Surface layer

Abstract

To provide a surface water-repellent layer with excellent abrasion resistance. [Solution] A surface layer formed on a substrate by a surface treatment agent, wherein the surface treatment agent contains an alkyl group-containing compound having at least one alkyl group and a substrate adhesion group at the other end, and the surface layer exhibits a peak intensity of 287.5 eV obtained by CK edge X-ray absorption near-edge structure (XANES) measurement, which decreases with decreasing X-ray incidence angle (incidence angle parallel to the sample surface is defined as 0°, and incidence angle normal to the sample surface is defined as 90°), and a peak intensity of 292.5 eV which increases with decreasing X-ray incidence angle. TIFF2026061546000035.tif27151 is 0.90 or less The surface layer.

Description

[Technical Field]

[0001] The present invention relates to a surface layer applied to the surface of a substrate, and provides water repellency and abrasion resistance through an oriented thin film in which alkyl chains are erected on the substrate surface. [Background technology]

[0002] In general, the surfaces of semiconductor manufacturing process components, mold components, precision instrument components, medical device parts, automotive parts, building materials, home appliances, office automation equipment, and household goods are treated with a water-repellent coating to protect them.

[0003] For water-repellent treatment, alkyl group-containing silane compounds (Patent Documents 1 and 2: Japanese Patent Publication No. 2002-038092 and Japanese Patent Publication No. 2021-123678) and fluoropolyether group-containing silane compounds (Patent Documents 3 to 8: Japanese Patent Publication No. 6260579, Japanese Patent Publication No. 6828744, Japanese Patent Publication No. 5761305, Japanese Patent Publication No. 6451279, Japanese Patent Publication No. 6741074 and Japanese Patent Publication No. 6617853) are used. When these silane compounds are applied to and cured on the surface of a substrate such as metal, porcelain, glass, or plastic, a water-repellent layer is formed on the surface of the substrate, adding the ability to prevent dust, fingerprints, and other stains to the substrate.

[0004] The silane compounds described above have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air, etc., to form a coating. This coating becomes a strong and durable film because the hydrolyzable silyl group chemically and physically bonds with the substrate surface.

[0005] Furthermore, it is disclosed that the friction and wear durability can be improved by providing a silicon oxide layer between the above silane compound and the substrate. (Patent Documents 9 to 17: International Publication No. 2014 / 097388, Japanese Patent Application Laid-Open No. 2020-132498, Japanese Patent Application Laid-Open No. 2020-090652, Japanese Patent No. 5655215, Japanese Patent No. 6601492, Japanese Patent No. 5494656, International Publication No. 2019 / 035271, International Publication No. 2023 / 013476, International Publication No. 2023 / 013477).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Patent Document 12

Patent Document 13

Patent Document 14

[0007] It was found that when alkyl group-containing compounds are applied to the surface of a substrate, wear resistance may not be obtained depending on the orientation of the alkyl chains oriented on the outermost surface of the substrate.

[0008] This invention has been made in view of these circumstances, and aims to provide a surface water-repellent layer having excellent abrasion resistance. [Means for solving the problem]

[0009] As a result of diligent research to solve the above objectives, the inventors of the present invention have found that when a surface layer formed on a substrate by a surface treatment agent containing an alkyl group compound is within a specific range in the near-edge structure (XANES) measurement of the CK edge X-ray absorption described later, the alkyl chains oriented on the outermost surface are close to being upright relative to the substrate, and excellent water repellency and abrasion resistance can be obtained, leading to the present invention. The specific means for achieving the objectives of this invention are as follows. [1] A surface layer formed on a substrate by a surface treatment agent, The surface treatment agent comprises an alkyl group-containing compound having at least one alkyl group and a substrate adhesion group, The aforementioned surface layer shows that the peak intensity of 287.5 eV, obtained by CK edge X-ray absorption near-edge structure (XANES) measurement, decreases with decreasing X-ray incidence angle (incidence angle parallel to the sample surface is defined as 0°, and incidence angle normal to the sample surface is defined as 90°), and the peak intensity of 292.5 eV increases with decreasing X-ray incidence angle.

number

[0010] The surface layer of the present invention is characterized by excellent water repellency and durability. [Brief Description of the Drawings]

[0011] [Figure 1] It is the X-ray absorption near edge structure (XANES) spectrum of the surface layer of Example 1. [Figure 2] It is the X-ray absorption near edge structure (XANES) spectrum of the surface layer of Comparative Example 1. [Modes for Carrying Out the Invention]

[0012] In the present invention, the "partial (hydrolyzed) condensate" means a partial condensate or a partial (hydrolyzed) condensate.

[0013] In the present invention, the "alkyl group" means a linear or branched saturated hydrocarbon group having 1 or more carbon atoms.

[0014] In the present invention, a "hydrocarbon group" refers to the remaining atomic group obtained by removing one or more hydrogen atoms from a hydrocarbon composed of carbon atoms and hydrogen atoms, and may be linear, branched, or cyclic (including aromatic). Furthermore, in the present invention, the hydrocarbon group may have substituents; that is, some or all of the hydrogen atoms in the hydrocarbon group may be substituted with a group containing atoms other than carbon atoms and hydrogen atoms, or it may have a group containing atoms other than carbon atoms and hydrogen atoms between carbon atoms.

[0015] The present invention will be described in more detail below. [Base material] Examples of substrates on which the surface layer of the present invention is formed include glass, metal, and plastic. Examples of glass include, but are not limited to, soda-lime glass, crown glass, lead glass, borosilicate glass, crystallized glass, quartz glass, aluminosilicate glass, Tempax, Pyrex®, and Neoceram. Furthermore, the glass may be chemically or physically strengthened. The glass substrate may be in the shape of a plate, film, or other form.

[0016] Examples of the above metals include, but are not limited to, pure metals such as aluminum, titanium, chromium, iron, cobalt, zinc, nickel, and copper, as well as alloys such as stainless steel (e.g., SUS304 mirror finish), brass, Kovar, and Inconel, and metals that have been plated with zinc, nickel, chromium, etc. The shape of the metal substrate may be plate-shaped, rod-shaped, spherical, or other forms.

[0017] Examples of the above-mentioned plastics include, but are not limited to, polyethylene, polypropylene, cellulosic resins such as triacetylcellulose, polyester resins such as polyethylene terephthalate, polycarbonate, polyimide, polyolefin resins, polyvinyl chloride, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylic resin, nylon, and polyetheretherketone. The plastic substrate may be in the form of a plate, rod, sphere, film, or other shapes.

[0018] The substrate may be pre-treated. The pretreatment is not particularly limited as long as it removes contaminants from the substrate surface and makes the substrate surface hydrophilic. Examples include alcohol cleaning with alcohols such as ethanol and 2-propanol, alkaline cleaning with alkaline cleaning agents, and plasma cleaning with oxygen or argon plasma. These methods may be used in combination. Alkaline cleaning with alkaline cleaning agents and plasma cleaning with plasma are preferred, and it is even more preferable to perform plasma cleaning with plasma following alkaline cleaning with alkaline cleaning agents.

[0019] The effect of the substrate pretreatment is confirmed by the degree of hydrophilicity of the substrate surface. Hydrophilicity can be evaluated by the water contact angle on the substrate, which is preferably 40° or less, more preferably 20° or less, and even more preferably 10° or less. The water contact angle is measured in accordance with JIS R 3257:1999.

[0020] In the present invention, a functional layer may be formed between the substrate and the surface layer. An example of the functional layer is an anti-reflective coating layer. Alternatively, a primer layer may be formed between the substrate and the surface layer, or between the functional layer and the surface layer.

[0021] [Primer layer] The primer layer is a thin film containing 30% by mass or more of silicon dioxide, preferably 50% by mass or more, and more preferably 80% by mass or more.

[0022] The primer layer can be formed by applying an aqueous dispersion of silica nanoparticles to the substrate surface using a wet coating method, particularly immersion, brush application, spin coating, spray coating, or pouring, and then drying the solvent. To increase the density of the primer layer, it is recommended to heat it at 50-500°C for 10 minutes to 24 hours within a temperature range that does not affect the substrate. Furthermore, a primer layer can also be formed using dry coating methods such as physical vapor deposition or chemical vapor deposition. Examples of dry coating methods include electron beam deposition, ion-assisted deposition, sputter deposition, and resistance heating deposition.

[0023] The thickness of the primer layer is appropriately selected depending on the type of substrate, but is usually 1 to 50 nm, preferably 1 to 20 nm, and particularly preferably 1 to 10 nm. If the thickness is thinner than this range, the surface coating may be insufficient and the adhesion of the surface layer may be inadequate. If the thickness is thicker than this range, appearance defects such as haze and color changes may occur. In this invention, the thickness can be measured by X-ray reflectance measurement, spectroscopic ellipsometry, etc.

[0024] [Surface layer] The surface layer of the present invention is a surface layer formed on the outer surface of a substrate or on the outer surface of a substrate on which a primer layer has been formed, and the surface layer is formed of a cured product of a surface treatment agent containing an alkyl group having substrate adhesion groups that exhibit surface water repellency, and preferably it is formed of a cured product of a surface treatment agent containing an alkyl group that does not contain fluorine atoms and / or a partial (hydrolysis) condensate thereof.

[0025] <Surface treatment agent containing alkyl group-containing compounds having substrate adhesion groups and / or partial (hydrolysis) condensates thereof> The surface treatment agent for forming the surface layer of the present invention comprises an alkyl group-containing compound having at least one alkyl group and a substrate adhesion group. The alkyl group-containing compound having a substrate adhesion group is preferably a compound having two alkyl groups in one molecule, and more preferably a compound in which the total number of carbon atoms of the alkyl group is 19 or more.

[0026] In alkyl-containing compounds, the total number of carbon atoms of one or more alkyl groups is preferably 19 or more, more preferably 20 or more, even more preferably 22 or more, and particularly preferably 25 or more. Within the above range, the surface layer formed using a surface treatment agent containing an alkyl-containing compound is expected to exhibit high orientation of alkyl groups that are unevenly distributed on the outermost surface of the substrate (the alkyl groups are upright relative to the substrate), and the formed surface layer will exhibit high water repellency and durability. Furthermore, when there are two or more alkyl groups, each alkyl group is preferably a linear alkyl group, and each alkyl group has 10 or more carbon atoms, more preferably 13 or more, and particularly preferably 15 or more. Moreover, it is even more preferable that the two or more alkyl groups are the same.

[0027] In alkyl group-containing compounds, the substrate-adhering group is not particularly limited as long as it adheres to various substrates, but it is preferably one of a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

[0028] In hydrolyzable silyl groups, examples of hydrolyzable groups include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlor, bromo, and iodine. Among these, methoxy, ethoxy, isopropenoxy, and chlor groups are preferred.

[0029] Furthermore, alkyl group-containing compounds are preferably alkyl group-containing compounds represented by the following formulas (11), (12), or (13) (where formula (12) represents the molecular formula of the monomer or the compositional formula of the polymer). Compounds represented by the following formula (11) are particularly preferred. [ka] (In the formula, A is an alkyl group having 10 to 50 carbon atoms, and B 1 is a hydrogen atom or a hydroxyl group, E 1 A and E are hydrogen atoms or alkyl groups having 9 to 50 carbon atoms. 1 The total number of carbon atoms contained in Y is 19 or more. 1 R is a divalent hydrocarbon group containing one or more selected from the group consisting of a single bond, an alkylene group, or a silicon atom and a siloxane bond, and R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X 1 (These are independently hydrolyzable groups, z is 2 or 3, and a is 1 or 2.) [ka] (In the formula, A, B 1 , E 1 , Y 1The above is the same, where y is a number from 0 to 3, and x is (3-y) / 2. When y=3, equation (12) represents the molecular formula of the monomer, and when y<3, equation (12) represents the empirical formula of the polymer. [ka] (In the formula, G 1 These are independently monovalent hydrocarbon groups having 10 to 30 carbon atoms, and J 1 (Each is independently a hydrogen atom, a hydroxyl group, or a methyl group.)

[0030] In the above formulas (11) and (12), A is an alkyl group having 10 to 50 carbon atoms, preferably 17 to 50, more preferably 17 to 40 carbon atoms, and B 1 is a hydrogen atom or a hydroxyl group, E 1 A and E are hydrogen atoms or alkyl groups having 9 to 50 carbon atoms, preferably 10 to 50 carbon atoms. 1 Examples of alkyl groups include the following:

[0031] [ka] (In the formula, a1 is an integer between 8 and 49, preferably between 9 and 49, and b1 is an integer of 1 or more, where the sum of the number of carbon atoms in each structure is 50 or less, preferably between 9 and 43.) A is preferably a linear alkyl group, and B 1 Preferably, it is a hydroxyl group, E 1 Preferably, it is a linear alkyl group having 10 to 50 carbon atoms. However, in equations (11) and (12), A and E 1 The total number of carbon atoms contained in is 19 or more, preferably 20 to 60, and more preferably 22 to 60.

[0032] In the above equations (11) and (12), Y 1The C1-C20 alkylene group may have a single bond or one or more selected from silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the divalent hydrocarbon group include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via diorganosilylene groups, sylalkylene structures or sylarylene structures, and divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to the binding sites of linear organopolysiloxane residues having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic organopolysiloxane residues having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0033] 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.

[0034] Such Y 1 Examples of such groups include the following. In the structure below, it is preferable that the bond on the left is bonded to a carbon atom and the bond on the right is bonded to a silicon atom. [ka] [ka] (In the formula, f1 is an independent integer between 1 and 10, g1 and h1 are each integers between 1 and 8, and the sum of g1 and h1 is an integer between 2 and 10. j1 is an integer between 1 and 9, and k1 is an integer between 2 and 4.)

[0035] In the above equation (11), X 1 These are independently hydrolyzable groups. Examples of hydrolyzable groups include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlor, bromo, and iodine. Among these, methoxy, ethoxy, isopropenoxy, and chlor are preferred.

[0036] In the above formula (11), R is an alkyl group or phenyl group having 1 to 4 carbon atoms, with methyl and ethyl groups being preferred. In the above formula (11), z is 2 or 3, preferably 3.

[0037] In equation (12) above, y is a number between 0 and 3 (a positive number less than or equal to 3), preferably a number between 0 and 2, and preferably 0. Also, x is (3-y) / 2, preferably 1.5. Note that when y=3, equation (12) represents the molecular formula of the monomer, and when y<3, equation (12) represents the compositional formula of the polymer.

[0038] In the above equation (13), G 1 These are independently monovalent hydrocarbon groups having 10 to 30 carbon atoms, preferably 10 to 28 carbon atoms, and the following are examples. [ka] (In the formula, m1 is an integer between 9 and 29, preferably between 9 and 27 carbon atoms, and n1 is an integer of 1 or more such that the sum of the carbon atoms in each structure is between 10 and 30, preferably between 10 and 28.) In the above formula (13), J 1 The group is independently a hydrogen atom, a hydroxyl group, or a methyl group, with the methyl group being preferred.

[0039] Examples of compounds represented by formula (11) above include eicosyltrichlorosilane, docosenyltriethoxysilane, triacontyltrichlorosilane, and those listed below. [ka]

[0040] Examples of compounds represented by formula (12) above include those listed below. [ka] [ka] [ka]

[0041] Examples of compounds represented by formula (13) above include 1,3-dioctadecyl-1,1,3,3-tetramethyldisilazane, 1,3-didodecyl-1,1,3,3-tetramethyldisilazane, and 1,3-didecyl-1,1,3,3-tetramethyldisilazane.

[0042] In the compound represented by the above formula (11), E 1 Examples of methods for producing a molecule in which the alkyl group has 9 to 50 carbon atoms include the following methods. It can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end with a compound having an SiH group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst (Preparation Method 1). Alternatively, it can be produced by mixing a hydrocarbon-terminal group-containing compound having a SiH group at the terminal end with a compound having an alkenyl group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst (Preparation Method 2).

[0043] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include the compound shown in formula (11a) below. [ka] (In the formula, A, B 1 This is the same as above. E 1' A and E are alkyl groups with 9 to 50 carbon atoms. 1' The total number of carbon atoms contained in Y is 19 or more. 1' (This may have one or more elements selected from silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms.)

[0044] In the above formula (11a), E 1' This is an alkyl group having 9 to 50 carbon atoms, and examples similar to the alkyl group with 9 to 50 carbon atoms of E mentioned above can be given. In the above equation (11a), Y 1' The group may have one or more selected from silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, as shown below as examples. In the structure below, the left-hand bonds are A and B. 1 , E 1' It is preferable that the carbon atom bonded to the right-hand side is bonded to a vinyl group. [ka] [ka] (In the formula, g1, j1, and k1 are the same as above, f1' is an integer between 0 and 8, h1' is an integer between 0 and 6, and the sum of g1 and h1' is an integer between 2 and 8.)

[0045] Examples of compounds represented by formula (11a) are listed below. [ka] (In the formula, a1 and f1' are independently the same as above.)

[0046] Examples of compounds having an SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0047] In preparation method 1, the amount of compound having a 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.

[0048] Furthermore, examples of hydrocarbon terminal group-containing compounds having a SiH group at the terminal include the compound shown in formula (11b) below. [ka] (In the formula, A, B 1 , E 1' The above is the same as Y 1" (This refers to a divalent hydrocarbon group having a silicon atom or a siloxane bond.)

[0049] In the above equation (11b), Y 1" This is a divalent hydrocarbon group having a silicon atom or a siloxane bond, and examples are shown below. In the structure below, it is preferable that the bond on the left is bonded to a carbon atom and the bond on the right is bonded to a hydrogen atom. [ka] (In the formula, f1 and k1 are the same as above.)

[0050] Examples of compounds represented by formula (11b) are listed below. [ka] (In the formula, a1 and f1 are independently the same as above.)

[0051] Examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.

[0052] In preparation method 2, the amount of compound having an alkenyl group and a hydrolyzable silyl group used is preferably 1 to 5 moles, particularly 1 to 3 moles, per mole of SiH group in the hydrocarbon-terminated compound having a SiH group at the terminal end.

[0053] In preparation methods 1 and 2, examples of hydrosilylation reaction catalysts 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, a platinum-based compound such as a vinylsiloxane coordination compound is used. It is preferable to dissolve the platinum-based compound in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone-based solvent before use. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1000 ppm, more preferably 0.01 to 100 ppm, in terms of transition metal mass, relative to the mass of the hydrocarbon-terminal group-containing compound having an alkenyl group or SiH group at the terminal end.

[0054] In preparation methods 1 and 2, solvents 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 1000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon-terminated compound having an alkenyl group or SiH group at its terminus.

[0055] In preparation methods 1 and 2, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the compound having an SiH group and a hydrolyzable silyl group, and the reaction conditions for the hydrocarbon terminal group-containing compound having an SiH group at the terminal and the compound having an alkenyl 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, respectively.

[0056] In the compound represented by the above formula (12), E 1 Examples of methods for producing a molecule in which the alkyl group has 9 to 50 carbon atoms include the following methods. It can be produced by mixing a hydrocarbon-terminal compound having an alkenyl group at the terminal end with trichlorosilane, reacting them in the presence of a hydrosilylation catalyst, and then reacting the resulting compound with ammonia gas.

[0057] Here, the reaction product of a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus and trichlorosilane can be prepared in the same manner as in preparation method 1 described above.

[0058] In the method for preparing the compound shown in formula (12), the amount of ammonia gas used is preferably 1 to 300 cc / min, and more preferably 30 to 200 cc / min.

[0059] In the method for preparing the compound shown in formula (12), the reaction conditions for the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end and trichlorosilane with ammonia gas are preferably at room temperature (23±15℃, the same applies hereinafter), particularly 20-30℃, for 2-36 hours, particularly 4-12 hours.

[0060] Surface treatment agents containing alkyl group-containing compounds and / or partial (hydrolysis) condensates thereof having substrate-adhering groups may optionally contain hydrolysis condensation catalysts, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate), organic acids (e.g., acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), or inorganic acids (e.g., hydrochloric acid, sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly preferred. The amount added is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the alkyl group-containing compound and / or partial (hydrolysis) condensate thereof.

[0061] Furthermore, surface treatment agents containing alkyl group-containing compounds having substrate adhesion groups and / or partial (hydrolysis) condensates thereof may contain a solvent. The solvent is preferably a hydrocarbon solvent (petroleum benzine, mineral spirits, toluene, xylene, etc.), a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an alcohol solvent (ethanol, 1-propanol, 2-propanol, butanol, etc.), or an ether solvent (tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc.).

[0062] The above solvents may be mixed in two or more forms, and it is preferable that they uniformly dissolve alkyl group-containing compounds having substrate adhesion groups and / or their partial (hydrolysis) condensates. The optimal concentration of alkyl group-containing compounds having substrate adhesion groups and / or their partial (hydrolysis) condensates to be dissolved in the solvent can be appropriately selected according to the method of use of the surface treatment agent and is not limited. The concentration of alkyl group-containing compounds having substrate adhesion groups in the surface treatment agent is preferably 0.01 to 30% by mass, more preferably 0.02 to 25% by mass, and even more preferably 0.05 to 20% by mass.

[0063] The surface layer is preferably formed by wet or dry application of a surface treatment agent containing an alkyl group having substrate adhesion groups exhibiting surface water repellency onto the outer surface of the primer layer formed above, followed by drying and removing the solvent from the surface treatment agent, and curing the alkyl group having substrate adhesion groups and / or its partial (hydrolysis) condensate.

[0064] The formation of a surface layer using a surface treatment agent can be achieved using wet coating methods such as brush coating, dip coating, or spray coating, or dry coating methods such as vapor deposition (physical vapor deposition (PVD) or chemical vapor deposition (CVD)).

[0065] After applying the surface treatment agent, the solvent is dried and removed, and a curing treatment is performed. In the case of the wet coating method, this can be done at 60 to 150°C, preferably 60 to 120°C, and a relative humidity of 95% or less for 30 minutes to 24 hours, preferably 30 minutes to 2 hours. In the case of the dry coating method, this can be done at 25°C to 150°C, preferably 25°C to 80°C, and a relative humidity of 95% or less for 30 minutes to 48 hours, preferably 30 minutes to 24 hours.

[0066] The thickness of the surface layer is 2 to 5 nm. If the thickness of the surface layer is less than 2 nm, the mechanical strength of the surface layer may be low and durability may not be obtained, and if it exceeds 5 nm, the adhesion to the substrate and primer layer may decrease, resulting in reduced water repellency and durability. In this invention, the thickness can be measured by X-ray reflectance measurement, spectroscopic ellipsometry, etc.

[0067] When the surface layer formed on the substrate is used as a measurement sample for CK edge X-ray absorption near-edge structure (XANES) measurement, the surface layer of the present invention yields a 287.5 eV 1s → Rydberg / σ. * The intensity of the peak attributed to (CH) decreases with decreasing X-ray incidence angle (incidence angle parallel to the sample surface is defined as 0°, and incidence angle normal to the sample surface is defined as 90°), and the intensity of the peak at 292.5 eV in 1 s → σ * The intensity of the peak attributed to (CC) increases with decreasing X-ray incidence angle. This indicates that the alkyl chains of the alkyl compounds constituting the surface layer are oriented. moreover,

number

[0068] The water-repellent articles of the present invention can be applied to a variety of uses, such as casings, frames, floors, touch panels, windows, lenses, display covers, protective films, etc., for mobile electronic devices, household electrical appliances, automobiles, outdoor equipment, building materials, housing equipment, eyeglasses, etc. [Examples]

[0069] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the molar amount of the compound is, with respect to the measured mass of the target compound, 1 This value was calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. The test environment conditions were 23°C and 50% relative humidity.

[0070] [Example 1] [Alkaline cleaning of substrates] The soda-lime glass substrate was immersed in an alkaline cleaning solution (an aqueous solution of Yokohama Oil & Fat Co., Ltd. Semi-Clean LGL diluted to 5% by mass) and ultrasonically cleaned for 5 minutes. Afterward, it was immersed in deionized water and ultrasonically cleaned for 6 minutes. The substrate was then dried by blowing off the moisture with compressed air.

[0071] [Formation of the primer layer] A 10 nm thick SiO2 film was deposited on the surface of the glass substrate that had undergone the aforementioned alkaline cleaning using a sputtering deposition apparatus under the following conditions. Oxygen plasma irradiation was performed before SiO2 deposition. The deposition rate of SiO2 was 0.3 nm / second, and the film thickness was controlled by the deposition time.

[0072] [SiO2 film formation conditions] Thin film deposition system: RAS-1100B (manufactured by 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 supply power: 3000W Processing time: 50 seconds SiO2 film deposition conditions Target material: Silicon Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF supply power: 8000W Deposition speed: 0.3nm / s Oxygen plasma irradiation conditions during SiO2 film deposition Oxygen gas flow rate: 70 sccm RF supply power: 3000W

[0073] [Preparation of surface layer forming agent 1] In the reaction vessel, the following formula (a) [ka] 1.00g of the compound represented by (1.82 × 10) -3 (mol), toluene 1.00g, trimethoxysilane 0.667g (5.46 × 10) -3 6.62 × 10⁻⁶ mol) and toluene solution of chloroplatinate / vinylsiloxane complex -3 g(Pt alone: ​​2.05 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. The solvent and unreacted materials were then removed by reduced pressure distillation to obtain the product. The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (A). [ka]

[0074] The compound represented by formula (A) above was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 1.

[0075] [Method for forming the surface layer] The above-mentioned SiO2-coated soda-lime glass substrate and a mirror-polished Si wafer substrate were set in a resistance-heating vacuum deposition apparatus (VTR-350M, manufactured by ULVAC KIKO). 10 μL of the following surface layer forming agent was dropped into the resistance heating section, and the pressure was reduced. The internal pressure of the container was 6 × 10⁻⁶. -3 Once the pressure was reduced to below Pa, resistance heating was initiated. The power supplied to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal film thickness gauge, located approximately 20 cm away from the resistance heating section, was 1.0 nm / second or higher, and the resistance heating was continued for 300 seconds. After waiting for 5 minutes for the apparatus to cool, the system was opened to the atmosphere, and a glass substrate with a surface layer coated was obtained. The above substrate was left for 4 hours in an environment of 80°C and 80% relative humidity to fix the surface layer, and a glass substrate having a surface layer of cured compound (A) was obtained.

[0076] [XANES measurement and analysis] The X-ray absorption near-edge structure (XANES) spectrum was measured by irradiating a glass substrate having the above-described surface layer with X-rays and measuring the amount of absorption. The measurement and analysis conditions were as follows. The XANES spectrum of the CK absorption edge is shown in Figure 1, and the analysis results are shown in Table 1. Detection method: Total electron yield method Absorption edge: K absorption edge of C (carbon) Horizontal axis correction: The Π* peak of highly oriented pyrolysis graphite is corrected to 255.5 eV. For the XANES spectrum of the K absorption edge of C, let θ be the angle between the incident X-ray and the longitudinal vector of the surface of the Si wafer substrate with a surface layer, and then calculate the 1s → Rydberg / σ at 287.5 eV. * The peak intensity values ​​assigned to (CH) were calculated for both θ=90° and θ=15°. The respective peak intensities are expressed as follows.

number

number

[0077] [Measuring the thickness of the surface layer] The thickness of the surface layer was obtained by X-ray reflectance measurement. Specifically, the thickness was determined by performing a simulation fitting on the measured profile. The results are shown in Table 1. The measurement conditions are as follows. Measurement device: SmartLab (manufactured by Rigaku) X-ray source: Rotating cathode (Cu), output 45kV, 200mA Incident optical system: Ge(111) asymmetric beam compression crystal Solar slit on the light-receiving side: 5.0° Slit: Incident side IS = 0.05 mm Light receiving side RS1=0.1mm, RS2=0.1mm Scanning conditions: Scanning axis 2θ / ω Scanning speed: 0.2° / min Step width: 0.002°

[0078] [Measuring the water contact angle on the surface layer] The water contact angle of the surface layer was measured using a Drop Master contact angle meter (DMo-701SA, manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement involved capturing a photograph of the droplet 1 second after dropping using a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software included with the contact angle meter, to determine the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions were as follows. The results are shown in Table 1. [Analysis conditions] Method: Droplet method (θ / 2 method) Droplet recognition: automatic Droplet detection line (distance from needle tip): 50 dots Algorithm: Automatic Image Mode: Frame Threshold level: Automatic

[0079] [Wear resistance test] The surface layer of a soda-lime glass substrate coated with SiO2 was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. Rubbing material: Steel wool #0000 (Bonstar) Load: 1kgf Round trip distance: 40mm Round-trip speed: 60 round trips per minute The water contact angle of the friction-worn portion was measured every 500 friction cycles using the same method as described above. The number of friction cycles required to maintain a water contact angle of 90° or higher was defined as the wear endurance cycle. The results are shown in Table 1.

[0080] [Comparative Example 1] In the reaction vessel, the following formula (b) [ka] 1.00g (3.08 × 10) of the compound represented by [formula] -3 (mol), toluene 1.00g, trimethoxysilane 1.129g (9.24 × 10) -3 (mol) and 1.01 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -2 g(Pt alone: ​​3.08 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. The solvent and unreacted materials were then removed by reduced pressure distillation to obtain the product. The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B). [ka] The compound represented by formula (B) above was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 2.

[0081] A glass substrate with a surface layer formed in the same manner as in Example 1 was prepared, and XANES measurements, film thickness measurements, water contact angle measurements, and abrasion resistance tests were performed. The XANES spectrum at the CK absorption edge is shown in Figure 2, and the other results are shown in Table 1.

[0082] [Table 1]

[0083] In the surface layer shown in the example, the peak intensity of 287.5 eV obtained by CK edge X-ray absorption near-edge structure (XANES) measurement decreased with decreasing X-ray incidence angle, and the peak intensity of 292.5 eV increased with decreasing X-ray incidence angle. It was confirmed that the peak intensity ratio was 0.90 or less, indicating that high wear resistance can be obtained.

Claims

1. A surface layer formed on a substrate by a surface treatment agent, The surface treatment agent comprises an alkyl group-containing compound having at least one alkyl group and a substrate adhesion group, The surface layer shows that the peak intensity of 287.5 eV, obtained by C-K edge X-ray absorption near-edge structure (XANES) measurement, decreases with decreasing X-ray incidence angle (incidence angle parallel to the sample surface is defined as 0°, and incidence angle normal to the sample surface is defined as 90°), and the peak intensity of 292.5 eV increases with decreasing X-ray incidence angle. [Math 1] is 0.90 or less The surface layer.

2. The surface layer according to claim 1, wherein the alkyl group-containing compound contains two alkyl groups.

3. The surface layer according to claim 1, wherein the total number of carbon atoms of the alkyl group is 19 or more.

4. The surface layer according to claim 1, wherein the alkyl group-containing compound is a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

5. The surface layer according to claim 1, wherein the alkyl group-containing compound is represented by any one of the following general formulas (11), (12), or (13). 【Chemistry 1】 (In the formula, A is an alkyl group having 10 to 50 carbon atoms, and B 1 is a hydrogen atom or a hydroxyl group, E 1 A and E are hydrogen atoms or alkyl groups having 9 to 50 carbon atoms. 1 The total number of carbon atoms contained in Y is 19 or more. 1 R is a divalent hydrocarbon group containing one or more selected from the group consisting of a single bond, an alkylene group, or a silicon atom and a siloxane bond, and R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X 1 (These are independently hydrolyzable groups, z is 2 or 3, and a is 1 or 2.) 【Chemistry 2】 (In the formula, A, B 1 , E 1 , Y 1 The same applies as above, where y is a number between 0 and 3, and x is (3-y) / 2. When y=3, equation (12) represents the molecular formula of the monomer, and when y<3, equation (12) represents the empirical formula of the polymer. 【Transformation 3】 (wherein, G 1 is independently a monovalent hydrocarbon group having 10 to 30 carbon atoms, and J 1 is independently a hydrogen atom, a hydroxyl group or a methyl group.)

6. The surface layer according to claim 1, wherein the film thickness is 2 nm to 5 nm.

7. The surface layer according to claim 1, wherein the number of abrasion resistance cycles when tested under the following conditions is 1,000 or more. [Evaluation of wear resistance] For the surface layer formed on the glass, an abrasion test is performed using a reciprocating abrasion tester under the following conditions. The number of reciprocating cycles during which the water contact angle of the surface remains at 90° or higher after the test is defined as the abrasion endurance cycle. Rubbing material: Steel wool #0000 (Bonstar) Load: 1 kgf Round trip distance: 40 mm Round-trip speed: 60 round trips per minute

Images