Water-repellent and oil-repellent member and method for producing the same

Abstract

The present invention relates to a water-repellent and oil-repellent component, which has a functional film layer as the first layer on at least one surface of a substrate, a primer layer as the second layer on the outer surface of the functional film layer, and then a water-repellent and oil-repellent component as the third layer on the outer surface of the primer layer, the primer layer is composed of a layer with a film thickness of 10 to 500 nm with an organosilicon compound having multiple silanol groups in a molecule as the main component, and the water-repellent and oil-repellent layer is composed of a layer with a film thickness of 0.5 to 50 nm with a cured product of a hydrolyzable fluorine-containing compound as the main component, and has excellent rubber wear resistance and excellent antistatic property. In addition, for various substrates, a water-repellent and oil-repellent layer with excellent rubber wear resistance and excellent antistatic property can be formed.

Description

Technical Field

[0001] The present invention relates to a water-repellent and oil-repellent component having excellent wear resistance and a method for manufacturing the water-repellent and oil-repellent component. Specifically, the present invention relates to a water-repellent and oil-repellent component having a functional film layer with silicon dioxide as the main component as the first layer or a functional film layer with silicon dioxide as the top layer on the surface of a substrate, a layer formed using an organosilicon compound having multiple silanol groups (hydroxyl groups bonded to silicon atoms) in the molecule as the second layer, and a layer formed using a fluorine-containing organosilicon compound as the third layer, and a method for manufacturing the water-repellent and oil-repellent component. Background Art

[0002] In recent years, in order to improve outward appearance, visibility, the demand of the technology that dirt is difficult to adhere to, the technology that dirt is easily come off improves year by year, particularly the surface of the main body of the packaging, kitchen rack, transportation equipment of the housing of liquid crystal display, organic EL display, eyeglass lens, smart mobile phone, wearable terminal, car navigation, electronic equipment, cosmetics etc. is because sebum, oily dirt easily adhere to, therefore wish to arrange water-repellent and oil-repellent layer.But, the compound with fluorine group used as water-repellent and oil-repellent agent is very little because its surface free energy, has non-adhesiveness, non-fitness for various base materials, therefore is difficult to make water-repellent and oil-repellent agent directly fit with base material.

[0003] In order to solve such adhesion problems, a fluorooxyalkylene group-containing polymer composition represented by the following average composition formula is disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-116947 (Patent Document 1) as a treatment agent capable of performing water- and oil-repellent treatment on the surface of a substrate such as glass.

[0004] [Chemistry 1]

[0005] A-R 1 -B

[0006] (Rf 1 To include -C d F 2d O- (d is an integer of 1 to 6, which may be different for each repeating unit) with 5 to 100 repeating units of a divalent straight-chain fluorooxyalkylene group, A and B are independently selected from Rf 2 or by the following formula

[0007] [Chemistry 2]

[0008]

[0009] The group in the group represented by Rf 2is F, H, a monovalent fluorine-containing group with a terminal -CF3 group or -CF2H group, Q is a divalent organic group, Z is a 2-7 valent organopolysiloxane residue having a siloxane bond, R is an alkyl group with 1-4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, b is 1-6, c is an integer of 1-5, and β is an integer of 0 or 1.)

[0010] However, although the treatment agent proposed in Patent Document 1 shows relatively excellent durability, it is not sufficient, and it is difficult to obtain excellent adhesion to resins, sapphire, ceramics, etc. in particular.

[0011] As a method for improving adhesion, a method for setting a SiO2 layer as a primer layer by a dry method (evaporation method, sputtering method, CVD method) is disclosed (International Publication No. 2014 / 097388: Patent Document 2). It is shown that if this method is used, a water-repellent and oil-repellent layer with excellent durability can be formed on a glass substrate, but in the case of a strict reliability test such as rubbing the surface with an eraser, sufficient durability is not shown.

[0012] On the other hand, a polysilazane solution capable of providing a primer layer by a wet method is disclosed (International Publication No. 2010 / 038648: Patent Document 3). After the polysilazane solution is applied, it is converted into silica glass by reacting with water. This method is superior to the dry method in that it does not use a vacuum process, but still does not show sufficient durability in the case of a strict reliability test such as rubbing the surface with an eraser.

[0013] And then, the component that adopts the above-mentioned method to be provided with water-repellent and oil-repellent layer is mostly that the surface resistance value of this component is larger than the surface resistance value of base material, causes the problem of being easily charged.Therefore, various antistatic agents are proposed, from the viewpoint of adding antistatic agent in composition, the water-repellent and oil-repellent property and antifouling property on the surface are insufficient, and it is difficult to have high wear resistance and antistatic property on water-repellent and oil-repellent surface concurrently.

[0014] In addition, as prior arts related to the present invention, the following documents are listed together with the above-mentioned documents.

[0015] Prior art literature

[0016] Patent Literature

[0017] Patent Document 1: Japanese Patent Application Publication No. 2011-116947

[0018] Patent Document 2: International Publication No. 2014 / 097388

[0019] Patent Document 3: International Publication No. 2010 / 038648

[0020] Patent Document 4: Japanese Patent Application Publication No. 2007-197425

[0021] Patent Document 5: Japanese Patent Application Publication No. 2007-297589

[0022] Patent Document 6: Japanese Patent Application Publication No. 2007-297543

[0023] Patent Document 7: Japanese Patent Application Publication No. 2008-088412

[0024] Patent Document 8: Japanese Patent Application Publication No. 2008-144144

[0025] Patent Document 9: Japanese Patent Application Publication No. 2010-031184

[0026] Patent Document 10: Japanese Patent Application Publication No. 2010-047516

[0027] Patent Document 11: Japanese Patent Application Publication No. 2011-178835

[0028] Patent Document 12: Japanese Patent Application Publication No. 2014-084405

[0029] Patent Document 13: Japanese Patent Application Publication No. 2014-105235

[0030] Patent Document 14: Japanese Patent Application Publication No. 2013-253228

[0031] Patent Document 15: Japanese Patent Application Publication No. 2014-218639

[0032] Patent Document 16: International Publication No. 2013 / 121984 Summary of the invention

[0033] Problems to be solved by the invention

[0034] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water- and oil-repellent member having excellent rubber abrasion resistance and excellent antistatic properties, and a method for producing a water- and oil-repellent member having a water- and oil-repellent layer having excellent antistatic properties for various substrates.

[0035] Means for solving problems

[0036] The inventors of the present invention have repeatedly conducted in-depth studies to achieve the above-mentioned purpose, and as a result, found that: a method having a functional film layer with silicon dioxide as the main component or a functional film layer with silicon dioxide as the outermost layer on at least one surface of a substrate is obtained by adopting a process of forming a functional film layer with silicon dioxide as the main component on at least one surface of a substrate; a process of wet-coating a solution containing an organosilicon compound having multiple silanol groups in the molecule and a solvent; a process of evaporating the solvent to form and laminate a primer layer on at least one surface of the substrate; a process of wet-coating a solution containing a hydrolyzable fluorine-containing compound and a solvent on the outer surface of the primer layer, evaporating the solvent, or dry-coating a hydrolyzable fluorine-containing compound from which the solvent has been evaporated; and a process of curing the hydrolyzable fluorine-containing compound to form and laminate a water-repellent and oil-repellent layer on the outer surface of the primer layer, etc. The present invention is completed by providing a functional film layer (first layer) in which a functional film layer or at least the outermost layer is silicon dioxide, a primer layer (second layer) of a specific thickness having an organosilicon compound having multiple silanol groups in the molecule as the main component on the outer surface of the functional film layer, and a water- and oil-repellent layer (third layer) of a specific thickness having a cured product of a hydrolyzable fluorine-containing compound as the main component on the outer surface of the primer layer, and having excellent rubber abrasion resistance and antistatic properties (i.e., the surface resistance value of the outer surface is reduced by more than 10Ω / □ compared with the case where the second layer is not provided). Furthermore, a water- and oil-repellent film having such excellent rubber abrasion resistance and antistatic properties (i.e., the surface resistance value of the outer surface is reduced by more than 10Ω / □ compared with the case where the second layer is not provided) can be stably and simply formed on various substrates.

[0037] That is, the present invention provides the following water-repellent and oil-repellent member and method for producing the water-repellent and oil-repellent member.

[0038] [1] A water-repellent and oil-repellent member having a functional film layer as a first layer on at least one surface of a substrate, a primer layer as a second layer on the outer surface of the functional film layer, and a water-repellent and oil-repellent layer as a third layer on the outer surface of the primer layer, wherein the primer layer is composed of a layer having a film thickness of 10 to 500 nm and having an organic silicon compound having a plurality of silanol groups in the molecule as a main component, and the water-repellent and oil-repellent layer is composed of a layer having a film thickness of 0.5 to 50 nm and having a cured product of a hydrolyzable fluorinated compound as a main component.

[0039] [2] The water- and oil-repellent member according to [1], wherein the entire functional film layer contains silicon dioxide as a main component or at least the outermost layer contains silicon dioxide.

[0040] [3] The water- and oil-repellent member according to [1] or [2], wherein the organosilicon compound having a plurality of silanol groups in a molecule is a hydrolyzed partial condensate of tetraalkoxysilane.

[0041] [4] The water- and oil-repellent member according to any one of [1] to [3], wherein the hydrolyzable fluorine-containing compound has at least one hydrolyzable silyl group at at least one molecular chain end, and 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, or a silazane group.

[0042] [5] The water- and oil-repellent member according to any one of [1] to [4], wherein the hydrolyzable fluorine-containing compound has a molecule consisting of -(CF2) d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d -(wherein, p, q, r, s, and t are each independently an integer of 0 to 200, and p+q+r+s+t=3 to 500, each repeating unit shown in the brackets may be randomly bonded, d is independently an integer of 0 to 8, and the unit may be linear or branched.)

[0043] a fluorooxyalkylene group-containing organosilicon compound having a divalent linear perfluorooxyalkylene polymer residue represented by

[0044] [6] The water- and oil-repellent member according to any one of [1] to [5], wherein the hydrolyzable fluorine-containing compound is at least one selected from the group consisting of fluorine-containing hydrolyzable organosilicon compounds represented by the following general formulas (1) to (5).

[0045] (A-Rf) α -ZW β (1)

[0046] Rf-(ZW β )twenty two)

[0047] Z'-(Rf-ZW β ) γ (3)

[0048] [wherein, Rf is -(CF2) d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t-(CF2) d -represents a divalent straight-chain perfluoroalkylene oxide polymer residue, p, q, r, s, t are each independently an integer of 0 to 200, and p+q+r+s+t=3 to 500, each repeating unit shown in the brackets may be randomly bonded, d is independently an integer of 0 to 8, and the unit may be straight-chain or branched. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, Z, Z' are independently a single bond, or a divalent to octavalent organic group that may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be substituted with fluorine, and W is a monovalent organic group having a hydrolyzable group at the terminal. α, β are each independently an integer of 1 to 7, and α+β=2 to 8. γ is an integer of 2 to 8. ]

[0049] A-Rf-Q-(Y) δ -B (4)

[0050] Rf-(Q-(Y) δ -B)2 (5)

[0051] (In the formula, Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is independently an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)

[0052] [7] The water- and oil-repellent member according to [6], wherein the fluorinated hydrolyzable organic silicon compound is selected from the following compounds.

[0053] [Chemistry 3]

[0054]

[0055] [Chemistry 4]

[0056]

[0057] [Chemistry 5]

[0058]

[0059] [Chemistry 6]

[0060]

[0061] [Chemistry 7]

[0062]

[0063] [Chemistry 8]

[0064]

[0065] [Chemistry 9]

[0066]

[0067] [Chemistry 10]

[0068]

[0069] [Chemistry 11]

[0070]

[0071] [Chemistry 12]

[0072]

[0073] [Chemistry 13]

[0074]

[0075] [Chemistry 14]

[0076]

[0077] [Chemistry 15]

[0078]

[0079] [Chemistry 16]

[0080]

[0081] [Chemistry 17]

[0082] [Chemistry 18]

[0083]

[0084] [Chemistry 19]

[0085]

[0086] [Chemistry 20]

[0087]

[0088] [Chemistry 21]

[0089]

[0090] [Chemistry 22]

[0091]

[0092] [Chemistry 23]

[0093]

[0094] [Chemistry 24]

[0095]

[0096] [Chemistry 25]

[0097]

[0098] [Chemistry 26]

[0099]

[0100] [Chemistry 27]

[0101]

[0102] [Chemistry 28]

[0103]

[0104] [Chemistry 29]

[0105]

[0106] [Chemistry 30]

[0107]

[0108] (In the formula, Me is a methyl group, p1, q1, r1, s1, and t1 are each independently an integer of 1 to 200, and the total of p1, q1, r1, s1, and t1 is 3 to 500, and each repeating unit shown in the parentheses may be randomly bonded.)

[0109] [8] The water- and oil-repellent member according to any one of [1] to [7], wherein the substrate is a resin, ceramic, metal, quartz, glass, sapphire or diamond.

[0110] [9] A method for producing a water- and oil-repellent member as described in any one of [1] to [8], comprising: a step of forming a functional film layer having silicon dioxide as a main component or a functional film layer having silicon dioxide as at least the outermost layer on at least one surface of a substrate; a step of wet-coating a solution comprising an organic silicon compound having multiple silanol groups in its molecule and a solvent on the outer surface of the functional film layer; a step of evaporating the solvent to form and laminate a primer layer on at least one surface of the substrate; a step of wet-coating a solution comprising a hydrolyzable fluorine-containing compound and a solvent on the outer surface of the primer layer and then evaporating the solvent, or dry-coating a hydrolyzable fluorine-containing compound from which the solvent has been evaporated; and a step of curing the hydrolyzable fluorine-containing compound to form and laminate a water- and oil-repellent layer on the outer surface of the primer layer.

[0111] It should be noted that in the present invention, the so-called "straight-chain perfluoroalkylene oxide polymer residue" means that the divalent fluoroalkylene oxide repeating units of the perfluoroalkylene oxide structure constituting the main chain are connected in a straight chain, and each divalent fluoroalkylene oxide unit itself can be a fluoroalkylene oxide unit having a branched structure such as -[CF2CF(CF3)O]-.

[0112] Effects of the Invention

[0113] According to the present invention, it is possible to form a water-repellent and oil-repellent member having both antistatic and water-repellent and oil-repellent surfaces and excellent resistance to rubber abrasion.With regard to the manufacture method of the water-repellent and oil-repellent member, it is possible to adopt vacuum process, wet method (brush coating, spin coating, spray coating, gravure coating, die coating, rod coating, slit coating) process formation, it is possible to be applied to various purposes, especially, it is suitable for the purposes of finger, object contact surface.For example, for the housing of touch panel display, flexible display, electronic equipment, wearable terminal, eyeglass lens, protective film, protective glass, glass for copier, vehicle-mounted camera, radar cover for automatic driving, quartz glass for semiconductor product manufacturing, etc., products, dust, etc., due to electrostatic adhesion, avoid visibility reduction, scratched products, due to fingerprints, oil, water, etc., adhesion and damage visibility, beautiful products, kitchen sinks, faucets, showers, etc., scale, dirt adhesion, dirt wiping products are particularly useful. DETAILED DESCRIPTION

[0114] The present invention is described in more detail below.

[0115] The water-repellent and oil-repellent component of the present invention is a water-repellent and oil-repellent component having a functional film layer as a first layer on at least one surface of a substrate, a primer layer as a second layer on the outer surface of the functional film layer, and further having a water-repellent and oil-repellent layer as a third layer on the outer surface of the primer layer, wherein the primer layer is composed of a layer with a film thickness of 10 to 500 nm having an organosilicon compound having a plurality of silanol groups in the molecule as a main component, and the water-repellent and oil-repellent layer is composed of a layer with a film thickness of 0.5 to 50 nm having a cured product of a hydrolyzable fluorinated compound as a main component.

[0116] The present invention, for example, forms a functional film layer with silicon dioxide as the main component or a functional film layer with silicon dioxide as the outermost layer on the surface (at least one surface) of various substrates, and then wet-coats a solution containing an organosilicon compound having multiple silanol groups in the molecule and a solvent on the outer surface of the functional film layer, and then evaporates the solvent to form and laminate a primer layer (the second layer), and then wet-coats a solution containing a hydrolyzable fluorine-containing compound and a solvent on the outer surface of the primer layer, and then evaporates the solvent or removes the solvent from the solution (the second layer). The invention relates to a method of dry coating a hydrolyzable fluorinated compound from which a solvent is evaporated in a water-repellent and oil-repellent agent) and simultaneously curing the hydrolyzable fluorinated compound to form and laminate a water-repellent and oil-repellent layer (the third layer) on the outer surface of the primer layer, etc., to obtain a primer layer (the second layer) having a film thickness of 10 to 500 nm with an organosilicon compound having a plurality of silanol groups in the molecule as the main component on the surface of various substrates, and further having a water-repellent and oil-repellent layer (the third layer) having a film thickness of 0.5 to 50 nm with a cured product of the hydrolyzable fluorinated compound as the main component on the surface.

[0117] The substrate used in the present invention is not particularly limited, but is particularly preferably a resin, ceramic, metal, quartz, glass, sapphire, or diamond.

[0118] Among them, the resin as the base material may be a thermoplastic resin or a thermosetting resin, and specifically may be the following resins. Celluloid, cellulose acetate, cellulose propionate, cellulose butyrate, triacetyl cellulose, aliphatic polyamides such as 6-nylon, 6,6-nylon, and 12-nylon, aromatic polyamides, ABS resins, AS resins, polystyrene, polyethylene (low density or high density), polyolefins such as polypropylene, cycloolefin polymers, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymers, polyvinyl alcohol, polyacetal, polycarbonate, saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate, aromatic polyesters, polyether ketones, polyether ether ketones, polysulfones, polyether sulfones, polyether imides, polyarylates may be listed. , polymethylpentene, ionomer, liquid crystal polymer, polyimide, polyamideimide, fluororesin, polyphenylene sulfide, (modified) polyphenylene ether, thermoplastic polyurethane and other thermoplastic resins, or, epoxy resin, unsaturated polyester, thermosetting polyurethane, polyimide, polymer of diethylene glycol dicarbonate allyl ester (commonly known as CR-39), (co)polymer of di(meth)acrylate of (halogenated) bisphenol A, (co)polymer of di(meth)acrylate modified by carbamate of (halogenated) bisphenol A, diacrylate compound or copolymer of vinyl benzyl alcohol and unsaturated thiol compound and other thermosetting resins.

[0119] The functional film layer (first layer) formed and stacked on at least one surface of the above-mentioned substrate is a functional film layer such as a hard coating layer, an anti-reflection film layer, an IR cut-off filter layer, etc. The function of the functional film layer is not limited to these, as long as the entire layer has silicon dioxide as the main component or at least the outermost layer of the layer is silicon dioxide, as for the film thickness of the functional film layer (first layer), as long as the functional film layer as a whole (silicon dioxide layer) or the outermost layer of the functional film (silicon dioxide layer) is preferably 10 to 500nm, more preferably about 10 to 150nm.

[0120] Among them, the functional film layer specifically includes a hard coating layer having a silicon dioxide layer as a main component, a hard coating layer composed of a two-layer structure or a stacked structure of three or more layers in which a silicon dioxide layer is formed on the hard coating layer, an anti-reflection layer composed of a two-layer structure or a stacked structure of three or more layers formed on a substrate with silicon dioxide as the outermost layer, an IR cutoff filter layer composed of a two-layer structure or a stacked structure of three or more layers formed on a substrate with silicon dioxide as the outermost layer, etc.

[0121] The primer layer (second layer) formed and laminated on the outer surface of the functional film layer is a layer with a thickness of 10 to 500 nm, which is mainly composed of an organosilicon compound having multiple silanol groups in the molecule, preferably containing more than 50% by mass of the organosilicon compound. The primer layer can be formed (laminated) by, for example, wet coating a solution containing an organosilicon compound having multiple silanol groups in the molecule and a solvent on the outer surface of the functional film layer and then evaporating and removing the solvent.

[0122] The organosilicon compound having multiple silanol groups in the molecule has preferably more than 2, more preferably more than 3, and further preferably more than 4 silanol groups in one molecule. If the number of silanol groups in the molecule is too small, the adhesion to the outer surface of the water-repellent and oil-repellent layer (the third layer) stacked on the outer surface of the primer layer (the second layer) deteriorates, and sometimes the surface resistance value does not decrease. In addition, the amount of silanol groups in the organosilicon compound having multiple silanol groups in the molecule is preferably 0.002 to 0.042 mol / g, particularly preferably 0.004 to 0.035 mol / g, and particularly preferably 0.005 to 0.030 mol / g.

[0123] The organosilicon compound having a plurality of silanol groups in the molecule can be obtained by hydrolyzing and partially condensing an organosilicon compound having a plurality of hydrolyzable groups such as alkoxy groups such as methoxy groups and ethoxy groups, or halogen atoms such as chlorine atoms in the molecule.

[0124] Among them, examples of the organosilicon compound having a plurality of hydrolyzable groups in the molecule include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxy)silane, cyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylvinyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, tris (trimethoxysilylpropyl) isocyanurate, trichlorosilane, dichlorosilane, etc., and two or more of these may be used in combination.

[0125] In the present invention, as the organosilicon compound having a plurality of silanol groups in the molecule, it is preferred to use a product (partial condensate) obtained by hydrolyzing the organosilicon compound such as the organosilicon compound having a plurality of hydrolyzable groups and partially dehydrating and condensing the organosilicon compound to obtain a high molecular weight. In the present invention, the so-called partial condensate means an organopolysiloxane compound having a plurality of residual silanol groups in the molecule obtained by partially dehydrating and condensing an organosilicon compound such as the organosilicon compound having a plurality of hydrolyzable groups and having a plurality of silanol groups (hydroxyl groups bonded to silicon atoms) in the molecule obtained by hydrolyzing the organosilicon compound such as the organosilicon compound having a plurality of hydrolyzable groups.

[0126] The weight average molecular weight of the hydrolyzed partial condensate of the organosilicon compound having a plurality of hydrolyzable groups in the molecule (organosilicon compound having a plurality of silanol groups in the molecule) is preferably 300 to 100000, more preferably 5000 to 50000. It should be noted that in the present invention, the weight average molecular weight can be determined, for example, as a polystyrene conversion value in gel permeation chromatography (GPC) analysis using toluene as a developing solvent (the same below).

[0127] As the organosilicon compound having a plurality of silanol groups in the molecule used in the present invention, a hydrolysis partial condensate of tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane is particularly preferred.

[0128] The organosilicon compound having multiple silanol groups in the molecule is preferably diluted with a solvent. As the solvent for dissolving the organosilicon compound having multiple silanol groups in the molecule, alcohols such as methanol, ethanol, isopropanol, butanol, ethers such as propylene glycol monomethyl ether, polyethylene glycol monopropyl ether, etc. are preferred, but there is no particular limitation, and it can be appropriately selected from the wettability with the first layer and the boiling point. The concentration of the organosilicon compound having multiple silanol groups in the molecule in the solution containing the organosilicon compound having multiple silanol groups in the molecule and the solvent is preferably 0.01 to 10% by mass, and more preferably 0.6 to 4% by mass. If the concentration is too low, the uncoated portion increases, and if the concentration is too high, secondary aggregation may occur between the silanol groups.

[0129] In addition, in the solution containing the organosilicon compound having multiple silanol groups in the molecule and the solvent, components such as ultraviolet absorbers, light stabilizers, antioxidants, leveling agents, defoamers, pigments, dyes, dispersants, antistatic agents, antifogging agents and other surfactants can be used as needed. In addition, it is preferred to add these components in the range of 50% by mass or more (50-100% by mass), especially 80-100% by mass (that is, the above-mentioned arbitrary components are made less than 50% by mass (0-50% by mass), preferably 0-20% by mass) of the organosilicon compound having multiple silanol groups in the molecule in the primer layer obtained excluding the solvent.

[0130] A solution containing the organosilicon compound having multiple silanol groups in the molecule and a solvent is applied to the outer surface of the functional film layer by wet coating, particularly dipping, brush coating, spin coating, spray coating, gravure coating, die coating, rod coating, slit coating, flow coating, etc., and the solvent is evaporated, thereby forming a primer layer having the organosilicon compound having multiple silanol groups in the molecule as a main component. In addition, heating can 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.

[0131] The thickness of the primer layer (second 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 250 nm. It should be noted that in the present invention, the film thickness can be measured by known methods such as spectroscopic ellipsometer and X-ray reflectivity method (the same below).

[0132] Next, the water- and oil-repellent layer (third layer) formed and laminated on the outer surface of the primer layer is composed of a layer having a film thickness of 0.5 to 50 nm and containing a cured product of a hydrolyzable fluorine-containing compound as a main component.

[0133] The water- and oil-repellent layer can be formed and laminated, for example, by applying a solution (water- and oil-repellent agent) containing a hydrolyzable fluorine-containing compound and a solvent on the outer surface of the formed primer layer surface (second layer) and curing the solution.

[0134] As the hydrolyzable fluorine-containing compound, there can be used Japanese Patent Application Laid-Open No. 2007-197425, Japanese Patent Application Laid-Open No. 2007-297589, Japanese Patent Application Laid-Open No. 2007-297543, Japanese Patent Application Laid-Open No. 2008-088412, Japanese Patent Application Laid-Open No. 2008-144144, Japanese Patent Application Laid-Open No. 2010-031184, Japanese Patent Application Laid-Open No. 2010-047516, Japanese Patent Application Laid-Open No. 2010-088412 ... The hydrolyzable fluorinated organosilicon compounds described in Japanese Unexamined Patent Application Publication No. 011-116947, Japanese Unexamined Patent Application Publication No. 2011-178835, Japanese Unexamined Patent Application Publication No. 2014-084405, Japanese Unexamined Patent Application Publication No. 2014-105235, Japanese Unexamined Patent Application Publication No. 2013-253228, Japanese Unexamined Patent Application Publication No. 2014-218639, and International Publication No. 2013 / 121984 (Patent Documents 1, 4 to 16) and the like.

[0135] The hydrolyzable fluorine-containing compound will be described in more detail.

[0136] The hydrolyzable fluorine-containing compound of the present invention is preferably a hydrolyzable fluorine-containing compound having at least one, preferably 1 to 6, more preferably 1 to 4 hydrolyzable silyl groups (e.g., silyl groups having 1 to 3 hydrolyzable groups such as alkoxy groups bonded to silicon atoms, such as trialkoxysilyl, dialkoxy (organic) silyl, and alkoxy (diorganic) silyl groups) at at least one, preferably 1 to 14, more preferably 1 to 7 molecular chain ends (e.g., at least one, preferably 1 to 20, more preferably 2 to 14, and even more preferably 2 to 8 hydrolyzable silyl groups in one molecule) The compound is more preferably an organosilicon compound having in one molecule an alkoxy group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, an alkoxy group having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, an acyloxy group having 1 to 10 carbon atoms, such as acetoxy, propionyloxy, an alkenyloxy group having 2 to 10 carbon atoms, such as vinyloxy, isopropenyloxy, a halogen group such as chloro, bromo, iodo, or a hydrolyzable silyl group having 1 to 3 hydrolyzable groups such as primary or secondary amino groups, or a hydrolyzable silyl group such as silazane, and having a fluorine atom.

[0137] The hydrolyzable fluorine-containing compound is preferably a compound having a fluorooxyalkylene group (i.e., a monovalent or divalent perfluoropolyether residue) in the molecule. j F 2jA compound having a (poly)fluoroalkylene oxide structure (a divalent linear perfluoroalkylene oxide polymer residue) in which a plurality of repeating units represented by O are bonded (in this structure, j is an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 4). In particular, the number of such repeating units may be 3 to 500, preferably 15 to 200, more preferably 20 to 100, and even more preferably 25 to 80.

[0138] Regarding the above repeating unit-C j F 2j O- may be either a linear type or a branched type. For example, the following units may be mentioned, and two or more types of these repeating units may be bonded.

[0139] -CF2O-

[0140] -CF2CF2O-

[0141] -CF2CF2CF2O-

[0142] -CF(CF3)CF2O-

[0143] -CF2CF2CF2CF2O-

[0144] -CF2CF2CF2CF2CF2O-

[0145] -C(CF3)2O-

[0146] The above-mentioned (poly)fluoroalkylene oxide structure (divalent linear perfluoroalkylene oxide polymer residue) is particularly -(CF2) d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d -, p, q, r, s, t are each independently an integer of 0 to 200, preferably, p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, s is an integer of 0 to 50, t is an integer of 0 to 100, and p+q+r+s+t=an integer of 3 to 500, preferably an integer of 10 to 105. In addition, each repeating unit shown in the brackets may be randomly bonded. d is independently an integer of 0 to 8, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and the unit may be linear or branched. In particular, it can be represented by the following structure.

[0147] [Chemistry 31]

[0148] -(CF2) d′-O-(CF2CF2O) q′ -(CF2) d′ -

[0149] -(CF2) d′ -O-(CF2CF2CF2O) r′ -(CF2) d′ -

[0150]

[0151] -(CF2) d′ -O-(CF2O) p′ (CF2CF2O) q′ -(CF2) d′ -

[0152] -(CF2) d′ -O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ -(CF2) d′ -

[0153] -(CF2) d′ -O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ -(CF2) d′ -

[0154]

[0155] -(CF2) d′ -O-(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ -(CF2) d -

[0156]

[0157] -(CF2) d′ -O-(CF2CF2O) q′ (CF2CF2CF2CF2O) s′ -(CF2) d′ -

[0158] (In the formula, p', q', r', s', and t' are each independently an integer of 1 to 200, and the total of p', q', r', s', and t' is 3 to 500. Each repeating unit shown in the parentheses may be randomly bonded. d' is independently an integer of 0 to 5, and the unit may be linear or branched.)

[0159] The hydrolyzable fluorine-containing compound of the present invention is more preferably a fluorine-containing hydrolyzable organosilicon compound (fluorine-containing hydrolyzable organosilicon compound) represented by any one of the following general formulas (1) to (5). These may be used alone or in combination of two or more.

[0160] (A-Rf) α -ZW β (1)

[0161] Rf-(ZW β )twenty two)

[0162] Z'-(Rf-ZW β ) γ (3)

[0163] A-Rf-Q-(Y) δ -B (4)

[0164] Rf-(Q-(Y) δ -B)2 (5)

[0165] In formulas (1) to (5), Rf is -(CF2) d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d-represents a divalent linear perfluoroalkylene oxide polymer residue, p, q, r, s, t are each independently an integer of 0 to 200, and p+q+r+s+t=3 to 500, each repeating unit shown in the brackets may be randomly bonded, d is independently an integer of 0 to 8, and the unit may be linear or branched. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, Z, Z' are independently a single bond, or a divalent to octavalent organic group that may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be substituted with fluorine, and W is a monovalent organic group having a hydrolyzable group at the terminal. α, β are each independently an integer of 1 to 7, preferably, α is an integer of 1 to 3, more preferably 1, β is an integer of 1 to 3, and α+β=2 to 8 integers, preferably 2 to 4 integers. γ is an integer of 2 to 8, and is preferably 2 or 3.

[0166] Furthermore, Q is a single bond or a divalent organic group, δ is independently an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

[0167] In the above formulae (1) to (5), Rf is -(CF2) which is the above-mentioned (poly)fluorooxyalkylene structure (a divalent linear perfluorooxyalkylene polymer residue). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d -, and the same groups as mentioned above can be exemplified.

[0168] In the above formulas (1) and (4), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group. As the monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, specifically, -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, -CH2OCF2CFH-OC3F7 group, etc. can be exemplified. As A, -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2OCF2CFH-OC3F7 group are preferred.

[0169] In the above formulae (1) to (3), Z and Z' are independently a single bond, or a 2- to 8-valent organic group which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be substituted with fluorine. The organic group may be (L)e -M (e is an integer of 1 to 7, preferably an integer of 1 to 3).

[0170] Wherein, L is a single bond, or an oxygen atom, a sulfur atom, or a divalent organic group. In the above formulas (1) to (3), L of Z is a linking group between the Rf group and the M group (or the W group), and L of Z' is a linking group between the M group (or the Rf group) and the Rf group. As a divalent organic group, it is preferred that it may contain a diorganosilylene group selected from an amide bond, an ether bond, a carbonyl bond, an ester bond, a dimethylsilylene group, or a -Si[OH][(CH2) f Si(CH3)3]- (f is an integer from 2 to 4)], one or more unsubstituted or substituted divalent organic groups having 2 to 12 carbon atoms in the group represented by - (f is an integer from 2 to 4), and more preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms that may contain the above structure.

[0171] As the above-mentioned unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, for example, alkylene groups such as ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, arylene groups such as phenylene, or combinations of two or more of these groups (arylene, arylene, etc.) can be listed. Furthermore, groups in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as fluorine and iodine may be used. Among them, unsubstituted or substituted alkylene groups or phenylene groups having 2 to 4 carbon atoms are preferred.

[0172] Examples of the divalent organic group for L include groups represented by the following structures, or groups in which two or more of these structures are bonded.

[0173] [Chemistry 32]

[0174] -(CH2) u -O-(CH2) v -

[0175] [Chemistry 33]

[0176]

[0177] [Chemistry 34]

[0178]

[0179] [Chemistry 35]

[0180]

[0181] [Chemistry 36]

[0182]

[0183] [Chemistry 37]

[0184]

[0185] (In the formula, f is an integer of 2 to 4, b is an integer of 2 to 6, preferably an integer of 2 to 4, u and v are integers of 1 to 4, g is an integer of 2 to 4, and Me is a methyl group.)

[0186] In addition, M is a single bond, or an organic group containing a nitrogen atom, a silicon atom, a carbon atom, a phosphorus atom, or a 2- to 8-valent (the above-mentioned (e+1)-valent) organic group thereof. 1 A divalent group represented by 2C-, -R 3 A divalent group represented by 2Si-, -NR 4 -, a divalent group represented by -N=, a trivalent group represented by -N= (including a trivalent group consisting of an isocyanuric acid ring structure), a trivalent group represented by -P=, a trivalent group represented by -PO=, a trivalent group represented by -R 1 C= trivalent group represented by -R 3 A trivalent group represented by Si=, a tetravalent group represented by -C≡, a tetravalent group represented by -OC≡, and a group among the tetravalent groups represented by -Si≡, or a siloxane residue with 2 to 8 valencies. In the above formulae (1) to (3), M of Z is a linking group of L (or Rf group) and W group, and M of Z' is a group connecting L to Rf group (or connecting Rf groups to each other).

[0187] In the above, R 1 Preferably, each of them is independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a group having a repeating unit of an oxyalkylene group having 1 to 3 carbon atoms which may be connected via a diorganosiloxane structure having 2 to 51 silicon atoms, or a group consisting of R 2 3SiO-represented silyl ether group, R 2 R is independently a hydrogen atom, preferably an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, or an alkoxy group having 1 to 3 carbon atoms. 3 Preferably, R is independently an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chloro group. 4 It is an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, such as a phenyl group. When M is a siloxane residue, it preferably has a linear, branched or cyclic organopolysiloxane structure having 2 to 51 silicon atoms, preferably 2 to 13 silicon atoms, more preferably 2 to 11 silicon atoms, and further preferably 2 to 5 silicon atoms. The organopolysiloxane may have a methyl group, an ethyl group, a propyl group, a butyl group, and an unsubstituted or fluorine-substituted alkyl group or a phenyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as C3F7-C3H6-. In addition, it may contain a silylene structure in which two silicon atoms are bonded by an alkylene group, i.e., Si-(CH2) n-Si. In the above formula, n is an integer of 2-6, preferably an integer of 2-4.

[0188] Examples of such M include the following groups.

[0189] [Chemistry 38]

[0190]

[0191] [Chemistry 39]

[0192]

[0193] [Chemistry 40]

[0194]

[0195] [Chemistry 41]

[0196]

[0197] [Chemistry 42]

[0198]

[0199] [Chemistry 43]

[0200]

[0201] [Chemistry 44]

[0202]

[0203] [Chemistry 45]

[0204]

[0205] (In the formula, i is an integer of 1 to 20, c is an integer of 1 to 50, and Me is a methyl group.)

[0206] In the above formulae (1) to (3), W is a monovalent organic group having a hydrolyzable group at the terminal, and is preferably represented by the following formula.

[0207] [Chemistry 46]

[0208]

[0209] (In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and m is an integer of 0 to 10.)

[0210] In the above formula, examples of the hydrolyzable group of X include alkoxy groups having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, alkoxyalkoxy groups having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, acyloxy groups having 1 to 10 carbon atoms, such as acetoxy, alkenyloxy groups having 2 to 10 carbon atoms, such as isopropenyloxy, halogen groups such as fluoro, chloro, bromo, iodo, and amino groups. Among them, methoxy and ethoxy are preferred.

[0211] Furthermore, R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group, or a phenyl group, and among these, a methyl group is preferred.

[0212] a is 2 or 3, and is preferably 3 from the viewpoint of reactivity and adhesion to the primer layer (second layer). m is an integer of 0 to 10, and is preferably an integer of 2 to 8, and is more preferably 2 or 3.

[0213] In formulas (1) to (3), as -ZW β The structure represented by can be listed as follows.

[0214] [Chemistry 47]

[0215]

[0216] [Chemistry 48]

[0217]

[0218] [Chemistry 49]

[0219]

[0220] (In the formula, L, R, X, f, c and a are as described above, m1 is an integer of 0 to 10, preferably an integer of 2 to 8, m2 is an integer of 1 to 10, preferably an integer of 2 to 8, and Me is a methyl group.)

[0221] In the above formulae (4) and (5), Q is a single bond or a divalent organic group, and is a linking group between the Rf group and the Y group. The divalent organic group of Q is preferably a diorganosilylene group selected from an amide bond, an ether bond, an ester bond, or a dimethylsilylene group, a -Si[OH][(CH2) f Si(CH3)3]- (f is an integer from 2 to 4)], one or more unsubstituted or substituted divalent organic groups having 2 to 12 carbon atoms in the group represented by - (f is an integer from 2 to 4), and more preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms that may contain the above structure.

[0222] Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include the same groups as those exemplified for the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms in L above.

[0223] Examples of the divalent organic group represented by Q include groups represented by the following structures.

[0224] [Chemistry 50]

[0225] -(CH2) u -O-(CH2) v -

[0226] [Chemistry 51]

[0227]

[0228] [Chemistry 52]

[0229]

[0230] [Chemistry 53]

[0231]

[0232] (In the formula, f is an integer of 2 to 4, b is an integer of 2 to 6, preferably an integer of 2 to 4, u and v are integers of 1 to 4, g is an integer of 2 to 4, and Me is a methyl group.)

[0233] In the above formulae (4) and (5), Y is independently a divalent organic group having a hydrolyzable group, and preferably has a structure represented by the following formula.

[0234] [Chemistry 54]

[0235]

[0236] (In the formula, R, X and a are as described above. k is an integer of 0 to 10, preferably an integer of 1 to 10, and more preferably an integer of 2 to 8. h is an integer of 1 to 6, preferably 1 or 2, and M' is an unsubstituted or substituted 3 to 8-valent, preferably 3-valent or 4-valent hydrocarbon group, a part or all of the carbon atoms in the hydrocarbon group may be replaced by silicon atoms, and a part or all of the hydrogen atoms bonded to the carbon atoms may be replaced by halogen atoms such as fluorine atoms.)

[0237] As M', a group represented by the following structure is preferred.

[0238] [Chemistry 55]

[0239]

[0240] (In the above, M 1 is a single bond, an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, or a diorganosilylene group such as a dimethylsilylene group, M 2 For-R 1C=a trivalent group represented by -R 3 Si=represents a trivalent group, R 1 , R 3 Same as above. 5 It is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, or a propyl group having 1 to 6 carbon atoms.

[0241] As M 1 , single bond, phenylene, dimethylsilylene, tetrafluoroethylene, etc. can be exemplified. 2 , the groups shown below can be listed.

[0242] [Chemistry 56]

[0243]

[0244] (In the formula, Me is a methyl group.)

[0245] Examples of such Y include the following groups.

[0246] [Chemistry 57]

[0247]

[0248] [Chemistry 58]

[0249]

[0250] (In the formula, X is the same as above, k1 is an integer of 0 to 10, preferably an integer of 0 to 8, k2 is an integer of 2 to 10, preferably an integer of 2 to 8, and Me is a methyl group.)

[0251] In the above formulae (4) and (5), δ is independently an integer of 1 to 10, and preferably an integer of 1 to 4.

[0252] Furthermore, B is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, or a halogen atom such as fluorine, chlorine, bromine and iodine.

[0253] Examples of the fluorine-containing hydrolyzable organosilicon compound (fluorine-containing hydrolyzable organosilicon compound) represented by the above formulae (1) to (5) include the following structures.

[0254] [Chemistry 59]

[0255]

[0256] [Chemistry 60]

[0257]

[0258] [Chemistry 61]

[0259]

[0260] [Chemistry 62]

[0261]

[0262] [Chemistry 63]

[0263]

[0264] [Chemistry 64]

[0265]

[0266] [Chemistry 65]

[0267]

[0268] [Chemistry 66]

[0269]

[0270] [Chemistry 67]

[0271]

[0272] [Chemistry 68]

[0273]

[0274] [Chemistry 69]

[0275]

[0276] [Chemistry 70]

[0277]

[0278] [Chemistry 71]

[0279]

[0280] [Chemistry 72]

[0281]

[0282] [Chemistry 73]

[0283]

[0284] [Chemistry 74]

[0285]

[0286] [Chemistry 75]

[0287]

[0288] [Chemistry 76]

[0289]

[0290] [Chemistry 77]

[0291]

[0292] [Chemistry 78]

[0293]

[0294] [Chemistry 79]

[0295]

[0296] [Chemistry 80]

[0297]

[0298] [Chemistry 81]

[0299]

[0300] [Chemistry 82]

[0301]

[0302] [Chemistry 83]

[0303]

[0304] [Chemistry 84]

[0305] [Chemistry 85]

[0306]

[0307] [Chemistry 86]

[0308]

[0309] (In the formula, Me is a methyl group, p1, q1, r1, s1, and t1 are each independently an integer of 1 to 200, and the total of p1, q1, r1, s1, and t1 is 3 to 500, and each repeating unit shown in the parentheses may be randomly bonded.)

[0310] Furthermore, the fluorinated hydrolyzable organosilicon compounds (fluorinated hydrolyzable organosilicon compounds) represented by the general formulae (1) to (5) of the present invention may include compounds in which part or all of the hydrolyzable groups (X) are hydrolyzed (compounds in which X is an OH group), and may also include compounds in which part or all of these OH groups are condensed.

[0311] It is preferred that the above-mentioned hydrolyzable fluorinated compound is diluted with a solvent in advance. As such a solvent, as long as the above-mentioned hydrolyzable fluorinated compound is uniformly dissolved, it is not particularly limited. For example, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-trifluoromethylbenzene, etc.), fluorine-modified unsaturated hydrocarbon solvents (hexafluoroolefin, hexafluoropropylene trimer), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran)), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, in terms of solubility and stability, fluorine-modified solvents are preferred, and fluorine-modified ether solvents and fluorine-modified aromatic hydrocarbon solvents are particularly preferred.

[0312] The above solvents may be used alone or in combination of two or more.

[0313] The solvent is preferably contained so that the hydrolyzable fluorinated compound in the water-and-oil repellent (solution containing the hydrolyzable fluorinated compound and the solvent) is 0.01 to 50 mass %, preferably 0.03 to 10 mass %, more preferably 0.05 to 1 mass %.

[0314] The water- and oil-repellent agent containing the above-mentioned hydrolyzable fluorinated compound can adopt the known methods such as wet coating method (dipping method, brush coating, spin coating, spraying, gravure coating, die coating, rod coating, slit coating), evaporation method to apply substrate.Coating conditions etc. can be according to the known method in the past, owing to adopting wet coating method (wet method) to coat, form primer layer, therefore the water- and oil-repellent agent containing the hydrolyzable fluorinated compound also adopts wet coating method (wet method) to coat to be efficient.

[0315] The hydrolyzable fluorine-containing compound can be cured in 1 to 24 hours at room temperature (25°C). To cure it in a shorter time, it can be heated at 30 to 200°C for 1 minute to 1 hour. Curing is preferably carried out under humidification (50 to 90% RH) to promote hydrolysis.

[0316] Before applying the water- and oil-repellent containing the hydrolyzable fluorinated compound, the surface of the primer layer on the substrate may be subjected to a treatment such as plasma treatment, UV treatment, ozone treatment, etc. for cleaning or surface activation.

[0317] The film thickness of the fluorine layer (water-repellent and oil-repellent layer) of the water-repellent and oil-repellent member of the present invention is 0.5 to 50 nm, and particularly preferably 1 to 20 nm. If the film thickness is too thick, the surface resistance value of the outer surface of the water-repellent and oil-repellent layer sometimes increases, and if it is too thin, the surface characteristics and wear resistance are sometimes insufficient.

[0318] In the water-repellent and oil-repellent member of the present invention obtained in this way, the surface resistance value of the outer surface of the water-repellent and oil-repellent layer is compared with when there is no second layer, and reduces more than 10Ω / □. If the surface resistance value of the outer surface of the water-repellent and oil-repellent layer is too high, sometimes electronic devices such as organic EL will malfunction, and in addition, due to the attachment of dust etc., the visibility of the surface is reduced, damaging optical properties and texture. And then, the surface becomes easy to pollute. In the present invention, the surface resistance value can be measured by Hiresta UX MCP-HT800 manufactured by commercially available resistivity meter such as Mitsubishi Chemical Analysis Co., Ltd.

[0319] In addition, the surface resistance value of the outer surface of the water- and oil-repellent layer can be set to 1.0×10 11 Ω / □ or less, preferably 1.0×10 7 ~1.0×10 11 Ω / □, more preferably 1.0×10 8 ~9.8×10 10 Furthermore, in order to make the surface resistance value of the outer surface of the water-repellent and oil-repellent layer within the above range, it is preferred that the film thickness of the primer layer as the second layer with an organosilicon compound having a plurality of silanol groups in the molecule as the main component be 10 to 500 nm, and further the film thickness of the water-repellent and oil-repellent layer as the second layer formed on the outer surface of the primer layer with a cured product of a hydrolyzable fluorinated compound as the main component be 0.5 to 50 nm.

[0320] As the water-repellent and oil-repellent member of the present invention thus obtained, examples include housings of car navigation, tablet computers, smartphones, foldable smartphones, foldable smartphones, flexible devices, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, etc., camera lenses, security cameras, vehicle-mounted lenses, eyeglass lenses, sunglasses, AR lenses, VR lenses, etc., endoscopes, scalpels, sphygmomanometers, medical devices such as X-ray CT and MRI, liquid crystal displays, organic EL displays, touch panel surfaces of flexible devices, etc., protective films, anti-reflection films, infrared cut filters, CDs, DVDs, Blu-ray discs and other optical articles, window glass of automobiles, trains, aircraft, etc., headlight covers, headlight lenses, etc., tiles, building materials for outer walls, system kitchens, bathtubs, shower heads, faucets, exhaust hoods, other kitchen building materials, waiting rooms, artworks, main bodies of transportation equipment, reflectors, radar covers of millimeter wave sensors, etc.

[0321] Example

[0322] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. It should be noted that Me represents a methyl group.

[0323] [Examples 1 to 13 and Comparative Examples 1 to 9]

[0324] As described below, a test body of a water- and oil-repellent member having a substrate, a functional film layer, a primer layer, and a water- and oil-repellent layer was prepared.

[0325] [Base material]

[0326] PET film treated with a clear hard coat layer (Hard coat film FHC-53EEM2 manufactured by Toyama Film Co., Ltd., test piece substrate with a thickness of 188 μm, a width of 50 mm, and a length of 100 mm, pencil hardness: H (JIS K5400 500 g))

[0327] [Formation of functional film layer (first layer)]

[0328] Functional film layers were formed on the above substrates by the methods described below.

[0329] [Formation of Functional Film Layer 1]

[0330] Silicon dioxide was sputtered to form a functional film layer 1 with a thickness of 100 nm on the outer surface of the substrate.

[0331] [Formation of Functional Film Layer 2]

[0332] The substrate was dip-coated with a treatment solution containing perhydropolysilazane diluted with dibutyl ether to a solid content of 2.0% by mass, and then cured at 80°C / 80%RH for 24 hours to form a functional film layer 2 with a thickness of 96nm on the outer surface of the substrate. In the dip coating, the substrate was immersed in the treatment solution for 30 seconds and then lifted at 150mm / min. In addition, the perhydropolysilazane as a raw material of the functional film layer 2 reacts with moisture (water) in the atmosphere as it cures, produces ammonia and dehydrogenates, thereby forming a SiO2 (silicon dioxide) layer.

[0333] [Formation of Functional Film Layer 3]

[0334] Silicon dioxide was sputtered to form a functional film layer 3 with a thickness of 10 nm on the outer surface of the substrate.

[0335] [Formation of Functional Film Layer 4]

[0336] As the outermost layer of the anti-reflection layer formed on the surface of the substrate, silicon dioxide was stacked by sputtering to form a functional film layer 4. It should be noted that the anti-reflection layer has a stacked structure of Nb2O5 (12nm), SiO2 (34nm), Nb2O5 (116nm), and SiO2 (76nm) from the substrate side.

[0337] [Formation of primer layer (second layer)]

[0338] A primer layer was formed on the substrate or the functional film layer by the following method.

[0339] [Formation of Primer Layer 1]

[0340] A hydrolyzed partial condensate of tetraethoxysilane (weight average molecular weight: 25,000, silanol group content: 0.015 mol / g) was diluted with butanol to a treatment liquid having a solid content of 0.2% by mass. The substrate was coated with a rod coater (Rod coater No. 2 manufactured by Daiichi Rika Co., Ltd.) and then dried at 80°C for 1 minute to evaporate the butanol, thereby forming a 10 nm primer layer 1 on the outer surface of the substrate.

[0341] [Formation of Primer Layer 2]

[0342] A treatment solution prepared by diluting a hydrolyzed partial condensate of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol to a solid content of 0.78% by mass was used. The substrate was dip-coated (the substrate was immersed in the treatment solution for 60 seconds and then lifted at a speed of 150 mm / min). The substrate was then dried at room temperature (25°C) for 60 minutes to evaporate the butanol, thereby forming a 30 nm primer layer 2 on the outer surface of the substrate.

[0343] [Formation of Primer Layer 3]

[0344] A treatment liquid prepared by diluting a hydrolyzed partial condensate of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol to a solid content of 2.0 mass% was used, and the substrate was dip-coated (the substrate was immersed in the treatment liquid for 60 seconds and then lifted at 150 mm / min), followed by drying at room temperature (25°C) for 60 minutes to evaporate the butanol, thereby forming a 91 nm primer layer 3 on the outer surface of the substrate.

[0345] [Formation of Primer Layer 4]

[0346] A treatment liquid having a solid content of 4.0% by mass is prepared by diluting a hydrolyzed partial condensate of tetraethoxysilane (weight-average molecular weight: 25,000, silanol group content: 0.015 mol / g) with butanol, and the substrate is dip-coated (the substrate is immersed in the treatment liquid for 60 seconds and then lifted at a speed of 150 mm / min). The substrate is then dried at room temperature (25°C) for 60 minutes to evaporate the butanol, thereby forming a primer layer 4 of 210 nm on the outer surface of the substrate.

[0347] [Formation of Primer Layer 5]

[0348] A hydrolyzed partial condensate of tetraethoxysilane (weight average molecular weight: 25,000, silanol group content: 0.015 mol / g) was diluted with butanol to a treatment liquid having a solid content of 0.1% by mass. The substrate was coated with a rod coater (Rod coater No. 2 manufactured by Daiichi Rika Co., Ltd.) and then dried at 80°C for 1 minute to evaporate the butanol, thereby forming a 5 nm primer layer 5 on the outer surface of the substrate.

[0349] [Formation of water- and oil-repellent layer (third layer)]

[0350] Furthermore, a water- and oil-repellent layer was formed and laminated on the outer surface of the substrate, the functional film layers 1 to 4 shown in Table 1, or the primer layer of the substrate having the primer layers 1 to 5 shown in Table 1 formed thereon by the following method.

[0351] [Formation of water- and oil-repellent layer 1]

[0352] Preparation Compound 1 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether)) to a treatment solution of 0.1% by mass in terms of solid content, and the treatment solution was sprayed on the primer layer of the above-mentioned substrate using a spraying device (NST-51 made by T&K Co., Ltd.). Then, it was heated at 80°C for 30 minutes, and the solid component in the treatment solution was cured while evaporating the fluorine-modified ether solvent to form a cured film (water- and oil-repellent layer), and a test body was prepared. The average film thickness of the water- and oil-repellent layer 1 calculated by the F detection amount obtained using a fluorescent X-ray device (ZSXmini2 made by RIGAKU Co., Ltd.) was about 10nm.

[0353] [Compound 1]

[0354] [Chemistry 87]

[0355]

[0356] (p1+q1=48, p1:q1=24:24)

[0357] [Formation of water- and oil-repellent layer 2]

[0358] Preparation The compound 2 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd.) to a treatment solution of 20% by mass in terms of solid content, and the treatment solution was vacuum-evaporated and coated on the primer layer of the above-mentioned substrate using a vacuum evaporation device (VTR-250 manufactured by ULVAC Mechanism Co., Ltd.). Then, the solid component of the vacuum evaporation coating was cured at 25°C to form a cured film (water-repellent and oil-repellent layer), and a test body was prepared. The average film thickness of the water-repellent and oil-repellent layer 2 calculated by the F detection amount obtained by using a fluorescent X-ray device (ZSXmini2 manufactured by RIGAKU Co., Ltd.) is about 11nm.

[0359] [Compound 2]

[0360] [Chemistry 88]

[0361]

[0362] (p1+q1+t1=35, p1:q1:t1=17:16:2)

[0363] [Formation of water- and oil-repellent layer 3]

[0364] Preparation The compound 3 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd.) to a treatment solution of 0.2% by mass in terms of solid content, and the treatment solution was applied on the primer layer of the above-mentioned substrate using a rod coater (rod coater No. 2 made by the first physical and chemical company) and allowed to stand for 60 minutes at 25°C, and the solid component in the treatment solution was cured while the fluorine-modified ether solvent was evaporated to form a cured film (water-repellent and oil-repellent layer), and a test body was prepared. The average film thickness of the water-repellent and oil-repellent layer 3 calculated by the F detection amount obtained by using a fluorescent X-ray device (ZSXmini2 made by RIGAKU Co., Ltd.) was about 15nm.

[0365] [Compound 3]

[0366] [Chemistry 89]

[0367]

[0368] (p1+q1=60, p1:q1=29:31)

[0369] [Formation of water- and oil-repellent layer 4]

[0370] Preparation The compound 4 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd.) to a treatment solution of 0.1% by mass in terms of solid content, and the treatment solution was sprayed on the primer layer of the above-mentioned substrate using a spraying device (NST-51 made by T&K Co., Ltd.). Then, it was heated at 80°C for 30 minutes, and the solid component in the treatment solution was solidified while the fluorine-modified ether solvent was evaporated to form a cured film (water-repellent and oil-repellent layer), and a test body was prepared. The average film thickness of the water-repellent and oil-repellent layer 4 calculated by the F detection amount obtained by using a fluorescent X-ray device (ZSXmini2 made by RIGAKU Co., Ltd.) was about 13nm.

[0371] [Compound 4]

[0372] [Chemistry 90]

[0373]

[0374] (p1+q1=42, p1:q1=20:22)

[0375] [Formation of water- and oil-repellent layer 5]

[0376] Preparation Compound 5 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd.) to a treatment solution of 0.1% by mass in terms of solid content, and the treatment solution was sprayed on the primer layer of the above-mentioned substrate using a spraying device (NST-51 made by T&K Co., Ltd.). Then, it was heated at 80°C for 30 minutes, and the solid component in the treatment solution was solidified while the fluorine-modified ether solvent was evaporated to form a cured film (water- and oil-repellent layer), and a test body was prepared. The average film thickness of the water- and oil-repellent layer 5 calculated by the F detection amount obtained by using a fluorescent X-ray device (ZSXmini2 made by RIGAKU Co., Ltd.) was about 13nm.

[0377] [Compound 5]

[0378] [Chemistry 91]

[0379]

[0380] (p1+q1=50, p1:q1=26:24)

[0381] [Formation of water- and oil-repellent layer 6]

[0382] Preparation Compound 6 shown below was diluted with a fluorine-modified ether solvent (Novec7200 (manufactured by 3M Co., Ltd.) to a treatment solution of 0.1% by mass in terms of solid content, and the treatment solution was sprayed on the primer layer of the above-mentioned substrate using a spraying device (NST-51 made by T&K Co., Ltd.). Then, it was heated at 80°C for 30 minutes, and the solid component in the treatment solution was cured while the fluorine-modified ether solvent was evaporated to form a cured film (water-repellent and oil-repellent layer), and a test body was prepared. The average film thickness of the water-repellent and oil-repellent layer 6 calculated by the F detection amount obtained by using a fluorescent X-ray device (ZSXmini2 made by RIGAKU Co., Ltd.) was about 12nm.

[0383] [Compound 6]

[0384] [Chemistry 92]

[0385]

[0386] (p1+q1=38, p1:q1=19:19)

[0387] The following measurements were performed on the test specimens of the water- and oil-repellent members having the functional film layer, the primer layer, or the water- and oil-repellent layer shown in Table 1 below. The results are also shown in Table 1.

[0388] [Antistatic properties]

[0389] As an evaluation of antistatic properties, the surface resistance value was measured under the following conditions using a resistivity meter (Hiresta UXMCP-HT800) manufactured by Mitsubishi Chemical Analytical Science Corporation.

[0390] Applied voltage: 1000V

[0391] [Water and oil repellency]

[0392] The contact angle of the cured film (water- and oil-repellent layer) of the test piece with respect to water and the contact angle with respect to oleic acid were measured using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.).

[0393] [Rubber abrasion resistance]

[0394] For the cured film (water-repellent and oil-repellent layer) of the test body made above, a friction tester (manufactured by Shinto Science Co., Ltd.) was used to measure the contact angle (water repellency) for water after 100 reciprocating wear under the following conditions in the same manner as above, and the number of wears at which the water contact angle was kept at 100 degrees was set as the rubber wear durability number. The test environment conditions were 25°C and 50% humidity.

[0395] Eraser: Made by Minoan Co., Ltd.

[0396] Contact area:

[0397] Moving distance (one way): 30mm

[0398] Moving speed: 3600mm / min

[0399] Load:

[0400] [Table 1]

[0401]

[0402] *1) The surface resistance value was too high to be measured.

[0403] As can be seen from the results of Table 1, Examples 1 to 13 have excellent water and oil repellency and excellent rubber abrasion resistance. On the other hand, the rubber abrasion resistance of Comparative Examples 1 to 9 is less than 500 times, and the wear resistance is insufficient. In Comparative Example 1, since the water and oil repellent is directly applied on the hard coating layer, the initial water and oil repellency is poor. In Comparative Example 2, since no primer layer is provided, the wear resistance is insufficient. In Comparative Example 3, since a polysilazane layer is provided in the functional film layer, but no primer layer is provided, the wear resistance is insufficient. Comparative Examples 4 to 8 do not provide a primer layer, change the type of water and oil repellent, and have insufficient wear resistance. In Comparative Example 9, since the film thickness of the primer layer is too thin, the wear resistance is insufficient.

[0404] In Examples 1 to 13, since the primer layer was made 10 nm or more, the surface resistance value of the outer surface of the water- and oil-repellent layer could be made 1.0×10 11 Ω / □ or less.

Claims

1. A water- and oil-repellent member having a functional film layer as a first layer on at least one surface of a substrate, a primer layer as a second layer on the outer surface of the functional film layer, and a water- and oil-repellent layer as a third layer on the outer surface of the primer layer, The functional film layer is a single layer composed of silicon dioxide with a film thickness of 10 to 500 nm or a laminated structure having at least an outermost layer composed of silicon dioxide with a film thickness of 10 to 500 nm. The primer layer is composed of a layer with a thickness of 10 to 500 nm, which is a hydrolyzed partial condensate of tetraalkoxysilane and an organic polysiloxane compound having multiple silanol groups in the molecule with a silanol group content of 0.002 to 0.042 mol / g, and the water- and oil-repellent layer is composed of a layer with a thickness of 0.5 to 50 nm, which has a cured product of a hydrolyzable fluorinated compound as the main component.

2. The water- and oil-repellent member according to claim 1, wherein The functional film layer is any one of a single silica layer, a hard coating layer consisting of a two-layer structure or a stacked structure of three or more layers having a silica layer as the outermost layer, an anti-reflection layer consisting of a two-layer structure or a stacked structure of three or more layers having a silica layer as the outermost layer, and an IR cutoff filter layer consisting of a two-layer structure or a stacked structure of three or more layers having a silica layer as the outermost layer.

3. The water- and oil-repellent member according to claim 1, wherein The weight average molecular weight of the organopolysiloxane compound having a plurality of silanol groups in the molecule is 300 to 100,000.

4. The water- and oil-repellent member according to claim 1, wherein The hydrolyzable fluorine-containing compound has at least one hydrolyzable silyl group at at least one molecular chain end, and the hydrolyzable silyl group is a silyl group or a silazane 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.

5. The water- and oil-repellent member according to claim 1, wherein Hydrolyzable fluorinated compounds are compounds with -(CF2) in their molecules. d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d -represented by a divalent straight-chain perfluoroalkylene oxide polymer residue and having at least one hydrolyzable silyl group at at least one molecular chain end, wherein p, q, r, s, and t are each independently an integer of 0 to 200, and p+q+r+s+t=3 to 500, each repeating unit shown in the brackets may be randomly bonded, d is independently an integer of 0 to 8, and the unit may be straight-chain or branched.

6. The water- and oil-repellent member according to claim 1, wherein The hydrolyzable fluorine-containing compound is at least one selected from the group consisting of fluorine-containing hydrolyzable organosilicon compounds represented by the following general formulae (1) to (5): (A-Rf) α -ZW β (1) Rf-(ZW β )2(2) Z’-(Rf-ZW β ) γ (3) In the formula, Rf is -(CF2) d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d -represented by a divalent linear perfluoroalkylene oxide polymer residue, p, q, r, s, t are each independently an integer of 0 to 200, and p+q+r+s+t=3 to 500, each repeating unit shown in the brackets may be randomly bonded, d is independently an integer of 0 to 8, the unit may be linear or branched, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, Z, Z' are independently a single bond, or a divalent to octavalent organic group which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be substituted with fluorine, W is a monovalent organic group having a hydrolyzable group at the terminal, α, β are each independently an integer of 1 to 7, and α+β=2 to 8 integers, γ is an integer of 2 to 8, A-Rf-Q-(Y) δ -B(4) Rf-(Q-(Y) δ -B)2(5) In the formula, Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is independently an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

7. The water- and oil-repellent member according to claim 6, wherein The fluorine-containing hydrolyzable organosilicon compound is selected from the following compounds: [Chemistry 1] [Chemistry 2] [Chemistry 3] [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [Chemistry 17] [Chemistry 18] [Chemistry 19] [Chemistry 20] [Chemistry 21] [Chemistry 22] [Chemistry 23] [Chemistry 24] [Chemistry 25] [Chemistry 26] [Chemistry 27] [Chemistry 28] In the formula, Me is a methyl group, p1, q1, r1, s1, and t1 are each independently an integer of 1 to 200, and the total of p1, q1, r1, s1, and t1 is 3 to 500, and each repeating unit shown in the parentheses may be randomly bonded.

8. The water- and oil-repellent member according to any one of claims 1 to 7, wherein The substrate is resin, ceramic, metal, quartz, glass, sapphire or diamond.

9. according to the manufacture method of any one of claims 1 to 8, it comprises: on at least one surface of substrate, form the functional film layer of film thickness 10~500nm that is made of silicon dioxide or the functional film layer of the laminated structure of the outermost layer that at least has film thickness 10~500nm that is made of silicon dioxide; On the outer surface of this functional film layer, will comprise as the hydrolysis partial condensation product of tetraalkoxysilane, the silanol group amount in molecule is 0.002~0.042mol / g, and the solution wet coating process of the organopolysiloxane compound and solvent with multiple silanol groups in molecule; Make this solvent evaporate to form and laminate the process of primer layer of film thickness 10~500nm; On the outer surface of this primer layer, will comprise the solution wet coating process of the hydrolyzable fluorine-containing compound and solvent, make this solvent evaporate, or, make the hydrolyzable fluorine-containing compound that solvent is evaporated from this solution, dry coating process; With make this hydrolyzable fluorine-containing compound solidify to form and laminate the process of water-repellent and oil-repellent layer on the outer surface of primer layer.

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