Water-repellent member and method for producing water-repellent member

Abstract

Provided is a water-repellent member comprising a functional film layer on at least one surface of a substrate, a primer layer on the outer surface of the functional film layer, and a water-repellent layer on the outer surface of the primer layer, wherein the primer layer includes an organosilicon compound having a plurality of silanol groups in the molecule and has a film thickness of 10-500 nm, and the water-repellent layer includes a cured product of a hydrolyzable non-fluorine compound and has a film thickness of 0.5-50 nm. The water-repellent member is capable of stably and easily applying, to various substrates, a functional water-repellent coating film having excellent wear resistance and antistatic properties (i.e., the surface resistance value of the water-repellent member is reduced by one or more orders of magnitude as compared with a case in which the primer layer is not provided).

Description

Water-repellent material and method for manufacturing a water-repellent material

[0001] The present invention relates to a water-repellent member with excellent abrasion resistance and a method for manufacturing the water-repellent member, and more particularly to a water-repellent member having a functional film layer on the surface of a substrate, a layer formed on the functional film layer using an organosilicon compound having multiple silanol groups (hydroxyl groups bonded to silicon atoms) in its molecule, and a layer formed on the primer layer using a hydrolyzable nonfluorine compound, and a method for manufacturing the water-repellent member.

[0002] In recent years, there has been a growing demand for technologies that make surfaces resistant to dirt and easier to clean, in order to improve appearance and visibility. In particular, the surfaces of liquid crystal displays, organic EL displays, eyeglass lenses, smartphones, wearable devices, car navigation systems, electronic device casings, cosmetic packaging, kitchen countertops, and transport equipment bodies are prone to the adhesion of sebum and oil stains, making the application of a water-repellent layer desirable. However, fluorine compounds that possess water-repellent properties have very low surface free energy and exhibit non-stick and non-adherent properties to various substrates, making it difficult to directly adhere these fluorine compounds to the substrate. Furthermore, water-repellent films obtained from fluorine compounds tend to be easily charged, making it difficult to easily realize a water-repellent surface with excellent antistatic properties.

[0003] To solve this adhesion problem, as a treatment agent that can water-repellent the surface of a substrate such as glass, for example, Japanese Patent Application Publication No. 2011-116947 (Patent Document 1) discloses a fluorooxyalkylene group-containing polymer composition represented by the following average composition formula. (In the formula Rf 1 Ha-C d F 2d A and B are divalent linear fluorooxyalkylene groups containing 5 to 100 repeating units of O- (where d is an integer from 1 to 6 and may differ for each repeating unit), independently of each other, Rf 2 The base or the following formula A group selected from the groups shown by Rf 2(where F, H, or a monovalent fluorine-containing group with a -CF3 or -CF2H terminal, Q is a divalent organic group, Z is a 2-7 valent organopolysiloxane residue having a siloxane bond, R is a C1-C4 alkyl group or phenyl group, X is a hydrolyzable group, a is an integer from 2 to 3, b is an integer from 1 to 6, c is an integer from 1 to 5, and β is an integer from 0 to 1.)

[0004] However, the treatment agent proposed in Patent Document 1 exhibits relatively good durability, but it is not sufficient, and it is particularly difficult to obtain excellent adhesion to metals, metal oxides, resins, sapphires, ceramics, etc.

[0005] As a method to improve adhesion, a method has been disclosed in which an SiO2 layer is provided as a primer layer using a dry method (vapor deposition, sputtering, or CVD) (International Publication No. 2014 / 097388: Patent Document 2). While it has been shown that this method can form a water-repellent layer with excellent durability, it does not show sufficient durability when subjected to rigorous reliability tests such as surface abrasion.

[0006] Furthermore, components with a water-repellent layer formed by the above method often have a surface resistance value greater than that of the base material, leading to the problem of static electricity. While it has been proposed to incorporate various antistatic agents into the primer layer and water-repellent layer, from the perspective of adding antistatic agents to the composition, the water-repellency and stain resistance of the surface are insufficient, making it difficult to achieve both high abrasion resistance and antistatic properties on a water-repellent surface.

[0007] Furthermore, as mentioned above, fluorine compounds exhibit excellent properties such as water repellency, but in recent years, their use may be avoided depending on the application. This is because fluorine compounds are difficult to decompose in nature and tend to accumulate in the environment. Against this backdrop, there has been a growing demand for the development of surface protective agents for non-fluorine materials.

[0008] Japanese Patent Publication No. 2011-116947, International Publication No. 2014 / 097388

[0009] The present invention has been made in view of the above circumstances, and aims to provide a water-repellent member that has excellent abrasion resistance (particularly fabric abrasion resistance) and antistatic properties, and a method for manufacturing a water-repellent member that forms a water-repellent layer with excellent antistatic properties and abrasion resistance (particularly fabric abrasion resistance) on various substrates.

[0010] The inventors, after diligent research to achieve the above objectives, have developed a method comprising: forming a functional film layer mainly composed of silicon dioxide or a functional film layer in which at least the outermost layer is silicon dioxide on at least one surface of a substrate; wet coating a solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent onto the outer surface of the functional film layer; drying the solvent to form and laminate a primer layer on at least one surface of the substrate; wet coating a solution containing a hydrolyzable nonfluorine compound and a solvent onto the outer surface of the primer layer, followed by drying the solvent, or dry coating a hydrolyzable nonfluorine compound obtained by evaporating the solvent from the solution; and curing the hydrolyzable nonfluorine compound to form the outer surface of the primer layer. The present invention was made by discovering that a water-repellent member obtained by a method including the step of forming and laminating a water-repellent layer on a surface, having a functional film layer on at least one surface of a substrate, a primer layer on the outer surface of the functional film layer, and a water-repellent layer on the outer surface of the primer layer, wherein the primer layer is a layer with a thickness of 10 to 500 nm containing an organosilicon compound having multiple silanol groups in its molecule, and the water-repellent layer is a layer with a thickness of 0.5 to 50 nm containing a cured product of a hydrolyzable nonfluorine compound, can stably and easily impart a functional water-repellent coating with excellent abrasion resistance and antistatic properties (i.e., the surface resistance value of the water-repellent member is more than an order of magnitude lower than when no primer layer is provided), to various substrates.

[0011] In other words, the present invention provides the following water-repellent members and methods for manufacturing water-repellent members. [1] A water-repellent member having a functional film layer on at least one surface of a substrate, a primer layer on the outer surface of the functional film layer, and a water-repellent layer on the outer surface of the primer layer, wherein the primer layer is a layer with a thickness of 10 to 500 nm containing an organosilicon compound having a plurality of silanol groups in its molecule, and the water-repellent layer is a layer with a thickness of 0.5 to 50 nm containing a cured product of a hydrolyzable nonfluorine compound. [2] The water-repellent member according to [1], wherein the functional film layer is entirely composed of silicon dioxide as its main component, or at least the outermost layer is silicon dioxide. [3] The water-repellent member according to [1] or [2], wherein the organosilicon compound having a plurality of silanol groups in its molecule is a hydrolyzed and partially condensed product of a silane compound having four hydrolyzable groups. [4] The hydrolyzable nonfluorine compound has at least one hydrolyzable silyl group or silazane group at the end of at least one molecular chain, as described in any of [1] to [3]. [5] The hydrolyzable silyl group is a silyl group having 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 or an amino group, as described in [4]. [6] The hydrolyzable nonfluorine compound is a hydrocarbon terminal group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon terminal group having 3 to 32 carbon atoms and at least one reactive silyl group in the molecule, as described in any of [1] to [5]. [7] The hydrolyzable nonfluorine compound is a compound of the following general formula (1) (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms, U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is independently a single bond, or a divalent hydrocarbon group that may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group that may contain at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, A is independently a monovalent reactive silyl group, k1 is an integer of 1 to 3, k2 is 0 or 1, k3 is an integer of 1 to 3, k1 + k2 + k3 is 3 or 4, and m is an integer of 1 to 7. ) is a hydrocarbon terminal group-containing compound, and the water-repellent member according to any one of [1] to [6]. [8] In the above formula (1), A is the following general formula (2) (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3. ) is the group represented by, and the water-repellent member according to [7]. [9] In the above formula (2), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms. The water-repellent member according to [8].

[10] In the above formula (1), R 1 is the following formulas (3a) to (3c) (In the formula, R AQ is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, or a carbamate group. Q' is a divalent group selected from the group consisting of a urea group and a divalent nitrogen-containing heterocyclic group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group, Q'' is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A A water-repellent member according to any of [7] to [9], which is any group represented by (3a) to (3c) above, where R AThe water-repellent member according to

[10] , wherein Y is a monovalent hydrocarbon group having 11 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof.

[12] The water-repellent member according to any one of [7] to

[11] , wherein Y in formula (1) above is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from oxygen atoms, nitrogen atoms, and sulfur atoms, an alkylene group having 1 to 10 carbon atoms which includes an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms.

[13] In formula (1) above, Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 (A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4The water-repellent member according to any one of [7] to

[12] , wherein the group is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a linear or branched or cyclic trivalent to octavalent organopolysiloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms; a trivalent amide group; a trivalent carbamate group; a trivalent or tetravalent urea group; and a trivalent to octavalent nitrogen-containing heterocyclic group.

[14] A water-repellent member according to any one of [7] to

[13] , wherein in formula (1) above, U is a trivalent or tetravalent group selected from the group consisting of carbon atoms, silicon atoms, nitrogen atoms, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group.

[15] A water-repellent member according to any one of [1] to

[14] , wherein the base material is a resin, ceramic, metal, quartz, glass, sapphire, or diamond.

[16] A water-repellent member according to any one of [1] to

[14] , wherein the surface resistance is 1.0 × 10 12 A water-repellent member according to any one of [1] to

[15] , wherein the Ω / □ is less than or equal to

[17] . A method for manufacturing a water-repellent member according to any one of [1] to

[16] , comprising the steps of: forming a functional film layer mainly composed of silicon dioxide or a functional film layer in which at least the outermost layer is silicon dioxide on at least one surface of a substrate; wet coating a solution containing an organosilicon compound having a plurality of silanol groups in its molecule and a solvent on the outer surface of the functional film layer; drying the solvent to form and laminate a primer layer on at least one surface of the substrate; wet coating a solution containing a hydrolyzable nonfluorine compound and a solvent on the outer surface of the primer layer and then drying the solvent, or dry coating a hydrolyzable nonfluorine compound obtained by evaporating the solvent from the solution; and curing the hydrolyzable nonfluorine compound to form and laminate a water-repellent layer on the outer surface of the primer layer.

[0012] According to the present invention, a water-repellent member with excellent antistatic properties and abrasion resistance can be formed. The water-repellent member can be manufactured using a vacuum process or a wet process (brush coating, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating), and can be applied to a variety of applications.

[0013] The present invention will be described in more detail below. The water-repellent member of the present invention is a water-repellent member having a functional film layer on at least one surface of a substrate, a primer layer on the outer surface of the functional film layer, and a water-repellent layer on the outer surface of the primer layer, wherein the primer layer is a layer with a thickness of 10 to 500 nm containing an organosilicon compound having a plurality of silanol groups in its molecule, and the water-repellent layer is a layer with a thickness of 0.5 to 50 nm containing a cured product of a hydrolyzable nonfluorine compound.

[0014] The water-repellent member of the present invention can be obtained, for example, by forming a functional film layer mainly composed of silicon dioxide or a functional film layer in which at least the outermost layer is silicon dioxide on the surface (at least one surface) of various substrates; then wet-coating a solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent onto the outer surface of the functional film layer; then drying the solvent to form and laminate a primer layer on at least one surface of the substrate; and further wet-coating a water-repellent agent containing a hydrolyzable nonfluorine compound onto the outer surface of the primer layer and then drying the solvent, or by dry-coating a hydrolyzable nonfluorine compound obtained by evaporating the solvent from the water-repellent agent containing the hydrolyzable nonfluorine compound, and then curing the hydrolyzable nonfluorine compound to form and laminate a water-repellent layer on the outer surface of the primer layer.

[0015] [Substrate] The substrate used in the present invention is not particularly limited, but examples include resins, ceramics, metals, quartz, glass, sapphires, diamonds, etc. It is preferable that the substrate does not have silanol groups on its surface, and resins and ceramics are particularly preferred.

[0016] Here, examples of resins include thermoplastic resins and thermosetting resins. Specifically, these include celluloid, cellulose acetate, cellulose propionate, cellulose butyrate, triacetylcellulose, aliphatic polyamides such as 6-nylon, 6,6-nylon, and 12-nylon, aromatic polyamides, ABS resin, AS resin, polystyrene, polyethylene (low-density or high-density), polyolefins such as polypropylene, cycloolefin polymers, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyacetal, polycarbonate, saturated polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate, aromatic polyesters, polyether ketones, polyether ether ketones, polysulfone, and polyethersulfone. Examples of thermoplastic resins include phenyl acetate, polyetherimide, polyarylate, polymethylpentene, ionomer, liquid crystal polymer, polyimide, polyamideimide, fluororesin, polyphenylene sulfide, (modified) polyphenylene oxide, thermoplastic polyurethane, or thermosetting resins such as epoxy resin, unsaturated polyester, thermosetting polyurethane, polyimide, polymers of diethylene glycol bisallyl carbonate (commonly known as CR-39), (halogenated) bisphenol A di(meth)acrylate copolymer, (halogenated) bisphenol A urethane-modified di(meth)acrylate copolymer, diacrylate compounds, vinyl benzyl alcohol and unsaturated thiol compounds, etc.

[0017] Examples of ceramics include aluminum oxide, zirconium oxide, silicon oxide, titanium oxide, yttrium oxide, magnesium oxide, aluminum nitride, zirconium nitride, silicon nitride, titanium nitride, boron nitride, silicon carbide, titanium carbide, boron carbide, as well as composite ceramics and glass ceramics made from these materials.

[0018] Specifically, examples of metals include silver, gold, cobalt, chromium, copper, iron, iridium, molybdenum, nickel, palladium, platinum, silicon, titanium, vanadium, tungsten, zirconium, their alloys, and various types of stainless steel (SUS).

[0019] Examples of glass include soda-lime glass, borosilicate glass, aluminosilicate glass, quartz glass, lead glass, and alkali-free glass. Furthermore, any of these glasses may be chemically strengthened.

[0020] [Functional film layer (first layer)] Examples of functional film layers include hard coat layers, anti-reflective layers, and IR cut filter layers, but the functional film layer is not limited to these, and any layer in which the entire layer is mainly composed of silicon dioxide, or at least the outermost layer of the layer is made of silicon dioxide, is acceptable. Here, "mainly composed of silicon dioxide" means that the functional film layer contains 50% by mass or more, particularly 90-100% by mass, of silicon dioxide. The functional film layer can be formed (laminated), for example, by coating it on the outer surface of the substrate using a known method.

[0021] Here, examples of functional film layers include a hard coat layer mainly composed of a silicon dioxide layer, a hard coat layer consisting of a two-layer structure or a laminated structure of three or more layers in which a silicon dioxide layer is formed on a hard coat layer, an anti-reflective layer consisting of a two-layer structure formed on a substrate so that silicon dioxide is the outermost layer, or a laminated structure of three or more layers such as a silicon dioxide layer and a high refractive index layer, and an IR cut filter layer consisting of a two-layer structure or a laminated structure of three or more layers formed on a substrate so that silicon dioxide is the outermost layer.

[0022] In addition, in functional film layers consisting of two or more laminated structures, layers other than the silicon dioxide layer include titanium dioxide, niobium pentoxide, tungsten oxide, cerium oxide, tantalum pentoxide, zinc oxide, indium tin oxide, indium zinc oxide, zirconium oxide, silicon nitride, magnesium fluoride, and the like.

[0023] The functional film layer can be formed (laminated) by coating the outer surface of the substrate using known methods such as wet coating (dipping, brush coating, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating) or vapor deposition.

[0024] The thickness of the functional film layer is preferably 5 to 500 nm for the entire functional film layer (silicon dioxide layer) or the outermost layer of the functional film (silicon dioxide layer), and more preferably 5 to 150 nm. If the silicon dioxide layer of the entire functional film layer or the outermost layer of the functional film is less than 5 nm, adhesion with the primer layer may be insufficient, and if it exceeds 500 nm, transparency may be impaired. In this invention, the film thickness can be measured by known methods such as spectroscopic ellipsometry or X-ray reflectivity.

[0025] [Primer layer (second layer)] The primer layer is a layer with a thickness of 10 to 500 nm containing an organosilicon compound having multiple silanol groups in its molecule. The primer layer can be formed (laminated), for example, by wet coating the outer surface of the functional film layer with a solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent, and then drying and removing the solvent.

[0026] Organosilicon compounds having multiple silanol groups in their molecules preferably have two or more, more preferably three or more, and even more preferably four or more silanol groups in their molecules. If the number of silanol groups in the molecule is too small, the adhesion with the water-repellent layer (third layer) laminated on the outer surface of the primer layer (second layer) may be poor, or the surface resistance value of the resulting water-repellent member may not be low enough. The amount of silanol groups in the organosilicon compound having multiple silanol groups in its molecule is preferably 0.002 to 1.00 mol / g, particularly 0.004 to 0.85 mol / g, and especially 0.005 to 0.70 mol / g. The amount of silanol groups can be measured by the Grignard method, which quantifies the amount of methane gas generated using a methyl Grignard reagent.

[0027] Organosilicon compounds having multiple silanol groups (hydroxyl groups bonded to silicon atoms) in their molecule can be obtained by hydrolysis and partial condensation of organosilicon compounds having multiple hydrolyzable groups bonded to silicon atoms, such as alkoxy groups (methoxy groups, ethoxy groups, etc.) and halogen atoms (chlorine atoms, etc.).

[0028] Here, organosilicon compounds having multiple hydrolyzable groups in the molecule include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4- Examples include epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, trichlorosilane, dichlorosilane, etc. Two or more of these may be used in combination.

[0029] In the present invention, it is preferable to use an organosilicon compound having multiple silanol groups in its molecule, which is obtained by hydrolyzing an organosilicon compound such as an organosilane having multiple hydrolyzable groups as described above, and then partially dehydrating and condensing it to increase its molecular weight (partial condensate). In the present invention, a partial condensate means an organopolysiloxane compound having multiple residual silanol groups in its molecule, obtained by partially dehydrating and condensing an organosilane having multiple silanol groups (hydroxyl groups bonded to silicon atoms) in its molecule, which is obtained by hydrolyzing an organosilicon compound such as an organosilane having multiple hydrolyzable groups as described above.

[0030] The hydrolysis and partial condensation products of organosilicon compounds having multiple hydrolyzable groups in the molecule (organosilicon compounds having multiple silanol groups in the molecule) preferably have a weight-average molecular weight of 200 to 100,000, and more preferably 300 to 50,000. In this invention, the weight-average molecular weight can be determined, for example, as the polystyrene equivalent value in gel permeation chromatography (GPC) analysis using THF as the developing solvent (the same applies hereinafter).

[0031] In the present invention, organosilicon compounds having multiple silanol groups in the molecule are particularly preferred as hydrolysis and partial condensation products of silane compounds having four hydrolyzable groups, and among these, hydrolysis and partial condensation products of tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane are preferred.

[0032] Organosilicon compounds having multiple silanol groups in their molecule are preferably diluted with a solvent. Preferred solvents for dissolving organosilicon compounds having multiple silanol groups in their molecule include alcohols such as methanol, ethanol, isopropanol, and butanol, and ethers such as propylene glycol monomethyl ether and polyethylene glycol monopropyl ether, but are not particularly limited and can be appropriately selected based on wettability with the functional film layer and boiling point. The concentration of the organosilicon compound having multiple silanol groups in its molecule in the solution containing the organosilicon compound and the solvent is preferably 0.01 to 10% by mass, and more preferably 0.1 to 4% by mass. If the concentration is too low, the uncoated area will increase, and if the concentration is too high, secondary aggregation of silanol groups may occur.

[0033] Furthermore, the solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent may optionally contain components such as UV absorbers, light stabilizers, antioxidants, leveling agents, defoamers, pigments, dyes, dispersants, antistatic agents, and surfactants such as antifogging agents. It is preferable that these components be added in a range where the amount of organosilicon compound having multiple silanol groups in its molecule in the primer layer obtained after removing the solvent is 50% by mass or more (50 to 100% by mass), particularly 80 to 100% by mass (i.e., any of the above components are 50% by mass or less (0 to 50% by mass), preferably 0 to 20% by mass). From the viewpoint of further improving the water repellency and stain resistance of the water-repellent member, it is preferable not to contain antistatic agents such as alkali metal atoms (or their metal salts), and from the viewpoint of adhesion, it is preferable to use a solution consisting substantially of an organosilicon compound having multiple silanol groups in its molecule and a solvent.

[0034] Furthermore, a hydrolysis condensation catalyst, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate, tetra-n-propyl titanate), organozirconium compounds (e.g., tetra-n-butyl zirconate, tetra-n-propyl zirconate), organic acids (e.g., acetic acid, methanesulfonic acid, carboxylic acid), inorganic acids (e.g., hydrochloric acid, sulfuric acid), solid acids (e.g., resin-supported acids, silica-supported acids), organic bases (e.g., amines, trialkylamines, nitrogen-containing cyclic compounds), or solid bases (e.g., resin-supported bases, silica-supported bases) may be added as needed to a solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent. Among these, organic acids, organotitanium compounds, and organozirconium compounds are particularly desirable. These are preferably added in such a range that the amount of organosilicon compounds having multiple silanol groups in the molecule in the primer layer obtained after removing the solvent is 90% by mass or more (90 to 100% by mass), and more particularly 98 to 99.9% by mass (i.e., any of the above components is 10% by mass or less (0 to 10% by mass), preferably 0.1 to 2% by mass).

[0035] A solution containing an organosilicon compound having multiple silanol groups in its molecule and a solvent can be applied to the outer surface of the functional film layer by wet coating, particularly by dipping, brush coating, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating, or pour coating, and the solvent is dried off to form a primer layer containing an organosilicon compound having multiple silanol groups in its molecule. Alternatively, heating may be performed at a temperature range that does not affect the substrate, for example, at 40 to 500°C for 10 seconds to 24 hours.

[0036] The thickness of the primer layer formed and laminated on the outer surface of the functional film layer is 10 to 500 nm, preferably 30 to 400 nm, and particularly preferably 30 to 200 nm. If the thickness of the primer layer is less than 10 nm, adhesion with the water-repellent layer may be insufficient, and if it exceeds 500 nm, transparency may be impaired or the material surface may become rough. The thickness can be measured by known methods such as spectroscopic ellipsometry or X-ray reflectivity.

[0037] [Water-repellent layer (third layer)] Next, the water-repellent layer is a layer with a thickness of 0.5 to 50 nm containing a cured product of a hydrolyzable nonfluorine compound. In the present invention, it is preferable that the water-repellent layer is made of a cured product of a hydrolyzable nonfluorine compound. The water-repellent layer can be formed and laminated, for example, by applying a water-repellent agent containing a hydrolyzable nonfluorine compound to the outer surface of the primer layer formed above and curing it.

[0038] Let's explain hydrolyzable nonfluorine compounds in detail.

[0039] The hydrolyzable nonfluorine compound according to the present invention is preferably an organic compound that does not have a fluorine atom and has at least one hydrolyzable silyl group at each of the molecular chain ends, preferably 1 to 14, more preferably 1 to 7 (for example, having at least one hydrolyzable silyl group in the molecule, preferably 2 to 60, more preferably 3 to 30), or has at least one silazane group in the molecule, preferably 1 to 7, more preferably 1 to 3. The hydrolyzable silyl group described above is preferably a silyl group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as a methoxy group, ethoxy group, propoxy group, or butoxy group; alkoxy groups having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, such as a methoxymethoxy group or methoxyethoxy group; acyloxy groups having 1 to 10 carbon atoms, such as an acetoxy group; alkenyloxy groups having 2 to 10 carbon atoms, such as an isopropenoxy group; halogen groups such as a chlor group, bromo group, or iodine group; or an amino group.

[0040] The hydrolyzable nonfluorine compound is preferably a compound having at least one hydrocarbon chain in its molecule, and more preferably a linear hydrocarbon chain. Here, "linear hydrocarbon chain" means an unsubstituted linear alkyl group.

[0041] The linear alkyl group has three or more carbon atoms, preferably six or more, and more preferably eleven or more, from the viewpoint of water repellency and abrasion resistance. From the viewpoint of ease of manufacture, the number of carbon atoms is preferably 40 or less, more preferably 36 or less, and even more preferably 32 or less. From this viewpoint, the number of carbon atoms is preferably 3 to 40, more preferably 6 to 36, and even more preferably 11 to 32.

[0042] The hydrolyzable nonfluorine compound according to the present invention is preferably a hydrocarbon terminal group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon terminal group having 3 to 32 carbon atoms and at least one reactive silyl group in the molecule.

[0043] The hydrolyzable nonfluorine compound according to the present invention is more preferably a hydrocarbon-terminal group-containing compound represented by the following general formula (1). (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 (where k1 is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is independently a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a trivalent to octavalent organic group; Y is independently a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is independently a monovalent reactive silyl group; k1 is an integer from 1 to 3; k2 is 0 or 1; k3 is an integer from 1 to 3; k1 + k2 + k3 is 3 or 4; and m is an integer from 1 to 7.)

[0044] The hydrocarbon terminal group-containing compound represented by formula (1) has one or more hydrocarbon terminal groups of a predetermined number of carbon atoms, particularly one or more groups selected from alkyl groups having 3 to 32 carbon atoms, preferably 6 to 32 carbon atoms, and aryl groups having 6 to 32 carbon atoms, at its terminal end, and a reactive silyl group that exhibits adhesion to the substrate at the other terminal end, and these are linked via a linking group. By having one or more hydrocarbon terminal groups of a predetermined number of carbon atoms, particularly groups selected from alkyl groups having 3 to 32 carbon atoms, preferably 6 to 32 carbon atoms, and aryl groups having 6 to 32 carbon atoms at its terminal end, the mobility at the molecular chain terminals is improved, and as a result the cured film of the surface treatment agent containing the compound has excellent water repellency and abrasion resistance.

[0045] In the above formula (1), R 1This group may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 32 carbon atoms, more preferably 11 to 32 carbon atoms. Here, when it contains at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, it may be an ether group (-O-), a carbonyl (ketone) group (-C(=O)-), an ester group (-C(=O)O-), a carbonate group (-OC(=O)O-), a thioether group (-S-), a sulfinyl group (-S(=O)-), a sulfonyl group (-S(=O)2-), a thioester group (-C(=O)-S-), a thiocarbonate group (-SC(=S)S-), or a thiocarbamate group (-OC(=S)NR 6 -, -SC(=O)NR 6 - (R 6 (These are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, the same applies hereinafter), an amino group (-NR 6 -), amide group (-C(=O)NR 6 -), carbamate group (-OC(=O)NR 6 -), urea group (-NR 6 C(=O)NR 6 It is preferable to include divalent groups such as oxazole groups, imidazole groups, triazole groups, cyanurate groups, isocyanurate groups, diorganosilylene groups, organopolysiloxane residues, sylalkylene groups, and sylarylene groups.

[0046] R 1 As such, groups represented by the following formulas (3a) to (3c) are preferred. (In the formula, R AQ is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, or a divalent nitrogen-containing heterocyclic group (divalent oxazole group, divalent imidazole group). Q' is a divalent group selected from the group consisting of a group (such as a divalent triazole group), Q' is a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, or a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group), and Q'' is a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, or R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A (or a hydrogen atom, where p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 32 or less.)

[0047] In the above formulas (3a) to (3c), R A R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 32 carbon atoms, more preferably 11 to 32 carbon atoms, and may be linear, branched, cyclic, or a combination thereof. A For example, the following can be cited: (In the formula, x is an integer between 2 and 31, preferably between 5 and 31, more preferably between 10 and 31, and y and y' are integers of 1 or more such that the sum of the number of carbon atoms in each structure is 32 or less.)

[0048] In formula (3a) above, Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a divalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear structure with 2 to 8 silicon atoms, or a branched or cyclic structure with 3 to 10 silicon atoms, particularly a 3 to 8 silicon atom, a carbonyl (ketone) group (-C(=O)-), an ester group (-C(=O)O-), a carbonate group (-OC(=O)O-), a sulfinyl group (-S(=O)-), a sulfonyl group (-S(=O)2-), a thioester group (-C(=O)-S-), a thiocarbonate group (-SC(=S)S-), a thiocarbamate group (-OC(=S)NR 6 -, -SC(=O)NR 6 - (R 6 (The above is the same), amino group (-NR 6 -), amide group (-C(=O)NR 6 -), carbamate group (-OC(=O)NR 6 -), urea group (-NR 6 C(=O)NR 6 It is a divalent group selected from the group consisting of divalent nitrogen-containing heterocyclic groups (such as divalent oxazole groups, divalent imidazole groups, and divalent triazole groups).

[0049] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Moreover, the organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0050] Examples of such Q include those shown below. In the structure below, the left-hand coupling is R A or R B It is joined to the right side, and the joining hand is R B It combines with it. (In the formula, f is an integer between 2 and 4, and e is an integer between 1 and 9.)

[0051] In the above formula (3b), Q' is a trivalent group selected independently from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear group having 2 to 8 silicon atoms, or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly a branched or cyclic group having 3 to 8 silicon atoms, a trivalent amide group (-C(=O)N=), and a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).

[0052] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0053] Examples of such Q' include those shown below. In the structure below, the left-hand coupling is R A or R B And the coupling on the right is R B And the other bonds are R C It combines with it. (In the formula, f is an integer between 2 and 4.)

[0054] In the above formula (3c), Q'' is a tetravalent group independently selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0055] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0056] Examples of such Q'' include those shown below. In the structure below, the left-hand coupling is R A or R B And the coupling on the right is R B And the other bonds are R C It combines with it.

[0057] In the above formulas (3a) to (3c), R B These are divalent hydrocarbon groups having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, and the following are examples: (In the formula, z is an integer between 1 and 10.)

[0058] In the above equations (3b) and (3c), R C R is independent A Or it is a hydrogen atom. Note that R C RA In that case, the above R A It may be the same as or different from it.

[0059] In the above formulas (3a) to (3c), p is an integer from 0 to 10, and is preferably 0, 1, or 2. However, R 1 The total number of carbon atoms in each structure is 32 or less.

[0060] This kind of R 1 The following are preferred for use. (In the formulas, x, y, y', and z are the same as above, except that the total number of carbon atoms in each structure is between 3 and 32.)

[0061] In the above formula (1), R 2 R is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms (methyl group, ethyl group). 2 Preferably, the atoms are hydrogen atoms, chlorine atoms, hydroxyl groups, methyl groups, and ethyl groups.

[0062] In formula (1) above, U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, and the trivalent or tetravalent organic group is a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, especially 2 to 8 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, especially 3 to 8 silicon atoms, a trivalent amide group (-C(=O)N=), a trivalent carbamate group (-OC(=O)N=), or a trivalent or tetravalent urea group (-NR 6 C(=O)N= or =NC(=O)N=(R 6 Preferably, the group is a trivalent or tetravalent group selected from (the same as above) and trivalent or tetravalent nitrogen-containing heterocyclic groups (such as trivalent cyanurate groups, trivalent isocyanurate groups, and trivalent triazine ring-containing groups).

[0063] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0064] Examples of such U are shown below. In the structure below, it is preferable that the right-hand coupling bond connects to V.

[0065] In formula (1) above, V may independently contain a single bond or at least one selected from oxygen, nitrogen, and sulfur atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the U group and the Z group. When Z is a single bond, V is preferably a single bond. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms which may contain at least one selected from oxygen, nitrogen, and sulfur atoms, an alkylene group having 1 to 10 carbon atoms which includes an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms).

[0066] Examples of such V include, in addition to single bonds, the following. In the structure below, the bond on the left is bonded to U, and the bond on the right is bonded to Z. (In the formula, q is an integer between 1 and 10, r, s, and t are each integers between 1 and 8, the sum of r and s is an integer between 2 and 10, and the sum of r, s, and t is an integer between 3 and 10.)

[0067] In formula (1) above, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a 3- to 8-valent organic group, and the 3- to 8-valent organic group is a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3(A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 (where is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms) trivalent groups, linear groups with 2 to 10 silicon atoms, especially 2 to 8 silicon atoms, or branched or cyclic tri- to octavalent organopolysiloxane residues with 3 to 10 silicon atoms, especially 3 to 8 silicon atoms, trivalent amide groups (-C(=O)N=), trivalent carbamate groups (-OC(=O)N=), trivalent or tetravalent urea groups (-NR 6 C(=O)N= or =NC(=O)N=(R 6 Examples include 3- to 8-valent groups such as (the same as above), and 3- to 8-valent nitrogen-containing heterocyclic groups (such as trivalent cyanurate groups, trivalent isocyanurate groups, and trivalent or tetravalent triazine ring-containing groups).

[0068] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0069] Examples of such Z bonds include, in addition to single bonds, those shown below. In the structure below, the bond on the left is bonded to V, and the other bonds are bonded to Y. (In the formula, f is an integer between 2 and 4.)

[0070] In formula (1) above, Y may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the Z group and the A group. Examples of the divalent hydrocarbon group include, specifically, an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms); a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0071] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Moreover, the organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0072] Examples of such Y groups include the following. In the structure below, the left-hand bond is bonded to Z, and the right-hand bond is bonded to A. It is preferable that there are two or more repeating units represented by (CH2) that bond to A. (In the formula, a is an independent integer between 1 and 10, b, c, and d are each integers between 1 and 8, the sum of b and c is an integer between 2 and 10, and the sum of b, c, and d is an integer between 3 and 10. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0073] In formula (1) above, A is independently a monovalent reactive silyl group, and examples include monovalent groups such as hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups. Among these, hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups are preferred.

[0074] As the hydroxyl group-containing silyl group and hydrolyzable silyl group, the group represented by the following general formula (2) is preferred. (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer from 1 to 3.)

[0075] In formula (2) above, R is independently an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 4 carbon atoms, or a phenyl group, with the methyl group being preferred. Also, in formula (2) above, X is independently a hydroxyl group or a hydrolyzable group, and examples of such X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy and cyclopentenyloxy groups; halogen groups such as chlor, bromo, and iodine groups; and dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, acetoxy, and chlor groups are preferred. X may be the same or different.

[0076] The following structures are examples of hydrocarbon terminal group-containing compounds represented by the above formula (1). 1 , R 2By changing the combinations of U, V, Z, Y, A, k1, k2, k3, and m, several different hydrocarbon end-group-containing compounds can be obtained.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] (In the formula, x, y, y', z, q, r, s, a, b, c, d, e, and f are all independently the same as above.)

[0086] Examples of methods for preparing hydrocarbon terminal group-containing compounds represented by general formula (1) include the following: [Preparation Method 1] A hydrocarbon terminal group-containing compound having an alkenyl group at its terminus and a compound having an SiH group and a hydrolyzable silyl group can be mixed and subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst to produce a hydrocarbon terminal group-containing compound represented by formula (1). If a compound having an SiH group and a hydrolyzable silyl group has a halogen group as the hydrolyzable group, the compound can then be produced by converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.

[0087] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formula (4). (In the formula, R 1 , R 2 U, V, Z, k1, k2, k3, k1+k2+k3, and m are the same as above, and Y' is a divalent hydrocarbon group that may independently contain a single bond or at least one selected from oxygen, nitrogen, sulfur, and silicon atoms.

[0088] In formula (4) above, Y' may independently consist of a single bond or at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, the following being examples. In the structure below, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. (In the formula, a' is an independent integer between 0 and 8, b and c are integers between 1 and 8, c' and d' are integers between 0 and 6, the sum of b and c' is an integer between 2 and 8, and the sum of b, c, and d' is an integer between 3 and 8. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0089] Examples of compounds represented by formula (4) are listed below. (In the formula, x, y, y', z, q, a, a', b, c, and c' are all independently the same as above.)

[0090] The compound having an SiH group and a hydrolyzable silyl group is preferably a silane compound represented by the following general formula (5). (In the formula, R, X, and n are the same as above.)

[0091] Examples of silane compounds represented by the above formula (5) include trimethoxysilane, methyldimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0092] In preparation method 1, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 6 moles, particularly 1.5 to 4 moles, per mole of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0093] In preparation method 1, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. It is preferable to dissolve the platinum-based compound in a solvent such as toluene, lower alcohol, higher alcohol, or silicone-based solvent before use. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, in terms of transition metal (mass), relative to the mass of the hydrocarbon end-group-containing compound having an alkenyl group at the terminal end.

[0094] In manufacturing method 1, a co-catalyst to accelerate the reaction may be added to the above reaction. Examples of such co-catalysts include organic acids (formic acid, acetic acid, etc.), organic nitrogen compounds (pyridine, tributylamine, formamide, etc.), organic sulfur compounds (dimethyl sulfide, etc.), and organic phosphorus compounds (triphenylphosphine, tributylphosphine). When a co-catalyst is used, the amount used is preferably 100 to 4,000 ppm, more preferably 100 to 2,000 ppm, and particularly preferably 100 to 1,000 ppm, relative to the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0095] In preparation method 1, a solvent can be used when carrying out the reaction. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. The amount of solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0096] In preparation method 1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at its terminus and the compound having an SiH group and a hydrolyzable silyl group are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0097] In preparation method 1, if a compound having a SiH group and a hydrolyzable silyl group is used, such as trichlorosilane, in which the hydrolyzable group is a halogen group (a compound containing an SiH group and a silyl halogen group), the substituent (halogen atom) on the silyl group can then be converted to another hydrolyzable group, such as an alkoxy group like a methoxy group. Examples of compounds that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, and trimethyl orthoformate. The amount used is preferably 3 to 9 moles, particularly 3 to 5 moles, per mole of halogen atoms in the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the SiH group and silyl halogen group-containing compound.

[0098] In preparation method 1, the reaction conditions for converting substituents (halogen atoms) on the silyl group to other hydrolyzable groups are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0099] Subsequently, by removing the solvent and unreacted products under reduced pressure, a hydrocarbon terminal group-containing compound represented by the above general formula (1) can be obtained.

[0100] Furthermore, the hydrocarbon terminal group-containing compound represented by formula (1) according to the present invention may include a compound in which some or all of the above hydrolyzable groups have been hydrolyzed (a compound in which X is an OH group), and may also include a compound in which some or all of these OH groups are condensed.

[0101] It is preferable to dilute the above hydrolyzable nonfluorine compound with a solvent beforehand, and such a solvent is not particularly limited as long as it can uniformly dissolve the above hydrolyzable nonfluorine compound. Examples include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate), and hexamethyldisiloxane. Among these, toluene, hexane, ethylcyclohexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and hexamethyldisiloxane are preferred in terms of solubility, wettability, etc.

[0102] The above solvents may be mixed in two or more forms, and it is preferable to uniformly dissolve the hydrolyzable nonfluorine compound. The optimal concentration of the hydrolyzable nonfluorine compound to be dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh is acceptable. However, when direct coating, it is preferable to use 0.01 to 100 parts by mass, particularly 0.05 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the hydrolyzable nonfluorine compound. When vapor deposition is performed, it is preferable to use 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the hydrolyzable nonfluorine compound. In either coating case, 100 parts by mass refers to the case where no solvent is used and the coating is performed directly.

[0103] The water repellent containing the hydrolyzable nonfluorine compound may optionally contain hydrolysis condensation catalysts, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate, tetra-n-propyl titanate), organozirconium compounds (e.g., tetra-n-butyl zirconate, tetra-n-propyl zirconate), organic acids (e.g., acetic acid, methanesulfonic acid, carboxylic acid), inorganic acids (e.g., hydrochloric acid, sulfuric acid), and organic bases (e.g., amines, trialkylamines, nitrogen-containing cyclic compounds). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. The amount of hydrolysis condensation catalyst added is a catalytic amount, usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrolyzable nonfluorine compound.

[0104] Water repellents containing hydrolyzable nonfluorine compounds further include the following general formula (6) SiR 5 n1-4 X 1 n1 (6) (wherein, R 5 X is independently a hydrogen atom or a monovalent hydrocarbon group having 1 or 2 carbon atoms, 1 (where n1 is an integer from 1 to 4, where n1 is independently a hydroxyl group or a hydrolyzable group.) This may include at least one silane compound represented by .

[0105] In the above formula (6), R 5R is independently a hydrogen atom or a monovalent hydrocarbon group having one or two carbon atoms. Examples of monovalent hydrocarbon groups having one or two carbon atoms include alkyl groups such as methyl and ethyl groups, and alkenyl groups such as vinyl groups. 5 Among these, methyl groups and vinyl groups are preferred.

[0106] In the above formula (6), X 1 X is independently a hydroxyl group or a hydrolyzable group. 1 Examples include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy and cyclopentenyloxy groups; halogen groups such as chlor, bromo, and iodine groups; and dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, and chlor groups are preferred. 1 They may be the same or different.

[0107] In the above formula (6), n1 is an integer from 1 to 4, preferably 3 or 4.

[0108] Particularly preferred examples of silane compounds represented by the above formula (6) include the following compounds: Si(OCH3)4, Si(OC2H5)4, Si(OC3H7)4, Si(OC4H9)4, CH2=CHSi(OCH3)3, CH2=CHSi(OC2H5)3, CH2=CHSi(OC3H7)3, CH2=CHSi(OC4H9)3, CH2=CHSi(OCOCH3)3, CH3Si(OCH3)3, CH3Si(OC2H5)3, CH3Si(OC3H7)3, CH3Si(OC4H9)3, CH3Si(OCOCH3)3

[0109] When incorporating the silane compound represented by formula (6), the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the hydrolyzable nonfluorine compound.

[0110] The water repellent containing the hydrolyzable nonfluorine compound may further contain one or more nonfluorine-based materials selected from paraffin compounds (hereinafter referred to as paraffin oil) that are nonreactive with the hydrolyzable nonfluorine compound, polyol ester compounds (hereinafter referred to as polyol ester oil) that are nonreactive with the hydrolyzable nonfluorine compound, silicone compounds (hereinafter referred to as silicone oil) that are nonreactive with the hydrolyzable nonfluorine compound, halide ions, silane coupling agents, and compounds containing atoms with lone pairs of electrons in their molecular structure, to the extent that it does not impair the purpose of the present invention.

[0111] The paraffin oils mentioned above include linear, branched, or cyclic paraffin oils with 2,000 or fewer carbon atoms. Specific examples of paraffin oils include liquid paraffin, paraffin wax, polyethylene, polypropylene, and PAO (polyalphaolefin). While paraffin oils that are liquid at room temperature (25°C) are preferred, solid paraffin oils can also be used.

[0112] When paraffin oil is included, the amount is preferably 0.001 to 80 parts by mass per 100 parts by mass of the above hydrolyzable nonfluorine compound.

[0113] Examples of the polyol ester oils mentioned above include polyol ester compounds consisting of condensates of di- to hexavalent alcohols and fatty acids having 3 to 22 carbon atoms. Specifically, examples of polyol ester compounds include di(2-ethylhexanoic acid) neopentyl glycol ester, di(oleic acid) neopentyl glycol ester, di(stearic acid) neopentyl glycol ester, tri(2-ethylhexanoic acid) trimethylolethane ester, tri(oleic acid) trimethylolethane ester, tri(stearic acid) trimethylolethane ester, tri(2-ethylhexanoic acid) trimethylolpropane ester, tri(oleic acid) trimethylolpropane ester, tri(stearic acid) trimethyl Examples include rolpropane esters, tri(2-ethylhexanoic acid) glycerol esters, tri(oleic acid) glycerol esters, tri(stearic acid) glycerol esters, tetra(2-ethylhexanoic acid) pentaerythritol esters, tetra(oleic acid) pentaerythritol esters, tetra(stearic acid) pentaerythritol esters, hexa(2-ethylhexanoic acid) dipentaerythritol esters, hexa(oleic acid) dipentaerythritol esters, and hexa(stearic acid) dipentaerythritol esters. Polyol ester oils that are liquid at room temperature (25°C) are preferred, but those that are solid can also be used.

[0114] When polyol ester oil is incorporated, the amount is preferably 0.001 to 80 parts by mass per 100 parts by mass of the above hydrolyzable nonfluorine compound.

[0115] Examples of the above-mentioned silicone oils include linear, branched, or cyclic silicone oils having 2,000 or fewer siloxane bonds. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid esters, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil. While it is preferable that the silicone oil is liquid at room temperature (25°C), solid silicone oils can also be used.

[0116] When silicone oil is incorporated, the amount is preferably 0.001 to 80 parts by mass per 100 parts by mass of the above hydrolyzable nonfluorine compound.

[0117] Water-repellent agents containing hydrolyzable nonfluorine compounds can be applied to substrates by known methods such as wet coating (dipping, brush coating, spin coating, spraying, gravure coating, die coating, bar coating, slit coating) and vapor deposition. Coating conditions can follow conventional methods, but since the primer layer is coated and formed by a wet coating method, it is more efficient to apply the water-repellent agent containing the hydrolyzable nonfluorine compound by a wet coating method as well. Hydrolyzable nonfluorine compounds can be cured at room temperature (25°C) in 1 to 24 hours, but heating at 30 to 200°C for 1 minute to 1 hour may further shorten the curing time. Curing under humid conditions (50 to 90% RH) is preferable to promote hydrolysis.

[0118] Furthermore, before applying the water-repellent agent containing a hydrolyzable nonfluorine compound, the surface of the primer layer on the substrate may be treated with a cleaning or surface activation treatment such as plasma treatment, UV treatment, or ozone treatment.

[0119] The film thickness of the water-repellent layer formed and laminated on the outer surface of the primer layer is 0.5 to 50 nm, particularly preferably 1 to 20 nm. If the film thickness is too thick, the surface resistance value of the resulting water-repellent member will be high, and if it is too thin, the surface characteristics and abrasion resistance of the resulting water-repellent member will not be sufficient. The film thickness can be measured by means such as spectroscopic reflectance measurement method, X-ray reflectance measurement method, spectroscopic ellipsometry measurement method, etc.

[0120] In the water-repellent member of the present invention thus obtained, the surface resistance value can be made 1.0×10 12 Ω / □ or less, preferably 1.0×10 7 to 1.0×10 12 Ω / □, more preferably 1.0×10 8 to 1.0×10 11 Ω / □. If the surface resistance value is too large, electronic devices such as organic EL may malfunction, and also, the visibility of the surface may decrease due to the adhesion of dust etc., and the optical characteristics and texture may be impaired. Furthermore, the surface becomes easily soiled. In the present invention, the surface resistance value can be measured by a commercially available resistivity meter, for example, High Rester UX MCP-HT800 manufactured by Mitsubishi Chemical Analytech Co., Ltd. In order to make the surface resistance value within the above range, it is preferable that the film thickness of the primer layer as the second layer is 10 to 500 nm, and further, the film thickness of the water-repellent layer as the third layer formed on the outer surface of the primer layer is 0.5 to 50 nm.

[0121] The surface resistance value of the water-repellent member of the present invention is one digit or more lower than that in the case where there is no primer layer (second layer).

[0122] Examples of water-repellent members obtained in this manner include casings for car navigation systems, tablet PCs, smartphones, foldable smartphones, bendable smartphones, flexible devices, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game equipment, etc., lenses such as camera lenses, security cameras, in-vehicle lenses, eyeglass lenses, sunglasses, AR lenses, VR lenses, etc., medical equipment such as endoscopes, scalpels, blood pressure monitors, X-ray CT scanners, MRI scanners, etc., touch panel surfaces for liquid crystal displays, organic EL displays, flexible devices, etc., protective films, anti-reflective films, IR cut filters, optical articles such as compact discs, DVDs, Blu-ray discs, window glass for automobiles, trains, aircraft, etc., headlamp covers, headlight lenses, etc., tiles, exterior building materials, system kitchens, bathtubs, shower heads, faucets, range hoods, other kitchen building materials, waiting rooms, works of art, bodies of transportation equipment, mirrors, radar covers for millimeter-wave sensors, etc.

[0123] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. In the following examples, the mol amount of the compound is, 1 The values ​​were calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. The film thickness was measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The weight-average molecular weight of the hydrolysis / partial condensate of tetraethoxysilane or tetramethoxysilane used to form the primer layer was measured by static light scattering (SLS), and the amount of silanol groups was measured by the amount of methane gas generated when each product was reacted with Grignard reagent (methylmagnesium iodide) using a gas burette. The room temperature was 25°C.

[0124] [Synthesis of hydrolyzable nonfluorine compounds] [Synthesis example 1] In a reaction vessel, prepare the following formula (a) 1.00 g (2.55 x 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.934 g (7.64 x 10-3 mol), and 9.73×10 -3 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 3.01×10 -8 mol of elemental Pt) were mixed and aged at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.28 g of hydrolyzable non-fluorine compound 1.

[0125] The obtained compound 1 was 1 confirmed by ¹H-NMR to have a structure represented by the following formula (A).

[0126] [Synthesis Example 2] In a reaction vessel, 1.00 g (1.82×10 mol) of the compound represented by the following formula (b), 1.00 g of toluene, 0.668 g (5.47×10 -3 mol) of trimethoxysilane, and 6.96×10 -3 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.15×10 -3 mol of elemental Pt) were mixed and aged at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.21 g of hydrolyzable non-fluorine compound 2. -8

[0127] The obtained compound 2 was 1 confirmed by ¹H-NMR to have a structure represented by the following formula (B).

[0128] [Synthesis Example 3] In a reaction vessel, 1.00 g (1.32×10 mol) of the compound represented by the following formula (c), 1.00 g of toluene, 0.815 g (3.95×10 -3 mol) of triacetoxysilane, and 5.03×10 -3 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.56×10 -3 mol of elemental Pt) were mixed and aged at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.25 g of hydrolyzable non-fluorine compound 3. -8

[0129] The obtained compound 3 was 1¹H-NMR confirmed that the structure is represented by the following formula (C). (In the formula, Ac represents an acetyl group.)

[0130] [Synthesis Example 4] In the reaction vessel, prepare the following formula (d) 1.00 g (1.59 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 1.16 g (9.51 x 10 -3 mol), and toluene solution of chloroplatinate / vinylsiloxane complex 6.06 × 10 -3 g (as Pt alone, 1.87 × 10⁻⁶) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.35 g of hydrolyzable nonfluorine compound 4.

[0131] The resulting compound 4 is 1 ¹H-NMR confirmed that the structure is represented by the following formula (D).

[0132] [Synthesis Example 5] In the reaction vessel, prepare the following formula (e) 1.00 g (1.48 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.544 g (4.45 x 10 -3 mol), and 5.67 × 10¹³ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (as Pt alone, 1.75 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.12 g of hydrolyzable nonfluorine compound 5.

[0133] The resulting compound 5 is 1 ¹H-NMR confirmed that the structure is represented by the following formula (E).

[0134] [Synthesis Example 6] In the reaction vessel, prepare the following formula (f) 1.00 g (1.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, triethoxysilane 0.815 g (4.96 x 10 -3mol), and toluene solution of chloroplatinate / vinylsiloxane complex 6.32 × 10 -3 g (as Pt alone, 1.95 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.26 g of hydrolyzable nonfluorine compound 6.

[0135] The resulting compound 6 is 1 ¹H-NMR confirmed that the structure is represented by the following formula (F).

[0136] [Synthesis Example 7] In the reaction vessel, prepare the following formula (g) 1.00 g (2.06 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 2.26 g (1.85 x 10 -2 mol), and 7.85 × 10¹³ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (Pt alone: ​​2.43 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.20 g of hydrolyzable nonfluorine compound 7.

[0137] The resulting compound 7 is 1 ¹H-NMR confirmed that the structure is represented by the following formula (G).

[0138] [Synthesis Example 8] In the reaction vessel, prepare the following formula (h) 1.00 g (1.39 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.509 g (4.16 x 10 -3 mol), and 7.85 × 10¹³ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (Pt alone: ​​2.43 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.15 g of hydrolyzable nonfluorine compound 8.

[0139] The resulting compound 8 is 1¹H-NMR confirmed that the structure is represented by the following formula (H).

[0140] [Synthesis Example 9] In the reaction vessel, prepare the following formula (i) 1.00 g (1.99 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 2.19 g (1.79 x 10) -2 mol), and 7.85 × 10¹³ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (Pt alone: ​​2.43 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation to obtain 1.65 g of hydrolyzable nonfluorine compound 9.

[0141] The resulting compound 9 is 1 ¹H-NMR confirmed that the structure is represented by the following formula (I).

[0142] [Examples 1-24 and Comparative Examples 1-12] Water-repellent members (test specimens) having a substrate, each of the functional film layers shown in Table 1, a primer layer, or a water-repellent layer were prepared using the formation method described below.

[0143] [Substrate] Clear hard-coated PET film (KB Stick 50S01S hard-coated film manufactured by Kimoto Co., Ltd., 50 μm thick, 50 mm wide, 100 mm long test specimen substrate)

[0144] [Formation of Functional Film Layer (First Layer)] Functional film layers were formed on the above substrates using the methods described below.

[0145] [Formation of Functional Film Layer 1] A silicon dioxide layer with a thickness of 100 nm was formed on the outer surface of the above substrate using a sputtering method, and this was designated as Functional Film Layer 1. The deposition rate of SiO2 was 0.3 nm / second, and the film thickness was controlled by the deposition time. [Film Deposition Conditions] Film deposition apparatus: RAS-1100B (Synchron) Oxygen plasma irradiation conditions during substrate pretreatment Oxygen gas flow rate: 70 sccm (Standard Cubic CentiMeters) Argon gas flow rate: 100 sccm Film deposition chamber pressure: 0.1 Pa rf Power supply: 3,000 W Processing time: 50 seconds Silicon dioxide layer deposition conditions Target material: Silicon Argon gas flow rate: 100 sccm Film deposition chamber pressure: 0.1 Pa rf Power supply: 8,000 W Film deposition rate: 0.3 nm / s Oxygen plasma irradiation conditions during silicon dioxide layer deposition Oxygen gas flow rate: 70 sccm rf Power supply: 3,000 W

[0146] [Formation of Functional Film Layer 2] The substrate was dipped in a treatment solution prepared by diluting perhydropolysilazane with dibutyl ether to a solid content of 2.0% by mass. The substrate was then cured at 80°C / 80% RH for 24 hours to form a functional film layer 2 with a thickness of 96 nm on the outer surface of the substrate. The dipping coating was performed by immersing the substrate in the treatment solution for 30 seconds and then pulling it out at 150 mm / min. The perhydropolysilazane, which is the raw material for functional film layer 2, reacts with moisture in the atmosphere during curing, generating ammonia and undergoing dehydrogenation to form an SiO2 (silicon dioxide) layer.

[0147] [Formation of Functional Film Layer 3] A silicon dioxide layer with a thickness of 10 nm was formed on the outer surface of the above substrate using a sputtering method, forming the functional film layer 3. The deposition rate of SiO2 was 0.3 nm / second, and the film thickness was controlled by the deposition time. [Film Deposition Conditions] Film deposition apparatus: RAS-1100B (Synchron) Oxygen plasma irradiation conditions during substrate pretreatment Oxygen gas flow rate: 70 sccm (Standard Cubic CentiMeters) Argon gas flow rate: 100 sccm Film deposition chamber pressure: 0.1 Pa rf Power supply: 3,000 W Processing time: 50 seconds Silicon dioxide layer deposition conditions Target material: Silicon Argon gas flow rate: 100 sccm Film deposition chamber pressure: 0.1 Pa rf Power supply: 8,000 W Film deposition rate: 0.3 nm / s Oxygen plasma irradiation conditions during silicon dioxide layer deposition Oxygen gas flow rate: 70 sccm rf Power supply: 3,000 W

[0148] [Formation of Functional Film Layer 4] A functional film layer 4 was formed by laminating silicon dioxide by sputtering as the outermost layer of the anti-reflective layer formed on the surface of the above substrate. The anti-reflective layer has a laminated structure of Nb2O5 (12 nm), SiO2 (34 nm), Nb2O5 (116 nm), and SiO2 (76 nm) from the substrate side. The deposition rate of SiO2 was 0.3 nm / second, and the deposition rate of Nb2O5 was 0.4 nm / second, and the film thickness of each layer was controlled by the deposition time. [Anti-reflective layer deposition conditions] Deposition apparatus: RAS-1100B (Synchron) Oxygen plasma irradiation conditions during substrate pretreatment Oxygen gas flow rate: 70 sccm (Standard Cubic Centimeters) Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF power supply: 3,000 W Processing time: 50 seconds Low refractive index layer deposition conditions Target material: Silicon Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF power supply: 8,000 W Deposition rate: 0.3 nm / s Oxygen plasma irradiation conditions during low refractive index layer deposition Oxygen gas flow rate: 70 sccm RF power supply: 3,000 W High refractive index layer deposition conditions Target material: Niobium Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF power supply: 5,000W Deposition rate: 0.4 nm / s Oxygen plasma irradiation conditions during high refractive index layer deposition Oxygen gas flow rate: 70 sccm RF supply power: 3,000W

[0149] [Formation of functional film layer 5] A silicon dioxide layer with a thickness of 20 nm was formed on the outer surface of the above substrate using an EB method with a silicon dioxide evaporation source, and this was formed as the functional film layer 5.

[0150] [Formation of the primer layer (second layer)] A primer layer was formed on the functional film layer of the above substrate using the method described below.

[0151] [Formation of Primer Layer 1] A treatment solution was prepared by diluting a hydrolyzed and partially condensed product of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol to a solid content of 0.2% by mass. The functional film layer surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.), and then dried at 80°C for 1 minute to form a 10 nm primer layer 1 on the outer surface of the functional film layer.

[0152] [Formation of Primer Layer 2] A hydrolysis and partial condensate of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) was diluted with butanol to a solid content of 0.78% by mass. The substrate on which the functional film layer was formed was then dipped in this treatment solution (immersed in the treatment solution for 60 seconds, then pulled out at 150 mm / min), and dried at room temperature (25°C) for 1 hour to form a 30 nm primer layer 2 on the outer surface of the functional film layer.

[0153] [Formation of Primer Layer 3] A hydrolysis and partial condensate of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) was diluted with butanol to a solid content of 2.0% by mass. The substrate on which the functional film layer was formed was then dipped in the treatment solution (immersed in the treatment solution for 60 seconds, then pulled out at 150 mm / min), and dried at room temperature (25°C) for 1 hour to form a 91 nm primer layer 3 on the outer surface of the functional film layer.

[0154] [Formation of Primer Layer 4] A substrate with the functional film layer formed on it was dipped in a treatment solution prepared by diluting a hydrolyzed and partially condensed product of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol to a solid content of 4.0% by mass. The substrate was then dried at room temperature (25°C) for 1 hour to form a 210 nm primer layer 4 on the outer surface of the functional film layer.

[0155] [Formation of Primer Layer 5] A hydrolysis and partial condensate of tetraethoxysilane (weight-average molecular weight: 4,000, silanol group content: 0.090 mol / g) was diluted to a solid content of 0.1% by mass with a butanol / isopropanol mixture (mass ratio 50 / 50). The functional film layer surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.), and then dried at 80°C for 1 minute to form a 41 nm primer layer 5 on the outer surface of the functional film layer.

[0156] [Formation of Primer Layer 6] A treatment solution was prepared by diluting a hydrolyzed and partially condensed product of tetraethoxysilane (weight-average molecular weight: 750, silanol group content: 0.40 mol / g) with butanol to a solid content of 1.0% by mass. The functional film layer surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.), and then dried at 80°C for 1 minute to form a 38 nm primer layer 6 on the outer surface of the functional film layer.

[0157] [Formation of Primer Layer 7] A hydrolysis and partial condensate of tetramethoxysilane (weight-average molecular weight: 480, silanol group content: 0.65 mol / g) was diluted to a solid content of 1.0% by mass with a butanol / isopropanol mixture (mass ratio 50 / 50). The functional film layer surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.), and then dried at 80°C for 1 minute to form a 35 nm primer layer 7 on the outer surface of the functional film layer.

[0158] [Formation of Primer Layer 8] A treatment solution was prepared by diluting a hydrolyzed and partially condensed product of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol to a solid content of 0.1% by mass. The functional film layer surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.), and then dried at 80°C for 1 minute to form a 5 nm primer layer 8 on the outer surface of the functional film layer.

[0159] [Formation of the water-repellent layer (third layer)] Furthermore, a water-repellent layer was formed on the substrate, the functional film layer of the substrate, or the primer layer of the substrate, respectively, using the method described below.

[0160] [Formation of Water-Repellent Layer 1] Compound 1, shown below and obtained in Synthesis Example 1, was diluted with isononane to a solid content of 0.1% by mass, and then spray-coated onto the primer layer (or substrate or functional film layer of the substrate) of the above substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of water-repellent layer 1 was 3 nm. [Compound 1]

[0161] [Formation of Water-Repellent Layer 2] Compound 2, shown below and obtained in Synthesis Example 2, was diluted with dibutyl ether to a solid content of 10% by mass. Then, it was vacuum-deposited onto the primer layer (or functional film layer of the substrate) of the substrate using a vacuum deposition apparatus (VTR-250, manufactured by ULVAC, Inc.). Afterward, it was cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of water-repellent layer 2 was 6 nm. [Compound 2]

[0162] [Formation of Water-Repellent Layer 3] Compound 3, shown below and obtained in Synthesis Example 3, was diluted with toluene to a solid content of 0.2% by mass. The primer layer (or functional film layer of the substrate) surface of the substrate was coated with this solution using a bar coater (Bar Coater No. 2, manufactured by Daiichi Rika Co., Ltd.). The coating was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of the water-repellent layer 3 was 7 nm. [Compound 3] (In the formula, Ac represents an acetyl group.)

[0163] [Formation of Water-Repellent Layer 4] Compound 4, shown below and obtained in Synthesis Example 4, was diluted with butyl acetate to a solid content of 0.2% by mass, and then spray-coated onto the primer layer (or functional film layer of the substrate) of the above substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of the water-repellent layer 4 was 6 nm. [Compound 4]

[0164] [Formation of Water-Repellent Layer 5] Compound 5, shown below and obtained in Synthesis Example 5, was diluted with isononane to a solid content of 0.3% by mass, and then spray-coated onto the primer layer (or functional film layer of the substrate) of the above substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of the water-repellent layer 5 was 9 nm. [Compound 5]

[0165] [Formation of Water-Repellent Layer 6] Compound 6, shown below and obtained in Synthesis Example 6, was diluted with ethylcyclohexane to a solid content of 0.2% by mass, and then spray-coated onto the primer layer (or functional film layer of the substrate) of the above substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average film thickness of the water-repellent layer 6 was 7 nm. [Compound 6]

[0166] [Formation of Water-Repellent Layer 7] Compound 7, shown below and obtained in Synthesis Example 7, was diluted with isooctane to a solid content of 0.2% by mass, and then spray-coated onto the primer layer of the substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average thickness of the water-repellent layer 7 was 5 nm. [Compound 7]

[0167] [Formation of Water-Repellent Layer 8] Compound 8, obtained in Synthesis Example 8 and shown below, was diluted with butyl acetate to a solid content of 0.2% by mass, and then spray-coated onto the primer layer of the substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average thickness of the water-repellent layer 8 was 8 nm. [Compound 8]

[0168] [Formation of Water-Repellent Layer 9] Compound 9, shown below and obtained in Synthesis Example 9, was diluted with hexamethyldisiloxane to a solid content of 0.2% by mass, and then spray-coated onto the primer layer of the substrate using a spray coating apparatus (NST-51, manufactured by T&K Corporation). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average thickness of the water-repellent layer 9 was 6 nm. [Compound 9]

[0169] [Formation of Water-Repellent Layer 10] Compound 10, shown below, was diluted with Novec 7200 (3M ethyl perfluorobutyl ether) to a solid content of 0.2% by mass, and then spray-coated onto the primer layer of the substrate using a spray coating apparatus (T&K Corporation NST-51). The mixture was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film (water-repellent layer), and test specimens were prepared. The average thickness of the water-repellent layer 10 was 8 nm. [Compound 10]

[0170] The following measurements were performed on water-repellent members (test specimens) having a functional film layer, primer layer, or water-repellent layer as shown in Table 1 below.

[0171] [Antistatic Properties] To evaluate the antistatic properties, the surface resistance of the water-repellent material prepared as described above was measured using a resistivity meter (HighLester UX MCP-HT800) manufactured by Mitsubishi Chemical Analytec Co., Ltd. under the following conditions. The results (surface resistance values) are shown in Table 1. Applied voltage: 1,000V

[0172] [Water Repellency] For the water-repellent member prepared as described above, the contact angle (water repellency) of the water-repellent layer or primer layer, which is the outermost layer, was measured with respect to water using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the water-repellent member surface and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results (water contact angle) are shown in Table 1. In this invention, a good (water-repellent) water contact angle is defined as 90 degrees or higher. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0173] [Fabric Abrasion Resistance] For the water-repellent material prepared as described above, the contact angle (water repellency) of the water-repellent layer or primer layer, which is the outermost layer, was measured with a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions, and the fabric abrasion resistance was evaluated in the same manner as described above. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after fabric abrasion test, change in contact angle after abrasion) are shown in Table 1. [Fabric Abrasion Resistance Test Conditions] Nonwoven fabric: Bencot (manufactured by Asahi Kasei Corporation) Contact area: 4 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2 Number of wear cycles: 2,000

[0174]

[0175] As is clear from the results in Table 1, Examples 1 to 24 exhibited excellent water repellency and excellent fabric abrasion resistance. On the other hand, Comparative Examples 1 to 9 showed insufficient abrasion resistance, with the water contact angle after fabric abrasion decreasing by more than 10 degrees from the initial value. Comparative Examples 1 and 2 lacked sufficient abrasion resistance because they did not provide a functional film layer or a primer layer, respectively. Comparative Example 3 provided a polysilazane layer in the functional film layer, but lacked a primer layer, resulting in insufficient abrasion resistance. Comparative Examples 4 to 9 provided an anti-reflective layer in the functional film layer, did not provide a primer layer, and changed the type of water repellent (water-repellent layer) containing a hydrolyzable non-fluorine compound, but still lacked sufficient abrasion resistance. Comparative Example 10 provided a functional film layer and a primer layer, but did not provide a water-repellent layer, resulting in antistatic properties but no water repellency. Comparative Example 11 lacked sufficient abrasion resistance because the primer layer was too thin. Comparative Example 12 used a fluorine compound as the water-repellent layer, resulting in water repellency but poor fabric abrasion resistance. Furthermore, in Examples 1 to 24, the primer layer was made 10 nm or longer, resulting in a surface resistance value of 1.0 × 10⁻⁶. 12 The ratio could be reduced to Ω / □ or less (resulting in good antistatic properties).

Claims

A water-repellent member comprising a functional film layer on at least one surface of a substrate, a primer layer on the outer surface of the functional film layer, and a water-repellent layer on the outer surface of the primer layer, wherein the primer layer is a layer with a thickness of 10 to 500 nm containing an organosilicon compound having a plurality of silanol groups in its molecule, and the water-repellent layer is a layer with a thickness of 0.5 to 50 nm containing a cured product of a hydrolyzable nonfluorine compound. 　 The water-repellent member according to claim 1, wherein the functional film layer is entirely composed of silicon dioxide, or at least the outermost layer is made of silicon dioxide. 　 The water-repellent member according to claim 1, wherein the organosilicon compound having multiple silanol groups in its molecule is a hydrolyzed and partially condensed product of a silane compound having four hydrolyzable groups. 　 The water-repellent member according to any one of claims 1 to 3, wherein the hydrolyzable nonfluorine compound has at least one hydrolyzable silyl group or silazane group at the end of at least one molecular chain. 　 The water-repellent member according to claim 4, wherein the hydrolyzable silyl group is a silyl group having 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, or an amino group. 　 The water-repellent member according to any one of claims 1 to 3, wherein the hydrolyzable nonfluorine compound is a hydrocarbon terminal group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon terminal group having 3 to 32 carbon atoms and at least one reactive silyl group in the molecule. 　 Hydrolyzable nonfluorine compounds are defined by the following general formula (1) (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 (where k1 is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is independently a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a trivalent to octavalent organic group; Y is independently a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is independently a monovalent reactive silyl group; k1 is an integer from 1 to 3; k2 is 0 or 1; k3 is an integer from 1 to 3; k1 + k2 + k3 is 3 or 4; and m is an integer from 1 to 7.) A water-repellent member according to any one of claims 1 to 3, which is a hydrocarbon terminal group-containing compound represented by [the specified compound]. 　 In the above equation (1), A is the following general equation (2) (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer from 1 to 3.) The water-repellent member according to claim 7, wherein the base is represented by the base. 　 The water-repellent member according to claim 8, wherein in formula (2) above, X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms. 　 In the above formula (1), R 1 However, the following equations (3a) to (3c) (In the formula, R A Q is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, or a carbamate group. Q' is a divalent group selected from the group consisting of a urea group and a divalent nitrogen-containing heterocyclic group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group, Q'' is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A (or a hydrogen atom, where p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 32 or less.) The water-repellent member according to claim 7, wherein the group is any of the groups represented by the following: 　 In the above formulas (3a) to (3c), R A The water-repellent member according to claim 10, wherein the water-repellent member is a monovalent hydrocarbon group having 11 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. 　 The water-repellent member according to claim 7, wherein in formula (1) above, Y is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from oxygen atoms, nitrogen atoms, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms which includes an arylene group having 6 to 8 carbon atoms; a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. 　 In the above formula (1), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 is a trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent to octavalent nitrogen-containing heterocyclic group-containing group, and the water-repellent member according to claim 7, which is a trivalent to octavalent group selected from the group consisting of 　 The water-repellent member according to claim 7, wherein in formula (1) above, U is a trivalent or tetravalent group selected from the group consisting of carbon atoms, silicon atoms, nitrogen atoms, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group. 　 The water-repellent member according to any one of claims 1 to 3, wherein the base material is resin, ceramic, metal, quartz, glass, sapphire, or diamond. 　 The surface resistance value is 1.0 × 10 12 A water-repellent member according to any one of claims 1 to 3, wherein the Ω / □ is less than or equal to Ω. 　 A method for manufacturing a water-repellent member according to claim 1, comprising the steps of: forming a functional film layer mainly composed of silicon dioxide or a functional film layer in which at least the outermost layer is silicon dioxide on at least one surface of a substrate; wet coating a solution containing an organosilicon compound having a plurality of silanol groups in its molecule and a solvent on the outer surface of the functional film layer; drying the solvent to form and laminate a primer layer on at least one surface of the substrate; wet coating a solution containing a hydrolyzable nonfluorine compound and a solvent on the outer surface of the primer layer, followed by drying the solvent, or dry coating a hydrolyzable nonfluorine compound obtained by evaporating the solvent from the solution; and curing the hydrolyzable nonfluorine compound to form and laminate a water-repellent layer on the outer surface of the primer layer.

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