Items with water- and oil-repellent layers

Abstract

Provided is an article having a water repellent and oil repellent layer, the water repellent and oil repellent layer exhibiting excellent anti-friction properties.　This article having a water repellent and oil repellent layer has: a substrate; a water repellent and oil repellent layer comprising a hydrolytic condensation product of a compound represented by the formula [A-(OX)m-]jY1[-Si(R)[-Si(R)nL3-n]g; and a silicon oxide layer which contains an alkali metal atom and is present between the substrate and the water repellent and oil repellent layer. The average concentration of alkali metal ions in a prescribed region of the silicon oxide layer is a prescribed value or higher. In the formula, X denotes a fluoroalkylene group, the value of m is 2 or more, the values of j, g and k are each 1 or more, Y1 and Y2 denote linking groups, R denotes a monovalent hydrocarbon group, L denotes a hydrolyzable group or a hydroxyl group, the value of n is 0-2, and A denotes a perfluoroalkyl group or -Y2[-Si(R)nL3-n]k. In cases where A is -Y2[-Si(R)nL3-n]k, the value of j is 1, and in cases where A is a perfluoroalkyl group and the value of j is 1, the value of g is 2 or more.

Description

[Technical field]

[0001] The present invention relates to an article with a water- and oil-repellent layer. [Background technology]

[0002] In order to impart water- and oil-repellent properties, fingerprint stain removability, lubricity (smoothness when touched with a finger) and the like to the surface of a substrate, it is known to form a water- and oil-repellent layer made of a condensate of a fluorine-containing compound on the surface of the substrate by surface treatment using a fluorine-containing compound having a poly(oxyperfluoroalkylene) chain and a reactive silyl group.

[0003] In order to improve adhesion between the substrate and the water- and oil-repellent layer, a base layer is provided between them. For example, Patent Document 1 discloses providing a silicon oxide layer between the substrate and the water- and oil-repellent layer. For example, Patent Documents 1 and 2 disclose providing a silicon oxide layer by vapor deposition between the substrate and the water- and oil-repellent layer, and Patent Document 3 discloses providing an underlayer made of a hydrolysis condensate such as Si(NCO)4 between the substrate and the water- and oil-repellent layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-218639 A [Patent Document 2] JP 2012-72272 A [Patent Document 3] International Publication No. 2014 / 126064 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, the performance required for a water- and oil-repellent layer formed using a fluorine-containing compound has been increasing. For example, when the water- and oil-repellent layer is applied to a member that constitutes a surface that is touched by fingers, the water- and oil-repellent layer is required to have a performance (e.g., water repellency) that is not likely to decrease even when repeatedly rubbed, that is, a water- and oil-repellent layer with excellent abrasion resistance. The present inventors evaluated an article with a water- and oil-repellent layer, which has a water- and oil-repellent layer formed using a fluorine-containing compound on a base layer containing silicon oxide as described in Patent Document 1, and found that there is room for improvement in the abrasion resistance of the water- and oil-repellent layer.

[0006] Therefore, an object of the present invention is to provide an article with a water- and oil-repellent layer, which has a water- and oil-repellent layer that is excellent in abrasion resistance. [Means for solving the problem]

[0007] As a result of intensive research into the above-mentioned problems, the present inventors have found that in an article with a water- and oil-repellent layer, which has a substrate, a water- and oil-repellent layer, and a silicon oxide layer containing alkali metal atoms present between the substrate and the water- and oil-repellent layer, the water- and oil-repellent layer has excellent abrasion resistance if a silicon oxide layer having an alkali metal atom concentration within a specific range in a specific depth region is used, and if a water- and oil-repellent layer is formed using a fluorine-containing compound having a specific structure is used, and thus the present invention has been completed.

[0008] That is, the inventors discovered that the above problems can be solved by the following configuration. [1] A water- and oil-repellent layer comprising a substrate, a hydrolysis condensate of a fluorine-containing compound represented by formula (1), and a silicon oxide layer containing alkali metal atoms present between the substrate and the water- and oil-repellent layer, wherein the silicon oxide layer has an average concentration of alkali metal atoms in a region having a depth of 0.1 to 0.3 nm from a surface in contact with the water- and oil-repellent layer of 2.0×10 19 atoms / cm 3 An article with a water- and oil-repellent layer, characterized in that: [A-(OX) m -O-] j Y 1 [-Si(R) n L3-n ] g (1) In the formula (1), X is a fluoroalkylene group having one or more fluorine atoms, m is an integer of 2 or more, j is an integer of 1 or more, and Y 1 is a (j+g)-valent linking group, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer of 0 to 2, g is an integer of 1 or more, A is a perfluoroalkyl group or -Y 2 [-Si(R) n L 3-n ] k and Y 2 is a (k+1)-valent linking group, where k is an integer of 1 or more. 2 [-Si(R) n L 3-n ] k When A is a perfluoroalkyl group and j is 1, then g is an integer of 2 or greater. [2] The article according to [1], wherein the fluorine-containing compound is a compound represented by formula (1-1): R f1 -(OX) m -OY 11 [-Si(R) n L 3-n ] g1 (1-1) In formula (1-1), X, m, R, n, and L are defined as X, m, R, n, and L in formula (1), respectively. f1 is a perfluoroalkyl group, and Y 11 is a (g1+1)-valent linking group, where g1 is an integer of 2 or greater. [3] The article according to [1], wherein the fluorine-containing compound is a compound represented by formula (1-2): [R f2 -(OX) m -O-] j2 Y 21 [-Si(R) n L 3-n ] g2 (1-2) In the formula (1-2), X, m, R, n, and L are defined as X, m, R, n, and L in the formula (1), respectively. f2 is a perfluoroalkyl group, j2 is an integer of 2 or more, and Y 21 represents a (j2+g2)-valent linking group, and g2 is an integer of 2 or greater. [4] The article according to [1], wherein the fluorine-containing compound is a compound represented by formula (1-3): [L 3-n (R) n Si-] k3 Y 32 -(OX) m -OY 31 [-Si(R) n L 3-n ] g3 (1-3) In the formula (1-3), X, m, R, n, and L are defined as X, m, R, n, and L in the formula (1), respectively; k3 is an integer of 1 or more; Y 32 is a (k3+1)-valent linking group, and Y 31 is a (g3+1)-valent linking group, and g3 is an integer of 1 or greater.

[0009] [5] The average concentration of the above alkali metal atoms is 4.0 × 10 22 atoms / cm 3 Any of the following items: [1] to [4]. [6] Any of the items [1] to [5], wherein at least a portion of the alkali metal atoms are sodium atoms. [7] The article according to any one of [1] to [6], wherein the silicon oxide in the silicon oxide layer comprises a condensate of silicic acid or a hydrolysis condensate of an alkoxysilane. [8] The article according to any one of [1] to [7], wherein the silicon oxide in the silicon oxide layer is a deposit of silicon oxide containing alkali metal atoms. [9] The article according to any one of [1] to [7], wherein the silicon oxide layer is a silicon oxide layer formed on the surface of the substrate by a wet coating method using a coating liquid containing a silicon oxide precursor, an alkali metal source, and a solvent.

[10] The article according to any one of [1] to [8], wherein the silicon oxide layer is a silicon oxide layer formed on the substrate by a dry coating method using silicon oxide containing alkali metal atoms. Effect of the Invention

[0010] According to the present invention, an article with a water- and oil-repellent layer having a water- and oil-repellent layer with excellent abrasion resistance can be provided. [Brief description of the drawings]

[0011] [Figure 1] 1 is a cross-sectional view showing an example of an article with a water- and oil-repellent layer of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In this specification, a compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulae are also referred to in the same manner. A group represented by formula (A) is referred to as group (A). Groups represented by other formulae are also referred to in the same manner. In this specification, when it says that "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or may have an A group at the terminal, such as alkylene group-A group-. In this specification, the "aryl group" in the "aryloxy group" includes not only aryl groups but also heteroaryl groups.

[0013] The terms used in the present invention have the following meanings. The "divalent organopolysiloxane residue" is a group represented by the following formula: x is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. Furthermore, g1 is an integer of 1 or more, preferably 1 to 9, and particularly preferably 1 to 4.

[0014] [ka]

[0015] The "number average molecular weight" of a compound is 1 H-NMR and 19 It is calculated by determining the number (average value) of oxyfluoroalkylene groups based on the terminal groups using F-NMR.

[0016] "Alkali metal atom" means a lithium (Li) atom, a sodium (Na) atom, a potassium (K) atom, a rubidium (Rb) atom, and a cesium (Cs) atom.

[0017] The dimensional ratio in FIG. 1 is different from the actual ratio for the sake of convenience of explanation.

[0018] [Items with water- and oil-repellent layer] The article with a water- and oil-repellent layer of the present invention has a substrate, a water- and oil-repellent layer made of a hydrolysis condensate of a fluorine-containing compound represented by formula (1) described below, and a silicon oxide layer containing alkali metal atoms present between the substrate and the water- and oil-repellent layer. In addition, the average concentration of alkali metal atoms in the silicon oxide layer in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer is 2.0×10 19 atoms / cm 3 That's all.

[0019] The article with the water- and oil-repellent layer of the present invention has excellent abrasion resistance of the water- and oil-repellent layer. Although the details of the reason for this are not clear, it is presumed to be due to the following reasons. That is, a high average concentration of alkali metal atoms means that there is a large amount of highly reactive Si-OM (wherein M is an alkali metal) on the surface of the silicon oxide layer. Si-OM is highly reactive with silanol groups (Si-OH) formed by hydrolysis of reactive silyl groups in the fluorine-containing compound used to form the water- and oil-repellent layer. Therefore, the presence of a large amount of Si-OM increases the number of Si-O-Si bonds, which are the junctions between the silicon oxide layer and the water- and oil-repellent layer. In addition, since the fluorine-containing compound represented by the formula (1) described later has two or more reactive silyl groups, the number of reaction points between the silanol groups derived from the reactive silyl groups of the fluorine-containing compound and the Si-OM of the silicon oxide layer increases, which is considered to improve the adhesion between the water- and oil-repellent layer and the silicon oxide layer. As a result, the water- and oil-repellent layer is less likely to peel off due to friction, and the water- and oil-repellent layer has excellent friction resistance.

[0020] 1 is a cross-sectional view showing an example of an article with a water- and oil-repellent layer of the present invention. The article with a water- and oil-repellent layer 10 has a substrate 12, a silicon oxide layer 14 formed on the surface of the substrate 12, and a water- and oil-repellent layer 16 formed on the surface of the silicon oxide layer 14. 1, the silicon oxide layer 14 is formed over the entire surface of one of the surfaces of the substrate 12, but this is not limiting, and the silicon oxide layer 14 may be formed only on a partial region of the substrate 12. Also, in the example of FIG. 1, the water- and oil-repellent layer 16 is formed over the entire surface of the silicon oxide layer 14, but this is not limiting, and the water- and oil-repellent layer 16 may be formed only on a partial region of the silicon oxide layer 14. In the example of FIG. 1, the silicon oxide layer 14 and the water- and oil-repellent layer 16 are formed on only one side of the substrate 12, but this is not limited thereto, and the silicon oxide layer 14 and the water- and oil-repellent layer 16 may be formed on both sides of the substrate 12.

[0021] (base material) The substrate is not particularly limited as long as it is a substrate to which water and oil repellency is required. Materials for the substrate include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. The substrate is preferably a substrate for a touch panel or a substrate for a display, and more preferably a substrate for a touch panel. The substrate for a touch panel has light-transmitting properties. "Having light-transmitting properties" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. The substrate for a touch panel is preferably made of glass or a transparent resin.

[0022] Examples of the substrate include the following: glass or resin used for building materials, decorative building materials, interior goods, transport equipment (e.g., automobiles), signs and bulletin boards, drinking vessels and tableware, aquariums, ornamental equipment (e.g., frames and boxes), laboratory equipment, furniture, art, sports and games, and glass and resin used for the exterior parts (excluding the display parts) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles and remote controls are also preferred. The substrate may be in the form of a plate or a film.

[0023] The substrate may be a substrate having one or both surfaces subjected to a surface treatment such as a corona discharge treatment, a plasma treatment, or a plasma graft polymerization treatment. The surface-treated surface has better adhesion between the substrate and the silicon oxide layer, and as a result, the water- and oil-repellent layer has better abrasion resistance. Therefore, it is preferable to perform the surface treatment on the surface of the substrate that contacts the silicon oxide layer. Among the surface treatments, corona discharge treatment is preferred in that the water- and oil-repellent layer has better abrasion resistance. In corona treatment, the degree of surface modification of the substrate tends to change in proportion to the input power, so it is recommended to use the largest possible discharge amount (W·min / m) according to the type of substrate. 2 ) is preferably carried out.

[0024] (Silicon oxide layer) The silicon oxide layer is a layer containing silicon oxide and alkali metal atoms, and from the viewpoint of more excellent friction resistance of the water- and oil-repellent layer and ease of production, it is preferable that at least a part of the alkali metal atoms is a sodium atom, that is, it contains silicon oxide and sodium atoms. The silicon oxide is preferably a condensate of silicic acid or a hydrolysis condensate of alkoxysilane. It is more preferable that the silicon oxide is a condensate of silicic acid, because the adhesion between the silicon oxide layer and the water- and oil-repellent layer is more excellent, resulting in further excellent friction resistance of the water- and oil-repellent layer. The silicon oxide in the silicon oxide layer is preferably a vapor deposition of silicon oxide containing alkali metal atoms, since this provides a water- and oil-repellent layer with superior abrasion resistance.

[0025] The thickness of the silicon oxide layer is preferably 2 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the silicon oxide layer is equal to or greater than the lower limit, the silicon oxide layer is likely to provide a sufficient effect of improving adhesion. If the thickness of the silicon oxide layer is equal to or less than the upper limit, the silicon oxide layer itself is highly resistant to friction. There are no particular limitations on the method for measuring the thickness of the silicon oxide layer, but examples of such methods include a method of observing the cross section of the silicon oxide layer using an electron microscope (SEM, TEM, etc.), or a method using an optical interference film thickness meter, a spectroscopic ellipsometer, or a step gauge.

[0026] In the silicon oxide layer, the average concentration of alkali metal atoms in the region 0.1 to 0.3 nm deep from the surface in contact with the water-repellent and oil-repellent layer is 2.0 × 10 19 atoms / cm 3 Above 5.0 x 10 19 atoms / cm 3 More than 1.5×10 is preferable. 20 atoms / cm 3 When the average concentration of alkali metal atoms is equal to or higher than the lower limit, the adhesion between the silicon oxide layer and the water- and oil-repellent layer is excellent, and as a result, the water- and oil-repellent layer has excellent abrasion resistance.

[0027] The concentration of alkali metal atoms refers to the concentration of the alkali metal atom if only one type of alkali metal atom is contained in the region, and refers to the sum of the concentrations of those alkali metal atoms if two or more types of alkali metal atoms are contained in the region. Therefore, even if the region contains two or more types of alkali metal atoms and the average concentration of each alkali metal atom is less than the above-mentioned lower limit, it is sufficient that the average sum of the concentrations of each alkali metal atom is equal to or greater than the above-mentioned lower limit. Specifically, for example, the alkali metal atoms contained in the above region include Na, and the average Na atom concentration in the above region is 2.0×10 19 atoms / cm 3 If the alkali metal atoms contained in the above region are Na and K, and the average concentration of Na atoms and the average concentration of K atoms in the above region are both 2.0×10 or more, the requirement for the concentration of alkali metal atoms in the present invention is met regardless of the presence or absence of alkali metal atoms other than Na. 19 atoms / cm 3 Even if the sum of the average concentration of Na atoms and the average concentration of K atoms is less than 2.0 × 10 19 atoms / cm 3 If it is equal to or greater than this, the requirement for the alkali metal atom concentration in the present invention is satisfied.

[0028] The upper limit of the average concentration of alkali metal atoms is not particularly limited. However, in order to form a sufficient number of Si-O-Si bonds in the silicon oxide layer and to ensure sufficient mechanical properties of the silicon oxide layer, it is preferable that the upper limit be 4.0×10 22 atoms / cm 3 is preferred, and 1.0×10 22 atoms / cm 3 is particularly preferred.

[0029] The average concentration of alkali metal atoms is determined by obtaining a depth profile of the concentration of alkali metal atoms by TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) depth analysis using ion sputtering, and then calculating the average value of the alkali metal atom concentration in a region of 0.1 to 0.3 nm in depth in the profile. TOF-SIMS depth profile analysis by ion sputtering is performed by alternately repeating TOF-SIMS measurement and surface etching by ion sputtering using an ion gun built into the TOF-SIMS instrument.

[0030] The reason for excluding the alkali metal atom concentration in the region of the silicon oxide layer that is less than 0.1 nm deep from the surface in contact with the water- and oil-repellent layer is that if the surface of the silicon oxide layer is contaminated with an external substance containing alkali metal atoms, the contamination by alkali metal atoms will be reflected in the concentration profile of alkali metal atoms in that region, and it may not be possible to accurately measure the concentration of alkali metal atoms originating from Si-OM in the silicon oxide layer. The surface roughness (Ra) of the silicon oxide layer (at the interface with the water-repellent and oil-repellent layer) measured by a scanning probe microscope is preferably 0.5 nm or more from the viewpoint of abrasion resistance. The upper limit of the surface roughness is not particularly limited, but is preferably 10 nm.

[0031] The silicon oxide layer is not particularly limited, but is preferably a layer formed on the surface of the substrate by a wet coating method using a coating liquid consisting of a solution containing a silicon oxide precursor, an alkali metal source, and a solvent (water, a water-soluble organic solvent, etc.), or a layer formed on the surface of the substrate by a dry coating method using silicon oxide containing an alkali metal atom. The details of the method for producing the silicon oxide layer are as described below.

[0032] (Water and oil repellent layer) The water- and oil-repellent layer is made of a hydrolysis condensate of a fluorine-containing compound represented by formula (1). The fluorine-containing compound represented by formula (1) is a fluorine-containing compound having a reactive silyl group, and the reactive silyl group means a hydrolyzable silyl group and a silanol group (Si-OH). Specific examples of the hydrolyzable silyl group include a group represented by formula (1) in which L is a hydrolyzable group. The hydrolyzable silyl group becomes a silanol group represented by Si-OH through hydrolysis. The silanol group further undergoes a dehydration condensation reaction with itself to form a Si-O-Si bond. The silanol group also undergoes a condensation reaction with a silanol group or an OM group (Si-OM) on the surface of the silicon oxide layer to form a chemical bond (Si-O-Si bond). In other words, the water- and oil-repellent layer contains a condensate formed by hydrolysis and dehydration condensation of a part or all of the reactive silyl group of the fluorine-containing compound.

[0033] The thickness of the water- and oil-repellent layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the water- and oil-repellent layer is equal to or greater than the lower limit, the effect of the water- and oil-repellent layer can be sufficiently obtained. If the thickness of the water- and oil-repellent layer is equal to or less than the upper limit, the utilization efficiency is high. In the present invention, the thickness obtained by a thin film analysis X-ray diffractometer is defined as the thickness of the water- and oil-repellent layer. The thickness of the water- and oil-repellent layer can be calculated from the vibration period of an interference pattern of reflected X-rays obtained by an X-ray reflectance method using a thin film analysis X-ray diffractometer (ATX-G manufactured by RIGAKU Corporation).

[0034] The compound (1) is a fluorine-containing compound represented by the formula (1). Two or more kinds of the compound (1) may be used in combination. [A-(OX) m -O-] j Y 1 [-Si(R) n L 3-n ] g (1)

[0035] (OX) in formula (1) m is a poly(oxyfluoroalkylene) chain. X is a fluoroalkylene group having one or more fluorine atoms. The number of carbon atoms in the fluoroalkylene group is preferably 1 to 6, and particularly preferably 2 to 4, in that the water- and oil-repellent layer will have better weather resistance and corrosion resistance. The fluoroalkylene group may be linear, branched or cyclic. The number of fluorine atoms in the linear and branched fluoroalkylene groups is preferably 1 to 2 times, and more preferably 1.7 to 2 times, the number of carbon atoms in terms of better corrosion resistance of the water- and oil-repellent layer. The number of fluorine atoms in the cyclic fluoroalkylene groups is preferably (1 to 2 times -2) the number of carbon atoms, and more preferably (1.7 to 2 times -2). The fluoroalkylene group is preferably a fluoroalkylene group in which all hydrogen atoms have been substituted with fluorine atoms (perfluoroalkylene group).

[0036] Specific examples of (OX) include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF ...CF2CF2C H2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, -OCF(CF3)CF2CF 2-, -О-CF(CF2CF3)CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 -- are some examples. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. -cycloC5F8- means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,2-diyl group. -cycloC6F 10 "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0037] m is an integer of 2 or more, more preferably 2-200, further preferably 5-150, particularly preferably 5-100, and most preferably 10-50. (OX) m may contain only one type of (OX), or may contain two or more types of (OX). The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks. Containing two or more types of (OX) means that in compound (1), there are two or more types of (OX) having a different number of carbon atoms, there are two or more types of (OX) having a different number of hydrogen atoms, there are two or more types of (OX) having different positions of hydrogen atoms, and there are two or more types of (OX) having the same number of carbon atoms but different in the presence or absence of side chains or the type of side chain (the number of side chains, the number of carbon chains in the side chain, etc.). For the arrangement of two or more (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure represented by} indicates that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. m25 The structure represented by the formula (1) represents that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are arranged alternately.

[0038] (OX) m As an example, [(OCH ma F (2-ma) ) m11 ·(OC2Hmb F (4-mb) ) m12 ·(OC3H mc F (6-mc) ) m13 ·(OC4H md F (8-md) ) m14 ·(OC5H me F (10-me) ) m15 ·(OC6H mf F (12-mf) ) m16 (O-cycloC4H mg F (6-mg) ) m17 (O-cycloCH mh F (8-mh) ) m18 (O-cycloCH mi F (10-mi) ) m19 In this case, -cycloCH mg F (6-mg) represents a fluorocyclobutanediyl group, and preferably a fluorocyclobutane-1,2-diyl group. mh F (8-mh) represents a fluorocycloheptanediyl group, and preferably a fluorocycloheptane-1,2-diyl group. mi F (10-mi) represents a fluorocyclohexanediyl group, and is preferably a fluorocyclohexane-1,4-diyl group. ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, mf is an integer from 0 to 11, mg is an integer from 0 to 5, mh is an integer from 0 to 7, and mi is an integer from 0 to 9. m11, m12, m13, m14, m15, m16, m17, m18 and m19 each independently represent an integer of 0 or more and preferably 100 or less. m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer of 2 or more, more preferably 2-200, more preferably 5-150, even more preferably 5-100, and particularly preferably 10-50. Among them, m12 is preferably an integer of 2 or more, and particularly preferably 2 to 200. Also, C3H mc F (6-mc) , C4H md F (8-md) , C5H me F (10-me) and C6H mf F (12-mf) The may be linear or branched, and is preferably linear in that the water- and oil-repellent layer has better abrasion resistance.

[0039] In addition, m11 (OCH ma F (2-ma) ), m12 pieces (OC2H mb F (4-mb) ), m13 (OC3H mc F (6-mc) ), m14 (OC4H md F (8-md) ), m15 (OC5H me F (10-me) ), m16 (OC6H mf F (12-mf) ), m17 (O-cycloC4H mg F (6-mg) ), m18 (O-cycloCH mh F (8-mh) ), m19 (O-cycloCH mi F (10-mi) ) may be joined in any order. If m11 is 2 or more, multiple (OCH ma F (2-ma) ) may be the same or different. If m12 is 2 or more, multiple (OC2H mb F (4-mb) ) may be the same or different. If m13 is 2 or more, multiple (OC3H mc F (6-mc) ) may be the same or different. If m14 is 2 or more, multiple (OC4H md F (8-md) ) may be the same or different. If m15 is 2 or more, multiple (OC5H meF (10-me) ) may be the same or different. If m16 is 2 or more, multiple (OC6H mf F (12-mf) ) may be the same or different. When m17 is 2 or more, multiple (O-cycloC4H mg F (6-mg) ) may be the same or different. When m18 is 2 or more, multiple (O-cycloCH mh F (8-mh) ) may be the same or different. When m19 is 2 or more, multiple (O-cycloCH mi F (10-mi) ) may be the same or different.

[0040] (OX) m It is preferable that the compound has the following structure: {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2) m23 , (OCF(CF3)CF2) m24 , (OCF(CF2F3)CF2) m24 , (OCF2CF2CF2) m24 , (OCF(CF3)CF2CF2) m24 , (OCF2CF2-OCF2CF2CF2CF2) m25 , {(OCF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26·(OCF2CF2) m27 }、 (OCF2CF2CF2CF2CF2-OCF2) m28 、 (OCF2CF2CF2CF2CF2-OCF2CF2) m28 、 (OCF2CF2CF2CF2CF2CF2-OCF2) m28 、 (OCF2CF2CF2CF2CF2CF2-OCF2CF2) m28 、 (OCF2-OCF2CF2CF2CF2CF2) m28 、 (OCF2-OCF2CF2CF2CF2CF2CF2) m28 、 (OCF2CF2-OCF2CF2CF2CF2CF2) m28 、 (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 。 (OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 }、 (OCF(CF3)CF2) m29 (OCF2CF2) m22-2 、 (OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 、 (OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 }、 (OCF(CF3)CF2CF2) m29 {(OCF2CF2) m22-2 }、 (OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 wherein m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, m25 is an integer of 1 to 250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2 to 500, m28 is an integer of 1 to 250, m29 is an integer of 2 to 500, m21+m22+m29 is an integer of 2 to 500, m22+m29 is an integer of 2 to 500, and m24+m29 is an integer of 2 to 500. Examples of fluoroalkylene groups having a ring structure include groups of the following formula. In the formula, * indicates a bond. In addition, the group may be one in which some of the fluorine atoms in the formula are replaced with hydrogen atoms.

[0041] [ka]

[0042] (OX) m is more preferably the following structure from the viewpoint of ease of production of compound (1). {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2CF2) m24 , (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}, (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2, (OCF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2. (OCF(CF3)CF2) m29 {(OCF2) m21 (OCF2CF2) m22-2}, (OCF(CF3)CF2) m29 (OCF2CF2) m22-2 , (OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 , (OCF(CF3)CF2CF2) m29 {(OCF2) m21 (OCF2CF2) m22-2}, (OCF(CF3)CF2CF2) m29 {(OCF2CF2) m22-2}, (OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 However, the numbers m22, m25 and m28 are selected so that m22-2, m25-1 and m28-1 are integers of 1 or greater. Among these, (OX) is the most preferred because of its excellent abrasion resistance of the water- and oil-repellent layer. m is {(OCF2) m21 (OCF2CF2) m22} is preferred. {(OCF2) m21 (OCF2CF2) m22 In the above formula, m22 / m21 is preferably from 0.1 to 10, more preferably from 0.2 to 5.0, even more preferably from 0.2 to 2.0, particularly preferably from 0.2 to 1.5, and most preferably from 0.2 to 0.85, in that the water- and oil-repellent layer has better abrasion resistance and fingerprint stain removability.

[0043] (OX) m The number average molecular weight is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and particularly preferably from 3,000 to 10,000. If the number average molecular weight is equal to or greater than the lower limit, the molecular chain of compound (1) becomes longer, improving the flexibility of the molecular chain of compound (1). This increases the probability of reaction between the silanol group derived from the reactive silyl group of compound (1) and the silanol group or Si-OM of the silicon oxide layer, improving the adhesion between the water- and oil-repellent layer and the silicon oxide layer. As a result, the friction resistance of the water- and oil-repellent layer becomes more excellent. In addition, the fluorine content of the water- and oil-repellent layer increases, improving the water- and oil-repellency. In addition, when the number average molecular weight is equal to or less than the upper limit, the handling properties during film formation are superior.

[0044] R is a monovalent hydrocarbon group, and is preferably a monovalent saturated hydrocarbon group. R preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0045] L is a hydrolyzable group or a hydroxyl group. The hydrolyzable group of L is a group that becomes a hydroxyl group by hydrolysis. That is, a hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by hydrolysis. The silanol groups further react with each other to form Si-O-Si bonds. In addition, the silanol groups can form Si-O-Si bonds by dehydration condensation reaction with silanol groups derived from oxides contained in the silicon oxide layer.

[0046] Specific examples of L, which is a hydrolyzable group, include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms. As L, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferred because compound (1) can be produced more easily. As L, an alkoxy group having 1 to 4 carbon atoms is preferred because outgassing during coating is less and storage stability of compound (1) is more excellent, an ethoxy group is particularly preferred when long-term storage stability of compound (1) is required, and a methoxy group is particularly preferred when the reaction time after coating is short.

[0047] n is an integer from 0 to 2. n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of Ls enhances the adhesion of the water- and oil-repellent layer to the silicon oxide layer. When n is 0 or 1, the multiple Ls present in one molecule may be the same or different. From the viewpoints of availability of raw materials and ease of production of compound (1), it is preferable that they are the same. When n is 2, the multiple Rs present in one molecule may be the same or different. From the viewpoints of availability of raw materials and ease of production of compound (1), it is preferable that they are the same.

[0048] A is a perfluoroalkyl group or -Y 2 [-Si(R) n L 3-n ] k It is. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3, in terms of providing a water- and oil-repellent layer with better abrasion resistance. The perfluoroalkyl group may be linear, branched or cyclic. However, A is -Y 2 [-Si(R) n L 3-n ] k When A is a perfluoroalkyl group and j is 1, g is an integer of 2 or more. That is, compound (1) is a reactive silyl group (-Si(R) n L 3-n ) is a compound having two or more.

[0049] Examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)-, and the like. As the perfluoroalkyl group, CF3-, CF3CF2-, and CF3CF2CF2- are preferred since they provide superior water and oil repellency to the water and oil repellent layer. A may be a fluoroalkyl group (also called a fluorocycloalkyl group) having a ring structure. The number of carbon atoms is preferably 3 to 20, more preferably 4 to 8, and particularly preferably 4 to 6. Examples of the fluoroalkyl group having a ring structure include groups of the following formula. In the formula, * indicates a bond.

[0050] [ka]

[0051] Y 2 is a (k+1)-valent linking group. Y 2 The group may be any group that does not impair the effects of the present invention, and examples thereof include an alkylene group which may have an ethereal oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane residue, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9) described below.

[0052] Y 1 is a (j+g)-valent linking group. Y 1 may be any group that does not impair the effects of the present invention, and examples thereof include alkylene groups which may have an ethereal oxygen atom or a divalent organopolysiloxane residue, carbon atoms, nitrogen atoms, silicon atoms, divalent to octavalent organopolysiloxane residues, and groups (g2-1) to (g2-9) and groups (g3-1) to (g3-9) described below.

[0053] j is an integer of 1 or more, preferably 1 to 6 in terms of providing better water and oil repellency of the water and oil repellent layer, and particularly preferably 1 in terms of ease of production of compound (1). g is an integer of 1 or more, and from the viewpoint of providing a water- and oil-repellent layer with better abrasion resistance, is preferably 1 to 15, more preferably 1 to 8, even more preferably 2 to 6, particularly preferably 2 or 3, and most preferably 3. However, as described above, when A is a perfluoroalkyl group and j is 1, g is an integer of 2 or more. k is an integer of 1 or more, and is preferably an integer from 1 to 15, more preferably from 1 to 8, and particularly preferably from 2 to 6, in that the water- and oil-repellent layer has better abrasion resistance. k+g is preferably from 2 to 30, more preferably from 2 to 20, further preferably from 3 to 18, and particularly preferably from 4 to 15, in that the water- and oil-repellent layer has better abrasion resistance.

[0054] Compound (1) is [-Si(R) n L 3-n When there are multiple [-Si(R) n L 3-n ] may be the same or different.

[0055] Compound (1) is preferable to compound (1-1), compound (1-2) and compound (1-3) in terms of the initial water contact angle and abrasion resistance of the water- and oil-repellent layer. Among these, compound (1-1) and compound (1-2) are particularly excellent in the initial water contact angle of the water- and oil-repellent layer, and compound (1-3) is particularly excellent in the abrasion resistance of the water- and oil-repellent layer.

[0056] R f1 -(OX) m -OY 11 [-Si(R) n L 3-n ] g1 (1-1) [R f2 -(OX) m -O-] j2 Y 21 [-Si(R) n L 3-n ] g2(1-2) [L 3-n (R) n Si-] k3 Y 32 -(OX) m -OY 31 [-Si(R) n L 3-n ] g3 (1-3)

[0057] In formula (1-1), X, m, R, n and L are defined as X, m, R, n and L in formula (1), respectively. R f1 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above. Y 11 is a (g1+1)-valent linking group, and specific examples thereof are Y 1 is the same as: g1 is an integer of 2 or more, and is preferably an integer from 2 to 15, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 3, in that the water- and oil-repellent layer has better abrasion resistance.

[0058] In formula (1-2), X, m, R, n and L are defined the same as X, m, R, n and L in formula (1), respectively. R f2 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above. j2 is an integer of 2 or more, preferably 2 to 6, and more preferably 2 to 4. Y 21 is a (j2+g2)-valent linking group, and specific examples thereof are Y 1 is the same as: g2 is an integer of 2 or more, and is preferably from 2 to 15, more preferably from 2 to 6, even more preferably from 2 to 4, and particularly preferably 4, in that the water- and oil-repellent layer has better abrasion resistance.

[0059] In formula (1-3), X, m, R, n and L are defined as X, m, R, n and L in formula (1), respectively. k3 is an integer of 1 or more, preferably 1 to 4, more preferably 2 or 3, and particularly preferably 3. Y 32 is a (k3+1)-valent linking group, and specific examples thereof are Y 2 is the same as: Y 31 is a (g3+1)-valent linking group, and specific examples thereof include Y 1 is the same as: g3 is an integer of 1 or more, preferably 1 to 4, more preferably 2 or 3, and particularly preferably 3.

[0060] Y in formula (1-1) 11 may be a group (g2-1) (where d1+d3=1 (i.e., d1 or d3 is 0), g1=d2+d4, d2+d4≧2), a group (g2-2) (where e1=1, g1=e2, e2≧2), a group (g2-3) (where g1=2), a group (g2-4) (where h1=1, g1=h2, h2≧2), a group (g2-5) (where i1=1, g1=i2, i2≧2), a group (g2-7) (where g1=i3+1), a group (g2-8) (where g1=i4, i4≧2), or a group (g2-9) (where g1=i5, i5≧2). Y in formula (1-2) 21 may be a group (g2-1) (where j2=d1+d3, d1+d3≧2, g2=d2+d4, d2+d4≧2), a group (g2-2) (where j2=e1, e1=2, g2=e2, e2=2), a group (g2-4) (where j2=h1, h1≧2, g2=h2, h2≧2), or a group (g2-5) (where j2=i1, i1=2, g2=i2, i2=2). In addition, Y in formula (1-3) 31 and Y 32may each independently be a group (g2-1) (wherein g3=d2+d4, k3=d2+d4), a group (g2-2) (wherein g3=e2, k3=e2), a group (g2-3) (wherein g3=2, k3=2), a group (g2-4) (wherein g3=h2, k3=h2), a group (g2-5) (wherein g3=i2, k3=i2), a group (g2-6) (wherein g3=1, k3=1), a group (g2-7) (wherein g3=i3+1, k3=i3+1), a group (g2-8) (wherein g3=i4, k3=i4), or a group (g2-9) (wherein g3=i5, k3=i5).

[0061] [ka]

[0062] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 (g2-2) -A 1 -N(-Q 23 -)2···(g2-3) (-A 1 -) h1 Z 1 (-Q 24 -) h2 (g2-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 (g2-5) -A 1 -Q 26 - (g2-6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 (g2-7) -A 1-[CH2C(R e4 )(-Q 27 -)] i4 -R e5 (g2-8) -A 1 -Z a (-Q 28 -) i5 (g2-9)

[0063] However, in formulas (g2-1) to (g2-9), A 1 Side is (OX) m Connect to Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 The side is [-Si(R) n L 3-n ]

[0064] A 1 represents a single bond, an alkylene group, or -C(O)-, -C(O)O-, -OC(O)O-, -OC(O)O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -NR 6 C(O)-, -NHC(O)O-, -NHC(O)NR 6 -, -O- or -SONR 6 In each formula, when two or more A1 are present, the two or more A1 may be the same or different. A hydrogen atom of the alkylene group may be substituted with a fluorine atom.

[0065] Q 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the end of the alkylene group not connected to Si 6 -, -C(O)-, -NR 6 - or -O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms 6 -, -C(O)-, -NR6 - or -O- and -C(O)NR at the end not connected to Si 6 -, -NR 6 C(O)-, -C(O)-, -C(O)O-, -OC(O)-, -NR 6 - or -O-, 22 If there are two or more, then there are two or more Q 22 may be the same or different. Q 23 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different. Q 24 Q 24 Z bonded to 1 If the atom in is a carbon atom, then Q 22 And Q 24 Z bonded to 1 If the atom in is a nitrogen atom, Q 23 In each formula, Q 24 If there are two or more, then there are two or more Q 24 may be the same or different. Q 25 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, 25 If there are two or more, then there are two or more Q 25 may be the same or different. Q 26 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Q 27 is a single bond or an alkylene group. Q 28 is an alkylene group, or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms in an alkylene group having two or more carbon atoms.

[0066] Z 1 A 1 has a carbon atom or nitrogen atom to which Q is directly bonded 24 is a group having an h1+h2 valent ring structure having a carbon atom or nitrogen atom to which is directly bonded.

[0067] R e1 is a hydrogen atom or an alkyl group, and in each formula, R e1 If there are two or more, there are two or more R e1 may be the same or different. R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. R e3 is an alkyl group. R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom in terms of ease of production of the compound. e4 If there are two or more, there are two or more R e4 may be the same or different. R e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in terms of ease of production of the compound.

[0068] d1 is an integer of 0 to 3, and preferably 1 or 2. d2 is an integer of 0 to 3, and preferably 1 or 2. d1+d2 is an integer of 1 to 3. d3 is an integer of 0 to 3, and preferably 0 or 1. d4 is an integer of 0 to 3, and preferably 2 or 3. d3+d4 is an integer of 1 to 3. d1+d3 is Y 11 or Y 21 is an integer of 1 to 5, preferably 1 or 2; Y 11 , Y31 and Y 32 In this case, the value is 1. d2+d4 is Y 11 or Y 21 is an integer of 2 to 5, preferably 4 or 5; Y 31 and Y 32 is an integer of 3 to 5, and preferably 4 or 5. e1+e2 is 3 or 4. e1 is Y 11 is 1 in Y 21 is an integer between 2 and 3, and Y 31 and Y 32 e2 is 1 in Y 11 or Y 21 In 31 and Y 32 In this case, it is 2 or 3. h1 is Y 11 is 1 in Y 21 is an integer of 2 or more (preferably 2), and Y 31 and Y 32 h2 is 1 in Y 11 or Y 21 is an integer of 2 or more (preferably 2 or 3); 31 and Y 32 is an integer of 1 or more (preferably 2 or 3). i1+i2 is Y 11 In 12 In Y 31 and Y 32 In the case of i1, it is 3 or 4. 11 is 1 in Y 21 In Y 31 and Y 32 In Y 11 In 12 In Y 31 and Y 32 In this case, it is 2 or 3. i3 is either 2 or 3. i4 is Y 11 is an integer of 2 or more (preferably 2 to 10, particularly preferably 2 to 6); 31 and Y 32 is an integer of 1 or more (preferably 1 to 10, and particularly preferably 1 to 6). i5 is an integer from 2 to 7.

[0069] Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , Q 28 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of compounds (1-1), (1-2), and (1-3) and of further improving the abrasion resistance, light resistance, and chemical resistance of the water- and oil-repellent layer. However, in the case where the alkylene group has a specific bond between carbon and carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0070] Z 1 The ring structure in the formula (I) is the same as that described above, and the preferred forms are also the same. 1 The ring structure in 1 Or Q 24 is directly bonded to the ring structure, for example, an alkylene group is connected to the alkylene group, and A 1 Or Q 24 are never linked. Z a is an organopolysiloxane residue having a valence of (i5+1), and the following group is preferable. a is an alkyl group (preferably one having 1 to 10 carbon atoms) or a phenyl group.

[0071] [ka]

[0072] R e1 , R e2 , R e3 or R e4The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (1-1), (1-2), and (1-3). R e2 The number of carbon atoms in the alkyl group of the acyloxy group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (1). h1 is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1, in terms of ease of production of compound (1-1), compound (1-2), and compound (1-3), and of further improving the abrasion resistance and fingerprint stain removability of the water- and oil-repellent layer. h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of ease of production of compound (1-1), compound (1-2), and compound (1-3) and of further improving the abrasion resistance and fingerprint stain removability of the water- and oil-repellent layer.

[0073] Y 11 Other forms of include the group (g3-1) (where d1+d3=1 (i.e., d1 or d3 is 0), g1=d2×r1+d4×r1), the group (g3-2) (where e1=1, g1=e2×r1), the group (g3-3) (where g1=2×r1), the group (g3-4) (where h1=1, g1=h2×r1), the group (g3-5) (where i1=1, g1=i2×r1), the group (g3-6) (where g1=r1), the group (g3-7) (where g1=r1×(i3+1)), the group (g3-8) (where g1=r1×i4), and the group (g3-9) (where g1=r1×i5). Y 21Other forms of include a group (g3-1) (wherein j2=d1+d3, d1+d3≧2, and g2=d2×r1+d4×r1), a group (g3-2) (wherein j2=e1, e1=2, g2=e2×r1, and e2=2), a group (g3-4) (wherein j2=h1, h1≧2, and g2=h2×r1), and a group (g3-5) (wherein j2=i1, i1 is 2 or 3, g2=i2×r1, and i1+i2 is 3 or 4). Y 31 and Y 32 Other forms of the formula include the group (g3-1) (wherein g3=d2×r1+d4×r1 and k3=d2×r1+d4×r1), the group (g3-2) (wherein g3=e2×r1 and k3=e2×r1), the group (g3-3) (wherein g3=2×r1 and k3=2×r1), the group (g3-4) (wherein g3=h2×r1 and k3=h2×r1), and the group (g3-5) (wherein , g3=i2×r1, k3=i2×r1), group (g3-6) (where g3=r1, k3=r1), group (g3-7) (where g3=r1×(i3+1), k3=r1×(i3+1)), group (g3-8) (where g3=r1×i4, k3=r1×i4), and group (g3-9) (where g3=r1×i5, k3=r1×i5).

[0074] [ka]

[0075] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 (g3-2) -A 1 -N(-Q 23 -G 1 )2···(g3-3) (-A 1 -) h1 Z 1 (-Q 24 -G 1 )h2 (g3-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 (g3-5) -A 1 -Q 26 -G 1 (g3-6) -A 1 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 (g3-7) -A 1 -[CH2C(R e4 )(-Q 27 -G 1 )] i4 -R e5 (g3-8) -A 1 -Z a (-Q 28 -G 1 ) i5 (g3-9)

[0076] However, in formulas (g3-1) to (g3-9), A 1 Side is (OX) m Connect to G 1 The side is [-Si(R) n L 3-n ]

[0077] G 1 is a group (g3), and in each formula, G 1 If there are two or more, there are two or more G 1 may be the same or different. G 1 The symbols other than are the same as those in formulas (g2-1) to (g2-9). -Si(R 8 ) 3-r1 (-Q 3 -) r1 (g3) However, in formula (g3), the Si side is Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connect to Q 3 The side is [-Si(R) n L 3-n ]. R 8 is an alkyl group. 3 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-, or -(OSi(R 9 )2) p -O- and 2 or more Q 3 may be the same or different. r1 is 2 or 3. R 6 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 9 )2) may be the same or different.

[0078] Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of compounds (1-1), (1-2), and (1-3) and of further improving the abrasion resistance, light resistance, and chemical resistance of the water- and oil-repellent layer. However, in the case where the alkylene group has a specific bond between carbon and carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 8 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (1-1), (1-2), and (1-3). R 9The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compounds (1-1), (1-2), and (1-3). R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of excellent storage stability of compound (1-1), compound (1-2), and compound (1-3). It is preferred that p is 0 or 1.

[0079] Examples of compound (1-1), compound (1-2) or compound (1-3) include compounds of the following formula. The compounds of the following formula are preferred because they are easy to produce industrially, easy to handle, and have excellent water and oil repellency, abrasion resistance, fingerprint stain removal properties, lubricity, chemical resistance, light resistance and chemical resistance of the water and oil repellent layer, and are particularly excellent in light resistance. R in the compounds of the following formula is f is R in the above formula (1-1). f1 -(OX) m -O- or R in formula (1-2) f2 -(OX) m The same applies to the preferred embodiments as well. f represents -(OX) in formula (1-3). m The same applies to --O-- and preferred embodiments are also the same. Specifically, suitable R f Examples of such measures include the following:

[0080] CF3-{(OCF2) m21 (OCF2CF2) m22} CF3CF2-{(OCF2) m21 (OCF2CF2) m22} CF3CF2CF2-{(OCF2) m21 (OCF2CF2) m22} CF3CF2CF2CF2-{(OCF2) m21 (OCF2CF2) m22} CF3CF2CF2CF2CF2-{(OCF2) m21 ·(OCF2CF2) m22 } CF3CF2CF2CF2CF2CF2-{(OCF2) m21 ·(OCF2CF2) m22 } CF3CF(CF3)-{(OCF2) m21 ·(OCF2CF2) m22 } F-cycloC4F6-{(OCF2) m21 ·(OCF2CF2) m22 } F-cycloC6F 10 -{(OCF2) m21 ·(OCF2CF2) m22 } CF3-(OCF2CF2CF2) m24 CF3CF2-(OCF2CF2CF2) m24 CF3CF2CF2-(OCF2CF2CF2) m24 CF3CF2CF2CF2-(OCF2CF2CF2) m24 CF3CF2CF2CF2CF2-(OCF2CF2CF2) m24 CF3CF2CF2CF2CF2CF2-(OCF2CF2CF2) m24 CF3CF(CF3)-(OCF2CF2CF2) m24 F-cycloC4F6-(OCF2CF2CF2) m24 F-cycloC6F 10 -(OCF2CF2CF2) m24 CF3-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2CF2-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2CF2CF2-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF(CF3)-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 }

[0081] F-cycloC4F6-(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } F-cycloC6F 10 -(OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2 } CF3-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF2-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF2CF2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 CF3CF(CF3)-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 F-cycloC4F6-(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2 F-cycloC6F 10 -(OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2

[0082] CF3-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF2-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF2CF2-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF2CF2CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3CF(CF3)-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 F-cycloC4F6-(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 F-cycloC6F 10 -(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2 CF3-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2CF2-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 }、

[0083] CF3CF2CF2CF2CF2CF2-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF(CF3)-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } F-cycloC4F6-(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } F-cycloC6F 10 -(OCF(CF3)CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3CF2-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2-(OCF(CF3)CF2) m29-(OCF2CF2CF2) m24 CF3CF2CF2CF2-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2CF2CF2-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2CF2CF2CF2-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3CF(CF3)-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 F-cycloC4F6-(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24

[0084] F-cycloC6F 10 -(OCF(CF3)CF2) m29 -(OCF2CF2CF2) m24 CF3-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF2CF2CF2CF2-(OCF(CF3)CF2CF2) m29 {(OCF2) m21·(OCF2CF2) m22-2 } CF3CF2CF2CF2CF2CF2-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3CF(CF3)-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } F-cycloC4F6-(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } F-cycloC6F 10 -(OCF(CF3)CF2CF2) m29 {(OCF2) m21 ·(OCF2CF2) m22-2 } CF3-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 CF3CF2-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2CF2-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 CF3CF2CF2CF2CF2-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24

[0085] CF3CF2CF2CF2CF2CF2-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 CF3CF(CF3)-(OCF(CF3)CF2CF2) m29-(OCF2CF2CF2) m24 F-cycloC4F6-(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24 F-cycloC6F 10 -(OCF(CF3)CF2CF2) m29 -(OCF2CF2CF2) m24

[0086] Y 11 As the compound (1-1) in which is a group (g2-1), for example, the compound of the following formula can be mentioned. [ka]

[0087] Y 11 As the compound (1-1) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0088] Y 21 As the compound (1-2) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0089] Y 11 As the compound (1-1) in which is a group (g2-3), for example, the compound of the following formula can be mentioned. [ka]

[0090] Y 11 As the compound (1-1) in which is a group (g2-4), for example, the compound of the following formula can be mentioned. [ka]

[0091] Y 11 As the compound (1-1) in which is a group (g2-5), for example, the compound of the following formula can be mentioned. [ka]

[0092] Y 11 As the compound (1-1) in which is a group (g2-7), for example, the compound of the following formula can be mentioned. [ka]

[0093] Y 11 As the compound (1-1) in which is a group (g3-1), for example, the compound of the following formula can be mentioned. [ka]

[0094] Y 11 As the compound (1-1) in which is a group (g3-2), for example, the compound of the following formula can be mentioned. [ka]

[0095] Y 11 As the compound (1-1) in which is a group (g3-3), for example, the compound of the following formula can be mentioned. [ka]

[0096] Y 11 As the compound (1-1) in which is a group (g3-4), for example, the compound of the following formula can be mentioned. [ka]

[0097] Y 11 Examples of the compound (1-1) in which is a group (g3-5) include compounds of the following formula: [ka]

[0098] Y 11 Examples of the compound (1-1) in which is a group (g3-6) include compounds of the following formula: [ka]

[0099] Y 11 Examples of the compound (1-1) in which is a group (g3-7) include compounds of the following formula: [ka]

[0100] Y 21 As the compound (1-2) in which is a group (g2-1), for example, the compound of the following formula can be mentioned. [ka]

[0101] Y 31 and Y 32 As the compound (1-3) in which is a group (g2-1), for example, the compound of the following formula can be mentioned. [ka]

[0102] Y 31 and Y 32 As the compound (1-3) in which is a group (g2-2), for example, the compound of the following formula can be mentioned. [ka]

[0103] Y 31 and Y 32 As the compound (1-3) in which is a group (g2-3), for example, the compound of the following formula can be mentioned. [ka]

[0104] Y 31 and Y 32 As the compound (1-3) in which is a group (g2-4), for example, the compound of the following formula can be mentioned. [ka]

[0105] Y 31 and Y 32 As the compound (1-3) in which is a group (g2-5), for example, the compound of the following formula can be mentioned. [ka]

[0106] Y 31 and Y 32 Examples of the compound (1-3) in which is a group (g2-6) include compounds of the following formula: [ka]

[0107] Y 31 and Y 32 Examples of the compound (1-3) in which is a group (g2-7) include compounds of the following formula: [ka]

[0108] Y 31 and Y 32As the compound (1-3) in which is a group (g3-2), for example, the compound of the following formula can be mentioned. [ka]

[0109] Specific examples of compound (1) include those described in the following documents: Perfluoropolyether-modified aminosilanes described in JP-A-11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP-A-2000-144097, Perfluoropolyether-modified aminosilanes described in JP-A-2000-327772; Fluorinated siloxanes described in JP-T-2002-506887, The organic silicone compounds described in JP-A-2008-534696, Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A, Organosilicon compounds described in WO 2011 / 060047 and WO 2011 / 059430; Fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in JP2012-72272A; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP2014-080473A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP2014-218639A, WO2017 / 022437A, WO2018 / 079743A, and WO2018 / 143433A; Fluoropolyether group-containing polymer-modified silanes described in JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, and WO 2019 / 163282.

[0110] [Method of manufacturing an article with a water- and oil-repellent layer] An example of the method for producing an article with a water- and oil-repellent layer of the present invention includes a method for producing an article with a water- and oil-repellent layer, which comprises: (a) forming a silicon oxide layer containing alkali metal atoms on the surface of a substrate using a silicon oxide-forming material containing a silicon oxide precursor and an alkali metal source; and then (b) forming a water- and oil-repellent layer made of a hydrolysis condensate of the above-mentioned compound (1) on the surface of the silicon oxide layer, wherein the silicon oxide layer has the above-mentioned alkali metal atom concentration.

[0111] Specific examples of silicon oxide precursors include silicic acid, partial condensates of silicic acid, alkali metal silicates, silane compounds having a hydrolyzable group bonded to a silicon atom, and partial hydrolyzed condensates of the silane compounds. Silica and its partial condensates can be converted to silicon oxide by dehydration condensation, and alkali metal silicates can be converted to silicic acid and its partial condensates by the action of acids or cation exchange resins, and the resulting silicic acid and its partial condensates can then be converted to silicon oxide by dehydration condensation. Specific examples of the hydrolyzable group in the silane compound having a hydrolyzable group bonded to a silicon atom include an alkoxy group and a chlorine atom. The hydrolyzable group of the silane compound can be hydrolyzed to a hydroxyl group, and the resulting silanol compound can be dehydrated and condensed to form silicon oxide. Specific examples of silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxysilanes such as tetraalkoxysilane and alkyltrialkoxysilane, and tetrachlorosilane. As the silicon oxide precursor, silicic acid, a partial condensate of silicic acid, tetraalkoxysilane and a partial hydrolysis condensate thereof are preferred. Examples of the alkali metal source include alkali metal hydroxides, water-soluble alkali metal salts, etc. Examples of the water-soluble alkali metal salts include alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydrochlorides, alkali metal nitrates, etc. Examples of the alkali metal source include alkali metal hydroxides and alkali metal carbonates. Furthermore, alkali metal silicate can be used as a silicon oxide precursor and an alkali metal source. As described above, alkali metal silicate can be converted into silicon oxide via silicic acid, but at that time, a small amount of alkali metal may remain in the silicon oxide produced. Therefore, the amount of the remaining alkali metal can be intentionally adjusted to obtain silicon oxide containing a predetermined amount of alkali metal atoms.

[0112] As a method for forming a silicon oxide layer containing alkali metal atoms, the following (a1) and (a2) are preferred. The method (a1) is a method using wet coating, and the method (a2) is a method using dry coating. (a1): A method for forming a silicon oxide layer on a substrate surface using a coating liquid containing at least one silicon oxide precursor selected from the group consisting of silicic acid, partial condensates of silicic acid, alkoxysilanes and partial hydrolysis and condensations thereof, an alkali metal source, and a solvent. (a2): A method of forming a silicon oxide layer on the surface of a substrate using silicon oxide containing alkali metal atoms.

[0113] (a1) From the viewpoint of facilitating the formation of a silicon oxide layer, the coating liquid for forming a silicon oxide layer preferably contains, as a silicon oxide precursor, at least one selected from the group consisting of silicic acid and partial condensates thereof, and particularly preferably contains a partial condensate of silicic acid. As a raw material for producing silicic acid or a partial condensate thereof, it is preferable to use an alkali metal silicate. By using an alkali metal silicate, a predetermined concentration of alkali metal atoms can be contained in the silicon oxide layer to be formed. In addition, the concentration of alkali metal atoms in the silicon oxide layer to be formed can be adjusted by using an alkali metal source such as an alkali metal hydroxide. Specifically, the method of preparation is preferably such that an aqueous solution of silicic acid is obtained by desalting an aqueous solution of an alkali metal silicate, and then a water-soluble organic solvent is added to the aqueous solution of silicic acid. By appropriately selecting the desalting conditions, a preferred amount of alkali metal atoms can be contained in the aqueous solution of silicic acid. As a method of desalting, for example, a method of mixing an aqueous solution of an alkali metal silicate with a cation exchange resin, stirring, and then removing the cation exchange resin can be mentioned. As the alkali metal silicate used in this method, sodium silicate is preferable.

[0114] Alkali metal silicates include silicates represented by M2O·nSiO2, and specific examples include metasilicate (M2SiO3), orthosilicate (M4SiO4), disilicate (M2Si2O5), and tetrasilicate (M2Si4O9). An example of sodium silicate is Na2O·nSiO2 as specified in JIS K1408-1966, and specific examples thereof include sodium metasilicate (Na2SiO3), sodium orthosilicate (Na4SiO4), sodium disilicate (Na2Si2O5), and sodium tetrasilicate (Na2Si4O9).

[0115] The solvent is preferably water or a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include an alcohol-based organic solvent, a ketone-based organic solvent, an ether-based organic solvent, and an ester-based organic solvent, and the alcohol-based organic solvent is preferred. Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol, and n-butanol. The solid content concentration (in terms of SiO2) of the coating liquid is preferably from 0.001 to 10 mass %, particularly preferably from 0.1 to 3 mass %.

[0116] Specific examples of methods for wet-coating the surface of a substrate with a coating liquid include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0117] The surface of the substrate is wet-coated with a coating liquid to form a wet film, after which the solvent in the wet film is removed and silicic acid and its partial condensates are condensed to form a silicon oxide layer. The temperature for removing the solvent from the wet film and the temperature for condensing silicic acid and its partial condensate are preferably 0 to 600° C., and particularly preferably 200 to 600° C., from the viewpoint of forming a dense silicon oxide layer.

[0118] (a2) As a method for performing dry coating using silicon oxide containing alkali metal atoms, the vacuum deposition method, CVD method, and sputtering method are preferred from the viewpoint of ease of process, and the vacuum deposition method is particularly preferred from the viewpoint of ease of equipment. In the vacuum deposition method, when two or more kinds of silicon oxides containing alkali metal atoms are deposited, they may be used as one deposition source, or may be co-deposited as separate deposition sources. In particular, it is preferable to use one deposition source made of silicon oxide containing alkali metal atoms. For example, when forming a silicon oxide layer containing two or more kinds of alkali metal atoms, it is preferable to use one deposition source made of silicon oxide containing two or more kinds of alkali metal atoms.

[0119] The alkali metal atom-containing silicon oxide used in the dry coating method, such as the deposition source in the vacuum deposition method, is preferably an alkali metal atom-containing silicon oxide having an alkali metal atom content of 200 ppm or more relative to Si. The alkali metal atom content is more preferably 1,000 ppm or more relative to Si, and particularly preferably 10,000 ppm or more. If the alkali metal atom content is equal to or greater than the lower limit, the adhesion between the formed silicon oxide layer and the water- and oil-repellent layer is excellent, and as a result, the water- and oil-repellent layer has excellent abrasion resistance. The upper limit of the alkali metal atom content is preferably 200,000 ppm relative to Si, and particularly preferably 100,000 ppm. The method for producing the silicon oxide containing alkali metal atoms includes a method of adding silicon dioxide to an aqueous solution containing an alkali metal source, stirring the mixture, and removing water. As the silicon dioxide, porous silicon dioxide such as silica gel is preferable. As the aqueous solution containing an alkali metal source, an aqueous solution of an alkali metal hydroxide, an aqueous solution of an alkali metal carbonate, etc. can be mentioned. In addition, the silicon oxide containing alkali metal atoms can be produced from the coating liquid for forming the silicon oxide layer of (a1) above. Also usable as the alkali metal atom-containing silicon oxide are porous silica gel containing alkali metal atoms produced from an alkali metal silicate such as sodium silicate, and porous silica gel containing alkali metal atoms obtained by impregnating the porous silica gel with an aqueous solution containing an alkali metal source and drying or baking the same. The silicon oxide containing alkali metal atoms may be a commercially available product, and examples of the silicon oxide containing alkali metal atoms include porous spherical silica gel produced from sodium silicate, such as MSGEL (trade name: manufactured by AGC Si-Tech Co., Ltd.).

[0120] The shape of the alkali metal atom-containing silicon oxide is not limited, and specific examples thereof include powder, beads, pellets, and cullets. Beads, pellets, and cullets are preferred from the viewpoint of ease of use as a deposition source, etc. The method for producing pellets is not limited, and an example is a method in which the powder is compressed into a pellet-shaped body. The size of the pellet-shaped body is not particularly limited, but a diameter of 1 cm or more is preferred, since a small pellet-shaped body is undesirably too large to fly off during coating. Examples of the method for producing cullets include a method in which calcium is added to vitrified material and then cut with a cutter or crushed.

[0121] (b) After forming a silicon oxide layer containing alkali metal atoms, a water- and oil-repellent layer made of a hydrolysis condensate of compound (1) is formed on the exposed surface. This can be done by dry coating or wet coating. The exposed surface of the silicon oxide layer in the substrate with a silicon oxide layer refers to the surface of the silicon oxide layer on which the water- and oil-repellent layer is formed.

[0122] (Dry coating) Specific examples of the dry coating method include vacuum deposition, CVD, and sputtering, with the vacuum deposition being preferred from the standpoint of preventing decomposition of compound (1) and the simplicity of the equipment required. The temperature during the vacuum deposition is preferably from 20 to 300°C, particularly preferably from 30 to 200°C. The pressure during vacuum deposition is 1×10 -1 Pa or less is preferable, and 1×10 -2 Pa or less is particularly preferred.

[0123] In the dry coating, one type of compound (1) may be used alone, two or more types of compound (1) may be used as a mixture, or a composition containing compound (1) and other components (excluding the solvent) may be used.

[0124] (Wet Coating) Specific examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating. In the wet coating, a coating liquid for forming a water- and oil-repellent layer is used. The coating liquid for forming a water- and oil-repellent layer is a solution or dispersion containing the compound (1) and a solvent.

[0125] The solvent is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents. Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. As the non-fluorinated organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents.

[0126] The coating liquid for forming a water- and oil-repellent layer may contain, in addition to compound (1) and a solvent, other components and impurities (such as by-products produced in the production process of compound (1)) within the scope that does not impair the effects of the present invention. Examples of other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups.

[0127] The solid content concentration of the coating liquid for forming a water- and oil-repellent layer is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass. The solid content concentration of the coating liquid for forming a water- and oil-repellent layer is a value calculated from the mass of the coating liquid for forming a water- and oil-repellent layer before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.

[0128] (Post-processing) In (b), in order to improve the abrasion resistance of the water- and oil-repellent layer, an operation for promoting the reaction between the compound (1) and the silicon oxide layer may be carried out as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate with the silicon oxide layer on which the water- and oil-repellent layer is formed can be heated in a humid atmosphere to promote reactions such as hydrolysis of hydrolyzable silyl groups to silanol groups, generation of siloxane bonds by condensation of silanol groups, and condensation reaction of silanol groups and OM groups on the surface of the silicon oxide layer with silanol groups of the fluorine-containing compound. After the surface treatment, compounds in the water- and oil-repellent layer that are not chemically bonded to other compounds or the silicon oxide layer may be removed as necessary. Specific methods for removing the compounds include, for example, pouring a solvent onto the water- and oil-repellent layer, or wiping the compounds off with a cloth soaked in the solvent. EXAMPLES

[0129] The present invention will be described in detail below with reference to examples. Examples 1-1 to 1-12, 1-14 to 1-25, and 2-1 to 2-9 are working examples, and Examples 1-13 and 2-10 are comparative examples. However, the present invention is not limited to these examples.

[0130] [Physical properties and evaluation] (number average molecular weight) The number average molecular weight of the fluorine-containing compound is 1 H-NMR and 19 The number (average value) of oxyperfluoroalkylene groups was calculated based on the number of terminal groups by F-NMR. The terminal group is, for example, A or Si(R) in formula (1). n X 3-n It is.

[0131] (Thickness of silicon oxide layer) The thickness of the silicon oxide layer was measured with a spectroscopic ellipsometer (FE-3000 manufactured by Otsuka Electronics Co., Ltd.).

[0132] (TOF-SIMS) The average sodium concentration in the region of the silicon oxide layer at a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer was determined using a time-of-flight secondary ion mass spectrometry (TOF-SIMS) device according to the following procedure.

[0133] (I) First, a standard sample for quantifying sodium concentration was prepared. A quartz glass substrate with the same composition as the silicon oxide layer to be evaluated was prepared, and sodium was ion-implanted into this substrate to prepare a standard sample. A medium current ion implanter (ULVAC IMX-3500RS) was used for ion implantation, with an energy of 110 keV and a sodium injection amount of 6.0×10 14 ions / cm 2 It was decided.

[0134] (II) Next, the substrate with the silicon oxide layer to be evaluated and the standard sample prepared in (I) are simultaneously transported into the TOF-SIMS device, and TOF-SIMS depth profile analysis is performed by ion sputtering in sequence. 23 Na + and 28 S + The profile of the intensity (vertical axis) was obtained. The sputtering time on the horizontal axis of the obtained profile was then converted to a depth using the depth of the standard sample, which was measured using a stylus-type surface profiler (Dektak150, manufactured by ULVAC, Inc.). Next, the intensity on the vertical axis of the obtained profile was calculated based on the sputtering rate (0.0282 nm / s) of the sputtered ions obtained from the standard sample and the RSF (2.8182 × 10 20 The relative sensitivity factor (Relative Sensitivity Factor) was used to convert the measured sodium concentration to a sodium concentration profile in the silicon oxide layer in the depth direction. The TOF-SIMS analysis conditions used in this study are as follows: TOF-SIMS equipment: TOF.SIMS5 manufactured by ION-TOF GmbH, Primary ion species: Bi1 + , Primary ion acceleration voltage: 25 keV, Primary ion current value: 1pA (at 10kHz), Primary ion raster size: 100 x 100 μm 2 , Primary ion bunching: yes, Cycle time: 100μs, Number of pixels: 128 x 128 pixels, Sputter ion species: C 60 ++ , Sputtering acceleration voltage: 10 keV, Sputter current: 1nA (at 10kHz), Sputter ion raster size: 400 x 400 μm 2 , Sputtering time per time: 1.634 seconds, Vacuum degree: 5.0×10 -6 mbar (oxygen flow into the measurement chamber), Na secondary ion mass number: 23, Si secondary ion mass number: 28, Neutralizing gun: Yes.

[0135] (III) Finally, from the sodium concentration depth profile of the silicon oxide layer obtained in (II), the average sodium concentration in the region of the silicon oxide layer that is 0.1 nm or more and 0.3 nm or less in depth from the surface in contact with the water- and oil-repellent layer was calculated. In the sodium concentration depth profile, the number of plotted points in the region of 0.1 nm or more and 0.3 nm or less was four. The average sodium concentration was calculated as the average value of these four points. When the measurement is performed under the above conditions, four plotted points can be present in the region that is 0.1 nm or more and 0.3 nm or less in depth from the surface in contact with the water- and oil-repellent layer.

[0136] It is desirable that the silicon oxide layer is exposed before TOF-SIMS depth profile analysis by ion sputtering. That is, if a water- and oil-repellent layer is present on the surface of the silicon oxide layer or if surface contamination is clearly advanced, it is preferable to remove these. Removal methods include oxygen plasma ashing treatment and ultraviolet (UV) ozone treatment. Depending on the thickness of the water- and oil-repellent layer and the degree of surface contamination, it may be better to carry out both of these. In this embodiment, the oxygen plasma ashing process was performed, followed by the UV ozone process. In the oxygen plasma ashing process, a low-temperature ashing device (LTA-102 model manufactured by Yanaco Analytical Industries Co., Ltd.) was used. The processing conditions were high-frequency output: 50 W, oxygen flow rate: 50 mL / min, and processing time: 60 minutes. In the UV ozone process, an ultraviolet ray irradiation device (PL30-200 manufactured by Sen Engineering Co., Ltd.) was used, and UB2001D-20 was used as the ultraviolet ray irradiation device power source. The processing conditions were ultraviolet ray wavelength: 254 nm, and processing time: 10 minutes. In this embodiment, this is not necessary because TOF-SIMS depth analysis by ion sputtering was performed on a substrate with a silicon oxide layer, but if TOF-SIMS depth analysis by ion sputtering is performed on an article with a water- and oil-repellent layer, it is preferable to confirm that fluorine has been removed by monitoring the fluorine peak using X-ray photoelectron spectroscopy. The concentrations of alkali metals other than sodium were also measured in the same manner as in the measurement of the sodium concentration.

[0137] (water contact angle) The contact angle of approximately 2 μL of distilled water placed on the surface of the water- and oil-repellent layer was measured at 20° C. using a contact angle measuring device (DM-701 manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface of the water- and oil-repellent layer, and the average value was calculated to determine the initial contact angle. The 2θ method was used to calculate the contact angle. The criteria for evaluation are as follows: Excellent: The initial contact angle is 115 degrees or more. ◯ (Good): The initial contact angle is 105 degrees or more and less than 115 degrees. △ (Fair): The initial contact angle is 100 degrees or more and less than 105 degrees. × (unacceptable): The initial contact angle is less than 100 degrees.

[0138] (Friction resistance (felt wear)) For the water- and oil-repellent layer, a felt abrasion tester was used to move a felt (dimensions: 10 mm x 10 mm x 50 mm) back and forth at a load of 9.8 N and a speed of 80 rpm. The maximum number of reciprocations at which the water- and oil-repellent layer could maintain a water contact angle of 100 degrees or more, and the maximum number of reciprocations at which the water- and oil-repellent layer could maintain a water contact angle of 80 degrees or more were measured, and the abrasion resistance was evaluated according to the following criteria. <Number of times the felt can be moved back and forth to maintain a water contact angle of 100 degrees> ◎ (Excellent): The number of round trips is more than 15,000. ◯ (Good): The number of reciprocations is 10,000 or more and less than 15,000. △ (Acceptable): The number of round trips is between 5,000 and 10,000. × (Not acceptable): The number of round trips is less than 5,000. <Number of times the felt can be moved back and forth to maintain a water contact angle of 80 degrees> ◎ (Excellent): The number of round trips is more than 25,000. ◯ (Good): The number of reciprocations is 15,000 or more and less than 25,000. △ (Acceptable): The number of round trips is between 8,000 and 15,000. × (Not acceptable): The number of round trips is less than 8,000.

[0139] [Synthesis Example 1] Compound (1-1A) was obtained according to the method described in Example 3 of WO 2017 / 038832. CF3-(OCF2CF2-OCF2CF2CF2CF2) x3 (OCF2CF2)-OCF2CF2CF2-CH2-N[CH2CH2CH2-Si(OCH3)3]2...(1-1A) Average value of unit number x3: 13, Mn of compound (1-1A): 5,020, (OX) of the above formula (1) in compound (1-1A) m The part corresponding to Mn: 4,600

[0140] [Synthesis Example 2] Compound (1-1B) was obtained according to the method described in Example 11 of WO 2017 / 038830. CF3-(OCF2CF2OCF2CF2CF2CF2) n (OCF2CF2)-OCF2CF2CF2-C(O)NH-CH2-C[CH2CH2CH2-Si(OCH3)3]3...(1-1B) Average value of unit number n: 13, Mn of compound (1-1B): 5,400, (OX) of the above formula (1) in compound (1-1B) m The part corresponding to Mn: 4,600

[0141] [Synthesis Example 3] Compound (1-1C) was obtained according to the method described in Synthesis Example 15 of Japanese Patent No. 5761305. CF3 (OCF2CF2) 15 (OCF2) 16 OCF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3...(1-1C) Mn of compound (1-1C): 3,600, (OX) of the above formula (1) in compound (1-1C) m The part corresponding to Mn:2,900

[0142] [Synthesis Example 4] Compound (1-2A) was obtained according to Example 16 of WO 2017 / 187775. In addition, the group represented by "PFPE" in formula (1-2A) is CF3(OCF2CF2OCF2CF2CF2CF2CF2) x3 In the formula, the average value of the number of units X3 is 13. Mn of compound (1-2A): 10,100, (OX) of the above formula (1) in compound (1-2A) m The part corresponding to Mn:9,200

[0143] [ka]

[0144] [Synthesis Example 5] Compound (1-2B) was synthesized by the following procedure.

[0145] In a nitrogen-purged reactor, 21.8 g of NaH weighed in a nitrogen-purged box was added to 100 g of dehydrated THF (tetrahydrofuran), stirred in an ice bath, and 40 g of a 50% by mass solution of malononitrile in dehydrated THF was added, followed by 80.6 g of allyl bromide, and stirred in an ice bath for 4 hours. After adding a dilute hydrochloric acid solution to stop the reaction, the mixture was washed with water and saturated saline, and the organic phase was recovered. The recovered solution was concentrated with an evaporator to obtain a crude product. The crude product was developed in a silica gel column chromatography to separate 42 g of compound (X5-1). In a 300 mL recovery flask purged with nitrogen, 31.1 g of LiAlH4 and 100 g of dehydrated THF were added and stirred in an ice bath until the temperature reached 0°C. 40 g of compound (X5-1) was slowly added dropwise. After confirming the disappearance of compound (X5-1) by thin layer chromatography, the reaction crude liquid was quenched by slowly adding Na2SO4·10H2O, filtered through Celite, and washed with water and saturated saline. The collected organic layer was evaporated under reduced pressure and purified by column chromatography to obtain 32.5 g of compound (X5-2). [ka]

[0146] In a 50 mL eggplant flask, add 0.4 g of compound (X5-2) and CF3 (OCF2CF2OCF2CF2CF2CF2CF2) 13 27 g of OCF2CF2OCF2CF2CF2-C(O)-CH3 was added and stirred for 12 hours. NMR confirmed that all of compound (X5-2) was converted to compound (X5-3). In addition, methanol was produced as a by-product. The resulting solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography to obtain 16.3 g of compound (X5-3). In the formula below, PFPE is CF3(OCF2CF2OCF2CF2CF2CF2CF2) 13OCF2CF2OCF2CF2CF2-. [ka]

[0147] In a 100mL PFA eggplant flask, 5.0g of compound (X5-3), 0.5g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.3g of HSi(OCH3)3, 0.02g of dimethylsulfoxide, and 5.0g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred at 40°C for 10 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain compound (1-2B) in which two allyl groups of compound (X5-3) were hydrosilylated. The conversion rate of hydrosilylation was 100%, and no compound (X5-3) remained. In the formula below, PFPE is CF3(OCF2CF2OCF2CF2CF2CF2CF2) 13 OCF2CF2OCF2CF2CF2-. [ka]

[0148] Mn of compound (1-2B): 9,800, (OX) of the above formula (1) in compound (1-2B) m The part corresponding to Mn:9,200

[0149] [Synthesis Example 6] A mixture (M1) containing the following compound (1-3A) and the following compound (1-1D) was synthesized by the following procedure.

[0150] (Synthesis Example 6-1) Compound (X6-1) was obtained according to the method described in Example 1-1 of the Examples of WO 2013-121984. CF2=CFO-CF2CF2CF2CH2OH (X6-1)

[0151] (Synthesis Example 6-2) In a 200 mL eggplant flask, 16.2 g of HO-CH2CF2CF2CH2-OH and 13.8 g of potassium carbonate were placed and stirred at 120°C. 278 g of compound (X6-1) was added and stirred at 120°C for 2 hours. The temperature was returned to 25°C, and the mixture was stirred in AC-2000 (product name, manufactured by AGC, C6F 13 H) and hydrochloric acid (50 g each) were added, the liquids were separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 117.7 g of compound (X6-2). [ka]

[0152] NMR spectrum of compound (X6-2); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 4.6 (20H), 4.2 (4H), 4.1 (4H). 19 F-NMR (282.7MHz, solvent: CDCl3, standard: CFCl3) δ(ppm): -85(24F), -90(24F), -120(20F), -122(4F), -123(4F), -126(24F), -144(12F) Average number of units m+n:10.

[0153] (Synthesis Example 6-3) In a 50 mL eggplant flask connected to a reflux condenser, 20 g of the compound (X6-2) obtained in Synthesis Example 6-2, 2.4 g of sodium fluoride powder, 20 g of AC-2000, and 18.8 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of compound (X6-3). [ka]

[0154] NMR spectrum of compound (X6-3); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 5.0 (4H), 4.6 (20H), 4.2 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -85 (24F), -90 (24F), -119 (4F), -120 (20F), -122 (4F), -126 (24F), -129 (4F), -131 (2F), -144 (12F). Average number of units m+n:10.

[0155] (Synthesis Example 6-4) 250 mL of ClCF2CFClCF2OCF2CF2Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. A CFE-419 solution of compound (X6-3) obtained in Synthesis Example 6-3 (concentration: 10% by mass, compound (X6-3): 24 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (X6-3) (mol / hour) was controlled to be 2:1. After the introduction of compound (X6-3) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the benzene was added, fluorine gas was bubbled for 1 hour, and finally, the inside of the reactor was fully replaced with nitrogen gas. The solvent was distilled off to obtain 25.3 g of compound (X6-4). [ka]

[0156] NMR spectrum of compound (X6-4); 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -83 (48F), -87 (44F), -124 (48F), -129 (4F), -131 (2F). Average number of units:10.

[0157] (Synthesis Example 6-5) In a 50mL eggplant flask, 25.3g of the compound (X6-4) obtained in Synthesis Example 6-4, 2.2g of sodium fluoride, and 25mL of AC-2000 were placed and stirred in an ice bath. 1.7g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 15g of compound (X6-5) was obtained. [ka]

[0158] NMR spectrum of compound (X6-5); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (44F), -87 (44F), -119 (4F), -124 (44F). Average number of units:11.

[0159] (Synthesis Example 6-6) In a 50 mL eggplant flask, 15 g of the compound (X6-5) obtained in Synthesis Example 6-5, 3.2 g of H2NCH2C(CH2CH=CH2)3, and 15 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography and separated into three fractions containing the target product. Of these, a total of 11.2 g of compound (X6-6) was obtained. The three fractions were named (C4-6a), (C4-6b), and (C4-6c). Fractions (C4-6a) to (C4-6c) contained compounds (X6-6) and (X6-7). 19 The ratio (CF3 / CF2) was determined by F-NMR. In the ratio, CF3 means the number of moles of the -CF3 group (the -CF3 group in the dotted frame in the formula) at one end of the compound (X6-7), 19 In F-NMR, it is observed at -85 to -87 ppm. In addition, CF2 in the ratio means the total number of moles of the -CF2- group in the vicinity of one terminal of compound (X6-7) (the -CF2- group in the dotted frame in the formula) and the -CF2- groups in the vicinity of both terminals of compound (X6-6) (the -CF2- groups in the dotted frame in the formula), 19 It is observed at -120 ppm in F-NMR. CF3 / CF2=0.11 in fraction (C4-6a) CF3 / CF2=0.06 in fraction (C4-6b) CF3 / CF2=0.05 in fraction (C4-6c)

[0160] [ka]

[0161] NMR spectrum of compound (X6-6); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F). Average number of units:11.

[0162] [ka]

[0163] (Synthesis Example 6-7) In a 50 mL recovery flask, 1 g of the fraction (C4-6a) obtained in Synthesis Example 6-6, 0.21 g of trimethoxysilane, 0.001 g of aniline, 1.0 g of AC-6000, and 0.0033 g of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed and stirred overnight at 25° C. The solvent and the like were distilled off under reduced pressure to obtain 1.2 g of a mixture (M1). The mixture (M1) contained the compound (1-1D) and the compound (1-3A). Using the mixture (M1), 19 The ratio (CF3 / CF2) was determined by F-NMR in the same manner as in Synthesis Example 6-6. The group in the dotted frame in the formula is 19 This is the group that was the subject of F-NMR measurement. CF3 / CF2=0.11 in mixture (M1)

[0164] [ka]

[0165] [ka]

[0166] NMR spectrum of compound (1-3A); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F). The average value of the number of units m+n: 10, Mn of compound (1-3A): 5,200, (OX) of the above formula (1) in compound (1-3A) m The part corresponding to Mn: 4,100

[0167] [Synthesis Example 7] Compound (1-3B) was obtained according to Example 4 of JP2015-199906A. [ka]

[0168] In the above formula (1-3B), p1:q1≒47:53, and p1+q1≒43. Mn of compound (1-3B): 4,800, (OX) of the above formula (1) in compound (1-3B) m The part corresponding to Mn: 4,090

[0169] [Synthesis Example 8] The compound described in paragraph 0048 of JP2015-037541A was used as compound (1-3C). [ka]

[0170] In the above formula (1-3C), p1 / q1=1.0, and p1+q1≒45. Mn of compound (1-3C): 5,390, (OX) of the above formula (1) in compound (1-3C) m The part corresponding to Mn: 4,360

[0171] [Synthesis Example 9] 10 g of the compound (X6-5) obtained according to the above "Synthesis Example 6-5" was purified by column chromatography. The purified product was analyzed by NMR, and it was confirmed that no peaks derived from CF3 were detected. 5 g of the compound (X6-5) and 0.61 g of 3-aminopropyltrimethoxysilane were placed in a 100 mL round-bottom flask and stirred at room temperature for 3 hours. After the reaction was completed, the unreacted materials and by-products were distilled off under reduced pressure to obtain compound (1-3D). (CH3O)3Si-C3H6-NHC(O)-C3F6OC2F4-(OC4F8-OC2F4) n -OC2F4O-(C2F4O-C4F8O) m -C2F4OC3F6-C(O)NH-C3H6-Si(OCH3)3...(1-3D) Mn of compound (1-3D): 5,390, (OX) of the above formula (1) in compound (1-3D) m The portion equivalent to Mn:5,000

[0172] [Synthesis Example 10] Compound (2-1A) was obtained according to Example 10 of WO 2017-038832. CF3-(OCF2CF2-OCF2CF2CF2CF2) 13 OCF2CF2OCF2CF2CF2C(O)NHCH2CH2CH2Si(OCH3)3...(2-1A) Mn of compound (2-1A): 4,870, (OX) of the above formula (1) in compound (2-1A) m The part corresponding to Mn: 4,600

[0173] [Synthesis Example 11] Compound (1-3E) was obtained according to Example 1 of WO 2020-162371. Average value of x1+x2: 10. [ka]

[0174] [Synthesis Example 11] Compound (1-3F) was obtained according to Example 4 of WO 2020-162371. Average value of x1+x2: 10. [ka]

[0175] [Synthesis Example 12] Mixture (M2) was obtained according to Example 1 (Mixture (CB-1a)) of WO 2020-166488.

[0176] [Synthesis Example 13] Mixture (M3) was obtained according to Example 3 (Mixture (CC-1a)) of WO 2020-166488. [Synthesis Example 14] 1-1A and 1A-2 were mixed in a mass ratio of 5:5 to obtain a mixture (M4). 1-1A and 1-3F were mixed in a mass ratio of 5:5 to obtain a mixture (M5). 1-1B and 1-3E were mixed in a mass ratio of 7:3 to obtain a mixture (M6). 1-1B and 1-3E were mixed in a mass ratio of 5:5 to obtain a mixture (M7). 1-1B and 1-3E were mixed in a mass ratio of 3:7 to obtain a mixture (M8). 1-1B and 1-3E were mixed in a mass ratio of 1:9 to obtain a mixture (M9).

[0177] [Example 1-1] 12 g of cation exchange resin (SK1B manufactured by Mitsubishi Chemical Corporation) was added to 20 g of 5 mass% sodium silicate aqueous solution (Showa Chemical Industry Co., Ltd. No. 3 sodium silicate solution) and stirred for 10 minutes. The cation exchange resin was removed by filtration to obtain an aqueous silicic acid solution. 0.25 g of the aqueous silicic acid solution was added to 4.75 g of isopropyl alcohol to obtain a coating solution 1 for forming a silicon oxide layer (solid concentration (SiO2 equivalent): 0.25 mass%). The following measurements were carried out on the silicon oxide layer forming coating solution 1, and it was confirmed that a silicon oxide powder containing 300 ppm of sodium, 0 ppm of lithium, 0 ppm of potassium, 0 ppm of rubidium, and 0 ppm of cesium relative to Si was obtained. (Measurement method) The silicon oxide layer-forming coating solution 1 was dried at 150°C to remove the organic solvent and water, thereby obtaining a silicon oxide powder. The contents of sodium, lithium, potassium, rubidium, and cesium relative to Si contained in the silicon oxide powder were measured by ICP emission spectrometry (SPS5520 manufactured by Hitachi High-Tech Science Corporation).

[0178] One surface of a glass substrate (AGC Corporation's Dragontrail (registered trademark)) was subjected to a corona discharge treatment under conditions of 80 V and 3.5 A using a high-frequency power supply (Kasuga Electric Co., Ltd.'s CG102A). The silicon oxide layer-forming coating solution 1 was applied to the corona discharge-treated surface of the glass substrate by spin coating at a rotation speed of 3,000 rpm for a rotation time of 20 seconds to form a wet film. The wet film was baked at a baking temperature of 550°C for a baking time of 30 minutes to produce a glass substrate with a silicon oxide layer having a thickness of about 10 nm. The average sodium concentration of the resulting silicon oxide layer was determined by TOF-SIMS in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer. The results are shown in Table 1-1.

[0179] 0.5 g of compound (1-1A) was placed as a deposition source in a molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC KIKOU CO., LTD.). The glass substrate with the silicon oxide layer was placed in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 5×10 -3 The inside of the boat was evacuated until the pressure reached a pressure of not more than Pa. The boat was heated to 300° C., and the compound (1-1A) was vacuum-deposited onto the silicon oxide layer to form a deposited film having a thickness of 10 nm. The glass substrate on which the vapor-deposited film was formed was left to stand overnight under conditions of temperature: 25° C. and humidity: 40%, to form a water- and oil-repellent layer having a thickness of 10 nm. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0180] [Example 1-2] MSGEL-D-100-60A (product name, manufactured by AGC Si-Tech Co., Ltd., spherical porous silica gel having an average particle size of 50 to 300 μm. Hereinafter referred to as "MS gel") was molded using a hydrostatic press (180 MPa for 1 minute) to obtain a molded body. The sodium content relative to Si in the MS gel was measured by ICP emission spectroscopy (SPS5520, Hitachi High-Tech Science Corporation) and was found to be 23 ppm. The lithium content was 0 ppm, the potassium content was 0 ppm, the rubidium content was 0 ppm, and the cesium content was 0 ppm.

[0181] The obtained molded body was placed as a deposition source in a molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC KIKOU CO., LTD.). A glass substrate that had been subjected to the same corona discharge treatment as in Example 1-1 was placed in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 5×10 -3 The interior of the boat was evacuated until the pressure reached 10 Pa or less. The boat was heated to 1,000° C., and silicon oxide was vacuum-deposited on the corona discharge-treated surface of the glass substrate, to produce a glass substrate with a silicon oxide layer having a thickness of 10 nm. The average sodium concentration of the resulting silicon oxide layer was determined by TOF-SIMS in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water- and oil-repellent layer. The results are shown in Table 1-1.

[0182] A water- and oil-repellent layer of Example 1-2 was formed in the same manner as in Example 1-1, except that the thus-obtained glass substrate with a silicon oxide layer was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0183] [Example 1-3] The water- and oil-repellent layer of Example 1-3 was formed in the same manner as in Example 1-1, except that the fluorine-containing compound shown in Table 1-1 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0184] [Example 1-4] The water- and oil-repellent layer of Example 1-4 was formed in the same manner as in Example 1-1, except that the baking temperature for forming the silicon oxide layer was changed to 250° C. and a fluorine-containing compound shown in Table 1-1 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0185] [Example 1-5] The water- and oil-repellent layer of Example 1-5 was formed in the same manner as in Example 1-1, except that the fluorine-containing compound shown in Table 1-1 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0186] [Example 1-6] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-2, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of depth 0.1 nm to 0.3 nm became the value in Table 1-1, thereby obtaining the glass substrate with a silicon oxide layer in Example 1-6. The water- and oil-repellent layer of Example 1-6 was formed in the same manner as in Example 1-2, except that the fluorine-containing compound shown in Table 1-1 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0187] [Example 1-7 to Example 1-10] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-1, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of depth 0.1 nm to 0.3 nm became the value in Table 1-1, thereby obtaining the glass substrates with a silicon oxide layer in Examples 1-7 to 1-10. The water- and oil-repellent layers of Examples 1-7 to 1-10 were formed in the same manner as in Example 1-1, except that the fluorine-containing compounds shown in Table 1-1 were used. The water- and oil-repellent layers were evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0188] [Example 1-11] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-2, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of 0.1 to 0.3 nm in depth became the value in Table 1-1, thereby obtaining the glass substrate with a silicon oxide layer of Example 1-11. The water- and oil-repellent layer of Example 1-11 was formed in the same manner as in Example 1-2, except that the fluorine-containing compound shown in Table 1-1 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0189] [Example 1-12~Example 1-13] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-1, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of 0.1 to 0.3 nm in depth became the value in Table 1-1, thereby obtaining the glass substrates with a silicon oxide layer in Examples 1-12 to 1-13. The water- and oil-repellent layers of Examples 1-12 to 1-13 were formed in the same manner as in Example 1-1, except that the fluorine-containing compounds shown in Table 1-1 were used. The water- and oil-repellent layers were evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-1.

[0190] [Example 1-14 to Example 1-25] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-1, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of depth 0.1 nm to 0.3 nm became the value in Table 1-2, thereby obtaining the glass substrates with a silicon oxide layer of Examples 1-14 to 1-25. The water- and oil-repellent layers of Examples 1-14 to 1-25 were formed in the same manner as in Example 1-1, except that the fluorine-containing compounds shown in Table 1-2 were used. The water- and oil-repellent layers were evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 1-2.

[0191] [Table 1-1]

[0192] [Table 1-2]

[0193] [Example 2-1] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-1, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of depth 0.1 nm to 0.3 nm became the value in Table 2, thereby obtaining the glass substrate with a silicon oxide layer in Example 2-1.

[0194] Compound (1-1A) and AC-6000 as a liquid medium were mixed on a dry, clean glass substrate to prepare a coating solution with a solid content of 0.1%. A coating film was formed on the surface of the silicon oxide layer by applying the coating solution using a spray coating device (manufactured by Nordson Corporation). The substrate on which the coating film was formed was baked at 120°C for 60 minutes to form a water- and oil-repellent layer. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 2.

[0195] [Example 2-2] A glass substrate with a silicon oxide layer of Example 2-2 was obtained in the same manner as in Example 1-1, except that the firing temperature in forming the silicon oxide layer was changed to 250°C. The water- and oil-repellent layer of Example 2-2 was formed in the same manner as in Example 2-1, except that the fluorine-containing compound shown in Table 2 was used. The water- and oil-repellent layer was evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 2.

[0196] [Example 2-3 to Example 2-10] With reference to the manufacturing method of the glass substrate with a silicon oxide layer in Example 1-1, the manufacturing conditions of the silicon oxide layer were adjusted so that the average value of the sodium concentration in the region of depth 0.1 nm to 0.3 nm became the value in Table 1-1, thereby obtaining the glass substrates with a silicon oxide layer in Examples 2-3 to 2-10. The water- and oil-repellent layers of Examples 2-3 to 2-10 were formed in the same manner as in Example 2-1, except that the fluorine-containing compounds shown in Table 2 were used. The water- and oil-repellent layers were evaluated for initial water contact angle and abrasion resistance. The results are shown in Table 2.

[0197] [Table 2]

[0198] As shown in Tables 1-1, 1-2, and 2, the average concentration of alkali metal atoms in the region 0.1 to 0.3 nm deep from the surface in contact with the water- and oil-repellent layer is 2.0×10 19 atoms / cm 3It was confirmed that the use of an article having the above-described silicon oxide layer and a water- and oil-repellent layer made of a hydrolysis condensate of a fluorine-containing compound represented by formula (1) provided the water- and oil-repellent layer with excellent abrasion resistance (Examples 1-1 to 1-12 and Examples 2-1 to 2-9). [Industrial Applicability]

[0199] The article with the water- and oil-repellent layer of the present invention can be used in various applications where water- and oil-repellent properties are required. For example, it can be used in display input devices such as touch panels; transparent glass or transparent plastic members, lenses for glasses, and kitchen stain-proof members; water- and moisture-repellent and stain-proof members for electronic devices, heat exchangers, batteries, and the like; stain-proof members for toiletries; members that require liquid repellency while being conductive; water-repellent, waterproof, and water-slippery members for heat exchangers; low-friction surface members for vibration sieves and cylinder interiors, and the like. More specific examples of use include front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays, or those with anti-reflection film treatment on their surfaces, and various devices having display input devices for operating the screen with a person's finger or palm, such as touch panel sheets and touch panel displays for devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls (e.g., glass or film used for the display unit, etc., and glass or film used for the exterior parts other than the display unit). In addition to the above, other examples include decorative building materials for wet areas such as toilets, baths, washrooms, and kitchens; waterproof materials for wiring boards; water-repellent, waterproof, and water-slippery materials for heat exchangers; water-repellent materials for solar cells; waterproof and water-repellent materials for printed wiring boards; waterproof and water-repellent materials for electronic device housings and electronic components; materials for improving the insulation of power transmission lines; waterproof and water-repellent materials for various filters; waterproof materials for radio wave absorbing materials and sound absorbing materials; stain-resistant materials for bath, kitchen equipment, and toiletries; low-friction surface materials for vibrating sieves and the inside of cylinders, etc.; machine parts, vacuum equipment parts, bearing parts, and transportation equipment parts for automobiles, etc.; and surface protection materials for tools, etc. The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2019-185182, filed on October 8, 2019, are hereby incorporated by reference as the disclosure of the specification of the present invention. [Explanation of symbols]

[0200] 10. Articles with water- and oil-repellent layers 12 Base material 14 Silicon oxide layer 16 Water- and oil-repellent layer

Claims

1. A substrate; a water- and oil-repellent layer made of a hydrolysis condensate of a fluorine-containing compound represented by formula (1-3); a silicon oxide layer containing alkali metal atoms, the silicon oxide layer being present between the substrate and the water- and oil-repellent layer; In the silicon oxide layer, the average concentration of alkali metal atoms in a region having a depth of 0.1 to 0.3 nm from the surface in contact with the water-repellent and oil-repellent layer is 2.0×10 １９ atoms / cm ３ An article with a water- and oil-repellent layer, characterized in that: [L 3-n (R) n Si-] k3 Y 32 -(OX) m -O-Y 31 [-Si(R) n L 3-n] g3...(1-3) However, in formula (1-3), X is a fluoroalkylene group having one or more fluorine atoms; m is an integer of 2 or more, R is a monovalent hydrocarbon group; L is a hydrolyzable group or a hydroxyl group; n is an integer from 0 to 2, k3 is an integer of 2 or 3; Y 32 represents a (k3+1)-valent linking group; Y 31 represents a (g3+1)-valent linking group; g3 is an integer of 2 or 3.

2. The average concentration of the alkali metal atoms is 4.0×10 ２２ atoms / cm ３ 2. The article of claim 1 , wherein:

3. 3. The article of claim 1 or 2, wherein at least a portion of the alkali metal atoms are sodium atoms.

4. The article according to any one of claims 1 to 3, wherein the silicon oxide in the silicon oxide layer comprises a condensate of silicic acid or a hydrolysis condensate of an alkoxysilane.

5. The article of any one of claims 1 to 4, wherein the silicon oxide in the silicon oxide layer comprises a deposit of silicon oxide containing alkali metal atoms.

6. The article according to any one of claims 1 to 4, wherein the silicon oxide layer is a silicon oxide layer formed on the surface of the substrate by a wet coating method from a coating liquid containing a silicon oxide precursor, an alkali metal source, and a solvent.

7. The article according to any one of claims 1 to 5, wherein the silicon oxide layer is a silicon oxide layer formed on the substrate by a dry coating method from silicon oxide containing alkali metal atoms.

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