Coating film

Abstract

[Problem] To provide a coating film which can reduce the contact angle of water droplets with respect to the surface of the film and increase the contact area of the water droplets with respect to the surface of the film, and which can sufficiently utilize antibacterial-antiviral functions, an antifungal function, and a function of removing odors. [Solution] This coating film is a glass-based coating film which is based on silicon oxide (SiO2), and in which the film surface of the coating film is coated with a hydrophilic polymer coating, conductive glass particles mixed and dispersed in the coating film contain at least one of silver ions (Ag+), copper ions (Cu2+), and zinc ions (Zn2+), and the contact angle θ of water droplets as measured in accordance with JIS R3257 on the surface of the coating film formed on the surface of a base material is 50° or less. The coating film has an antiviral function, an antibacterial function, an antifungal function, and a deodorizing function.

Description

coating film

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

[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 effectiveness and durability. 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 having a hydrophilic group, 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 moisture to penetrate into the antibacterial film, allowing moisture to reach the antibacterial agent microparticles in the antibacterial film and facilitating the release of silver ions.

[0004] JP 2015-189152 A JP 2015-189196 A JP 2023-027804 A JP 2023-019188 A

[0005] Silicon oxide (SiO ２ In glass-based coating films based on silver ions, it is difficult to introduce a large amount of silver ions into the coating film, and therefore 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 and antiviral functions, antifungal functions, and deodorizing functions to all coating objects immediately after coating, without limiting the objects to be coated.

[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 feature of the present invention based on the above premise is that the coating film is made of silicon oxide (SiO ２ ), and the conductive glass particles dispersed 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 liquid contact: 15 seconds) is 50° or less.

[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 or more of the above.

[0011] In another embodiment of the present invention, 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 ) and is a glass based on

[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＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-based glass, silver ion (Ag ＋ ) and copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-barium oxide (BaO)-based glass.

[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.

[0020] According to the coating film of the present invention, it is silicon oxide (SiO ２ ), and the conductive glass particles dispersed 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 a coating film formed on the surface of a 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. 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 silver ions (Ag ＋ ) and copper ions (Cu ２＋ ), zinc ions (Zn ２＋The coating film can fully utilize the antibacterial, antiviral, antifungal, and deodorizing functions of water droplets containing various bacteria, viruses, and mold. Even if the water droplets contain bacteria, viruses, and 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. The coating film allows water droplets to come into contact with a wide area of ​​the coating film surface, shortening the drying time of the water droplets on the coating film surface and reliably shortening the survival time of the bacteria, viruses, and mold contained in the water droplets, thereby quickly killing the bacteria, viruses, and mold. The coating film is not limited to any particular object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to any object.

[0021] The coating film has a contact angle θ of 30° or less when measured according to JIS R3257 (pure water drop amount 1 μL and waiting time for stabilization of the liquid contact 15 seconds). This means that the contact angle of the water droplet (liquid) with the surface of the coating film is extremely small, and the contact area of ​​the water droplet with the surface of the coating film can be reliably increased. The water droplet comes into contact with a wide area of ​​the surface of the coating film, 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 the proliferation of the bacteria, viruses, and mold while reliably removing 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 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 thus killing the bacteria, viruses, and mold 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＋ ) and therefore, 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 the water droplets contain various bacteria, viruses and mold, the bacteria, viruses and mold contained in the water droplets can be killed, and unpleasant odors such as cigarette smoke, putrid odors and nonenal odors can be removed.

[0023] The coating film is made of conductive glass particles with vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ ) and silver ion (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) is vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ ) are dispersed and mixed in the conductive glass particles containing 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＋ ), the coating film has excellent antibacterial, antiviral, antifungal and deodorizing functions, and even if the water droplets contain various bacteria, viruses and molds, the various bacteria, viruses and molds contained in the water droplets can be reliably killed, the proliferation of the bacteria, viruses and molds can be prevented and unpleasant odors such as cigarette smoke, putrid odor and nonenal odor can be reliably removed. ＋ ) 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＋), the coating film has excellent antibacterial, antiviral, antifungal and deodorizing functions, and even if the water droplets contain various bacteria, viruses and molds, the various bacteria, viruses and molds contained in the water droplets can be reliably killed, the proliferation of the bacteria, viruses and molds can be prevented and unpleasant odors such as cigarette smoke, putrid odor and nonenal odor can be reliably removed. ＋ ) 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＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-based glass, silver ion (Ag ＋ ) and copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-barium oxide (BaO)-based 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, and 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 functions, and even if the water droplets contain various bacteria, viruses and molds, it can reliably kill the bacteria, viruses and molds contained in the water droplets, preventing the proliferation of bacteria, viruses and molds, and reliably removing unpleasant odors such as cigarette smoke, putrid odors and nonenal odors. ＋ ) 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-based solution, which is the starting material for the coating film. The siloxane-based solution has a dense molecular structure, and 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 can contain a large amount of silver ions (Ag ＋ ) and copper ions (Cu ２＋), it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and 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 the growth of the bacteria, viruses, and mold, and reliably removing 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 the coating film is formed, preventing scratches on the surface of the substrate on which the coating film is formed. The coating film is not limited to any particular object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all objects.

[0027] The coating film has its surface hydrophilized by surface treatment, and by imparting hydrophilicity to the surface of the coating film, 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 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 functions, and even if water droplets contain various bacteria, viruses, or molds, it can kill the bacteria, viruses, and molds contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. The coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, shortening the drying time of the water droplets on the coating film surface and reliably shortening the survival time of the bacteria, viruses, and molds contained in the water droplets, thereby quickly killing the bacteria, viruses, and molds.

[0028] The coating film has a surface coated with a hydrophilic polymer coating having excellent hydrophilicity, so that 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 functions, and even if water droplets contain various bacteria, viruses, or molds, it can kill the bacteria, viruses, and molds contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. The coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, shortening the drying time of the water droplets on the coating film surface and reliably shortening the survival time of the bacteria, viruses, and molds contained in the water droplets, thereby quickly killing the bacteria, viruses, and molds.

[0029] The coating film has a plurality of fine irregularities formed on its surface by chemical etching or dry etching, and the surface of the coating film on which the plurality of fine irregularities has been formed is coated with a hydrophilic polymer coating, so that the hydrophilic polymer coating and the coating film are bonded together in a state in which the hydrophilic polymer coating is embedded in the plurality of fine 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 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 silver ions (Ag ＋ ) and copper ions (Cu ２＋ ), zinc ions (Zn ２＋ The coating film has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and even if water droplets contain various bacteria, viruses, or molds, it can kill the bacteria, viruses, and molds contained in the water droplets, preventing their proliferation and eliminating unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. The coating film allows water droplets to come into contact with a wide area of ​​the coating film's surface, shortening the drying time of the water droplets on the coating film surface and reliably shortening the survival time of the bacteria, viruses, and molds contained in the water droplets, thereby quickly killing the bacteria, viruses, and molds.

[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＋ The coating film can rapidly exhibit the antiviral, antibacterial, antifungal, and deodorizing functions of water droplets. Because the coating film rapidly exhibits the 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 proliferation of the bacteria, viruses, and mold, while also removing unpleasant odors such as cigarette smoke, putrid odors, and nonenal odors. The coating film is not limited to any object to be coated, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all objects immediately after coating.

[0032] 1 is an enlarged cross-sectional image showing a glass particle-containing hydrophilic composite coating film (coating film and hydrophilic polymer coating) formed on the surface of a substrate; FIG. 1 is a cross-sectional view illustrating, in time sequence, 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; FIG. 2 is a cross-sectional view schematically showing an example of a state immediately after the coating liquid has been applied to the surface of a substrate; FIG. 3 is a cross-sectional view schematically showing an example of a coating film formed on the surface of a substrate a predetermined time after the coating liquid has been applied to the surface of the substrate; FIG. 4 is an image showing an example of the structure of an inorganic coating film formed on the surface of a substrate; FIG. 5 is an image showing an example of the structure of an organic / inorganic hybrid coating film 10a formed on the surface of a substrate; FIG. 6 is a cross-sectional view schematically showing another example of a state immediately after the coating liquid has been applied to the surface of a substrate; FIG. 7 is a cross-sectional view schematically showing another example of a coating film formed on the surface of a substrate a predetermined time after the coating liquid has been applied to the surface of the substrate; Graph showing the relationship between the content of conductive glass particles in a coating film and the antibacterial activity value. Diagram showing the relationship between the passage of time and the logarithmic average viable cell count (cells / mL) in a coating film formed from a coating liquid containing conductive glass particles mixed in with organopolysiloxane (siloxane-based solution) as the main component. Diagram showing antibacterial test results (reduction rate). Diagram showing the mold resistance evaluation of a coating film formed from a coating liquid containing conductive glass particles mixed in with organopolysiloxane (siloxane-based solution) as the main component. Diagram showing the correlation between the survival time (min) of influenza virus (IFV) and the contact angle (°) of a water droplet with respect to the film surface of a glass particle-containing hydrophilic composite coating film. Diagram showing the correlation between the survival time (h) of feline calicivirus (FCV) and the contact angle (°) of a water droplet with respect to the film surface of a glass particle-containing hydrophilic composite coating film. Diagram showing an example of the state of a water droplet attached to the film surface of a glass particle-containing hydrophilic composite coating film. Fig. 17 is a diagram showing a simulation of the state of metal ions in the water droplets of Fig. 16. Fig. 18 is a diagram showing the results of a deodorizing test on a glass particle-containing hydrophilic composite coating film 10.

[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 image 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 a 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] 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 the 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.), and food supplies (food trays, kitchen supplies, tableware, etc.).In addition to these, the list also includes all molded articles that are subject to antibacterial, antiviral, antifungal, and deodorizing properties.

[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 of organopolysiloxane, alkylsilicate condensate, an 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 in the coating liquid 13 contain silver ions 15a (Ag ＋ ) 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 exhibit ionic conductivity.

[0042] An example of the conductive glass particles 14 is vanadium oxide (V ２ O ５ ) (electron conductive glass), tungsten oxide (WO ３ ) (electron conductive glass), molybdenum oxide (MoO ３ ) (electron conductive glass), and phosphorus oxide (P ２ O ５ ) (electron-conductive glass). An example of the conductive glass particles 14 is a glass based on vanadium oxide (V ２ O ５ ) (electron conductive glass), tungsten oxide (WO ３ ) (electron conductive glass), molybdenum oxide (MoO ３ ) (electron conductive glass), and phosphorus oxide (P ２ O ５ ) (electron conductive glass) and barium oxide (BaO) based glass.

[0043] Specific examples of the conductive glass particles 14 include silver ions (Ag ＋ ) and copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-based glass, and another specific example of the conductive glass particles 14 is silver ion (Ag ＋ ) and copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ The conductive glass particles 14 have a layered structure, and silver ions 15a (Ag ＋ ), copper ion 15b (Cu ２＋ ), zinc ion 15c (Zn２＋ ) is present, 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) are generated by dissociating 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 up into the cells of the microorganisms, and the taken-up silver ions 15a, copper ions 15b, and zinc ions 15c bind to proteins, etc., inhibiting their functions and preventing cell division, etc., and the dysfunction of the proteins generates reactive oxygen species, which kills the microbial cells.

[0045] As the siloxane-based solution, inorganic polysilazanes such as Si—N-based perhydropolysilazane solution (perhydropolysilazane solution), Si—C—N-based organopolysilazane solution, Si—C-based polycarbosilane solution, SiC—O-based organopolysilazane solution, Si—B—C—N-based organopolysilazane solution, Si—Ti—N-based organopolysilazane solution, and organopolysiloxane can be used.

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

[0047] The inorganic polysilazane includes a linear structure having structural units, has a molecular weight of 690 to 2,000, and has 3 to 10 SiH groups in one molecule. ３ groups, and the element ratios as determined by chemical analysis are Si: 59 to 61, N: 31 to 34, and H: 6.5 to 7.5 by weight, respectively; and perhydropolysilazane having a polystyrene-equivalent average molecular weight in the range of 3,000 to 20,000.

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

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

[0050] Another example of the perhydropolysilazane compound group is represented by the following general formula (Chemical Formula 4), which has a Si—N bond and a functional group (R １ ~R ３ ) and -(SiR １ R ２ -NR ３ )-units, and a functional group R １ , R ２ At least one of the above is an organic polymer formed from an organic functional group such as an alkyl group having carbon (C).

[0051] Perhydropolysilazane is a functional group (R １ ~R ３ ) is a methyl group (CH ３ The content of -(SiR) is 50% or more. １ R ２ -NR ３ )-units as well as polymers formed from functional groups (R １ ~R ３ ) with different compositions １ R ２ -NR ３ Furthermore, the perhydropolysilazane may be a polymer having a chain, cyclic or crosslinked structure, or may be a polymer having a combination of these structures. 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 silicon is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. １ , R ２ , R ３ At least one of is a hydrogen atom.

[0052] As an example, perhydropolysilazane (A) is represented by the following general formula (Chemical Formula 5): -(SiH(CH３ )-NH)- unit, -(Si(CH ３ )2-NH)- unit, -(SiR １ (CH ３ )-NR ３ )-units. １ (CH ３ )-NR ３ The functional group R1 in the )-unit is H or CH ３ 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 the coating film 10a can be formed on the surface 12 of the substrate 11 at an early stage.

[0053] Another example of perhydropolysilazane (B) is —(SiH(CH)) represented by the following general formula (Chemical Formula 6): ３ )-NH)- unit, -(SiR １ (CH ３ )-NH)- units, and １ (CH ３ )-NH)- unit functional group R 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] The perhydropolysilazane contained in the coating liquid 13 may be a mixture of multiple types of perhydropolysilazanes containing 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 greater 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] Organopolysilazane is a compound represented by the general formula (Chemical Formula 4) where R １ and R ２ a hydrogen atom, R ３ has an organic group. ２ polysilazanes having a cyclic structure with a degree of polymerization of 3 to 5, with (R ３ SiHNH) ｘ [(R ２ SiH) １．５ N] １－Ｘ Polysilazane having both a chain structure and a cyclic structure in the molecule represented by the chemical formula (0.4<X<1), １ a hydrogen atom, R ２ , R ３ Polysilazane having an organic group in R １ and R ２ an organic group, R ３ has a hydrogen atom in -(R １ R ２ SiNR ３ )- as a repeating unit, and mainly includes polysilazanes having a cyclic structure with a degree of polymerization of 3 to 5.

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

[0057] Also, for example, R １ Six ３Polysilazane R having a crosslinked structure obtained by ammonia decomposition of (X: halogen) １ Si(NH) ｘ , R １ Six ３ and R ２ ２ Six ２ The polysilazane having the structure obtained by co-ammoniolysis of the above is represented by the following general formula (Chemical Formula 8).

[0058] The organopolysiloxane may be, for example, a polysiloxane having an average unit formula (A): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d The polymer has the average unit formula (A) １ are each independently a monovalent organic group, and are preferably a monovalent ethylenically unsaturated group, a monovalent hydrocarbon group (excluding ethylenically unsaturated groups), or a monovalent substituted hydrocarbon group (excluding ethylenically unsaturated groups). 1 The number of carbon atoms in R is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less. The monovalent substituted hydrocarbon group has a hydrocarbon group as a basic skeleton and contains at least one functional group selected from the group consisting of, for example, a hydroxy group, a mercapto group, an amino group, an isothiocyanate group, a nitro group, and a carbonyl group. 1 is preferably a monovalent ethylenically unsaturated group or a monovalent hydrocarbon group, more preferably a monovalent ethylenically unsaturated group.

[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, that is, groups represented by the formula (B): -R 12 -OC(=O)-CR11 There are also groups represented by =CH2. Specifically, there are acryloyloxypropyl groups and methacryloyloxypropyl groups. 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 the monovalent substituted hydrocarbon group include a 3-mercaptopropyl group (-(CH2)3-SH) and a 3-aminopropyl group (-(CH2)3-NH2). 1 From the viewpoint of fine particle formation, each of the groups is preferably independently an alkyl group or an alkenyl group, more preferably independently 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 the 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, and 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 1The 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 each represent the respective structural units (R 1 3SiO 1 / 2 ), (R 1 2SiO 2 / 2 ), (R 1 SiO 3 / 2 ) and (SiO 4 / 2 The sum of the molar fractions of each structural unit, a, b, c, and d, is 1. a represents the average value of the molar fractions of R 1 3SiO 1 / 2 a is the mole fraction of siloxane units represented by M units. a is from 0 to 0.5, 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 c 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 / 2is 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 structural unit (R 1 3SiO 1 / 2 When the structural unit (R) in the average unit formula (A) is present, the structural unit may be of only one type, or may be of two or more types. 1 2SiO 2 / 2 ) and (R 1 SiO 3 / 2 The same applies to the R 1 At least a 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 to 3.

[0067] The R in each of the structural units 1 At least a part of 2 The amount of the structural unit replaced 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 later, and remains in the molecule without being hydrolyzed or polycondensed. The hydroxy group in this structural unit is, for example, a hydroxy group that remains in the molecule after the alkoxy group is hydrolyzed without being polycondensed.

[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 The organopolysiloxane contains a silsesquioxane having a random structure, a complete cage structure, an incomplete cage structure, and a ladder structure, and 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 the alkoxysilane, R 1 3Si(OR 2 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 the alkoxysilane, 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 the alkoxysilane, 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. 4 / 2 As the alkoxysilane forming Si(OR 2 ) 4. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0072] The alkyl silicate condensate is one selected from 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, or a condensate (mixture) of two or more of these. 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 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 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 (organosilicon 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, which 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 having an appropriate thickness and 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 relative to the total mass of the coating liquid 13 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 becomes high, and the thickness of the coating film 13 formed from the coating liquid 14 becomes larger than necessary. If the blending ratio of the inert organic solvent exceeds 60% by mass, the viscosity of the coating liquid 14 becomes lower than necessary, and it is not possible to form a coating film 13 of a predetermined thickness having excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11. Since 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 having 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 coating having an average thickness in the range of 5 nm to 20 μm, preferably 50 nm to 1 μm.

[0078] In forming (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 (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 left at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating with ultraviolet light. 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 heated to a temperature of less than 400°C while irradiating with infrared light while irradiating with ultraviolet light, 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 (water (H ２ When the coating liquid 13 is applied to the surface 12 of the substrate 11 in a thin film, the inorganic polysilazane, organopolysilazane, or organopolysiloxane contained in the coating liquid 13 reacts with the moisture (H ２ 0), an organic composite structure is generated on the surface 12 of the substrate 11, in which an organic functional group is bonded as a side chain to a part of the main chain formed by a siloxane bond (Si—O—Si). ３ , H ２ These gases do not remain on the surface 12 of the substrate 11 but are volatilized (emitted) into the atmosphere.

[0080] The coating liquid 13 containing inorganic polysilazane, organo polysilazane, or organo polysiloxane undergoes a chemical reaction (deammonia crosslinking) with moisture contained 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 initially 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 intermediate layers. Finally, a coating film 10 a (inorganic coating film 10 a) having the structure shown in FIG. 5 or a coating film 10 a (organic / inorganic hybrid coating film 10 a) 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 10 a 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 (H ２ O) or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a. ２ In this way, silver ions (Ag ＋ ), copper ions (Cu２＋ ), zinc ions (Zn ２＋ ) precipitates rapidly.

[0083] In addition, as a pre-treatment step prior to the coating step of the coating liquid 13, water such as purified water (H ２ O) may be sprayed onto the surface 12 of the substrate 11 to allow the water to adhere 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 properties (durability) of the coating film 10a are 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, a plurality of 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 (surface 12 of the substrate 11) is heated to a temperature of about 80°C by irradiating it with infrared rays, and then 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 within 30 minutes to 1 hour after being applied to the surface of the coating film 10a, forming the hydrophilic polymer coating 10b (film formation). 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 the superhydrophilic effect.

[0088] As the hydrophilic polymer coating agent (hydrophilic functional polymer), an alkoxysilane-based compound (main component: alkoxysilane, alkoxysilane oligomer) or a polysilazane-based compound (main component: perhydropolysilazane) can be used. 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 being coated on the surface, forming a 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 between their surfaces and water, so water droplets do not form droplets, but rather spread out. Glass particle-containing hydrophilic composite coating film 10 is formed from coating film 10a formed (deposited) on surface 12 of substrate 11 and hydrophilic polymer coating 10b formed (deposited) 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 vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ Conductive glass particles 14 of silver ions (Ag) are dispersed and mixed in the coating liquid 13. ＋ ) 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 coated on the surface 12 of the substrate 11, silver ions (Ag ＋ ) and copper ions (Cu ２＋ and vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ Conductive glass particles 14 of barium oxide (BaO)-based glass 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 (Cu２＋ 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) the 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 through the inside of 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) toward the surface layer (surface) of the hydrophilic polymer coating 10b, and precipitate 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, vanadium oxide (V ２ O ５ The conductive glass particles 14 having a high content of hydroxybenzoates (H), exhibit a high deposition rate of the metal ions 15, and as described above, after a predetermined time (10 to 20 minutes) has elapsed since the surface 12 of the substrate 11 was coated with the coating liquid 13, 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 surface 12 of the substrate 11 is coated with the coating liquid 13, water (H), such as purified water, is applied to the surface of the coating film 10a. ２ O) or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a, whereby silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) can be rapidly precipitated.

[0101] Phosphorus oxide (P ２ O ５), the conductive glass particles 14 having a high content of barium oxide (BaO) have a slow deposition rate of the metal ions 15, and the metal ions 15 do not deposit on the surface layer (surface) of the coating film 10a in a short time after the coating liquid 13 is coated on the surface 12 of the substrate 11. Instead, the metal ions 12 deposit on the surface layer (surface) of the coating film 10a over a long period of time (3 months to 3 years), and the metal ions 15 remain inside the coating film 10a for a long period of time.

[0102] In the glass particle-containing hydrophilic composite coating film 10 (coating film 10a), vanadium oxide (V ２ O ５ ) and phosphorus oxide (P ２ O ５ By using two or more types of conductive glass particles with different compositions, including conductive glass particles 14 with a high content of fluorine (fluorine), or barium oxide (BaO), the present invention achieves 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 decreases, its protective function is lost, and it is unable to adequately protect the surface 12 of the substrate 11. If the average thickness of the coating film 10a exceeds 20 μm, the flexibility of the coating film 10a decreases, 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 is a coating film whose main component is SiO2, the coating film 10a 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, which causes deformation, and can maintain the coating state of the coating film 10a by following the deformation of the surface 12.

[0105] In the glass particle-containing hydrophilic composite coating film 10, the content of the conductive glass particles 14 dispersed in the coating film 10a in the coating film 13 is in the range of 0.1 volume % to 20 volume % and preferably in the range of 0.3 volume % to 5 volume %. If the content of the conductive glass particles 14 dispersed in the coating film 13 is less than 0.1 volume %, the content of the 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 the conductive glass particles 14 dispersed in the coating film 10a exceeds 20 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 and mixed 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 diameter 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 functions, and the antiviral, antibacterial, antifungal, and deodorizing functions are maintained for a long period of time. Furthermore, the coating has high adhesion to the surface 12 of the substrate 11, and can form a smooth thin film on the surface 12 of the substrate 11.

[0109] FIG. 7 is a cross-sectional view schematically showing another example of a 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 a 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] 7 is made from a siloxane-based solution, an alkyl silicate condensate, an inert organic solvent, and conductive glass particles 14. The siloxane-based solution, the alkyl silicate condensate, and the inert organic solvent are the same as those in the coating solution 13 shown 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 liquid 13 contains silver ions 15a (Ag ＋ ions), and copper ions 15b (Cu ２＋ ions), and zinc ions 15c (Zn ２＋ The coating liquid 13 contains dispersed conductive glass particles 14c containing silver ions 15a (Ag ＋ ions), and copper ions 15b (Cu 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 ＋ ions), and copper ions 15b (Cu ２＋ions), and zinc ions 15c (Zn ２＋ The conductive glass particles 14a to 14c contained in the coating film 10a 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 shown in FIGS.

[0114] The coating film 10a contains silver ions 15a (Ag ＋ ions), and copper ions 15b (Cu ２＋ ions), and zinc ions 15c of zinc oxide (ZnO) (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 (H ions) such as purified water is applied to the surface of the coating film 10a. ２ O) or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a, whereby 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＋ However, after a predetermined time has passed 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, in the coating film 10a (coating liquid 13) of FIG. 8, vanadium oxide (V ２ O ５ The conductive glass particles 14a to 14c have a high content of phosphorus oxide (P ２ O ５ By using two or more types of conductive glass particles 14a to 14c having different compositions, one type having a high content of fluorine (fluorine), the other type having a high content of fluorine (fluorine), or barium oxide (BaO), the present invention achieves 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) (substrate 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 (substrate 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 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 12 of the acrylic substrate 11 (substrate 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(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 to the surface 12 of the acrylic substrate 11 (substrate 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. 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 (50×50×5 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 organopolysiloxane (siloxane solution) as the main component and 7% by volume of conductive glass particles 14 to the surface 12 of an acrylic substrate 11 (50×50×5 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. ５０ is 5 μm or less.

[0121] As described above, the conditions for forming the coating film 10a on the acrylic substrates 11(2) to 11(4) were as follows: after coating the surfaces 12 of the acrylic substrates 11(2) to 11(4) (substrates 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 substrates 11(2) to 11(4) (substrate 11) with the coating liquid 13, the surfaces 12 of the acrylic substrates 11(2) to 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 substrates 11(2) to 11(4) with the coating liquid 13, the surfaces 12 of the acrylic substrates 11(2) to 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 substrates 11(2) to 11(4) with ultraviolet light, or after coating the surfaces 12 of the acrylic substrates 11(2) to 11(4) with the coating liquid 13, the surfaces 12 of the acrylic substrates 11(2) to 11(4) are heated to a temperature of less than 400°C by irradiating the surfaces 12 of the acrylic substrates 11(2) to 11(4) with infrared light while irradiating the surfaces 12 of the acrylic substrates 11(2) to 11(4) 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 diameter 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 7% by volume of conductive glass particles 14, 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, and 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] The 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＋ ) can kill Staphylococcus aureus and Escherichia coli, preventing them from multiplying.

[0125] The 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 (Zn ２＋) can kill Staphylococcus aureus and Escherichia coli, preventing them from multiplying.

[0126] The acrylic substrate 11(4) on whose surface 12 a coating film 10a made from a coating liquid 13 containing 7% 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(4), the silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) 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 above-mentioned conductive glass particles 14 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 value of viable bacteria 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 results of an antibacterial test (reduction rate).

[0129] A coating liquid 13 containing organopolysiloxane (siloxane-based solution) as a main component and conductive glass particles 14 mixed therein was applied to the 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; 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) while irradiating the surface 12 of the acrylic substrate 11 with ultraviolet rays; 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 heated to a temperature of less than 400°C by irradiating the surface 12 of the acrylic substrate 11 with infrared rays while irradiating the surface 12 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 diameter 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 FIG. 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 the coating of the coating liquid 13 onto the acrylic substrate 11 (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 the coating of the coating liquid 13 onto the acrylic substrate 11 (inoculation of E. coli onto the acrylic substrate 11) was reduced by 99.99% compared to that immediately after the coating of the coating liquid 13 onto the acrylic substrate 11 (inoculation of E. coli onto the acrylic substrate 11).

[0134] The antibacterial activity value 30 minutes after the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of 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 the coating of the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11).

[0136] As is clear from FIGS. 11 and 12 , when a coating film 10 a having conductive glass particles 14 dispersed therein is formed on an acrylic substrate 11, the antibacterial activity value rises to >4.1 with the passage of time from coating the acrylic substrate 11 with the coating liquid 13 (inoculation of E. coli onto the acrylic substrate 11), and the logarithmic average value of the viable E. coli cell count decreases significantly. This indicates that the coating film 10 a 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) (substrate 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 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(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 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 (50×50×5 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 (50×50×5 mm) and forming a coating film 10a on the surface 12 of the acrylic substrate 11. ５０ is 5 μm or less.

[0139] The film formation conditions for acrylic substrate 11(2) to acrylic substrate 11(4) are the same as those for acrylic substrate 11(2) to acrylic substrate 11(4) in the evaluation of antibacterial activity values ​​shown in Figures 11 and 12. A predetermined time has passed since coating liquid 13 was applied to surface 12 of acrylic substrate 11 for acrylic substrate 11(2) to acrylic substrate 11(4), and a coating film 10a has been formed (deposited) on surface 12. The coating film 10a deposited on surface 12 of acrylic substrate 11(2) contains 3% by volume of conductive glass particles 14, and the average particle size D of the conductive glass particles 14 is 100%. 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 7% by volume of conductive glass particles 14, and the average particle diameter D ５０ is 5 μm or less.

[0140] After forming 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 five-species mixture of fungi: Aspergillus niger NBRC 105649, Penicillium pinophilum NBRC 100533, Paecilomyces variotii NBRC 107725, Trichoderna virens NBRC 6355, and Chaetomium globosum NBRC 6347. The fungi 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 strains) was sprayed onto the media; the culture was then incubated at approximately 29°C and 95% RH or higher for four weeks; and the state of mold growth in containers 1 to 4 was then assessed visually and microscopically.

[0141] The evaluation of mold growth status is as follows: (5) Mycelium growth is vigorous and 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 is not visible to 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 from (0) to (2).

[0142] The acrylic substrate 11(1) placed on the mineral-glucose-containing agar medium in the first container was evaluated as (4), with the mold area covering more than 50% of the total surface area of ​​the medium. The acrylic substrate 11(2) placed on the mineral-glucose-containing agar medium in the second container, the acrylic substrate 11(3) placed on the mineral-glucose-containing agar medium in the third container, and the acrylic substrate 11(4) placed on the mineral-glucose-containing agar medium in the fourth container were evaluated as (2), demonstrating mold resistance in the acrylic substrates 11(2) to 11(4). As is clear from Figure 13, the coating film 10a containing the conductive glass particles 14 described above exhibited excellent mold-proofing properties and was able to 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 simulation 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 solution after cultivating a predetermined 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. The conductive glass particles 14 are V ２ O ５ -P ２ O ５ -Ag ２ O--CuO--ZnO based glass is used.

[0145] As for influenza viruses (IFV), as shown in FIG. 14 , when the contact angle θ of a water droplet W with respect to a coating film not containing conductive glass particles 14 is 20°, the survival time of the influenza viruses (IFV) is approximately 550 (min); when the contact angle θ is 40°, the survival time of the influenza viruses (IFV) is approximately 850 (min); when the contact angle θ is 60°, the survival time of the influenza viruses (IFV) is approximately 2000 (min); and when the contact angle θ is 90°, the survival time of the influenza viruses (IFV) is approximately 11000 (min). In other words, the larger the contact angle θ with the water droplet W, the longer the survival time of the influenza viruses (IFV).

[0146] In contrast, when the contact angle θ of the water droplet W with respect to the glass particle-containing hydrophilic composite coating film 10 containing the 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, it was found that the smaller the contact angle θ of the water droplet W, the shorter the survival time of the influenza virus (IFV), and 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 not containing 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 for feline calicivirus (FCV), as shown in FIG. 15 , when the contact angle θ of the water droplet W with respect to the coating film not containing the 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 the water droplet W with respect to the glass particle-containing hydrophilic composite coating film 10 containing the conductive glass particles 14 was 20° or less, the survival time of the feline calicivirus (FCV) was approximately 9 (min) or less, when the contact angle θ was 40°, the survival time of the feline calicivirus (FCV) was approximately 10 (min), when the contact angle θ was 60°, the survival time of the feline calicivirus (FCV) was approximately 30 (min), and when the contact angle θ was 90°, the survival time of the feline calicivirus (FCV) was approximately 70 (h).

[0150] 15, it was found that the smaller the contact angle θ of the water droplet W, the shorter the survival time of the feline calicivirus (FCV), and 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 droplets 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 droplets W with the film surface is large, 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, 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 glass particle-containing hydrophilic composite coating film 10 has a large contact area with the film surface of the water droplets W, 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 that 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 film surface, 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 on the film 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 is a diagram showing 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 (film-formed) on a 100 cm ２ Acrylic substrate test piece (1), silver ion 15a (Ag ＋ ions) precipitated (film-formed) on a 100 cm ２ The acrylic substrate test piece (2) was coated with a 100 cm 3 hydrophilic composite coating film 10 containing glass particles and having iron ions precipitated on its surface. ２ acrylic substrate test piece (3), a 100 cm 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 2 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 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 by dissolving a siloxane-based solution (silicon oxide (SiO ２ The glass-based coating film 10a is formed of a glass-based coating film based on silver ions (Ag) and a hydrophilic polymer coating 10b that covers the surface of the glass-based coating film. Conductive glass particles dispersed and mixed in the coating film 10a are converted into 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 a wide area of ​​the film surface of the glass particle-containing hydrophilic composite coating film 10, and silver ions (Ag ＋ ) and copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) can fully utilize 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, thereby 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 enabling the various germicides, viruses, and molds to be killed in a short period of time. The 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.

[0162] In the glass particle-containing hydrophilic composite coating film 10, the original solution of the coating liquid (starting material of the coating film) that forms the coating film 10a is a siloxane-based solution, and by using a siloxane-based solution with a dense molecular structure as the original solution of 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] The glass particle-containing hydrophilic composite coating film 10 has excellent strength and excellent scratch resistance because the coating film 10a forming it is a glass-based coating film made from a siloxane-based solution, and can smooth the surface 12 of the substrate 11 on which the glass particle-containing hydrophilic composite coating film 10 (coating film 10a) is formed, thereby preventing scratches on the surface 12 of the substrate 11 on which the glass particle-containing hydrophilic composite coating film 10 is formed. The glass particle-containing hydrophilic composite coating film 10 is not limited to a specific object, and can impart excellent antibacterial and antiviral functions, antifungal functions, and deodorizing functions to all objects.

[0164] Phosphorus oxide (P ２ O ５ ), and silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ The deposition rate of the metal ions 15 in vanadium oxide (V) 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. Therefore, the antiviral, antibacterial, antifungal, and deodorizing functions of the metal ions 12 can be maintained. ２ O ５ In the conductive glass particles 14 having a high content of silver ions (Ag ＋), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ The deposition rate of the metal ions 15 of vanadium oxide (V) is fast, and the metal ions 12 are deposited toward the surface layer (surface) of the coating film 13 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, so that the antiviral, antibacterial, antifungal, and deodorizing functions of the metal ions 12 can be quickly utilized. ２ O ５ ) and phosphorus oxide (P ２ O ５ By using two or more types of conductive glass particles 14 having different compositions, including conductive glass particles 14 with a high content of fluorine (fluorine), or barium oxide (BaO), it is possible to achieve both immediate and long-lasting antiviral, antibacterial, antifungal, and deodorizing functions.

[0165] The glass particle-containing hydrophilic composite coating film 10 is formed by coating the surface 12 of the substrate 11 with the coating liquid 13, and then immediately applying water (H ２ O) or a predetermined aqueous solution is sprayed or brushed onto the surface of the coating film 10a, whereby silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) can be rapidly precipitated.

[0166] 10 Glass particle-containing hydrophilic composite coating film (coating film) 10a Coating film 10b Hydrophilic polymer coating 11 Substrate 12 Surface (front surface, back surface) (contact surface) 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＋Contact angle of water droplet θ (°)

Claims

1. A coating film in which predetermined conductive glass particles are dispersed and mixed, wherein 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. 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 are ＋ ) 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. The coating film according to claim 1, wherein the original solution of the coating liquid (starting material of the coating film) that forms the coating film is a siloxane-based solution, and the conductive glass particles are dispersed and mixed in the siloxane-based solution.

8. The coating film according to claim 1, wherein the surface of the coating film is made hydrophilic by 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. The coating film according to claim 9, wherein a plurality of minute 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 minute irregularities are formed.

11. The coating film according to claim 1, which has one or more of the following functions: antiviral, antibacterial, antifungal, and deodorizing.

12. The coating film is made by coating the coating liquid onto the surface of a specific substrate, and then immediately applying water or an aqueous solution to the surface of the coating film to deposit 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.

Images