Water- and oil-repellent member having antibacterial, antifungal, and antiviral properties, method for producing the water- and oil-repellent member, and article

Abstract

Provided is a water-repellent, oil-repellent member having anti-microbial, anti-mold, and anti-viral properties, the water-repellent, oil-repellent member having a primer layer as a first layer on at least one surface of a substrate, and furthermore having a water-repellent, oil-repellent layer as a second layer on the outer surface of the primer layer, wherein: the primer layer comprises a layer that has a film thickness of 10-5,000 nm and that contains a silicon-compound-based binder together with metal microparticles and / or metal oxide microparticles having anti-microbial, anti-mold, and anti-viral properties; and the water-repellent, oil-repellent layer comprises a layer that has a film thickness of 0.5-50 nm and that contains, as a principal component, a cured product of a fluorine-containing organic silicon compound. This water-repellent, oil-repellent member has exceptional production properties, makes it possible to maintain a hygienic, excellent anti-fouling surface over an extended period, and also has exceptional water repellency, oil repellency, and anti-microbial, anti-mold, and anti-viral properties.

Description

Technical Field

[0001] The present invention relates to a water and oil repellent member having antibacterial, antifungal, antiviral properties and water and oil repellency, and a method for manufacturing the water and oil repellent member. Specifically, the present invention relates to a water and oil repellent member in which an antibacterial, antifungal, antiviral layer is formed between a base material and a water and oil repellent layer, a method for manufacturing the water and oil repellent member, and an article.

Background Art

[0002] In order to improve the appearance and visibility of articles, the demand for technologies that make it difficult for dirt to adhere and technologies that make it easy to remove dirt has been increasing. In particular, the surfaces of spectacle lenses, smartphones, wearable terminals, car navigation systems, housings of electronic devices, kitchen countertops, and the interiors of transportation equipment are likely to be contaminated with sebum and oil stains, so it is desirable to provide a water and oil repellent layer. On the other hand, from the perspective of preventing the spread of viruses and public health, there has also been a growing demand for providing a layer having antibacterial, antifungal, and antiviral properties. However, it is difficult to simply achieve both water and oil repellency and antibacterial, antifungal, and antiviral properties.

[0003] In order to solve such problems, Japanese Patent Application Laid-Open No. 2017-513800 (Patent Document 1) discloses a technique of applying a water and oil repellent to a base material such as glass having antibacterial properties. Specifically, it is solved by incorporating Ag + ions into the base material by an ion exchange method.

[0004] However, the antibacterial base materials that can be prepared by the method proposed in Patent Document 1 are limited, and the scope of application is limited. In addition, since it is necessary to manufacture an antibacterial base material, there are still problems in terms of productivity and production cost.

[0005] On the other hand, Japanese Patent Application Laid-Open No. 2018-521199 (Patent Document 2) discloses a technique in which an antibacterial primer is applied to the surface of a base material such as glass by a vacuum deposition method, and then a water and oil repellent is treated by a vacuum deposition method. It is characterized in that an organic substance is used as an antibacterial substance vapor-deposited simultaneously with a silane coupling agent as a primer component.

[0006] However, the primer proposed in Patent Document 2 is processed by a vacuum evaporation method, so the substrates that can be processed are limited, and its scope of application is limited in terms of productivity and production cost. In addition, organic antibacterial agents often can only exert effects on specific microorganisms, and their usage methods are limited. Furthermore, problems such as the easy emergence of resistant bacteria, poor heat resistance, excellent immediate effectiveness but low persistence, and concerns about the impact on the human body and the environment have been increasing, and caution is required when using in places where people can touch. In addition, as prior arts related to the present invention, the following documents are cited together with the above-mentioned documents.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Patent Document 12

[0008] [Non-Patent Document 1] Miyano, Iron and Steel, 93(2007)1, 57-65 [Non-Patent Document 2] H. Kawakami, ISIJ Intern., 48(2008)9, 1299-1304 [Summary of the Invention] [Problems to be Solved by the Invention]

[0009] The present invention has been made in view of the above circumstances, and an object thereof is to provide a water / oil repellent member excellent in antibacterial, antifungal, and antiviral properties that is excellent in productivity and can maintain a clean and good antifouling surface over a long period of time, a method for producing a water / oil repellent member excellent in antibacterial, antifungal, and antiviral properties for various base materials, and an article. [Means for Solving the Problems]

[0010] As a result of intensive studies to achieve the above object, the present inventors have found that a liquid containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and a dispersion medium is wet-coated on at least one surface of a substrate, and the dispersion medium in the liquid is removed to form and laminate a primer layer containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties on at least one surface of the substrate. A method including a step of wet-coating a solution containing a fluorine-containing organosilicon compound or dry-coating the fluorine-containing organosilicon compound on the outer surface of the primer layer, and a step of curing the fluorine-containing organosilicon compound to form and laminate a water / oil repellent layer on the outer surface of the primer layer. A water / oil repellent member having a primer layer as a first layer on at least one surface of a substrate, and further having a water / oil repellent layer as a second layer on the outer surface of the primer layer, wherein the primer layer is composed of a layer having a film thickness of 10 to 5,000 nm containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and the water / oil repellent layer is composed of a layer having a film thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organosilicon compound. The water / oil repellent member can stably and simply provide a water / oil repellent coating excellent in wear resistance and antibacterial, antifungal, and antiviral properties to various substrates. Furthermore, it has been found that the primer layer and the water / oil repellent layer can be coated even in a room temperature (25°C) process, leading to the completion of the present invention.

[0011] That is, the present invention provides a water / oil repellent member having antibacterial, antifungal, and antiviral properties, a method for producing the water / oil repellent member, and an article as described below. 〔1〕 A water / oil repellent member having a primer layer as a first layer on at least one surface of a substrate, and further having a water / oil repellent layer as a second layer on the outer surface of the primer layer, wherein the primer layer contains a silicon compound-based binder and has antibacterial, antifungal, and antiviral properties having an average particle diameter of 1 to 1,000 nm metal fine particles and / or having an average particle diameter of 3 to 100 nmIt consists of a layer with a thickness of 10 to 5,000 nm containing metal oxide fine particles, and the water- and oil-repellent layer consists of a layer with a thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organosilicon compound. and the content of the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties in the primer layer is 1 to 99% by mass based on the entire primer layer A water- and oil-repellent member having antibacterial, antifungal, and antiviral properties. 〔2〕 The water- and oil-repellent member according to 〔1〕, wherein the silicon compound-based binder is a silica-based or siloxane-based silicon compound containing a silanol group. 〔3〕 The water- and oil-repellent member according to 〔1〕 or 〔2〕, wherein the metal fine particles having antibacterial, antifungal, and antiviral properties are fine particles of at least one metal selected from silver, copper, and zinc. 〔4〕 The water- and oil-repellent member according to any one of 〔1〕 to 〔3〕, wherein the metal oxide fine particles having antibacterial, antifungal, and antiviral properties are fine particles of titanium oxide. 〔5〕 The fluorine-containing organosilicon compound is a fluorine-containing organosilane compound, a fluorine-containing organosiloxane compound, or a fluorine-containing polysilazane compound having at least one hydrolyzable silyl group at at least one molecular chain end, and the hydrolyzable silyl group is a silyl group having a group selected from an alkoxy group having 1 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and an amino group. The water- and oil-repellent member according to any one of 〔1〕 to 〔4〕. 〔6〕 The fluorine-containing organosilicon compound has -C d F 2d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -C d F 2d-(wherein p, q, r, s, and t are each independently an integer from 0 to 200, and p + q + r + s + t = 3 to 500, and each repeating unit shown in the parentheses to which p, q, r, s, and t are attached may be randomly combined, and d is independently an integer from 0 to 8 for each unit, and the unit may be linear or branched.) having a divalent linear perfluorooxyalkylene polymer residue, and having at least one hydrolyzable silyl group at at least one molecular chain end, a fluorooxyalkylene group-containing organosilane compound or a fluorooxyalkylene group-containing organosiloxane compound, or a fluorooxyalkylene group-containing polysilazane compound having the above divalent linear perfluorooxyalkylene polymer residue, which is the water and oil repellent member according to any one of [1] to [5]. [7] The fluorine-containing organosilicon compound is at least one selected from a fluorooxyalkylene group-containing organosilane compound or a fluorooxyalkylene group-containing organosiloxane compound represented by the following general formulas (1) to (5) and a fluorooxyalkylene group-containing polysilazane compound represented by the following general composition formula (6), which is the water and oil repellent member according to any one of [1] to [6]. (A-Rf) α ZW β (1) Rf(ZW β )2(2) Z’(Rf-ZW β ) γ (3) [wherein, Rf is independently -C d F 2d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -C d F 2d- is a divalent linear perfluorooxyalkylene polymer residue represented by, where p, q, r, s, and t are each independently an integer from 0 to 200, and p + q + r + s + t = 3 to 500. Each repeating unit shown within the parentheses to which p, q, r, s, and t are attached may be randomly bonded. d is independently an integer from 0 to 8 for each unit, and the unit may be linear or branched. A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF3 group, -CF2H group, or -CH2F group at the terminal. Z and Z' are each independently a single bond or a divalent to octavalent organic group that may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom and may be fluorine-substituted. W is independently a monovalent organic group having a hydrolyzable group at the terminal. α and β are each independently an integer from 1 to 7, and α + β = 2 to 8. γ is an integer from 2 to 8. A-Rf-Q-(Y) δ -B (4) Rf(Q-(Y) δ -B)2(5) (In the formula, Rf and A are the same as described above. Q is independently a single bond or a divalent organic group. δ is independently an integer from 1 to 10. Y is independently a divalent organic group having a hydrolyzable group. B is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.) A-Rf-Q-Si(NH) 3 / 2 (6) (In the formula, Rf, A, and Q are the same as described above.) 〔8〕 The fluorooxyalkylene group-containing organosilane compound, fluorooxyalkylene group-containing organosiloxane compound, and fluorooxyalkylene group-containing polysilazane compound represented by formulas (1) to (6) are the water- and oil-repellent members described in 〔7〕 shown below.

Chemical formula

Chemical formula

Chemical formula

[10] The silicon compound-based binder is an emulsion obtained by removing the dispersion medium from any one of colloidal silica, a hydrolyzed and partially condensed product solution of tetraalkoxysilane, a hydrolyzed and partially condensed product of organoalkoxysilane or a hydrolyzed and partially condensed product of alkoxysiloxane, an emulsion of organosilsesquioxane resin, an emulsion of a copolymer resin containing triorganosiloxy units and SiO 2 units, an emulsion of a silicone resin-acrylic resin copolymer, and an emulsion of a silicone resin-urethane resin copolymer. The water- and oil-repellent member according to [1]. 11 An article using the water- and oil-repellent member according to any one of [1] to [9]. 12 ​​​​An article which is a building member, a kitchen member, furniture, an electronic device, a transportation device, or sanitary ware 11 〕 The article described in 〔 13 〕 On at least one surface of the base material, a liquid containing a silicon compound binder, metal fine particles having antibacterial, antifungal, and antiviral properties and / or having an average particle diameter of 1 to 1,000 nm metal oxide fine particles and a dispersion medium is wet-coated, and the dispersion medium in the liquid is removed to form and laminate a primer layer containing a silicon compound binder, metal fine particles having antibacterial, antifungal, and antiviral properties and / or having an average particle diameter of 3 to 100 nm metal oxide fine particles on at least one surface of the base material. A method for producing a water / oil repellent member according to any one of [1] to [9], comprising a step of wet-coating a solution containing a fluorine-containing organosilicon compound or dry-coating the fluorine-containing organosilicon compound on the outer surface of the primer layer, and a step of curing the fluorine-containing organosilicon compound to form and laminate a water / oil repellent layer on the outer surface of the primer layer. having an average particle diameter of 1 to 1,000 nm metal fine particles and / or having an average particle diameter of 3 to 100 nm containing metal oxide fine particles and the content of the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties is 1 to 99% by mass based on the entire primer layer 〔14〕 The silicon compound-based binder contained in the liquid used in the wet coating step is an emulsion of colloidal silica, a hydrolyzed and partially condensed product solution of tetraalkoxysilane, a hydrolyzed and partially condensed product of organoalkoxysilane or a hydrolyzed and partially condensed product of alkoxysiloxane, an emulsion of organosilsesquioxane resin, an emulsion of a copolymer resin containing triorganosiloxy units and SiO 2 units, an emulsion of a silicone resin-acrylic resin copolymer, or an emulsion of a silicone resin-urethane resin copolymer. The method for producing a water- and oil-repellent member according to

[13] .

[0012] In the present invention, the "linear perfluorooxyalkylene polymer residue" means that divalent fluorooxyalkylene repeating units constituting the perfluorooxyalkylene structure of the main chain are linearly linked, and each divalent fluorooxyalkylene unit itself may be a fluorooxyalkylene unit having a branched structure such as -[CF2CF(CF3)O]-.

Advantages of the Invention

[0013] According to the present invention, it is possible to form a water / oil repellent member having a surface that combines antibacterial, antifungal, antiviral properties and water / oil repellency. The manufacturing method of the water / oil repellent member can be formed by a wet process (brush coating, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating) without requiring a vacuum process or a high-temperature heating process, and can be applied to various uses. In particular, it is suitable for uses that require antibacterial, antifungal, antiviral properties and stain resistance. For example, it is used for the casings and display parts of smartphones, smartwatches, smart glasses, PCs, TVs, toys, medical devices, etc., the surfaces and frame parts of optical lenses such as spectacle lenses and camera lenses, touch panel displays, protective films, protective glasses used in transportation equipment such as automobiles, buses, trains, airplanes, and ships, cover glasses, cover resins, reflective plate materials for communication, parts that people touch such as tables, dashboards, windows, floors, etc., and floors, walls, toilets, bathrooms, beds, desks, chairs, walls, floors, windows, handrails, etc. in hospitals, buildings, schools, condominiums, apartments, houses, stores, etc. that are touched by an unspecified number of people.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, the present invention will be described in more detail. The water / oil repellent member of the present invention is a water / oil repellent member having a primer layer as a first layer on at least one surface of a substrate, and further having a water / oil repellent layer as a second layer on the outer surface of the primer layer. The primer layer is composed of a layer having a thickness of 10 to 5,000 nm containing a silicon compound-based binder and metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and the water / oil repellent layer is composed of a layer having a thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organosilicon compound.

[0015] The present invention is, for example, by wet-applying a liquid containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and a dispersion medium onto the surface (at least one surface) of various substrates, removing the dispersion medium in the liquid, and forming and laminating a primer layer (first layer) containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties on at least one surface of the substrate. Further, a solution containing a fluorine-containing organic silicon compound (water- and oil-repellent agent) is wet-applied onto the outer surface of the primer layer, or the fluorine-containing organic silicon compound or a mixture containing the fluorine-containing organic silicon compound is dry-applied, and the fluorine-containing organic silicon compound is cured to form and laminate a water- and oil-repellent layer (second layer) on the outer surface of the primer layer. By such a method, etc., on the surface (at least one surface) of various substrates, there is a primer layer (first layer) having a film thickness of 10 to 5,000 nm containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and further on the surface thereof, there is a water- and oil-repellent layer (second layer) having a film thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organic silicon compound, and a water- and oil-repellent member having antibacterial, antifungal, and antiviral properties can be obtained.

[0016] The substrate applied in the present invention is not particularly limited, and examples include resin, metal, ceramic, quartz, glass, sapphire, diamond, marble, and artificial marble, and resin, metal, ceramic, glass, sapphire, marble, and artificial marble are particularly preferred.

[0017] Here, examples of the resin include thermoplastic resins or thermosetting resins, and specifically, the following are preferable. Celluloid, cellulose acetate, cellulose propionate, cellulose butyrate, aliphatic polyamides such as 6-nylon, 6,6-nylon, 12-nylon, aromatic polyamides, ABS resin, AS resin, polystyrene, polyolefins such as polyethylene (low density or high density), polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyacetal, polycarbonate, saturated polyesters such as polyethylene terephthalate, polybutylene terephthalate, aromatic polyesters, polyether ketone, polyether ether ketone, polysulfone, polyether sulfone, polyether imide, polyarylate, polymethylpentene, ionomer, liquid crystal polymer, polyimide, polyamideimide, fluororesin, polyphenylene sulfide, (modified) polyphenylene oxide, thermoplastic resins such as thermoplastic polyurethane, or epoxy resin, unsaturated polyester, thermosetting polyurethane, polyimide, polymer of diethylene glycol bisallyl carbonate (commonly known as CR-39), (co)polymer of (halogenated) bisphenol A di(meth)acrylate, (co)polymer of urethane-modified (halogenated) bisphenol A di(meth)acrylate, copolymer of diacrylate compound and vinylbenzyl alcohol and unsaturated thiol compound, etc., thermosetting resins. Also, a coating may be applied.

[0018] Examples of the metal include magnesium, magnesium alloy, titanium, titanium alloy, chromium, iron, nickel, cobalt, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, platinum, gold, stainless steel, aluminum, aluminum alloy, duralumin, hastelloy, etc.

[0019] Examples of the ceramic include alumina, zirconia, silicon nitride, silicon carbide, aluminum nitride, boron nitride, forsterite, steatite, cordierite, sialon, machinable ceramics, barium titanate, lead zirconate titanate, ferrite, mullite, zircon, etc. Examples of the glass include soda glass, crown glass, lead glass, borosilicate glass, devitrified glass, fused silica, aluminosilicate glass, Temperax, Pyrex (registered trademark), Neoceram, etc., and those that have been chemically or physically strengthened may also be used.

[0020] The primer layer (first layer) formed and laminated on at least one surface of the base material is a layer having a film thickness of 10 to 5,000 nm and containing a silicon compound-based binder and metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties.

[0021] Here, the silicon compound-based binder is a colloidal dispersion, solution, or emulsion of a solid or liquid silicon compound, preferably a silica-based or siloxane-based silicon compound containing a silanol group (hydroxy group bonded to a silicon atom) in a dispersion medium such as water or an aqueous dispersion medium, and excluding the dispersion medium therefrom. Specifically, it includes colloidal silica (preferred particle size of 1 to 150 nm); silicate solutions such as silicate (hydrolysis and partial condensate of tetraalkoxysilane); emulsions of hydrolysis and partial condensates of organoalkoxysilane and alkoxysiloxane; emulsions of silicone resins such as organosilsesquioxane resins and copolymer resins containing triorganosiloxy units and SiO2 units; emulsions of copolymers of silicone resins and other organic resins such as silicone resin-acrylic resin copolymers and silicone resin-urethane resin copolymers, etc., excluding the dispersion medium therefrom.

[0022] In the primer layer, the content of the silicon compound binder is in the range of 1 to 99% by mass, preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass with respect to the entire primer layer. When the content of the silicon compound binder is less than 1% by mass, the strength of the film may decrease and peel off, or it may dissolve in water. When it exceeds 99% by mass, the antibacterial, antifungal, and antiviral components may not be sufficiently exposed, and the antibacterial, antifungal, and antiviral effects may decrease.

[0023] In the present invention, the metal fine particles having antibacterial, antifungal, and antiviral properties used as antibacterial components are those of a single metal or an alloy composition containing at least one or more metal components that enhance antibacterial, antifungal, and antiviral properties. The metal components that enhance antibacterial, antifungal, and antiviral properties refer to metal components that are harmful to microorganisms such as bacteria, molds, and viruses but are relatively less harmful to the human body. For example, when the metal component particles are coated on a film and the standard test for antibacterial processed products of JIS Z 2801 is performed, a decrease in the viable cell count of Staphylococcus aureus and Escherichia coli is confirmed. Examples include silver, copper, zinc, platinum, palladium, nickel, aluminum, titanium, cobalt, zirconium, molybdenum, tungsten, etc. (Non-Patent Document 1: Miyano, Iron and Steel, 93 (2007) 1, 57-65; Non-Patent Document 2: H. Kawakami, ISIJ Intern., 48 (2008) 9, 1299-1304). The metal fine particles used in the present invention are preferably components containing at least one of these metals, and particularly preferably contain at least one of silver, copper, and zinc.

[0024] More specifically, for example, fine particles containing metal components such as silver, copper, zinc, silver-copper alloy, silver-palladium alloy, silver-platinum alloy, silver-tin alloy, gold-copper alloy, silver-nickel alloy, silver-antimony alloy, silver-copper-tin alloy, gold-copper-tin alloy, silver-nickel-tin alloy, silver-antimony-tin alloy, platinum-manganese alloy, silver-titanium alloy, copper-tin alloy, cobalt-copper alloy, zinc-magnesium alloy, silver-zinc alloy, copper-zinc alloy, silver-copper-zinc alloy can be mentioned.

[0025] The metal fine particles having antibacterial, antifungal, and antiviral properties preferably have an average particle diameter of 1 to 1,000 nm, more preferably 2 to 200 nm. Regarding the lower limit value of the average particle diameter of the metal fine particles, theoretically, it can be used down to the minimum particle diameter that can have antibacterial, antifungal, and antiviral properties, but in practical use, an average particle diameter of 1 nm or more is sufficient. If the average particle diameter is too large, the coating film (primer layer) may be strongly colored or the coating film may become turbid (the transparency decreases), impairing the appearance. Also, the antibacterial, antifungal, and antiviral properties may decrease due to a decrease in the surface area of the metal fine particles. The average particle diameter can be determined as the cumulative weight average value D50 (or median diameter) using a particle size distribution measuring device such as the laser light diffraction method (the same shall apply hereinafter).

[0026] The content of the metal component that enhances the antibacterial, antifungal, and antiviral properties in the metal fine particles can be such that the antibacterial, antifungal, and antiviral metal is 1 to 100% by mass, preferably 10 to 100% by mass, more preferably 50 to 100% by mass, and still more preferably 75 to 100% by mass with respect to the total mass of the metal fine particles. This is because when the content of the metal component that enhances the antibacterial, antifungal, and antiviral properties is less than 1% by mass, the antibacterial, antifungal, and antiviral performance may not be fully exhibited.

[0027] In the present invention, metal oxide fine particles having antibacterial, antifungal, and antiviral properties used as an antibacterial component are preferably those having a photocatalytic action. A photocatalyst refers to a general term for substances that exhibit a photocatalytic action when irradiated with light having energy equal to or higher than a predetermined band gap. As such substances, fine particles of known metal oxide semiconductors such as titanium oxide, tungsten oxide, zinc oxide, tin oxide, iron oxide, bismuth oxide, bismuth vanadate, and strontium titanate can be used alone or in combination of two or more. Among them, it is desirable to use titanium oxide fine particles that have a particularly high photocatalytic action, are chemically stable, and are relatively easy to synthesize nano-sized particles and disperse the nano-sized particles in a solvent under irradiation with light including ultraviolet light having a wavelength of 400 nm or less.

[0028] As the crystal phases of titanium oxide fine particles, usually three types, rutile type, anatase type, and brookite type are known. However, it is preferably to use mainly the anatase type or rutile type. Here, the term "mainly" means that it is usually contained in an amount of 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass, of the entire titanium oxide fine particle crystal.

[0029] As the titanium oxide fine particles, in order to enhance its photocatalytic activity, those in which metal compounds such as platinum, gold, palladium, iron, copper, and nickel are supported on the titanium oxide fine particles, or those doped with elements such as tin, nitrogen, sulfur, and carbon can also be used.

[0030] The metal oxide fine particles having antibacterial, antifungal, and antiviral properties preferably have an average particle diameter of 3 to 100 nm, more preferably 4 to 30 nm. If the average particle diameter is too small, the activity (antibacterial, antifungal, and antiviral properties) of the metal oxide fine particles may not be fully exhibited. If it is too large, the coating film (primer layer) may become turbid and the appearance may be impaired.

[0031] In the primer layer, the total content of the metal fine particles and metal oxide fine particles having antibacterial, antifungal, and antiviral properties is in the range of 1 to 99% by mass, preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, based on the entire primer layer. If the content of the metal fine particles and metal oxide fine particles (in total) having antibacterial, antifungal, and antiviral properties is less than 1% by mass, the antibacterial, antifungal, and antiviral properties may not be fully exhibited. If it exceeds 99% by mass, the appearance of the film such as turbidity may be significantly damaged, or the strength of the film may decrease. For the same reasons as described above, the content of the metal oxide fine particles having antibacterial, antifungal, and antiviral properties in the primer layer is in the range of 1 to 99% by mass, preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass with respect to the entire primer layer. Also, the content of the metal fine particles having antibacterial, antifungal, and antiviral properties is 30% by mass or less (0 to 30% by mass), preferably 25% by mass or less (0 to 25% by mass), more preferably 20% by mass or less (0 to 20% by mass), and still more preferably 17% by mass or less (0 to 17% by mass) with respect to the entire primer layer.

[0032] The primer layer can be formed (laminated) by, for example, wet-applying a liquid containing a silicon compound-based binder, metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and a dispersion medium (such as water or an aqueous dispersion medium) onto the surface (at least one surface) of various substrates, and then drying and removing the dispersion medium.

[0033] Here, as the dispersion medium, it is preferable to use water, but a mixed solvent (aqueous dispersion medium) of water and a hydrophilic organic solvent mixed at an arbitrary ratio with water may also be used. As the water, for example, purified water such as filtered water, deionized water, distilled water, and pure water is preferable. Also, as the hydrophilic organic solvent, for example, alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol-n-propyl ether, and glymes are preferable. When using a mixed solvent, the ratio of the hydrophilic organic solvent in the mixed solvent is more than 0% by mass, preferably 0.1% by mass or more, and preferably 50% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

[0034] The dispersion medium is preferably diluted so that the solid content (total of the silicon compound-based binder and the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties) is 0.01 to 2% by mass, particularly 0.05 to 1% by mass. If this concentration is too low, it may be difficult to form a uniform film and the antibacterial effect may not be easily exhibited. If it is too high, the film may become thick and cause appearance abnormalities such as cloudiness and cracking.

[0035] In addition, in the liquid containing the silicon compound-based binder, the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and the dispersion medium (water or an aqueous dispersion medium, etc.), components such as ultraviolet absorbers, photocatalysts, light stabilizers, antioxidants, leveling agents, defoaming agents, pigments, dyes, dispersants, and surfactants such as antifogging agents may be used as necessary. These are preferably added in such a range that the silicon compound-based binder in the primer layer obtained excluding the dispersion medium is 1% by mass or more (particularly 1 to 99% by mass), and the metal fine particles and / or metal oxide fine particles (total) having antibacterial, antifungal, and antiviral properties are 1% by mass or more (particularly 1 to 99% by mass).

[0036] The liquid containing the silicon compound-based binder, the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties, and the dispersion medium is applied to the surface of the above-mentioned substrate by methods such as wet coating, particularly dipping, brushing, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating, and flow coating, and the solvent is removed by volatilization through a drying process to form a primer layer (first layer). As the drying process, it may be left at room temperature, but it may also be heated at, for example, 40 to 500°C for 1 minute to 24 hours within a temperature range that does not affect the substrate.

[0037] The film thickness of the primer layer (first layer) formed and laminated on at least one surface of the base material is 10 to 5,000 nm, preferably 15 to 600 nm. If the film thickness of the primer layer is less than 10 nm, sufficient adhesion between the base material and the cured product of the fluorine-containing organosilicon compound (the water- and oil-repellent layer as the second layer) cannot be obtained, or sufficient antibacterial, antifungal, and antiviral properties may not be exhibited. If it exceeds 5,000 nm, cracks may occur in the film, which may cause appearance defects or adhesion defects. In the present invention, the film thickness can be measured by known methods such as spectroscopic ellipsometry, X-ray reflectometry, and cross-sectional TEM method (hereinafter the same).

[0038] Next, the water- and oil-repellent layer (second layer) formed and laminated on the outer surface of the primer layer is composed of a layer with a film thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organosilicon compound. In the water- and oil-repellent layer (second layer) of the present invention, the "main component" means that the content of the cured product of the fluorine-containing organosilicon compound in the total components constituting the water- and oil-repellent layer is 50% by mass or more (50 to 100% by mass), preferably 51 to 100% by mass, more preferably 75 to 100% by mass, and still more preferably 95 to 100% by mass.

[0039] Here, the fluorine-containing organosilicon compound is preferably a fluorine-containing organosilane compound, a fluorine-containing organosiloxane compound, or a fluorine-containing polysilazane compound having at least one hydrolyzable silyl group at at least one molecular chain end.

[0040] Examples of the fluorine-containing organosilane compound or fluorine-containing organosiloxane compound having at least one hydrolyzable silyl group at at least one molecular chain end include hydrolyzable fluorine-containing organosilicon compounds described in JP-A-2007-197425, JP-A-2007-297589, JP-A-2007-297543, JP-A-2008-088412, JP-A-2008-144144, JP-A-2010-031184, JP-A-2010-047516, JP-A-2011-116947, JP-A-2011-178835, JP-A-2014-084405, JP-A-2014-105235, JP-A-2013-253228, JP-A-2014-218639, International Publication No. 2013 / 121984 (Patent Documents 3 to 16), etc. can be used.

[0041] The fluorine-containing organosilicon compound will be described in more detail.

[0042] In the fluorine-containing organosilicon compound according to the present invention, the fluorine-containing organosilane compound or fluorine-containing organosiloxane compound having at least one hydrolyzable silyl group at at least one molecular chain end preferably has at least one, preferably 1 to 14, more preferably 1 to 7 molecular chain ends each having at least one hydrolyzable silyl group, preferably 1 to 6, more preferably 2 to 4 (for example, having at least one, preferably 2 to 60, more preferably 3 to 30 hydrolyzable silyl groups in one molecule), and the compound preferably has a hydrolyzable silyl group such as an alkoxy group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms such as a methoxy group, ethoxy group, propoxy group, butoxy group, an alkoxyalkoxy group having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms such as a methoxymethoxy group, methoxyethoxy group, an acyloxy group having 1 to 10 carbon atoms such as an acetoxy group, an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoxy group, a halogen group such as a chlorine group, bromine group, iodine group or an amino group-containing silyl group in one molecule, and is more preferably an organosilicon compound having a fluorine atom.

[0043] In the fluorine-containing organosilicon compound, the fluorine-containing organosilane compound, fluorine-containing organosiloxane compound, or fluorine-containing polysilazane compound having at least one hydrolyzable silyl group at at least one molecular chain end is preferably a compound having a fluorooxyalkylene group (i.e., a monovalent or divalent perfluoropolyether residue) in the molecule. The fluorooxyalkylene group is a (poly)fluorooxyalkylene structure (divalent linear perfluoropolyether polymer residue) in which a plurality of repeating units represented by -C j F 2j O- are bonded (where j is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4 in this structure). In particular, it preferably has 3 to 500, more preferably 6 to 200, still more preferably 8 to 100, and even more preferably 10 to 80 of these repeating units.

[0044] The above repeating unit -C j F 2j O- may be either linear or branched. For example, the following units can be mentioned, and those in which two or more of these repeating units are bonded may also be used. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O- -C(CF3)2O-

[0045] The above (poly)fluorooxyalkylene structure (divalent linear perfluoropolyether polymer residue) is particularly -C d F 2d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O)t -C d F 2d - wherein p, q, r, s, and t are each independently an integer from 0 to 200, preferably p is an integer from 0 to 100, q is an integer from 0 to 100, r is an integer from 0 to 100, s is an integer from 0 to 50, t is an integer from 0 to 100, and p + q + r + s + t is an integer from 3 to 500, preferably an integer from 10 to 100. Each repeating unit shown in the parentheses with p, q, r, s, and t may be randomly combined. d is independently an integer from 0 to 8, preferably an integer from 0 to 5, more preferably an integer from 0 to 2, and the unit may be linear or branched. In particular, it can be represented by the following structure.

Chemical formula

[0046] The fluorine-containing organosilicon compound according to the present invention is more preferably at least one selected from a fluorooxyalkylene group-containing organosilane compound or a fluorooxyalkylene group-containing organosiloxane compound represented by the following general formulas (1) to (5), and a fluorooxyalkylene group-containing polysilazane compound represented by the following general composition formula (6) (fluorine-containing organosilicon compound). These may be used alone or in combination of two or more. (A-Rf) α ZW β (1) Rf(ZW β )2(2) Z’(Rf-ZW β ) γ (3) A-Rf-Q-(Y) δ -B (4) Rf(Q-(Y) δ -B)2(5) A-Rf-Q-Si(NH) 3 / 2 (6)

[0047] In formulas (1) to (6), each Rf independently represents a divalent linear perfluorooxyalkylene polymer residue represented by -C d F 2d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -C d F 2d -, p, q, r, s, and t are each independently an integer from 0 to 200, and p + q + r + s + t = 3 to 500. Each repeating unit shown in the parentheses with p, q, r, s, or t may be randomly bonded. d is independently an integer from 0 to 8 for each unit, and the unit may be linear or branched. A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group with a -CF3 group, -CF2H group, or -CH2F group at the end. Z and Z' are each independently a single bond or a divalent organic group that may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom and may be fluorine-substituted. W is independently a monovalent organic group with a hydrolyzable group at the end. α and β are each independently an integer from 1 to 7, preferably α is an integer from 1 to 3, more preferably 1, β is an integer from 1 to 3, and α + β = an integer from 2 to 8, preferably an integer from 2 to 4. γ is an integer from 2 to 8, preferably 2 or 3. Also, Q is independently a single bond or a divalent organic group, δ is each independently an integer from 1 to 10, Y is independently a divalent organic group with a hydrolyzable group, and B is independently a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen atom.

[0048] In the above formulas (1) to (6), each Rf independently represents the above-described (poly)fluorooxyalkylene structure (divalent linear perfluorooxyalkylene polymer residue) -C d F 2d -O-(CF2O) p(CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -C d F 2d - and the same as the above can be exemplified.

[0049] In the above formulas (1), (4) and (6), A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF3 group, -CF2H group or -CH2F group. Specific examples of the monovalent fluorine-containing group whose terminal is a -CF3 group, -CF2H group or -CH2F group include a -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, -CH2OCF2CFH-OC3F7 group and the like. Among them, as A, a -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2OCF2CFH-OC3F7 group are preferable.

[0050] In the above formulas (1) to (3), Z and Z’ are each independently a single bond, or an organic group having 2 to 8 valences which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be fluorine-substituted. The organic group can be represented by (L) α M (α is an integer of 1 to 7, preferably an integer of 1 to 3, more preferably 1).

[0051] Here, L is a single bond, or an oxygen atom, a sulfur atom, or a divalent organic group. In the above formulas (1) to (3), L of Z is a linking group between the Rf group and the M group (or W group), and L of Z’ is a linking group between the M (or Rf group) and the Rf group. As the divalent organic group, preferably, an amide bond, an ether bond, a carbonyl bond, an ester bond, or a diorganosilylene group such as a dimethylsilylene group, -Si[OH][(CH2) fA non-substituted or substituted divalent organic group having 2 to 12 carbon atoms, which may contain one or more selected from the group consisting of groups represented by Si(CH3)3]-(where f is an integer of 2 to 4), and more preferably a non-substituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain the above structure.

[0052] Examples of the non-substituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include alkylene groups such as ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, arylene groups such as phenylene group, or combinations of two or more of these groups (alkylene-arylene group, etc.). Further, a group in which a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as fluorine and iodine may also be used. Among them, a non-substituted or substituted alkylene group having 2 to 4 carbon atoms or a phenylene group is preferable.

[0053] Examples of the divalent organic group of L include a group represented by the following structure, or a group in which two or more of these are bonded. In the case of L of Z, the left bond preferably binds to Rf, and the right bond preferably binds to M or W. In the case of L of Z’, the left bond preferably binds to Rf, and the right bond preferably binds to M.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0054] Further, M is a single bond, or a nitrogen atom, a silicon atom, a carbon atom, a phosphorus atom, or a group containing these, or an organic group having a valence of 2 to 8, preferably 2 to 4 (the above (α + β) valence, α is the same as above, and β is an integer of 1 to 7, preferably an integer of 1 to 3). Specifically, a single bond, -R 1 A divalent group represented by -R 3 A divalent group represented by -R 4 A divalent group represented by -NR 1 A trivalent group represented by -N=, a trivalent group represented by -C(=O)-N=, a trivalent group represented by -P=, a trivalent group represented by -PO=, -R 3 A trivalent group represented by -C=, a trivalent group represented by -R

[0055] In the above, R 1 are independently of each other, preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a group having a repeating unit of an oxyalkylene group having 1 to 3 carbon atoms which may have a diorganosiloxane structure having 2 to 51 silicon atoms intervening, or R 2 A silyl ether group represented by -R 2 are independently of each other, a hydrogen atom, preferably an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms such as a phenyl group, or an alkoxy group having 1 to 3 carbon atoms. R 3 are independently of each other, preferably an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chlorine group. R 4is an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms such as a phenyl group. When M is a siloxane residue, it preferably has a linear, branched or cyclic organopolysiloxane structure having 2 to 51 silicon atoms, preferably 2 to 13 silicon atoms, more preferably 2 to 11 silicon atoms, and still more preferably 2 to 5 silicon atoms. The organopolysiloxane preferably has a methyl group, ethyl group, propyl group, butyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and an unsubstituted or fluorine-substituted alkyl group such as C3F7-C3H6- or a phenyl group. Further, it may contain a silaalkylene structure in which two silicon atoms are bonded by an alkylene group, that is, Si-(CH2) n -Si. In the above formula, n is an integer of 2 to 6, preferably an integer of 2 to 4.

[0056] Examples of such M include those shown below. In the case of M of Z, the left bond preferably binds to L (or Rf), and the other bonds preferably bind to W (in the case of M of Z’, both bind to L (or Rf)). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In the formula, i is an integer of 1 to 20, c is an integer of 1 to 50, and Me is a methyl group.)

[0057] In the above formulas (1) to (3), W is independently a monovalent organic group having a hydrolyzable group at the terminal, and is preferably represented by the following formula.

Chemical formula

[0058] In the above formula, examples of the hydrolyzable group of X include alkoxy groups having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group; alkoxyalkoxy groups having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms such as methoxymethoxy group and methoxyethoxy group; acyloxy groups having 1 to 10 carbon atoms such as acetoxy group; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy group; halogen groups such as chloro group, bromo group, and iodo group; amino group, etc. Among them, methoxy group and ethoxy group are preferred. Further, R is an alkyl group such as a methyl group or an ethyl group having 1 to 4 carbon atoms, or a phenyl group, and among them, a methyl group is preferred. a is 2 or 3, and from the viewpoints of reactivity and adhesion to the substrate, 3 is preferred. m is an integer of 0 to 10, preferably an integer of 2 to 8, and more preferably 2 or 3.

[0059] In formulas (1) to (3), (-) α ZW β , -ZW β Examples of the structure represented by include the following structures.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

[0060] In the above formulas (4), (5), and (6), Q is independently a single bond or a divalent organic group, which is a linking group between the Rf group and the Y group or a silicon atom. As the divalent organic group of Q, preferably, an amide bond, an ether bond, an ester bond, or a diorganosilylene group such as a dimethylsilylene group, -Si[OH][(CH2) f Si(CH3)3]-(where f is an integer from 2 to 4), and it may contain one or more selected from the group consisting of unsubstituted or substituted divalent organic groups having 2 to 12 carbon atoms, and more preferably, it may contain the above structure and is an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms.)

[0061] Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include the same as those exemplified for the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms by L above.)

[0062] Examples of the divalent organic group of Q include, for example, groups represented by the following structures. It is preferable that the left bond is bonded to Rf and the right bond is bonded to Y or a silicon atom.)

Chem.

Chem.

Chem.

Chem.

[0063] In the above formulas (4) and (5), Y is an independent divalent organic group having a hydrolyzable group, and preferably has a structure represented by the following formula.

Chemical formula

[0064] As M', it is preferably a group represented by the following structure. Note that the left bond is in the direction of bonding to Q (or Rf), the right bond is in the direction of bonding to B, and the other bonds are preferably bonded to the unit enclosed by h.

Chemical formula

[0065] M 1Examples thereof include a single bond, a phenylene group, a dimethylsilylene group, a tetrafluoroethylene group, etc. Further, M 2 Examples thereof include those shown below.

Chemical formula

[0066] Examples of such Y include, for example, the following groups. It should be noted that the left bond preferably binds to Q (or Rf) and the right bond preferably binds to B.

Chemical formula

[0067]

Chemical formula

[0068] In the above formulas (4) and (5), δ is independently an integer from 1 to 10, preferably an integer from 1 to 4. Further, B is independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group having 1 to 4 carbon atoms, or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0069] Examples of the fluorooxyalkylene group-containing organosilane compound, fluorooxyalkylene group-containing organosiloxane compound, and fluorooxyalkylene group-containing polysilazane compound (fluorine-containing organosilicon compound) represented by the above formulas (1) to (6) include, for example, the following structures.

Chemical formula

Chemical formula

[0070] Note that the fluorooxyalkylene group-containing organosilane compounds and fluorooxyalkylene group-containing organosiloxane compounds (fluorine-containing organosilicon compounds) represented by the general formulas (1) to (5) according to the present invention may include compounds in which some or all of the above hydrolyzable groups (X) are hydrolyzed (compounds in which X is an OH group), and may also include compounds in which some or all of these OH groups are condensed.

[0071] The water and oil repellent layer (second layer) formed and laminated on the outer surface of the primer layer can be formed and laminated, for example, by wet-applying a solution (water and oil repellent) containing the above fluorine-containing organosilicon compound on the outer surface of the formed primer layer (first layer), or by dry-applying the fluorine-containing organosilicon compound or a mixture containing the fluorine-containing organosilicon compound, and curing the fluorine-containing organosilicon compound.

[0072] In addition to the above-mentioned fluorine-containing organosilicon compound as the main component, the water and oil repellent or the mixture containing the fluorine-containing organosilicon compound (hereinafter also referred to as the mixture) may further contain, if necessary, a fluorine-containing organosilicon compound (non-functional perfluoropolyether polymer) represented by the following formula (X). A-Rf-A (X) (In the formula, A and Rf are the same as above.)

[0073] In the above formula (X), A and Rf can be exemplified by the same ones as A and Rf exemplified in the above formulas (1) to (6), and these A and Rf may be the same as or different from A and Rf in the above formulas (1) to (6).

[0074] Examples of the non-functional polymer represented by the formula (X) include the following.

Chemical formula

[0075] The content of the fluorine-containing organosilicon compound (non-functional perfluoropolyether polymer) represented by the above formula (X) may be 0 to 100 parts by mass, preferably 0 to 60 parts by mass, more preferably about 0 to 1 part by mass, based on 100 parts by mass of the above-mentioned fluorine-containing organosilicon compound as the main component.

[0076] Furthermore, the water and oil repellent or mixture may contain unreacted raw materials or reaction intermediates before introducing terminal hydroxyl groups or hydrolyzable groups into the fluorine-containing organosilicon compound as the main component. Also, the water and oil repellent or mixture may contain a partial (hydrolysis) condensate obtained by condensing the terminal hydroxyl group of the fluorine-containing organosilicon compound (fluoropolyether group-containing polymer having a terminal hydroxyl group or hydrolyzable group) as the main component, or a hydroxyl group obtained by partially hydrolyzing the terminal hydrolyzable group by a known method in advance.

[0077] Furthermore, in addition to the above-mentioned fluorine-containing organosilicon compound as the main component, a hydrolysis condensation catalyst, for example, an organotin compound (such as dibutyltin dimethoxide, dibutyltin dilaurate), an organotitanium compound (such as tetra-n-butyl titanate), an organic acid (such as acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), or an inorganic acid (such as hydrochloric acid, sulfuric acid) may be added to the water and oil repellent or mixture as needed. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The content of the hydrolysis condensation catalyst may be a catalytic amount, and usually, it may be about 0.01 to 5 parts by mass, particularly about 0.1 to 1 part by mass, based on 100 parts by mass of the above-mentioned fluorine-containing organosilicon compound as the main component.

[0078] The optional components that can be blended as needed in the above water and oil repellent or mixture can be blended within a range such that the content of the cured product of the fluorine-containing organosilicon compound in the resulting water and oil repellent layer (second layer) is 50% by mass or more (50 to 100% by mass), preferably 51 to 100% by mass, more preferably 75 to 100% by mass, and still more preferably 95 to 100% by mass.

[0079] When used as a water and oil repellent, it is desirable to dilute the above fluorine-containing organosilicon compound with a solvent in advance. Such a solvent is not particularly limited as long as it can uniformly dissolve the above fluorine-containing organosilicon compound. For example, fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (such as 1,3-trifluoromethylbenzene), fluorine-modified ether solvents (such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and perfluoro(2-butyltetrahydrofuran)), fluorine-modified olefin solvents (such as cis-1-chloro-3,3,3-trifluoropropene and methoxyperfluoroheptene), fluorine-modified alkylamine solvents (such as perfluorotributylamine and perfluorotripentylamine), hydrocarbon solvents (such as petroleum benzine, toluene, and xylene), and ketone solvents (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone) can be mentioned. Among these, fluorine-modified solvents are desirable in terms of solubility and stability, and particularly, fluorine-modified ether solvents and fluorine-modified aromatic hydrocarbon solvents are preferred. The above solvent may be used alone or in combination of two or more. It is desirable that the solvent contains the fluorine-containing organosilicon compound in the water and oil repellent (a solution containing the fluorine-containing organosilicon compound and, if necessary, other components and the solvent) in an amount of 0.01 to 50% by mass, preferably 0.03 to 10% by mass, and more preferably 0.05 to 1% by mass.

[0080] The water and oil repellent containing the above fluorine-containing organosilicon compound can be applied to a substrate by a known method such as a wet coating method (dipping method, brushing, spin coating, spraying, gravure coating, die coating, bar coating, slit coating), etc., or the above fluorine-containing organosilicon compound or a mixture containing the fluorine-containing organosilicon compound can be applied by a vapor deposition method, etc. Coating conditions and the like may follow the conventionally known methods. However, since the primer layer is coated and formed by a wet coating method (wet method), it is more efficient to coat the water and oil repellent containing the fluorine-containing organosilicon compound by a wet coating method (wet method). The fluorine-containing organosilicon compound can be cured at room temperature (25 °C) in 1 to 24 hours, but it may also be heated at 30 to 200 °C for 1 minute to 1 hour to cure in a shorter time. Curing is preferably carried out under humidification (50 to 90% RH) to promote hydrolysis.

[0081] Before applying a water and oil repellent containing a fluorine-containing organosilicon compound, etc., the surface of the primer layer on the substrate may be subjected to a treatment such as plasma treatment, UV treatment, ozone treatment, etc. for cleaning or surface activation.

[0082] The film thickness of the fluorine layer (water and oil repellent layer) of the water and oil repellent member of the present invention is 0.5 to 50 nm, and particularly preferably 1 to 25 nm. If the film thickness is too thick, the antibacterial, antifungal, and antiviral properties of the outer surface of the water and oil repellent layer may become insufficient, and if it is too thin, the surface characteristics and wear resistance may not be sufficient.

[0083] The water and oil repellent member of the present invention thus obtained is preferably used for building members, kitchen members, furniture, electronic devices, transportation devices, sanitary ceramics, etc. Specific examples of use include the casings of car navigation systems, tablet PCs, PCs, smartphones, smartwatches, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, TVs, toys, etc., lenses such as camera lenses, spectacle lenses, sunglasses, AR lenses, VR lenses, medical devices such as endoscopes, scalpels, blood pressure monitors, X-ray CTs, MRIs, inspection devices, beds, etc., the surfaces of liquid crystal displays, organic EL displays, LED displays, flexible devices, etc., optical articles such as protective films, antireflection films, compact discs, DVDs, Blu-ray discs, etc., the windows, bodies, operating devices, chairs, safety belts, etc. of automobiles, buses, trains, airplanes, ships, drones, etc., exterior building materials, kitchen building materials, waiting rooms, mirrors, the surfaces of artworks, etc.

Examples

[0084] Hereinafter, examples and comparative examples will be shown to specifically describe the present invention, but the present invention is not limited thereto. In the following examples, the average particle diameter indicates a value obtained as the cumulative weight average value D50 (or median diameter) using a particle size distribution measuring apparatus by the laser light diffraction method. Also, Me represents a methyl group.

[0085] [Examples 1 to 8 and Comparative Examples 1 to 9] As shown below, test specimens of a water and oil repellent member having a base material, a primer layer, and a water and oil repellent layer were prepared.

[0086] [Base material] A glass base material (a test piece substrate of Corning Gorilla 3 glass, thickness 0.5 mm, width 50 mm, length 100 mm)

[0087] [Formation of primer layer] The primer layers were respectively formed on the above base materials by the methods shown below. As the silicon compound binder, water-soluble silicate Scutum S (manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and the following Primers 1 and 2 were prepared. [Primer 1] Primer 1 was a mixture of rutile-type titanium oxide (average particle diameter 10 nm), silver fine particles (average particle diameter 20 nm), and silicate in a mass ratio of 5:2:5. [Primer 2] Primer 2 was a mixture of anatase-type titanium oxide (average particle diameter 15 nm) and silicate in a mass ratio of 1:1.

[0088] [Formation of primer layer 1] The above base material was spray-coated using a spray coating apparatus (manufactured by T & K Co., Ltd., NST-51) with a treatment liquid obtained by diluting Primer 1 with pure water to a solid content of 0.1% by mass, and then dried at room temperature (25°C) for 12 hours to form a primer layer 1 with a film thickness of about 20 nm on the outer surface of the above base material.

[0089] [Formation of primer layer 2] The treatment liquid in which Primer 1 was diluted with pure water to a solid content of 0.7% by mass was spray-coated onto the above substrate using a spray coater (manufactured by T & K Co., Ltd., NST-51), and then dried at room temperature (25 °C) for 12 hours to form a primer layer 2 with a film thickness of about 100 nm on the outer surface of the above substrate.

[0090] [Formation of Primer Layer 3] The operation of spray-coating the treatment liquid in which Primer 1 was diluted with pure water to a solid content of 0.7% by mass onto the above substrate using a spray coater (manufactured by T & K Co., Ltd., NST-51) and then drying at room temperature (25 °C) for 12 hours was repeated 3 times to form a primer layer 3 with a film thickness of about 500 nm on the outer surface of the above substrate.

[0091] [Formation of Primer Layer 4] The operation of spray-coating the treatment liquid in which Primer 2 was diluted with pure water to a solid content of 0.7% by mass onto the above substrate using a spray coater (manufactured by T & K Co., Ltd., NST-51) and then drying at room temperature (25 °C) for 12 hours was repeated 3 times to form a primer layer 4 with a film thickness of about 500 nm on the outer surface of the above substrate.

[0092] [Formation of Primer Layer 5] The treatment liquid in which ScutumS was diluted with pure water to a solid content of 0.5% by mass was spray-coated onto the above substrate using a spray coater (manufactured by T & K Co., Ltd., NST-51), and then dried at room temperature (25 °C) for 1 hour to form a primer layer 5 with a film thickness of about 100 nm on the outer surface of the above substrate.

[0093] [Formation of Primer Layer 6] The substrate was dip-coated (the substrate was immersed in the treatment liquid for 60 seconds and then pulled up at 150 mm / min) with the treatment liquid in which the hydrolyzed and partially condensed product of tetraethoxysilane (weight average molecular weight: 25,000, silanol group content: 0.015 mol / g) was diluted with butanol to a solid content of 1.5% by mass, and then dried at room temperature (25 °C) for 1 hour to form a primer layer 6 with a film thickness of 62 nm on the outer surface of the above substrate.

[0094] [Formation of Primer Layer 7] The substrate was dip-coated with a treatment liquid obtained by diluting perhydropolysilazane with dibutyl ether to a solid content of 2.0% by mass (the substrate was immersed in the treatment liquid for 30 seconds and then pulled up at 150 mm / min), and then cured at 80°C / 80% RH for 24 hours to form a primer layer 7 with a thickness of 95 nm on the outer surface of the substrate.

[0095] [Formation of Primer Layer 8] The substrate was dip-coated with a treatment liquid obtained by diluting silica with an average particle size of 10 nm to a solid content of 1.0% by mass (the substrate was immersed in the treatment liquid for 60 seconds and then pulled up at 150 mm / min), and then dried at 150°C for 1 hour to form a primer layer 8 with a film thickness of 62 nm on the outer surface of the substrate.

[0096] [Formation of Primer Layer 9] The substrate was dip-coated with an organic antibacterial agent (Sunazol 200, zinc pyrithione-based organic antibacterial agent) (the substrate was immersed in the treatment liquid for 60 seconds and then pulled up at 150 mm / min), and then dried at room temperature (25°C) for 1 hour to form a primer layer 9 with a film thickness of 50 nm on the outer surface of the substrate.

[0097] Furthermore, a water / oil repellent layer was formed and laminated on the outer surface of the primer layer of the substrate on which the primer layers 1 to 9 were formed based on the following method.

[0098] [Formation of Water / Oil Repellent Layer] Compounds 1 to 5 shown below were each diluted with a fluorinated solvent (Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether)) to a solid content of 0.1% by mass, and then spray-coated on each primer layer of the substrate with a spray coating device (manufactured by T&C Co., Ltd., NST-51). Thereafter, it was cured at 80°C for 30 minutes to form a cured film (water / oil repellent layer), and a test specimen was prepared. The film thickness of the water / oil repellent layer in each test specimen was calculated from the F detection amount by a fluorescent X-ray device (manufactured by Rigaku Corporation, ZSXmini2). Regarding Compound 6 shown below, after diluting it with ion-exchanged water to a solid content concentration of 10% by mass, it was applied onto the primer layer of the above-mentioned substrate using a wire bar. Then, it was cured at 100 °C for 20 minutes to form a cured film (water- and oil-repellent layer), and a test piece was prepared. The film thickness of the water- and oil-repellent layer in the test piece was calculated from the F detection amount using a fluorescent X-ray apparatus (manufactured by Rigaku Corporation, ZSXmini2).

[0099] [Compound 1] [Chemical formula] (p1 + q1 = 60, p1:q1 = 23:22)

[0100] [Compound 2] [Chemical formula] (t1 = 30)

[0101] [Compound 3] [Chemical formula] (q1 + s1 = 30, s1:q1 = 10:10)

[0102] [Compound 4] [Chemical formula] (p1 + q1 = 48, p1:q1 = 10:10)

[0103] [Compound 5] [Chemical formula] (p1 + q1 = 10, p1:q1 = 10:9)

[0104] [Compound 6] Zefflu SE-310 (manufactured by Daikin Industries, Ltd., a mixture of polyvinylidene fluoride and polymethyl methacrylate, pH 7 - 8, anionic / nonionic)

[0105] Note that in Comparative Examples 6 and 8, no water / oil repellent layer was provided. In Comparative Example 9, the water / oil repellent layer was formed directly on the glass substrate by the above method without forming a primer layer. Table 1 shows the primer layer used in each Example and Comparative Example, the compounds used in the water / oil repellent layer, and the film thicknesses of the primer layer and the water / oil repellent layer. The film thickness of the primer layer is the value measured by a differential spectroscopic film thickness meter OPTM-A1 (Otsuka Electronics Co., Ltd.).

[0106] Using the specimens obtained above, various evaluations were performed by the following methods. These results are shown in Table 1.

[0107] 〔Antibacterial property〕 The antibacterial performance was tested for the specimens obtained above by a method conforming to Japanese Industrial Standard JIS Z 2801:2010 "Antibacterial processed products - Antibacterial test method - Antibacterial effect" and evaluated according to the following criteria. ·Good (indicated by ○)···When the antibacterial activity value is 2.0 or more ·Poor (indicated by ×)···When the antibacterial activity value is less than 2.0

[0108] 〔Mildew resistance〕 The mildew resistance performance was evaluated for the specimens obtained above by a method conforming to Japanese Industrial Standard JIS Z 2911:2010 "Mildew resistance test method" up to 8 weeks later. The evaluation was performed based on the evaluation of the mildew growth state specified in Appendix A and evaluated according to the following criteria. ·Very good (indicated by ◎)···Mildew growth state is 0 - 1 ·Good (indicated by ○)···Mildew growth state is 2 - 3 ·Poor (indicated by ×)···Mildew growth state is 4 - 5

[0109] 〔Antiviral property〕 The antiviral performance was tested for the specimens obtained above by a method conforming to Japanese Industrial Standard JIS R 1706:2020 "Fine ceramics - Test method for antiviral property of photocatalytic materials - Method using bacteriophage Qβ" and evaluated according to the following criteria. ·Good (indicated by ○)···When the antiviral activity value is 1.0 or more ·Defect (marked as ×)···When the antiviral activity value is less than 1.0

[0110] 〔Water and oil repellency〕 Using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured film (water and oil repellent layer) of the test piece with respect to water and the contact angle with respect to oleic acid were measured.

[0111] 〔Wear resistance test〕 Using a reciprocating wear test machine (HEIDON 30S, manufactured by Shin-Tech Co., Ltd.), the wear resistance test of the cured film (water and oil repellent layer) of the test piece was carried out under the following conditions. The contact angle of the cured film (water and oil repellent layer) with respect to water after the wear resistance test was measured using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.). Evaluation environmental conditions: 25°C, humidity 40% Abrasive material: Eight non-woven fabrics (BEMCOT M-3II, manufactured by Asahi Kasei Corporation) were stacked and wrapped around the tip (20 mm × 20 mm) of the tester in contact with the sample, and fixed with a ring rubber. Load: 1 kg Wiping distance (one way): 40 mm Wiping speed: 4,800 mm / min Number of reciprocations: 3,000 reciprocations

[0112] 〔Coefficient of kinetic friction〕 The coefficient of kinetic friction of the cured film (water and oil repellent layer) of the test piece with respect to Benkot (manufactured by Asahi Kasei Corporation) was measured using a surface property tester manufactured by Shin-Tech Co., Ltd. under the following conditions. Contact area: 10 mm × 30 mm Load: 100 g

[0113] 〔Removability of sebum stain〕 Seven panelists transferred sebum on the forehead to the surface of the cured film (water and oil repellent layer) of the test piece with their fingers, and the removability when wiped with Benkot (manufactured by Asahi Kasei Corporation) was evaluated according to the following evaluation criteria. A: Completely removable within 2 wipes B: Completely removable within 3 - 5 wipes C: After 5 wipes, there are still some parts that cannot be wiped off D: Almost impossible to wipe off with 5 wipes

[0114] [Table 1]

[0115] As is clear from the results in Table 1, in Examples 1 to 8, due to the high water and oil repellency of the outer surface of the water and oil repellent layer, the sebum stain wiping property was excellent as a result, and the antibacterial, antifungal, and antiviral properties of the primer layer were also fully exhibited. Since the water and oil repellent layer is a thin film and the molecular chain mobility is good, it is considered that the antibacterial, antifungal, and antiviral properties of the primer layer were effective against bacteria and mold adhering to the surface of the water and oil repellent layer. In Comparative Examples 1 to 4, a general primer for imparting a water and oil repellent layer was used, but since the primer itself has no antibacterial, antifungal, and antiviral properties, naturally, even when a water and oil repellent layer was provided, the antibacterial, antifungal, and antiviral properties were poor. In Comparative Example 5, a general antibacterial layer was used as the primer layer, but the adhesion to the water and oil repellent layer was insufficient, resulting in significantly inferior abrasion resistance. Comparative Examples 6 and 8 provided only an antibacterial, antifungal, and antiviral layer (primer layer) without providing a water and oil repellent layer. Although the antibacterial, antifungal, and antiviral properties were sufficient, oil stains such as fingerprints could not be wiped off when they adhered. In Comparative Example 7, a fluorine-based compound was used as the water and oil repellent layer, but the antibacterial, antifungal, and antiviral properties were lost. Comparative Example 9 provided only a water and oil repellent layer without providing a primer layer, but the antibacterial, antifungal, and antiviral properties were not sufficient. The antibacterial, antifungal, and antiviral primers (Primers 1 and 2) used as the primer layer have residual silanol groups, which are considered to help the adhesion to the water and oil repellent layer. Even when Compound 6 was used as the water and oil repellent layer on its surface (Comparative Example 7), the effect was not lost. Therefore, a film with both water and oil repellency and antibacterial, antifungal, and antiviral properties could be formed.

[0116] [Examples 9 and 10 and Comparative Examples 10 and 11] Next, in the same manner as described above, a water / oil repellent layer using Compound 1 was formed and laminated to a thickness shown in Table 2 on the outer surface of the primer layer of the substrate formed to the thickness shown in Table 2 for the primer layer 2, to prepare a test piece. When the same evaluation as described above was performed using the obtained test piece, the results shown in Table 2 below were obtained.

[0117]

Table 2

[0118] As is clear from the results in Table 2, it was confirmed that when the water / oil repellent layer becomes too thick, the antibacterial, antifungal, and antiviral properties of the outer surface of the water / oil repellent layer are impaired (Comparative Examples 10 and 11). In order to achieve both water / oil repellency and antibacterial, antifungal, and antiviral properties, it is important that the water / oil repellent layer be a thin layer within a specific film thickness range.

Industrial Applicability

[0119] According to the present invention, a water / oil repellent member having a cured film (primer layer + water / oil repellent layer) excellent in water / oil repellency and antibacterial, antifungal, and antiviral properties can be formed by a wet coating process only at room temperature. Furthermore, the present invention is a technology that enables coating on a large area and on-site construction. Therefore, the water / oil repellent member of the present invention enables the production of a functional film in a roll shape, and can maintain a clean and good antifouling surface over a long period of time even for the housing of an electronic device or an object that is frequently used and touched in daily life.

Claims

1. A water and oil repellent member having a primer layer as the first layer on at least one surface of a substrate, and further having a water and oil repellent layer as the second layer on the outer surface of the primer layer, wherein the primer layer is composed of a layer having a thickness of 10 to 5,000 nm containing a silicon compound-based binder, metal fine particles having an average particle diameter of 1 to 1,000 nm and having antibacterial, antifungal and antiviral properties, and / or metal oxide fine particles having an average particle diameter of 3 to 100 nm, and the water and oil repellent layer is composed of a layer having a thickness of 0.5 to 50 nm mainly composed of a cured product of a fluorine-containing organosilicon compound, and the content of the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal and antiviral properties in the primer layer is 1 to 99% by mass based on the whole primer layer, and the water and oil repellent member has antibacterial, antifungal and antiviral properties.

2. The water and oil repellent member according to claim 1, wherein the silicon compound-based binder is a silica-based or siloxane-based silicon compound containing a silanol group.

3. The water and oil repellent member according to claim 1 or 2, wherein the metal fine particles having antibacterial, antifungal and antiviral properties are fine particles of at least one metal selected from silver, copper and zinc.

4. The water and oil repellent member according to any one of claims 1 to 3, wherein the metal oxide fine particles having antibacterial, antifungal and antiviral properties are fine particles of titanium oxide.

5. The fluorine-containing organosilicon compound is a fluorine-containing organosilane compound or a fluorine-containing organosiloxane compound having at least one hydrolyzable silyl group at at least one molecular chain end, or a fluorine-containing polysilazane compound, and the hydrolyzable silyl group is a silyl group having a group selected from an alkoxy group having 1 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group and an amino group. The water and oil repellent member according to any one of claims 1 to 4.

6. The fluorine-containing organosilicon compound has a -C d F 2d -O-(CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r (CF 2 CF 2 CF 2 CF 2 O) s (CF(CF 3 )CF 2 O) t -C d F 2d -(wherein p, q, r, s, and t are each independently an integer from 0 to 200, and p + q + r + s + t = 3 to 500, and each repeating unit shown in the parentheses to which p, q, r, s, and t are attached may be randomly bonded, d is an integer from 0 to 8 independently for each unit, and the unit may be linear or branched.) having a divalent linear perfluorooxyalkylene polymer residue, and having at least one hydrolyzable silyl group at at least one molecular chain end, a fluorooxyalkylene group-containing organosilane compound or a fluorooxyalkylene group-containing organosiloxane compound, or a fluorooxyalkylene group-containing polysilazane compound having the above divalent linear perfluorooxyalkylene polymer residue, which is the water- and oil-repellent member according to any one of claims 1 to 5.

7. The water and oil repellent member according to any one of claims 1 to 6, wherein the fluorine-containing organosilicon compound is at least one selected from a fluorooxyalkylene group-containing organosilane compound or a fluorooxyalkylene group-containing organosiloxane compound represented by the following general formulas (1) to (5) and a fluorooxyalkylene group-containing polysilazane compound represented by the following general composition formula (6). (A - Rf) α ZW β (1) Rf(ZW β ) 2 (2) Z'(Rf - ZW β ) γ (3) [wherein, each Rf independently represents a divalent linear perfluorooxyalkylene polymer residue represented by -C d F 2d -O-(CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r (CF 2 CF 2 CF 2 CF 2 O) s (CF(CF 3 )CF 2 O) t -C d F 2d -; p, q, r, s and t each independently represent an integer of 0 to 200, and p + q + r + s + t = 3 to 500. Each repeating unit shown in the parentheses to which p, q, r, s and t are attached may be randomly bonded. d each independently represents an integer of 0 to 8 for each unit, and the unit may be linear or branched. Each A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF 3 group, -CF 2 H group or -CH 2 F group. Z and Z' each independently represent a single bond, or a divalent to octavalent organic group which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be fluorine-substituted. W each independently represents a monovalent organic group having a hydrolyzable group at the terminal. α and β each independently represent an integer of 1 to 7, and α + β = 2 to 8. γ represents an integer of 2 to 8.] A-Rf-Q-(Y) δ -B (4) Rf(Q-(Y) δ -B) 2 (5) (In the formula, Rf and A are the same as described above, Q is independently a single bond or a divalent organic group, δ is independently an integer of 1 to 10, Y is independently a divalent organic group having a hydrolyzable group, and B is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.) A-Rf-Q-Si(NH) 3 / 2 (6) (In the formula, Rf, A, and Q are the same as described above.)

8. The water- and oil-repellent member according to claim 7, wherein the fluorooxyalkylene group-containing organosilane compound, fluorooxyalkylene group-containing organosiloxane compound, and fluorooxyalkylene group-containing polysilazane compound represented by formulas (1) to (6) are as follows. 【Chemical 1】 【Chemical 2】 [Chemical Formula 3] 【Chemical Formula 4】 [Chemical Formula 5] 【Chemical Formula 6】 【Chemical Formula 7】 【Chemical 8】 【Chemical Formula 9】 【Chemical Formula 10】 【Chemical 11】 【Chemical Formula 12】 【Chemical 13】 【Chemical Formula 14】 【Chemical Formula 15】 【Chemical 16】 【Chemical 17】 【Chemical Formula 18】 【Chemical Formula 19】 【Chemical 20】 【Chemical 21】 【Chemical 22】 【Chemical 23】 【Chemical 24】 【Chemical 25】 【Chemical 26】 【Chemical 27】 【Chemical 28】 【Chemical Formula 29】 【Chemical Formula 30】 【Chemical 31】 【Chemical 32】 (In the formula, Me is a methyl group, p1, q1, r1, s1, and t1 are each independently an integer of 1 to 200, and the sum of p1, q1, r1, s1, and t1 is 3 to 500. Each repeating unit shown in the parentheses to which p1, q1, r1, s1, and t1 are attached may be randomly bonded.)

9. The water- and oil-repellent member according to any one of claims 1 to 8, wherein the base material is resin, metal, ceramic, glass, sapphire, marble, or artificial marble.

10. The silicon compound-based binder is obtained by removing the dispersion medium from any one of colloidal silica, a hydrolysis / partial condensation product solution of tetraalkoxysilane, a hydrolysis / partial condensate of organoalkoxysilane, an emulsion of a hydrolysis / partial condensate of alkoxysiloxane, an emulsion of an organosilsesquioxane resin, an emulsion of a copolymer resin containing triorganosiloxy units and SiO2 units, an emulsion of a silicone resin-acrylic resin copolymer, and an emulsion of a silicone resin-urethane resin copolymer. The water- and oil-repellent member according to claim 1.

11. An article using the water- and oil-repellent member according to any one of claims 1 to 9.

12. The article according to claim 11, which is a building member, a kitchen member, furniture, an electronic device, a transportation device, or sanitary ware.

13. A step of wet-applying a liquid containing a silicon compound-based binder, metal fine particles having an average particle diameter of 1 to 1,000 nm and having antibacterial, antifungal, and antiviral properties and / or metal oxide fine particles having an average particle diameter of 3 to 100 nm, and a dispersion medium on at least one surface of a base material; removing the dispersion medium in the liquid to form and laminate a primer layer containing a silicon compound-based binder, metal fine particles having an average particle diameter of 1 to 1,000 nm and having antibacterial, antifungal, and antiviral properties and / or metal oxide fine particles having an average particle diameter of 3 to 100 nm on at least one surface of the base material, wherein the content of the metal fine particles and / or metal oxide fine particles having antibacterial, antifungal, and antiviral properties is 1 to 99% by mass based on the entire primer layer; a step of wet-applying a solution containing a fluorine-containing organosilicon compound or dry-applying the fluorine-containing organosilicon compound on the outer surface of the primer layer; and a step of curing the fluorine-containing organosilicon compound to form and laminate a water- and oil-repellent layer on the outer surface of the primer layer. The method for producing a water- and oil-repellent member according to any one of claims 1 to 9.

14. The method for producing a water- and oil-repellent member according to claim 13, wherein the silicon compound-based binder contained in the liquid used in the wet-applying step is colloidal silica, a hydrolysis / partial condensate solution of tetraalkoxysilane, an emulsion of a hydrolysis / partial condensate of organoalkoxysilane or a hydrolysis / partial condensate of alkoxysiloxane, an emulsion of an organosilsesquioxane resin, an emulsion of a copolymer resin containing triorganosiloxy units and SiO2 units, an emulsion of a silicone resin-acrylic resin copolymer, or an emulsion of a silicone resin-urethane resin copolymer.

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