Coating film

Abstract

To provide a coating film which has a small contact angle of a water droplet to a film surface, can increase a contact area of the water droplet to the film surface, and can sufficiently utilize an antibacterial / antiviral function, an antifungal function, and a deodorizing function.SOLUTION: The coating film is a silicon-oxide-based (SiO2) glass-based coating film, the film surfaces of the coating film are coated with a hydrophilic polymer coating, conductive glass particles dispersed and mixed in the coating film contain at least one or more of silver ions (Ag +), copper ions (Cu2 +), and zinc ions (Zn2 +), and the contact angles θ of water droplets measured by JISR3257 on the surfaces of the coating film formed on the surfaces of the base material are 50 ° or less. The coating film has an antiviral function, an antibacterial function, an antifungal function, and a deodorizing function.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a coating film. [Background technology]

[0002] It is widely known that coating with silver ions, copper ions, and zinc ions (hereinafter collectively referred to as effective metal ions) is effective in antibacterial, antiviral, antifungal, and deodorizing properties, and various studies and proposals have been made from the viewpoint of immediate and sustained effectiveness. In order to improve the immediate effectiveness, it is necessary to increase the amount of effective metal ions deposited on the surface. The following Patent Documents 1 to 4 are disclosed as prior art related to silver ions, which are representative effective metal ions.

[0003] In the substrates with antibacterial layers disclosed in Patent Documents 1 and 2 (paragraph 33 of the specification), it is proposed to reduce the water contact angle to improve the removability of contaminants on the antibacterial layer by cleaning or the like. In the antiviral molded article disclosed in Patent Document 3 (each claim), it is proposed to control the surface wetting tension within a certain range, add a resin with hydrophilic groups, and reduce the water contact angle. In the antibacterial laminate disclosed in Patent Document 4 (paragraph 66 of the specification), it is proposed to make the antibacterial film hydrophilic, thereby making it easier for water to penetrate into the antibacterial film, and for water to reach the antibacterial agent microparticles in the antibacterial film and release silver ions. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-189152 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-189196 [Patent Document 3] Japanese Patent Publication No. 2023-027804 [Patent Document 4] Japanese Patent Publication No. 2023-019188 Summary of the Invention [Problem to be solved by the invention]

[0005] With glass-based coating films based on silicon oxide (SiO2), it is difficult to introduce a large amount of silver ions into the coating film, and it is not possible to make the coating film contain a large amount of silver ions. As a result, the antibacterial, antiviral, antifungal, and deodorizing functions of the coating film are small, and it is difficult to reliably kill germs, various viruses, and various mold spores, and it is difficult to reliably remove unpleasant odors. In addition, the antibacterial, antiviral, antifungal, and deodorizing functions of the coating film cannot be maintained for a long period of time.

[0006] An object of the present invention is to provide a coating film that has a small contact angle of water droplets (liquids) with the film surface, can increase the contact area of ​​water droplets with the film surface, and can fully utilize its antibacterial, antiviral, antifungal, and deodorizing functions. Another object of the present invention is to provide a coating film that can kill various bacteria, viruses, and molds contained in water droplets and eliminate unpleasant odors. Another object of the present invention is to provide a coating film that can incorporate large amounts of silver ions, copper ions, and zinc ions, and by containing large amounts of silver ions, copper ions, and zinc ions, has excellent antibacterial, antiviral, antifungal, and deodorizing functions, can reliably kill germs, various viruses, and various molds, reliably eliminate unpleasant odors, and can maintain its antibacterial, antiviral, antifungal, and deodorizing functions for a long period of time. An object of the present invention is to provide a coating film that can precipitate large amounts of silver ions, copper ions, and zinc ions immediately after coating with a coating liquid, and has excellent antibacterial, antiviral, antifungal, and deodorizing functions immediately after coating with the coating liquid. Another object of the present invention is to provide a coating film that can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all coating objects immediately after coating, regardless of the object to be coated. [Means for solving the problem]

[0007] The present invention, which aims to solve the above-mentioned problems, is premised on a coating film in which predetermined conductive glass particles are dispersed and mixed.

[0008] The present invention is characterized in that the coating film is a glass-based coating film based on silicon oxide (SiO2), and the conductive glass particles dispersed and mixed in the coating film are silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) and the contact angle θ of a water droplet measured on the surface of the coating film formed on the surface of the substrate is 50° or less, as measured according to JIS R3257 (pure water drop amount 1 μL and waiting time for stabilization of the liquid contact 15 seconds).

[0009] In one example of the present invention, the contact angle θ of a water droplet is 30° or less.

[0010] In another embodiment of the present invention, the conductive glass particles contain silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) and includes at least two of the following.

[0011] In another example of the present invention, the conductive glass particles are glass based on at least one of vanadium oxide (V2O5), tungsten oxide (WO3), and molybdenum oxide (MoO3), and phosphorus oxide (P2O5).

[0012] In another embodiment of the present invention, the conductive glass particles include barium oxide (BaO).

[0013] In another embodiment of the present invention, the conductive glass particles contain silver ions (Ag + ) and copper ions (Cu 2+ ), vanadium oxide (V2O5)-phosphorus oxide (P2O5) glass containing at least one of silver ions (Ag + ) and copper ions (Cu 2+) and vanadium oxide (V2O5)-phosphorus oxide (P2O5)-barium oxide (BaO) glass containing at least one of the following.

[0014] In another example of the present invention, the original coating solution (starting material of the coating film) for forming the coating film is a siloxane-based solution, and conductive glass particles are dispersed and mixed in the siloxane-based solution.

[0015] In another example of the present invention, the surface of the coating film is made hydrophilic by surface treatment.

[0016] In another example of the present invention, the surface of the coating membrane is coated with a hydrophilic polymer coating.

[0017] In another example of the present invention, a coating film has a plurality of fine irregularities formed on its surface by chemical etching or dry etching, and a hydrophilic polymer coating covers the surface of the coating film on which the plurality of fine irregularities have been formed.

[0018] In another example of the present invention, the coating film has one or more functions selected from the group consisting of an antiviral function, an antibacterial function, an antifungal function, and a deodorizing function.

[0019] In another example of the present invention, a coating film is prepared by coating a coating liquid onto the surface of a predetermined substrate, and then immediately applying water or an aqueous solution to the surface of the coating film to form silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) is precipitated on the surface of the coating film. [Effects of the Invention]

[0020] According to the coating film of the present invention, it is a glass-based coating film based on silicon oxide (SiO2), and the conductive glass particles dispersed and mixed in the coating film are silver ions (Ag +), copper ions (Cu 2+ ), zinc ions (Zn 2+ ), and the contact angle θ of the water droplet measured on the surface of the coating film formed on the surface of the substrate according to JIS R3257 (pure water drop amount 1μL and waiting time for stabilization of the liquid contact 15 seconds) is 50° or less. Therefore, the contact angle of the water droplet (liquid) with the surface of the coating film is small, the contact area of ​​the water droplet with the surface of the coating film can be increased, the water droplet comes into contact with the surface of the coating film widely, and the silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ This allows the antibacterial, antiviral, antifungal, and deodorizing properties of the coating film to be fully utilized. Even if the water droplets contain various bacteria, viruses, or mold, the coating film can kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, the drying time of the water droplets on the coating film surface is shortened, ensuring a shorter survival time for the bacteria, viruses, and mold contained in the water droplets, allowing them to be killed in a short period of time. The coating film is not limited to any particular object, and can provide excellent antibacterial, antiviral, antifungal, and deodorizing properties to all objects.

[0021] The contact angle θ of the coating film is 30° or less, as measured according to JIS R3257 (pure water drop amount 1μL and waiting time for stabilization of the liquid contact 15 seconds). This means that the contact angle of the water droplet (liquid) with the coating film surface is extremely small, and the contact area of ​​the water droplet with the coating film surface can be reliably increased. The water droplet comes into contact with a wide area of ​​the coating film surface, and silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+) can be fully utilized. Even if the water droplets contain various bacteria, viruses, or mold, the coating film can reliably kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and reliably eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, the drying time of the water droplets on the coating film surface is shortened, reliably shortening the survival time of the bacteria, viruses, and mold contained in the water droplets, and allowing the bacteria, viruses, and mold to be killed in a short period of time.

[0022] The coating film is made of conductive glass particles that react with silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) contains at least two or more types of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be fully utilized, and the coating film has excellent antibacterial, antiviral, antifungal and deodorizing properties, so even if the water droplets contain various bacteria, viruses or mold, they can be killed and unpleasant odors such as cigarette smoke, putrid odors and nonenal odors can be removed.

[0023] The coating film is a glass based on conductive glass particles of at least one of vanadium oxide (V2O5), tungsten oxide (WO3), and molybdenum oxide (MoO3) and phosphorus oxide (P2O5), and silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+) are dispersed and mixed in conductive glass particles containing at least one of vanadium oxide (V2O5), tungsten oxide (WO3), molybdenum oxide (MoO3) and phosphorus oxide (P2O5), so a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be introduced into the surface of the coating film, and a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ The coating film can deposit a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ), it has excellent antibacterial, antiviral, antifungal and deodorizing properties, and even if the water droplets contain various bacteria, viruses and mold, it can completely kill the bacteria, viruses and mold contained in the water droplets, preventing the proliferation of bacteria, viruses and mold, and completely removing unpleasant odors such as cigarette smoke, putrid odors and nonenal odors. The coating film is made of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can rapidly exhibit the antiviral, antibacterial, antifungal and deodorizing functions of silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) is not lost prematurely, and the antiviral, antibacterial, antifungal and deodorizing functions of the water-soluble glass composition can be maintained for a long period of time.

[0024] The coating film is made of conductive glass particles containing barium oxide (BaO) and silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) are dispersed and mixed in conductive glass particles containing barium oxide (BaO), so a large amount of silver ions (Ag +) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be introduced into the surface of the coating film, and a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ The coating film can deposit a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ), it has excellent antibacterial, antiviral, antifungal and deodorizing properties, and even if the water droplets contain various bacteria, viruses and mold, it can completely kill the bacteria, viruses and mold contained in the water droplets, preventing the proliferation of bacteria, viruses and mold, and completely removing unpleasant odors such as cigarette smoke, putrid odors and nonenal odors. The coating film is made of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can rapidly exhibit the antiviral, antibacterial, antifungal and deodorizing functions of silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) is not lost prematurely, and the antiviral, antibacterial, antifungal and deodorizing functions of the water-soluble glass composition can be maintained for a long period of time.

[0025] The coating film is made of conductive glass particles that react with silver ions (Ag + ) and copper ions (Cu 2+ ), vanadium oxide (V2O5)-phosphorus oxide (P2O5) glass containing at least one of silver ions (Ag + ) and copper ions (Cu 2+ ) and at least one of the vanadium oxide (V2O5)-phosphorus oxide (P2O5)-barium oxide (BaO) glass, the conductive glass particles have excellent electronic conductivity, and the coating film contains a large amount of silver ions (Ag + ) and copper ions (Cu 2+) can be introduced into the coating film, resulting in a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ) can be contained, and a large amount of silver ions (Ag + ) and copper ions (Cu 2+ The coating film can deposit a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), it has excellent antibacterial, antiviral, antifungal and deodorizing properties, and even if the water droplets contain various bacteria, viruses and mold, it can completely kill the bacteria, viruses and mold contained in the water droplets, preventing the proliferation of bacteria, viruses and mold, and completely removing unpleasant odors such as cigarette smoke, putrid odors and nonenal odors. The coating film is made of silver ions (Ag + ) and copper ions (Cu 2+ ) can rapidly exhibit the antiviral, antibacterial, antifungal and deodorizing functions of silver ions (Ag + ), copper ions (Cu 2+ ) is not lost prematurely, and the antiviral, antibacterial, antifungal and deodorizing functions of the water-soluble glass composition can be maintained for a long period of time.

[0026] The coating film is made of a siloxane solution, which is the starting material for the coating liquid that forms it. By using a siloxane solution with a dense molecular structure as the starting material for the coating liquid, a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be dispersed and mixed, and a large amount of silver ions (Ag + ) and copper ions (Cu 2+ The coating film is made from a siloxane solution and contains a large amount of silver ions (Ag + ) and copper ions (Cu 2+), it has excellent antibacterial, antiviral, antifungal, and deodorizing properties. Even if the water droplets contain various bacteria, viruses, or mold, it can reliably kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and reliably eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film is a glass-based coating film made from a siloxane solution, it has excellent strength and excellent scratch resistance, and can smooth the surface of the substrate on which it is formed, preventing scratches on the surface of the substrate on which it is formed. The coating film is not limited to any particular object, and can provide excellent antibacterial, antiviral, antifungal, and deodorizing properties to all coated objects.

[0027] The coating film has its surface made hydrophilic by surface treatment, and by giving the surface of the coating film hydrophilicity, the contact angle of the water droplet with the surface of the coating film can be reliably reduced, and the contact area of ​​the water droplet with the surface of the coating film can be increased, so that the water droplet can come into contact with the surface of the coating film widely, and the silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ The coating film has excellent antibacterial, antiviral, antifungal, and deodorizing properties, and even if water droplets contain various bacteria, viruses, or mold, it can kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, the drying time of the droplets on the coating film surface is shortened, effectively shortening the survival time of the bacteria, viruses, and mold contained in the droplets, and allowing the bacteria, viruses, and mold to be killed in a short period of time.

[0028] The coating film has a surface coated with a hydrophilic polymer coating that has excellent hydrophilicity, so the contact angle of the water droplet with the surface of the coating film can be reliably reduced, the contact area of ​​the water droplet with the surface of the coating film can be increased, and the water droplet can be brought into contact with the surface of the coating film widely, and the silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ The coating film has excellent antibacterial, antiviral, antifungal, and deodorizing properties, and even if water droplets contain various bacteria, viruses, or mold, it can kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, the drying time of the droplets on the coating film surface is shortened, effectively shortening the survival time of the bacteria, viruses, and mold contained in the droplets, and allowing the bacteria, viruses, and mold to be killed in a short period of time.

[0029] The coating film has a plurality of minute irregularities formed on its surface by chemical etching or dry etching, and the hydrophilic polymer coating covers the surface of the coating film on which the plurality of minute irregularities have been formed, so that the hydrophilic polymer coating and the coating film are bonded together while the hydrophilic polymer coating is embedded in the plurality of minute irregularities, and therefore the hydrophilic polymer coating and the coating film can be firmly bonded together by an anchor effect, and inadvertent peeling of the hydrophilic polymer coating from the coating film can be prevented. The coating film has a hydrophilic polymer coating that coats the surface of the coating film, and therefore the hydrophilic polymer coating has excellent hydrophilicity, so that the contact angle of a water droplet with the surface of the coating film can be reliably reduced, the contact area of ​​the water droplet with the surface of the coating film can be increased, the water droplet can come into contact with a wide area of ​​the surface of the coating film, and the silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ The coating film has excellent antibacterial, antiviral, antifungal, and deodorizing properties, and even if water droplets contain various bacteria, viruses, or mold, it can kill the bacteria, viruses, and mold contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. Because the coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, the drying time of the droplets on the coating film surface is shortened, effectively shortening the survival time of the bacteria, viruses, and mold contained in the droplets, and allowing the bacteria, viruses, and mold to be killed in a short period of time.

[0030] If the coating film has antiviral and antibacterial functions, it can kill various bacteria and viruses contained in the water droplets, even if they contain bacteria and viruses, and prevent their proliferation.If the coating film has antifungal functions, it can kill various bacteria and viruses contained in the water droplets, even if they contain mold, and prevent their proliferation.If the coating film has deodorizing functions, it can remove unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors.

[0031] The coating film is made by applying the coating liquid to the surface of a given substrate, and then immediately applying water or an aqueous solution to the surface of the coating film. + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be quickly precipitated on the surface of the coating film, and silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can rapidly exhibit the antiviral, antibacterial, antifungal, and deodorizing functions of the coating film. Because the coating film rapidly exhibits antiviral, antibacterial, antifungal, and deodorizing functions, even if the water droplets contain various bacteria, viruses, or mold, it can kill the bacteria, viruses, and mold contained in the water droplets, preventing the growth of the bacteria, viruses, and mold while also eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. The coating film is not limited to any object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all objects immediately after coating. [Brief explanation of the drawings]

[0032] [Figure 1] FIG. 1 is an enlarged cross-sectional image of a glass particle-containing hydrophilic composite coating film (coating film and hydrophilic polymer coating) formed on the surface of a substrate. [Figure 2] This is a cross-sectional view that explains in chronological order the mechanism by which a coating film is formed from a coating liquid on the surface of a substrate to which the coating liquid has been applied. [Figure 3] FIG. 2 is a cross-sectional view schematically showing an example of a state immediately after a coating liquid is applied to a surface of a substrate. [Figure 4] FIG. 1 is a cross-sectional view schematically showing an example of a coating film formed on the surface of a substrate after a predetermined time has elapsed after the coating liquid has been applied to the surface of the substrate. [Figure 5] FIG. 2 is an image diagram showing an example of the structure of an inorganic coating film formed on the surface of a substrate. [Figure 6] FIG. 1 is an image diagram showing an example of the structure of an organic / inorganic hybrid coating film 10a formed on the surface of a substrate. [Figure 7] FIG. 10 is a cross-sectional view schematically showing another example of a state immediately after the coating liquid is applied to the surface of the substrate. [Figure 8] FIG. 10 is a cross-sectional view schematically showing another example of a coating film formed on the surface of a substrate after a predetermined time has elapsed after the coating liquid has been applied to the surface of the substrate. [Figure 9] FIG. 1 is a graph showing the antibacterial activity value of a coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles mixed therein. [Figure 10] 1 is a graph showing the relationship between the content of conductive glass particles in a coating film and antibacterial activity value. [Figure 11] This figure shows the relationship between the passage of time and the logarithmic mean viable bacteria count (cells / mL) for a coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles mixed in. [Figure 12] FIG. 1 shows the results of an antibacterial test (reduction rate). [Figure 13] FIG. 1 shows the evaluation of the mold resistance of a coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles mixed therein. [Figure 14]1 is a graph showing the correlation between the survival time (min) of influenza virus (IFV) and the contact angle (°) of a water droplet on the surface of a glass particle-containing hydrophilic composite coating film. [Figure 15] 1 is a graph showing the correlation between the survival time (h) of feline calicivirus (FCV) and the contact angle (°) of a water droplet on the surface of a glass particle-containing hydrophilic composite coating film. [Figure 16] FIG. 2 is a diagram showing an example of the state of water droplets attached to the film surface of a glass particle-containing hydrophilic composite coating film. [Figure 17] FIG. 17 is a diagram showing a simulation of the state of metal ions in the water droplets of FIG. 16. [Figure 18] FIG. 10 is a diagram showing the results of a deodorizing test on a glass particle-containing hydrophilic composite coating film 10. DETAILED DESCRIPTION OF THE INVENTION

[0033] The glass particle-containing hydrophilic composite coating film 10 according to the present invention will be described in detail below with reference to the accompanying drawings. Fig. 1 is an enlarged cross-sectional view of the glass particle-containing hydrophilic composite coating film 10 (coating film 10a and hydrophilic polymer coating 10b) formed on the surface 12 of a substrate 11. Fig. 2 is a cross-sectional view illustrating, in time sequence, the mechanism by which a coating film 10a is formed from a coating liquid 13 on the surface 12 of the substrate 11 to which the coating liquid 13 has been applied. Fig. 3 is a cross-sectional view schematically illustrating an example of a state immediately after the coating liquid 13 has been applied to the surface 12 of the substrate 11. Fig. 4 is a cross-sectional view schematically illustrating an example of a coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) formed on the surface 12 of the substrate 11 a predetermined time after the coating liquid 13 has been applied to the surface 12 of the substrate 11.

[0034] FIG. 5 is a conceptual diagram showing an example of the structure of an inorganic coating film 10a formed on the surface 12 of a substrate 11, and FIG. 6 is a conceptual diagram showing an example of the structure of an organic / inorganic hybrid coating film 10a formed on the surface 12 of a substrate 11. In FIGS. 3 and 4 (including FIGS. 7 and 8), conductive glass particles 14, silver ions 15a (Ag + ), copper ion 15b (Cu 2+ ), zinc ion 15c (Zn 2+ ) is illustrated as a visible image of the metal ions 15, but in reality the metal ions 15 cannot be seen with the naked eye.

[0035] The coating film 10a and hydrophilic polymer coating 10b are formed on the surface 12 (front and back surfaces) (contact surface) of the substrate 11. The coating film 10a is produced by coating the surface 12 of the substrate 11 to be coated with a coating liquid 13 (organic and inorganic hybrid polymer). The hydrophilic polymer coating 10b is produced by forming the organic / inorganic hybrid coating film 10a on the surface 12 of the substrate 11, and then coating the surface of the coating film 10a with a hydrophilic polymer coating agent (hydrophilic functional polymer).

[0036] The substrate 11 to be coated with the glass particle-containing hydrophilic composite coating film 10 (coating film) (the substrate to be coated with the coating film 10a and the hydrophilic polymer coating 10b) may be metal (metallic molded product), plastic (plastic molded product and molded product having plastic as the outermost layer), glass (glass molded product), rubber (rubber molded product), leather (leather molded product), wood (wooden molded product), paper (paper molded product), woven or knitted fabric using fiber (woven or knitted fabric molded product), etc., but is not particularly limited to the substrate 11. Note that each molded product is not particularly limited, and includes all molded products of a predetermined shape made from metal, plastic, glass, rubber, leather, wood, paper, synthetic fiber, natural fiber, and woven or knitted fabric.

[0037] Metals include iron, aluminum, duralumin, stainless steel, copper, gold, silver, titanium, nickel, and various alloys. Plastics include polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ABS, polycarbonate, polystyrene, epoxy, unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, polyvinyl fluoride resin, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene-tetrafluoroethylene copolymer resin, and ethylene-chlorotrifluoroethylene copolymer resin. Rubbers include polybutadiene rubber, polyisoprene (natural rubber), styrene-butadiene rubber, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, polysulfide, and butyl rubber.

[0038] Examples of molded articles include medical clothing (masks, white coats, protective clothing, gloves, etc.), medical bedding (futons, pillowcases, curtains, patient amenities, etc.), medical instruments (scissors, scalpels, other equipment, etc.), hospital facilities (handrails, doorknobs, walls, floors, elevators, escalators, etc.), means of transportation (trains, buses, airplanes, ships, vehicles, etc.), clothing (underwear, T-shirts, socks, sportswear, diapers, etc.), pet supplies (pet toilets, pet cages, etc.), sanitary products (kitchen supplies, toilet supplies, bath supplies, sinks, etc.), food supplies (food trays, kitchen supplies, tableware, etc.), and in addition, all molded articles that are subject to antibacterial, antiviral, antifungal, and deodorizing treatments are also included.

[0039] A siloxane-based solution (liquid organosilicon material) is used as the starting material (raw coating solution) for the coating liquid 13 (organic and inorganic hybrid polymer) used to make the coating film 10a. One example of the siloxane-based solution is organopolysiloxane, in which silicon atoms (Si) having organic groups are linked by siloxane bonds (≡Si-O-Si≡).

[0040] The coating liquid 13 is made from the main components organopolysiloxane, alkylsilicate condensate, inert organic solvent, and conductive glass particles 14, which will be described later. The organopolysiloxane, alkylsilicate condensate, and inert organic solvent are mixed and stirred in a predetermined ratio, and the conductive glass particles 14 are mixed into the mixture. In the coating liquid 13, the organopolysiloxane and alkylsilicate condensate are diluted with the inert organic solvent. The organopolysiloxane has a number average molecular weight in the range of 3,000 to 150,000 g / mol.

[0041] The glass particles 14 mixed into the coating liquid 13 contain silver ions 15a (Ag) which have antiviral, antibacterial, antifungal and deodorizing functions. + ) and copper ion 15b (Cu 2+ ) and zinc ion 15c (Zn 2+ ) and silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+ The conductive glass particles 14 containing the metal ions 15 of the formula (I) exhibit ionic conductivity.

[0042] An example of the conductive glass particles 14 is a glass based on phosphorus oxide (P2O5) (electronically conductive glass), and at least one of vanadium oxide (VO) (electronically conductive glass), tungsten oxide (WO3) (electronically conductive glass), and molybdenum oxide (MoO3) (electronically conductive glass).An example of the conductive glass particles 14 is a glass based on phosphorus oxide (P2O5) (electronically conductive glass), and at least one of vanadium oxide (VO) (electronically conductive glass), tungsten oxide (WO3) (electronically conductive glass), and molybdenum oxide (MoO3) (electronically conductive glass), and barium oxide (BaO).

[0043] Specific examples of the conductive glass particles 14 include silver ions (Ag + ) and copper ions (Cu 2+ ), and other specific examples of the conductive glass particles 14 include vanadium oxide (V2O5)-phosphorus oxide (P2O5) glass containing at least one of silver ions (Ag + ) and copper ions (Cu 2+ The conductive glass particles 14 have a layered structure, and silver ions 15a (Ag + ), copper ion 15b (Cu 2+ ), zinc ion 15c (Zn 2+ ) exists, water molecules penetrate between the layers of the conductive glass particles 14, and the metal ions are eluted onto the surface.

[0044] Silver ions 15a (Ag) produced by dissociation with oxygen + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+) are in an unstable state (positively charged), so they try to bind with the oxygen of microorganisms (viruses, bacteria, fungi, algae, etc.) and are taken into the cells of the microorganisms. The taken-up silver ions 15a, copper ions 15b, and zinc ions 15c then bind to proteins, etc., inhibiting their function and preventing cell division, etc., and the dysfunction of the proteins generates reactive oxygen species, which causes the microbial cells to die.

[0045] The siloxane-based solution can be an inorganic polysilazane such as a Si-N perhydropolysilazane solution (perhydropolysilazane solution), a Si-CN organopolysilazane solution, a Si-C polycarbosilane solution, a SiC-O organopolysilazane solution, a Si-BCN organopolysilazane solution, a Si-Ti-N organopolysilazane solution, or an organopolysiloxane.

[0046] The inorganic polysilazane is represented by the general formula (Chemical Formula 1).

[0047] [ka] Examples of inorganic polysilazanes include perhydropolysilazanes that include a linear structure having structural units, have a molecular weight of 690 to 2,000, have 3 to 10 SiH groups per molecule, and have element ratios of Si: 59 to 61, N: 31 to 34, and H: 6.5 to 7.5 by weight, as determined by chemical analysis, and have an average molecular weight in the range of 3,000 to 20,000 in terms of polystyrene.

[0048] Perhydropolysilazane contains chain and cyclic portions in its molecule and is represented by the following chemical formula (Chemical Formula 2).

[0049] [ka] An example of the structure of perhydropolysilazane is represented by the following chemical formula (Chemical Formula 3).

[0050] [ka] Another example of the perhydropolysilazane compound group is represented by the following general formula (Chemical Formula 4), which contains a Si-N bond and a functional group (R 1 ~R 3 ) and is a polymer formed from -(SiR1R2-NR3)- units, and at least one of the functional groups R1 and R2 directly bonded to Si is an organic polymer formed from an organic functional group such as an alkyl group having carbon (C).

[0051] [ka] Perhydropolysilazane is an organic compound with a functional group (R 1 ~R 3 The content of methyl groups (CH3), which is one of the functional groups, is 50% or more. Furthermore, perhydropolysilazane may not only be a polymer formed from one type of -(SiR1R2-NR3)- unit, but also a polymer formed from multiple types of -(SiR1R2-NR3)- units with different compositions of functional groups (R1 to R3). Furthermore, perhydropolysilazane may be a polymer having a chain, cyclic or crosslinked structure, or may be a polymer having a combination of these structures. R 1 , R 2 , R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to the silicon atom is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. 1 , R 2 , R 3 At least one of the is a hydrogen atom.

[0052] As an example, perhydropolysilazane (A) is a compound having a -(SiH(CH3)-NH)- unit, a -(Si(CH3)2-NH)- unit, a -(SiR 1 It is a polymer containing (CH3)-NR3)- units.1 (CH3)-NR 3 The functional group R1 in the )-unit is H or CH3, and the functional group R3 directly bonded to N is an organic functional group that promotes the reaction. The inclusion of perhydropolysilazane (A) in the coating liquid 13 promotes the reaction after the coating liquid 13 is applied to the surface 12 of the substrate 11, and allows the coating film 10a to be formed on the surface 12 of the substrate 11 quickly.

[0053] [ka] Another example of perhydropolysilazane (B) is a compound having a -(SiH(CH3)-NH)- unit, a -(SiR 1 is a polymer containing (CH3)-NH)- units, 1 Functional group R of the (CH3)-NH)- unit 1 is an organic functional group that realizes high heat resistance. By including perhydropolysilazane (B) in the coating liquid 13, the heat resistance of the coating film 10a that covers the surface 12 of the substrate 11 can be improved.

[0054] [ka] The perhydropolysilazane contained in the coating liquid 13 may be a mixture of multiple types of perhydropolysilazanes with different polymer structures. For example, the perhydropolysilazane may be a mixture of perhydropolysilazane (A) and perhydropolysilazane (B). Experiments on mixing these perhydropolysilazanes (A) and (B) have confirmed that a mixture of 50% by mass of perhydropolysilazane (A) and 50% by mass of perhydropolysilazane (B) exhibits rust prevention properties equal to or better than that of perhydropolysilazane (A) alone, and also shortens the curing time (time to form the coating film 10a) compared to perhydropolysilazane (B) alone.

[0055] The organopolysilazane has a hydrogen atom in R and an organic group in R in the above general formula (Chemical Formula 4). - (R SiHNH)- is a repeating unit, and the polysilazane has a cyclic structure with a degree of polymerization of 3 to 5. The polysilazane having both a chain structure and a cyclic structure in the molecule represented by the chemical formula of (R SiHNH) [(R SiH)N] (0.4 < X < 1), the polysilazane having a hydrogen atom in R and an organic group in R, R and R in the above general formula (Chemical Formula 4), the polysilazane having an organic group in R and R and a hydrogen atom in R, and - (R R SiNR)- as a repeating unit, and mainly having a cyclic structure with a degree of polymerization of 3 to 5. 1 and R 2 have a hydrogen atom, and R 3 has an organic group. - (R SiHNH)- is a repeating unit, and the polysilazane has a cyclic structure with a degree of polymerization of 3 to 5. The polysilazane having both a chain structure and a cyclic structure in the molecule represented by the chemical formula of (R SiHNH) [(R SiH)N] (0.4 < X < 1), the polysilazane having a hydrogen atom in R and an organic group in R, R and R in the above general formula (Chemical Formula 4), the polysilazane having an organic group in R and R and a hydrogen atom in R, and - (R R SiNR)- as a repeating unit, and mainly having a cyclic structure with a degree of polymerization of 3 to 5. 2 SiHNH)- is a repeating unit, and the polysilazane has a cyclic structure with a degree of polymerization of 3 to 5. The polysilazane having both a chain structure and a cyclic structure in the molecule represented by the chemical formula of (R SiHNH) [(R SiH)N] (0.4 < X < 1), the polysilazane having a hydrogen atom in R and an organic group in R, R and R in the above general formula (Chemical Formula 4), the polysilazane having an organic group in R and R and a hydrogen atom in R, and - (R R SiNR)- as a repeating unit, and mainly having a cyclic structure with a degree of polymerization of 3 to 5. 3 SiHNH) x 〔(R 2 SiH) 1.5 N〕 1-X (0.4 < X < 1), the polysilazane having a hydrogen atom in R and an organic group in R, R and R in the above general formula (Chemical Formula 4), the polysilazane having an organic group in R and R and a hydrogen atom in R, and - (R R SiNR)- as a repeating unit, and mainly having a cyclic structure with a degree of polymerization of 3 to 5. 1 has a hydrogen atom, and R 2 , R 3 has an organic group. The polysilazane having an organic group in R and R and a hydrogen atom in R, and - (R R SiNR)- as a repeating unit, and mainly having a cyclic structure with a degree of polymerization of 3 to 5. 1 and R 2 have an organic group, and R 3 has a hydrogen atom, and - (R 1 R 2 SiNR 3 )- is a repeating unit, and there is a polysilazane mainly having a cyclic structure with a degree of polymerization of 3 to 5.

[0056] For example, the organopolysilazane having a crosslinked structure in the molecule other than the above general formula (Chemical Formula 4) is represented by the following general formula (Chemical Formula 7).

[0057]

Chemical Formula

[0058]

Chemical Formula

[0059] Examples of the monovalent ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl. The number of carbon atoms in the alkenyl group is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 3 or less. Examples of the monovalent ethylenically unsaturated group include (meth)acryloyloxyalkyl groups, i.e., groups represented by the formula (B): -R 12 -OC(=O)-CR 11 There are also groups represented by =CH2. Specifically, there are acryloyloxypropyl groups and methacryloyloxypropyl groups. R in formula (B) 11 is a hydrogen atom or a methyl group, and R 12 is an alkanediyl group, preferably an alkanediyl group having 1 to 5 carbon atoms. Note that (meth)acrylic is used as a general term for acrylic and methacrylic, and (meth)acryloyl is used as a general term for acryloyl and methacryloyl.

[0060] Among the monovalent ethylenically unsaturated groups, alkenyl groups are preferred, vinyl groups and allyl groups are preferred, and vinyl groups are more preferred. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, and heptyl groups; aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as benzyl groups and phenethyl groups. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 3.

[0061] Examples of monovalent substituted hydrocarbon groups include a 3-mercaptopropyl group (-(CH2)3-SH) and a 3-aminopropyl group (-(CH2)3-NH2). R 1 From the viewpoint of fine particle formation, each of the groups is preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, a vinyl group, or an allyl group, and even more preferably a methyl group or a vinyl group.

[0062] In one molecule of organopolysiloxane having the average unit formula (A), at least a portion of R 1 is a group containing a functional group (L) such as a monovalent ethylenically unsaturated group, an aryl group, or an aralkyl group, and is preferably a monovalent ethylenically unsaturated group, more preferably an alkenyl group. The total proportion of the monovalent ethylenically unsaturated group, aryl group, or aralkyl group is determined based on the total R in one molecule of the organopolysiloxane. 1 Based on this, it is preferably 50 mol % or more, more preferably 60 mol % or more, even more preferably 70 mol % or more, still more preferably 80 mol % or more, and particularly preferably 90 mol % or more. The monovalent ethylenically unsaturated group, aryl group, or aralkyl group is a hydrophobic group containing a nonionic functional group capable of coordinating to a metal ion.

[0063] In the average unit formula (A), a, b, c, and d represent the respective constituent units (R 1 3SiO 1 / 2 ), (R 1 2SiO 2 / 2 ), (R 1 SiO3 / 2 ) and (SiO 4 / 2 The sum of the mole fractions of each structural unit, a, b, c, and d, is 1. a represents the average value of the mole fraction of R 1 3SiO 1 / 2 a is the mole fraction of siloxane units represented by (M units). a is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less.

[0064] b is R 1 2SiO 2 / 2 b is the mole fraction of siloxane units represented by R (D units). b is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. c is the mole fraction of siloxane units represented by R 1 SiO 3 / 2 is the mole fraction of siloxane units represented by (T units). c is 0.3 or more and 1 or less, preferably 0.4 or more, 0.5 or more, or 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0065] d is SiO 4 / 2 is the mole fraction of siloxane units represented by (Q units). d is 0 or more and 0.7 or less, preferably 0.6 or less, 0.5 or less, or 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. The sum of c and d, which represents the total number of branched structural units, is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0066] The organopolysiloxane is a polysiloxane having a constitutional unit (R 1 3SiO 1 / 2 When the structural unit (R) in the average unit formula (A) is present, it may contain only one type of structural unit, or may contain two or more types of structural units. 1 2SiO 2 / 2 ) and (R 1 SiO 3 / 2The same applies to the R 1 At least part of 2 In the average unit formula (A), R may be replaced by O. 2 is a hydrogen atom or an alkyl group. 2 O represents a hydroxy group or an alkoxy group bonded to a silicon atom contained in the organopolysiloxane skeleton. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 3 or less.

[0067] The above R in each of the structural units 1 At least part of 2 The amount of the structural units substituted with O is preferably 0 or more and 0.10 or less, more preferably 0 or more and 0.05 or less, and even more preferably 0 or more and 0.03 or less, relative to the sum of the molar fractions of the structural units, a, b, c, and d, which is 1. The alkoxy group in the structural unit is, for example, an alkoxy group that is a hydrolyzable group contained in an alkoxysilane described below, and remains in the molecule without undergoing hydrolysis and polycondensation. The hydroxy group in this structural unit is, for example, a hydroxy group that remains in the molecule after hydrolysis of an alkoxy group without undergoing polycondensation.

[0068] The organopolysiloxane is preferably a silsesquioxane. Silsesquioxane has a main chain skeleton consisting of Si—O bonds and a main structural unit (R 1 SiO 3 / 2 ) units, and the value of c is 0.7 or greater. Examples of the silsesquioxane structure include a random structure, a complete cage structure, an incomplete cage structure, and a ladder structure. Among these, silsesquioxanes having a random structure are preferred from the viewpoint of ease of production.

[0069] The structural unit (R 1 3SiO 1 / 2 As the alkoxysilane forming R 1 3Si(OR2 Specific examples thereof include methoxydimethylvinylsilane, ethoxydimethylvinylsilane, methoxydimethylphenylsilane, and ethoxydimethylphenylsilane; and methoxytrimethylsilane and ethoxytrimethylsilane.

[0070] The structural unit (R 1 2SiO 2 / 2 As the alkoxysilane forming R 1 2Si(OR 2 ) 2. Specific examples thereof include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and dimethoxybenzylmethylsilane; as well as dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, and dipropoxydiethylsilane.

[0071] The structural unit (R 1 SiO 3 / 2 As the alkoxysilane forming R 1 Si(OR 2 )3. Specific examples thereof include trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyallylsilane, triethoxyallylsilane, (3-(meth)acryloyloxypropyl)trimethoxysilane, and (3-(meth)acryloyloxypropyl)triethoxysilane; as well as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyltrimethoxysilane. The structural unit (SiO 4 / 2 As the alkoxysilane that forms Si(OR 2 ) 4. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0072] The alkyl silicate condensate is a condensate (mixture) of one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, tetra-sec-butyl orthosilicate, methyl polysilicate, and ethyl polysilicate. The inert organic solvent is inert to the organic polysilazane, siloxane, and alkyl silicate condensate, and is selected from dibutyl ether, turpentine oil, benzene, toluene, xylene, and propylene glycol monomethyl ether acetate.

[0073] Because the number-average molecular weight of the inorganic polysilazane, organo polysilazane, or organo polysiloxane in the coating liquid 13 is within the above-mentioned range, the coating liquid 13 containing the inorganic polysiloxane, organo polysilazane, or organo polysiloxane can maintain a predetermined viscosity, and a coating film 10a can be formed from the coating liquid 13. Because the coating liquid 13 is applied to the surface 12 of the substrate 11 to be coated while maintaining the predetermined viscosity, even if the coating liquid 13 is applied to the surface 12 of the substrate 11 having minute pores or a mesh formed therein, the coating liquid 13 does not penetrate into the interior of the substrate 11, and a coating film 10a with a substantially uniform thickness can be formed on the surface 12 of the substrate 11.

[0074] In the coating liquid 13, the blending ratio of silicon oxide (inorganic polysilazane, organopolysilazane, organopolysiloxane) to the total mass is in the range of 30 to 60 mass%, the blending ratio of alkyl silicate condensate to the total mass is in the range of 10 to 15 mass%, and the blending ratio of inert organic solvent to the total mass is in the range of 30 to 60 mass%. If the blending ratio of silicon oxide (organic silicon material) is less than 30 mass%, the silicon oxide content is low, and it is not possible to form a coating film 10a of the specified thickness on the surface 12 of the substrate 11 that has excellent flexibility, impact resistance, and corrosion resistance. If the blending ratio of silicon oxide exceeds 60 mass%, the viscosity of the coating liquid 13 increases more than necessary, and the thickness of the coating film 10a becomes larger than necessary. Since the coating liquid 13 has a silicon oxide content in the above range relative to its total mass, a coating film 10a of an appropriate thickness having excellent flexibility, impact resistance, and corrosion resistance can be formed on the surface 12 of the substrate 11.

[0075] If the alkyl silicate condensate content is less than 10% by mass, the alkyl silicate condensate's cross-linking effect is weak, and a sufficient cross-linked structure is not formed in the coating film 10a. If the alkyl silicate condensate content exceeds 15% by mass, an unnecessary cross-linked structure is formed in the coating film 10a, and the flexibility of the coating film 10a becomes greater than necessary. Since the alkyl silicate condensate content of the coating liquid 13 relative to its total mass is within the above range, the coating liquid 13 can be used to produce a coating film 10a with an appropriate cross-linked structure and appropriate flexibility.

[0076] If the blending ratio of the inert organic solvent is less than 30% by mass, the viscosity of the coating liquid 14 will be high, and the thickness of the coating film 13 formed from the coating liquid 14 will be greater than necessary. If the blending ratio of the inert organic solvent exceeds 60% by mass, the viscosity of the coating liquid 14 will be lower than necessary, and it will be impossible to form a coating film 13 of the desired thickness on the surface 12 of the substrate 11 that has excellent flexibility, impact resistance, and corrosion resistance. Because the blending ratio of the inert organic solvent to the total mass of the coating liquid 14 is within the above range, the coating liquid 14 can be used to form a coating film 13 of appropriate viscosity that has excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0077] The coating liquid 13 is applied to the surface 12 of the substrate 11 to be coated, and chemically reacts with water to form (deposit) an ultra-thin coating film 10a. The coating film 10a is deposited as a film having an average thickness in the range of 5 nm to 20 μm, preferably 50 nm to 1 μm.

[0078] In forming the coating film 10a (inorganic coating film 10a), the surface 12 of the substrate 11 is irradiated with ultraviolet light while irradiating with infrared light to heat the surface 12 of the substrate 11 to 400°C or higher. In forming the coating film 10a (organic / inorganic hybrid coating film 10a), the surface 12 of the substrate 11 is coated with the coating liquid 12, and then the surface 12 of the substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating. Alternatively, the surface 12 of the substrate 11 is coated with the coating liquid 13, and then the surface 12 of the substrate 11 is irradiated with ultraviolet light while being left at room temperature (normal temperature) for a predetermined time (24 hours or more). Alternatively, the surface 12 of the substrate 11 is coated with the coating liquid 13, and then the surface 12 of the substrate 11 is irradiated with ultraviolet light while being irradiated with infrared light to heat the surface 12 of the substrate 11 to a temperature below 400°C, and then left for a predetermined time (24 hours or more).

[0079] A small amount of moisture (water droplets) adheres to the surface 12 of the substrate 11 due to condensation or humidity in the air (including when water (H2O) is sprayed). When the surface 12 of the substrate 11 is coated with a thin film of the coating liquid 13, the inorganic polysilazanes, organopolysilazanes, and organopolysiloxanes contained in the coating liquid 13 chemically react with the moisture (H2O) in the air, producing an organic composite structure on the surface 12 of the substrate 11, in which organic functional groups are attached as side chains to part of the main chain formed by siloxane bonds (Si-O-Si). Furthermore, trace amounts of gases (NH3, H2) are produced as by-products of the above chemical reaction. These gases volatilize (emit) into the atmosphere without remaining on the surface 12 of the substrate 11.

[0080] The coating liquid 13 containing inorganic polysilazane, organopolysilazane, or organopolysiloxane undergoes a chemical reaction (deammonia crosslinking) with moisture in the air in the surface layer in contact with the air, causing gases such as hydrogen and ammonia, which are by-products of the coating film 10a (inorganic coating film 10a, organic / inorganic hybrid coating film 10a), to volatilize from the surface 12 (surface layer) into the outside air, and a coating layer is formed (deposited) on the surface 12 side of the coating film 11. The coating liquid 13 coated on the surface 12 of the substrate 11 undergoes a chemical reaction (deammonia crosslinking) with moisture (water droplets) attached to the surface 12 or hydroxyl groups -OH present as terminals on the surface 12 in the back layer in contact with the surface 12 of the substrate 11, causing gases such as hydrogen and ammonia to rise within the coating layer and volatilize from the surface 12 (surface layer) into the outside air, and a coating layer is formed (deposited) on the back side of the coating film 10a.

[0081] As shown in FIG. 2, coating layers (glass coating layer, vitrified (inorganized) portion and organic portion) are formed on the surface layer and back layer of the coating liquid 14 first coated on the surface 12. Next, the coating layer (glass coating layer, vitrified (inorganized) portion and organic portion) is formed and expanded from the surface layer side toward the back layer side, and the coating layer is formed and expanded from the back layer side toward the surface layer side, thereby sequentially forming (forming) coating layers of the intermediate layer. Finally, a coating film 10a (inorganic coating film 10a) having the structure shown in FIG. 5 or a coating film 10a (organic / inorganic hybrid coating film 10a) having the structure shown in FIG. 6 is formed on the surface layer in contact with the outside air and the back layer and intermediate layer in contact with the surface 12 of the substrate 11. The coating film 10a has high density and high hardness (pencil hardness of approximately 6H to 9H).

[0082] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, water (H2O) such as purified water or a predetermined aqueous solution may be sprayed or brushed onto the surface of the coating film 10a, so that the water (H2O) or aqueous solution adheres to the surface of the coating film 10a. By doing so, silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) precipitates rapidly.

[0083] As a pre-treatment step prior to the coating step with the coating liquid 13, water (H2O) such as purified water may be sprayed onto the surface 12 of the substrate 11 to adhere the water to the surface 12 of the substrate 11. This promotes a chemical reaction between the water adhered to the surface 12 of the substrate 11 and the components contained in the coating liquid 13, and allows the coating film 10a to be rapidly formed on the surface 12 of the substrate 11.

[0084] Furthermore, a coating liquid containing inorganic polysilazane as a main component can be coated as a primer on the surface 12 of the substrate 11 as a pretreatment step prior to the coating step with the coating liquid 13. For example, when a solution of inorganic polysilazane (1 wt % solution) is coated and then the coating liquid 13 is coated, the rust prevention (durability) of the coating film 10a is improved compared to when only the coating liquid 13 is simply coated.

[0085] After the coating film 10a is formed on the surface 12 of the substrate 11, multiple fine irregularities are formed on the surface of the coating film 10a by chemical etching or dry etching. Chemical etching uses a specific chemical to form irregularities on the surface of the coating film 10a. Dry etching generates plasma of a gas that is reactive with the coating film 10a, and applies a bias to the substrate 11 to attract reactive ions in the plasma into the coating film 10a, thereby etching it.

[0086] After forming a plurality of minute irregularities on the surface of the coating film 10a by chemical etching or dry etching, a hydrophilic polymer coating agent (hydrophilic functional polymer) is coated (applied) onto the etched surface of the coating film 10a. After the hydrophilic polymer coating agent is applied, the hydrophilic polymer coating agent is irradiated with infrared rays to heat the temperature of the hydrophilic polymer coating agent (surface 12 of the substrate 11) to about 80°C, and is left for a predetermined time.

[0087] A photocatalytic coating agent (main components: titanium dioxide + binder) can be used as the hydrophilic polymer coating agent (hydrophilic functional polymer) used to create the hydrophilic polymer coating 10b. When the hydrophilic polymer coating agent is a photocatalytic coating agent, it dries and hardens in about 30 minutes to an hour after being coated on the surface of the coating film 10a, forming (depositing) the hydrophilic polymer coating 10b. When ultraviolet light is irradiated onto the surface of the photocatalytic coating film, the surface becomes more easily wetted by water. One of the effects of photocatalysis is its superhydrophilic effect.

[0088] The hydrophilic polymer coating agent (hydrophilic functional polymer) can be an alkoxysilane-based compound (main component: alkoxysilane, alkoxysilane oligomer) or a polysilazane-based compound (main component: perhydropolysilazane). When the hydrophilic polymer coating agent is an alkoxysilane-based compound or a polysilazane-based compound, the hydrophilic polymer coating agent hardens on the surface of the coating film 10a within about 12 hours after coating, forming the hydrophilic polymer coating 10b (film formation). Alkoxysilane-based compounds and polysilazane-based compounds are silicon compounds that react with water in the air to convert to silica, forming a glassy film.

[0089] Photocatalytic coating agents, alkoxysilane compounds, and polysilazane compounds are hydrophilic because their surfaces are covered with hydroxyl groups. The surface free energy of the solid is greater than the cohesive force (surface tension) of water, and the hydroxyl groups form weak bonds with water, such as hydrogen bonds. Photocatalytic coating agents, alkoxysilane compounds, and polysilazane compounds have a high affinity for water, so water droplets do not form droplets but spread out. Glass particle-containing hydrophilic composite coating film 10 is formed from coating film 10a formed on surface 12 of substrate 11 and hydrophilic polymer coating 10b formed on the surface of coating film 10a.

[0090] The hydrophilic polymer coating agent (hydrophilic functional polymer) may contain one or more hydrophilic polymers selected from the group consisting of homopolymers or copolymers of vinylpyrrolidone, ethylene glycol, and vinyl alcohol, or the hydrophilic polymer coating agent (hydrophilic functional polymer) may contain one of poly(vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), and poly(vinyl alcohol) (PVA).

[0091] The hydrophilic polymer coating agent is coated or sprayed onto the surface of the coating film 10a formed on the surface 12 of the substrate 11 (molded product) to form (deposit) a hydrophilic polymer coating 10b. The hydrophilic polymer coating 10b is deposited as a film having an average thickness in the range of 2 nm to 0.1 μm.

[0092] In the glass particle-containing hydrophilic composite coating film 10, a plurality of fine irregularities are formed on the surface of the coating film 10a by chemical etching or dry etching, and the hydrophilic polymer coating 10b and the coating film 10a are bonded together in a state in which the hydrophilic polymer coating 10b penetrates into the plurality of fine irregularities formed on the surface of the coating film 10a. Therefore, the hydrophilic polymer coating 10b and the coating film 10a can be firmly bonded together by the anchor effect, and inadvertent peeling of the hydrophilic polymer coating 10b from the coating film 10a can be prevented.

[0093] The coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) that forms the glass particle-containing hydrophilic composite coating film 10 contains silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ Conductive glass particles 14 containing metal ions 15 (ion) are dispersed and mixed.

[0094] Immediately after the coating liquid 13a is applied to the surface 12 of the substrate 11, the conductive glass particles 14 mixed in the coating liquid 13a are dispersed and mixed inside the coating liquid 13a, as shown in FIG. 3, but the silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) do not deposit (migrate) toward the surface of the coating liquid 13a.

[0095] As a specific example, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions (Ag + ) and copper ions (Cu 2+ ) and at least one of vanadium oxide (V2O5)-phosphorus oxide (P2O5)-based conductive glass particles 14 are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ) do not diffuse toward the surface layer (surface) of the coating liquid 13. As another specific example, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions (Ag + ) and copper ions (Cu 2+ ) and at least one of vanadium oxide (V2O5)-phosphorus oxide (P2O5)-barium oxide (BaO)-based conductive glass particles 14 are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ) does not diffuse toward the surface layer (surface) of the coating liquid 13.

[0096] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion) and copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ions) are not precipitated, the glass particle-containing hydrophilic composite coating film 10 does not exhibit antiviral, antibacterial, antifungal, or deodorizing functions.

[0097] In the process of forming (forming) a coating film 10a (glass particle-containing hydrophilic composite coating film 10) from the coating liquid 13, as shown in FIG. 4, after the coating liquid 13 is coated on the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) migrate from the conductive glass particles 14 into the coating liquid 13 due to moisture in the air. After a predetermined time has passed since the coating liquid 13 was applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) move inside the coating film 10a from the back layer (bottom) of the coating film 10a toward the surface layer (surface) of the coating film 10a, and are precipitated toward the surface layer (surface) of the coating film 10a.

[0098] Furthermore, over time, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) migrate from the surface of the coating film 10a to the inside of the hydrophilic polymer coating 10b due to moisture in the air. After a predetermined time has passed since the coating liquid 13 was applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ions) move through the inside of the hydrophilic polymer coating 10b from the back layer (bottom) of the hydrophilic polymer coating 10b toward the surface layer (surface), and are precipitated toward the surface layer (surface) of the hydrophilic polymer coating 10b.

[0099] After a predetermined time has passed since the coating liquid 13 was applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) are precipitated on the surface of the coating film 10a, and then the metal ions 15 are precipitated on the surface of the hydrophilic polymer coating 10b, thereby imparting antiviral, antibacterial, antifungal, and deodorizing functions to the glass particle-containing hydrophilic composite coating film 10.

[0100] In addition, the conductive glass particles 14 having a high content of vanadium oxide (VO) have a high deposition rate of metal ions 15, and as described above, after a predetermined time (10 to 20 minutes) has elapsed since the coating liquid 13 was applied to the surface 12 of the substrate 11, the metal ions 12 are deposited toward the surface layer (surface) of the coating film 13, and the metal ions 15 are deposited toward the surface of the hydrophilic polymer coating 10b. As described above, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, water (HO) such as purified water or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a, thereby depositing silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be rapidly precipitated.

[0101] Conductive glass particles 14 containing a high content of phosphorus oxide (P2O5) and barium oxide (BaO) have a slow deposition rate of metal ions 15, and the metal ions 15 do not deposit on the surface layer (surface) of coating film 10a in a short time after coating liquid 13 is applied to surface 12 of substrate 11. Instead, metal ions 12 deposit on the surface layer (surface) of coating film 10a over a long period of time (3 months to 3 years), and metal ions 15 remain inside coating film 10a for a long time.

[0102] The glass particle-containing hydrophilic composite coating film 10 (coating film 10a) uses two or more types of conductive glass particles with different compositions: conductive glass particles 14 with a high content of vanadium oxide (VO) and conductive glass particles 14 with a high content of phosphorus oxide (PO) or barium oxide (BaO), thereby achieving both immediate and long-lasting antiviral, antibacterial, antifungal, and deodorizing functions.

[0103] In the glass particle-containing hydrophilic composite coating film 10, the average thickness of the coating film 10a is in the range of 0.2 μm to 20 μm, preferably 0.5 μm to 20 μm. If the average thickness of the coating film 10a is less than 0.2 μm, the strength of the coating film 10a is reduced, its protective function is lost, and the surface 12 of the substrate 11 cannot be adequately protected. If the average thickness of the coating film 10a exceeds 20 μm, the flexibility of the coating film 10a is reduced, and deformation of the surface 12 of the substrate 11 may cause the coating film 10a to peel off from the surface 12.

[0104] Although the glass particle-containing hydrophilic composite coating film 10 has a coating film 10a mainly composed of SiO2, it has excellent flexibility and will not peel off even if the surface 12 of the substrate 11 is made of a cloth material, nonwoven fabric, or the like that causes deformation, and can follow the deformation of the surface 12 to maintain the coating state of the coating film 10a.

[0105] In the glass particle-containing hydrophilic composite coating film 10, the content of conductive glass particles 14 dispersed in the coating film 10a in the coating film 13 is in the range of 0.1 to 20% by volume, preferably 0.3 to 5% by volume. If the content of conductive glass particles 14 dispersed in the coating film 13 is less than 0.1% by volume, the content of conductive glass particles 14 in the coating film 13 is low, and the glass particle-containing hydrophilic composite coating film 10 cannot exhibit sufficient antiviral, antibacterial, antifungal, and deodorizing functions. If the content of conductive glass particles 14 dispersed in the coating film 10a exceeds 20% by volume, the adhesion of the coating film 10a to the surface 12 of the substrate 11 decreases, and a smooth glass particle-containing hydrophilic composite coating film 10 cannot be formed on the surface 12.

[0106] The glass particle-containing hydrophilic composite coating film 10 has excellent antiviral, antibacterial, antifungal, and deodorizing functions, and these functions are maintained for a long period of time, since the content of the conductive glass particles 14 dispersed in the coating film 13 is within the above range. Furthermore, the glass particle-containing hydrophilic composite coating film 10 has high adhesion to the surface 12 of the substrate 11, and forms a smooth thin film on the surface 12 of the substrate 11.

[0107] In the glass particle-containing hydrophilic composite coating film 10, the average particle diameter D of the conductive glass particles 14 dispersed and mixed in the coating film 10a is 50 The average particle size D of the conductive glass particles 14 in the coating film 10a is 5 μm or less, preferably 1 μm or less. 50 If the thickness exceeds 5 μm, silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+) cannot sufficiently diffuse inside the coating film 10a toward the surface layer (surface) of the coating film 10a, and the coating film 10a cannot exhibit sufficient antiviral, antibacterial, antifungal, and deodorizing functions. Furthermore, the adhesion of the coating film 10a to the surface 12 of the substrate 11 is significantly reduced, and a smooth coating film 10a cannot be formed on the surface 12.

[0108] The glass particle-containing hydrophilic composite coating film 10 has an average particle diameter D of the conductive glass particles 14 contained in the coating film 10a. 50 Since the viscosity of the coating is within the above range, the coating has excellent antiviral, antibacterial, antifungal, and deodorizing properties, and these antiviral, antibacterial, antifungal, and deodorizing properties are maintained for a long period of time. Furthermore, the coating has high adhesion to the surface 12 of the substrate 11, and a smooth thin film can be formed on the surface 12 of the substrate 11.

[0109] FIG. 7 is a cross-sectional view schematically showing another example of the state immediately after the coating liquid 13 is coated on the surface 12 of the substrate 11, and FIG. 8 is a cross-sectional view schematically showing another example of the coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) formed on the surface 12 of the substrate 11 after a predetermined time has elapsed since the coating liquid 13 was coated on the surface 12 of the substrate 11.

[0110] The coating liquid 13 that forms the coating film 10a in Fig. 7 is made from the main components of a siloxane-based solution, an alkyl silicate condensate, an inert organic solvent, and conductive glass particles 14. The siloxane-based solution, alkyl silicate condensate, and inert organic solvent are the same as those in the coating liquid 13 in Figs.

[0111] The blending ratios of the siloxane solution, alkyl silicate condensate, and inert organic solvent in the coating liquid 13, the blending ratios of silicon oxide (inorganic polysilazane, organo polysilazane, organo polysiloxane) in the coating liquid 13, the blending ratio of the alkyl silicate condensate in the coating liquid 13, and the blending ratio of the inert organic solvent in the coating liquid 13 are the same as those of the coating liquid 13 in Figures 3 and 4. The film formation procedure and film formation process of the coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) and the average film thickness of the coating film 10a are the same as those of the coating film 10a in Figures 3 and 4.

[0112] The coating solution 13 contains silver ions 15a (Ag + Conductive glass particles 14a containing copper ions (Cu ions), 2+ ions), and zinc ions 15c (Zn 2+ The coating liquid 13 contains dispersed conductive glass particles 14c containing silver ions 15a (Ag + Conductive glass particles 14a containing copper ions (Cu ions), 2+ ions), and zinc ions 15c (Zn 2+ In some cases, one type of conductive glass particles 14c containing silver ions 15a (Ag ions) or two types selected from the conductive glass particles 14a to 14c are dispersed and mixed in the coating liquid 13. + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ Conductive glass particles containing two of these ions may be dispersed and mixed in.

[0113] The coating film 10a has a high density and a high hardness (pencil hardness of about 6H to 9H). The coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) contains silver ions 15a (Ag + Conductive glass particles 14a containing copper ions (Cu ions),2+ ions), and zinc ions 15c (Zn 2+ Conductive glass particles 14c containing ions are dispersed and mixed in. The content of the conductive glass particles 14a to 14c in the coating film 10a is the same as that in the coating film 10a of FIGS.

[0114] The coating film 10a contains silver ions 15a (Ag + Conductive glass particles 14a containing copper ions (Cu ions), 2+ ions) of zinc oxide (ZnO) 15c (Zn 2+ The coating film 10a may contain one type of conductive glass particles 14c containing silver ions 15a (Ag ions), or two types selected from the conductive glass particles 14a to 14c may be dispersed and mixed. + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ Conductive glass particles containing two of these ions may be dispersed and mixed.

[0115] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, as shown in FIG. 7, the conductive glass particles 14a to 14c mixed in the coating liquid 13 are dispersed and mixed inside the coating liquid 13, but the silver ions 15a (Ag + ions), copper ions 15b (Cu 2+ ions), zinc ions 15c (Zn 2+ ions) do not deposit (migrate) toward the surface of the coating liquid 13.

[0116] In the process of forming (forming) the coating film 10a (inorganic coating film 10a or organic / inorganic hybrid coating film 10a) from the coating liquid 13, as shown in FIG. 8, after the coating liquid 13 is coated on the surface 12 of the substrate 11, silver ions 15a (Ag + ion) and copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) migrate from the conductive glass particles 14a to 14c into the coating liquid 13 due to moisture in the air. After a predetermined time has passed since the coating liquid 13 was applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ As described above, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, water (H2O) such as purified water or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a, thereby depositing silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be rapidly precipitated.

[0117] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+Since the metal ions 15a (Ag ions) are not precipitated, the glass particle-containing hydrophilic composite coating film 10 does not exhibit antiviral, antibacterial, antifungal, or deodorizing functions. However, after a predetermined time has elapsed since the coating liquid 13 was applied to the surface 12 of the substrate 11, the silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ ions) precipitate on the surface of the coating film 10a, and the metal ions 15 precipitate toward the surface of the hydrophilic polymer coating 10b, thereby providing the glass particle-containing hydrophilic composite coating film 10 with antiviral, antibacterial, antifungal, and deodorizing functions.

[0118] In addition, the coating film 10a (coating liquid 13) in FIG. 8 uses two or more types of conductive glass particles 14a-14c with different compositions, namely, conductive glass particles 14a-14c with a high content of vanadium oxide (VO) and conductive glass particles 14a-14c with a high content of phosphorus oxide (PO) or barium oxide (BaO), thereby achieving both immediate and long-lasting antiviral, antibacterial, antifungal, and deodorizing functions.

[0119] FIG. 9 is a diagram showing the antibacterial activity value of a coating film 10a formed from a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles 14 mixed therein, and FIG. 10 is a graph showing the relationship between the content of conductive glass particles 14 in the coating film 10a and the antibacterial activity value.

[0120] In the evaluation of the antibacterial activity value shown in Figures 9 and 10, an acrylic substrate 11(1) (base material 11) (50 x 50 x 5 mm) on which no coating film 10a was formed (film-formed), an acrylic substrate 11(2) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 3% by volume of conductive glass particles 14 was applied to the surface 12 of the acrylic substrate 11 (base material 11) (50 x 50 x 5 mm) and a coating film 10a (containing 3% by volume of conductive glass particles 14) was formed on the surface 12 of the acrylic substrate 11, and an acrylic substrate 11(3) on which a coating film 10a (containing 3% by volume of conductive glass particles 14) was formed on the surface 12 of the acrylic substrate 11 was applied, and an acrylic substrate 11(4) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 5% by volume of conductive glass particles 14 was applied was applied. An acrylic substrate 11 (3) was prepared by applying a coating liquid 13 containing particles 14 to the surface 12 of an acrylic substrate 11 (50 x 50 x 5 mm) and forming a coating film 10a (containing 5% by volume of conductive glass particles 14) on the surface 12 of the acrylic substrate 11. An acrylic substrate 11 (4) was prepared by applying a coating liquid 13 containing 7% by volume of conductive glass particles 14, mainly composed of organopolysiloxane (siloxane-based solution), to the surface 12 of an acrylic substrate 11 (50 x 50 x 5 mm) and forming a coating film 10a (containing 7% by volume of conductive glass particles 14) on the surface 12 of the acrylic substrate 11. The average particle diameter D of the glass particles 14 50 is 5 μm or less.

[0121] As described above, the conditions for forming the coating film 10a on the acrylic substrate 11(2) to the acrylic substrate 11(4) were as follows: after coating the surfaces 12 of the acrylic substrates 11(2) to 11(4) (substrate 11) with the coating liquid 13, the surfaces 12 of the acrylic substrates 11 were heated to 400°C or higher. Alternatively, after coating the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) (base material 11) with the coating liquid 13, the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) are left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating, or after coating the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) with the coating liquid 13, the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) are left at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) with ultraviolet light, or after coating the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) with the coating liquid 13, the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) are heated to a temperature of less than 400°C by irradiating the surfaces 12 of the acrylic substrate 11 with infrared light while irradiating the surfaces 12 of the acrylic substrate 11 with ultraviolet light, and then left for a predetermined time (24 hours or more).

[0122] A predetermined time has passed since the acrylic substrates 11(2) to 11(4) were coated with the coating liquid 13 on their surfaces 12, and a coating film 10a has been formed (deposited) on the surfaces 12. The coating film 10a deposited on the surface 12 of the acrylic substrate 11(2) contains 3% by volume of conductive glass particles 14, and the average particle size D 50 The coating film 10a formed on the surface 12 of the acrylic substrate 11(3) contains conductive glass particles 14 at a content of 5% by volume, and the average particle diameter D of the conductive glass particles 14 is 5 μm or less. 50 The coating film 10a formed on the surface 12 of the acrylic substrate 11(4) contains conductive glass particles 14 at 7% by volume, and the average particle diameter D 50After forming the coating film 10a on the surfaces 12 of the acrylic substrates 11(2) to 11(4), Staphylococcus aureus and Escherichia coli were inoculated onto the surfaces 12 of the acrylic substrates 11(1) to 11(4), and the antibacterial activity values ​​against these bacteria were measured.

[0123] As shown in Figures 9 and 10, the acrylic substrate 11(1) has an antibacterial activity value of 0 against Staphylococcus aureus and E. coli. If Staphylococcus aureus or E. coli adheres to the surface 12 of the acrylic substrate 11(1), the Staphylococcus aureus or E. coli cannot be killed, and depending on the conditions, the Staphylococcus aureus or E. coli may grow on the acrylic substrate 11(1).

[0124] An acrylic substrate 11(2) on whose surface 12 a coating film 10a made from a coating liquid 13 containing 3 volume % of conductive glass particles 14 is formed (deposited) has an antibacterial activity value of 4.7 against Staphylococcus aureus and an antibacterial activity value of 2 against Escherichia coli, which meets the antibacterial activity value of 2 or more. Even if Staphylococcus aureus or Escherichia coli adheres to the surface 12 of the acrylic substrate 11(2), the silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+ ) metal ions 15 can kill Staphylococcus aureus and Escherichia coli, preventing them from multiplying.

[0125] An acrylic substrate 11(3) on whose surface 12 a coating film 10a made from a coating liquid 13 containing 5% by volume of conductive glass particles 14 is formed (deposited) has an antibacterial activity value of 4.7 against Staphylococcus aureus and an antibacterial activity value of 2 against Escherichia coli, which meets the antibacterial activity value of 2 or more. Even if Staphylococcus aureus or Escherichia coli adheres to the surface 12 of the acrylic substrate 11(3), the silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn2+ ) metal ions 15 can kill Staphylococcus aureus and Escherichia coli, preventing them from multiplying.

[0126] The acrylic substrate 11(4) has a coating film 10a formed (film-formed) on its surface 12, which is made from a coating liquid 13 containing 7% by volume of conductive glass particles 14. The antibacterial activity value against Staphylococcus aureus is 4.7, and the antibacterial activity value against Escherichia coli is 2, which meets the antibacterial activity value of 2 or more. Even if Staphylococcus aureus or Escherichia coli adheres to the surface 12 of the acrylic substrate 11(4), the silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+ ) metal ions 15 can kill Staphylococcus aureus and Escherichia coli, preventing them from multiplying.

[0127] As is clear from Figures 9 and 10, the coating film 10a containing the conductive glass particles 14 described above has excellent antibacterial properties against Staphylococcus aureus and Escherichia coli, achieving an inactivation rate of 99.9999% of Staphylococcus aureus and Escherichia coli, and it was found that it can reliably kill Staphylococcus aureus and Escherichia coli.

[0128] FIG. 11 is a graph showing the relationship between the passage of time and the logarithmic mean viable cell count (cells / mL) in a coating film 10a formed from a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles 14 mixed therein, and FIG. 12 is a graph showing the antibacterial test results (reduction rate).

[0129] A coating liquid 13 containing organopolysiloxane (siloxane-based solution) as a main component and mixed with conductive glass particles 14 was applied to a surface 12 of an acrylic substrate 11 (base material 11) (50 × 50 × 5 mm), and a coating film 10a was formed on the surface 12 of the acrylic substrate 11. As described above, the film formation conditions were as follows: after the coating liquid 13 was coated on the surface 12 of the acrylic substrate 11, the surface 12 of the acrylic substrate 11 was heated to 400°C or higher.

[0130] Alternatively, after coating the surface 12 of the acrylic substrate 11 (base material 11) with the coating liquid 13, the surface 12 of the acrylic substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating, or after coating the surface 12 of the acrylic substrate 11 (base material 11) with the coating liquid 13, the surface 12 of the acrylic substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating it with ultraviolet rays, or after coating the surface 12 of the acrylic substrate 11 (base material 11) with the coating liquid 13, the surface 12 of the acrylic substrate 11 is heated to a temperature of less than 400°C by irradiating it with infrared rays while irradiating it with ultraviolet rays, and then left for a predetermined time (24 hours or more).

[0131] The surface 12 of the acrylic substrate 11 is coated with silver ions 15a (Ag + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ The coating film 10a formed (deposited) on the surface 12 of the acrylic substrate 11 contains 15% by volume of glass particles 14, and the average particle size D 50 is 5 μm or less.

[0132] After coating the acrylic substrate 11 with the coating liquid 13, E. coli, a bacteria that causes food poisoning, was ingested onto the surface 12 of the acrylic substrate 11, and the logarithmic average viable E. coli count was measured over time. The logarithmic average viable E. coli count was measured immediately after inoculating the acrylic substrate 11 with E. coli (time 0), 5 minutes after inoculating the acrylic substrate 11 with E. coli, 10 minutes after inoculating the acrylic substrate 11 with E. coli, 30 minutes after inoculating the acrylic substrate 11 with E. coli, 1 hour after inoculating the acrylic substrate 11 with E. coli, 5 hours after inoculating the acrylic substrate 11 with E. coli, and 24 hours after inoculating the acrylic substrate 11 with E. coli. An antibacterial activity value of 2 or higher indicates antibacterial function. As shown in Figure 10, the antibacterial activity value for the acrylic plate 11 not coated with the coating liquid 13 was 0.

[0133] Immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11), the logarithmic average value of the viable E. coli cell count was 4 (cells / mL). In contrast, as shown in Figures 11 and 12, the antibacterial activity value 5 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >4.1, and the logarithmic average value of the viable E. coli cell count 5 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11). The antibacterial activity value 10 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >4.1, and the logarithmic average value of the viable cell count 10 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11).

[0134] The antibacterial activity value 30 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >4.1, and the logarithmic average value of the viable cell count 30 minutes after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11). The antibacterial activity value 1 hour after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >4.1, and the logarithmic average value of the viable cell count 1 hour after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11).

[0135] The antibacterial activity value 5 hours after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >4.1, and the logarithmic average value of the viable cell count 5 hours after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11). The antibacterial activity value 24 hours after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was >6.0, and the logarithmic average value of the viable cell count 24 hours after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.9999% compared to that immediately after coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11).

[0136] As is clear from Figures 11 and 12, when a coating film 10a containing dispersed conductive glass particles 14 was formed on an acrylic substrate 11, the antibacterial activity value increased to >4.1 over time from the coating of the coating liquid 13 onto the acrylic substrate 11 (from the inoculation of E. coli onto the acrylic substrate 11), and the logarithmic average value of the viable E. coli count decreased significantly, demonstrating that the coating film 10a has excellent antibacterial and antiviral functions and can reliably kill E. coli.

[0137] FIG. 13 is a diagram showing the evaluation of the mold resistance of a coating film 10a formed from a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and conductive glass particles 14 mixed therein.

[0138] In the mold resistance evaluation shown in FIG. 13, an acrylic substrate 11(1) (base material 11) (50×50×5 mm) on which no coating film 10a was formed (deposited), an acrylic substrate 11(2) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 3% by volume of conductive glass particles 14 was applied to the surface of the acrylic substrate 11 (50×50×5 mm) and a coating film 10a was formed on the surface 12 of the acrylic substrate 11, and an acrylic substrate 11(3) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 5% by volume of conductive glass particles 14 was applied to the surface of the acrylic substrate 11 (50×50×5 mm) and a coating film 10a was formed on the surface 12 of the acrylic substrate 11. An acrylic substrate 11 (3) was prepared by applying a coating liquid 13 containing conductive glass particles 14 to the surface of an acrylic substrate 11 (50 x 50 x 5 mm) and forming a coating film 10a on the surface 12 of the acrylic substrate 11, and an acrylic substrate 11 (4) was prepared by applying a coating liquid 13 containing 7 volume % of conductive glass particles 14, mainly composed of organopolysiloxane (siloxane-based solution), to the surface 12 of the acrylic substrate 11 (50 x 50 x 5 mm) and forming a coating film 10a on the surface 12 of the acrylic substrate 11. The average particle diameter D of the conductive glass particles 14 50 is 5 μm or less.

[0139] The film formation conditions for the acrylic substrates 11(2) to 11(4) are the same as those for the acrylic substrates 11(2) to 11(4) in the evaluation of antibacterial activity values ​​shown in Figures 11 and 12. A predetermined time has passed since the coating liquid 13 was applied to the surfaces 12 of the acrylic substrates 11 for the acrylic substrates 11(2) to 11(4), and a coating film 10a has been formed (deposited) on the surfaces 12. The coating film 10a deposited on the surface 12 of the acrylic substrate 11(2) contains 3% by volume of conductive glass particles 14, and the average particle size D 50 The coating film 10a formed on the surface 12 of the acrylic substrate 11(3) contains conductive glass particles 14 at a content of 5% by volume, and the average particle diameter D of the conductive glass particles 14 is 5 μm or less. 50 The coating film 10a formed on the surface 12 of the acrylic substrate 11(4) contains conductive glass particles 14 at 7% by volume, and the average particle diameter D 50 is 5 μm or less.

[0140] After forming a coating film 10a on surfaces 12 of acrylic substrates 11(2) to 11(4), surfaces 12 of acrylic substrates 11(1) to 11(4) were inoculated with spores of a mixture of five fungal species: Aspergillus niger NBRC 105649, Penicillium pinophilum NBRC 100533, Paecilomyces variotii NBRC 107725, Trichoderma virens NBRC 6355, and Chaetomium globosum NBRC 6347. The fungal spores were then cultured for four weeks, and the fungal resistance of acrylic substrates 11(1) to 11(4) was measured. The culture conditions were as follows: acrylic substrates 11(1) to 11(4) were placed on mineral- and glucose-containing agar media contained in containers 1 to 4; a mineral- and glucose-containing mold spore solution (a mixture of five bacterial species) was sprayed onto the media; the media was cultured at approximately 29°C and 95% rh or higher for four weeks; and the growth of the mold in containers 1 to 4 was then visually and microscopically determined.

[0141] The mold growth status is evaluated as follows: (5) when the mycelium grows vigorously and the mold covers the entire medium; (4) when the mold area is 50% or more of the total area of ​​the medium under microscope observation; (3) when the mold area is 50% or more but less than 50% of the total area of ​​the medium under microscope observation; (2) when the mold area is less than 25% of the total area of ​​the medium under microscope observation; (1) when mold growth cannot be seen with the naked eye but can be confirmed under microscope observation; and (0) when mold growth is not observed either with the naked eye or under microscope observation. Mold resistance is recognized with ratings (0) to (2).

[0142] The acrylic substrate 11(1) placed on the mineral- and glucose-containing agar medium in the first container was evaluated as (4), meaning that the mold area was 50% or more of the total surface area of ​​the medium. The acrylic substrate 11(2) placed on the mineral- and glucose-containing agar medium in the second container, the acrylic substrate 11(3) placed on the mineral- and glucose-containing agar medium in the third container, and the acrylic substrate 11(4) placed on the mineral- and glucose-containing agar medium in the fourth container were evaluated as (2), indicating that the acrylic substrates 11(2) to 11(4) were mold-resistant. As is clear from Figure 13, the coating film 10a containing the conductive glass particles 14 described above has excellent mold-proofing properties and can reliably kill various types of mold.

[0143] Figure 14 is a graph showing the correlation between the survival time (min) of influenza virus (IFV) and the contact angle θ (°) of a water droplet W with the film surface of a glass particle-containing hydrophilic composite coating film 10, Figure 15 is a graph showing the correlation between the survival time (h) of feline calicivirus (FCV) and the contact angle θ (°) of a water droplet W with the film surface of a glass particle-containing hydrophilic composite coating film 10, Figure 16 is a graph showing an example of the state of a water droplet W attached to the film surface of a glass particle-containing hydrophilic composite coating film 10, and Figure 17 is a diagram showing a simulated view of the state of metal ions in the water droplet W of Figure 16.

[0144] The water droplets W are made of a virus culture medium after culturing a specific virus. The correlations shown in Figures 14 and 15 show the correlation between the survival time of each virus and the contact angle θ for a coating film that does not contain conductive glass particles 14, and also show the correlation between the survival time of each virus and the contact angle θ for a glass particle-containing hydrophilic composite coating film 10 that contains conductive glass particles 14. VO-PO-AgO-CuO-ZnO-based glass is used as the conductive glass particles 14.

[0145] As shown in Figure 14, for influenza viruses (IFV), when the contact angle θ of a water droplet W to a coating film that does not contain conductive glass particles 14 is 20°, the survival time of the influenza virus (IFV) is approximately 550 (min); when the contact angle θ is 40°, the survival time of the influenza virus (IFV) is approximately 850 (min); when the contact angle θ is 60°, the survival time of the influenza virus (IFV) is approximately 2000 (min); and when the contact angle θ is 90°, the survival time of the influenza virus (IFV) is approximately 11000 (min).The larger the contact angle θ with the water droplet W, the longer the survival time of the influenza virus (IFV).

[0146] In contrast, when the contact angle θ of a water droplet W on a glass particle-containing hydrophilic composite coating film 10 containing conductive glass particles 14 was 20° or less, the survival time of the influenza virus (IFV) was 9 min or less, when the contact angle θ was 40°, the survival time of the influenza virus (IFV) was approximately 15 min, when the contact angle θ was 60°, the survival time of the influenza virus (IFV) was approximately 30 min, and when the contact angle θ was 90°, the survival time of the influenza virus (IFV) was approximately 70 min.

[0147] 14, the smaller the contact angle θ of the water droplet W, the shorter the survival time of the influenza virus (IFV), and it was found that the survival time of the influenza virus (IFV) corresponding to each contact angle θ of the water droplet W on the glass particle-containing hydrophilic composite coating film 10 containing conductive glass particles 14 was very short compared to the survival time of the influenza virus (IFV) corresponding to each contact angle θ of the water droplet W on a coating film that did not contain conductive glass particles 14. Furthermore, it was found that the survival time of the influenza virus (IFV) was very short when each contact angle θ of the water droplet W on the glass particle-containing hydrophilic composite coating film 10 was 60° or less, and that the survival time of the influenza virus (IFV) was extremely short when each contact angle θ of the water droplet W on the glass particle-containing hydrophilic composite coating film 10 was 20° or less.

[0148] As shown in Figure 15, for feline calicivirus (FCV), when the contact angle θ of a water droplet W to a coating film that does not contain conductive glass particles 14 is 20°, the survival time of the feline calicivirus (FCV) is approximately 10,000 (min), when the contact angle θ is 40°, the survival time of the feline calicivirus (FCV) is approximately 15,000 (min), when the contact angle θ is 60°, the survival time of the feline calicivirus (FCV) is approximately 40,000 (min), and when the contact angle θ is 90°, the survival time of the feline calicivirus (FCV) is approximately 400,000 (min).The larger the contact angle θ with the water droplet W, the longer the survival time of the feline calicivirus (FCV).

[0149] In contrast, when the contact angle θ of a water droplet W on a glass particle-containing hydrophilic composite coating film 10 containing conductive glass particles 14 was 20° or less, the survival time of feline calicivirus (FCV) was approximately 9 min or less, when the contact angle θ was 40°, the survival time of feline calicivirus (FCV) was approximately 10 min, when the contact angle θ was 60°, the survival time of feline calicivirus (FCV) was approximately 30 min, and when the contact angle θ was 90°, the survival time of feline calicivirus (FCV) was approximately 70 h.

[0150] 15, the smaller the contact angle θ of the water droplet W, the shorter the survival time of the feline calicivirus (FCV), and it was found that the survival time of the feline calicivirus (FCV) corresponding to each contact angle θ of the virus culture solution (water droplet W) on the glass particle-containing hydrophilic composite coating film 10 containing conductive glass particles 14 was shorter than the survival time of the feline calicivirus (FCV) corresponding to each contact angle θ of the water droplet W on the coating film not containing conductive glass particles 14. Furthermore, it was found that the survival time of the feline calicivirus (FCV) was very short when each contact angle θ of the water droplet W on the glass particle-containing hydrophilic composite coating film 10 was 60° or less, and that the survival time of the feline calicivirus (FCV) was extremely short when each contact angle θ of the water droplet W on the glass particle-containing hydrophilic composite coating film 10 was 20° or less.

[0151] The smaller the contact angle θ of the water droplets W with the coating film, the more spread out the water droplets W become, and the shorter the drying time of the water droplets W. This is thought to shorten the survival time of the virus. However, due to the influence of contaminants in the air, the surface of the coating film may not be able to maintain a contact angle θ of 30° or less for a long period of time, which may result in a longer survival time of the virus. In contrast, with the glass particle-containing hydrophilic composite coating film 10, even if the contact angle θ becomes somewhat larger, the effect of the glass particles has little effect on the survival time of the virus.

[0152] The contact angle θ of the water droplets W with the surface of the glass particle-containing hydrophilic composite coating film 10 is 50° or less, preferably 30° or less. If the contact angle θ of the water droplets W with the film surface exceeds 50°, the contact area of ​​the water droplets W with the film surface of the glass particle-containing hydrophilic composite coating film 10 becomes small, and the antibacterial, antiviral, and antifungal functions of the glass particle-containing hydrophilic composite coating film 10 cannot be fully utilized, and various viruses contained in the water droplets W cannot be killed or prevented from multiplying. Furthermore, even if the water droplets W contain various germicides or various mold bacteria, the various germicides and various mold bacteria contained in the water droplets W cannot be killed or prevented from multiplying.

[0153] Since the contact angle θ of the water droplet W with respect to the film surface of the glass particle-containing hydrophilic composite coating film 10 is within the above range, the contact area of ​​the water droplet W with the film surface is large, the water droplet W comes into contact with a wide area of ​​the film surface of the glass particle-containing hydrophilic composite coating film 10, and the antibacterial, antiviral and antifungal functions of the glass particle-containing hydrophilic composite coating film 10 can be fully and reliably utilized.

[0154] In the glass particle-containing hydrophilic composite coating film 10, as shown in FIG. 17, silver ions 15a (Ag + ) and copper ions 15b (Cu 2+ ), zinc ion 15c (Zn 2+ ) diffuse from the surface of the hydrophilic polymer coating 10b into the water droplets W, and the metal ions 15 diffused into the water droplets W kill various viruses in the water droplets W. Furthermore, the contact area of ​​the water droplets W with the surface of the glass particle-containing hydrophilic composite coating film 10 is large, and the water droplets W come into contact with a wide area of ​​the film surface of the glass particle-containing hydrophilic composite coating film 10, so the drying time of the water droplets W is short, and the survival time of the viruses contained in the water droplets W is short.

[0155] Furthermore, the glass particle-containing hydrophilic composite coating film 10 has a large contact area for water droplets W on its surface, and the water droplets W come into contact with a wide area on the surface of the glass particle-containing hydrophilic composite coating film 10, so the drying time of the water droplets W on the surface of the glass particle-containing hydrophilic composite coating film 10 is shortened, and the survival time of various bacteria, viruses, and molds contained in the water droplets W is shortened.

[0156] FIG. 18 shows the results of a deodorizing test on the glass particle-containing hydrophilic composite coating film 10. An example of the test procedure for the deodorizing test is as follows. + ion), copper ion 15b (Cu 2+ ion), zinc ion 15c (Zn 2+ions) precipitated on a 100 cm 2 Acrylic substrate test piece (1), silver ion 15a (Ag + ions) precipitated on a 100 cm 2 The acrylic substrate test piece (2) and the 100 cm 2 The acrylic substrate test piece (3) was coated with a glass particle-containing hydrophilic composite coating film (10) on its surface. 2 The acrylic substrate test pieces (4) were prepared and conditioned for 24 hours or more.

[0157] The acrylic substrate test pieces were placed in each sampling bag, which was then sealed and degassed. Next, odorous gas adjusted to a specified concentration was placed in each sampling bag and left for two hours. The concentration of the odorous gas in each sampling bag was measured using a detector tube, and the odor reduction rate (%) was calculated using the formula: odor reduction rate (%) = (Sb - Sm) / Sb x 100. Sb is the average value of the blank test, and Sm is the average value of the measurements.

[0158] As shown in Figure 18, for acrylic substrate test piece (1), the ammonia odor reduction rate was 79%, the acetic acid odor reduction rate was 47%, and the hydrogen sulfide odor reduction rate was 58%. For acrylic substrate test piece (2), the ammonia odor reduction rate was 98%, the acetic acid odor reduction rate was 61%, the methyl mercaptan odor reduction rate was 99%, the hydrogen sulfide odor reduction rate was 99%, and the pyridine (nicotine) odor reduction rate was 50%. It was found that acrylic substrate test piece (1) and acrylic substrate test piece (2) had a higher deodorizing function than acrylic substrate test piece (3) and acrylic substrate test piece (4). As is clear from Figure 18, it was found that the glass particle-containing hydrophilic composite coating film 10 has excellent deodorizing function.

[0159] The glass particle-containing hydrophilic composite coating film 10 (coating film) is formed from a glass-based coating film 10a based on a siloxane-based solution (silicon oxide (SiO2)) and a hydrophilic polymer coating 10b that covers the film surface of the glass-based coating film. The conductive glass particles dispersed and mixed in the coating film 10a react with silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ), and the contact angle θ of the water droplet W measured on the surface of the coating film formed on the surface of the substrate according to JIS R3257 (pure water drop amount 1 μL and waiting time for stabilization of the liquid contact 15 seconds) is 50° or less (preferably 30° or less). Therefore, the contact angle θ of the water droplet W (liquid) with the film surface of the glass particle-containing hydrophilic composite coating film 10 is small, and the contact area of ​​the water droplet W with the film surface of the glass particle-containing hydrophilic composite coating film 10 can be increased, the water droplet W comes into contact with the film surface of the glass particle-containing hydrophilic composite coating film 10 widely, and silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be fully utilized to its antibacterial, antiviral, antifungal, and deodorizing properties.

[0160] The glass particle-containing hydrophilic composite coating film 10 (coating film) can kill the various bacteria, viruses, and mold contained in the water droplets W, even if the water droplets W contain various bacteria, viruses, and mold, and can prevent the proliferation of the bacteria, viruses, and mold, as well as remove unpleasant odors such as cigarette smoke, putrid odor, and nonenal odor.

[0161] The glass particle-containing hydrophilic composite coating film 10 (coating film) allows water droplets W to come into contact with a wide area of ​​the film surface of the glass particle-containing hydrophilic composite coating film 10, shortening the drying time of the water droplets W on the film surface of the glass particle-containing hydrophilic composite coating film 10 and reliably shortening the survival time of various germicides, viruses, and molds contained in the water droplets W, thereby quickly killing the germicides, viruses, and molds. The glass particle-containing hydrophilic composite coating film 10 is not limited to any particular object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all objects.

[0162] The glass particle-containing hydrophilic composite coating film 10 uses a siloxane-based solution as the starting material for the coating liquid that forms the coating film 10a. By using a siloxane-based solution with a dense molecular structure as the starting material for the coating liquid, a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can be dispersed and mixed, and a large amount of silver ions (Ag + ) and copper ions (Cu 2+ ) can be contained.

[0163] Glass particle-containing hydrophilic composite coating film 10 has excellent strength and excellent scratch resistance because coating film 10a forming it is a glass-based coating film made from a siloxane-based solution, and can smooth surface 12 of substrate 11 on which glass particle-containing hydrophilic composite coating film 10 (coating film 10a) is formed, thereby preventing scratches on surface 12 of substrate 11 on which glass particle-containing hydrophilic composite coating film 10 is formed. Glass particle-containing hydrophilic composite coating film 10 is not limited to a specific object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all objects.

[0164] Conductive glass particles 14 containing a high content of phosphorus oxide (P2O5) and barium oxide (BaO) are used to + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ The deposition rate of the metal ions 15 in the coating liquid 13 is slow, and the metal ions 12 are deposited on the surface layer (surface) of the coating film 10a over a long period of time (3 months to 3 years) after the coating liquid 13 is applied to the surface 12 of the substrate 11. This allows the antiviral, antibacterial, antifungal, and deodorizing functions of the metal ions 12 to be sustained. On the other hand, in the conductive glass particles 14 with a high content of vanadium oxide (VO), silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ The deposition rate of metal ions 15 in the coating liquid 13 is fast, and metal ions 12 deposit toward the surface layer (surface) of the coating film 13 a predetermined time (10 to 20 minutes) after the coating liquid 13 is applied to the surface 12 of the substrate 11. This allows the antiviral, antibacterial, antifungal, and deodorizing functions of the metal ions 12 to be utilized quickly. The glass particle-containing hydrophilic composite coating film 10 uses two or more types of conductive glass particles 14 with different compositions: conductive glass particles 14 with a high content of vanadium oxide (VO) and conductive glass particles 14 with a high content of phosphorus oxide (PO) or barium oxide (BaO). This allows the glass particle-containing hydrophilic composite coating film 10 to achieve both immediate and sustained antiviral, antibacterial, antifungal, and deodorizing functions.

[0165] The glass particle-containing hydrophilic composite coating film 10 is formed by spraying or brushing water (H2O) such as purified water or a predetermined aqueous solution onto the surface of the coating film 10a immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, thereby forming silver ions (Ag + ), copper ions (Cu 2+ ), zinc ions (Zn 2+ ) can rapidly precipitate metal ions 15. [Explanation of symbols]

[0166] 10. Glass particle-containing hydrophilic composite coating film (coating film) 10a coating film 10b Hydrophilic polymer coating 11 Base material 12 sides (front, back) (contact surfaces) 13 Coating liquid (organic and inorganic hybrid polymer) 14 Conductive glass particles 14a Conductive glass particles 14b Conductive glass particles 14c Conductive glass particles 15 Metal ions 15a Silver ions (Ag + ) 15b Copper ion (Cu 2+ ) 15c Zinc ion (Zn 2+ ) W water drop θ Contact angle (°)

Claims

1. In a coating film in which predetermined conductive glass particles are dispersed and mixed, The coating film is made of silicon oxide (SiO ２ )-based glass-based coating film, and the conductive glass particles dispersed and mixed in the coating film are silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) and the contact angle θ of a water droplet measured on the surface of the coating film formed on the surface of the substrate in accordance with JIS R3257 (pure water drop amount: 1 μL, waiting time for stabilization of the contact of the water droplet: 15 seconds) is 50° or less.

2. 2. The coating film according to claim 1, wherein the contact angle θ of the water droplet is 30° or less.

3. The conductive glass particles contain the silver ions (Ag ＋ ), the copper ions (Cu ２＋ ), the zinc ions (Zn ２＋ 2. The coating film according to claim 1, comprising at least two of the following:

4. The conductive glass particles are made of vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ 2. The coating film according to claim 1, which is a glass based on

5. The coating film according to claim 4, wherein the conductive glass particles contain barium oxide (BaO).

6. The conductive glass particles contain the silver ions (Ag ＋ ) and the copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-based glass, the silver ion (Ag ＋ ) and the copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ 6. The coating film according to claim 5, wherein the coating film is either a glass based on titanium dioxide (TiO 2 ) or a barium oxide (BaO 2 ) based glass.

7. 2. The coating film according to claim 1, wherein a raw solution of a coating liquid (a starting material of the coating film) for forming the coating film is a siloxane-based solution, and the conductive glass particles are dispersed and mixed in the siloxane-based solution.

8. 2. The coating film according to claim 1, wherein the surface of the coating film is made hydrophilic by a surface treatment.

9. The coating film according to claim 8, wherein the surface of the coating film is coated with a hydrophilic polymer coating.

10. 10. The coating film according to claim 9, wherein a plurality of fine irregularities are formed on the surface of the coating film by chemical etching or dry etching, and the hydrophilic polymer coating covers the surface of the coating film on which the plurality of fine irregularities are formed.

11. The coating film according to claim 1, which has at least one of an antiviral function, an antibacterial function, an antifungal function, and a deodorizing function.

12. The coating film is made by coating a coating liquid onto the surface of a predetermined substrate, and then immediately applying water or an aqueous solution to the surface of the coating film to form silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ 2. The coating film according to claim 1, wherein the coating film is formed by depositing a compound of formula (I) on the surface of the coating film.

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