Method for improving the wear resistance of a water-repellent and oil-repellent surface layer in articles having a water-repellent and oil-repellent surface layer.

Abstract

This invention provides a method for improving the abrasion resistance (eraser abrasion resistance) of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer on a glass substrate. [Solution] An article comprising a glass substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the glass substrate, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, wherein the water-repellent and oil-repellent surface layer mainly consists of a fluoropolyether group-containing polymer having hydrolyzable silyl groups of a specific structure and / or a cured product of a partially hydrolyzed condensate thereof, wherein the film density of the silicon oxide base layer is 1.8 to 2.2 g / cm³ 3 Let's assume that.

Description

[Technical Field]

[0001] The present invention relates to a method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer with excellent water-repellent and oil-repellent properties and slipperiness on a glass substrate. [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 (a thin film of anti-fouling coating) on ​​the surface of the substrate, adding the ability to prevent oily stains, fingerprints, and other types of dirt to the substrate. In other words, this fluoropolyether group-containing polymer is used to form a thin film of anti-fouling coating on the surface of a touch panel display of a portable electronic device or on the surface of the device's casing (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).

[0003] Furthermore, in addition to preventing dirt buildup, the anti-fouling coating thin film layer on the surface of touch panel displays has also been valued for its user-friendliness during touch panel use (good glide and smooth tactile feel). Good user-friendliness is related to a low coefficient of friction (Patent Document 4: Japanese Patent No. 6451279).

[0004] 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, 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).

[0005] However, even with a silicon dioxide underlayer, sufficient abrasion resistance was sometimes not achieved. [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 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 Publication No. 2011-116947 [Patent Document 16] Japanese Patent Publication No. 2007-197425 [Patent Document 17] Japanese Patent Publication No. 2007-297589 [Patent Document 18] Japanese Patent Publication No. 2007-297543 [Patent Document 19] Japanese Patent Publication No. 2008-088412 [Patent Document 20] Japanese Patent Publication No. 2008-144144 [Patent Document 21] Japanese Patent Publication No. 2010-031184 [Patent Document 22] Japanese Patent Publication No. 2010-047516 [Patent Document 23] Japanese Patent Publication No. 2011-178835 [Patent Document 24] Japanese Patent Publication No. 2014-084405 [Patent Document 25] Japanese Patent Publication No. 2014-105235 [Patent Document 26] Japanese Patent Publication No. 2013-253228 [Patent Document 27] Japanese Patent Publication No. 2014-218639 [Patent Document 28] International Publication No. 2013 / 121984 [Patent Document 29] Japanese Patent Publication No. 2007-11033 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention has been made in view of the above circumstances, and aims to provide a method for improving the abrasion durability of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer with excellent water-repellent and oil-repellent properties and slipperiness on a glass substrate. [Means for solving the problem]

[0008] As a result of diligent research to solve the above objective, the present inventors have found that in an article composed of a glass substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the glass substrate, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, sufficient abrasion resistance may not be obtained if the film density of the silicon oxide base layer is high. As a result of further investigations, in the above-mentioned article, when the film density of the silicon oxide base layer is 1.8 to 2.2 g / cm 3 and 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 its partial hydrolysis condensate, and the fluoropolyether group-containing polymer having a hydrolyzable silyl group contains a fluoropolyether group-containing polymer having a specific structure described later, it has been found that a water and oil repellent surface layer excellent in water and oil repellency, wear durability, and slipperiness can be formed, and the present invention has been accomplished.

[0009] Therefore, the present invention provides a method for improving the wear durability of a water and oil repellent surface layer in an article having the following water and oil repellent surface layer. 1. An article comprising a glass substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the glass substrate, and a water and oil repellent surface layer formed on the outer surface of the silicon oxide base layer, 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 its partial hydrolysis condensate, 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): The film density of the silicon oxide base layer is 1.8 to 2.2 g / cm 3 A method for improving the wear durability of a water and oil repellent surface layer in an article having a water and oil repellent surface layer, characterized in that the film density is set to 1.8 to 2.2 g / cm. [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-(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 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. [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 formulas, Y, S, and W are the same as above, and f is an integer from 1 to 3 (however, if e=1 in formula (8) and S does not contain W in formulas (8) and (9), then f is 2 or 3).) e is either 1 or 2. 2. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer as described in 1, wherein the silicon oxide underlayer is formed by physical vapor deposition (PVD) or chemical vapor deposition (CVD). 3. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer as described in 1, wherein the silicon oxide underlayer is formed by a method using silica nanoparticles, a sol-gel method using silicon alkoxide, or by silica glass conversion by reaction of polysilazane with water. 4. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein the film thickness of the silicon oxide underlayer is 3 to 300 nm. 5. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein the thickness of the water-repellent and oil-repellent surface layer is 0.1 to 100 nm. 6. A method for improving the abrasion resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, 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 silicon atom, a nitrogen atom, and a 3 to 8 valent organopolysiloxane residue having a siloxane bond. 7. A method for improving the wear durability of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein in formula (6) above, T is 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 silicon atom, a siloxane bond, a sylalkylene bond, a sylarylene bond, and a diorganosilylene group. 8. 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 improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein the article contains a cured product of a fluoropolyether group-containing polymer and / or a partial (hydrolysis) condensate thereof. 9. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein the water-repellent and oil-repellent surface layer is formed by physical vapor deposition (PVD), spraying, or immersion. 10. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of 1 to 3, wherein the glass substrate has been pre-treated by alkaline cleaning or plasma cleaning. [Effects of the Invention]

[0010] The article comprising a glass substrate, a base layer with a specific film density mainly composed of silicon oxide formed on the outer surface of the glass substrate, and a water-repellent and oil-repellent surface layer mainly composed of a cured product of a fluoropolyether group-containing polymer having hydrolyzable silyl groups of a specific structure and / or a partially hydrolyzed condensate thereof, formed on the outer surface of the silicon oxide base layer, exhibits excellent water-repellency, oil-repellency, abrasion resistance, and slipperiness. [Modes for carrying out the invention]

[0011] The article of the present invention is composed of a glass substrate, a silicon oxide underlayer, and a water-repellent and oil-repellent surface layer. In particular, the water-repellent and oil-repellent surface layer is characterized in that it is formed on the outer surface of the underlayer, which is mainly composed of silicon oxide and formed on the glass substrate, by 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.

[0012] [Glass substrate] Examples of glass used as a glass substrate include, but are not limited to, soda-lime glass, crown glass, lead glass, borosilicate glass, crystallized glass, quartz glass, aluminosilicate glass, Tempax, Pyrex (registered trademark), and Neoceram. The glass may also be chemically or physically strengthened. The glass substrate may be in the shape of a plate, film, or other form.

[0013] The glass substrate that can be used in the present invention is not particularly limited, and the glass plates and the like described above can be suitably used as the substrate, but it may also be a material on which a functional layer is formed. Examples of functional layers include anti-reflective layers and hard coat layers.

[0014] The glass substrate surface may be pre-treated before the formation of the silicon oxide underlayer. Pre-treatment ensures good adhesion between the glass substrate and the silicon oxide underlayer, resulting in high abrasion resistance.

[0015] The pretreatment method for the glass substrate is not particularly limited as long as it removes contaminants from the surface of the glass substrate and makes the 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.

[0016] The effect of pretreatment of the glass substrate is confirmed by the degree of hydrophilicity of the glass substrate surface. 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 water contact angle is measured in accordance with JIS R 3257:1999.

[0017] [Silicon oxide underlayer] The silicon oxide underlayer consists of a silicon oxide film, and dry or wet coating methods can be used to form this film. Dry coating methods include physical vapor deposition (PVD) and chemical vapor deposition (CVD). 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.

[0018] The above-mentioned CVD methods can include thermal CVD, species-assisted CVD, and photoCVD. From the viewpoint of suppressing the rise in temperature of the glass substrate, species-assisted CVD can be preferably used.

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

[0020] 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.

[0021] The CVD conditions for silicon oxide film formation are appropriately set depending on the type of glass substrate and precursor used. Since the silicon oxide film density changes particularly depending on the glass substrate temperature, when SiH4 is used as the precursor, the glass 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 glass substrate temperature is preferably 30 to less than 250°C, more preferably 30 to 150°C. This prevents the silicon oxide from being packed most densely during film formation, and the following film densities are achieved.

[0022] An example of a method using silica nanoparticles in the aforementioned wet coating method is the method described in Patent Document 13 (International Publication No. 2019 / 035271). In this method, the density of the formed film is approximately 2.0 g / cm³. 3 It will be to that extent.

[0023] Examples of sol-gel methods using silicon alkoxide in the aforementioned wet coating method include the method described in Patent Document 29 (Japanese Patent Application Publication No. 2007-11033).

[0024] In the wet coating method described above, polysilazane can be used by applying perhydropolysilazane as a precursor by spraying, brushing, spin coating, dipping, etc., and then leaving it in an atmospheric environment to convert it to silicon dioxide. An example of this method is the method described in Patent Document 10 (Japanese Patent No. 5655215). The ambient temperature during the leaving process 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 mentioned above is 1.8-2.2 g / cm³. 3 Therefore, 1.80~2.20 g / cm³ 3 Preferably, it is 1.84 to 2.15 g / cm³. 3 It is more preferable that the film density of the silicon dioxide underlayer be 1.8 g / cm³. 3 Below 2.2 g / cm³, the number of voids within the silicon oxide sublayer increases, and although the adhesion between the silicon oxide sublayer and the water-repellent / oil-repellent surface layer improves due to the increased surface area, the strength of the silicon oxide sublayer itself decreases. 3 If the density exceeds a certain limit, the strength of the silicon oxide underlayer itself is maintained, but the adhesion between the silicon oxide underlayer and the water-repellent and oil-repellent surface layer decreases. The film density of the silicon oxide underlayer can be measured by X-ray reflectometry (XRR). In this invention, by forming the silicon oxide film using the method and conditions described above, the film density of the silicon oxide underlayer can be kept within the above range.

[0026] The thickness of the silicon oxide underlayer described above is preferably 3 to 300 nm, and more preferably 3 to 200 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 300 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 X-ray reflectometry (XRR).

[0027] The hydrogen concentration in the silicon oxide underlayer film is preferably 2 at% or more and 8 at% or less, and 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.

[0028] 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.

[0029] 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.

[0030] [Water-repellent and oil-repellent surface layer] 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, and is formed on a silicon oxide underlayer using a surface treatment agent containing a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof. Examples of the fluoropolyether group-containing polymer having hydrolyzable silyl groups include those listed in Japanese Patent Publication No. 6260579, Japanese Patent Publication No. 6828744, Japanese Patent Publication No. 5761305, Japanese Patent Publication No. 6451279, Japanese Patent Publication No. 6741074, Japanese Patent Publication No. 6617853, Japanese Patent Publication No. 2011-116947, Japanese Patent Publication No. 2007-197425, Japanese Patent Publication No. 2007-297589, Japanese Patent Publication No. 2007-297543, and Japanese Patent Publication No. 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, 15-28) can be used.

[0031] A more detailed explanation will be given regarding polymers containing fluoropolyether groups having hydrolyzable silyl groups.

[0032] 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).

[0033] 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.

[0034] 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.

[0035] The following are examples of the bases in formula (11) above. [ka]

[0036] 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.

[0037] 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-

[0038] 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.

[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 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 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 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. [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.

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

[0041] In equation (1) above, 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 2dThe group containing a divalent polyfluorooxyalkylene structure (perfluoropolyether structure) is represented by -, where d is an integer from 0 to 5 independently for each unit, preferably an integer from 0 to 2, and more preferably 0 or 1. p, q, r, s, t, and u are each an integer from 0 to 150 independently, preferably an integer from 0 to 100, and more preferably an integer from 0 to 60, and the sum of p, q, r, s, t, and u is an integer from 1 to 250, preferably an integer from 3 to 140, and more preferably an integer from 7 to 70. Each of these units may be linear or branched. Note that each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly combined.

[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' are each independent integers between 1 and 150, and the sum of p', q', r', s', t', and u' is between 12 and 250. 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 combined. d' is an independent integer between 0 and 5 for each unit. Each of these units may be linear or branched.)

[0043] The above formula (1); A 1 In -Rf-D, A 1 This is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or D(i.e., formula (2);-QZ(W) described later) α The monovalent fluorine-containing hydrocarbon group is a monovalent group represented by , and its terminal end is CF3- or CF2H-, which may contain an oxygen atom. Preferably, it is a fluoroalkyl group having 1 to 6 carbon atoms, and in particular, one in which the polymer terminal end is CF3- or CF2H-.

[0044] Such A1 Examples 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]

[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 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), and 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 aforementioned bonds.

[0047] 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, more 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. 2These 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.

[0048] 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, v is an integer between 2 and 4.)

[0049] 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).

[0050] Furthermore, examples of 3- to 8-valent organopolysiloxane residues containing siloxane bonds are listed below. [ka] (In the formula, R 1 The 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 independent1 or the following formula (a) [Chemical formula] (In the formula, R 1 is the same as above, j1 is an integer from 1 to 6, preferably 1, and the left bond is bonded to Si.) is a group represented by, and R 5 is independently a single bond or the following formula (b) [Chemical formula] (In the formula, R 2 , R 4 is the same as above, j2 is an integer from 0 to 6, preferably an integer from 0 to 3, j3 is an integer from 0 to 6, preferably an integer from 0 to 2, and each repeating unit shown in the parentheses may be randomly bonded. The left bond is bonded to Si.) is a group represented by, and at least one of R 4 is formula (a).]

[0051] Examples of such Z include those shown below. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0052] In the above formula (2); -Q-Z(W) α , W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). [Chemical formula] (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.)

[0053] 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.

[0054] In formula (3) above, Y is preferably a C1-C20 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-C10 atoms, an alkylene group having 1-C10 atoms containing a fluorine atom, an alkylene group having 6-C8 atoms containing an arylene group (alkylene-arylene group), a divalent group in which alkylene groups are bonded to each other via a sylalkylene structure or a sylarylene structure, and a divalent group in which an alkylene group having 2-C10 atoms is bonded to the binding site of a linear or branched or cyclic divalent organopolysiloxane residue having 2-C10 silicon atoms.

[0055] Examples of Y other than single bonds include the following: [ka]

[0056] The following are examples of the bases in formula (3) above. [ka]

[0057] Equation (2) above; -QZ(W) α In this case, α, which represents the number of W, is an integer between 2 and 7.

[0058] The group -Q-Z(W) in the above formula (2) α (That is, D in formula (1)) includes the following. [Chemical formula]

[0059] Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include the following. [Chemical formula] (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. [Chemical formula] In the above formula (4), Rf is the same as above, and those similar to those exemplified by Rf in the above formula (1) can be exemplified.​​​​​​​​​​​​​​​​​​​​​

[0063] 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.

[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 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.

[0066] Equation (6) above: -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, 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 silicon atom, 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). Specific examples of T other than a single bond are shown below. In the structure below, it is preferable that the right-hand bond is bonded to L or E. [ka]

[0067] 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) l In -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.

[0068] Equation (6) above: -T-(LO) l Examples of monovalent groups denoted by -E include the following: [ka]

[0069] Examples of monovalent groups represented by the above formula (5);-C(B)(W)2 (i.e., G in formula (4)) are listed below. [ka]

[0070] 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.)

[0071] 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.

[0072] 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 The monovalent fluorine-containing hydrocarbon group is a monovalent group represented by , and its terminal end is CF3- or CF2H-, which may contain an oxygen atom. Preferably, it is a fluoroalkyl group having 1 to 6 carbon atoms, and in particular, one in which the polymer terminal end is CF3- or CF2H-.

[0073] Such A 3 Examples 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]

[0074] The above formula (7); A 3 In -Rf-J, J is an independent monovalent group represented by the following formula (8), and J contains two or more W groups. [ka]

[0075] In equation (8) above, S is the same as above, and examples similar to those exemplified for S above can be given.

[0076] In formula (8) above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms, which may have a single bond or an ether bond. Specific examples of V other than a single bond are shown below. In the structure below, it is preferable that the bond on the right side is bonded to a carbon atom (-C(=O)-). [ka] In formula (8) above, e is 1 or 2, and is preferably 1. In equation (8) above, M is independently a monovalent group represented by equation (9) below. [ka]

[0077] 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.

[0078] 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]

[0079] Above formula (8);-VC(=O)N(S) 2-e (M) e Examples of monovalent groups represented by the symbol are listed below. [ka] [ka]

[0080] 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.)

[0081] In the article of the present invention, a surface treatment agent for forming a water-repellent and oil-repellent surface layer, comprising a fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, may further contain, in addition to the above-mentioned fluoropolyether group-containing polymer having hydrolyzable silyl groups and / or a partially hydrolyzed condensate thereof, a mixture (i.e., a fluoropolyether group-containing polymer composition) comprising a fluoropolyether group-containing polymer that does not contain hydrolyzable silyl groups represented by the following formula (10) (hereinafter referred to as a polymer that does not contain hydrolyzable silyl groups) and / or a partially (hydrolyzed) condensate thereof. 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.)

[0082] 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 3or -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 3 R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of monovalent hydrocarbon groups 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. 3 Preferred elements include hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and phenyl groups. A 4 -OR 3 ,-COOR 3 , -PO(OR 3 Examples of -OH, -OCH3, -COOH, -COOCH3, -PO(OH)2, -OC2H5, and -COOC2H5 can be found in the )2.

[0083] Examples of fluoropolyether group-containing polymers represented by the above formula (10) are listed below. [ka] (In the formula, p'', q'', r'', s'', t'', and u'' are each independent integers between 0 and 150, and the sum of p'', q'', r'', s'', t'', and u'' is between 12 and 250. 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 combined.)

[0084] In the 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 end of a molecular chain 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 chain 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.

[0085] In a fluoropolyether group-containing polymer mixture (fluoropolyether group-containing polymer composition) contained in a surface treatment agent, the mixing ratio of single-ended polymers and / or double-ended polymers to polymers that do not contain hydrolyzable silyl groups is not particularly limited. However, it is generally desirable that the ratio of polymers that do not contain hydrolyzable silyl groups to the entire fluoropolyether group-containing polymer composition consisting of single-ended polymers and / or double-ended polymers and polymers that do not contain hydrolyzable silyl groups is 0.01 to 30 mol%, and particularly 0.1 to 10 mol%, of the total fluoropolyether group-containing polymer composition consisting of single-ended polymers and / or double-ended polymers and polymers that do not contain hydrolyzable silyl groups.

[0086] 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, 19 It can be calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0087] 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 pre-setting the fluorine compound used in synthesizing the fluoropolyether group-containing polymer to have the above-mentioned number-average molecular weight.

[0088] 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.

[0089] 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.

[0090] The above solvents may be mixed in two or more forms, and it is preferable to 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, it is dissolved in an amount of 0.01 to 30% by mass, preferably 0.02 to 25% by mass, and more preferably 0.05 to 20% by mass.

[0091] The formation of a water-repellent and oil-repellent surface layer using a surface treatment agent can be achieved using known methods such as brush application, dipping, spraying, and vapor deposition (physical vapor deposition (PVD)). Among these, formation by physical vapor deposition (PVD), spraying, or dipping is preferred. The heating method during the vapor deposition process in physical vapor deposition (PVD) can be either resistance heating or electron beam heating, and is not particularly limited.

[0092] It is preferable to perform a curing treatment after forming the water-repellent and oil-repellent surface layer. The curing treatment involves exposure to an environment with 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 of forming the water-repellent and oil-repellent surface layer. For example, in the case of direct coating (brush application, dipping, spraying, etc.), it is preferable to expose the surface to an environment with 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 an environment with 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 typically 0.1 to 100 nm, with 1 to 20 nm being preferred. The thickness of the water- and oil-repellent surface layer can be measured by the XRR or spectroscopic ellipsometry methods described above. [Examples]

[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 value was calculated from the characteristic peak intensity ratio of the F-NMR analysis.

[0095] [Example 1] [Alkaline cleaning of glass substrates] A chemically strengthened glass substrate (Corning GORILLA, size: 100mm x 50mm x 0.7mm (thickness)) was immersed in an alkaline cleaning solution (a 5% by mass aqueous solution of Yokohama Oil & Fat Semiclean LGL) and ultrasonically cleaned for 5 minutes. Afterward, it was immersed in deionized water and ultrasonically cleaned for 6 minutes. The glass substrate was then dried by blowing off the moisture with compressed air.

[0096] [Plasma cleaning of glass substrates] The surface of the glass substrate, 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

[0097] [Formation of silicon oxide sublayer by CVD method using OH radicals] A silicon oxide underlayer was formed on the glass substrate using the CVD method described in Japanese Patent Publication No. 6569831 (Patent Document 14). Under the following processing conditions, the film thickness was 5 nm and the film density was 2.0 g / cm³. 3 This formed a silicon oxide underlayer. Precursor substance: tetraethoxysilane Base material temperature: 30℃ Processing gas (flow rate): Ozone gas (150 sccm) Ethylene gas (50 sccm) Tetraethoxysilane (1 sccm) Nitrogen gas (15 sccm)

[0098] The film thickness and density of the silicon oxide underlayer described above were obtained by X-ray reflectance measurement. Specifically, the film thickness and density were determined by performing 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°

[0099] [Formation of water- and oil-repellent surface layer by physical vapor deposition (PVD)] The glass substrate with the above-mentioned silicon oxide base layer was set in a resistance heating type vacuum evaporation apparatus (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 was reduced. When the pressure inside the container was reduced to 3×10 -3 Pa or less, resistance heating was started. The power input to the resistance heating was adjusted so that the maximum evaporation rate in the crystal oscillator thickness gauge installed at a position about 20 cm away from the resistance heating part became 1.0 nm / sec. Resistance heating was continued for 100 seconds after the evaporation rate in the crystal oscillator thickness gauge decreased to 0.1 nm / sec. For cooling of the apparatus, after waiting for 5 minutes, the atmosphere was released, and a glass substrate coated with a fluoropolyether group-containing polymer was obtained. The glass substrate coated with the above-mentioned fluoropolyether group-containing polymer was left standing in an environment of 25°C and a relative humidity of 50% for 24 hours to cure and fix the water- and oil-repellent surface layer, and a glass substrate having a water- and oil-repellent surface layer with a film thickness of 10 nm by the fluoropolyether group-containing polymer was obtained. The film thickness of the above-mentioned water- and oil-repellent surface layer was measured by a fluorescent X-ray measuring apparatus (manufactured by Rigaku Corporation, trade name: Fluorescent X-ray Measuring Apparatus Primini), and the fluorescent X-ray intensity derived from the fluorine element was quantified and calculated using a calibration curve.

[0100] [Preparation of surface treatment agent] The compound (A) (number average molecular weight 4,000) represented by the following formula was dissolved in a fluorine-based solvent (NOVEC HFE-7200 manufactured by 3M) to a concentration of 20% by mass to obtain a surface treatment agent. [Chemical formula] (p / q = 1.0, p + q = 46)<00​​​​A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that the film-forming time was adjusted so that the film thickness of the silicon oxide underlayer became 100 nm.

[0102] [Example 3] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that the film-forming time was adjusted so that the film thickness of the silicon oxide underlayer became 200 nm.

[0103] [Example 4] The formation conditions of the silicon oxide underlayer were changed as follows. A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that the film thickness of the silicon oxide underlayer was 200 nm and the film density was 2.2 g / cm 3 Precursor substance: hexamethyldisilazane Substrate temperature: 150 °C Processing gas (flow rate): ozone gas (200 sccm) ethylene gas (20 sccm) hexamethyldisilazane (5 sccm) nitrogen gas (15 sccm)

[0104] [Example 5] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that the silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer using silica nanoparticles] A glass substrate that had been subjected to the same alkali cleaning and plasma cleaning as in Example 1 was dip-coated with an aqueous dispersion of silica nanoparticles to form a silicon oxide underlayer having a film thickness of 4 nm and a film density of 2.0 g / cm 3 . The formation conditions are shown below. Average particle size of silica nanoparticles: 2 nm Concentration of silica nanoparticles: 0.1 mass% Immersion time: 30 seconds Pull-up speed: 0.5 mm / second Drying conditions: 150 °C, 30 minutes

[0105] [Example 6] 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 5, except that the film thickness of the silicon oxide underlayer was set to 10 nm by the following immersion conditions. Silica nanoparticle average particle size: 2nm Silica nanoparticle concentration: 0.1% by mass Immersion time: 30 seconds Lifting speed: 3.0 mm / second Drying conditions: 150°C, 30 minutes

[0106] [Example 7] 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 a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide sublayer using polysilazane] A glass substrate, which had undergone alkaline and plasma cleaning in the same manner as in Example 1, was spray-coated with a perhydropolysilazane solution (Aquamica NP-140-01, manufactured by AZ Electronic Materials). The solution was then left to cure for 24 hours in an atmospheric environment at 25°C and 85% relative humidity, resulting in a film thickness of 10 nm and a film density of 2.0 g / cm³. 3 This formed a silicon oxide underlayer.

[0107] [Example 8] 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 silicon oxide underlayment was left to cure for 24 hours in an atmospheric environment at 25°C and 40% relative humidity.

[0108] [Example 9] 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 thickness of the silicon oxide underlayer was set to 100 nm.

[0109] [Example 10] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that a surface treatment agent was used which was prepared by dissolving a 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% by mass. [Chemical formula] (p / q = 1.0, p + q = 42)

[0110] [Example 11] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 6, except that the surface treatment agent of the above compound (B) was used.

[0111] [Example 12] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 1, except that a surface treatment agent was used which was prepared by dissolving a 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% by mass. [Chemical formula] (p / q = 1.0, p + q = 42)

[0112] [Example 13] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 6, except that the surface treatment agent of the above compound (C) was used.

[0113] [Comparative Example 1] A substrate having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same procedure as in Example 7, except that the curing conditions of the silicon oxide underlayer were changed to standing for 24 hours in an atmosphere of 25°C and a relative humidity of 5%.

[0114] [Comparative Example 2] 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 the film thickness of the silicon oxide underlayer was set to 100 nm.

[0115] [Comparative Example 3] 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 a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer by physical vapor deposition (PVD)] A glass substrate, which had undergone alkaline and plasma cleaning in the same manner as in Example 1, was subjected to electron beam deposition of silicon dioxide, resulting in a film thickness of 5 nm and a film density of 2.3 g / cm³. 3 A silicon oxide underlayer was formed. The formation conditions are shown below. Vapor deposition source: SiO2 granules (2mm) Ultimate pressure: 1×10 -3 Pa Deposition rate: 1 nm / second

[0116] [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 3, except that the film thickness of the silicon oxide underlayer was set to 100 nm.

[0117] [Comparative Example 5] 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 3, except that the film thickness of the silicon oxide underlayer was set to 200 nm.

[0118] [Comparative Example 6] 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 a silicon oxide underlayer was formed by the following method. [Formation of silicon oxide underlayer by plasma CVD method] A silicon oxide underlayer was formed on a glass substrate that had undergone alkaline and plasma cleaning in the same manner as in Example 1, using plasma CVD. Under the following processing conditions, the film thickness was 10 nm and the film density was 2.4 g / cm³. 3 This formed a silicon oxide underlayer. Precursor material: SiH4 Base material temperature: 150℃ RF plasma source power supply: 300W Processing pressure: 150 Pa Processed gas (flow rate ratio): SiH4:N2O:H2 = 1:30:180

[0119] [Comparative Example 7] 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 6, except that the film thickness of the silicon oxide underlayer was set to 100 nm.

[0120] [Comparative Example 8] 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 6, except that the film thickness of the silicon oxide underlayer was set to 200 nm.

[0121] [Comparative Example 9] 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 3, except that the surface treatment agent of compound (B) described above was used.

[0122] [Comparative Example 10] 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 3, except that the surface treatment agent of compound (C) described above was used.

[0123] Evaluation of initial water repellency For the glass prepared as described above, which has a silicon oxide underlayer and a water-repellent / oil-repellent surface layer, the contact angle (water repellency) of the water-repellent / oil-repellent surface layer 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%). A water contact angle of 112 degrees or higher was rated ◎ (Excellent), 108 degrees or higher and less than 112 degrees was rated ○ (Good), 100 degrees or higher and less than 108 degrees was rated △ (Acceptable), and less than 100 degrees was rated × (Unacceptable), as shown in Table 1. In both the examples and comparative examples, an initial water contact angle of 112 degrees or higher was obtained, demonstrating good water repellency.

[0124] Evaluation of slipperiness The coefficient of dynamic friction was measured for glass with the silicon oxide underlayer and water-repellent / oil-repellent surface layer prepared as described above, using a surface properties measuring instrument (TYPE14FW, manufactured by Shinto Kagaku). The abrasive material used was a nonwoven fabric (Bencott M-3II, manufactured by Asahi Kasei), and the load was 100 gf / cm². 2 The rubbing speed was set to 500 mm / min. As an index for evaluating slip resistance, a dynamic friction coefficient of less than 0.05 was marked ◎ (Excellent), 0.05 to less than 0.1 was marked ○ (Good), 0.1 to less than 0.2 was marked △ (Acceptable), and 0.2 or more was marked × (Unacceptable), as shown in Table 1. The test environment conditions were 25°C and 40% relative humidity. The coefficients of dynamic friction in Examples 1-10, 12, and Comparative Examples 1-9 were less than 0.05, indicating good sliding properties.

[0125] Evaluation of wear resistance The glass with 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: Eraser (Minoan brand, 6mm diameter) Load: 1kgf Round trip distance: 40mm Round-trip speed: 40 round trips per minute Total number of friction cycles: 20,000 The water contact angle of the friction-worn portion was measured every 1,000 friction cycles. The number of friction cycles at which a water contact angle of 100 degrees or more was maintained was defined as the eraser wear endurance cycle. Erasers with an eraser wear endurance cycle of 20,000 or more were rated ◎ (Excellent), 15,000 to less than 20,000 were rated ○ (Good), 10,000 to less than 15,000 were rated △ (Acceptable), and less than 10,000 were rated × (Unacceptable), as shown in Table 1. The test environment conditions were 25°C and 40% relative humidity.

[0126] [Table 1]

Claims

1. An article comprising a glass substrate, a base layer mainly composed of silicon oxide formed on the outer surface of the glass substrate, and a water-repellent and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer, wherein the water-repellent and oil-repellent surface layer mainly consists 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), The film density of the silicon dioxide underlayer is 1.8 to 2.2 g / cm³. 3 A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer, characterized by the above. 【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 with p, q, r, s, t and u may be randomly combined.) A divalent polyfluorooxyalkylene structure-containing group represented by, A 1 is a monovalent fluorine-containing hydrocarbon group having a terminal of CF 3 - or CF 2 H- and may contain an oxygen atom, or D, and D is a monovalent group independently 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 formulas, Y, S, and W are the same as above, and f is an integer from 1 to 3 (however, if e = 1 in formula (8) and S does not contain W in formulas (8) and (9), then f is 2 or 3).) e is either 1 or 2.

2. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to claim 1, wherein the silicon oxide underlayer is formed by physical vapor deposition (PVD) or chemical vapor deposition (CVD).

3. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to claim 1, wherein the silicon oxide underlayer is formed by a method using silica nanoparticles, a sol-gel method using silicon alkoxide, or by silica glass conversion by reaction of polysilazane with water.

4. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, wherein the thickness of the silicon oxide underlayer is 3 to 300 nm.

5. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, wherein the thickness of the water-repellent and oil-repellent surface layer is 0.1 to 100 nm.

6. A method for improving the abrasion resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, 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.

7. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, 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 silalkylene group, or a diorganosilylene group which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a sylalkylene bond, a sylarylene bond, and a diorganosilylene group.

8. 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 improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, wherein the article contains a cured product of a fluoropolyether group-containing polymer and / or a partial (hydrolysis) condensate thereof.

9. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, wherein the water-repellent and oil-repellent surface layer is formed by a physical vapor deposition (PVD) method, a spray method, or an immersion method.

10. A method for improving the wear resistance of a water-repellent and oil-repellent surface layer in an article having a water-repellent and oil-repellent surface layer according to any one of claims 1 to 3, wherein the glass substrate is pre-treated by alkaline cleaning and / or plasma cleaning.

Images