide, cyanide, thiocyanate, Or it is preferable to consist of a mixture thereof. Of these, at least one monovalent copper compound is selected from the group consisting of CuCl, Cu (CH ₃ COO), CuI, CuBr, Cu ₂ O, Cu ₂ S, CuOH, CuCN, and CuSCN. Is preferred.

  Although the size of the monovalent copper compound contained is not particularly limited, it is preferable to use fine particles having an average particle size of 500 μm or less. When the average particle diameter is larger than 500 μm, the particle surface area per unit mass is decreased, and thus the antiviral effect may be reduced as compared with the case where the average particle diameter is 500 μm or less. In addition, compared to the case of 500 μm or less, when applied to the substrate and dried, the texture inherent to the surface is impaired, and the adhesion strength of the monovalent copper compound to the substrate is weakened, so that the frictional force, etc. This makes it easier to peel and drop off the substrate. Furthermore, in the case of fiber structures such as filters and nets, sheets or films that are one of the objects to be coated, the monovalent copper compound formed on the surface of the substrate such as fibers and sheets, depending on the usage environment and the passage of time, The coating film containing may peel off. Therefore, in consideration of the adhesion strength of the coating film, the average particle diameter of the monovalent copper compound is particularly preferably 10 nm or more and 1 μm or less.

  The coating material of this embodiment can be a coating material containing a coating film forming agent and a solvent as required. Specific examples include oil-based paints, alcoholic paints, cellulose paints, synthetic resin paints, water-based paints, and rubber-based paints. Regarding the paint of this embodiment, the ratio of the monovalent copper compound and the film forming agent to the total paint when the monovalent copper compound and the film forming agent are dispersed or dissolved in the solvent is not particularly limited. It can be appropriately changed depending on the application of the paint. Moreover, the case where the additive and pigment which are mentioned later are included can also be suitably changed similarly. Furthermore, the mixing method of each component in this embodiment is not specifically limited, For example, it can carry out by a well-known method.

  Moreover, you may make it the coating material of this embodiment contain a binder component as a coating-film formation agent. The binder component is a component on which the paint is hardened and is also called a vehicle. In this embodiment, although not particularly limited, for example, in a synthetic resin, polyester resin, amino resin, epoxy resin, polyurethane resin, acrylic resin, water-soluble resin, vinyl resin, fluorine resin, silicon resin, fiber resin, phenol As the resin, xylene resin, toluene resin, and natural resin, drying oils such as castor oil, linseed oil, and tung oil can be used.

  Here, in the antiviral paint of the present embodiment, the content of the monovalent copper compound is 0.1% by mass to 60% by mass with respect to 100% by mass (total amount) of nonvolatile components in the paint. The range of 10 to 40% by mass is more desirable. When the content of the monovalent copper compound is less than 0.1% by mass, the antiviral effect is smaller than that within the range, and when it exceeds 60% by mass, the cost increases and the coating strength increases. Causes a drop.

  In addition to the antiviral component and the binder component, the antiviral paint used in the present invention may contain a solvent, an additive, and a pigment as necessary.

  Solvents include water, methanol, ethanol, di-n-propyl ether, n-pentene, dibutyl ether, n-hexane, diethyl ether, n-heptane, diisobutyl ketone, methylcyclohexane, diisopropyl ketone, isobutyl chloride, cyclohexane, ethyl Amyl ketone, isobutyl acetate, benzonitrile, isopropyl acetate, methyl isobutyl ketone, amyl acetate, butyl acetate, cellosolve, diethyl carbonate, diethyl ketone, ethylbenzene, xylene, butyl carbitol, toluene, ethyl acetate, diacetone alcohol, benzene , Chloroform, methyl ethyl ketone, styrene, ethyl carbitol, methyl acetate, anone, anisole, cellosolve, diethylacetamide, diethyl carbonate , Dioxane, acetone, methyl isobutyl carbinol, nitrobenzene, acrylonitrile, diethylformamide, dimethylacetamide, butanol, cyclohexanol, acetonitrile, propyl alcohol, benzyl alcohol, butylene carbonate, dimethylformamide, ethylene carbonate, methylformamide or these A mixture or the like can be used.

  Additives include plasticizers, drying agents, curing agents, anti-skinning agents, leveling agents, anti-sagging agents, anti-fungal agents, antibacterial agents, UV absorbers, heat ray absorbers, lubricants, surfactants , Dispersants, thickeners, viscosity modifiers, stabilizers, drying modifiers, and the like. Furthermore, you may mix and use with another antiviral composition, an antibacterial composition, an antifungal composition, an antiallergen composition, a catalyst, an antireflection material, a material with a heat shielding characteristic, etc.

  In the antiviral paint of the present embodiment, the virus that can be inactivated is not particularly limited, and various viruses can be inactivated regardless of the type of genome, the presence or absence of an envelope, and the like. For example, rhinovirus, poliovirus, rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, type A, type B, type C influenza virus, parainfluenza virus, mumps virus (measles), measles Virus, Human metapneumovirus, RS virus, Nipah virus, Hendra virus, Yellow fever virus, Dengue virus, Japanese encephalitis virus, West Nile virus, Type B, Hepatitis C virus, Eastern and western equine encephalitis virus, Onyon Nyon virus, Rubella virus, Lassa virus, Junin virus, Machupoilus, Guanarito virus, Sabia virus, Crimea congo hemorrhagic fever virus, snubber fever, hantavirus, shinnonbreui Rabies virus, Ebola virus, Marburg virus, bat lyssa virus, human T cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, human porvovirus, polyomavirus, human papillomavirus, adenovirus, herpes Examples include viruses, chickenpox, zoster rash virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molasipox virus, parapox virus, and the like.

  The paint having antiviral properties of the present embodiment is coated and dried to form a coating film containing a monovalent copper compound on the surface of various forms such as a fiber structure, a film and a sheet, and a molded body. It can be set as the mode made. The coating material of the present invention is inorganic by known methods such as dipping, spraying, roll coater, bar coater, spin coating, gravure printing, offset printing, screen printing, and ink jet printing. A coating film can be formed on a base material by coating to a base material or an organic base material. Moreover, you may solidify a coating film by irradiation of solvent removal by heating drying etc., reheating, infrared rays, an ultraviolet-ray, an electron beam, a gamma ray etc. as needed. In the present specification, the term “drying” includes a case where drying is performed actively by applying heat or a case where drying is performed naturally.

  Although it does not specifically limit as a fiber structure in which the coating material of this embodiment can be applied and dried to form a coating film containing a monovalent copper compound, for example, a woven fabric, a nonwoven fabric, etc., and specific application examples thereof Examples include masks, filters for air conditioners, filters for air cleaners, filters for vacuum cleaners, filters for ventilation fans, filters for vehicles, filters for air conditioning, clothes, bedding, nets for screen doors, nets for poultry houses, and the like. These fiber structures are polyester, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, nylon, acrylic, polytetrafluoroethylene, polyvinyl alcohol, Kevlar, polyacrylic acid, polymethacrylic. Made of polymer materials such as methyl acid, rayon, cupra, tencel, polynosic, acetate, triacetate, cotton, hemp, wool, silk, bamboo, and metals such as aluminum, iron, stainless steel, brass, copper, tungsten, titanium Consists of fibers.

  The member to which the antiviral paint of this embodiment is applied and dried can be a film or a sheet. The film is made of resin such as polyester, polyethylene, polyamide, polyvinyl chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl acetate, polyimide, polyamideimide, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, etc. Is mentioned. In addition, as the sheet, polycarbonate resin sheet, film vinyl chloride sheet, fluororesin sheet, polyethylene sheet, silicone resin sheet, nylon sheet, ABS sheet, urethane sheet, and the like, titanium, aluminum, stainless steel, magnesium, The sheet | seat which consists of metals, such as a brass, is mentioned.

  In the case of films and sheets made of these polymers, it is better if they are made hydrophilic beforehand by corona treatment, atmospheric plasma treatment, flame treatment, etc., in order to enhance the adhesion of the coating film containing a monovalent copper compound. . In the case of a sheet made of metal, rolling oil and corrosion products adhering to the surface may be removed with a solvent, acid, alkali or the like. The sheet surface may be painted or printed.

  Sheets and films with coatings containing these monovalent copper compounds with antiviral properties include wallpaper, windows, ceilings, vehicle seats, doors, blinds, chairs, sofas, flooring, virus handling equipment and It can be used in various fields such as interior materials for trains and cars, and interior materials for buildings in hospitals.

  Furthermore, as a member to which the antiviral paint of this embodiment is applied and dried, a molded body such as a panel, a building material, or an interior material can be used. For example, a molded body made of a polymer such as ABS, polycarbonate, nylon, polypropylene, polystyrene, polyacetal, or polyester can be used. In the case of metals, aluminum, zinc, magnesium, brass, stainless steel, titanium and the like can be mentioned. The metal surface may be preliminarily subjected to metal thin film, coating, printing, etc. by electroplating or electroless plating. When a coating film containing a monovalent copper compound of the present invention is formed on a writing instrument, handrail, hanging leather, telephone, toy, door knob, etc., a healthy person can touch those products and members after being used by a virus-infected person. It can prevent situations such as infection.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

(Antiviral evaluation of monovalent copper compounds by anti-HA effect)
First, the antiviral property of the monovalent copper compound contained in the coating material of this embodiment was evaluated. Specifically, the virus solution is prepared by suspending the monovalent copper compound powder shown in Table 1 used in the present embodiment in a suspension adjusted to 10% by mass in PBS (phosphate buffered aqueous solution). The antiviral property was evaluated by adding an equal amount. In the present specification, the suspension concentration means that the mass of all components such as iodide and monovalent copper compound and solvent constituting the suspension is 100%, and a specific component (for example, iodide) Or a monovalent copper compound).

(Evaluation method)
For each of the above MEM suspensions, complete agglutination (HA value) was determined by visual inspection based on the titer (HA value) of red blood cell aggregation (HA). Influenza virus (influenza A / Kitakyushu / 159/93 (H3N2)) cultured using MDCK cells was used as the target virus.

  Specifically, 50 μL each of a 2-fold dilution series of virus solution in PBS was prepared in a plastic 96-well plate. Next, 50 μL of 0.5% chicken blood cell suspension was added to each of them, and the HA titer was measured after standing at 4 ° C. for 60 minutes. The HA value of the virus solution at this time was 256.

  Next, for each monovalent copper compound shown in Table 1, samples were prepared by diluting the suspension concentration to 10% by mass and 1% by mass with PBS, respectively. 450 μL of the above-mentioned virus solution having an HA value of 256 was added to 450 μL of each sample having two concentrations, and the mixture was reacted at room temperature for 10 minutes while stirring using a microtube rotator. As a control, 450 μL of the above-mentioned virus solution having an HA value of 256 was added to 450 μL of PBS, and the mixture was stirred for 10 minutes using a microtube rotator in the same manner as each sample.

  Thereafter, the solid content was precipitated by a microcentrifuge, and the supernatant was collected to obtain a sample solution. 50 μL each of a two-fold dilution series of this sample solution in PBS was prepared, 50 μL of 0.5% chicken blood cell suspension was mixed with each, and the HA titer was measured after standing at 4 ° C. for 60 minutes. The measurement results are shown in Table 2. Since each monovalent copper compound was evaluated by adding an equal amount of virus solution to the sample, the substance concentrations in the reaction solution were 5% by mass and 0.5% by mass, respectively.

From the results in Table 2, all monovalent copper compounds shown in Table 1 show virus inactivation effects, with a concentration of 0.5% and an HA value of 64 or less (50% or more of the virus is inactivated), concentration At 5%, the HA value was 16 or less (87.5% or more viruses were inactivated), and the high virus inactivating ability of these substances could be confirmed. In particular, for CuCl, CuBr, and Cu (CH ₃ COO), a high effect of inactivating 99% or more of the virus, which is the lower limit of the HA value measurement in this test, was confirmed.

Example 1
Polyvinyl alcohol (manufactured by Pure Chemical Co., Ltd., chemical use, degree of polymerization 1500) was dissolved in ion-exchanged water while heating. Then, copper chloride (I) powder (Wako Pure Chemical Industries, Ltd., Wako first grade) so that it becomes 10% by mass (0.5 g) with respect to 5.0 g of nonvolatile components (polyvinyl alcohol + copper (I) chloride powder) Further, ion-exchanged water was added so that the added amount of polyvinyl alcohol and copper (I) chloride powder was 5.0% by mass of the total weight. Next, copper (I) chloride was pulverized to an average particle size of 379 nm using a bead mill, and the antiviral paint of Example 1 was obtained. In addition, the average particle diameter here means a volume average particle diameter. Further, the antiviral paint of Example 1 was applied to a 125 μm thick polyester film (Lumirror, manufactured by Toray Industries, Inc.) hydrophilized by corona treatment, and dried overnight at room temperature. .

(Example 2)
The method of Example 2 was the same as Example 1 except that the copper (I) chloride powder was 40% by mass (2.0 g) with respect to 5.0 g of the non-volatile component (polyvinyl alcohol + copper chloride powder). An antiviral paint was prepared, and a polyester film was prepared by applying and drying the paint of Example 2 in the same manner as in Example 1.

(Example 3)
Example 3 was carried out in the same manner as in Example 1 except that the copper (I) chloride powder was changed to 0.1% by mass (0.005 g) with respect to 5.0 g of the nonvolatile component (polyvinyl alcohol + copper chloride powder). An antiviral paint was prepared, and a polyester film was prepared by applying and drying the paint of Example 3 in the same manner as in Example 1.

Example 4
Example 4 was conducted in the same manner as Example 1 except that the copper (I) chloride powder was changed to 0.05 mass% (0.0025 g) with respect to 5.0 g of the nonvolatile component (polyvinyl alcohol + copper chloride powder). An antiviral paint was prepared, and a polyester film was prepared by applying and drying the paint of Example 4 in the same manner as in Example 1.

(Example 5)
Example 5 was carried out in the same manner as Example 1 except that the copper (I) chloride powder was 80% by mass (4.0 g) with respect to 5.0 g of the nonvolatile component (polyvinyl alcohol + copper chloride powder). An antiviral paint was prepared, and a polyester film was prepared by applying and drying the paint of Example 5 in the same manner as in Example 1.

(Example 6)
A one-component acrylic resin paint (manufactured by Ohashi Chemical Industry Co., Ltd., Neopolynal No. 500) was dissolved in thinner at room temperature so that the weight ratio was 1: 1. After that, the copper (I) chloride powder pulverized with a jet mill to an average particle diameter of 5 μm so as to be 70% by mass (3.5 g) with respect to 5.0 g of the non-volatile component (acrylic resin paint + copper (I) chloride powder) added. Next, it was dispersed using a homogenizer to obtain an antiviral paint of Example 6. Further, the antiviral paint of Example 6 was applied to a 1 mm thick vinyl chloride plate (manufactured by Sumitomo Bakelite Co., Ltd.) using a bar coater and dried at 70 ° C. for 30 minutes.

(Example 7)
Example 7 was carried out in the same manner as Example 6 except that the copper (I) chloride powder was 40% by mass (2.0 g) based on 5.0 g of the non-volatile component (acrylic resin paint + copper chloride powder). An antiviral paint was prepared, and a vinyl chloride plate was prepared by applying and drying the paint of Example 7 in the same manner as in Example 6.

(Example 8)
The paint is a special polyester resin paint (Ohashi Chemical Industry Co., Ltd., Fastite No. 140 (N)), and copper chloride (I) powder is changed to 5.0 g of non-volatile components (special polyester resin paint + copper chloride (I) powder) The antiviral paint of Example 8 was prepared under the same conditions as in Example 6 except that the amount was 60% by mass (3.0 g), and the paint of Example 8 was the same as in Example 6. A vinyl chloride plate coated and dried by the method was prepared.

Example 9
Example under the same conditions as Example 8 except that the copper (I) chloride powder was 20% by mass (1.0 g) with respect to 5.0 g of non-volatile components (special polyester resin paint + copper (I) chloride powder) 9 was prepared, and a vinyl chloride plate was prepared by applying and drying the paint of Example 9 in the same manner as in Example 8.

(Example 10)
A one-pack acrylic resin paint (manufactured by Ohashi Chemical Industry Co., Ltd., Neopolynal No. 500) was dissolved in thinner so as to have a weight ratio of 1: 1. Thereafter, commercially available copper iodide (I) pulverized to an average particle size of 170 nm by a jet mill so as to be 70% by mass (3.5 g) with respect to 5.0 g of a nonvolatile component (acrylic resin paint + copper iodide (I)). ) Powder (Wako first grade manufactured by Wako Pure Chemical Industries, Ltd.) was added. Next, it was dispersed using a homogenizer to obtain an antiviral paint of Example 10. Further, the antiviral paint of Example 10 was applied to a vinyl chloride plate (manufactured by Sumitomo Bakelite Co., Ltd.) having a thickness of 1 mm using a bar coater and dried at 70 ° C. for 30 minutes.

(Example 11)
The same method as in Example 10 except that the copper iodide (I) powder was 40% by mass (2.0 g) with respect to 5.0 g of the nonvolatile component (acrylic resin paint + copper iodide (I)). Then, an antiviral paint of Example 11 was prepared, and a vinyl chloride plate was prepared by applying and drying the paint of Example 11 in the same manner as in Example 10.

(Example 12)
The paint is a special polyester resin paint (Ohashi Chemical Industry Co., Ltd., Fastite No. 140 (N)), copper iodide (I) powder is a non-volatile component (special polyester resin paint + copper iodide (I)) 5.0 The antiviral paint of Example 12 was prepared in the same manner as in Example 10 except that the amount was 60% by mass (3.0 g) based on g. A vinyl chloride plate coated and dried was prepared in the same manner as in.

(Example 13)
The same as Example 12, except that the copper iodide (I) powder was 20% by mass (1.0 g) with respect to 5.0 g of the non-volatile component (special polyester resin paint + copper iodide (I)). The antiviral paint of Example 13 was prepared by the method, and a vinyl chloride plate was prepared by applying and drying the paint of Example 13 in the same manner as in Example 12.

(Example 14)
A one-pack type acrylic resin paint (manufactured by Ohashi Chemical Industry Co., Ltd., Neopolynal No. 500) was dissolved in thinner so as to have a weight ratio of 1: 1. Thereafter, commercially available copper (I) oxide powder pulverized to an average particle size of 430 nm by a jet mill so as to be 70% by mass (3.5 g) with respect to 5.0 g of non-volatile components (acrylic resin paint + copper (I)) (Wako Pure Chemical Industries, Ltd. Wako first grade) was added. Next, it was dispersed using a homogenizer to obtain an antiviral paint of Example 14. Further, the antiviral paint of Example 14 was applied to a vinyl chloride plate (manufactured by Sumitomo Bakelite Co., Ltd.) having a thickness of 1 mm using a bar coater and dried at 70 ° C. for 30 minutes.

(Example 15)
Implemented in the same manner as in Example 14 except that the copper (I) oxide powder was 40% by mass (2.0 g) with respect to 5.0 g of the non-volatile component (acrylic resin paint + copper (I)). An antiviral paint of Example 15 was prepared, and a vinyl chloride plate was prepared by applying and drying the paint of Example 15 in the same manner as in Example 14.

(Example 16)
The paint is a special polyester resin paint (Ohashi Chemical Industry Co., Ltd., Fastite No. 140 (N)), copper iodide (I) powder is a non-volatile component (special polyester resin paint + copper iodide (I)) 5.0 The antiviral paint of Example 16 was prepared in the same manner as in Example 15 except that the amount was 60% by mass (3.0 g) with respect to g. The coating was applied to a mm aluminum plate (manufactured by Yuko Shokai Co., Ltd., A1050P) using a bar coater and dried at 70 ° C. for 30 minutes.

(Example 17)
Implemented in the same manner as in Example 16, except that the copper oxide (I) powder was 20% by mass (1.0 g) with respect to 5.0 g of the nonvolatile component (polyester resin paint + copper oxide (I)). An antiviral paint of Example 17 was prepared, and an aluminum plate was prepared by applying and drying the paint of Example 17 in the same manner as in Example 16.

(Comparative Example 1)
Polyvinyl alcohol was dissolved in ion-exchanged water so as to be 5.0% by mass, and then coated by the same method as in Example 1.

(Comparative Example 2)
The one-component acrylic resin paint was dissolved in thinner so as to have a weight ratio of 1: 1, and then a vinyl chloride plate coated and dried in the same manner as in Example 6 was prepared.

(Comparative Example 3)
The special polyester resin paint was dissolved in thinner so as to have a weight ratio of 1: 1, and then a vinyl chloride plate coated and dried in the same manner as in Example 6 was prepared.

(Comparative Example 4)
The special polyester resin paint was dissolved in thinner so as to have a weight ratio of 1: 1, and then an aluminum plate coated and dried in the same manner as in Example 16 was prepared.

(Antiviral evaluation against feline calicivirus)
For antiviral properties, antiviral properties against feline calicivirus (FCV F9 strain), which is commonly used as a substitute virus for Norovirus, were evaluated. First, each sample (4 cm × 4 cm) was placed in a plastic petri dish, 0.2 ml of working virus was added and allowed to act at room temperature for 5 minutes. At this time, the test product was covered with a film, and the test was performed by increasing the contact area between the virus solution and the test product. Thereafter, 0.1 ml of the virus solution was collected, diluted 10-fold using MEM medium, and inoculated into 0.1 ml of confluent CrFK cells. After 90 minutes of virus adsorption, overlay with 0.7% agar medium, culture for 48 hours at 34 ° C in a 5% CO ₂ incubator, fix with formalin, and stain with methylene blue to count the number of plaques formed. Infectious titer (PFU / 0.1 ml, Log10); (PFU: plaque-forming units) was calculated and compared with the viral infectious titer in the control to compare the virus activity.

(Antiviral evaluation against influenza virus)
Next, antiviral properties against influenza virus (A / Kitakyushu / 159/93 (H3N2) strain) were evaluated. First, each sample (5 cm × 5 cm) was placed in a plastic petri dish, 0.1 ml of working virus was added, and the mixture was allowed to act at room temperature for 60 minutes. At this time, by covering the upper surface of the test product with a PP film (4 cm × 4 cm), the contact area between the virus solution and the test product was made constant, and the test was performed. After acting for 60 minutes, 1.9 ml of 20 mg / ml bouillon protein solution was added to make the total volume 2.0 ml, and the virus was washed out by pipetting. Furthermore, 10-fold serial dilution was performed using MEM medium, and 0.1 ml was inoculated into confluent MDCK cells. After 90 minutes of virus adsorption, layered with 0.7% agar medium, cultured for 48 hours in 34 ° C, 5% CO ₂ incubator, fixed with formalin and stained with methylene blue, and counted the number of plaques formed. Infectious titer (PFU / 0.1 ml, Log10); (PFU: plaque-forming units) was calculated and compared with the viral infectious titer in the control to compare the virus activity.

(Control 1)
MEM dilution without addition of sample was used as a control for feline calicivirus.

(Control 2)
A MEM dilution without addition of sample was used as a control for influenza virus.

(Membrane strength measurement)
Using a friction tester, a polishing paper of No. 10000 was placed on the test piece, and the friction paper was slid by 2 cm to the left and right while applying a weight of 100 g. The case where there was no scratch was indicated as (◯), the state where the surface was slightly scratched (Δ), and the case where the film was peeled off was indicated as (×). The results are shown in Table 1.

From the above results, the antiviral paint and member of the present invention have a high resistance of 99.9999% or less at 10% by mass in a short time of 5 minutes and 99.9% or less at 0.1% by mass with respect to feline calicivirus having no envelope. Viral effect was observed. Furthermore, against influenza viruses with envelopes, after 60 minutes, high antiviral effects of 99.995% or less at 40% by mass and 99.98% or less at 20% by mass were observed. Further, none of the samples on which the coating film of the antiviral paint of the present invention was formed had any film peeled off, and the film strength was satisfactory.

Claims (3)

Including at least one monovalent copper compound particle selected from the group consisting of CuCl, Cu (CH ₃ COO), CuI, CuBr, Cu ₂ S , CuCN, and CuSCN as an active ingredient that inactivates viruses;
An antiviral paint in which a virus is inactivated by particles of the monovalent copper compound exposed from the surface when a coating film is formed.   2. The antiviral paint according to claim 1, wherein the content of the monovalent copper compound particles is 0.1% by mass to 60% by mass with respect to the total amount of nonvolatile components in the paint. A fibrous structure obtained by applying and drying the antiviral paint according to claim 1 or 2.