Articles with water- and oil-repellent surface layers

Abstract

The present invention provides an article having a water- and oil-repellent surface layer, as well as excellent water- and oil-repellent properties, abrasion resistance, and slipperiness, said article being constituted from: a plastic substrate; an underlayer formed upon the outer surface of the plastic substrate and having a silicon oxide as the main component thereof; and a water- and oil-repellent surface layer formed upon the outer surface of the silicon oxide underlayer. The film density of the silicon oxide underlayer is 1.8-2.2 g / cm3. The film thickness of the silicon oxide underlayer is 80-300 nm. The water- and oil-repellent surface layer has, as the main component thereof: a fluoropolyether group-containing polymer having a hydrolyzable silyl group with a specific structure; and / or a cured product of a partially hydrolyzed condensate thereof.

Description

[Technical Field]

[0001] The present invention relates to an article having, on a plastic substrate, a water- and oil-repellent surface layer that is excellent in water- and oil-repellency, abrasion resistance, and slipperiness. [Background technology]

[0002] When a fluoropolyether group-containing polymer is applied to and cured on the surface of a substrate such as metal, porcelain, glass, or plastic, it forms a water- and oil-repellent layer (an antifouling thin film coating layer) on the surface of the substrate, imparting to the substrate the ability to prevent oily stains, fingerprint smudges, and other stains. That is, the fluoropolyether group-containing polymer is used to form an antifouling thin film coating layer on the surface of a touch panel display of a portable electronic device terminal, the surface of the terminal housing, and the like (Patent Documents 1 to 6: Japanese Patent Nos. 6260579, 6828744, 5761305, 6451279, 6741074, and 6617853).

[0003] In addition to preventing stains, the anti-fouling coating thin film layer on the surface of a touch panel display has also been considered important for its usability (good slipperiness and smooth feel) when using the touch panel. A good usability is related to a low coefficient of friction (Patent Document 4: Japanese Patent No. 6451279).

[0004] Furthermore, the water- and oil-repellent layer is exposed to friction and abrasion caused by fingers, clothing, stylus pens, etc. during use, which can cause the water- and oil-repellent properties and stain-resistant performance to deteriorate. To ensure the durability of the water- and oil-repellent layer, a silicon oxide underlayer has been used (Patent Documents 7 to 13: WO 2014 / 097388, JP 2020-132498 A, JP 2020-090652 A, Japanese Patent No. 5655215 A, Japanese Patent No. 6601492 A, Japanese Patent No. 5494656 A, WO 2019 / 035271 A).

[0005] However, even when a silicon oxide underlayer is used, sufficient wear resistance is not always obtained. [Prior art documents] [Patent documents]

[0006] [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 Application 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] Patent No. 6569831 [Patent Document 15] Japanese Patent Application Laid-Open No. 2011-116947 [Patent Document 16] Japanese Patent Application Laid-Open No. 2007-197425 [Patent Document 17] Japanese Patent Application Laid-Open No. 2007-297589 [Patent Document 18] Japanese Patent Application Laid-Open No. 2007-297543 [Patent Document 19] Japanese Patent Application Laid-Open No. 2008-088412 [Patent Document 20] Japanese Patent Application Laid-Open No. 2008-144144 [Patent Document 21] Japanese Patent Application Laid-Open No. 2010-031184 [Patent Document 22] Japanese Patent Application Laid-Open No. 2010-047516 [Patent Document 23] Japanese Patent Application Laid-Open No. 2011-178835 [Patent Document 24] Japanese Patent Application Laid-Open No. 2014-084405 [Patent Document 25] Japanese Patent Application Laid-Open No. 2014-105235 [Patent Document 26] Japanese Patent Application Laid-Open No. 2013-253228 [Patent Document 27] Japanese Patent Application Laid-Open No. 2014-218639 [Patent Document 28] International Publication No. 2013 / 121984 [Patent Document 29] Japanese Patent Application Laid-Open No. 2007-11033 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an article having, on a plastic substrate, a water- and oil-repellent surface layer that is excellent in water- and oil-repellency, abrasion resistance, and slipperiness. [Means for solving the problem]

[0008] As a result of intensive research into achieving the above object, the inventors have found that in an article comprising a plastic substrate, a base layer composed mainly of silicon oxide formed on the outer surface of the plastic substrate, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, if the film density of the silicon oxide base layer is high, sufficient abrasion resistance may not be obtained. As a result of further investigation, it was found that in the above-mentioned article, the film density of the silicon oxide underlayer is 1.8 to 2.2 g / cm3 The present inventors have found that a water- and oil-repellent surface layer having excellent water- and oil-repellent properties, abrasion resistance, and slipperiness can be formed when the thickness of the silicon oxide underlayer is 80 to 300 nm, the water- and oil-repellent surface layer is composed mainly of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a cured product of a partial hydrolysis condensate thereof, and the fluoropolyether group-containing polymer having a hydrolyzable silyl group includes a fluoropolyether group-containing polymer having a specific structure described below, and have completed the present invention.

[0009] Therefore, the present invention provides an article having a water- and oil-repellent surface layer as follows: [1] An article comprising a plastic substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the plastic substrate, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, wherein the film density of the silicon oxide base layer is 1.8 to 2.2 g / cm 3 The thickness of the silicon oxide underlayer is 80 to 300 nm, and the water- and oil-repellent surface layer is mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a cured product of a partial hydrolysis condensate thereof, and the fluoropolyether group-containing polymer having a hydrolyzable silyl group comprises one or more fluoropolyether group-containing polymers represented by the following formula (1), (4) or (7): [ka] [Wherein 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 independently an integer of 0 to 5 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. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, and 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 trivalent to octavalent group, α is an integer of 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (wherein R is an alkyl group or a 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 bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.) [ka] [Wherein Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or G, and 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] (wherein 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.) [ka] [Wherein Rf is the same as above, A 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J has two or more Ws: [ka] [In the formula, S is the same as defined 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 of 1 to 3.) e is 1 or 2. [2] The article according to [1], wherein in the 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 an amide bond, an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group, a silphenylene bond, and a silalkylene bond, and Z is a trivalent to octavalent group selected from a silicon atom, a nitrogen atom, and a trivalent to octavalent organopolysiloxane residue having a siloxane bond. [3] The article according to [1], wherein in the formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group, a divalent siloxane bond, a silalkylene group, or a diorganosilylene group. [4] The water- and oil-repellent surface layer is formed by mixing one or more fluoropolyether group-containing polymers represented by the formula (1), (4) or (7) and / or partial hydrolysis condensates thereof with a fluoropolyether group-containing polymer represented by the formula (10) [ka] [Wherein 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 independently an integer of 0 to 5 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. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 4 are independently a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and which has a terminal CF3- or CF2H-; -OR 3 , -COOR 3 OR-PO(OR 3 )2(R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. The article according to any one of [1] to [3], which contains a fluoropolyether group-containing polymer represented by the following formula: and / or a cured product of the partial (hydrolyzed) condensate thereof. [5] The article according to any one of [1] to [4], wherein the water- and oil-repellent surface layer is formed by physical vapor deposition (PVD), spraying, or dipping. [6] The article according to any one of [1] to [5], wherein the plastic substrate has been pretreated by wet cleaning or plasma cleaning. [7] The article according to [1], which is an article whose primary component is silicon oxide constituting the underlayer, excluding those containing 50% by mass or more of silica nanoparticles. [8] The article according to [1], wherein the silicon oxide underlayer is formed by a reactive species-assisted CVD method, a sol-gel method using silicon alkoxide, or a method of converting polysilazane into silica glass by reacting it with water. [9] The article according to [1], wherein the plastic substrate is a plastic base material on which a functional layer is formed. [Effects of the Invention]

[0010] The article of the present invention, which is composed of a plastic substrate, a base layer of a specific film density and a specific film thickness formed on the outer surface of the plastic substrate and mainly composed of silicon oxide, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer and mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group of a specific structure and / or a cured product of a partial hydrolysis condensate thereof, has excellent water- and oil-repellency, abrasion resistance, and slip resistance. DETAILED DESCRIPTION OF THE INVENTION

[0011] The article of the present invention comprises a plastic substrate, a silicon oxide underlayer, and a water- and oil-repellent surface layer. In particular, the water- and oil-repellent surface layer is characterized by being formed on the outer surface of the underlayer, which is primarily composed of silicon oxide and formed on the plastic substrate, using a surface treatment agent containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group of a specific structure and / or a partial hydrolysis condensate thereof.

[0012] [Plastic substrate] Examples of plastics that can be used for the plastic substrate 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 triacetyl cellulose, 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 thermoplastic organic resins such as (meth)acrylic resins. The plastic substrate may be in the form of a plate, a film, or any other shape.

[0013] The plastic substrate that can be used in the present invention is not particularly limited, and the above-mentioned plastic plates and the like can be suitably used as the substrate, but these materials may be used as a base material on which a functional layer is formed. Examples of the functional layer include an anti-reflection layer and a hard coat layer.

[0014] The surface of the plastic substrate may be pretreated before forming the silicon oxide underlayer, which provides good adhesion between the plastic substrate and the silicon oxide underlayer, resulting in high abrasion resistance.

[0015] The method for pretreating a plastic substrate is not particularly limited as long as it can remove contaminants from the surface of the plastic substrate and hydrophilize the surface of the plastic substrate. For example, wet cleaning methods include neutral detergent cleaning treatment using dishwashing detergent, alcohol cleaning treatment using alcohols such as ethanol and 2-propanol, and alkaline cleaning treatment using alkaline cleaners. Other cleaning methods include plasma cleaning treatment using oxygen or argon plasma, and radical cleaning treatment using OH radicals. These methods may also be used in combination. Neutral detergent cleaning treatment or alkaline cleaning treatment is preferred, with plasma cleaning treatment using plasma and radical cleaning treatment using OH radicals being more preferred. It is even more preferred to perform a neutral detergent cleaning treatment or alkaline cleaning treatment followed by a plasma cleaning treatment using plasma or a radical cleaning treatment using OH radicals.

[0016] The effectiveness of the pretreatment of a plastic substrate can be confirmed by the degree of hydrophilicity of the surface of the plastic substrate. The hydrophilicity can be evaluated by the contact angle of water on the substrate, which is preferably 40 degrees or less, more preferably 20 degrees or less, and even more preferably 10 degrees or less. The contact angle of water is measured in accordance with JIS R 3257:1999.

[0017] [Silicon oxide underlayer] The silicon oxide underlayer is made of a silicon oxide film, and the silicon oxide film can be formed by either a dry coating method or a wet coating method. Dry coating methods include physical vapor deposition (PVD) and chemical vapor deposition (CVD). Wet coating methods include a method using silica nanoparticles, a sol-gel method using silicon alkoxide, and a method that converts polysilazane into silica glass by reacting with water.

[0018] The CVD method may be a thermal CVD method, a reactive species-assisted CVD method, a photo-CVD method, etc. From the viewpoint of suppressing an increase in the temperature of the plastic substrate, the reactive species-assisted CVD method is preferably used.

[0019] Reactive species-assisted CVD is a method in which a precursor is converted into silicon oxide by a chemical reaction of reactive species, which is then deposited on a plastic substrate. The reactive species can be ions, electrons, or radicals contained in oxygen-containing plasma, or OH radicals produced by ozone gas and unsaturated hydrocarbon gas (e.g., ethylene gas). For example, methods for forming silicon oxide films using CVD methods that utilize oxygen-containing plasma can be described in Patent Documents 9 and 10 (JP 2020-090652 A and Japanese Patent No. 5655215 A), and a method for forming silicon oxide films using CVD methods that utilize OH radicals can be described in Patent Document 14 (JP Patent No. 6569831 A).

[0020] The silicon oxide precursor may be a silicon compound, such as SiH, SiH, tetraethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane. Tetraethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane is preferred.

[0021] The CVD conditions for forming the silicon oxide film are appropriately set depending on the type of plastic substrate and precursor used. Since the density of the silicon oxide film varies depending on the temperature of the plastic substrate, the temperature of the plastic substrate is preferably 30°C or higher and lower than 150°C, more preferably 30 to 140°C, when SiH4 is used as the precursor. The temperature of the plastic substrate is preferably 30 to lower than 250°C, more preferably 30 to 150°C, when tetraethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane is used as the precursor. This prevents the silicon oxide from being closely packed during film formation, achieving the following film density:

[0022] As an example of a method using silica nanoparticles in the wet coating method, a method described in Patent Document 13 (WO 2019 / 035271) can be mentioned. In this method, the density of the formed film is approximately 2.0 g / cm. 3 It will be about that amount.

[0023] As the sol-gel method using silicon alkoxide in the wet coating method, for example, the method described in Patent Document 29 (JP-A No. 2007-11033) can be mentioned.

[0024] In the wet coating method using polysilazane, perhydropolysilazane can be applied as a precursor by spraying, brushing, spin coating, dip coating, or the like, and then left in an air atmosphere to convert it to silicon oxide. Examples of this method include the method described in Patent Document 10 (Japanese Patent No. 5655215). The ambient temperature during leaving is preferably 15 to 30°C, the humidity (relative humidity) is preferably 30 to 95% RH, and the leaving time is preferably about 12 to 36 hours.

[0025] The film density of the silicon oxide underlayer is 1.8 to 2.2 g / cm 3 and 1.80 to 2.20 g / cm 3 It is preferable that the density is 1.84 to 2.15 g / cm 3 It is more preferable that the film density of the silicon oxide underlayer is 1.8 g / cm. 3 If the density is less than 2.2 g / cm, the voids in the silicon oxide underlayer will increase, and although the increased surface area will improve the adhesion between the silicon oxide underlayer and the water- and oil-repellent surface layer, the strength of the silicon oxide underlayer itself will decrease. 3 If the density exceeds this range, the strength of the silicon oxide underlayer itself will be maintained, but the adhesion between the silicon oxide underlayer and the water- and oil-repellent surface layer will decrease. The film density of the silicon oxide underlayer can be measured by X-ray reflectometry (XRR). In the present invention, the silicon oxide film can be formed using the above-mentioned method and conditions, thereby making it possible to keep the film density of the silicon oxide underlayer within the above range.

[0026] The thickness of the silicon oxide underlayer is 80 to 300 nm, preferably 80 to 220 nm. If the thickness of the silicon oxide underlayer is less than 80 nm, good adhesion between the silicon oxide underlayer and the substrate may not be obtained, while if it exceeds 300 nm, poor adhesion with the water- 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 X-ray reflectometry (XRR).

[0027] The hydrogen concentration in the silicon oxide underlayer is preferably 2 at % or more and 8 at % or less, more preferably 4 at % or more and 7 at % or less. The hydrogen concentration in the silicon oxide film can be measured by Rutherford backscattering spectroscopy.

[0028] The surface of the silicon oxide underlayer may be pretreated before the formation of the water- and oil-repellent surface layer, which provides good adhesion between the silicon oxide underlayer and the water- and oil-repellent surface layer and high abrasion resistance.

[0029] The method for pretreating the silicon oxide underlayer is not particularly limited as long as it can remove contaminants from the surface of the silicon oxide underlayer. For example, plasma cleaning treatment using oxygen plasma or argon plasma, radical cleaning treatment using OH radicals, etc. are preferably used. When pretreating, plasma cleaning treatment is particularly preferred.

[0030] [Water- and oil-repellent surface layer] 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 is formed on a silicon oxide underlayer using a surface treatment agent containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a partial hydrolysis condensate thereof. Examples of the fluoropolyether group-containing polymer having a hydrolyzable silyl group include those disclosed in Japanese Patent Nos. 6260579, 6828744, 5761305, 6451279, 6741074, 6617853, JP 2011-116947, 2007-197425, 2007-297589, 2007-297543, and 2008-0 Compounds described in JP-A-88412, JP-A-2008-144144, JP-A-2010-031184, JP-A-2010-047516, JP-A-2011-178835, JP-A-2014-084405, JP-A-2014-105235, JP-A-2013-253228, JP-A-2014-218639, and WO 2013 / 121984 (Patent Documents 1 to 6, 15 to 28) can be used.

[0031] The fluoropolyether group-containing polymer having a hydrolyzable silyl group will now be described in more detail.

[0032] The fluoropolyether group-containing polymer having a hydrolyzable silyl group has a fluoropolyether group represented by the following formula (11) at at least one, preferably 1 to 3, terminals in the molecule: [ka] (In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, and a is 2 or 3.) and has at least two, preferably 2 to 3 (i.e., at least 2, preferably 2 to 9, more preferably 2 to 6 in the molecule) groups (hydrolyzable silyl groups) represented by -(C b F 2b O) mIt is preferable that the polyfluorooxyalkylene structure has the following formula: - (wherein b is independently an integer of 1 to 6 for each unit, and m is an integer of 1 to 250).

[0033] In the above formula (11), X's are hydrolyzable groups which may be different from one another. Examples of such X's 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 chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred.

[0034] In the above formula (11), R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group or an ethyl group being particularly preferred. In the above formula (11), a is 2 or 3, and 3 is preferred from the viewpoints of reactivity and adhesion to the substrate.

[0035] Examples of the group in the above formula (11) include the following. [ka]

[0036] Also, the above-(C b F 2b O) m In the polyfluorooxyalkylene structure represented by -, b is independently an integer of 1 to 6, preferably an integer of 1 to 4 for each unit, and m is an integer of 1 to 250, preferably an integer of 1 to 140.

[0037] Above-C bF 2b Examples of the repeating unit represented by O- include units represented by the following formulas. -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-, -C(CF3)2O- Among these, the repeating units represented by the following formula are particularly preferred. -CF2O-, -CF2CF2O-

[0038] The polyfluorooxyalkylene structure may be composed of one type of the repeating units or a combination of two or more types.

[0039] 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 formula (1), (4) or (7). It is particularly preferred 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] [Wherein 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 independently an integer of 0 to 5 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. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, and 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 trivalent to octavalent group, α is an integer of 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [ka] (wherein 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 bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.) [ka] [Wherein Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or G, and 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] (wherein 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.) [ka] [Wherein Rf is the same as above, A 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or J, where J is independently a monovalent group represented by the following formula (8), and J has two or more Ws: [ka] [In the formula, S is the same as defined 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 of 1 to 3.) e is 1 or 2.

[0040] First, the fluoropolyether group-containing polymer represented by the following formula (1) will be described. [ka]

[0041] In the above formula (1), 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- is a divalent polyfluorooxyalkylene structure (perfluoropolyether structure)-containing group represented by the formula: -, and d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0 or 1 for each unit. p, q, r, s, t, and u are each independently an integer of 0 to 150, preferably an integer of 0 to 100, and 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, and more preferably an integer of 7 to 70. Each of these units may be linear or branched. The repeating units shown in parentheses with p, q, r, s, t, and u may be randomly bonded.

[0042] The divalent polyfluorooxyalkylene structure-containing group of Rf can be specifically represented by the following structure. [ka] (In the formula, p', q', r', s', t', and u' each independently represent an integer of 1 to 150, the sum of p', q', r', s', t', and u' is 12 to 250, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly. d' is independently an integer of 0 to 5 for each unit. Each of these units may be linear or branched.)

[0043] The above formula (1); A 1 -Rf-D, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D (i.e., a group represented by the formula (2) described below; -QZ(W) α The monovalent fluorine-containing hydrocarbon group, which is a monovalent group represented by the formula (a monovalent group represented by the formula (a)), and which has a terminal of CF3- or CF2H- and may contain an oxygen atom, is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably one in which the terminal of the polymer is CF3- or CF2H-.

[0044] Such an A1 Examples of the monovalent fluorine-containing hydrocarbon group which has a terminal group of CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0045] The above formula (1); A 1 In —Rf-D, D is independently a monovalent group represented by the following formula (2). [ka]

[0046] In the above formula (2), 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 an amide bond (for example, an unsubstituted amide bond, an N-methyl-substituted amide bond, or an N-phenyl-substituted amide bond), an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group (for example, a dialkylsilylene group such as a dimethylsilylene group), a silarylene bond (for example, a silphenylene bond), and a silalkylene bond (for example, a silethylene bond), and is preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, which may contain the bond.

[0047] Here, examples of the silalkylene bond and silarylene bond include those shown below. [ka] (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group; R 1 may be the same or different. 2is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, or a propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.

[0048] Examples of Q other than a single bond include the following groups: In the following structure, it is preferred that the left bond is bonded to Rf and the right bond is bonded to Z. [ka] (In the formula, v is an integer of 2 to 4.)

[0049] The above formula (2);-QZ(W) α In the formula, Z is a trivalent to octavalent group, preferably a trivalent to octavalent, preferably tri- or tetravalent group selected from trivalent to octavalent organopolysiloxane residues having a silicon atom, a nitrogen atom, and a siloxane bond, preferably a linear, branched, or cyclic organopolysiloxane residue having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms. Also preferred are silalkylene structures such as a silethylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group, i.e., Si-(CH2) n It may contain —Si (in the above formula, n is an integer of 2 to 6, preferably an integer of 2 to 4).

[0050] Examples of the trivalent to octavalent organopolysiloxane residue having a siloxane bond include those shown below. [ka] (In the formula, R 1 is the same as above. g is an integer of 3 to 12, preferably 3 or 4, h is an integer of 3 to 8, preferably 3 or 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 13, preferably an integer of 3 to 5, and k is 2 or 3. [ka] [In the formula, R 4 are independently R1 Or the following formula (a) [ka] (In the formula, R 1 is the same as above, j1 is an integer of 1 to 6, preferably 1, and the bond on the left side is bonded to Si. is a group represented by R 5 are independently a single bond or the following formula (b): [ka] (In the formula, R 2 , R 4 is the same as above, j2 is an integer of 0 to 6, preferably an integer of 0 to 3, j3 is an integer of 0 to 6, preferably an integer of 0 to 2, and each repeating unit shown in parentheses may be bonded randomly. The bond on the left side bonds to Si. is a group represented by R 4 At least one of the formulas is (a).

[0051] Examples of such Z include the following: [ka] [ka] [ka] [ka]

[0052] The above formula (2);-QZ(W) α In the formula (3), 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 bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.)

[0053] In the above formula (3), R, X, and a are the same as R, X, and a in the above formula (11), and examples thereof include the same as R, X, and a in the above formula (11).

[0054] In the above formula (3), Y is a single bond or a divalent hydrocarbon group preferably having 1 to 20 carbon atoms, which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups), divalent groups in which alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.

[0055] Specific examples of Y other than a single bond include those shown below. [ka]

[0056] Examples of the group in the above formula (3) include the following. [ka]

[0057] The above formula (2);-QZ(W) α In the formula, α, which indicates the number of Ws, is an integer of 2 to 7.

[0058] The group in the above formula (2): -QZ(W) α (i.e., D in formula (1)) includes the following. [ka]

[0059] Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include those shown below. [ka] (In the formula, A 1 , Rf is the same as above.)

[0060] Next, the fluoropolyether group-containing polymer represented by the following formula (4) will be described. [ka] In the above formula (4), Rf is the same as above, and examples thereof include those similar to those exemplified as Rf in the above formula (1).

[0061] The above formula (4); A 2 -Rf-G, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or G (i.e., a monovalent group represented by formula (5); -C(B)(W)2 described below), and the monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably one in which the polymer terminal is CF3- or CF2H-.

[0062] Such an A 2 Examples of the monovalent fluorine-containing hydrocarbon group which has a terminal group of CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0063] The above formula (4); A 2 In —Rf-G, G is independently a monovalent group represented by the following formula (5). [ka] In the above formula (5), W is the same as above, and examples thereof include those similar to those exemplified for W in the above formula (2).

[0064] 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]

[0065] Here, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for 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, with alkyl groups having 1 to 3 carbon atoms and phenyl groups being preferred.

[0066] The above formula (6); -T-(LO) l In -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 which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond (e.g., a silethylene bond or a silpropylene bond), a silarylene bond (e.g., a silphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group, or a dialkoxysilylene group such as a dimethoxysilylene group), a divalent siloxane bond, a silalkylene group, or a diorganosilylene group; specific examples of T other than a single bond include those shown below. In the following structure, it is preferable that the right bond is bonded to L or E. [ka]

[0067] The above formula (6); -T-(LO) l In -E, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as an alkylene group, including a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group), etc., and the number of carbon atoms in each (LO) unit may be the same or may be mixed. The above formula (6); -T-(LO) l In -E, l is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6. When (LO) is present, l is preferably 1 or more, particularly preferably 2 or more. The above formula (6); -T-(LO) l In -E, E is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a phenyl group, or W, where W is the same as defined above and can be exemplified by the same groups as those exemplified for W in formula (2) above.

[0068] The above formula (6); -T-(LO) l Examples of the monovalent group represented by -E include those shown below. [ka]

[0069] Examples of the monovalent group represented by the above formula (5): -C(B)(W)2 (that is, G in formula (4)) include those shown below. [ka]

[0070] Examples of the fluoropolyether group-containing polymer represented by the above formula (4) include those shown below. [ka] (In the formula, A 2, Rf is the same as above.)

[0071] Next, the fluoropolyether group-containing polymer represented by the following formula (7) will be described. [ka] In the above formula (7), Rf is the same as above, and examples thereof include those similar to those exemplified as Rf in the above formula (1).

[0072] The above formula (7); A 3 -Rf-J, A 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or J (i.e., a group represented by the formula (8) below; -VC(=O)N(S) 2-e (M) e The monovalent fluorine-containing hydrocarbon group, which is a monovalent group represented by the formula (a monovalent group represented by the formula (a)), and which has a terminal of CF3- or CF2H- and may contain an oxygen atom, is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably one in which the terminal of the polymer is CF3- or CF2H-.

[0073] Such an A 3 Examples of the monovalent fluorine-containing hydrocarbon group which has a terminal group of CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0074] The above formula (7); A 3 In —Rf-J, J is independently a monovalent group represented by the following formula (8), and J has two or more Ws. [ka]

[0075] In the above formula (8), S is the same as above, and examples thereof include the same as those exemplified for S above.

[0076] 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, and specific examples of V other than a single bond include those shown below. In the following structure, it is preferable that the bond on the right side is bonded to a carbon atom (-C(=O)-). [ka] In the above formula (8), e is 1 or 2, and is preferably 1. In the above formula (8), M is independently a monovalent group represented by the following formula (9). [ka]

[0077] In the above formula (9), Y, S, and W are the same as above, and examples thereof include the same as those exemplified for Y in the above formula (3), S in the above formula, and W in the above formula (2). In the above formula (9), f is an integer of 1 to 3.

[0078] The above formula (9); -YC(S) 3-f (W) f Examples of the monovalent group represented by the formula (that is, M in formula (8)) include those shown below. [ka]

[0079] Above formula (8);-VC(=O)N(S) 2-e (M) e Examples of the monovalent group represented by the formula include those shown below. [ka] [ka]

[0080] Examples of the fluoropolyether group-containing polymer represented by the above formula (7) include those shown below. [ka] [ka] (In the formula, A 3 , Rf is the same as above.)

[0081] In the article of the present invention, the surface treatment agent containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a partial hydrolyzed condensate thereof for forming the water- and oil-repellent surface layer may be a mixture (i.e., a fluoropolyether group-containing polymer composition) containing, in addition to the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or the partial hydrolyzed condensate of the polymer, a fluoropolyether group-containing polymer not containing a hydrolyzable silyl group represented by the following formula (10) (hereinafter referred to as a polymer not containing a hydrolyzable silyl group) and / or its partial (hydrolyzed) condensate. In the present invention, the "partial (hydrolyzed) condensate" refers to a partial condensate or a partial hydrolyzed condensate. [ka] [In the formula, Rf is the same as above, and examples thereof include those exemplified as Rf in formula (1) above. A 4 are independently a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and which has a terminal CF3- or CF2H-; -OR 3 , -COOR 3 OR-PO(OR 3 )2(R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0082] In the above formula (10), A 4 are independently a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and which has a terminal CF3- or CF2H-; -OR 3 , -COOR 3OR-PO(OR 3 )2, and the monovalent fluorine-containing hydrocarbon group having a terminal of CF3- or CF2H- and optionally containing an oxygen atom includes A 1 The terminal of the fluorine-containing hydrocarbon group is CF3- or CF2H- and may contain an oxygen atom, and examples thereof include the same as those given as examples of the fluorine-containing monovalent hydrocarbon group. where R 3 is 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, 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. R 3 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. A 4 -OR 3 , -COOR 3 , -PO(OR 3 )2 includes, for example, -OH, -OCH3, -COOH, -COOCH3, -PO(OH)2, -OC2H5, and -COOC2H5.

[0083] Examples of the fluoropolyether group-containing polymer represented by the above formula (10) include the following. [ka] (In the formula, p", q", r", s", t", and u" each independently represent an integer of 0 to 150, the sum of p", q", r", s", t", and u" is 12 to 250, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p", q", r", s", t", and u" may be bonded randomly.)

[0084] In the article of the present invention, the surface treatment agent used to form the water- and oil-repellent surface layer contains at least one fluoropolyether group-containing polymer having at least two hydrolyzable silyl groups at one end of the molecular chain, as represented by the above formula (1), (4), or (7), and / or a partial hydrolyzed condensate of such a polymer (single-end polymer), or at least one fluoropolyether group-containing polymer having at least two hydrolyzable silyl groups at each end of the molecular chain, as represented by the above formula (1), (4), or (7), and / or a partial hydrolyzed condensate of such a polymer (double-end polymer), or contains a mixture containing at least one such single-end polymer and at least one such double-end polymer, or contains a mixture of any of these, further containing a polymer that does not contain a hydrolyzable silyl group (fluoropolyether group-containing polymer composition).

[0085] In the fluoropolyether group-containing polymer mixture (fluoropolyether group-containing polymer composition) contained in the surface treatment agent, the mixing ratio of the one-terminated polymer and / or both-terminated polymer to the polymer not containing a hydrolyzable silyl group is not particularly limited, but it is usually desirable that the ratio of the polymer not containing a hydrolyzable silyl group is 0.01 to 30 mol %, particularly 0.1 to 10 mol %, relative to the entire fluoropolyether group-containing polymer composition consisting of the one-terminated polymer and / or both-terminated polymer and the polymer not containing a hydrolyzable silyl group.

[0086] In the surface treatment agent, the number average molecular weight of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolysis condensate, or the fluoropolyether group-containing polymer composition is preferably in the range of 1,000 to 20,000. The number average molecular weight is more preferably 2,000 to 10,000, and particularly preferably 3,000 to 8,000. The number average molecular weight is 19 It can be calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0087] The fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolyzed condensate, or the fluoropolyether group-containing polymer composition, having a number average molecular weight within the above range, can be obtained by rectifying or molecular distilling the fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolyzed condensate, or the fluoropolyether group-containing polymer composition. In addition, the fluoropolyether group-containing polymer and / or its partial hydrolysis condensate having a hydrolyzable silyl group, or the fluoropolyether group-containing polymer composition, having a number average molecular weight within the above range can also be prepared by adjusting the fluorine compound used in synthesizing the fluoropolyether group-containing polymer to have the above number average molecular weight in advance.

[0088] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolysis condensate.

[0089] The surface treatment agent may contain a solvent, preferably a fluorine-modified aliphatic hydrocarbon solvent (e.g., perfluoroheptane, perfluorooctane), a fluorine-modified olefin solvent (e.g., methoxyperfluoroheptene), a fluorine-modified aromatic hydrocarbon solvent (e.g., m-xylene hexafluoride, benzotrifluoride, 1,3-trifluoromethylbenzene), a fluorine-modified ether solvent (e.g., methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran)), a fluorine-modified alkylamine solvent (e.g., perfluorotributylamine, perfluorotripentylamine), a hydrocarbon solvent (e.g., petroleum benzine, mineral spirits, toluene, xylene), or a ketone solvent (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone). Among these, fluorine-modified solvents (referred to as fluorine-based solvents) are desirable in terms of solubility, wettability, etc., and 1,3-trifluoromethylbenzene, m-xylene hexafluoride, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.

[0090] Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolysis condensate, or the fluoropolyether group-containing polymer composition. The optimal concentration of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or its partial hydrolysis condensate to be dissolved in the solvent is not limited and may be appropriately selected depending on the method of use of the surface treatment agent. The concentration is usually 0.01 to 30 mass%, preferably 0.02 to 25 mass%, and more preferably 0.05 to 20 mass%.

[0091] The water- and oil-repellent surface layer can be formed using a surface treatment agent by known methods such as brushing, dipping, spraying, and vapor deposition (physical vapor deposition (PVD) method). Of these, physical vapor deposition (PVD), spraying, and dipping are preferred. The heating method used during vapor deposition in the physical vapor deposition (PVD) method may be either resistance heating or electron beam heating, and is not particularly limited.

[0092] After the water- and oil-repellent surface layer is formed, it is preferable to carry out a curing treatment. This curing treatment involves exposing the surface to an environment at a temperature of 20 to 200°C and a relative humidity of 95% or less for 0.5 hours or more, and the conditions are set appropriately depending on the method for forming the water- and oil-repellent surface layer. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to expose the surface to a temperature of 60 to 150°C and a relative humidity of 85% or less for 30 minutes to 24 hours, and in the case of vapor deposition coating, it is preferable to expose the surface to a temperature of 25 to 150°C and a relative humidity of 85% or less for 30 minutes to 24 hours.

[0093] The thickness of the water- and oil-repellent surface layer is usually 0.1 to 100 nm, preferably 1 to 20 nm. The thickness of the water- and oil-repellent surface layer can be measured by the above-mentioned XRR or spectroscopic ellipsometry. [Example]

[0094] 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 is a value calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0095] [Comparative Example 1] [Cleaning of plastic substrates] A silicone hard-coated polycarbonate (HC / PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD manufactured by Sabic) was cleaned using neutral dish detergent and an acrylic sponge. It was then rinsed thoroughly with ion-exchanged water, and the water on the plastic substrate was blown off with compressed air to dry it.

[0096] [Plasma cleaning of plastic substrates] The HC / PC substrate surface that had been cleaned as described above was treated with oxygen-argon mixed plasma under the following treatment conditions. Processing device: PDC510 (Yamato Scientific) Oxygen gas flow rate: 10sccm (Standard Cubic Centimeters) Argon gas flow rate: 100sccm Processing pressure: 60Pa RF supply power: 250W Processing time: 30 seconds

[0097] [Formation of silicon oxide underlayer by CVD method using OH radicals] A silicon oxide underlayer was formed on the HC / PC substrate using the CVD method described in Japanese Patent No. 6569831 (Patent Document 14). The film thickness was 5 nm and the film density was 2.0 g / cm under the following processing conditions: 3 A silicon oxide underlayer was formed. Precursor material: tetraethoxysilane Base material temperature: 30℃ Processing gas (flow rate): Ozone gas (150sccm) Ethylene gas (50sccm) Tetraethoxysilane (1sccm) Nitrogen gas (15sccm)

[0098] The thickness and density of the silicon oxide underlayer were obtained by X-ray reflectivity measurement. That is, the measured profile was subjected to simulation fitting to determine the thickness and density. The measurement conditions are as follows: Measurement device: SmartLab (Rigaku) X-ray source: Rotating anode (Cu), output 45kV, 200mA Incident optics: Ge(111) asymmetric beam compression crystal Receiving side solar slit: 5.0° Slit: Incident side IS=0.05mm Light receiving side RS1=0.1mm, RS2=0.1mm Scanning conditions: Scanning axis 2θ / ω Scanning speed 0.2° / min Step width 0.002°

[0099] [Formation of a water- and oil-repellent surface layer by physical vapor deposition (PVD)] The HC / PC substrate with the silicon oxide underlayer was set in a resistance heating vacuum deposition device (VTR-350M, manufactured by ULVAC Kiko Co., Ltd.), 5 μL of the following surface treatment agent was dropped onto the resistance heating part, and the pressure inside the container was reduced to 3 × 10 -3 Once the pressure was reduced to below 1 Pa, resistance heating was initiated. The power input to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal film thickness meter installed approximately 20 cm away from the resistance heating unit was 1.0 nm / sec. Resistance heating was continued for 100 seconds after the evaporation rate measured by the quartz crystal film thickness meter had decreased to 0.1 nm / sec. After waiting 5 minutes to allow the device to cool, it was opened to the atmosphere, yielding an HC / PC substrate coated with a fluoropolyether group-containing polymer. The HC / PC substrate coated with the above-mentioned fluoropolyether group-containing polymer was left for 24 hours in an environment of 25°C and 50% relative humidity, allowing the water- and oil-repellent surface layer to harden and fix, yielding an HC / PC substrate with a 10 nm thick water- and oil-repellent surface layer made of the fluoropolyether group-containing polymer. The thickness of the water- and oil-repellent surface layer was calculated by quantifying the intensity of fluorescent X-rays derived from elemental fluorine using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, trade name: fluorescent X-ray analyzer Primini) and using a calibration curve.

[0100] [Preparation of Surface Treatment Agent] Compound (A) represented by the following formula (number average molecular weight: 4,000) was dissolved in a fluorine-based solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 20% by mass to prepare a surface treatment agent. [ka] (p / q=1.0, p+q=46)

[0101] [Example 1] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that the film-forming time was adjusted so that the silicon oxide underlayer had a thickness of 100 nm.

[0102] [Example 2] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that the film-forming time was adjusted so that the silicon oxide underlayer had a thickness of 200 nm.

[0103] [Example 3] The conditions for forming the silicon oxide underlayer were changed as follows: the thickness of the silicon oxide underlayer was 200 nm, and the film density was 2.2 g / cm 3 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that: Precursor material: hexamethyldisilazane Base material temperature: 150℃ Processing gas (flow rate): Ozone gas (200sccm) Ethylene gas (20sccm) Hexamethyldisilazane (5sccm) Nitrogen gas (15sccm)

[0104] Comparative Example 2 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a silicon oxide underlayer was formed by the following method. [Formation of a silicon oxide underlayer using silica nanoparticles] An HC / PC substrate that had been cleaned and plasma cleaned in the same manner as in Comparative Example 1 was dip-coated with an aqueous dispersion of silica nanoparticles to form a film with a thickness of 4 nm and a film density of 2.0 g / cm. 3 The silicon oxide underlayer was formed under the following conditions. Silica nanoparticle average particle size: 2nm Silica nanoparticle concentration: 0.1% by mass Immersion time: 30 seconds Pulling speed: 3.0 mm / sec Drying conditions: 150°C, 30 minutes

[0105] Comparative Example 3 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 2, except that the thickness of the silicon oxide underlayer was set to 10 nm under the following immersion conditions. Silica nanoparticle average particle size: 2nm Silica nanoparticle concentration: 0.1% by mass Immersion time: 30 seconds Pulling speed: 0.5 mm / sec Drying conditions: 150°C, 30 minutes

[0106] Comparative Example 4 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a silicon oxide underlayer was formed by the following method. [Formation of Silicon Oxide Underlayer Using Polysilazane] A perhydropolysilazane solution (Aquamica NP-140-01 manufactured by AZ Electronic Materials Co., Ltd.) was spray-coated on an HC / PC substrate that had been cleaned and plasma-cleaned in the same manner as in Comparative Example 1, and the solution was left to stand for 24 hours in an air atmosphere at 25°C and a relative humidity of 85% to cure, resulting in a film thickness of 10 nm and a film density of 2.0 g / cm. 3 A silicon oxide underlayer was formed.

[0107] Comparative Example 5 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Comparative Example 4, except that the silicon oxide undercoat layer was cured by leaving it in an atmospheric atmosphere at 25°C and a relative humidity of 40% for 24 hours.

[0108] [Example 4] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0109] Comparative Example 6 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Comparative Example 4, except that the silicon oxide undercoat layer was cured by leaving it in an atmospheric atmosphere at 25°C and a relative humidity of 5% for 24 hours.

[0110] Comparative Example 7 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 6, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0111] [Comparative Example 8] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer by physical vapor deposition (PVD)] The HC / PC substrate was subjected to cleaning and plasma cleaning in the same manner as in Comparative Example 1, and silicon oxide was deposited by electron beam evaporation to a film thickness of 5 nm and a film density of 2.3 g / cm. 3 The silicon oxide underlayer was formed under the following conditions. Vapor deposition source: SiO2 granules (2mm) Ultimate pressure: 1×10 -3 Pa Deposition rate: 1 nm / sec

[0112] Comparative Example 9 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 8, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0113] [Comparative Example 10] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 8, except that the thickness of the silicon oxide underlayer was changed to 200 nm.

[0114] [Comparative Example 11] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer using plasma CVD method] A silicon oxide underlayer was formed by plasma CVD on an HC / PC substrate that had been cleaned and plasma cleaned in the same manner as in Comparative Example 1. Under the following processing conditions, a silicon oxide underlayer was formed with a film thickness of 10 nm and a film density of 2.4 g / cm. 3 A silicon oxide underlayer was formed. Precursor material: SiH4 Base material temperature: 150℃ RF plasma source power supply: 300W Processing pressure: 150Pa Processing gas (flow ratio): SiH4:N2O:H2 = 1:30:180

[0115] [Comparative Example 12] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 11, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0116] [Comparative Example 13] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 11, except that the thickness of the silicon oxide underlayer was changed to 200 nm.

[0117] [Comparative Example 14] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a surface treatment agent prepared by dissolving compound (B) (number-average molecular weight 4,000) represented by the following formula in a fluorine-based solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 20 mass % was used. [ka] (p / q=1.0, p+q=42)

[0118] [Example 5] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 2, except that the surface treatment agent of the above compound (B) was used.

[0119] [Example 6] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 3, except that the surface treatment agent of the above compound (B) was used.

[0120] [Example 7] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 4, except that the surface treatment agent of the above compound (B) was used.

[0121] [Comparative Example 15] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 7, except that the surface treatment agent of the above compound (B) was used.

[0122] [Comparative Example 16] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 10, except that the surface treatment agent of the above compound (B) was used.

[0123] [Comparative Example 17] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a surface treatment agent prepared by dissolving compound (C) (number-average molecular weight 4,000) represented by the following formula in a fluorine-based solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 20 mass % was used. [ka] (p / q=1.0, p+q=42)

[0124] [Example 8] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 2, except that the surface treatment agent of the above compound (C) was used.

[0125] [Example 9] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 3, except that the surface treatment agent of the above compound (C) was used.

[0126] [Example 10] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 4, except that the surface treatment agent of the above compound (C) was used.

[0127] [Comparative Example 18] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 7, except that the surface treatment agent of the above compound (C) was used.

[0128] Comparative Example 19 A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 10, except that the surface treatment agent of the above compound (C) was used.

[0129] [Comparative Example 20] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a hard-coated polyimide film (100 mm x 50 mm x 0.1 mm (thickness)) was used as the plastic substrate.

[0130] [Example 11] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that the film-forming time was adjusted so that the silicon oxide underlayer had a thickness of 100 nm.

[0131] [Example 12] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that the film-forming time was adjusted so that the thickness of the silicon oxide underlayer became 200 nm.

[0132] [Example 13] The conditions for forming the silicon oxide underlayer were changed as follows: the thickness of the silicon oxide underlayer was 200 nm, and the film density was 2.2 g / cm 3A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that: Precursor material: hexamethyldisilazane Base material temperature: 150℃ Processing gas (flow rate): Ozone gas (200sccm) Ethylene gas (20sccm) Hexamethyldisilazane (5sccm) Nitrogen gas (15sccm)

[0133] [Comparative Example 21] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that a silicon oxide underlayer was formed by the following method. [Formation of Silicon Oxide Underlayer Using Polysilazane] A perhydropolysilazane solution (Aquamica NP-140-01 manufactured by AZ Electronic Materials Co., Ltd.) was spray-coated on an HC / PI substrate that had been cleaned and plasma-cleaned in the same manner as in Comparative Example 20, and the solution was left to stand for 24 hours in an air atmosphere at 25°C and a relative humidity of 40% to cure, resulting in a film thickness of 10 nm and a film density of 1.8 g / cm. 3 A silicon oxide underlayer was formed.

[0134] [Example 14] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 21, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0135] [Comparative Example 22] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained using the same procedure as in Comparative Example 21, except that the silicon oxide undercoat layer was cured by leaving it for 24 hours in an atmospheric atmosphere at 25°C and a relative humidity of 5%.

[0136] [Comparative Example 23] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 22, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0137] [Comparative Example 24] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer by physical vapor deposition (PVD)] The HC / PI substrate was subjected to cleaning and plasma cleaning in the same manner as in Comparative Example 20, and silicon oxide was deposited by electron beam evaporation to a film thickness of 5 nm and a film density of 2.3 g / cm. 3 The silicon oxide underlayer was formed under the following conditions. Vapor deposition source: SiO2 granules (2mm) Ultimate pressure: 1×10 -3 Pa Deposition rate: 1 nm / sec

[0138] [Comparative Example 25] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 24, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0139] [Comparative Example 26] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer using plasma CVD method] A silicon oxide underlayer was formed by plasma CVD on an HC / PI substrate that had been cleaned and plasma cleaned in the same manner as in Comparative Example 20. The thickness was 10 nm and the density was 2.4 g / cm under the following processing conditions. 3 A silicon oxide underlayer was formed. Precursor material: SiH4 Base material temperature: 150℃ RF plasma source power supply: 300W Processing pressure: 150Pa Processing gas (flow ratio): SiH4:N2O:H2 = 1:30:180

[0140] [Comparative Example 27] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 26, except that the thickness of the silicon oxide underlayer was changed to 100 nm.

[0141] [Comparative Example 28] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that the surface treatment agent of the above compound (B) was used.

[0142] [Example 15] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 11, except that the surface treatment agent of the above compound (B) was used.

[0143] [Example 16] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 12, except that the surface treatment agent of the above compound (B) was used.

[0144] [Example 17] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 14, except that the surface treatment agent of the above compound (B) was used.

[0145] [Comparative Example 29] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 23, except that the surface treatment agent of the above compound (B) was used.

[0146] [Comparative Example 30] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 25, except that the surface treatment agent of the above compound (B) was used.

[0147] [Comparative Example 31] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 20, except that the surface treatment agent of the above compound (C) was used.

[0148] [Example 18] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 11, except that the surface treatment agent of the above compound (C) was used.

[0149] [Example 19] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 12, except that the above-mentioned compound (C) was used as the surface treatment agent.

[0150] [Example 20] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 14, except that the surface treatment agent of the above compound (C) was used.

[0151] [Comparative Example 32] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 23, except that the surface treatment agent of the above compound (C) was used.

[0152] [Comparative Example 33] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 25, except that the surface treatment agent of the above compound (C) was used.

[0153] Initial water repellency evaluation For the substrates having the silicon oxide underlayer and the water- and oil-repellent surface layer prepared above, the contact angle (water repellency) of the water- and oil-repellent surface layer was measured using a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). Water contact angles of 112° or more were rated as ◎ (excellent), 108° or more but less than 112° as ○ (good), 100° or more but less than 108° as △ (passable), and less than 100° as × (unacceptable), and the results are shown in Tables 1 and 2. In both the examples and comparative examples, the initial water contact angle was 112 degrees or more, indicating good water repellency.

[0154] Evaluation of slipperiness The coefficient of dynamic friction of the substrate having the silicon oxide underlayer and the water- and oil-repellent surface layer prepared above was measured using a surface property measuring instrument (TYPE14FW, manufactured by Shinto Scientific Co., Ltd.). The friction material was a nonwoven fabric (BEMCOT M-3II, manufactured by Asahi Kasei Co., Ltd.), and the load was 100 gf / cm. 2 The rubbing speed was 500 mm / min. The indices for evaluating slip resistance are shown in Tables 1 and 2: Excellent (◎) for a dynamic friction coefficient of less than 0.05, Good (○) for 0.05 or more but less than 0.1, Fair (△) for 0.1 or more but less than 0.2, and Poor (×) for 0.2 or more. The test environmental conditions were 25°C and a relative humidity of 40%. The dynamic friction coefficients of Examples 1 to 7, 11 to 17 and Comparative Examples 1 to 16, and 20 to 30 were less than 0.05, and showed good sliding properties.

[0155] Wear resistance evaluation [Friction and wear test using nonwoven fabric] The HC / PC substrate having the silicon oxide underlayer and the water- and oil-repellent surface layer prepared above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Scientific). Rubbing material: Nonwoven fabric (Bencotto M-3II, manufactured by Asahi Kasei) Load: 1kgf Round trip distance: 40mm Reciprocating speed: 60 reciprocations per minute Total number of friction cycles: 3,000 The water contact angle of the friction-wear area was measured every 500 reciprocating friction cycles. The number of reciprocating friction cycles at which a water contact angle of 100 degrees or more was maintained was taken as the nonwoven fabric abrasion durability cycle, with a nonwoven fabric abrasion durability cycle of 3,000 or more cycles being rated as ◎ (excellent), 2,000 to less than 3,000 cycles being ○ (good), 1,000 to less than 2,000 cycles being △ (passable), and less than 1,000 cycles being × (unacceptable), as shown in Table 1. The test environmental conditions were 25°C and a relative humidity of 40%.

[0156] [Eraser friction and wear test] The HC / PI substrate having the silicon oxide underlayer and the water- and oil-repellent surface layer prepared above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Scientific). Scraping material: eraser (Minoan, 6mm diameter) Load: 1kgf Round trip distance: 40mm Reciprocating speed: 40 reciprocations per minute Total number of friction cycles: 1,000 The water contact angle of the worn area was measured every 100 reciprocating friction cycles. The number of reciprocating friction cycles at which a water contact angle of 100 degrees or more was maintained was taken as the eraser abrasion durability cycle, with eraser abrasion durability of 1,000 or more cycles being rated as ◎ (excellent), 500 to less than 1,000 cycles being ○ (good), 200 to less than 500 cycles being △ (passable), and less than 200 cycles being × (unacceptable), as shown in Table 2. The test environmental conditions were 25°C and a relative humidity of 40%.

[0157] [Table 1]

[0158] [Table 2]

Claims

1. An article comprising a plastic substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the plastic substrate, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, wherein the film density of the silicon oxide base layer is 1.8 to 2.2 g / cm 3 The article has a silicon oxide underlayer having a thickness of 80 to 300 nm, and a water- and oil-repellent surface layer mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and / or a cured product of a partial hydrolysis condensate thereof, wherein the fluoropolyether group-containing polymer having a hydrolyzable silyl group comprises one or more fluoropolyether group-containing polymers represented by the following formula (1), (4) or (7): 【Chemical 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 -(wherein d is independently an integer of 0 to 5 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. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 ends in CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom, or D, where 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 trivalent to octavalent group, α is an integer of 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3): 【Chemistry 3】 (wherein R is an alkyl group or a 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 bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.) 【Chemistry 4】 [wherein Rf is the same as above, A 2 ends in CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H— and which may contain an oxygen atom, or G, where G is independently a monovalent group represented by the following formula (5): 【Chemistry 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): 【Chemistry 6】 (wherein 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.) 【Chemistry 7】 [wherein Rf is the same as above, A 3 ends in CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which 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 has two or more Ws: 【Chemistry 8】 [In the formula, S is the same as defined 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】 (wherein Y, S, and W are the same as above, and f is an integer of 1 to 3.) e is 1 or 2.

2. The article according to claim 1, 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 an amide bond, an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group, a silphenylene bond, and a silalkylene bond, and Z is a trivalent to octavalent group selected from a silicon atom, a nitrogen atom, and a trivalent to octavalent organopolysiloxane residue having a siloxane bond.

3. The article according to claim 1, wherein in formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group, a divalent siloxane bond, a silalkylene group, or a diorganosilylene group.

4. The water- and oil-repellent surface layer is formed by mixing one or more fluoropolyether group-containing polymers represented by the formula (1), (4) or (7) and / or partial hydrolysis condensates thereof with a polymer represented by the following formula (10): 【Chemistry 10】 [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 -(wherein d is independently an integer of 0 to 5 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. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 4 are independently terminated with CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H— and which may contain an oxygen atom, —OR 3 , -COOR 3 Or -PO(OR 3 ) 2 (R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

4. The article according to claim 1, which contains a cured product of a fluoropolyether group-containing polymer represented by the formula: and / or a partial (hydrolyzed) condensate thereof.

5. 5. The article according to claim 1, wherein the water- and oil-repellent surface layer is formed by a physical vapor deposition (PVD) method, a spray method, or a dipping method.

6. 6. The article according to any one of claims 1 to 5, wherein the plastic substrate is pretreated by wet cleaning and / or plasma cleaning.

7. An article as described in claim 1, which is an article whose main component is silicon oxide constituting the base layer, excluding those containing 50 mass% or more of silica nanoparticles.

8. The article according to claim 1, wherein the silicon oxide underlayer is formed by a reactive species-assisted CVD method, a sol-gel method using silicon alkoxide, or a silica glass conversion method by reacting polysilazane with water.

9. An article as described in claim 1, wherein the plastic substrate is a plastic base material on which a functional layer is formed.

Images