Coating film

Abstract

[Problem] To provide an organic-inorganic hybrid coating film which contains a large amount of silver ions, copper ions, and zinc ions, which has an excellent antibacterial / antiviral function, antifungal function, and a deodorization function, which makes it possible to reliably eliminate germs, various viruses, various mold fungi and which makes it possible to reliably remove unpleasant odors. [Solution] A organic-inorganic hybrid coating film that is a glass coating film which contains silicon oxide (SiO2) as a base, wherein in the coating film, glass particles are electrically conductive glass which includes at least one type of ion from among silver ions (Ag+), copper ions (Cu2+), and zinc ions (Zn2+), and the glass particles include glass which contains, as a base, at least one oxide from among vanadium oxide (V2O5), tungsten oxide (WO3), and molybdenum oxide (MoO3), and phosphorus oxide (P2O5).

Description

coating film

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

[0002] Disclosed is a coated glass comprising a glass substrate and a coating formed on the surface of the glass substrate, the coating having a silicon oxide matrix and containing silver ions and ions of at least one alkali metal selected from sodium, potassium, and lithium, the coating having a silicon oxide matrix and containing silver ions and ions of at least one alkali metal selected from sodium, potassium, and lithium, the coating measuring the yellowness index YI before and after a humidity resistance test in a high-temperature, high-humidity chamber at 85°C and 85% RH for 1000 hours and calculating the yellowness index YI according to JIS-K7373 (2006) by subtracting the value before from the value after the humidity resistance test, yielding a ΔYI of 1.8 or less, and the coating surface having an antibacterial activity value of 2.0 or more one hour after the start of an antibacterial test conducted in a dark place at 25°C according to JIS Z 2801 (2010) using Escherichia coli, Staphylococcus aureus, or an influenza virus surrogate phage (see Patent Document 1). This coated glass is used as glass windows for buildings and automobiles. The inclusion of silver in the coated glass gives it antibacterial and antiviral properties, and also helps prevent yellowing caused by silver.

[0003] JP 2016-33109 A

[0004] The coated glass disclosed in Patent Document 1 has a silicon oxide matrix coating, which makes it difficult to introduce a large amount of silver ions into the coating, and the coating does not contain a large amount of silver ions, so the antibacterial and antiviral functions of the coating are small, making it difficult to reliably kill germs and various viruses, and the antibacterial and antiviral functions of the coating cannot be maintained for a long period of time. Furthermore, this coated glass is made by forming a coating on the surface of a glass substrate, which has a silicon oxide matrix and contains silver ions and ions of at least one alkali metal selected from sodium, potassium, and lithium, and therefore does not anticipate the formation of a coating on substrates other than glass substrates, making it impossible to impart antibacterial or antiviral properties to substrates other than glass substrates.

[0005] An 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 that contains large amounts of silver ions, copper ions, and zinc ions. Another object of the present invention is to provide a coating film that has excellent antibacterial, antiviral, antifungal, and deodorizing functions and can reliably kill germs, various viruses, and various molds and reliably remove unpleasant odors. Another object of the present invention is to provide a coating film that can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all coating targets, regardless of the target, and that can maintain its antibacterial, antiviral, antifungal, and deodorizing functions for a long period of time.

[0006] The present invention, which aims to solve the above-mentioned problems, is premised on a coating film in which glass particles are dispersed and mixed.

[0007] The feature of the present invention in the above premise is that the coating film is made of silicon oxide (SiO ２ )-based glass coating film, and the glass particles are silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) is a conductive glass containing at least one of the above.

[0008] In one example of the present invention, glass particles dispersed and mixed in the coating film are ionized with silver ions (Ag ＋ ) and copper ions (Cu ２＋ ) and zinc ions (Zn ２＋ ) and silver ions (Ag ＋ ) and copper ions (Cu ２＋ ) and zinc ions (Zn ２＋ ) and conductive glass containing at least one of them.

[0009] In another example of the present invention, glass particles dispersed and mixed in the coating film are ionized with silver ions (Ag ＋ ), conductive glass containing only copper ions (Cu ２＋ ), conductive glass containing only ions (Zn ２＋ ) is a conductive glass containing only

[0010] In another example of the present invention, glass particles dispersed and mixed in the coating film are ionized with silver ions (Ag ＋ ) and a conductive glass containing only copper ions (Cu ２＋ ) and zinc ion (Zn ２＋ ) and conductive glass containing only silver ions (Ag ＋ ) is a conductive glass containing only

[0011] In one embodiment of the present invention, the 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 glass based on

[0012] In another embodiment of the present invention, the glass particles contain silver ions (Ag ＋ Vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ ) type glass.

[0013] In another embodiment of the present invention, the glass particles further include barium oxide (BaO).

[0014] In another example of the present invention, the content of glass particles dispersed and mixed in the coating film is 0.1% by volume or more and 30% by volume or less.

[0015] In another example of the present invention, the content of glass particles dispersed and mixed in the coating film is 0.2% by volume or more and 10% by volume or less.

[0016] In another example of the present invention, the average particle diameter D of the glass particles ５０ However, it is 5 μm or less.

[0017] In another example of the present invention, the average particle diameter D of the glass particles ５０ However, it is 3 μm or less.

[0018] In another example of the present invention, in the case of a coating film, after a coating liquid for forming the coating film is coated on the surface of a predetermined substrate, metal ions of glass particles mixed in the coating liquid diffuse into the inside of the coating film.

[0019] In another example of the present invention, in the coating film, metal ions of glass particles mixed in the coating liquid diffuse inside the coating film and move to the surface of the coating film.

[0020] In another example of the present invention, the original coating solution (starting material for the coating film) is a siloxane-based solution or a silica sol-based solution, and glass particles are mixed into the siloxane-based solution or the silica sol-based solution.

[0021] In another example of the present invention, the coating film is a glass-based organic / inorganic hybrid coating film.

[0022] According to the coating film of the present invention, the coating film is made of silicon oxide (SiO ２ )-based glass coating film, and the glass particles are silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ), and because the glass particles containing metal ions have electronic conductivity, large amounts of silver ions, copper ions, and zinc ions can be introduced, allowing the coating film to contain large amounts of silver ions, copper ions, and zinc ions. Because the coating film contains large amounts of silver ions, copper ions, and zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds and reliably eliminate unpleasant odors. The coating film is not limited to a specific object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated). By containing large amounts of silver ions, copper ions, and zinc ions, the antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0023] The glass particles contain silver ions (Ag ＋ ) and copper ions (Cu ２＋ ) and zinc ions (Zn ２＋ ) and silver ions (Ag ＋ ) and copper ions (Cu ２＋ ) and zinc ions (Zn ２＋ The coating film is a conductive glass containing at least one of silver ions (Ag) and zinc ions (Cu), and the glass particles containing these metal ions have electronic conductivity, so a large amount of silver ions, copper ions, or zinc ions can be introduced into the coating film. ＋ ), copper ions (Cu ２＋ ), zinc ions (Zn ２＋ ) of silver ions (Ag ＋ ) and copper ions (Cu ２＋ ) and zinc ions (Zn ２＋ ) and at least one of them, the composition has excellent antibacterial, antiviral, antifungal and deodorizing functions, can reliably kill germs, various viruses and various mold spores, can reliably remove unpleasant odors, and can maintain its antibacterial, antiviral, antifungal and deodorizing functions for a long period of time.

[0024] The glass particles contain silver ions (Ag ＋ ), conductive glass containing only copper ions (Cu ２＋ ), conductive glass containing only zinc ions (Zn ２＋ The coating film is made of conductive glass containing only silver ions, copper ions, and zinc ions diffuse from the glass particles into the coating film at approximately the same time, which gives the coating film excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various mold spores, and can reliably remove unpleasant odors.

[0025] The glass particles contain silver ions (Ag ＋ ) and a conductive glass containing only copper ions (Cu ２＋ ) and zinc ion (Zn ２＋) and conductive glass containing only silver ions (Ag ＋ The coating film, which is a conductive glass containing only silver ions, is provided with excellent antibacterial, antiviral, antifungal and deodorizing functions by diffusing at least silver ions from the glass particles into the coating film, and can reliably kill germs, various viruses and various mold spores and remove unpleasant odors.

[0026] The glass particles are vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ The coating film containing glass based on vanadium oxide (V) is ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ ), the glass particles have high electronic conductivity, allowing large amounts of silver ions, copper ions, and zinc ions to be introduced into the coating film, allowing the coating film to contain large amounts of silver ions, copper ions, and zinc ions. Because the coating film contains large amounts of silver ions, copper ions, and zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds, and can reliably remove unpleasant odors. The coating film is not limited to a specific object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated). By containing large amounts of silver ions, copper ions, and zinc ions, the antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0027] The glass particles contain silver ions (Ag ＋ Vanadium oxide (V) ２ O５ ) -phosphorus oxide (P ２ O ５ The coating film, which is a vanadium oxide-phosphorus oxide-based glass containing silver ions, uses vanadium oxide-phosphorus oxide-based glass containing silver ions as glass particles. The glass particles have high electronic conductivity, allowing large amounts of silver ions, copper ions, and zinc ions to be introduced into the coating film, allowing the coating film to contain large amounts of silver ions, copper ions, and zinc ions. Because the coating film contains large amounts of silver ions, copper ions, and zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds, and can reliably eliminate unpleasant odors. The coating film is not limited to a specific substrate, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (subjects to be coated). The inclusion of large amounts of silver ions, copper ions, and zinc ions allows the antibacterial, antiviral, antifungal, and deodorizing functions to be maintained for a long period of time.

[0028] The glass particles contain silver ions (Ag ＋ Vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５The coating film, which is a vanadium oxide (V)-barium oxide (BaO)-based glass, uses vanadium oxide-phosphorus oxide-based glass containing silver ions as glass particles. The glass particles have high electronic conductivity, allowing large amounts of silver, copper, and zinc ions to be introduced into the coating film, allowing the coating film to contain large amounts of silver, copper, and zinc ions. Because the coating film contains large amounts of silver, copper, and zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds, and reliably eliminate unpleasant odors. The coating film is not limited to a specific substrate, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (subjects to be coated). The inclusion of large amounts of silver, copper, and zinc ions allows the antibacterial, antiviral, antifungal, and deodorizing functions to be maintained for a long period of time.

[0029] A coating film having a glass particle content of 0.1% by volume or more and 30% by volume or less, dispersed and mixed therein, has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds and reliably remove unpleasant odors. The coating film is not limited to the object to be coated, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated), and by containing glass particles in the content range, the antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0030] A coating film having a glass particle content of 0.2% by volume or more and 10% by volume or less, dispersed and mixed therein, has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds and reliably remove unpleasant odors. The coating film is not limited to the object to be coated, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated), and by containing glass particles in the above-mentioned content range, the antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0031] Average particle size D of glass particles ５０ By using glass particles with this average particle size, a coating film having an average particle size of 5 μm or less can incorporate a large amount of silver ions, copper ions, or zinc ions into the coating film, allowing the coating film to contain a large amount of silver ions, copper ions, or zinc ions. Because the coating film contains a large amount of silver ions, copper ions, or zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds, and reliably remove unpleasant odors. The coating film is not limited to a specific object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated). By containing a large amount of silver ions, copper ions, or zinc ions, the antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0032] Average particle size D of glass particles ５０By using glass particles with this average particle size, a coating film having an average particle size of 3 μm or less can incorporate a large amount of silver ions, copper ions, or zinc ions into the coating film, allowing the coating film to contain a large amount of silver ions, copper ions, or zinc ions. Because the coating film contains a large amount of silver ions, copper ions, or zinc ions, it has excellent antibacterial, antiviral, antifungal, and deodorizing functions, and can reliably kill germs, various viruses, and various molds and reliably remove unpleasant odors. The coating film is not limited to a specific object, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to all substrates (objects to be coated), and by containing a large amount of silver ions, copper ions, or zinc ions, its antibacterial, antiviral, antifungal, and deodorizing functions can be maintained for a long period of time.

[0033] After the coating liquid that forms the coating film is coated on the surface of a specified substrate, the metal ions of the glass particles mixed in the coating liquid diffuse into the coating film, and the metal ions diffused into the coating film exhibit high antibacterial, antiviral, antifungal and deodorizing functions. Therefore, the coating film has excellent antibacterial, antiviral, antifungal and deodorizing functions, and can reliably kill germs, various viruses and various mold spores, and can reliably eliminate unpleasant odors.

[0034] The metal ions of the glass particles mixed in the coating liquid diffuse inside the coating film and migrate to the surface of the coating film, and the metal ions that diffuse inside the coating film and migrate to the surface of the coating film exhibit high antibacterial, antiviral, antifungal and deodorizing functions, so the coating film has excellent antibacterial, antiviral, antifungal and deodorizing functions, and can reliably kill germs, various viruses and various mold spores, and can reliably remove unpleasant odors.

[0035] In a coating film in which the coating liquid stock solution (the starting material for the coating film) is a siloxane-based solution or a silica sol-based solution and glass particles are mixed into the siloxane-based solution or the silica sol-based solution, by using a siloxane-based solution or a silica sol-based solution having a porous molecular structure as the coating liquid stock solution (the starting material for the coating film), a large amount of silver ions, copper ions, or zinc ions can be mixed into the siloxane-based solution or the silica sol-based solution, and a coating film made from the siloxane-based solution or the silica sol-based solution can contain a large amount of silver ions, copper ions, or zinc ions, allowing a large amount of metal ions to diffuse into the coating film. Because a large amount of silver ions, copper ions, or zinc ions diffuses into the coating film, the coating film has excellent antibacterial, antiviral, antifungal, and deodorizing properties, and can reliably kill various bacteria, viruses, and various molds and reliably eliminate unpleasant odors.

[0036] The glass-based organic / inorganic hybrid coating film contains a large amount of silver ions, copper ions, and zinc ions, and therefore has excellent antibacterial, antiviral, antifungal, and deodorizing properties, reliably killing germs, various viruses, and various molds and reliably eliminating unpleasant odors. The coating film is not limited to the substrate to be coated with the glass-based organic / inorganic hybrid coating film, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing properties to all substrates (subjects to be coated). The large amount of silver ions, copper ions, and zinc ions allows the antibacterial, antiviral, antifungal, and deodorizing properties to be maintained for a long period of time. The glass-based organic / inorganic hybrid coating film has excellent strength and scratch resistance, and therefore can prevent scratches on the substrate on which the glass-based organic / inorganic hybrid coating film is formed.

[0037] The coating film 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 an organic / inorganic hybrid coating film 10 formed on a surface 12 of a substrate 11. Fig. 2 is a cross-sectional view illustrating, in time sequence, the mechanism by which an organic / inorganic hybrid coating film 10 is formed from a coating liquid 13 on the surface 12 (front and back) 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 (front and back) of the substrate 11. Fig. 4 is a cross-sectional view schematically illustrating an example of a state after the organic / inorganic hybrid coating film 10 has been formed on the surface 12 of the substrate 11.

[0038] FIG. 5 is a cross-sectional view schematically showing another example of the state immediately after coating (applying) the coating liquid 13 on the surface 12 (front and back surfaces) of the substrate 11, and FIG. 6 is a cross-sectional view schematically showing another example of the state after the organic / inorganic hybrid coating film 10 has been formed on the surface 12 of the substrate 11. FIG. 7 is an image diagram showing an example of the structure of the organic / inorganic hybrid coating film 10, and FIG. 8 is an image diagram showing an example of the state of metal ions in the organic / inorganic hybrid coating film 10. In FIGS. 1, 3, 4, 5, 6, and 8, 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.

[0039] The organic / inorganic hybrid coating film 10 (coating film) is formed on a surface 12 (front surface, back surface) (contact surface) of a substrate 11. The organic / inorganic hybrid coating film 10 is produced by coating (applying) a coating liquid 13 (organic and inorganic hybrid polymer) onto the surface 12 of the substrate 11 to be coated. The substrate 11 to be coated with the coating liquid 13 (the substrate on which the organic / inorganic hybrid coating film 10 (coating film) is formed) can be plastic (plastic molded products and molded products having plastic as the outermost layer), glass (glass molded products), metal (metal molded products), rubber (rubber molded products), leather (leather molded products), wood (wood molded products), paper (paper molded products, woven / knitted fabrics using fibers (woven / knitted fabric molded products), or nonwoven fabric (nonwoven fabric molded products), but the substrate 11 is not particularly limited.

[0040] Examples of plastics include known thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide (nylon), vinyl chloride resin, acrylic resin, silicone resin, fluororesin, polyimide resin, and polysulfone resin, as well as thermosetting resins such as epoxy resin, melamine resin, phenolic resin, and unsaturated polyester resin. Examples of metals include iron, aluminum, duralumin, stainless steel, copper, gold, silver, titanium, nickel, and alloys.

[0041] 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.

[0042] The starting material (coating stock solution) for the coating liquid 13 (organic and inorganic hybrid polymer) is made from a liquid organosilicon material solution (silicon material solution) consisting of at least one of siloxane (siloxane-based solution), polysilazane (inorganic polysilazane, organic polysilazane), and silica sol (silica sol-based solution), an alkyl silicate condensate, an inert organic solvent, and glass particles 14 (described below). An example of the siloxane is an organopolysiloxane in which silicon atoms (Si) having organic groups are linked by siloxane bonds (≡Si—O—Si≡). The organopolysiloxane has a number average molecular weight in the range of 3,000 to 150,000 g / mol.

[0043] The coating liquid 13 (organic and inorganic hybrid polymer) may be either siloxane or polysilazane, or a mixture of both. An organosilicon material, an alkyl silicate condensate, and an inert organic solvent are mixed and stirred in a predetermined ratio, and glass particles 14 are mixed into the mixture to produce the coating liquid 13. In the coating liquid 13, the organosilicon material, which is at least one of siloxane and polysilazane, and the alkyl silicate condensate are diluted with the inert organic solvent.

[0044] The inorganic polysilazane used is a Si-N-based perhydropolysilazane (perhydropolysilazane). As the polysilazane, Si-C-N-based organopolysilazane, Si-C-based polycarbosilane, and SiC-O-based, Si-BC-N-based, and Si-Ti-N-based polysilazanes can also be used.

[0045] The organic polysilazane may be a modified polysilazane such as methylpolysilazane, dimethylpolysilazane, phenylpolysilazane, vinylpolysilazane, etc. Alternatively, a crosslinked polysilazane may be used that is chemically crosslinked with a compound such as a hydrocarbon compound having a reactive group such as a hydroxyl group, a vinyl group, an amino group, or a silyl group, which chemically reacts with polysilazane to form a crosslinked structure, a cyclic saturated hydrocarbon compound, a cyclic unsaturated hydrocarbon compound, a saturated heterocyclic compound, an unsaturated heterocyclic compound, or a silicone compound.

[0046] Other examples that can be used include polyborosilazane, inorganic silazane high polymers and modified polysilazanes, copolymerized silazanes, low-temperature ceramic polysilazanes obtained by adding or incorporating a catalytic compound to polysilazane to promote ceramicization, silicon alkoxide-added polysilazanes, glycidol-added polysilazanes, acetylacetonato complex-added polysilazanes, metal carboxylate-added polysilazanes, and polysilazane compositions obtained by adding amines and / or acids to the above-mentioned various polysilazanes or modified products.

[0047] The polysilazane may be a single type of polysilazane, a mixture of two or more types of polysilazanes selected from various polysilazanes, or a polysilazane copolymer consisting of two or more types of polysilazane structures, and each molecule contains at least one hydrogen atom directly bonded to a silicon atom. The polysilazane forming the coating liquid 13 has a weight-average molecular weight in the range of 100 to 100,000,000, preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000, from the viewpoints of solubility in solvents and ease of application. A weight-average molecular weight of 100 or greater results in low volatility, which can lead to deterioration of the coating film quality due to evaporation of the solvent and evaporation of the polysilazane itself during the curing process.

[0048] The inorganic polysilazane is represented by the general formula (Chemical Formula 1).

[0049] 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. ３groups, 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.

[0050] Perhydropolysilazane contains a chain portion and a cyclic portion in the molecule and is represented by the following chemical formula (Chemical Formula 2).

[0051] An example of the structure of perhydropolysilazane is represented by the following chemical formula (Chemical Formula 3).

[0052] 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).

[0053] 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.

[0054] As an example, perhydropolysilazane (A) is —(SiH(CH)) represented by the following general formula (Chemical Formula 5): ３ )-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 article 11, and the organic / inorganic hybrid coating film 13 can be formed on the surface 12 of the article 11 quickly.

[0055] 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 organic / inorganic hybrid coating film 13 that coats the surface 12 of the article 11 can be improved.

[0056] The perhydropolysilazane contained in the coating liquid 14 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 perhydropolysilazane (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 (the time it takes to form the organic / inorganic hybrid coating film 13) compared to perhydropolysilazane (B) alone.

[0057] 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.

[0058] 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).

[0059] Also, for example, R １ Six３ Polysilazane 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).

[0060] 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.

[0061] 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)-CR 11 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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 or more and 3 or less.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] The siloxane contained in the coating liquid 13 may be any one of a chain siloxane having a chain skeleton and a cyclic siloxane having a cyclic skeleton, or a mixture of two or more of these. Examples of the cyclic siloxane include hexamethylcyclotrisiloxane (C ６ H １８ O ３ Si ４ ), octamethylcyclotetrasiloxane (C ６ H ２４ O ４ Si ４ ), decamethylcyclopentasiloxane (C １０ H ３０ O ５ Si ５ The organic polysilazane may have a number average molecular weight in the range of 3,000 to 150,000 g / mol.

[0075] 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.

[0076] Because the number-average molecular weight of the organopolysiloxane and the number-average molecular weight of the organic polysilazane in the coating liquid 13 are within the above-mentioned ranges, the coating liquid 13 containing the organopolysiloxane and / or the organic polysilazane can maintain a predetermined viscosity, and an organic / inorganic hybrid coating film 10 can be formed from the coating liquid 13. Because the coating liquid 13 is coated onto the surface 12 of the substrate 11 (molded product) to be coated while maintaining the predetermined viscosity, even if the coating liquid 13 is coated onto 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 an organic / inorganic hybrid coating film 10 with a substantially uniform thickness can be formed on the surface 12 of the substrate 11.

[0077] In the coating liquid 13, the blending ratio of the organosilicon material (organopolysiloxane and / or organic polysilazane) relative to the total mass of the coating liquid 13 is in the range of 30 to 60 mass%, the blending ratio of the alkyl silicate condensate relative to the total mass of the coating liquid 13 is in the range of 10 to 15 mass%, and the blending ratio of the inert organic solvent relative to the total mass of the coating liquid 13 is in the range of 30 to 60 mass%. If the blending ratio of the organosilicon material (organopolysiloxane and / or organic polysilazane) is less than 30 mass%, the content of the organosilicon material is low, making it impossible to form an organic / inorganic hybrid coating film 10 of a predetermined thickness that has excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11 (molded product). If the blending ratio of the organosilicon material (organopolysiloxane and / or organic polysilazane) exceeds 60 mass%, the viscosity of the coating liquid 13 increases more than necessary, and the thickness of the organic / inorganic hybrid coating film 10 becomes larger than necessary. Since the coating liquid 13 has the blending ratio of the organosilicon material (organopolysiloxane and / or organic polysilazane) relative to its total mass within the above range, it is possible to form an organic / inorganic hybrid coating film 10 of an appropriate thickness that has excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0078] If the blending ratio of the alkyl silicate condensate is less than 10% by mass, the alkyl silicate condensate has a weak effect as a cross-linking agent, and a sufficient cross-linked structure is not formed in the organic / inorganic hybrid coating film 10. If the blending ratio of the alkyl silicate condensate exceeds 15% by mass, an unnecessary cross-linked structure is formed in the organic / inorganic hybrid coating film 10, and the flexibility of the organic / inorganic hybrid coating film 10 becomes greater than necessary. Since the blending ratio of the alkyl silicate condensate to the total mass of the coating liquid 13 is within the above range, the coating liquid 13 can be used to produce an organic / inorganic hybrid coating film 10 having an appropriate cross-linked structure and appropriate flexibility.

[0079] If the blending ratio of the inert organic solvent is less than 30% by mass, the viscosity of the coating liquid 13 becomes high, and the thickness of the organic / inorganic hybrid coating film 10 formed from the coating liquid 13 becomes unnecessarily large. If the blending ratio of the inert organic solvent exceeds 60% by mass, the viscosity of the coating liquid 13 becomes unnecessarily low, and it is not possible to form an organic / inorganic hybrid coating film 10 of a predetermined thickness having excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11 (molded product). Since the blending ratio of the inert organic solvent to the total mass of the coating liquid 13 is within the above range, the coating liquid 13 can be used to form an organic / inorganic hybrid coating film 10 of an appropriate viscosity having excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0080] The coating liquid 13 contains, relative to its total mass, an organosilicon material (organopolysiloxane and / or organic polysilazane) in the range of 30 to 60 mass % and an alkyl silicate condensate in the range of 10 to 15 mass %, so that the rate of formation (film formation) of the organic / inorganic hybrid coating film 10 made from the coating liquid 13 can be appropriately controlled. Specifically, the hydrolysis of the alkyl silicate condensate proceeds faster than the condensation of the organopolysiloxane and / or organic polysilazane, so that a portion of the water (H ２ Since alkyl silicate condensate (O) is consumed first, it is possible to delay the progress of the condensation reaction of the organopolysiloxane and / or organic polysilazane, thereby controlling the rate of formation (film formation) of the organic / inorganic hybrid coating film 10. Furthermore, since the hydrolysis of the alkyl silicate condensate occurs first, it is possible to reliably form a crosslinked structure in the organic / inorganic hybrid coating film 10, thereby imparting flexibility to the organic / inorganic hybrid coating film 10.

[0081] Furthermore, since the organic solvent is selected from dibutyl ether, turpentine oil, benzene, and toluene, which are inactive to organic polysilazane, siloxane, and alkyl silicate condensates, the condensation reaction of the organopolysiloxane and / or organic polysilazane does not proceed rapidly, making it possible to appropriately control the rate of formation (film formation) of the organic / inorganic hybrid coating film 10. The coating liquid 13, which can control the rate of formation (film formation) of the organic / inorganic hybrid coating film 10, can easily be used to coat the surface 12 of the substrate 11 (molded product).

[0082] 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＋ The glass particles 14 (conductive glass) containing metal ions 15 of silver ions 15a, copper ions 15b, and zinc ions 15c exhibit ionic conductivity. The glass particles 14 contain vanadium oxide (V ２ O ５ ) (electron conductive glass) and tungsten oxide (WO ３ ) (electron-conductive glass) and molybdenum oxide (MoO ３ ) (electron conductive glass), and phosphorus oxide (P ２ O ５ ) (electronically conductive glass) based glass particles (not shown).

[0083] An example of the glass particles 14 is 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＋ ) and zinc ion 15c (Zn ２＋ ) and 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＋ ) and zinc ion 15c (Zn ２＋ ) and glass particles 14 (conductive glass) containing at least one of vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ ) and glass based on it.

[0084] Another example of the glass particles 14 is 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＋ ) and zinc ion 15c (Zn ２＋ ) and glass particles 14 (conductive glass) containing at least one of vanadium oxide (V ２ O ５ ) and phosphorus oxide (P ２ O ５ )-based glass. Another example of the glass particles 14 is a conductive glass (electron-conductive glass) formed from 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＋ ) and zinc ion 15c (Zn ２＋ ) and tungsten oxide (WO ３ ) and phosphorus oxide (P ２ O ５)-based glass. Another example of the glass particles 14 is a conductive glass (electron-conductive glass) formed from 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＋ ) and zinc ion 15c (Zn ２＋ ) and molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ )-based glass and conductive glass (electron-conductive glass).

[0085] Another example of the glass particles 14 is silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) is a conductive glass (electronically conductive glass) containing only silver ions (Ag ＋ Another example of the glass particles 14 is a conductive glass (electronically conductive glass) containing only silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ )-based glass and conductive glass (electron-conductive glass).

[0086] Another example of the glass particles 14 is silver ions 15a (Ag＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only vanadium oxide (V ２ O ５ ) and phosphorus oxide (P ２ O ５ )-based glass. Another example of the glass particles 14 is a conductive glass (electron-conductive glass) formed from silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only tungsten oxide (WO ３ ) and phosphorus oxide (P ２ O ５ )-based glass. Another example of the glass particles 14 is a conductive glass (electron-conductive glass) formed from silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ )-based glass. Another example of the glass particles 14 is a conductive glass (electron-conductive glass) formed from silver ions 15a (Ag ＋ Vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ The glass particles 14 may contain barium oxide (BaO).

[0087] 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.

[0088] The coating liquid 13 (organic and inorganic hybrid polymer) is coated or sprayed onto the surface 12 of the substrate 11 (molded product) to be coated, and chemically reacts with water to form (deposit) a single-layer or multi-layer ultra-thin organic / inorganic hybrid coating film 10. The organic / inorganic hybrid coating film 10 is deposited as a coating having an average thickness in the range of 0.2 μm to 20 μm, preferably 0.5 μm to 20 μm.

[0089] There is no particular limitation on the method for coating the surface 12 (contact surface) of the substrate 11 (molded product) with the coating liquid 13, and the coating is performed by a coating method suited to the shape of the substrate 11 to be coated (covered). For example, coating can be performed by spraying, dipping, brushing, roll coating, gravure coating, flexography, inkjet coating, etc. There is no particular limitation on the amount of coating (application amount) of the coating liquid 13, and the amount of coating is determined according to the surface performance required of the substrate 11 (molded product) to be coated. Generally, the amount of coating is 0.1 to 20 g / m in terms of solid content. 2 The coating amount is 0.1 g / m 2 If the coating amount is less than 20 g / m, the organic / inorganic hybrid coating film 10 having the desired properties will not be formed. 2 If the thickness exceeds this value, the thickness of the organic / inorganic hybrid coating film 10 increases more than necessary, and the organic / inorganic hybrid coating film 10 loses its flexibility.

[0090] In addition, as a pre-treatment step prior to the coating step of the coating liquid 13, water (H ２ O) may be sprayed onto the surface 12 of the substrate 11 to deposit water on the surface 12 of the substrate 11. This promotes a chemical reaction between the water deposited on the surface 12 of the substrate 11 and the components contained in the coating liquid 13, allowing the organic / inorganic hybrid coating film 10 to be rapidly formed on the surface 12 of the substrate 11, and a strong organic / inorganic hybrid coating film 10 to be formed on the surface 12 of the substrate 11.

[0091] 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 (molded product) as a pretreatment step prior to the coating step with the coating liquid 13. For example, when a solution of inorganic polysilazane (1 wt % solution) is coated and then the coating liquid 13 is coated, the rust prevention (durability) of the organic / inorganic hybrid coating film 10 is improved compared to when only the coating liquid 13 is simply coated.

[0092] The mechanism by which the organic / inorganic hybrid coating film 10 is formed on the surface 12 of the substrate 11 is as follows. In forming (forming) the organic / inorganic hybrid coating film 10, the surface 12 of the substrate 11 is coated with the coating liquid 13 in a coating process, 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 being irradiated 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 by irradiating the surface 12 of the substrate 11 with infrared light while being irradiated with ultraviolet light, and then the surface 12 of the substrate 11 is left for a predetermined time (24 hours or more).

[0093] 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 ２When the coating liquid 13 is applied to the surface 12 of the substrate 11 in a thin film form by the coating step, organopolysiloxane contained in the coating liquid 13 is formed (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d is the moisture in the air (H ２ 0), or reacts chemically with -(SiR １ R ２ -NR ３ )-unit component and / or siloxane constituting -(SiR １ R ２ -NR ３ ) - the unit component is moisture in the air (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 article 11 but volatilize (emit) into the atmosphere.

[0094] 2( b), the coating liquid 13 containing organopolysiloxane and / or organic polysilazane undergoes a chemical reaction (deammonia crosslinking) with moisture contained in the air in the surface layer 16 that is in contact with the air, causing gases such as hydrogen and ammonia, which are by-products of the organic / inorganic hybrid coating film 10, to volatilize from the surface 12 (surface layer 16) to the outside air, and forming (producing) a coating layer 17 on the surface 12 side of the organic / inorganic hybrid coating film 10. 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 (see FIG. 7 ) present as terminals on the surface in the back layer 18 that is in contact with the surface 12 of the substrate 11, causing gases such as hydrogen and ammonia to rise within the coating layer 17 and volatilize from the surface 12 (surface layer 16) to the outside air, and forming (producing) a coating layer 17 on the back side 18 of the organic / inorganic hybrid coating film 10.

[0095] First, a coating layer 17 (a vitrified (inorganized) portion and an organic portion) is generated in the surface layer 16 and the back layer 18 of the coating liquid 13. Next, the coating layer 17 (a vitrified (inorganized) portion and an organic portion) is formed and expanded from the surface layer 16 side toward the back layer 18 side, and the coating layer 17 (a vitrified (inorganized) portion and an organic portion) is expanded from the back layer 18 side toward the surface layer 16 side, thereby sequentially forming (generating) the coating layer 17 (a vitrified (inorganized) portion and an organic portion) of the intermediate layer 19, and finally, an organic / inorganic hybrid coating film 10 is formed (generated) on the surface layer 16 in contact with the outside air, the back layer 18 in contact with the surface 12 of the substrate 11, and the intermediate layer 19 between the surface layer 16 and the back layer 18.

[0096] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, as shown in FIGS. 3 and 5, the glass particles 14 mixed in the coating liquid 13 are dispersed and mixed inside the coating liquid 13, and the silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋) metal ions 15 do not diffuse toward the surface of the coating liquid. Specifically, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) and glass particles 14 (conductive glass) containing at least one or more metal ions 15 selected from vanadium oxide (V ２ O ５ ) and tungsten oxide (WO ３ ) and molybdenum oxide (MoO ３ ) and at least one of phosphorus oxide (P ２ O ５ )-based glass and the electron conductive glass formed from the glass are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) metal ions 15 do not diffuse toward the surface layer 16 (surface) of the coating liquid 13.

[0097] In the cross-sectional view shown in FIG. 3, silver ions 15a (Ag ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) are dispersed and mixed in the coating liquid 13. As described above, the glass particles 14 are ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) and silver ions 15a (Ag ＋ ), and copper ions (Cu ２＋ ) or zinc ions (Zn ２＋ ) is contained. In the cross-sectional view shown in FIG. ＋ ) and copper ions 15b (Cu ２＋ ) and zinc ions 15c (Zn ２＋) and the glass particles 14 (conductive glass) containing only silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) are dispersed and mixed in the coating liquid 13.

[0098] Specifically, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) and glass particles 14 (conductive glass) containing at least one or more metal ions 15 of vanadium oxide (V ２ O ５ ) and phosphorus oxide (P ２ O ５ )-based glass and the electron conductive glass formed from the glass are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) do not diffuse toward the surface layer 16 (surface) of the coating liquid 13. Also, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, the silver ions 15a (Ag ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) and tungsten oxide (WO ３ ) and phosphorus oxide (P ２ O ５ )-based glass and the electron conductive glass formed from the glass are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋) do not diffuse toward the surface layer 16 (surface) of the coating liquid 13. Alternatively, silver ions 15a (Ag ＋ ) and copper ion 15b (Cu ２＋ ) and zinc ion 15c (Zn ２＋ ) and molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ )-based glass and the electron conductive glass formed from the glass are dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) does not diffuse toward the surface layer 16 (surface) of the coating liquid 13.

[0099] Furthermore, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only vanadium oxide (V ２ O ５ ) and phosphorus oxide (P ２ O ５ The conductive glass (electronically conductive glass) formed from the glass based on silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) do not diffuse toward the surface layer 16 (surface) of the coating liquid 13. Also, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, the silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only tungsten oxide (WO ３ ) and phosphorus oxide (P ２ O ５ The conductive glass (electronically conductive glass) formed from the glass based on silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) does not diffuse toward the surface layer 16 (surface) of the coating liquid 13.

[0100] Immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ), conductive glass containing only copper ions 15b (Cu ２＋ ), conductive glass containing only zinc ions 15c (Zn ２＋ ) of the conductive glass containing only silver ions 15a (Ag ＋ ) and glass particles 14 (conductive glass) containing only molybdenum oxide (MoO ３ ) and phosphorus oxide (P ２ O ５ The conductive glass (electronically conductive glass) formed from the glass based on silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) do not diffuse toward the surface layer 16 (surface) of the coating liquid 13. Also, immediately after the coating liquid 13 is applied to the surface 12 of the substrate 11, the silver ions 15a (Ag ＋ Vanadium oxide (V) ２ O ５ ) -phosphorus oxide (P ２ O ５ )-based conductive glass (electronically conductive glass) is dispersed and mixed inside the coating liquid 13, and silver ions 15a (Ag ＋ ) does not diffuse toward the surface layer 16 (surface) of the coating liquid 13.

[0101] In the process of forming (forming) an organic / inorganic hybrid coating film 10 from organopolysiloxane and / or organic polysilazane, as shown in FIGS. 4 and 6, after the coating liquid 13 is coated on the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) migrates inside the coating liquid 13 and becomes silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) metal ions 15 diffuse inside the coating film 10 toward the surface layer 16 (surface) of the organic / inorganic hybrid coating film 10 .

[0102] The organic / inorganic hybrid coating film 10 made from organopolysiloxane and / or organic polysilazane is formed from a glass coating layer (amorphous glass coating layer) and an organic coating layer. The organic / inorganic hybrid coating film 10 is mainly composed of SiO2 produced by reacting organopolysiloxane and / or organic polysilazane, and thus a coating layer 17 that is easy to spread in a plane and has high density and high hardness (pencil hardness of about 6H to 9H) is formed. Silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) metal ions 15 are diffused.

[0103] After the coating liquid 13 is applied to the surface 12 of the substrate 11, silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) metal ions 15 diffuse in the coating film 10 from the back layer 18 (bottom) of the organic / inorganic hybrid coating film 10 toward the surface layer 16 (surface), so silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋), zinc ion 15c (Zn ２＋ ) The metal ions 15 exert antibacterial, antiviral, antifungal and deodorizing functions on the organic / inorganic hybrid coating film 10 .

[0104] The organic / inorganic hybrid coating film 10 is formed as a thin film by including an organopolysiloxane and / or an organic polysilazane in the coating liquid 13. The average thickness of the organic / inorganic hybrid coating film 10 is in the range of 0.2 μm to 20 μm, preferably in the range of 0.5 μm to 20 μm. If the average thickness of the organic / inorganic hybrid coating film 10 is less than 0.2 μm, the strength of the organic / inorganic hybrid coating film 10 decreases, its protective function is lost, and the surface 12 of the substrate 11 cannot be adequately protected. If the average thickness of the organic / inorganic hybrid coating film 10 exceeds 20 μm, the flexibility of the organic / inorganic hybrid coating film 10 decreases, and deformation of the surface 12 of the substrate 11 may cause the organic / inorganic hybrid coating film 10 to peel off from the surface 12. Although the organic / inorganic hybrid coating film 10 is a coating film whose main component is SiO2, it has excellent flexibility, and coupled with the anchoring effect of the anchor parts 20, it 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 follow the deformation of the surface 12 to maintain the coating state of the organic / inorganic hybrid coating film 10.

[0105] As shown in an example of the structure image of the organic / inorganic hybrid coating film 10 in FIG. 5, alkyl silicate condensate is chemically reacted with water to produce -(Si(OH) ２ —O—Si(OH) ２It is assumed that a crosslinking reaction occurs between the hydrolysis product having the siloxane bond (≡Si—O—Si≡) and a part of the main chain of each coating layer 17 (surface layer 16, intermediate layer 19, back surface layer 18) and a crosslinked structure is formed, thereby giving the organic / inorganic hybrid coating film 10 a dense and flexible structure. In addition, the formation of the crosslinked structure allows hydrophobic methyl groups (CH ３ ) and hydrophilic hydroxyl groups (OH) derived from the hydrolysis product of the alkyl silicate condensate can be coordinated.

[0106] Unless a special surface treatment such as mirror finishing is performed, the surface 12 of the substrate 11 before being coated with the organic / inorganic hybrid coating film 10 has many microscopic irregularities formed due to small scratches that occur during the manufacturing process, etc. When the coating liquid 13 is coated onto the surface 12 of the substrate 11 and hardens while penetrating into the irregularities, the anchor portions 20 of the organic / inorganic hybrid coating film 10 that have hardened and penetrated into the irregularities exert an anchor effect, and the organic / inorganic hybrid coating film 10 adheres more firmly to the surface 12 of the substrate 11.

[0107] If the surface 12 of the substrate 11 is a smooth surface with almost no irregularities, the surface 12 may be roughened to form irregularities with an average roughness of approximately 1 to 500 μm on the surface 12 as a pretreatment before coating with the coating liquid 13. By performing the roughening treatment in this manner, the anchoring effect of the anchor portions 20 of the organic / inorganic hybrid coating film 10 can be obtained. After the roughening treatment, a cleaning treatment is performed using an air injection means such as an air gun to blow away metal powder, plastic powder, and the like that has occurred on the surface of the substrate. After the cleaning treatment, a predetermined time is allowed to pass to cause condensation, etc., to form on the surface 12 of the substrate 11, allowing naturally occurring moisture to adhere to the surface.

[0108] In this case, after roughening and cleaning the surface 12 of the substrate 11, moisture is actively applied to the surface 12, which has been roughened to form irregularities, using a moisture-applying means such as a sprayer, and then the coating liquid 13 is coated. This promotes a chemical reaction between the moisture applied to the surface 12 of the substrate 11 and the coating liquid 13 in contact with the surface 12. It is also possible to apply moisture using a moisture-applying means without roughening the surface 12 of the substrate 11. The irregularities initially formed on the surface 12 of the substrate 11 before being coated with the organic / inorganic hybrid coating film 10 made from organopolysiloxane and / or organic polysilazane are covered by the organic / inorganic hybrid coating film 10, resulting in a smoother surface 12 after coating than before coating.

[0109] As shown in FIG. 7, the organic / inorganic hybrid coating film 10 formed on the surface 12 of the substrate 11 has a porous structure, and therefore, silver ions 15a (Ag ＋ ), copper ion 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can move inside the organic / inorganic hybrid coating film 10, and the metal ions 15 are eluted from the organic / inorganic hybrid coating film 10.

[0110] In the organic / inorganic hybrid coating film 10, the content of glass particles 14 diffused and mixed therein is in the range of 0.1 vol% to 30 vol%, preferably in the range of 1 vol% to 10 vol%. If the content of glass particles 14 diffused and mixed in the organic / inorganic hybrid coating film 10 is less than 0.1 vol%, the content of glass particles 14 in the organic / inorganic hybrid coating film 10 is low, and the organic / inorganic hybrid coating film 10 cannot exhibit sufficient antibacterial, antiviral, antifungal, and deodorizing functions. If the content of glass particles 14 diffused and mixed in the organic / inorganic hybrid coating film 10 exceeds 30 vol%, the adhesion of the organic / inorganic hybrid coating film 10 to the surface 12 of the substrate 11 is significantly reduced, and a smooth organic / inorganic hybrid coating film 10 cannot be formed on the surface 12.

[0111] The organic / inorganic hybrid coating film 10 has excellent antibacterial, antiviral, antifungal, and deodorizing properties because the content of the glass particles 14 dispersed and mixed therein is within the above range. These properties are maintained for a long period of time. Furthermore, the coating film 10 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.

[0112] In the organic / inorganic hybrid coating film 10, the average particle diameter D of the glass particles 14 ５０ The average particle diameter D of the glass particles 14 in the organic / inorganic hybrid coating film 10 is 5 μm or less, preferably 3 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 10 toward the surface layer 16 (surface) of the organic / inorganic hybrid coating film 10, and the organic / inorganic hybrid coating film 10 cannot exhibit sufficient antibacterial, antiviral, antifungal, and deodorizing functions. Furthermore, the adhesion of the organic / inorganic hybrid coating film 10 to the surface 12 of the substrate 11 is significantly reduced, and a smooth organic / inorganic hybrid coating film 10 cannot be formed on the surface 12. The organic / inorganic hybrid coating film 10 has an average particle size D ５０ Since the viscosity of the coating is within the above range, the coating has excellent antibacterial, antiviral, antifungal and deodorizing functions, and these 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.

[0113] In the organic / inorganic hybrid coating film 10 (coating film), the glass particles 15 have electronic conductivity, so that a large amount of silver ions 15a (Ag ＋) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can be introduced, and the organic / inorganic hybrid coating film 10 can contain a large amount of metal ions 15 such as silver ions 15a, copper ions 15b, and zinc ions 15c.

[0114] The organic / inorganic hybrid coating film 10 (coating film) contains a large amount of silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) metal ions 15, it has excellent antibacterial, antiviral, antifungal and deodorizing functions, and can reliably kill germs, various viruses and various molds, and can reliably remove unpleasant odors.

[0115] The organic / inorganic hybrid coating film 10 (coating film) is not limited to a specific object to be coated, and can impart excellent antibacterial, antiviral, antifungal, and deodorizing functions to the surface 12 of any substrate 11 (object to be coated). It also contains a large amount of silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ By containing the metal ions 15, the antibacterial, antiviral, antifungal and deodorizing functions can be maintained for a long period of time.

[0116] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 14 are diffused and mixed is formed (deposited) on medical clothing (masks, white coats, protective clothing, gloves, etc.) or medical bedding (futons, pillowcases, curtains, patient amenities, etc.), even if various germs, various viruses, and various molds adhere to the medical clothing or medical bedding, the various germs, various viruses, and various molds are absorbed by silver ions 15a (Ag ions) diffused in the organic / inorganic hybrid coating film 10. ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋) can be killed by the metal ions 15, which can prevent the occurrence and proliferation of germs, various viruses, and various molds in medical clothing and medical bedding, and can also prevent the occurrence of unpleasant odors in medical clothing.

[0117] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 14 are diffused and mixed is formed (deposited) on medical instruments (scissors, scalpels, other equipment, etc.) or hospital facilities (handrails, doorknobs, walls, floors, elevators, escalators, etc.), even if germs, various viruses, and various molds adhere to the medical instruments and enter the hospital facilities, the germs, various viruses, and various molds are converted into silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can be killed by the metal ions 15, which can prevent the occurrence and proliferation of germs, various viruses, and various molds in medical instruments and hospital facilities, and can prevent biohazards in medical institutions as well as the occurrence of unpleasant odors in medical institutions.

[0118] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 14 are diffused and mixed is formed (deposited) on a means of transportation (train, bus, airplane, ship, vehicle, etc.), even if various germs, various viruses, and various molds enter the means of transportation, the various germs, various viruses, and various molds are converted into silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can be killed by the metal ions 15, which can prevent the generation and proliferation of germs, various viruses, and various molds in the means of transportation, and can prevent infection with germs and various viruses in the means of transportation.

[0119] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 14 are diffused and mixed is formed (formed) on clothing (underwear, T-shirts, socks, sportswear, diapers, etc.), even if various bacteria, various viruses, and various molds adhere to the clothing, the various bacteria, various viruses, and various molds are absorbed by the silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can be killed by the metal ions 15, which can prevent the occurrence and proliferation of germs, various viruses, and various molds on the clothes, as well as prevent the occurrence of unpleasant odors on the clothes.

[0120] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 10 are diffused and mixed is formed (deposited) on a pet product (pet toilet, pet cage, etc.), even if various bacteria, various viruses, and various molds adhere to the pet product, the various bacteria, various viruses, and various molds are absorbed by the silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋ ) can be killed by the metal ions 15, which can prevent the occurrence and proliferation of germs, various viruses, and various molds in pet supplies, and can also prevent infection of pets with germs and various viruses.

[0121] When the organic / inorganic hybrid coating film 10 (coating film) in which the glass particles 14 are diffused and mixed is formed (deposited) on sanitary products (kitchenware, toiletware, bathware, washbasin, etc.) or food products (food trays, kitchenware, tableware, etc.), even if various germs, various viruses, and various molds adhere to the sanitary products or food products, the various germs, various viruses, and various molds are removed by silver ions 15a (Ag ＋ ) and copper ions 15b (Cu ２＋ ), zinc ion 15c (Zn ２＋) can be killed by the metal ions 15, which can prevent the occurrence and proliferation of germs, various viruses, and various molds in sanitary products and food products, and allows the sanitary products and food products to be used hygienically.

[0122] FIG. 9 is a diagram showing the relationship between time and the antiviral activity value in organic / inorganic hybrid coating film 10 formed from coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and glass particles 14 mixed therein, and FIG. 10 is a graph showing the change in the antiviral activity value over time after coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and glass particles 14 mixed therein is applied to surface 12 of substrate 11.

[0123] A coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and glass particles 14 mixed therein was applied to a surface 12 of an acrylic substrate 11 (base material 11) (50 × 50 × 5 mm), and an organic / inorganic hybrid coating film 10 was formed on the surface 12 of the acrylic substrate 11. As described above, the film formation conditions are as follows: 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 (base material 11) is left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating; or after coating the surface 12 of the acrylic substrate 11 (base material 11) with the coating liquid 13, the surface 12 of the acrylic substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating the surface 12 of the acrylic substrate 11 with ultraviolet rays; or after coating the surface 12 of the acrylic substrate 11 (base material 11) with the coating liquid 13, the surface 12 of the acrylic substrate 11 is heated to a temperature of less than 400° C. by irradiating the surface 12 of the acrylic substrate 11 with infrared rays while irradiating it with ultraviolet rays, and then the surface 12 of the acrylic substrate 11 is left for a predetermined time (24 hours or more).

[0124] After a coating liquid 13 is applied to a surface 12 of an acrylic substrate 11, an organic / inorganic hybrid coating film 10 is formed (deposited) on the surface 12. The organic / inorganic hybrid coating film 10 formed (deposited) on the surface 12 of the acrylic substrate 11 (base material 11) contains 15% by volume of glass particles 14, and the average particle diameter D ５０is 5 μm or less.

[0125] After coating the acrylic substrate 11 with the coating liquid 13, an enveloped virus (influenza virus (or novel coronavirus, herpes virus, rubella virus)) was inoculated onto the surface 12 of the acrylic substrate 11, and the antiviral activity value against the enveloped virus (influenza virus) was measured over time. The antiviral activity value against the enveloped virus (influenza virus) was measured at the following times: 0.5 hours after inoculation of the acrylic substrate 11 with the enveloped virus, 2 hours after inoculation of the acrylic substrate 11 with the enveloped virus, 5 hours after inoculation of the acrylic substrate 11 with the enveloped virus, and 24 hours after inoculation of the acrylic substrate 11 with the enveloped virus.

[0126] After the acrylic substrate 11 was coated with the coating liquid 13, a non-enveloped virus (feline calicivirus (or rotavirus, norovirus)) was inoculated onto the surface 12 of the acrylic substrate 11, and the antiviral activity value against the non-enveloped virus (feline calicivirus) was measured over time. The antiviral activity value against the non-enveloped virus was measured at the following times: 0.5 hours after inoculation of the acrylic substrate 11 with the non-enveloped virus, 2 hours after inoculation of the acrylic substrate 11 with the non-enveloped virus, 5 hours after inoculation of the acrylic substrate 11 with the non-enveloped virus, and 24 hours after inoculation of the acrylic substrate 11 with the non-enveloped virus.

[0127] As shown in Figures 7 and 8, for enveloped viruses (influenza virus, novel coronavirus, herpes virus, rubella virus), the antiviral activity value was 0 0.5 hours after the acrylic substrate 11 was coated with the coating liquid 13, the antiviral activity value was 0.1 2 hours after the acrylic substrate 11 was coated with the coating liquid 13, and the antiviral activity value was 0.4 5 hours after the acrylic substrate 11 was coated with the coating liquid 13, meaning that the antiviral activity (antiviral function) was hardly expressed until 5 hours after the acrylic substrate 11 was coated with the coating liquid 13.

[0128] However, 24 hours after the coating liquid 13 was applied to the acrylic substrate 11, the antiviral activity increased to 2.2. An antiviral function is recognized when the antiviral activity is 2 or higher. As is clear from Figures 9 and 10, the organic / inorganic hybrid coating film 10 containing the glass particles 14 described above had excellent antiviral function against enveloped viruses 24 hours after the coating liquid 13 was applied to the acrylic substrate 11, and it was found that it was able to reliably kill various enveloped viruses.

[0129] Furthermore, with respect to non-enveloped viruses (feline calicivirus, rotavirus, norovirus), the antiviral activity value was 0 0.5 hours after the acrylic substrate 11 was coated with the coating liquid 13, the antiviral activity value was 0.1 2 hours after the acrylic substrate 11 was coated with the coating liquid 13, and the antiviral activity value was 0.3 5 hours after the acrylic substrate 11 was coated with the coating liquid 13, meaning that the antiviral activity (antiviral function) was hardly exhibited until 5 hours after the acrylic substrate 11 was coated with the coating liquid 13.

[0130] However, the antiviral activity increased to 4.5 24 hours after the coating liquid was applied to the acrylic substrate 11. As is clear from Figures 9 and 10, the organic / inorganic hybrid coating film 10 containing the above-described glass particles 14 had excellent antiviral function against non-enveloped viruses 24 hours after the coating liquid 13 was applied to the acrylic substrate 11, and it was found that it was able to reliably kill various non-enveloped viruses.

[0131] FIG. 11 is a diagram showing the antibacterial activity value of an organic / inorganic hybrid coating film 10 formed from a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and glass particles 14 mixed therein, and FIG. 12 is a graph showing the relationship between the content of glass particles 14 in the organic / inorganic hybrid coating film 10 and the antibacterial activity value.

[0132] In the evaluation of the antibacterial activity values ​​shown in Figures 11 and 12, an acrylic substrate 11(1) (substrate 11) (50 x 50 x 5 mm) on which an organic / inorganic hybrid coating film 10 was not formed (film-formed), an acrylic substrate 11 (substrate 11) (50 x 50 x 5 mm) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 3% by volume of glass particles 14 was applied to a surface 12 of the acrylic substrate 11 (substrate 11) (50 x 50 x 5 mm) and an organic / inorganic hybrid coating film 10 (containing 3% by volume of glass particles 14) was formed on the surface 12 of the acrylic substrate 11, and an acrylic substrate 11(2) on which a coating liquid 13 containing organopolysiloxane (siloxane-based solution) as the main component and 5% by volume of glass particles 14 was applied to a surface 12 of the acrylic substrate 11 (substrate 11) (50 x 50 x 5 mm) and an organic / inorganic hybrid coating film 10 (containing 3% by volume of glass particles 14) was formed on the surface 12 of the acrylic substrate 11 was also evaluated. The coating liquid 13 was applied to the surface 12 of an acrylic substrate 11 (substrate 11) (50 × 50 × 5 mm) to form an organic / inorganic hybrid coating film 10 (containing 5% by volume of glass particles 14) on the surface 12 of the acrylic substrate 11, thereby preparing an acrylic substrate 11(3). The coating liquid 13, which was mainly composed of organopolysiloxane (siloxane-based solution) mixed with 7% by volume of glass particles 14, was applied to the surface 12 of an acrylic substrate 11 (substrate 11) (50 × 50 × 5 mm) to form an organic / inorganic hybrid coating film 10 (containing 7% by volume of glass particles 14) on the surface 12 of the acrylic substrate 11, thereby preparing an acrylic substrate 11(4). ５０ is 5 μm or less.

[0133] As described above, the conditions for forming the organic / inorganic hybrid coating film 10 on the acrylic substrate 11(2) to the acrylic substrate 11(4) are as follows: after the coating liquid 13 is applied to the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) (substrate 11), the surfaces 12 of the acrylic substrate 11(2) to the acrylic substrate 11(4) (substrate 11) are left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating; or, After coating with the liquid 13, the surfaces 12 of the acrylic substrates 11(2) to 11(4) are irradiated with ultraviolet light while being left at room temperature (normal temperature) for a predetermined time (24 hours or more), or 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 irradiated with infrared light while being irradiated with ultraviolet light to heat the temperature of the surfaces 12 of the acrylic substrates 11 to less than 400°C, and are then left for a predetermined time (24 hours or more).

[0134] Twenty-four hours have passed since the coating liquid 13 was applied to the surfaces 12 of the acrylic substrates 11 (2) to 11 (4), and an organic / inorganic hybrid coating film 10 has been formed (deposited) on the surfaces 12. The organic / inorganic hybrid coating film 10 deposited on the surface 12 of the acrylic substrate 11 (2) (base material 11) contains 3% by volume of glass particles 14, and the average particle size D ５０ The organic / inorganic hybrid coating film 10 formed on the surface 12 of the acrylic substrate 11(3) (base material 11) has a glass particle 14 content of 5% by volume, and the average particle diameter D ５０ The organic / inorganic hybrid coating film 10 formed on the surface 12 of the acrylic substrate 11(4) (base material 11) has a glass particle 14 content of 7% by volume, and the average particle diameter D ５０After forming the organic / inorganic hybrid coating film 10 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.

[0135] As shown in Figures 11 and 12, 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).

[0136] An acrylic substrate 11(2) on whose surface 12 an organic / inorganic hybrid coating film 10 made from a coating liquid 13 containing 3 volume % of 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.

[0137] An acrylic substrate 11 (3) on whose surface 12 an organic / inorganic hybrid coating film 10 made from a coating liquid 13 containing 5% by volume of 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.

[0138] An acrylic substrate 11(4) on whose surface 12 an organic / inorganic hybrid coating film 10 made from a coating liquid 13 containing 7% by volume of 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.

[0139] As is clear from FIGS. 11 and 12, it was found that the organic / inorganic hybrid coating film 10 containing the above-described 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 can reliably kill Staphylococcus aureus and Escherichia coli.

[0140] FIG. 13 is a graph showing the evaluation of the mildew resistance of an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein.

[0141] In the mold resistance evaluation shown in FIG. 13, an acrylic substrate (1) (base material) (50×50×5 mm) on which no organic / inorganic hybrid coating film was formed (film-formed), an acrylic substrate (2) on which a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and 3% by volume of glass particles was applied to the surface of the acrylic substrate (base material) (50×50×5 mm) and an organic / inorganic hybrid coating film was formed on the surface of the acrylic substrate, and an acrylic substrate (3) on which a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and 5% by volume of glass particles was applied to the surface of the acrylic substrate (base material) (50×50×5 mm) and an organic / inorganic hybrid coating film was formed on the surface of the acrylic substrate. An acrylic substrate (3) was prepared by applying a coating liquid containing 7% by volume of glass particles to the surface of an acrylic substrate (base material) (50×50×5 mm) to form an organic / inorganic hybrid coating film on the surface of the acrylic substrate, and an acrylic substrate (4) was prepared by applying a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and 7% by volume of glass particles to the surface of an acrylic substrate (base material) (50×50×5 mm) to form an organic / inorganic hybrid coating film on the surface of the acrylic substrate. ５０ is 5 μm or less.

[0142] As described above, the film formation conditions for the acrylic substrate (2) to the acrylic substrate (4) are as follows: after coating the surfaces of the acrylic substrate (2) to the acrylic substrate (4) (substrate) with a coating liquid, the surfaces of the acrylic substrate (2) to the acrylic substrate (4) (substrate) are left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating; or after coating the surfaces of the acrylic substrate (2) to the acrylic substrate (4) (substrate) with a coating liquid, the surfaces of the acrylic substrate (2) to the acrylic substrate (4) are left at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating them with ultraviolet light; or after coating the surfaces of the acrylic substrate (2) to the acrylic substrate (4) (substrate) with a coating liquid, the surfaces of the acrylic substrate (2) to the acrylic substrate (4) are heated to a temperature of less than 400°C by irradiating them with infrared light while irradiating them with ultraviolet light, and then left for a predetermined time (24 hours or more).

[0143] Twenty-four hours have passed since the coating liquid was applied to the surfaces of the acrylic substrates (2) to (4), and an organic / inorganic hybrid coating film has been formed (deposited) on the surfaces. The organic / inorganic hybrid coating film deposited on the surface of the acrylic substrate (2) (base material) contains 3% by volume of glass particles 14, and the average particle diameter D of the glass particles 14 is 100 μm. ５０ The organic / inorganic hybrid coating film formed on the surface of the acrylic substrate (3) (base material) has a glass particle 14 content of 5% by volume, and the average particle diameter D of the glass particles 14 is 5 μm or less. ５０ The organic / inorganic hybrid coating film formed on the surface of the acrylic substrate (4) (base material) has a glass particle 14 content of 7% by volume, and the average particle diameter D ５０ is 5 μm or less.

[0144] After forming an organic / inorganic hybrid coating film on the surfaces of acrylic substrates (2) to (4), spores of a five-species mixture of fungi, namely, Aspergillus niger NBRC 105649, Penicillium pinophilum NBRC 100533, Paecilomyces variotii NBRC 107725, Trichoderna virens NBRC 6355, and Chaetomium globosum NBRC 6347, were inoculated onto the surfaces of acrylic substrates (1) to (4). After culturing the fungi for four weeks, the fungal resistance of acrylic substrates (1) to (4) was measured. The culture conditions were as follows: acrylic substrates (1) to (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.

[0145] 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).

[0146] The acrylic substrate (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 (2) placed on the mineral-glucose-containing agar medium in the second container, the acrylic substrate (3) placed on the mineral-glucose-containing agar medium in the third container, and the acrylic substrate (4) placed on the mineral-glucose-containing agar medium in the fourth container were evaluated as (2), demonstrating mold resistance in acrylic substrates (2) to (4). As is clear from Figure 13, the organic / inorganic hybrid coating film containing the glass particles described above possesses excellent mold-proofing properties and can reliably kill various types of mold.

[0147] 14 is a diagram showing an evaluation of the deodorizing performance of an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as a main component and glass particles mixed therein. In the evaluation of deodorizing performance shown in FIG. 14, the deodorizing performance was evaluated for ammonia, which is the source of sweat odor, aging odor, excrement odor, cigarette smoke odor, and food waste odor; acetic acid, which is the source of sweat odor, aging odor, excrement odor, and cigarette smoke odor; isovaleric acid, which is the source of sweat odor and aging odor; inenal, which is the source of aging odor; methyl mercaptan, which is the source of excrement odor and food waste odor; hydrogen sulfide, which is the source of excrement odor, cigarette smoke odor, and food waste odor; indole, which is the source of excrement odor; pyridine, which is the source of cigarette smoke odor; and trimethylamine, which is the source of food waste odor.

[0148] In the evaluation of deodorizing performance shown in Fig. 14, an aggregate of polyester fibers (1) (substrate) on which no organic / inorganic hybrid coating film was formed (film-formed) and an aggregate of polyester fibers (2) (substrate) in which the polyester fibers (substrate) were impregnated with a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and 7% by volume of glass particles mixed therein, and the organic / inorganic hybrid coating film was impregnated into the polyester fibers were prepared. ５０ is 5 μm or less.

[0149] The film formation conditions for the polyester fiber (2) are as follows: after impregnating the polyester fiber (2) (substrate) with a coating liquid, leave it at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating the surface of the polyester fiber (2) (substrate), as described above; or after impregnating the polyester fiber (2) (substrate) with a coating liquid, leave it at room temperature (normal temperature) for a predetermined time (24 hours or more) while irradiating the surface of the polyester fiber (2) with ultraviolet light; or after impregnating the polyester fiber (2) (substrate) with a coating liquid, heat the surface of the polyester fiber (2) to a temperature of less than 400°C by irradiating it with infrared light while irradiating it with ultraviolet light, and leave it for a predetermined time (24 hours or more).

[0150] The polyester fiber (2) has been impregnated with the coating liquid into an acrylic substrate (substrate) for 24 hours, and an organic / inorganic hybrid coating film has been formed (deposited) on the surface. The organic / inorganic hybrid coating film deposited on the surface of the polyester fiber (2) (substrate) has a glass particle content of 7% by volume, and the average particle diameter D ５０ The aggregate of polyester fibers (1) (substrate) and the gas to be measured were placed in a first sampling bag, and the aggregate of polyester fibers (2) (substrate) and the gas to be measured were placed in a second sampling bag. After leaving them for 2 hours, the gas concentrations in the sampling bags were measured with a detector tube, and the reduction rates were calculated.

[0151] The first sampling bag containing an aggregate of polyester fibers (1) had a zero reduction in gas concentrations (ammonia, acetic acid, isovaleric acid, inenal, methyl mercaptan, hydrogen sulfide, indole, pyridine, and trimethylamine) after being left standing for two hours. In contrast, the first sampling bag containing an aggregate of polyester fibers (2) had a 29% reduction in ammonia, a 64% reduction in acetic acid, a 54% reduction in isovaleric acid, a 34% reduction in inenal, a 25% reduction in methyl mercaptan, a 30% reduction in hydrogen sulfide, a 92% reduction in indole, a 9% reduction in pyridine, and a 13% reduction in trimethylamine. With polyester fibers (2), the concentrations of all gases were reduced. As is clear from FIG. 14 , the organic / inorganic hybrid coating film containing the glass particles described above was found to have an excellent deodorizing effect.

[0152] FIG. 1 is an enlarged cross-sectional image showing an organic / inorganic hybrid coating film formed on the surface of a substrate. FIG. 1 is a cross-sectional view illustrating, in time sequence, the mechanism by which an organic / inorganic hybrid coating film is formed from a coating liquid on the surface of a substrate to which the coating liquid has been applied. FIG. 1 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. 2 is a cross-sectional view schematically showing an example of a state after an organic / inorganic hybrid coating film has been formed on the surface of a substrate. FIG. 2 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. 3 is a cross-sectional view schematically showing another example of a state after an organic / inorganic hybrid coating film has been formed on the surface of a substrate. FIG. 3 is an image showing an example of the structure of an organic / inorganic hybrid coating film. FIG. 4 is an image showing an example of the state of metal ions in an organic / inorganic hybrid coating film. FIG. 4 is a graph showing the relationship between time and antiviral activity value for an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein. Graph showing the change in antiviral activity value over time after a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein is applied to the surface of a substrate. FIG. 1 shows the antibacterial activity value of an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein. Graph showing the relationship between the glass particle content and antibacterial activity value of an organic / inorganic hybrid coating film. FIG. 2 shows an evaluation of the mold resistance of an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein. FIG. 3 shows an evaluation of the deodorizing performance of an organic / inorganic hybrid coating film formed from a coating liquid containing organopolysiloxane (siloxane-based solution) as the main component and glass particles mixed therein.

[0153] 10 Organic / inorganic hybrid coating film (coating film) 11 Substrate 12 Surface (front surface, back surface) (contact surface) 13 Coating liquid (organic and inorganic hybrid polymer) 14 Glass particles 15 Metal ions 15a Silver ions (Ag ＋ ) 15b Copper ion (Cu ２＋ ) 15c Zinc ion (Zn ２＋ ) 16 Surface layer 17 Covering layer 18 Back layer 19 Intermediate layer 20 Anchor portion

Claims

1. A coating film in which glass particles are dispersed and mixed, ２ ), wherein the glass particles are silver ions (Ag ＋ ), copper ions (Cu ２＋ ), zinc ion (Zn ２＋ ) ) ) ) ).

2. The glass particles dispersed and mixed in the coating film react with the silver ions (Ag ＋ ) and the copper ion (Cu ２＋ ) and the zinc ion (Zn ２＋ ) and the silver ion (Ag ＋ ) and the copper ion (Cu ２＋ ) and the zinc ion (Zn ２＋ 2. The coating film according to claim 1, which is a conductive glass containing at least one of:

3. The glass particles dispersed and mixed in the coating film react with the silver ions (Ag ＋ ) only, the conductive glass containing copper ions (Cu ２＋ ), conductive glass containing only zinc ions (Zn ２＋ 2. The coating film according to claim 1, which is a conductive glass containing only .

4. The glass particles dispersed and mixed in the coating film react with the silver ions (Ag ＋ ) and the copper ion (Cu ２＋ ) and the conductive glass containing only zinc ions (Zn ２＋ ) and a conductive glass containing only silver ions (Ag ＋ 4. The coating film according to claim 3, which is a conductive glass containing only .

5. The glass particles are made of vanadium oxide (V ２ O ５ ), tungsten oxide (WO ３ ), molybdenum oxide (MoO ３ At least one of phosphorus oxide (P ２ O ５ 4. The coating film according to claim 2 or 3, comprising a glass based on 6. The glass particles are ＋ Vanadium oxide (V ２ O ５ ) -phosphorus oxide (P ２ O ５ 6. The coating film according to claim 5, which is a glass of the type SiO2.

7. The coating film according to claim 6, wherein the glass particles further contain barium oxide (BaO).

8. The coating film according to claim 7, wherein the content of the glass particles dispersed and mixed in the coating film is 0.1% by volume or more and 30% by volume or less.

9. The coating film according to claim 8, wherein the content of the glass particles dispersed and mixed in the coating film is 0.2 volume % or more and 10 volume % or less.

10. Average particle size D of the glass particles ５０ The coating film according to claim 9, wherein the thickness is 5 μm or less.

11. Average particle size D of the glass particles ５０ The coating film according to claim 10, wherein the thickness is 3 μm or less.

12. The coating film according to claim 11, in which a coating liquid for forming the coating film is coated on the surface of a specified substrate, and then metal ions of the glass particles mixed in the coating liquid diffuse into the interior of the coating film.

13. The coating film according to claim 12, wherein metal ions of the glass particles mixed in the coating liquid diffuse inside the coating film and move to the surface of the coating film.

14. The coating film according to claim 13, wherein the original coating liquid (starting material of the coating film) is a siloxane-based solution or a silica sol-based solution, and the glass particles are mixed into the siloxane-based solution or the silica sol-based solution.

15. The coating film according to claim 14, which is a glass-based organic / inorganic hybrid coating film.

Images