Method for manufacturing water-repellent and oil-repellent articles and method for improving the water and oil removal properties of water-repellent and oil-repellent articles

Abstract

A water- and oil-repellent article obtained by a production method according to the present invention comprises: a substrate; a silicon oxide underlayer formed on an outer surface of the substrate by a dry method; and a water- and oil-repellent surface layer which is mainly composed of a fluoropolyether group-containing polymer having a specific structure of a hydrolyzable silyl group and / or a partially hydrolyzed-condensed product thereof, and which is formed on the outer surface of the silicon oxide underlayer by a wet method. Said water- and oil-repellent article exhibits excellent water- and oil-repellency, and wear resistance.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a water-repellent and oil-repellent article comprising a base material, a surface layer having excellent water-repellent, oil-repellent, and abrasion-resistant properties, and an underlayer provided between the base material and the surface layer, and a method for improving the water and oil removal properties of a water-repellent and oil-repellent article. [Background technology]

[0002] In recent years, the advancement of IoT has led to the increasing electronification of automobiles, industrial equipment, and other devices, and the integration of touch panel display devices, camera devices, and various other types of sensor devices is rapidly progressing. Touch panel displays are frequently touched by fingers and other body parts, making them prone to accumulating dirt such as oil and sebum. Similarly, in the case of cameras and sensors, for example, when used outdoors, the adhesion of water droplets from rain, dust, and oil to the device surface can be a problem. To make it more difficult for water and oil to adhere, or to make it easier to remove water and oil that has adhered, there is a demand for water- and oil-repellent properties on the surface of such devices.

[0003] While the static contact angle of water and oil is used as an indicator for water and oil repellency, the dynamic contact angle of water and oil is also an important indicator. The dynamic contact angle is the advancing contact angle (θ) described in JIS R3257. A ) and receding contact angle (θ R ) are listed, and the difference between them (θ A -θ R It is known that the smaller θ is, the easier it is for the droplet to move (Non-Patent Document 1). A -θ R When the droplet size is small, it is easy to remove, indicating high water-repellent and oil-repellent properties.

[0004] Compounds containing fluoropolyether groups have very low surface free energy, giving them properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. These properties are utilized industrially in a wide range of applications, including water, oil, and antifouling agents for paper and textiles, lubricants for magnetic recording media, oil inhibitors and mold release agents for precision equipment, cosmetics, and protective films. However, these properties also mean non-stickiness and poor adhesion to other substrates; while they can be applied to substrate surfaces, achieving a strong bond between the coating and the substrate is difficult.

[0005] On the other hand, silane coupling agents are well known for bonding organic compounds to substrate surfaces such as glass and cloth, and are widely used as coating agents for various substrate surfaces. A silane coupling agent has 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 to form a film. This film becomes a strong and durable coating because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0006] Therefore, compositions have been disclosed that use a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, which can easily adhere to the substrate surface and form a coating on the substrate surface that has water-repellent and oil-repellent properties, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1-6: Japanese Patent No. 6260579, Japanese Patent No. 6828744, Japanese Patent No. 5761305, Japanese Patent No. 6451279, Japanese Patent No. 6741074, Japanese Patent No. 6617853).

[0007] A hardened coating (water- and oil-repellent layer (also called an anti-fouling coating thin film layer)) on the surface of a glass substrate or the like, treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound, exhibits excellent abrasion resistance against steel wool and high slipperiness.

[0008] Furthermore, the water-repellent and oil-repellent layer deteriorates in water-repellent and oil-repellent properties and stain-resistant performance due to friction and abrasion from fingers, clothing, stylus pens, cleaning cloths, wiper rubbers, etc., during use. To ensure the durability of the water-repellent and oil-repellent layer, a silicon oxide underlayer has been used (Patent Documents 7-13: International Publication No. 2014 / 097388, Japanese Patent Publication No. 2020-132498, Japanese Patent Publication No. 2020-090652, Japanese Patent No. 5655215, Japanese Patent No. 6601492, Japanese Patent No. 5494656, International Publication No. 2019 / 035271).

[0009] The water- and oil-repellent surface layer can be fabricated using both dry and wet methods, such as vacuum deposition, spray coating, and dip coating. Furthermore, the silicon oxide underlayer can be fabricated using dry methods such as electron beam deposition, sputtering, and chemical vapor deposition, or wet methods such as dip coating and spin coating.

[0010] From the standpoint of production efficiency, when the base layer is manufactured using a dry method, it is preferable to manufacture the surface layer using a dry method as well. Similarly, when the base layer is manufactured using a wet method, it is preferable to manufacture the surface layer using a wet method. However, in some cases, the water-repellent and oil-repellent properties were not fully exhibited. In addition to the documents mentioned above, the following documents can be cited as prior art related to the present invention. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Patent No. 6260579 [Patent Document 2] Patent No. 6828744 [Patent Document 3] Patent No. 5761305 [Patent Document 4] Patent No. 6451279 [Patent Document 5] Patent No. 6741074 [Patent Document 6] Patent No. 6617853 [Patent Document 7] International Publication No. 2014 / 097388 [Patent Document 8] Japanese Patent Publication No. 2020-132498 [Patent Document 9] Japanese Patent Publication No. 2020-090652 [Patent Document 10] Patent No. 5655215 [Patent Document 11] Patent No. 6601492 [Patent Document 12] Patent No. 5494656 [Patent Document 13] International Publication No. 2019 / 035271 [Patent Document 14] Japanese Patent Publication No. 2011-116947 [Patent Document 15] Japanese Patent Publication No. 2007-197425 [Patent Document 16] Japanese Patent Publication No. 2007-297589 [Patent Document 17] Japanese Patent Publication No. 2007-297543 [Patent Document 18] Japanese Patent Publication No. 2008-088412 [Patent Document 19] Japanese Patent Publication No. 2008-144144 [Patent Document 20] Japanese Patent Publication No. 2010-031184 [Patent Document 21] Japanese Patent Publication No. 2010-047516 [Patent Document 22] Japanese Patent Publication No. 2011-178835 [Patent Document 23] Japanese Patent Publication No. 2014-084405 [Patent Document 24] Japanese Patent Publication No. 2014-105235 [Patent Document 25] Japanese Patent Publication No. 2013-253228 [Patent Document 26] Japanese Patent Publication No. 2014-218639 [Patent Document 27] International Publication No. 2013 / 121984 [Non-patent literature]

[0012] [Non-Patent Document 1] Accounts of Materials ResearchVol.3,1-7,2022. [Overview of the project] [Problems that the invention aims to solve]

[0013] The present invention has been made in view of the above circumstances, and aims to provide a method for manufacturing a water-repellent and oil-repellent article having a water-repellent and oil-repellent surface layer on a substrate that has excellent water-repellent and oil-repellent properties and abrasion resistance, and a method for improving the water and oil removal properties of a water-repellent and oil-repellent article. [Means for solving the problem]

[0014] As a result of diligent research to solve the above objective, the present inventors have found that in a method for manufacturing a water-repellent and oil-repellent article comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide underlayer, sufficient water-repellent and oil-repellent properties may not be obtained when the water-repellent and oil-repellent surface layer is formed by a dry method on a silicon oxide underlayer formed by a dry method. As a result of further investigation, we discovered that in the above-mentioned method for manufacturing water-repellent and oil-repellent articles, when a layer mainly composed of a hydrolyzable silyl group-containing polymer and / or a cured product of its partially hydrolyzed condensate, including a fluoropolyether group-containing polymer of a specific structure described later, is formed by a wet method on a silicon oxide substrate formed by a dry method, a water-repellent and oil-repellent surface layer can be formed with excellent water-repellent and oil-repellent properties and abrasion resistance, leading to the present invention.

[0015] Accordingly, the present invention provides a method for manufacturing a water-repellent and oil-repellent article having the following water-repellent and oil-repellent surface layer, and a method for improving the water and oil removal properties of a water-repellent and oil-repellent article. [1] A method for manufacturing a water and oil repellent article comprising a substrate, a silicon oxide underlayer formed on the outer surface of the substrate, and a water and oil repellent surface layer formed on the outer surface of the silicon oxide underlayer, wherein the water and oil repellent surface layer is mainly composed of a cured product of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a partial hydrolysis condensate thereof, and the fluoropolyether group-containing polymer having a hydrolyzable silyl group contains one or more fluoropolyether group-containing polymers represented by the following formula (1), (4) or (7). Film thickness 3-90 nm The silicon oxide underlayer is formed by a dry method. Film thickness between 2nm and less than 100nm The water and oil repellent surface layer A surface treatment agent containing a fluoropolyether group-containing polymer having the aforementioned hydrolyzable silyl group and / or a partially hydrolyzed condensate thereof is applied directly to the silicon oxide substrate. is formed by a wet method. A method for manufacturing a water and oil repellent article. [Chemical formula] [In the formula, Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(However, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are independently integers of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in the parentheses with p, q, r, s, t and u may be randomly bonded.) is a divalent polyfluorooxyalkylene structure-containing group, and A 1 is a monovalent fluorine-containing hydrocarbon group having a terminal of CF3- or CF2H- and may contain an oxygen atom, or D, and D is independently a monovalent group represented by the following formula (2). [Chemical formula] [In the formula, Q is a single bond or a divalent organic group, Z is a 3- to 8-valent group, α is an integer from 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.) [ka] [In the formula, Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5). [ka] [In the formula, W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). [ka] (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W, and l is an integer from 0 to 20.) [ka] [In the formula, Rf is the same as above, A 3 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and possibly containing an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J contains two or more W atoms. [ka] [In the formula, S is the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is independently a monovalent group represented by the following formula (9), [ka] (In the formula, Y, S, and W are the same as above, and f is an integer from 1 to 3.) e is either 1 or 2. [2] A method for producing a water-repellent and oil-repellent article according to [1], wherein the base material is glass, metal, or resin. [3] A method for producing a water-repellent and oil-repellent article according to [1] or [2], wherein a hard coat layer is formed between the substrate and the silicon oxide underlayer. [4] A method for manufacturing a water-repellent and oil-repellent article according to any one of [1] to [3], wherein an anti-reflective film layer is formed on a substrate, the outermost layer being a silicon oxide film, and the outermost silicon oxide film is the silicon oxide underlayer. [5] A method for producing a water-repellent and oil-repellent article according to any one of [1] to [4], wherein in formula (2), Q is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of amide bonds, ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups, silphenylene bonds, and sylalkylene bonds, and Z is a 3 to 8 valent group selected from a 3 to 8 valent organopolysiloxane residue having a silicon atom, a nitrogen atom, and a siloxane bond. [6] A method for producing a water-repellent and oil-repellent article according to any one of [1] to [5], wherein in formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms, a divalent siloxane bond, a sylalkylene group, a sylarylene bond, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a single bond, a siloxane bond, a sylalkylene bond, a sylarylene bond, and a diorganosilylene group. [7] The water-repellent and oil-repellent surface layer comprises one or more fluoropolyether group-containing polymers represented by formula (1), (4), or (7) and / or a partially hydrolyzed condensate thereof, and the following formula (10) [ka] [In the formula, Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 150 independently, the sum of p, q, r, s, t, and u is an integer from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2(R 3 (This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.) A method for producing a water-repellent and oil-repellent article according to any one of [1] to [6], comprising a cured product of a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof. [8] A method for manufacturing a water-repellent and oil-repellent article according to any one of [1] to [7], wherein the base material is glass or metal. [9] A method for producing a water-repellent and oil-repellent article according to any one of [1] to [8], wherein the method for forming the silicon oxide underlayer is a resistance heating deposition method or an electron beam deposition method.

[10] A method for producing a water-repellent and oil-repellent article according to any one of [1] to [8], wherein the method for forming the silicon oxide underlayer is the sputtering film deposition method.

[11] A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[10] , wherein the method for forming the water-repellent and oil-repellent surface layer is a dip coating method.

[12] A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[10] , wherein the method for forming the water-repellent and oil-repellent surface layer is a spray coating method.

[13] The substrate is alkaline cleaned and bipu A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[12] , wherein the article is pretreated by rasma washing.

[14] A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[13] , wherein the difference between the advancing contact angle and the receding contact angle of the water-repellent and oil-repellent surface layer with respect to water, as determined by the expansion / contraction method, is 20° or less, and the difference between the advancing contact angle and the receding contact angle with respect to oleic acid is 20° or less.

[15] A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[14] , wherein the receding contact angle of the water-repellent and oil-repellent surface layer with respect to water, determined by the expansion / contraction method, is 101° or more, and the receding contact angle with respect to oleic acid is 64° or more.

[16] A in equation (1) 1 The end is CF 3 -or CF 2 A is a monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, and A in formula (4) 2 The end is CF 3 -or CF 2 A is a monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, and A in formula (7) 3 The end is CF 3 -or CF 2 A method for producing a water-repellent and oil-repellent article according to any one of [1] to

[15] , wherein the monovalent fluorine-containing hydrocarbon group is H- and may contain an oxygen atom. [ 17 ] A water-repellent and oil-repellent article comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide underlayer, wherein the water-repellent and oil-repellent surface layer is mainly composed of a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a cured product of a partially hydrolyzed condensate thereof, and the fluoropolyether group-containing polymer having hydrolyzable silyl groups contains one or more fluoropolyether group-containing polymers represented by the following formulas (1), (4), or (7): Film thickness 3-90 nm A silicon oxide sublayer is formed by a dry method. Film thickness between 2nm and less than 100nm Water-repellent and oil-repellent surface layer A surface treatment agent containing a fluoropolyether group-containing polymer having the aforementioned hydrolyzable silyl group and / or a partially hydrolyzed condensate thereof is applied directly to the silicon oxide substrate. A method for improving the water and oil removability of water-repellent and oil-repellent articles, characterized by being formed by a wet method. [ka] [In the formula, Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 150 independently, the sum of p, q, r, s, t, and u is an integer from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or D, where D is independently a monovalent group represented by the following formula (2). [ka] [In the formula, Q is a single bond or a divalent organic group, Z is a 3- to 8-valent group, α is an integer from 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.) [ka] [In the formula, Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5). [ka] [In the formula, W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). [ka] (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W, and l is an integer from 0 to 20.) [ka] [In the formula, Rf is the same as above, A 3 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and possibly containing an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J contains two or more W atoms. [ka] [In the formula, S is the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is independently a monovalent group represented by the following formula (9), [ka] (In the formula, Y, S, and W are the same as above, and f is an integer from 1 to 3.) e is either 1 or 2. [Effects of the Invention]

[0016] A water-repellent and oil-repellent article obtained by the manufacturing method of the present invention, comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material by a dry method, and a water-repellent and oil-repellent surface layer mainly composed of a cured product of a fluoropolyether group-containing polymer having a specific structure of hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, formed on the outer surface of the silicon oxide underlayer by a wet method, exhibits excellent water-repellency, oil-repellency, and abrasion resistance. [Modes for carrying out the invention]

[0017] The present invention provides a method for manufacturing a water-repellent and oil-repellent article comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide underlayer, wherein the water-repellent and oil-repellent surface layer mainly comprises a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a cured product of a partially hydrolyzed condensate thereof, the fluoropolyether group-containing polymer having hydrolyzable silyl groups includes a fluoropolyether group-containing polymer of a specific structure, the silicon oxide underlayer is formed by a dry method, and the water-repellent and oil-repellent surface layer is formed by a wet method. Here, "mainly composed of a cured polymer containing hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof" means that the content of the cured polymer containing hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof is 50% by mass or more (50-100% by mass), preferably 70% by mass or more (70-100% by mass), and more preferably 90% by mass or more (90-100% by mass), relative to the total mass of the components constituting the water-repellent and oil-repellent surface layer.

[0018] The water-repellent and oil-repellent article obtained by the manufacturing method of the present invention consists of a base material, a silicon oxide underlayer formed by a dry method, and a water-repellent and oil-repellent surface layer formed by a wet method. In particular, the water-repellent and oil-repellent surface layer is formed on the outer surface of the silicon oxide underlayer formed on the base material using a surface treatment agent containing a fluoropolyether group-containing polymer having hydrolyzable silyl groups of a specific structure and / or a partially hydrolyzed condensate thereof.

[0019] [Base material] Glass, metal, or resin can be used as the base material. 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.

[0020] Examples of the aforementioned 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.

[0021] Examples of the aforementioned resins include, but are not limited to, polycarbonate resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide (PA) resins, polyimide (PI) resins, cellulose resins such as triacetylcellulose, styrene resins such as polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin), polyolefin resins such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer, norbornene resins, and (meth)acrylic resins. The resin substrate may be in the form of a plate, film, or other shapes.

[0022] The substrate surface may be pre-treated before the formation of the silicon oxide underlayer. Pre-treatment ensures good adhesion between the substrate and the silicon oxide underlayer, resulting in high abrasion resistance.

[0023] The method for pretreatment of the substrate 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, plasma cleaning with oxygen or argon plasma, and radical cleaning with OH radicals. These methods may be used in combination. Alkaline cleaning with alkaline cleaning agents is preferred, and plasma cleaning with plasma or radical cleaning with OH radicals is more preferred. It is even more preferable to perform plasma cleaning with plasma or radical cleaning with OH radicals following alkaline cleaning with alkaline cleaning agents.

[0024] 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.

[0025] In the present invention, a functional layer may be formed between the substrate and the silicon oxide underlayer. Examples of functional layers include an anti-reflective coating layer and a hard coat layer. Furthermore, when forming an anti-reflective coating layer as a functional layer, with the outermost layer being a silicon oxide film, the outermost silicon oxide film can be used as a silicon oxide underlayer.

[0026] [Silicon oxide underlayer] The silicon oxide underlayer consists of a silicon oxide film, and a dry method is employed for forming this silicon oxide film. Examples of dry methods include physical vapor deposition (PVD) and chemical vapor deposition (CVD), with physical vapor deposition (PVD) being preferred. Examples of wet coating methods include methods using silica nanoparticles, sol-gel methods using silicon alkoxides, and methods involving the conversion of polysilazane into silica glass through reaction with water. However, silicon oxide underlayers formed by these wet coating methods cannot exhibit sufficient water and oil repellency.

[0027] The above-mentioned PVD methods include resistance heating deposition, electron beam deposition, and sputtering deposition. In the present invention, electron beam deposition and sputtering deposition are preferably used because they yield a coating with high smoothness and adhesion.

[0028] Electron beam deposition methods include irradiating granular or plate-shaped SiO2 with an electron beam to evaporate the SiO2 and deposit it on a substrate, and depositing SiO2 while irradiating the substrate with an ion beam (ion beam assisted method). The deposition pressure is 1 × 10⁻⁶. -4 ~5×10 -1 Pa is preferred, and the deposition rate is preferably 0.01 to 2 nm / second. The deposition substrate temperature is preferably 25 to 300°C.

[0029] One sputtering deposition method is reactive sputtering, which involves sputtering a Si target onto a substrate, depositing it, and then oxidizing it on the substrate to obtain silicon oxide. Sputtering sources include DC plasma, RF plasma, electron cyclotron resonance (ECR) plasma, and ion beams. Oxidation of Si can be achieved by introducing oxygen gas or by irradiating with oxygen plasma (radical-assisted method). The deposition pressure is 1 × 10⁻⁶. -4 A pressure of ~1 Pa is preferred. A deposition rate of 0.1 to 1 nm / second is preferred. A deposition substrate temperature of 25 to 300°C is preferred.

[0030] The above-mentioned CVD methods can include thermal CVD, species-assisted CVD, and photoCVD.

[0031] A CVD method supported by reactive species is a method in which a precursor is converted into silicon oxide through a chemical reaction of reactive species and deposited on a glass substrate. Reactive species can include ions, electrons, radicals, etc., contained in an oxygen-containing plasma. For example, a method for forming a silicon oxide film by a CVD method using an oxygen-containing plasma can be found in Patent Documents 9 and 10 (Japanese Patent Application Publication No. 2020-090652 and Japanese Patent No. 5655215).

[0032] Silicon compounds are used as precursors to the silicon oxide. Examples include SiH4, Si2H6, tetraethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane. Tetraethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane are preferably used.

[0033] The CVD conditions for silicon oxide film formation are appropriately set depending on the type of substrate and precursor used. When SiH4 is used as the precursor, the substrate temperature is preferably 30°C or higher and less than 150°C, more preferably 30 to 140°C. When tetraethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane is used as the precursor, the substrate temperature is preferably 30°C or higher and less than 250°C, more preferably 30 to 150°C.

[0034] The thickness of the silicon oxide underlayer described above is preferably 3 to 150 nm, and more preferably 3 to 50 nm. If the thickness of the silicon oxide underlayer is less than 3 nm, good adhesion with the water-repellent and oil-repellent surface layer may not be obtained due to the presence of voids within the silicon oxide underlayer, and if it exceeds 150 nm, poor adhesion with the water-repellent and oil-repellent surface layer may occur due to insufficient strength of the silicon oxide underlayer itself. The thickness of the silicon oxide underlayer can be measured by cross-sectional observation using X-ray reflectometry (XRR) or an electron microscope.

[0035] The surface of the silicon oxide underlayer may be pre-treated before the formation of the water-repellent and oil-repellent surface layer. Pre-treatment ensures good adhesion between the silicon oxide underlayer and the water-repellent and oil-repellent surface layer, resulting in high wear resistance.

[0036] The method for pretreatment of the silicon oxide substrate is not particularly limited as long as it can remove contaminants from the surface of the silicon oxide substrate. For example, plasma cleaning treatment using oxygen plasma or argon plasma, or radical cleaning treatment using OH radicals can be suitably used. When pretreatment is performed, plasma cleaning treatment is particularly preferred.

[0037] [Water-repellent and oil-repellent surface layer] The water-repellent and oil-repellent surface layer is mainly composed of a cured polymer containing hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, and is formed on a silicon oxide underlayer using a surface treatment agent containing a polymer containing hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof. Examples of the fluoropolyether group-containing polymer containing hydrolyzable silyl groups include those listed in Japanese Patent Publication No. 6260579, No. 6828744, No. 5761305, No. 6451279, No. 6741074, No. 6617853, JP 2011-116947, JP 2007-197425, JP 2007-297589, JP 2007-297543, and JP 2008-0 Compounds described in Japanese Patent Publication No. 88412, Japanese Patent Publication No. 2008-144144, Japanese Patent Publication No. 2010-031184, Japanese Patent Publication No. 2010-047516, Japanese Patent Publication No. 2011-178835, Japanese Patent Publication No. 2014-084405, Japanese Patent Publication No. 2014-105235, Japanese Patent Publication No. 2013-253228, Japanese Patent Publication No. 2014-218639, and International Publication No. 2013 / 121984 (Patent Documents 1-6, 14-27) can be used.

[0038] A more detailed explanation will be given regarding polymers containing fluoropolyether groups having hydrolyzable silyl groups.

[0039] The fluoropolyether group-containing polymer having a hydrolyzable silyl group has at least one, preferably 1 to 3, terminals in the molecule, which are of the following formula (11) [ka] (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, and a is 2 or 3.) The molecule contains at least two, preferably two to three (i.e., at least two, preferably two to nine, more preferably two to six) groups represented by (hydrolyzable silyl groups), and the molecule contains -(C b F 2b O) mIt is preferable to have a polyfluorooxyalkylene structure represented by -(wherein b is an integer from 1 to 6 independently for each unit, and m is an integer from 1 to 250).

[0040] In formula (11) above, X is a hydrolyzable group that may be different from one another. Examples of such X 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.

[0041] In formula (11) above, R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, with methyl and ethyl groups being preferred. In the above formula (11), a is 2 or 3, and 3 is preferred from the viewpoint of reactivity and adhesion to the substrate.

[0042] The following are examples of the bases in formula (11) above. [ka]

[0043] Also, the above-(C b F 2b O) m In the polyfluorooxyalkylene structure represented by -, b is an integer from 1 to 6, preferably from 1 to 4, independently for each unit, and m is an integer from 1 to 250, preferably from 1 to 140.

[0044] The above -C bF 2b Examples of repeating units represented by O- include the unit shown in the following formula. -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-, -C(CF3)2O- Among these, the repeating unit shown in the following formula is particularly preferred. -CF2O-, -CF2CF2O-

[0045] The polyfluorooxyalkylene structure described above may be composed of one of the repeating units described above, or it may be composed of a combination of two or more units.

[0046] In the present invention, the fluoropolyether group-containing polymer having a hydrolyzable silyl group includes one or more fluoropolyether group-containing polymers represented by the following formulas (1), (4), or (7). In particular, it is preferable that all of the fluoropolyether group-containing polymers having a hydrolyzable silyl group are one or more fluoropolyether group-containing polymers represented by the formulas (1), (4), and (7). [ka] [In the formula, Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d-(wherein d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 150 independently, the sum of p, q, r, s, t, and u is an integer from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or D, where D is independently a monovalent group represented by the following formula (2). [ka] [In the formula, Q is a single bond or a divalent organic group, Z is a 3- to 8-valent group, α is an integer from 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (In the formula, R, X, and a are the same as above, and Y is a single bond, or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.) [ka] [In the formula, Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5). [ka] [In the formula, W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). [ka] (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W, and l is an integer of 0 to 20.)〕,

Chemical formula

Chemical formula

Chemical formula

[0047] First, the fluoropolyether group-containing polymer represented by the following formula (1) will be described.

Chemical formula

[0048] In the above formula (1), Rf is -C d F 2d -O-(CF₂O) p (C₂F₄O) q (C₃F₆O) r (C₄F₈O) s (C₅F 10 O) [[ID=X]] t (C₆F 12 O) u -C d F 2d ​​​​​​It is a divalent polyfluorooxyalkylene structure (perfluoropolyether structure) -containing group represented by, d is independently an integer of 0 to 5 for each unit, preferably an integer of 0 to 2, more preferably 0 or 1. p, q, r, s, t and u are each independently an integer of 0 to 150, preferably an integer of 0 to 100, more preferably an integer of 0 to 60, and the sum of p, q, r, s, t and u is an integer of 1 to 250, preferably an integer of 3 to 140, more preferably an integer of 7 to 70. Each of these units may be linear or branched. In addition, the repeating units shown in the parentheses with p, q, r, s, t and u may be randomly bonded.

[0049] As the divalent polyfluorooxyalkylene structure-containing group of Rf, specifically, it can be represented by the following structure.

Chemical formula

[0050] In the above formula (1); A 1 -Rf-D, A 1 is a monovalent fluorine-containing hydrocarbon group with a terminal of CF3- or CF2H- and may contain an oxygen atom, or D (that is, a monovalent group represented by -Q-Z(W) shown in formula (2) described later). α As the monovalent fluorine-containing hydrocarbon group with a terminal of CF3- or CF2H- and may contain an oxygen atom, it is preferably a fluoroalkyl group having 1 to 6 carbon atoms.

[0051] Such A 1Examples of monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0052] The above formula (1); A 1 In -Rf-D, D is independently a monovalent group represented by the following formula (2). [ka]

[0053] In formula (2) above, Q is a single bond or a divalent organic group, and Q other than a single bond is preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of amide bonds (e.g., unsubstituted amide bonds, N-methyl substituted amide bonds, N-phenyl substituted amide bonds), ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups (e.g., dialkylsilylene groups such as dimethylsilylene groups), silarylene bonds (e.g., silphenylene bonds), and silalkylene bonds (e.g., silethylene bonds). More preferably, it is an unsubstituted or fluorine-substituted divalent hydrocarbon group having 1 to 12 carbon atoms, which may contain the aforementioned bonds, and particularly preferably 2 to 12 carbon atoms. Examples of divalent hydrocarbon groups include methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), alkylene groups such as hexamethylene groups and octamethylene groups, arylene groups such as phenylene groups, or combinations of two or more of these groups (alkylene-arylene groups, etc.).

[0054] Examples of sylalkylene bonds and sylarylene bonds can be found below. [ka] (In the formula, R 1 R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, and an aryl group having 6 to 10 carbon atoms, such as a phenyl group. 1 They may be the same or different. 2 These are alkylene groups with 1 to 4 carbon atoms, such as methylene groups, ethylene groups, and propylene groups (trimethylene groups, methylethylene groups), and arylene groups with 6 to 10 carbon atoms, such as phenylene groups.

[0055] Examples of Q other than single bonds include the following groups. In the structure below, it is preferable that the left bond is bonded to Rf and the right bond is bonded to Z. [ka] (In the formula, t is an integer between 2 and 4.)

[0056] Equation (2) above; -QZ(W) α In this, Z is a 3- to 8-valent group, preferably a 3- to 8-valent organopolysiloxane residue having a silicon atom, a nitrogen atom, and a siloxane bond, preferably a linear, branched, or cyclic organopolysiloxane residue with 3 to 13 silicon atoms, more preferably a 3 to 5 silicon atoms, and is preferably a 3 or 4-valent group. Also, a silalkylene structure such as a silethylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group, i.e., Si-(CH2) n -Si may be included (in the above formula, n is an integer from 2 to 6, preferably an integer from 2 to 4).

[0057] Examples of linear, branched, or cyclic organopolysiloxane residues with siloxane bonds and a 3- to 8-valent nucleotide chain are shown below. [ka] (In the formula, R 1The same applies as above. g is an integer between 3 and 12, preferably 3 or 4; h is an integer between 3 and 8, preferably 3 or 4; j is an integer between 0 and 8, preferably 0 or 1; h+j is an integer between 3 and 13, preferably 3 and 5; and k is 2 or 3. [ka] [In the formula, R 4 R is independent 1 Or the following formula (a) [ka] (In the formula, R 1 The above is the same, where j1 is an integer from 1 to 6, preferably 1, and the left-hand bond connects to Si. It is a group represented by R 5 These are independently single bonds or the following formula (b) [ka] (In the formula, R 2 , R 4 The above is the same, where j2 is an integer from 0 to 6, preferably from 0 to 3, j3 is an integer from 0 to 6, preferably from 0 to 2, and j2 + j3 is an integer from 1 to 6, and each repeating unit shown in parentheses may be randomly coupled. The left-hand coupling bond to Si. It is a group represented by R 4 At least one of them is equation (a).

[0058] Examples of such Z include the following: [ka] [ka] [ka] [ka]

[0059] Equation (2) above; -QZ(W) α In this, W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (In the formula, R, X, and a are the same as above, and Y is a single bond, or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.)

[0060] In equation (3) above, R, X, and a are the same as R, X, and a in equation (11) above, and examples of R, X, and a similar to those in equation (11) above can be given.

[0061] In formula (3) above, Y is a divalent hydrocarbon group which may have a single bond or one or more selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond is selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing a fluorine atom, an alkylene group having 6 to 8 carbon atoms containing an arylene group (alkylene-arylene group), a divalent group in which alkylene groups having 2 to 10 carbon atoms are bonded to the bonding site of a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms.

[0062] Examples of Y other than single bonds include the following: [ka]

[0063] The following are examples of the bases in formula (3) above. [ka]

[0064] Equation (2) above; -QZ(W) α In this, α, which represents the number of W, is an integer between 2 and 7, preferably 2 or 3.

[0065] The base in equation (2) above: -QZ(W) α The following are examples of D in equation (1): [ka]

[0066] Examples of fluoropolyether group-containing polymers represented by the above formula (1) are listed below. [ka] (In the formula, A 1 (Rf is the same as above.)

[0067] Next, we will describe the fluoropolyether group-containing polymer represented by the following formula (4). [ka] In equation (4) above, Rf is the same as above, and the same example as the one exemplified for Rf in equation (1) above can be given.

[0068] The above formula (4); A 2 -In Rf-G, A 2 The terminal is a monovalent fluorine-containing hydrocarbon group having CF3- or CF2H- and may contain an oxygen atom, or G (i.e., a monovalent group represented by formula (5);-C(B)(W)2 described later), and the terminal is a monovalent fluorine-containing hydrocarbon group having CF3- or CF2H- and may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms.

[0069] Such A 2Examples of monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0070] The above formula (4); A 2 In -Rf-G, G is independently a monovalent group represented by the following formula (5). [ka] In equation (5) above, W is the same as above, and the same example as the one exemplified for W in equation (2) above can be given.

[0071] In the above formula (5);-C(B)(W)2, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). [ka]

[0072] Here, examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms in S include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenylethyl groups. C1 to C3 alkyl groups and phenyl groups are preferred.

[0073] Equation (6) above: -T-(LO) lIn -E, T is a single bond or a divalent group, preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms, a divalent siloxane bond, a sylalkylene group, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a siloxane bond, a sylalkylene bond (e.g., a sylethylene bond, a sylpropylene bond), a sylarylene bond (e.g., a sylphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group, a dialkoxysilylene group such as a dimethoxysilylene group). Here, examples of divalent hydrocarbon groups include methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), alkylene groups such as hexamethylene groups and octamethylene groups, arylene groups such as phenylene groups, or combinations of two or more of these groups (such as alkylene-arylene groups), with propylene groups being preferred.

[0074] Examples of T other than single bonds include those shown below. In the structures below, it is preferable that the right-hand bond is connected to L or E. [ka]

[0075] Equation (6) above: -T-(LO) l In -E, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group), or other alkylene groups, and the number of carbon atoms in each (LO) unit may be single or mixed. Equation (6) above: -T-(LO) l In -E, l is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 6. If (LO) is present, l is preferably 1 or greater, and particularly preferably 2 or greater. Equation (6) above: -T-(LO) lIn -E, E is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, or butyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group, or W, and W is the same as above, and examples similar to those exemplified by W in formula (2) above can be given.

[0076] Equation (6) above: -T-(LO) l Examples of monovalent groups denoted by -E include the following: [ka]

[0077] Examples of monovalent groups represented by the above formula (5);-C(B)(W)2 (i.e., G in formula (4)) are listed below. [ka]

[0078] Examples of fluoropolyether group-containing polymers represented by formula (4) above are listed below. [ka] (In the formula, A 2 (Rf is the same as above.)

[0079] Next, we will describe the fluoropolyether group-containing polymer represented by the following formula (7). [ka] In equation (7) above, Rf is the same as above, and an example similar to the one exemplified for Rf in equation (1) above can be given.

[0080] The above formula (7); A 3 In -Rf-J, A 3 This is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or J(i.e., formula (8) described later; -VC(=O)N(S) 2-e (M)e a monovalent group represented by the following formula), and the monovalent fluorine-containing hydrocarbon group having a terminal of CF3- or CF2H- and optionally containing an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms.

[0081] Such A 3 Examples of the monovalent fluorine-containing hydrocarbon group having a terminal of CF3- or CF2H- and optionally containing an oxygen atom include the following groups. [Chemical formula]

[0082] In the above formula (7); A 3 -Rf-J, J is independently a monovalent group represented by the following formula (8), and J has two or more of the above W (monovalent hydrolyzable silyl group-containing group). [Chemical formula]

[0083] In the above formula (8), S is the same as above, and those similar to those exemplified by the above S can be exemplified.

[0084] In the above formula (8), V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond. As V other than a single bond, specifically, the following can be exemplified. In the following structures, the right bond is preferably bonded to a carbon atom (-C(=O)-). [Chemical formula] In the above formula (8), e is 1 or 2, and preferably 1. In the above formula (8), M is independently a monovalent group represented by the following formula (9). [Chemical formula]

[0085] In equation (9) above, Y, S, and W are the same as above, and examples can be given that are the same as those exemplified in equation (3), S, and W in equation (2) above. In equation (9) above, f is an integer between 1 and 3.

[0086] Equation (9) above: -YC(S) 3-f (W) f Examples of monovalent groups represented by (i.e., M in formula (8)) are listed below. [ka]

[0087] Above formula (8);-VC(=O)N(S) 2-e (M) e Examples of monovalent groups represented by the symbol are listed below. [ka] [ka]

[0088] Examples of fluoropolyether group-containing polymers represented by formula (7) above are listed below. [ka] [ka] (In the formula, A 3 (Rf is the same as above.)

[0089] In the method for producing a water-repellent and oil-repellent article of the present invention, the surface treatment agent for forming a water-repellent and oil-repellent surface layer, which includes a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, may also be a mixture (i.e., a fluoropolyether group-containing polymer composition) that further includes, in addition to the fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, represented by the following formula (10) (hereinafter referred to as a polymer that does not contain hydrolyzable silyl groups). In the present invention, "partially (hydrolyzed) condensate" means a partial condensate or a partially hydrolyzed condensate. [ka] [In the formula, Rf is the same as above, and the same example as the one exemplified for Rf in formula (1) above can be given. A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2(R 3 (This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.)

[0090] In the above formula (10), A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2, and the terminal end is CF3- or CF2H- and may contain an oxygen atom, as a monovalent fluorine-containing hydrocarbon group, A 1 Examples of monovalent fluorine-containing hydrocarbon groups that have CF3- or CF2H- at their termini and may contain an oxygen atom are similar to those exemplified above. Here, R 3is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group; aralkyl groups such as benzyl group, phenylethyl group, etc. R 3 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. A 4 's -OR 3 , -COOR 3 , -PO(OR 3 )2 include, for example, -OH, -OCH3, -COOH, -COOCH3, -PO(OH)2, -OC2H5, -COOC2H5.

[0091] Examples of the fluoropolyether group-containing polymer represented by the above formula (10) include those shown below. [Chemical formula] (In the formula, p”, q”, r”, s”, t” and u” are each independently an integer from 0 to 150, and the sum of p”, q”, r”, s”, t” and u” is from 12 to 250. These units may be linear or branched. Also, the repeating units shown in the parentheses with p”, q”, r”, s”, t” and u” may be randomly bonded.)

[0092] In the method for producing a water-repellent and oil-repellent article of the present invention, the surface treatment agent used to form the water-repellent and oil-repellent surface layer contains at least one fluoropolyether group-containing polymer having at least two hydrolyzable silyl groups at the ends of the molecular chains represented by formula (1), (4), or (7) and / or a partially hydrolyzed condensate of said polymer (single-ended polymer), or at least one fluoropolyether group-containing polymer having at least two hydrolyzable silyl groups at each end of the molecular chains represented by formula (1), (4), or (7) and / or a partially hydrolyzed condensate of said polymer (double-ended polymer), or contains a mixture containing at least one of said single-ended polymers and at least one of said double-ended polymers, or contains a mixture (fluoropolyether group-containing polymer composition) which further contains a polymer that does not contain the above hydrolyzable silyl groups.

[0093] In a fluoropolyether group-containing polymer mixture (fluoropolyether group-containing polymer composition) contained in a surface treatment agent, the mixing ratio of a single-ended polymer and / or a double-ended polymer and a polymer that does not contain hydrolyzable silyl groups is not particularly limited as long as the formed water-repellent and oil-repellent surface layer is mainly composed of the fluoropolyether group-containing polymer having the hydrolyzable silyl groups and / or a cured product of its partially hydrolyzed condensate. However, it is generally desirable that the ratio of the polymer that does not contain hydrolyzable silyl groups is 0 to 30 mol%, particularly 0 to 10 mol%, relative to the entire fluoropolyether group-containing polymer composition consisting of a single-ended polymer and / or a double-ended polymer and a polymer that does not contain hydrolyzable silyl groups.

[0094] In the surface treatment agent, it is preferable that the number average molecular weight of the fluoropolyether group-containing polymer having the above-mentioned hydrolyzable silyl group and / or its partially hydrolyzed condensate, or the fluoropolyether group-containing polymer composition, is in the range of 1,000 to 20,000. More preferably, the number average molecular weight is 2,000 to 10,000, and particularly preferably 3,000 to 8,000. Note that the number average molecular weight is, 19It can be calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0095] A fluoropolyether group-containing polymer having hydrolyzable silyl groups within the above number-average molecular weight range and / or a partially hydrolyzed condensate thereof, or a fluoropolyether group-containing polymer composition, can be obtained by rectification or molecular distillation of the above fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, or a fluoropolyether group-containing polymer composition. Furthermore, a fluoropolyether group-containing polymer having a hydrolyzable silyl group within the above-mentioned number-average molecular weight range and / or a partially hydrolyzed condensate thereof, or a fluoropolyether group-containing polymer composition, can also be prepared by using a fluorine compound that has the above-mentioned number-average molecular weight in advance when synthesizing the fluoropolyether group-containing polymer.

[0096] The surface treatment agent 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, dibutyltin dilaurate, and fluorine-modified carboxylic acid are particularly desirable. 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 a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partially hydrolyzed condensate.

[0097] Furthermore, the surface treatment agent may contain a solvent. Preferably, the solvent is a fluorine-modified aliphatic hydrocarbon solvent (such as perfluoroheptane or perfluorooctane), a fluorine-modified olefin solvent (such as methoxyperfluoroheptene), a fluorine-modified aromatic hydrocarbon solvent (such as m-xylene hexafluoride, benzotrifluoride, or 1,3-trifluoromethylbenzene), a fluorine-modified ether solvent (such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether, or perfluoro(2-butyltetrahydrofuran)), a fluorine-modified alkylamine solvent (such as perfluorotributylamine or perfluorotripentylamine), a hydrocarbon solvent (such as petroleum benzine, mineral spirits, toluene, or xylene), or a ketone solvent (such as acetone, methyl ethyl ketone, or methyl isobutyl ketone). In particular, fluorine-modified solvents (referred to as fluorine-based solvents) are preferable in terms of solubility and wettability, and 1,3-trifluoromethylbenzene, m-xylenehexafluoride, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are preferred.

[0098] The above solvents may be mixed in two or more forms, and it is preferable that they uniformly dissolve the hydrolyzable silyl group-containing fluoropolyether group polymer and / or its partially hydrolyzed condensate, or the fluoropolyether group-containing polymer composition. The optimal concentration of the hydrolyzable silyl group-containing fluoropolyether group polymer and / or its partially hydrolyzed condensate to be dissolved in the solvent can be appropriately selected depending on the method of use of the surface treatment agent, and is not limited. Typically, the concentration is 0.01 to 30% by mass, preferably 0.02 to 25% by mass, and more preferably 0.05 to 20% by mass.

[0099] The formation of a water- and oil-repellent surface layer using a surface treatment agent employs wet methods such as brush application, dip coating, and spray coating. Among these, spray coating or dip coating is preferred. Water- and oil-repellent surface layers formed by dry methods such as vapor deposition (physical vapor deposition (PVD) or chemical vapor deposition (CVD)) cannot exhibit sufficient water- and oil-repellent properties.

[0100] It is preferable to perform a curing treatment after forming the water-repellent and oil-repellent surface layer. In the case of brush coating, dip coating, and spray coating methods, it is preferable to cure at 60 to 150°C, preferably 60 to 120°C, and at a relative humidity of 95% or less for 30 minutes to 24 hours, preferably 30 minutes to 2 hours.

[0101] The film thickness of the water-repellent and oil-repellent surface layer is typically 2 to 100 nm, with 3 to 20 nm being preferable. If the film thickness of the water-repellent and oil-repellent surface layer is less than 2 nm, the coverage of the water-repellent and oil-repellent surface layer may be low, resulting in reduced water-repellency and durability. If it exceeds 100 nm, curing may become difficult, resulting in reduced water-repellency and durability. The film thickness of the water-repellent and oil-repellent surface layer can be measured by the XRR or spectroscopic ellipsometry methods described above.

[0102] The water-repellent and oil-repellent article obtained by the manufacturing method of the present invention has a receding contact angle (θ) of the water-repellent and oil-repellent surface layer with respect to water. WR Preferably, the receding contact angle (θ) of the water-repellent and oil-repellent surface layer with respect to oleic acid is 101° or more. OR It is preferable that the angle is 64° or higher. Furthermore, the advancing contact angle (θ) of the water-repellent and oil-repellent surface layer with respect to water. WA ) and the receding contact angle (θ WR ) difference (Δ W Preferably, the advancing contact angle (θ) of the water-repellent and oil-repellent surface layer with respect to oleic acid is 20° or less. OA ) and the receding contact angle (θ OR ) difference (Δ O It is preferable that the advancing contact angle (θ) with water and oleic acid is 20° or less. WA , θ OA ) and the receding contact angle (θWR , θ OR ) difference (Δ W , Δ O If all of these angles are 20° or less, the droplets will roll off easily, making them easier to remove, and thus resulting in good water-repellent and oil-repellent properties. Note that these advancing contact angles (θ) WA , θ OA ) and the receding contact angle (θ WR , θ OR ) and their difference (Δ W , Δ O The contact angle can be determined by the expansion / contraction method using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) at a temperature of 25°C and a relative humidity of 40%.

[0103] The method for manufacturing a water-repellent and oil-repellent article of the present invention can improve the water and oil removal properties of the resulting water-repellent and oil-repellent article. [Examples]

[0104] 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 number average molecular weight is: 19 This value was calculated from the characteristic peak intensity ratio of the F-NMR analysis.

[0105] [Comparative Example 1] [Alkaline cleaning of substrates] Chemically strengthened aluminosilicate glass (Corning GORILLA, size: 100mm x 50mm x 0.7mm (thickness)) was immersed in an alkaline cleaning solution (aqueous solution of Yokohama Oils & Fat's 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 dried by blowing away moisture with compressed air.

[0106] [Plasma cleaning of substrates] The substrate surface, which had undergone the alkaline cleaning described above, was treated with an oxygen-argon mixed plasma. The treatment conditions are shown below. Processing unit: PDC510 (manufactured by Yamato Scientific Co., Ltd.) Oxygen gas flow rate: 10 sccm (Standard Cubic Centimeters) Argon gas flow rate: 100 sccm Processing pressure: 60 Pa RF supply power: 250W Processing time: 30 seconds

[0107] [Formation of a silicon oxide underlayer by dip coating with silica nanoparticles] The substrate, which had undergone the above-mentioned alkaline and plasma cleaning processes, was placed in a dip coater (DT-0303-S3, manufactured by SDI), and a silica nanoparticle aqueous dispersion was applied by immersion coating to form a silicon oxide underlayer with a thickness of 4 nm. The formation conditions are shown below. Silica nanoparticle average particle size: 2nm Silica nanoparticle concentration: 0.1% by mass Immersion time: 30 seconds Lifting speed: 0.5 mm / second Drying conditions: 150°C, 30 minutes

[0108] The thickness of the silicon oxide underlayer described above was obtained by X-ray reflectance measurement. Specifically, the thickness was determined by performing a simulation fitting on the measured profile. The measurement conditions are as follows. Measurement device: SmartLab (manufactured by Rigaku) X-ray source: Rotating cathode (Cu), output 45kV, 200mA Incident optics: 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°

[0109] [Formation of a water-repellent and oil-repellent surface layer by dip coating] The substrate with the silicon oxide underlayer described above was set in a dip coater (DT-0303-S3, manufactured by SDI), and immersion coating was performed using the dip coating surface treatment agent described below to form a water-repellent and oil-repellent surface layer with a thickness of 10 nm. The formation conditions are shown below. Immersion time: 30 seconds Pulling speed: 3mm / sec A substrate coated with the above-mentioned dip coating surface treatment agent (fluoropolyether group-containing polymer) was left for 30 minutes at 80°C and 80% relative humidity to cure and fix the water-repellent and oil-repellent surface layer, thereby obtaining a substrate having a water-repellent and oil-repellent surface layer with a thickness of 10 nm due to the fluoropolyether group-containing polymer. The film thickness of the water-repellent and oil-repellent surface layer described above was calculated using a calibration curve after quantifying the fluorescence X-ray intensity derived from the fluorine element with a fluorescence X-ray analyzer (manufactured by Rigaku Corporation, product name: fluorescence X-ray analyzer Primini).

[0110] [Preparation of surface treatment agent for dip coating] Compound (A) represented by the following formula (number average molecular weight 4,000) was dissolved in a fluorine solvent (NOVEC HFE-7200, manufactured by 3M) to a concentration of 0.1% by mass to prepare a surface treatment agent. [ka] (p / q=1.0, p+q=42)

[0111] [Comparative Example 2] [Formation of a water-repellent and oil-repellent surface layer by spray coating] A substrate with a silicon oxide underlayer, similar to that in Comparative Example 1, was set in a spray coater (API-40RD, manufactured by API), and spray coating was performed using the following spray coating surface treatment agent to form a water-repellent and oil-repellent surface layer with a thickness of 10 nm. A substrate coated with the above-mentioned spray coating surface treatment agent (fluoropolyether group-containing polymer) was left for 30 minutes in an environment of 80°C and 80% relative humidity to cure and fix the water-repellent and oil-repellent surface layer, thereby obtaining a substrate having a water-repellent and oil-repellent surface layer with a thickness of 10 nm due to the fluoropolyether group-containing polymer. The film thickness of the water-repellent and oil-repellent surface layer described above was calculated using a calibration curve after quantifying the fluorescence X-ray intensity derived from the fluorine element with a fluorescence X-ray analyzer (manufactured by Rigaku Corporation, product name: fluorescence X-ray analyzer Primini).

[0112] [Preparation of surface treatment agent for spray coating] Compound (A) of the above formula was dissolved in a fluorine solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0113] [Comparative Example 3] [Formation of a water-repellent and oil-repellent surface layer by vacuum deposition] A substrate with a silicon oxide underlayer, similar to that in Comparative Example 1, was set in a resistance-heating vacuum deposition apparatus (VTR-350M, manufactured by ULVAC KIKO). 5 μL of the following surface treatment agent was dropped into the resistance heating section, and the pressure was reduced. The internal pressure of the container was 3 × 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 thickness gauge, located approximately 20 cm away from the resistance heating section, was 1.0 nm / second. Resistance heating was continued for 100 seconds after the evaporation rate measured by the quartz crystal thickness gauge decreased to 0.1 nm / second. After waiting for 5 minutes for the apparatus to cool, the system was opened to the atmosphere, and a substrate coated with a fluoropolyether group-containing polymer was obtained. The glass substrate coated with the above-mentioned fluoropolyether group-containing polymer was left for 30 minutes at 80°C and 80% relative humidity to cure and fix the water-repellent and oil-repellent surface layer, thereby obtaining a glass substrate having a water-repellent and oil-repellent surface layer with a thickness of 10 nm due to the fluoropolyether group-containing polymer. The film thickness of the water-repellent and oil-repellent surface layer described above was calculated using a calibration curve after quantifying the fluorescence X-ray intensity derived from the fluorine element with a fluorescence X-ray analyzer (manufactured by Rigaku Corporation, product name: fluorescence X-ray analyzer Primini).

[0114] [Preparation of surface treatment agents for vacuum deposition] Compound (A) of the above formula was dissolved in a fluorine solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 20% by mass to prepare a surface treatment agent.

[0115] [Comparative Example 4] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Comparative Example 1, except that a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer by electron beam deposition] A substrate that had undergone alkaline cleaning and plasma cleaning using the same procedure as in Comparative Example 1 was set in an electron beam deposition apparatus (ACE-1350, manufactured by Synchron), and a silicon oxide underlayer with a thickness of 10 nm was formed using SiO2 granules as the deposition source. The formation conditions are shown below. Vapor deposition source: SiO2 granules (2mm) Ultimate pressure (pressure during film formation): 1 × 10 -3 Pa Deposition rate (film deposition rate): 1 nm / second Deposition substrate temperature: 25℃ The thickness of the silicon oxide underlayer described above was obtained by X-ray reflectivity measurement, similar to the measurement of the silicon oxide underlayer thickness by dip coating with silica nanoparticles described above.

[0116] [Comparative Example 5] The silicon oxide underlayer was formed using the same procedure as in Comparative Example 4, and the water-repellent and oil-repellent surface layer was formed using the same procedure as in Comparative Example 2, resulting in a substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer.

[0117] [Comparative Example 6] The silicon oxide underlayer was formed using the same procedure as in Comparative Example 4, and the water-repellent and oil-repellent surface layer was formed using the same procedure as in Comparative Example 3, resulting in a substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer.

[0118] [Comparative Example 7] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 1, except that a surface treatment agent was prepared using compound (B) (number average molecular weight 4,000) shown in the following formula. [ka] (p / q=1.0, p+q=42)

[0119] [Comparative Example 8] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 2, except that a surface treatment agent was prepared using compound (B) shown in the above formula.

[0120] [Comparative Example 9] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 3, except that a surface treatment agent was prepared using compound (B) shown in the above formula.

[0121] [Example 1] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 4, except that a surface treatment agent was prepared using compound (B) shown in the above formula.

[0122] [Example 2] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 5, except that a surface treatment agent was prepared using compound (B) shown in the above formula.

[0123] [Comparative Example 10] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 6, except that a surface treatment agent was prepared using compound (B) shown in the above formula.

[0124] [Comparative Example 11] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 1, except that a surface treatment agent was prepared using compound (C) (number average molecular weight 4,000) shown in the following formula. [ka] (p / q=1.0, p+q=42)

[0125] [Comparative Example 12] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 2, except that a surface treatment agent was prepared using compound (C) shown in the above formula.

[0126] [Comparative Example 13] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 3, except that a surface treatment agent was prepared using compound (C) shown in the above formula.

[0127] [Example 3] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 4, except that a surface treatment agent was prepared using compound (C) shown in the above formula.

[0128] [Example 4] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 5, except that a surface treatment agent was prepared using compound (C) shown in the above formula.

[0129] [Comparative Example 14] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 6, except that a surface treatment agent was prepared using compound (C) shown in the above formula.

[0130] [Comparative Example 15] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 1, except that a surface treatment agent was prepared using compound (D) (number average molecular weight 4,000) shown in the following formula. [ka] (p / q=1.0, p+q=42)

[0131] [Comparative Example 16] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 2, except that a surface treatment agent was prepared using compound (D) shown in the above formula.

[0132] [Comparative Example 17] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 3, except that a surface treatment agent was prepared using compound (D) shown in the above formula.

[0133] [Example 5] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 4, except that a surface treatment agent was prepared using compound (D) shown in the above formula.

[0134] [Example 6] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 5, except that a surface treatment agent was prepared using compound (D) shown in the above formula.

[0135] [Comparative Example 18] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 6, except that a surface treatment agent was prepared using compound (D) shown in the above formula.

[0136] [Comparative Example 19] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 1, except that a surface treatment agent was prepared using compound (E) (number average molecular weight 6,000) shown in the following formula. [ka] (p / q=0.94, p+q=63)

[0137] [Comparative Example 20] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 2, except that a surface treatment agent was prepared using compound (E) shown in the above formula.

[0138] [Comparative Example 21] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 3, except that a surface treatment agent was prepared using compound (E) shown in the above formula.

[0139] [Example 7] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 4, except that a surface treatment agent was prepared using compound (E) shown in the above formula.

[0140] [Example 8] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 5, except that a surface treatment agent was prepared using compound (E) shown in the above formula.

[0141] [Comparative Example 22] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 6, except that a surface treatment agent was prepared using compound (E) shown in the above formula.

[0142] [Comparative Example 23] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 1, except that a surface treatment agent was prepared using compound (F) (number average molecular weight 6,000) shown in the following formula. [ka] (p / q=0.94, p+q=63)

[0143] [Comparative Example 24] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 2, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.

[0144] [Comparative Example 25] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 3, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.

[0145] [Example 9] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.

[0146] [Example 10] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.

[0147] [Comparative Example 26] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Comparative Example 6, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.

[0148] [Comparative Example 27] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 7, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0149] [Comparative Example 28] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 8, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0150] [Comparative Example 29] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 9, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0151] [Example 11] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 1, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0152] [Example 12] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 2, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0153] [Comparative Example 30] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 10, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0154] [Comparative Example 31] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 11, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0155] [Comparative Example 32] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 12, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0156] [Comparative Example 33] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 13, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0157] [Example 13] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 3, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0158] [Example 14] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 4, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0159] [Comparative Example 34] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 14, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0160] [Comparative Example 35] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 19, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0161] [Comparative Example 36] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 20, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0162] [Comparative Example 37] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 21, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0163] [Example 15] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 7, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0164] [Example 16] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 8, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0165] [Comparative Example 38] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 22, except that the substrate was made of mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)) and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0166] [Example 17] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained by the same procedure as in Example 3, except that soda-lime glass (size: 100 mm x 50 mm x 0.7 mm (thickness)) was used as the substrate, the following anti-reflective film was formed on the substrate, and the outermost layer was used as a silicon oxide underlayer. [Formation of anti-reflective coating by sputter deposition] A substrate that had undergone alkaline cleaning and plasma cleaning using the same procedure as in Comparative Example 1 was set in a sputtering deposition apparatus (RAS-1100B, manufactured by Synchron), and an anti-reflective film with the following film thickness configuration was formed using a Si target and an Nb target. The formation conditions are shown below. [Si target] RF sputtering source power: 8kW Oxygen plasma source power: 3kW Pressure during film formation: 0.2 Pa Deposition rate: 0.4 nm / second Deposition substrate temperature: 25℃ [Nb target] RF sputtering power supply: 5kW Oxygen plasma source power: 3.5kW Pressure during film formation: 0.2 Pa Deposition rate: 0.4 nm / second Deposition substrate temperature: 25℃ Substrate / Nb2O5: 15nm thickness / SiO2: 40nm thickness / Nb2O5: 120nm thickness / SiO2: 90nm thickness Furthermore, the outermost layer of the anti-reflective coating, SiO2 with a thickness of 90 nm, was used as a silicon oxide underlayer. The film thickness of the anti-reflective coating described above was obtained by transmission electron microscopy observation of a cross-sectional sample.

[0167] [Example 18] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 17, except that the water-repellent and oil-repellent surface layer was formed using the same procedure as in Example 4.

[0168] [Comparative Example 39] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 17, except that the water-repellent and oil-repellent surface layer was formed using the same procedure as in Comparative Example 14.

[0169] [Comparative Example 40] Without forming a base layer on the substrate, a substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 17.

[0170] [Comparative Example 41] Without forming a base layer on the substrate, a substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 18.

[0171] [Comparative Example 42] Without forming a base layer on the substrate, a substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Comparative Example 39.

[0172] [Comparative Example 43] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 1, except that a silicone hard-coated polycarbonate (HC / PC) sheet (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0173] [Comparative Example 44] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 12, except that a silicone hard-coated polycarbonate (HC / PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0174] [Comparative Example 45] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 13, except that a silicone hard-coated polycarbonate (HC / PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0175] [Example 19] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 3, except that a silicone hard-coated polycarbonate (HC / PC) sheet (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0176] [Example 20] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Example 4, except that a silicone hard-coated polycarbonate (HC / PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0177] [Comparative Example 46] A substrate having a water-repellent and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as Comparative Example 14, except that a silicone hard-coated polycarbonate (HC / PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD, manufactured by Sabic) was used as the substrate, and alkaline cleaning and plasma cleaning were performed in the same procedure as in Comparative Example 1.

[0178] Evaluation of water contact angle For the substrates having the silicon oxide underlayer and water-repellent / oil-repellent surface layer prepared as described above, and for the substrates having only the water-repellent / oil-repellent surface layer, the contact angle (static contact angle) of the water-repellent / oil-repellent surface layer with respect to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement results are shown in Tables 4, 5, and 6. In both the examples and comparative examples, an initial water contact angle of 112° or higher was obtained, demonstrating good water repellency.

[0179] Evaluation of the dynamic contact angle of water (advancing contact angle, receding contact angle) For the substrates having the silicon oxide underlayer and the water-repellent / oil-repellent surface layer prepared as described above, and for the substrates having the water-repellent / oil-repellent surface layer, the advancing contact angle (θ) of the water-repellent / oil-repellent surface layer with respect to water was determined using the expansion / contraction method with a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). WA ) and the receding contact angle (θ WR The following measurements were taken (temperature: 25°C, relative humidity: 40%). WA , θ WR and the difference between them (Δ W The results are shown in Tables 4, 5, and 6. In Examples 1-20 and Comparative Examples 2, 3, 8, and 10, Δ W It showed a low value of 20° or less.

[0180] Evaluation of the dynamic contact angle of oil (advancing contact angle, receding contact angle) For the substrates having the silicon oxide underlayer and the water-repellent / oil-repellent surface layer prepared as described above, and for the substrates having the water-repellent / oil-repellent surface layer, the advancing contact angle (θ) of the water-repellent / oil-repellent surface layer with respect to oleic acid was determined using the expansion / contraction method with a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). OA ) and the receding contact angle (θ OR The following measurements were taken (temperature: 25°C, relative humidity: 40%). OA , θ OR and the difference between them (Δ O The results are shown in Tables 4, 5, and 6. In Examples 1-20 and Comparative Examples 1-6, 14, and 34, Δ O It showed a low value of 20° or less.

[0181] Evaluation of steel wool wear resistance The chemically strengthened aluminosilicate glass substrate having the silicon oxide underlayer and water-repellent / oil-repellent surface layer prepared as described above was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku) ​​under the following conditions. Rubbing material: Steel wool (#0000, Bonstar) Load: 1kgf Round trip distance: 40mm Round-trip speed: 60 round trips per minute Total number of friction cycles: 15,000 The water contact angle of the friction-worn portion was measured every 2,500 friction cycles. The number of friction cycles at which a water contact angle of 100° or more was maintained was defined as the steel wool wear endurance cycle. A steel wool wear endurance cycle of 15,000 or more was rated ◎ (Excellent), 10,000 to less than 15,000 was rated ○ (Good), 5,000 to less than 10,000 was rated △ (Acceptable), and less than 5,000 was rated × (Unacceptable), as shown in Table 4. The test environment conditions were 25°C and 40% relative humidity. Examples 1-10 and Comparative Examples 9, 10, 13, 14, and 17-26 demonstrated good steel wool abrasion resistance.

[0182] Evaluation of fabric abrasion resistance The SUS304 substrates having a silicon oxide underlayer and a water-repellent / oil-repellent surface layer, the soda-lime glass substrates having a silicon oxide underlayer and a water-repellent / oil-repellent surface layer, and the soda-lime glass substrates having a water-repellent / oil-repellent surface layer, prepared as described above, were tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku) ​​under the following conditions. Abrasive material: Nonwoven fabric (Bencott M-3II, manufactured by Asahi Kasei) Load: 1kgf Round trip distance: 40mm Round-trip speed: 60 round trips per minute Total number of friction cycles: 30,000 The water contact angle of the friction-worn portion was measured every 2,500 friction cycles. The number of friction cycles at which a water contact angle of 100° or more was maintained was defined as the fabric abrasion endurance cycle. A fabric abrasion endurance cycle of 30,000 or more was rated ◎ (Excellent), 20,000 to less than 30,000 was rated ○ (Good), 10,000 to less than 20,000 was rated △ (Acceptable), and less than 10,000 was rated × (Unacceptable), as shown in Table 5. The test environment conditions were 25°C and 40% relative humidity. Examples 11-18 and Comparative Examples 30-42 showed good fabric abrasion resistance.

[0183] [Table 1]

[0184] [Table 2]

[0185] [Table 3]

[0186] [Table 4]

[0187] [Table 5]

[0188] [Table 6]

Claims

1. A method for manufacturing a water-repellent and oil-repellent article comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide underlayer, A method for producing a water-repellent and oil-repellent article, wherein the water-repellent and oil-repellent surface layer is mainly composed of a cured product of a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, the fluoropolyether group-containing polymer having hydrolyzable silyl groups contains one or more fluoropolyether group-containing polymers represented by the following formulas (1), (4), or (7), a silicon oxide underlayer with a film thickness of 3 to 90 nm is formed by a dry method, and a water-repellent and oil-repellent surface layer with a film thickness of 2 nm or more and less than 100 nm is formed by a wet method in which a surface treatment agent containing the fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof is directly applied to the silicon oxide underlayer. 【Chemistry 1】 [wherein, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d -(where d is an integer of 0 to 5 independently for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in the parentheses to which p, q, r, s, t and u are attached may be randomly combined.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or D, and D is independently a monovalent group represented by the following formula (2). 【Chemistry 2】 [In the formula, Q is a single bond or a divalent organic group, Z is a 3- to 8-valent group, α is an integer from 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). 【Transformation 3】 (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.) 【Chemistry 4】 [In the formula, Rf is the same as above, A 2 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5). 【Transformation 5】 [In the formula, W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). 【Transformation 6】 (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W, and l is an integer from 0 to 20.) 【Transformation 7】 [In the formula, Rf is the same as above, A 3 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J contains two or more W atoms. 【Transformation 8】 [In the formula, S is the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is independently a monovalent group represented by the following formula (9), 【Chemistry 9】 (In the formula, Y, S, and W are the same as above, and f is an integer from 1 to 3.) e is either 1 or 2.

2. A method for producing a water-repellent and oil-repellent article according to claim 1, wherein the base material is glass, metal, or resin.

3. A method for producing a water-repellent and oil-repellent article according to claim 1, wherein a hard coat layer is formed between the substrate and the silicon oxide underlayer.

4. A method for manufacturing a water-repellent and oil-repellent article according to claim 1, wherein an anti-reflective film layer having a silicon oxide film as its outermost layer is formed on a substrate, and the silicon oxide film of the outermost layer is the silicon oxide underlayer.

5. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein in formula (2), Q is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of amide bonds, ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups, silphenylene bonds, and sylalkylene bonds, and Z is a 3 to 8 valent group selected from 3 to 8 valent organopolysiloxane residues having a silicon atom, a nitrogen atom, and a siloxane bond.

6. A method for producing a water- and oil-repellent article according to any one of claims 1 to 4, wherein in formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms, a divalent siloxane bond, a sylalkylene group, a sylarylene bond, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a siloxane bond, a sylalkylene bond, a sylarylene bond, and a diorganosilylene group.

7. The water-repellent and oil-repellent surface layer comprises one or more fluoropolyether group-containing polymers represented by formulas (1), (4), or (7) and / or a partially hydrolyzed condensate thereof, and the following formula (10) 【Chemistry 10】 [In the formula, Rf is -C] d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d - (wherein d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 150 independently, the sum of p, q, r, s, t, and u is an integer from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 4 The terminals are independently CF 3 - or CF 2 H- and possibly containing an oxygen atom, monovalent fluorine-containing hydrocarbon group, -OR 3 , -COOR 3 OR -PO(OR 3 ) 2 (R 3 (This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.) A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the article contains a cured product of a fluoropolyether group-containing polymer and / or a partial (hydrolysis) condensate thereof.

8. A method for manufacturing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the base material is glass or metal.

9. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the method for forming the silicon oxide underlayer is a resistance heating deposition method or an electron beam deposition method.

10. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the method for forming the silicon oxide underlayer is a sputtering film deposition method.

11. A method for manufacturing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the method for forming the water-repellent and oil-repellent surface layer is a dip coating method.

12. A method for manufacturing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the method for forming the water-repellent and oil-repellent surface layer is a spray coating method.

13. A method for manufacturing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the substrate is pretreated by alkaline cleaning and plasma cleaning.

14. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the difference between the advancing contact angle and the receding contact angle of the water-repellent and oil-repellent surface layer with respect to water, as determined by the expansion / contraction method, is 20° or less, and the difference between the advancing contact angle and the receding contact angle with respect to oleic acid is 20° or less.

15. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein the receding contact angle of the water-repellent and oil-repellent surface layer with respect to water, determined by the expansion / contraction method, is 101° or more, and the receding contact angle with respect to oleic acid is 64° or more.

16. A method for producing a water-repellent and oil-repellent article according to any one of claims 1 to 4, wherein A1 in formula (1) is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom, A2 in formula (4) is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom, and A3 in formula (7) is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom.

17. A water-repellent and oil-repellent article comprising a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide underlayer, wherein the water-repellent and oil-repellent surface layer is mainly composed of a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a cured product of its partially hydrolyzed condensate, and the fluoropolyether group-containing polymer having hydrolyzable silyl groups contains one or more fluoropolyether group-containing polymers represented by the following formulas (1), (4), or (7), and a silicon oxide underlayer with a film thickness of 3 to 90 nm is formed by a dry method, and a water-repellent and oil-repellent surface layer with a film thickness of 2 nm or more and less than 100 nm is formed by a wet method in which a surface treatment agent containing the fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or its partially hydrolyzed condensate is directly applied to the silicon oxide underlayer. 【Chemistry 11】 [In the formula, Rf is -C] d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d - (wherein d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 150 independently, the sum of p, q, r, s, t, and u is an integer from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or D, where D is independently a monovalent group represented by the following formula (2). 【Chemistry 12】 [In the formula, Q is a single bond or a divalent organic group, Z is a 3- to 8-valent group, α is an integer from 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). 【Chemistry 13】 (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond.) 【Chemistry 14】 [In the formula, Rf is the same as above, A 2 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5). 【Chemistry 15】 [In the formula, W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6). 【Chemistry 16】 (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W, and l is an integer from 0 to 20.) 【Chemistry 17】 [In the formula, Rf is the same as above, A 3 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J contains two or more W atoms. [Chemistry 18] [In the formula, S is the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is independently a monovalent group represented by the following formula (9), 【Chemistry 19】 (In the formula, Y, S, and W are the same as above, and f is an integer from 1 to 3.) e is either 1 or 2.

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