Substrate with water- and oil-repellent layer and method for manufacturing substrate with water- and oil-repellent layer

Abstract

Provided are a substrate provided with a water-and-oil-repellent layer having excellent abrasion resistance and a method for producing a substrate provided with a water-and-oil-repellent layer.　A substrate provided with a water-and-oil-repellent layer having a substrate, an underlayer formed on the surface of the substrate, and a water-and-oil-repellent layer formed on the surface of the underlayer, in which the underlayer contains an oxide that contains silicon and a specific element, and the water-and-oil-repellent layer comprises a hydrolytic condensate of a fluorine-containing ether compound selected from the group consisting of compounds represented by formula (A1) and compounds represented by formula (A2). Formula (A1): Rf-O-(Rf1O)m-Rf2[-R1-C(-R2-T)a(-R3)3-a]b Formula (A2): [(T-R2-)a(R3-)3-aC-R1-]bRf2-O-(Rf1O)m-Rf2[-R1-C(-R2-T)a(-R3)3-a]b

Description

[Technical Field]

[0001] The present invention relates to a substrate with a water- and oil-repellent layer, and a method for producing a substrate 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 hydrolysis condensate of a fluorine-containing compound on the surface of the substrate by surface treatment using a silane compound containing a perfluoro(poly)ether group (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 022437 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the performance requirements for water- and oil-repellent layers have become higher, and water- and oil-repellent layers with superior water- and oil-repellency and abrasion resistance are being sought. The water- and oil-repellent layer formed using the perfluoro(poly)ether group-containing silane compound described in Patent Document 1 had insufficient abrasion resistance.

[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a substrate with a water- and oil-repellent layer that is excellent in abrasion resistance, and a method for producing a substrate with a water- and oil-repellent layer. [Means for solving the problem]

[0006] The present invention includes the following [1] to

[12] . [1] A substrate, an underlayer formed on the surface of the substrate, and a water- and oil-repellent layer formed on the surface of the underlayer, the underlayer comprises an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table; A substrate with a water- and oil-repellent layer, wherein the water- and oil-repellent layer comprises a hydrolysis condensate of a fluorinated ether compound selected from the group consisting of a compound represented by formula (A1) and a compound represented by formula (A2): R f -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b ···(A1) [(TR 2 -) a (R 3 -) 3-a CR 1 -] b R f2 -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b ···(A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f2 is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R 1 The carbon atom bonded to R has a fluorine atom, f2 If there are multiple R f2 may be the same or different, R 1 is an alkylene group having 1 to 20 carbon atoms, R 2is an alkylene group having 2 to 20 carbon atoms which may have a fluorine atom, and a plurality of R 2 may be the same or different, R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 3 If there are multiple R 3 may be the same or different, T is -Si(R) 3-c (L) c where multiple T's may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different; m is an integer from 1 to 20; a is an integer of 1 to 3, and when there are multiple a's, the multiple a's may be the same or different; b is an integer of 1 or more, and when there are multiple b's, the multiple b's may be the same or different, c is 2 or 3, and multiple c's may be the same or different; When b is 1, a is 2 or 3.

[0007] [2] R f2 b partial structures "-CQF-* (where Q is a hydrogen atom, a fluorine atom or CF3, -* is R 1 The substrate with a water- and oil-repellent layer according to [1], wherein the hydrocarbon group has "a bond bonded to the water- and oil-repellent layer." [3] The b is 1, and the R f2 The substrate with a water- and oil-repellent layer according to [1] or [2], wherein is a perfluoroalkylene group having 1 to 6 carbon atoms. [4] The substrate with a water- and oil-repellent layer according to any one of [1] to [3], wherein the specific element is at least one selected from the group consisting of Group 1 elements, Group 2 elements, and Group 13 elements of the periodic table. [5] The substrate with a water- and oil-repellent layer according to any one of [1] to [4], wherein the specific element is an element of Group 1 of the periodic table. [6] The substrate with a water- and oil-repellent layer according to any one of [1] to [5], wherein b is 1. [7] The substrate with a water- and oil-repellent layer according to any one of [1] to [6], wherein a is 3. [8] The substrate with a water- and oil-repellent layer according to any one of [1] to [7], wherein the ratio of the total molar concentration of the specific elements to the molar concentration of silicon in the underlayer is 0.02 to 2.90.

[0008] [9] A method for producing a substrate with a water- and oil-repellent layer, the substrate having a substrate, an undercoat layer, and a water- and oil-repellent layer in this order, comprising: forming an underlayer on the substrate, the underlayer including an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table; Next, a water- and oil-repellent layer comprising a hydrolysis condensate of a fluorinated ether compound selected from the group consisting of a compound represented by formula (A1) and a compound represented by formula (A2) is formed on the underlayer. R f -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b ···(A1) [(TR 2 -) a (R 3 -) 3-a CR 1 -] b R f2 -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b···(A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f2 is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R 1 The carbon atom bonded to R has a fluorine atom, f2 If there are multiple R f2 may be the same or different, R 1 is an alkylene group having 1 to 20 carbon atoms, R 2 is an alkylene group having 2 to 20 carbon atoms which may have a fluorine atom, and a plurality of R 2 may be the same or different, R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 3 If there are multiple R 3 may be the same or different, T is -Si(R) 3-c (L) c where multiple T's may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different; m is an integer from 1 to 20; a is an integer of 1 to 3, and when there are multiple a's, the multiple a's may be the same or different; b is an integer of 1 or more, and when there are multiple b's, the multiple b's may be the same or different, c is 2 or 3, and multiple c's may be the same or different; When b is 1, a is 2 or 3.

[0009]

[10] R f2b partial structures "-CQF-* (where Q is a hydrogen atom, a fluorine atom or CF3, -* is R 1 The method for producing a substrate with a water- and oil-repellent layer according to [9], wherein the hydrocarbon group has "a bond bonded to the water- and oil-repellent layer."

[11] The b is 1, and the R f2 The method for producing a substrate with a water- and oil-repellent layer according to [9] or

[10] , wherein

[12] The substrate with a water- and oil-repellent layer according to any one of [1] to [8], which is used as an optical member. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a substrate with a water- and oil-repellent layer that is excellent in abrasion resistance, and a method for producing a substrate with a water- and oil-repellent layer. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a substrate with a water- and oil-repellent layer of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this specification, the compound represented by formula (A1) will be referred to as compound (A1), and the same applies to compounds represented by other formulas. As used herein, the following terms have the following meanings: The term "reactive silyl group" refers collectively to a hydrolyzable silyl group and a silanol group (Si-OH). The reactive silyl group is, for example, T in formula (A1) or formula (A2), i.e., -Si(R) 3-c (L) c is. The term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19The number average molecular weight is calculated by F-NMR to determine the number (average value) of oxyfluoroalkylene units based on the terminal group. The terminal group is, for example, R f Or it is T in formula (A1) or formula (A2). When the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is uniform, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 F-NMR f The molecular weight is calculated by determining the structure of the molecule.

[0013] [Base material with water- and oil-repellent layer] The substrate with a water- and oil-repellent layer of the present invention has a substrate, an underlayer, and a water- and oil-repellent layer in this order. 1 is a cross-sectional view schematically illustrating an example of a substrate with a water- and oil-repellent layer of the present invention. The substrate 10 with a water- and oil-repellent layer has a substrate 12, an underlayer 14 formed on one surface of the substrate 12, and a water- and oil-repellent layer 16 formed on the surface of the underlayer 14. 1, the substrate 12 and the underlayer 14 are in contact with each other, but the present invention is not limited to this, and the substrate with a water- and oil-repellent layer may have another layer (not shown) between the substrate 12 and the underlayer 14. Furthermore, in the example of FIG. 1, the underlayer 14 and the water- and oil-repellent layer 16 are in contact with each other, but the substrate with a water- and oil-repellent layer may have another layer (not shown) between the underlayer 14 and the water- and oil-repellent layer 16. 1, the base layer 14 is formed over the entire surface of one of the surfaces of the substrate 12, but this is not limiting, and the base layer 14 may be formed over only a partial region of the substrate 12. Furthermore, in the example of FIG. 1, the water- and oil-repellent layer 16 is formed over the entire surface of the base layer 14, but this is not limiting, and the water- and oil-repellent layer 16 may be formed over only a partial region of the base layer 14. In the example of Figure 1, the base 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 to this, and the base layer 14 and the water- and oil-repellent layer 16 may be formed on both sides of the substrate 12.

[0014] (base material) The substrate is not particularly limited as long as it is a substrate that is required to be water- and oil-repellent. Specific examples of substrate materials 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 particularly preferably a substrate for a touch panel. The substrate for a touch panel is preferably light-transmitting. "Light-transmitting" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the substrate for a touch panel is preferably glass or a transparent resin. Examples of substrates include the following: glass or resin used for building materials, decorative building materials, interior goods, transportation equipment (e.g., automobiles), signs and bulletin boards, drinking vessels and tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, art, sports, and games, and glass or resin used for the exterior parts (excluding the display) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls. The substrate may be in the form of a plate or film.

[0015] The substrate may be a substrate whose one or both surfaces have been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. The surface-treated surface improves adhesion between the substrate and the underlayer, resulting in improved abrasion resistance of the water- and oil-repellent layer. Therefore, it is preferable to apply the surface treatment to the surface of the substrate that comes into contact with the underlayer.

[0016] (base layer) The underlayer is a layer containing an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table.

[0017] Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") refer to lithium, sodium, potassium, rubidium, and cesium. As Group 1 elements, lithium, sodium, and potassium are preferred, with sodium and potassium being particularly preferred, in that they enable the water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, and in that variations in the composition of the underlayer between samples are further suppressed. The underlayer may contain two or more types of Group 1 elements.

[0018] Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") refer to beryllium, magnesium, calcium, strontium, and barium. As Group 2 elements, magnesium, calcium, and barium are preferred, with magnesium and calcium being particularly preferred, because they enable the water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, or because they further suppress variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 2 elements.

[0019] Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") refer to titanium, zirconium, and hafnium. As Group 4 elements, titanium and zirconium are preferred, with titanium being particularly preferred, because they enable the water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, and because they further suppress variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 4 elements.

[0020] The Group 5 elements of the periodic table (hereinafter also referred to as "Group 5 elements") refer to vanadium, niobium, and tantalum. Vanadium is particularly preferred as a Group 5 element because it provides the water- and oil-repellent layer with superior abrasion resistance. The underlayer may contain two or more Group 5 elements.

[0021] Group 13 elements of the periodic table (hereinafter also referred to as "Group 13 elements") refer to boron, aluminum, gallium, and indium. As Group 13 elements, boron, aluminum, and gallium are preferred, and boron and aluminum are particularly preferred, because they enable the water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, or because they further suppress variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 13 elements.

[0022] Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth. As Group 15 elements, phosphorus, antimony, and bismuth are preferred, with phosphorus and bismuth being particularly preferred, because they enable the water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, and because they further suppress variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 15 elements.

[0023] As the specific elements contained in the underlayer, Group 1 elements, Group 2 elements, and Group 13 elements are preferred because they provide the water- and oil-repellent layer with better abrasion resistance, Group 1 elements and Group 2 elements are more preferred, and Group 1 elements are particularly preferred. The specific element may be one kind of element or two or more kinds of elements.

[0024] The oxide contained in the underlayer may be a mixture of oxides of the above elements (silicon and specific element) alone (for example, a mixture of silicon oxide and an oxide of a specific element), a composite oxide containing two or more of the above elements, or a mixture of an oxide of the above elements alone and a composite oxide.

[0025] The ratio of the total molar concentration of the specific elements in the underlayer to the molar concentration of silicon in the underlayer (specific elements / silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and particularly preferably 0.20 to 1.80, in order to provide a water- and oil-repellent layer with better abrasion resistance. The molar concentration (mol %) of each element in the underlayer can be measured, for example, by depth direction analysis by X-ray photoelectron spectroscopy (XPS) using ion sputtering.

[0026] The underlayer may be a single layer or multiple layers. The underlayer may have an uneven surface. The thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the above lower limit, the adhesion of the underlayer to the water- and oil-repellent layer is further improved, and the abrasion resistance of the water- and oil-repellent layer is further improved. If the thickness of the underlayer is equal to or less than the above upper limit, the abrasion resistance of the underlayer itself is excellent. The thickness of the underlayer is measured by observing the cross section of the underlayer with a transmission electron microscope (TEM).

[0027] (Water and oil repellent layer) The water- and oil-repellent layer comprises a hydrolysis condensate of a fluorine-containing ether compound selected from the group consisting of the compound (A1) and the compound (A2). The fluorine-containing ether compound is a fluorine-containing compound having a reactive silyl group. That is, the water- and oil-repellent layer contains a condensate obtained by hydrolysis and dehydration condensation of some or all of the reactive silyl groups of the fluorine-containing compound. More specifically, the water- and oil-repellent layer may be composed of a hydrolysis condensate of compound (A1), or may be composed of a hydrolysis condensate of compound (A2), or may be composed of both a hydrolysis condensate of compound (A1) and a hydrolysis condensate of compound (A2). R f -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b (A1) [(TR 2 -) a (R 3 -) 3-a CR 1 -]b R f2 -O-(R f1 O) m -R f2 [-R 1 -C(-R 2 -T) a (-R 3 ) 3-a ] b ···(A2)

[0028] however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f2 is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R 1 The carbon atom bonded to R has a fluorine atom, f2 If there are multiple R f2 may be the same or different, R 1 is an alkylene group having 1 to 20 carbon atoms, R 2 is an alkylene group having 2 to 20 carbon atoms which may have a fluorine atom, and a plurality of R 2 may be the same or different, R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 3 If there are multiple R 3 may be the same or different, T is -Si(R) 3-c (L) c where multiple T's may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different; m is an integer from 1 to 20; a is an integer of 1 to 3, and when there are multiple a's, the multiple a's may be the same or different; b is an integer of 1 or more, and when there are multiple b's, the multiple b's may be the same or different, c is 2 or 3, and multiple c's may be the same or different; When b is 1, a is 2 or 3.

[0029] The compound (A1) and the compound (A2) both have a polyfluoropolyether chain [R f -O-(R f1 O) m -] or [-O-(R f1 O) m -], a reactive silyl group, and a specific linking group -R connecting the polyfluoropolyether chain and the reactive silyl group. f2 [-R 1 -C(-R 2 -) a ] b It has the following. Compound (A1) is a compound having a structure of "monovalent polyfluoropolyether chain-linking group-reactive silyl group", and compound (A2) is a compound having a structure of "reactive silyl group-linking group-divalent polyfluoropolyether chain-linking group-reactive silyl group".

[0030] In the compounds (A1) and (A2), the linking group is composed of a hydrocarbon group, which improves the chemical stability compared to linking groups containing an ether bond or the like, which are contained in conventionally widely used compounds.

[0031] R f is a fluoroalkyl group having 1 to 20 carbon atoms. R f The number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3, in that the water- and oil-repellent layer will have better water- and oil-repellency or abrasion resistance. R f The fluoroalkyl group R is preferably a perfluoroalkyl group, since the water- and oil-repellent layer has better water- and oil-repellency or abrasion resistance. fIn the compound (A1) in which the terminal is a perfluoroalkyl group, the terminal is CF3-. The compound (A1) in which the terminal is CF3- can form a water- and oil-repellent layer with low surface energy, and therefore the water- and oil-repellent layer has better water- and oil-repellency and abrasion resistance. R f Examples of the fluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0032] (R f1 O) m As the structure, a structure represented by the following formula (D1) is preferred, in that the water- and oil-repellent layer has better water- and oil-repellency or abrasion resistance. (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 (D1) however, R f11 is a fluoroalkylene group having one carbon atom, R f12 is a fluoroalkylene group having 2 carbon atoms, R f13 is a fluoroalkylene group having 3 carbon atoms, R f14 is a fluoroalkylene group having 4 carbon atoms, R f15 is a fluoroalkylene group having 5 carbon atoms, R f16 is a fluoroalkylene group having 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 200, and R f11 ~R f16 If there are multiple Rf11 ~R f16 may be the same or different. In addition, (R f11 O)~(R f16 O) can be bonded in any order. m1 to m6 in formula (D1) are each f11 O)~(R f16 O), not the arrangement. For example, (R f15 O) m5 is (R f15 O) is m5, and (R f5 O) m5 Similarly, (R f11 O)~(R f16 The order of the units does not represent the bonding order of the units.

[0033] The fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or may be a fluoroalkylene group having a branched or cyclic structure. R f1 As for the total number m of groups, it is preferable that 50 to 100% in number are perfluoroalkylene groups, more preferably 80 to 100% are perfluoroalkylene groups, and particularly preferably that all of them are perfluoroalkylene groups. R f11 Specific examples of R include CHF and CF2. f12 Specific examples of R include CF2CF2, CF2CHF, and CF2CH2. f13 Specific examples of R include CF2CF2CF2, CF2CF2CHF, CF2CHFCF2, CF2CF2CH2, CF2CH2CF2, and CF(CF3)CF2. f14 Specific examples of R include CF2CF2CF2CF2, CF2CF2CF2CH2, CHFCF2CF2CF2, CF2CH2CF2CF2, CF(CF3)CF2CF2, and perfluorocyclobutane-1,2-diyl group. f15Specific examples of R include CF2CF2CF2CF2CF2, CF2CF2CF2CF2CH2, CHFCF2CF2CF2CF2, and CF2CF2CH2CF2CF2. f16 Specific examples include CF2CF2CF2CF2CF2CF2, CF2CF2CF2CF2CF2CH2, and CF2CF2CF2CF2CF2CHF.

[0034] R f2 is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R 1 The carbon atom bonded to R has a fluorine atom. f2 As the compound, there are b partial structures "-CQF-* (wherein Q is a hydrogen atom, a fluorine atom, or CF3, and -* is R 1 It is preferable that the hydrocarbon group has a bond "(R)" which is a bond bonded to the alkyl group. The hydrocarbon group may be a linear or branched chain hydrocarbon group, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a combination thereof. The hydrocarbon group may have a double or triple bond in the carbon chain. Examples of the combination include a chain hydrocarbon group bonded to an aliphatic hydrocarbon ring, or a chain hydrocarbon group bonded to an aromatic hydrocarbon ring. R f2 The number of carbon atoms is preferably 1 to 18, and more preferably 1 to 16.

[0035] If b is 1, R f2 is a divalent group. In this case, R f2 In terms of the water- and oil-repellent properties or abrasion resistance of the water- and oil-repellent layer, when b is 1, R f2 Among these, R is preferably a fluoroalkylene group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkylene group having 1 to 6 carbon atoms. f2Specific examples of -CHF-*, -CF2-*, CF2CF2-*, CF2CHF-*, CH2CF2-*, CF2CF2CF2-*, CF2CF2CHF-*, CF2CHFCF2-*, CH2CF2CF2-*, CF2CH2CF2-*, CF(CF3)CF2-*, CF2CF2CF2CF2-*, CH2CF2CF2CF2-*, CHFCF2CF2CF2-*, CF 2CH2CF2CF2-*, CF(CF3)CF2CF2-*, CF2CF2CF2CF2CF2-*, CH2CF2CF2CF2CF2-*, CHFCF2CF2CF2CF2-*, CF2CF2CH2CF2CF2-*, CF2CF2CF2CF2CF2CF2-*, CH2CF2CF2CF2CF2CF2-*, CF2CF2CF2CF2CF2CHF-*.

[0036] If b is 2 or more, R f2 is a (1+b)-valent group having one or more branching points P selected from a tertiary carbon atom, a quaternary carbon atom, and a ring structure. The carbon atoms constituting the branch points are preferably tertiary or quaternary carbon atoms, as this facilitates the production of the compound and provides the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance. Examples of ring structures constituting the branching points include 3- to 8-membered aliphatic rings, 6- to 8-membered aromatic rings, and fused rings consisting of two or more of these rings, from the viewpoints of ease of compound production and superior water / oil repellency or abrasion resistance of the water / oil repellent layer. Examples of ring structures constituting the branching points include ring structures shown in the following formula. The following ring structures may be substituted with fluorine atoms. Furthermore, the ring structures may have, as a substituent, an alkyl group, cycloalkyl group, alkenyl group, aryl group, or the like, which may have a halogen atom.

[0037] [ka]

[0038] R f2 As R, a combination of two or more divalent fluoroalkylene groups and one or more branch points P is preferred.f2 When has a hydrocarbon ring, a combination of a hydrocarbon ring having three or more branching points P and two or more divalent fluoroalkylene groups is preferred. R f2 Preferred examples of when R is trivalent or more are shown below. F (R f1 O) m represents R, and -* represents R 1 represents the bond that bonds to R F is R f2 Do not configure. [ka]

[0039] R 1 is an alkylene group having 1 to 20 carbon atoms. 1 does not contain a fluorine atom. 1 The number of carbon atoms in R is preferably 5 to 20, particularly preferably 7 to 10, from the viewpoint of providing a water- and oil-repellent layer with better water- and oil-repellent properties or abrasion resistance. 1 The number of carbon atoms is preferably an odd number, and particularly preferably 3, 5, 7 or 9.

[0040] R 2 R is an alkylene group having 2 to 20 carbon atoms which may have a fluorine atom. 2 The number of carbon atoms in R is preferably 3 to 20, more preferably 3 to 10, in order to provide the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance. 2 At least one of these preferably has 3 to 10 carbon atoms, as this provides the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance.

[0041] R 3 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom. 3As the alkyl group, a hydrogen atom and an alkyl group having 1 to 8 carbon atoms which may have a fluorine atom are preferred, and a hydrogen atom is more preferred, in terms of providing the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance.

[0042] T is -Si(R) 3-c (L) c and is a reactive silyl group. The reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group then undergoes a dehydration condensation reaction between molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Specific examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 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 the hydrolyzable group, an alkoxy group and a halogen atom are preferred from the viewpoint of ease of compound production. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred from the viewpoint of less outgassing during coating and excellent storage stability of the compound, an ethoxy group is particularly preferred when long-term storage stability of the compound is required, and a methoxy group is particularly preferred when the reaction time after coating is short. The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound. As c, 2 and 3 are preferred, and 3 is more preferred, since the adhesion of the water- and oil-repellent layer is stronger. The plurality of T's may be the same or different. From the viewpoint of ease of production of the compound, it is preferable that the plurality of T's are the same group.

[0043] In addition, in order to improve the water / oil repellency or abrasion resistance of the water / oil repellent layer, it is preferable to have two or more Ts at each end. From this viewpoint, when b is 1, a is 2 or 3. In addition, in order to provide the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance, b is preferably 1. When there are multiple b's, it is preferable that all of the b's are 1. In order to provide the water- and oil-repellent layer with better water- and oil-repellency or abrasion resistance, it is preferable that a is 3. When there are a plurality of a's, it is preferable that all of them are 3.

[0044] Examples of the compound (A1) and the compound (A2) include compounds of the following formulae: From the viewpoint of durability, the weight average molecular weight (Mw) / number average molecular weight (Mn) of the present compound is preferably 1.2 or less.

[0045] [ka]

[0046] [ka] In the formula, n3 and n4 represent the number of repeating units and are each independently an integer of 1 to 100.

[0047] (Method for producing compound (A1) and compound (A2)) Compound (A1) can be produced, for example, by subjecting the following compound (A11) to a hydrosilylation reaction with compound (1a). Compound (A2) can be produced, for example, by subjecting the following compound (A21) to a hydrosilylation reaction with compound (1a). These hydrosilylation reactions can be carried out by known methods. R f -O-(R f1 O) m -R f2 [-R 1 -C(-R 20 -CH=CH2) a(-R 3 ) 3-a ] b (A11) [(CH2=CH-R 20 -) a (R 3 -) 3-a CR 1 -] b R f2 -O-(R f1 O) m -R f2 [-R 1 -C(-R 20 -CH=CH2) a (-R 3 ) 3-a ] b (A21) HSi® 3-c (L) c (1a) However, R in the formula 20 is a single bond or an alkylene group having 1 to 8 carbon atoms which may have a fluorine atom, and R 20 The symbols other than are the same as those in the above formula (A1) or formula (A2). -R 20 -CH=CH2 is converted to R after hydrosilylation 2 R 20 As for R 2 The same groups as those mentioned above can be mentioned, and the preferred forms are also the same.

[0048] (Method for producing compound (A11) and compound (A21)) Compound (A11) can be produced, for example, by reacting the following compound (A12) with the following compound (B2). Compound (A21) can be produced, for example, by reacting the following compound (A22) with the following compound (B2). R f -O-(R f1 O) m -R f2 -CH2-L 2 (A12) L 2 -CH2-R f2 -O-(R f1 O) m -Rf2 -CH2-L 2 (A22) (CH2=CH-R 20 -) a (R 3 -) 3-a CR 21 -MgX (B2) however, L 2 is a sulfonate group, R 21 is a single bond or an alkylene group having 1 to 19 carbon atoms, X is a chlorine atom, a bromine atom, or an iodine atom; The other symbols are the same as those in the above formula (A1) or formula (A2).

[0049] The compound (A12) or the compound (A22) reacts with the compound (B2) as shown in the following scheme (1).

[0050] Scheme (1) -R f2 -CH2-L 2 + XMg-R 21 - → -R f2 -CH2-R 21 - However, each symbol in the scheme (1) is as described above. After the above reaction, CH2-R 21 is the compound R 1 is equivalent to

[0051] L 2 is a sulfonate group (-O-SO2-R 22 ), the reaction proceeds. 22 is an organic group. 2 By selecting a sulfonate group as the aryl group, the reaction of the above scheme (1) can be carried out under relatively mild conditions and in high yield. Specific examples of the sulfonate group include a tosylate group (OTs), a mesylate group (OMs), a triflate group (OTf), and a nonaflate group (ONf). Among these, the triflate group is preferred in terms of the reaction yield of Scheme (1).

[0052] Compound (A12) or compound (A22) can be produced by a method in which a compound represented by the following compound (A13) or compound (A23) is reacted with trifluoromethanesulfonic anhydride, tosyl chloride, mesyl chloride, or the like in the presence of an organic amine compound such as triethylamine or pyridine to form a sulfonate. R f -O-(R f1 O) m -R f2 -CH2-OH (A13) L 2 -CH2-R f2 -O-(R f1 O) m -R f2 -CH2-OH (A23) However, A in the formula 1 , A 2 and n is as previously described.

[0053] Compound (A13) and compound (A23) can be produced by referring to, for example, WO 2017 / 038830.

[0054] The compound (B2) can be produced, for example, by reacting the following compound (B1) with metallic magnesium. (CH2=CH-R 20 -) a (R 3 -) 3-a CR 21 -X (B1) However, R in the formula 20 , R 21 , R 3 , X and a are the same as in compound (B2).

[0055] Specific preferred examples of the compound (B2) include the following: [ka]

[0056] In the reaction of scheme (1), the amount of compound (B2) used is determined based on the amount of compound (A12) or the sulfonate group L contained in compound (A12) from the viewpoint of improving the yield of the target compound. 2 The amount is preferably 1 to 30 equivalents, more preferably 3 to 20 equivalents, and particularly preferably 5 to 15 equivalents, relative to the total number of the above.

[0057] In the reaction of Scheme (1), it is preferable to use a transition metal compound as a catalyst, as this improves reactivity and enables a high yield. The transition metal compound can be appropriately selected from known catalysts used in Grignard reactions. As the transition metal compound, a compound containing an element from Groups 3 to 12 of the periodic table as a transition metal is preferred, and among these, a compound containing an element from Groups 8 to 11 is preferred. Among these, the element from Groups 8 to 11 preferably contains one or more elements selected from the group consisting of copper, nickel, palladium, cobalt, and iron, and it is particularly preferred that the compound further contains copper.

[0058] When the transition metal compound contains copper, the copper may be any of zero-, mono-, di-, and trivalent compounds, but from the viewpoint of catalytic activity, it is preferably a salt or complex salt of monovalent or divalent copper, and more preferably copper chloride from the viewpoint of availability. The amount of the transition metal compound used is determined by the amount of the sulfonate group L 2 The content is preferably 0.1 to 50 mol %, more preferably 1 to 30 mol %, and particularly preferably 2 to 20 mol %, based on the total number of the above.

[0059] The transition metal compound may be used in combination with a ligand. The use of a ligand improves the yield of the target product. However, in the present production method, a sufficient yield can be obtained without using a ligand, so the use of the ligand is not necessary. Specific examples of the ligand include 1,3-butadiene, phenylpropyne, and tetramethylethylenediamine (TMEDA). When a ligand is used, the amount used is determined so that the sulfonate group L 2 The amount used is preferably 0.01 to 2.0 equivalents, more preferably 0.1 to 1.2 equivalents, based on the total amount of the compounds.

[0060] The reaction of Scheme (1) is usually carried out in a solvent. The solvent can be appropriately selected from solvents capable of dissolving the above-mentioned Compound (A12), Compound (A13), and Compound (B2). The solvent may be a single solvent or a mixed solvent of two or more solvents. For example, when compound (A12) or compound (A13) is a compound having a relatively low fluorine atom content (the ratio of fluorine atoms to the molecular weight of the compound molecule), the solvent is not particularly limited as long as it is inert to the reaction. Among the solvents inert to the reaction, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane are preferred, and tetrahydrofuran is more preferred. When the compound (A12) or the compound (A13) has a relatively high fluorine atom content, a mixed solvent of an ether-based solvent and a fluorine-based solvent is preferred. Specific examples of fluorine-based solvents include hydrofluorocarbons (1H,4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 2H,3H-perfluoropentane, etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), etc.), hydrofluoroethers (CF3CH2OCF2CF2H(AE3000), (perfluorobutoxy)methane, (perfluorobutoxy)ethane, etc.), hydrochlorofluorocarbons (e.g., ... Examples of suitable fluoroolefins include (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z) form), (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(E) form), (Z)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z) form), (E)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E) form), etc.), and fluorine-containing aromatic compounds such as perfluorobenzene, m-bis(trifluoromethyl)benzene (SR-solvent), and p-bis(trifluoromethyl)benzene.

[0061] The reaction of Scheme (1) can be carried out, for example, by preparing a solution containing compound (A12) or compound (A13), adding a transition metal compound and, if necessary, a ligand, and then adding a separately prepared solution of compound (B2). The reaction temperature in scheme (1) may be, for example, from -20°C to 66°C (the boiling point of tetrahydrofuran), and is preferably from -20°C to 40°C.

[0062] The thickness of the water- and oil-repellent layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the water- and oil-repellent layer is equal to or greater than the lower limit, the effects of the water- and oil-repellent layer can be sufficiently obtained. When the thickness of the water- and oil-repellent layer is equal to or less than the upper limit, utilization efficiency is high. 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 X-ray reflectometry (XRR) using an X-ray diffractometer for thin film analysis.

[0063] [Method of manufacturing a substrate with a water- and oil-repellent layer] In the method for producing a substrate with a water- and oil-repellent layer of the present invention, an underlayer containing an oxide containing silicon and the specific element is formed on the substrate, and then a water- and oil-repellent layer consisting of a hydrolysis condensate of a fluorinated ether compound selected from the group consisting of compound (A1) and compound (A2) is formed on the underlayer. (Formation of base layer) The underlayer is formed by a vapor deposition method using a vapor deposition material or a wet coating method.

[0064] <Vapor deposition method> The deposition material used in the deposition method includes an oxide containing silicon and a specific element. Specific examples of the form of the deposition material include powder, melt, sintered body, granulated body, and crushed body, and from the viewpoint of handleability, melt, sintered body, and granulated body are preferred. Here, the term "molten body" refers to a solid obtained by melting a powder of a deposition material at a high temperature and then cooling and solidifying it. The term "sintered body" refers to a solid obtained by firing a powder of a deposition material, and if necessary, a molded body obtained by pressing the powder may be used instead of the powder of the deposition material. The term "granulated body" refers to a solid obtained by kneading a powder of a deposition material with a liquid medium (e.g., water or an organic solvent) to obtain particles, and then drying the particles.

[0065] The deposition material can be produced, for example, by the following method. A method of obtaining a powder of deposition material by mixing silicon oxide powder with a powder of an oxide of a specific element. A method in which the powder of the deposition material and water are kneaded to obtain particles, and then the particles are dried to obtain granules of the deposition material. A method of mixing powder containing silicon (e.g., powder made of silicon oxide, silica sand, silica gel), powder containing a specific element (e.g., powder of an oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide), and water, drying the mixture, and then firing the dried mixture or a compact obtained by pressing it to form a sintered body. A method in which a powder containing silicon (for example, powder made of silicon oxide, silica sand, silica gel) and a powder containing a specific element (for example, powder of an oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide) are melted at high temperature, and then the melt is cooled and solidified to obtain a molten material.

[0066] A specific example of a vapor deposition method using a vapor deposition material is a vacuum vapor deposition method, in which a vapor deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during vapor deposition (for example, the temperature of the boat on which the vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 100 to 3000°C, and particularly preferably 500 to 3000°C. The pressure during vapor deposition (for example, the pressure inside a tank in which the vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less. When the underlayer is formed using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used.

[0067] Specific examples of evaporation methods for the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method in which the deposition material is irradiated with an electron beam to directly heat the deposition material, melting and evaporating the surface. The electron gun method is preferred as an evaporation method for the deposition material because it can evaporate high-melting-point substances because it can heat locally, and areas not irradiated by the electron beam are at low temperatures, so there is no risk of reaction with the container or contamination with impurities. The evaporation method for the evaporation materials may use multiple boats, or all of the evaporation materials may be placed in a single boat. The evaporation method may be co-evaporation or alternating evaporation. Specific examples include a method in which silica and a specific source are mixed in the same boat, a method in which silica and a specific element source are placed in separate boats and co-evaporated, and a method in which they are placed in separate boats and alternately evaporated. The evaporation conditions, order, etc. are appropriately selected depending on the configuration of the underlayer.

[0068] <Wet coating method> In the wet coating method, a base layer is formed on a substrate by a wet coating method using a coating liquid containing a silicon-containing compound, a compound containing a specific element, and a liquid medium.

[0069] Specific examples of the silicon compound include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.

[0070] Specific examples of compounds containing a specific element include oxides of the specific element, alkoxides of the specific element, carbonates of the specific element, sulfates of the specific element, nitrates of the specific element, oxalates of the specific element, and hydroxides of the specific element.

[0071] Specific examples of the liquid medium include water and organic solvents. Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents. The organic solvents may be used alone or in combination of two or more.

[0072] Specific examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, CF 13 H (AC-2000: product name, manufactured by AGC), C6F 13 Examples include C2H5 (AC-6000: product name, manufactured by AGC), and C2F5CHFCHFCF3 (Bertrel: product name, manufactured by DuPont). Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, such as CF3CH2OCF2CF2H (AE-3000: product name, manufactured by AGC), C4F9OCH3 (Novec-7100: product name, manufactured by 3M), C4F9OC2H5 (Novec-7200: product name, manufactured by 3M), and C2F5CF(OCH3)C3F7 (Novec-7300: product name, manufactured by 3M). Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0073] The non-fluorine-based organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms, or a compound consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, and specific examples thereof include hydrocarbon-based organic solvents, ketone-based organic solvents, ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents. Specific examples of hydrocarbon organic solvents include hexane, heptane, and cyclohexane. Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether. Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate. Specific examples of the alcohol-based organic solvent include isopropyl alcohol, ethanol, and n-butanol.

[0074] The content of the liquid medium is preferably 0.01 to 20% by mass, and particularly preferably 0.1 to 10% by mass, based on the total mass of the coating liquid used to form the underlayer.

[0075] Specific examples of wet coating methods for forming the underlayer 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.

[0076] After wet-coating the coating liquid, it is preferable to dry the coating film. The drying temperature for the coating film is preferably 20 to 200°C, and particularly preferably 80 to 160°C.

[0077] (Formation of a water- and oil-repellent layer) The water- and oil-repellent layer can be formed by either a dry coating or wet coating manufacturing method using compound (A1) or compound (A2), or a composition containing compound (A1) or compound (A2) and a liquid medium (hereinafter also referred to as "composition"). Specific examples of the liquid medium contained in the composition are the same as those given in the coating liquid for forming the underlayer, and therefore, description thereof will be omitted.

[0078] The water- and oil-repellent layer can be produced, for example, by the following method. A method for forming a water- and oil-repellent layer on the surface of an underlayer by treating the surface of the underlayer by a dry coating method using compound (A1) or compound (A2) or a composition. A method in which a composition is applied to the surface of a base layer by wet coating and then dried to form a water- and oil-repellent layer on the surface of the base layer.

[0079] Specific examples of dry coating methods include vacuum deposition, CVD, and sputtering. Among these, vacuum deposition is preferred from the viewpoint of suppressing decomposition of the fluorine-containing compound and the simplicity of the equipment. For vacuum deposition, a pellet-like material may be used in which a porous metal such as iron or steel is impregnated with compound (A1) or compound (A2) or a composition.

[0080] A specific example of the wet coating method is the same as that used to form the underlayer by wet coating, and therefore the description thereof will be omitted. The drying temperature after wet-coating the composition is preferably 20 to 200°C, particularly preferably 80 to 160°C.

[0081] The content of the compound (A1) or the compound (A2) in the composition is preferably from 0.01 to 50 mass %, particularly preferably from 1 to 30 mass %, based on the total mass of the composition. The content of the liquid medium in the composition is preferably 50 to 99.99 mass %, particularly preferably 70 to 99 mass %, based on the total mass of the composition.

[0082] To improve the abrasion resistance of the water- and oil-repellent layer, an operation for promoting the reaction between compound (A1) or compound (A2) and the underlayer may be performed, if necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, by heating the substrate with the underlayer on which the water- and oil-repellent layer has been formed in a humid atmosphere, reactions such as hydrolysis of reactive silyl groups contained in compound (A1) or compound (A2) to silanol groups, condensation of the silanol groups to form siloxane bonds, and condensation of silanol groups on the surface of the underlayer with silanol groups of the fluorine-containing compound can be promoted. 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 needed by, for example, pouring a solvent over the water- and oil-repellent layer, wiping with a cloth soaked in the solvent, or washing the surface of the water- and oil-repellent layer with an acid.

[0083] The substrate with a water- and oil-repellent layer of the present invention is useful as an optical element, a touch panel, an anti-reflection film, an anti-reflection glass, an SiO-treated glass, a tempered glass, a sapphire glass, a quartz substrate, a mold metal, etc., which are used as parts of the following products: Products: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic light-emitting diode (OLED) displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc. [Example]

[0084] The present invention will be described in detail below with reference to examples. Examples 1 and 8 to 11 are comparative examples, and Examples 2 to 7 and 12 are working examples. However, the present invention is not limited to these examples. The blending amounts of each component in the tables below are based on mass.

[0085] [Synthesis Example 1: Synthesis of Compound (1-1)] According to the method described in Example 7 of WO 2013 / 121984, the following compound (1-1) was obtained. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) n (CF2CF2O)-CF2CF2CF2-CH2OH ···(1-1) The average number of repeating units, n, is 13.

[0086] [Synthesis Example 2: Synthesis of Compound (1-2)] The above compound (1-1) (6.80 g, 1.48 mmol), 2,6-lutidine (0.759 g, 7.08 mmol), and AE3000 (28.0 g) were mixed, and the resulting solution was stirred at 0°C. Trifluoromethanesulfonic anhydride (0.987 g, 3.50 mol) was added to the resulting solution, and the mixture was stirred at room temperature. The resulting solution was washed with water, and the solvent was evaporated. Flash column chromatography using silica gel was performed to obtain 6.81 g of the following compound (1-2). CF3-O-(CF2CF2O-CF2CF2CF2CF2O) n (CF2CF2O)-CF2CF2CF2-CH2OTf ···(1-2) The average number of repeating units, n, is 13, and OTf is triflate: -OS(=O)2(-CF3).

[0087] NMR spectrum of compound (1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):4.78(t,J=12.3Hz,2H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-55.28,-74.11,-82.86,-88.07,-90.20,-119.84,-125.28,-126.16.

[0088] [Synthesis Example 3: Synthesis of Compound (2-1)] Diethyldiallylmalonate (60.0 g, 250 mmol), lithium chloride (23.7 g, 559 mmol), water (6.45 g, 360 mmol), and dimethyl sulfoxide (263 g) were mixed, and the resulting solution was stirred at 160 °C. After the resulting solution was cooled to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the resulting organic layer, which was then washed with saturated saline and dried over sodium sulfate. The resulting solution was filtered, and the solvent was distilled off from the filtrate to obtain 39.5 g of the following compound (2-1). [ka]

[0089] NMR spectrum of compound (2-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):(ddt,J=17.1,10.1,7.0Hz,2H),5.06~4.94(m,4H),4.09(q,J=7.1Hz,2H),2.47(ddd,J=14.0 ,8.0,6.1Hz,1H),2.33(dt,J=14.9,7.5Hz,2H),2.22(dt,J=14.1,6.5Hz,2H),1.21(t,J=7.1Hz,3H).

[0090] [Synthesis Example 4: Synthesis of Compound (2-2)] THF (260 mL) and diisopropylamine (41.5 mL, 294 mmol) were mixed, and the solution was cooled to -78 °C. To the resulting solution, n-butyllithium hexane solution (2.76 M, 96.6 mL, 294 mmol) was added and the mixture was heated to 0 °C. The solution was stirred and then cooled to -78 °C to prepare a THF solution of lithium diisopropylamide (LDA). Compound (2-1) (39.5 g, 235 mmol) was added to the THF solution, stirred, and then allyl bromide (24.1 mL, 278 mmol) was added to the resulting solution. The resulting solution was heated to 0 °C, 1 M hydrochloric acid (100 mL) was added, and THF was evaporated under reduced pressure. The resulting components were extracted with dichloromethane, and sodium sulfate was added to the resulting solution. The resulting solution was filtered, and the solvent was evaporated from the filtrate. Flash column chromatography using silica gel was performed to obtain 45.0 g of compound (2-2). [ka]

[0091] NMR spectrum of compound (2-2); 1H-NMR(400MHz,Chloroform-d) δ(ppm):5.74~5.62(m,3H),5.04(dd,J=13.6,1.9Hz,6H),4.10(q,J=7.1Hz,2H),2.29(d,J=7.4Hz,6H),1.22(t,J=7.1Hz,3H).

[0092] [Synthesis Example 5: Synthesis of Compound (2-3)] The above compound (2-2) (45.0 g, 216 mmol) was dissolved in THF (620 mL), and the resulting solution was cooled to 0°C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added to the resulting solution, and the mixture was stirred. Water and a 15% aqueous sodium hydroxide solution were added to the resulting solution, and the mixture was stirred at room temperature and then diluted with dichloromethane. The resulting solution was filtered, and the solvent was distilled off from the filtrate. Flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (2-3). [ka]

[0093] NMR spectrum of compound (2-3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.76(m,3H),5.10~5.02(m,6H),3.38(s,2H),2.03(dt,J=7.5,1.2Hz,6H),1.45(s,1H).

[0094] [Synthesis Example 6: Synthesis of Compound (B1-1)] Acetonitrile (380 mL), the above compound (2-3) (31.3 g, 188 mmol), triphenylphosphine (64.3 g, 245 mmol), and carbon tetrachloride (33.9 g, 221 mmol) were mixed, and the resulting solution was stirred at 90°C. The resulting solution was concentrated, and then ethyl acetate / hexane was added and stirred. The resulting solution was filtered, and the filtrate was concentrated and then distilled (70°C, 3 hPa) to obtain 28.2 g of the following compound (B1-1). [ka]

[0095] NMR spectrum of compound (B1-1); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.83~5.67(m,3H),5.16~5.01(m,6H),3.32(s,2H),2.05(dt,J=7.5,1.1Hz,6H).

[0096] [Synthesis Example 7: Synthesis of Compound (B2-1)] To magnesium (2.36 g, 97.2 mmol), THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added, and the resulting solution was stirred at room temperature. To the resulting solution, a solution of the compound (B1-1) (14.0 g, 75.9 mmol) in THF (35 mL) was added, and the mixture was heated under reflux for 2 hours to prepare a 1.0 M solution of the compound (B2-1) below. [ka]

[0097] [Synthesis Example 8: Synthesis of Compound (A-1')] CuCl2 (16.0 mg, 0.119 mmol), 1-phenyl-1-propyne (0.052 g, 0.45 mmol), 1,3-bistrifluoromethylbenzene (24 mL), and the above compound (1-2) (4.00 g) were mixed, and then the above compound (B2-1) (5.0 mL, 1.0 M, 5.0 mmol) was added to the resulting solution. The resulting solution was stirred at room temperature, washed with 1 M hydrochloric acid, and dried over sodium sulfate. The solution was filtered, and the solvent was distilled off from the filtrate, followed by addition of AC6000. The resulting solution was washed with methanol and then subjected to flash column chromatography using silica gel to obtain 0.139 g of the following compound (A-1'), a precursor of compound (A-1). [ka] The average number of repeating units, n, is 10.

[0098] NMR spectrum of compound (A-1'); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.77(ddt,J=14.9,10.7,7.4Hz,3H),5.07~4.99(m,6H),2.19~2.05(m,2H),1.97(d,J=7.4Hz,6H),1.59~1.50(m,2H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-55.29,-82.90,-88.13,-90.24(d,J=8.0Hz),-114.62,-125.34,-126.49.

[0099] [Synthesis Example 9: Synthesis of Compound (A-1)] AC2000 (0.89 g), the above compound (A-1') (0.139 g), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 5.5 mg), aniline (0.8 mg), and trimethoxysilane (22.7 mg, 0.185 mmol) were mixed, and the resulting solution was stirred at 40° C. The solvent was then removed from the resulting solution by distillation under reduced pressure, yielding 0.140 g of the following compound (A-1). [ka] The average number of repeating units, n, is 10.

[0100] NMR spectrum of compound (A-1); 1 H-NMR (400MHz, Chloroform-d) δ3.60(s,27H),2.23~1.95(m,2H),1.63~1.28(m,14H),0.67(t,J=7.6Hz,6H). 19 F-NMR(376MHz,Chloroform-d) δ-55.33,-82.95,-88.17,-90.13~-90.40(m),-114.07~-114.32(m),-125.38,-126.04.

[0101] [Synthesis Example 10: Synthesis of Compound (A-2)] The following compound (A-2) was obtained according to the method described in Example 6 of WO 2017 / 038830. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) n (CF2CF2O)-CF2CF2CF2-CH2OCH2-C[CH2CH2CH2-Si(OCH3)3]3...(A-2) The average number of repeating units, n, is 13.

[0102] [Synthesis Example 11: Synthesis of Compound (B1-2)] 1-Bromo-3-chloropropane (2.90 g, 18.3 mmol), 1-phenyl-1-propyne (0.220 g, 1.89 mmol), and CuCl (0.051 g, 0.38 mmol) were mixed, and the resulting solution was stirred at 0°C. Compound (B2-1) (0.80 M, 26.0 mL, 20.9 mmol) was added to the resulting solution, and the mixture was further stirred. 1 M hydrochloric acid was added to the resulting solution, and the mixture was extracted with dichloromethane, followed by the addition of sodium sulfate. The resulting solution was filtered, and the filtrate was concentrated and then distilled (100°C, 3 hPa) to obtain 3.29 g of the following compound (B1-2). [ka]

[0103] NMR spectrum of compound (B1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.76(ddt,J=16.6,10.6,7.4Hz,3H),5.09~4.93(m,6H),3.50(t,J=6.7Hz,2H) ,1.96(dt,J=7.4,1.2Hz,6H),1.76~1.61(m,2H),1.45~1.29(m,2H),1.24~1.08(m,2H).

[0104] [Synthesis Example 12: Synthesis of Compound (B2-2)] To magnesium (0.174 g, 7.16 mmol), THF (2.6 mL) and iodine (12.7 mg, 0.050 mmol) were added, and the resulting solution was stirred at room temperature. To the resulting solution, a solution of the compound (B1-2) (1.30 g, 5.74 mmol) in THF (2.6 mL) was added, and the mixture was heated to reflux to prepare a 1.0 M solution of the compound (B2-2). [ka]

[0105] [Synthesis Example 13: Synthesis of Compound (3-1)] FLUOROLINK D4000 (Solvay Specialty Polymers) (4.03 g), 2,6-lutidine (0.759 g, 7.08 mmol), and AE3000 (28.0 g) were mixed, and the resulting solution was stirred at 0°C. Trifluoromethanesulfonic anhydride (0.987 g, 3.50 mol) was added to the resulting solution, and the mixture was further stirred at room temperature. The resulting solution was washed with water, and the solvent was distilled off. Flash column chromatography using silica gel was performed to obtain 3.56 g of the following compound (3-1). TfOCH2CF2(OCF2) p (OCF2CF2) q -OCF2CH2OTf (3-1) The average number of repeating units p is 22, the average number of repeating units q is 25, and OTf is triflate.

[0106] NMR spectrum of compound (3-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):4.89(q,J=8.4Hz,1H).

[0107] [Synthesis Example 14: Synthesis of Compound (A-3')] CuCl2 (7.0 mg, 0.052 mmol), 1-phenyl-1-propyne (0.026 g, 0.22 mmol), 1,3-bistrifluoromethylbenzene (15 mL), and the above compound (1-2) (1.62 g) were mixed, and then the above compound (3-1) (4.0 mL, 1.0 M, 4.0 mmol) was added to the resulting solution. The resulting solution was stirred at room temperature, washed with 1 M hydrochloric acid, and dried over sodium sulfate. The resulting solution was filtered, and the solvent was evaporated from the filtrate, followed by addition of AC6000. The resulting solution was washed with methanol and then subjected to flash column chromatography using silica gel to obtain 0.202 g of the following compound (A-3'), a precursor of compound (A-3). [ka] The average number of repeating units, p, is 22, and the average number of repeating units, q, is 25.

[0108] NMR spectrum of compound (A-3'); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.66(m,6H),5.07~4.90(m,12H),2.19~1.92(m,16H),1.70~1.10(m,16H).

[0109] [Synthesis Example 15: Synthesis of Compound (A-3)] AC2000 (1.2 g), the above compound (A-3') (0.202 g), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 7.0 mg), aniline (1.4 mg), and trimethoxysilane (51.7 mg, 0.423 mmol) were mixed, and the resulting solution was stirred at 40°C for 18 hours. The solvent was then distilled off under reduced pressure, yielding 0.188 g of the compound (A-3) shown below. [ka] The average number of repeating units, p, is 22, and the average number of repeating units, q, is 25.

[0110] NMR spectrum of compound (A-3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):3.61(s,54H),2.17~1.90(m,4H),1.70~1.14(m,40H),0.74~0.59(m,12H).

[0111] [Example 1] 30 g of silicon oxide (Canon Optron Inc.) and 0.11 g of compound (A-1) were placed in a molybdenum boat in a vacuum deposition apparatus (ULVAC Kiko VTR-350M). A glass substrate was placed in the vacuum deposition apparatus, and the interior of the vacuum deposition apparatus was heated to 5 × 10 -3 The pressure was evacuated to a pressure of 0.1 Pa or less. The boat carrying the silicon oxide was heated to 2,000°C, and the silicon oxide was vacuum-deposited onto the glass substrate to form a 10 nm thick underlayer. Furthermore, the boat carrying the compound (A-1) was heated to 700°C, and the compound (A-1) was vacuum-deposited on the surface of the underlayer to form a water- and oil-repellent layer with a thickness of 10 nm, followed by heat treatment at 140°C for 30 minutes. In this way, the substrate with the water- and oil-repellent layer of Example 1 was obtained.

[0112] [Example 2] A substrate with a water- and oil-repellent layer of Example 2 was obtained by carrying out the same procedure as in Example 1, except that sintered body 1 obtained by the following procedure was used as the deposition material for the underlayer. 2.5 g of soda ash (manufactured by Soda Ash Japan Co., Ltd.) and 250 g of silica particles SC5500-SQ (trade name, manufactured by Admatechs Co., Ltd.) were added to an Eirich Intensive Mixer EL-1 (manufactured by Nippon Eirich Co., Ltd., hereafter referred to as "EL-1") and stirred at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, and 40.2 g of distilled water was added while stirring. The mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds. The resulting particles were removed from the EL-1, dried at 150°C for 30 minutes, and then fired at 1150°C for 1 hour to obtain sintered body 1.

[0113] [Example 3] The amount of soda ash (manufactured by Soda Ash Japan Co., Ltd.) added was 7.5 g, and the amount of silica particles SC5500-SQ (trade name, manufactured by Admatechs Co., Ltd.) added was 250 g, and the same procedure as in Example 2 was carried out to obtain sintered body 2. Except for using sintered body 2, the same procedure as in Example 1 was carried out to obtain a substrate with a water- and oil-repellent layer of Example 3.

[0114] [Example 4] The amount of soda ash (manufactured by Soda Ash Japan Co., Ltd.) added was 25 g, and the amount of silica particles SC5500-SQ (trade name, manufactured by Admatechs Co., Ltd.) added was 250 g, and the same procedure as in Example 2 was carried out to obtain sintered body 3. Except for using sintered body 3, the same procedure as in Example 1 was carried out to obtain a substrate with a water- and oil-repellent layer of Example 4.

[0115] [Example 5] The same procedure as in Example 2 was carried out except that the amount of soda ash (manufactured by Soda Ash Japan Co., Ltd.) added was 50 g and the amount of silica particles SC5500-SQ (trade name, manufactured by Admatechs Co., Ltd.) added was 250 g, to obtain sintered body 4. The same procedure as in Example 1 was carried out except that sintered body 3 was used, to obtain a substrate with a water- and oil-repellent layer of Example 5.

[0116] [Example 6] A substrate with a water- and oil-repellent layer of Example 6 was obtained by carrying out the same procedure as in Example 1, except that sintered body 5 obtained by the following procedure was used as the deposition material for the underlayer. 7.5 g of magnesium oxide (MgO, manufactured by Wako Pure Chemical Industries, Ltd.) and 250 g of silica particles SC5500-SQ (trade name, manufactured by Admatechs Co., Ltd.) were added to EL-1 and stirred at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, and 40.2 g of distilled water was added while stirring. The mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds. The resulting particles were removed from EL-1, dried at 150°C for 30 minutes, and then fired at 1150°C for 1 hour to obtain sintered body 5.

[0117] [Example 7] A substrate with a water- and oil-repellent layer of Example 7 was obtained by carrying out the same procedure as in Example 1, except that sintered body 6 obtained by the following procedure was used as the deposition material for the underlayer. 7.5 g of boric acid particles (Optibor, product name, manufactured by Hayakawa Shoji Co., Ltd.) and 250 g of silica particles SC5500-SQ (product name, manufactured by Admatechs Co., Ltd.) were added to EL-1 and stirred at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, and 40.2 g of distilled water was added while stirring. The mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds. The resulting particles were removed from EL-1, dried at 150°C for 30 minutes, and then fired at 1150°C for 1 hour to obtain sintered body 6.

[0118] [Example 8] A substrate with a water- and oil-repellent layer of Example 8 was formed in the same manner as in Example 1, except that 0.12 g of compound (A-2) was placed as the vapor deposition material (vapor deposition source).

[0119] [Example 9] A substrate with a water- and oil-repellent layer of Example 9 was formed using sintered body 2 in the same manner as in Example 3, except that 0.15 g of compound (A-2) was placed as the vapor deposition material (vapor deposition source).

[0120] [Example 10] A substrate with a water- and oil-repellent layer of Example 10 was formed in the same manner as in Example 7, except that 0.15 g of compound (A-2) was placed as the vapor deposition material (vapor deposition source).

[0121] [Example 11] A substrate with a water- and oil-repellent layer of Example 11 was formed in the same manner as in Example 1, except that 0.16 g of compound (A-3) was placed as the vapor deposition material (vapor deposition source).

[0122] [Example 12] A substrate with a water- and oil-repellent layer of Example 12 was formed in the same manner as in Example 3, except that 0.14 g of compound (A-3) was placed as the vapor deposition material (vapor deposition source).

[0123] [Physical properties and evaluation] (Content of each element in the base layer) C 60A depth profile of the molar concentration (mol%) of each element was obtained using X-ray photoelectron spectroscopy (XPS) using ion sputtering. Here, the point where the molar concentration (mol%) of fluorine derived from the water- and oil-repellent layer relative to all elements detected by XPS analysis, considered from the surface side of the depth profile of the substrate with the water- and oil-repellent layer, became 10 mol% or less was defined as starting point A. Furthermore, the point where the molar concentration (mol%) of any element present only in the substrate relative to all elements detected by XPS analysis first exceeded 30% of the molar concentration (mol%) in the substrate was defined as end point B. The region from starting point A to end point B was defined as the underlayer, and the ratio of the average molar concentration (mol%) of the target element to the average molar concentration (mol%) of silicon in the underlayer was calculated. <Device> X-ray photoelectron spectrometer: ULVAC-PHI ESCA-5500 <Measurement conditions> X-ray source: monochromated AlKα radiation Photoelectron detection angle: 75 degrees to the sample surface Pass energy: 117.4 eV Step energy: 0.5 eV / step Sputtering ions; accelerating voltage 10 kV C 60 ion Sputter gun raster size: 3 x 3 mm 2 Sputter interval: 0.4 min Sputtering rate of thermal oxide film (SiO2 film) on silicon wafer of sputtering gun: 2.20 nm / min Measurement pitch: 0.88 nm (equivalent to thermal oxide film on silicon wafer)

[0124] <Contact angle measurement method> The contact angle of approximately 2 μL of distilled water placed on the surface of the water- and oil-repellent layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different locations on the surface of the water- and oil-repellent layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.

[0125] <Initial contact angle> The initial water contact angle of the water- and oil-repellent layer was measured by the above-mentioned measurement method. The evaluation criteria are as follows: Initial water contact angle: ○ (Excellent): Over 115 degrees. △ (Acceptable): 105 degrees or more but less than 115 degrees. × (Not acceptable): Less than 105 degrees.

[0126] <Abrasion resistance (steel wool)> The water- and oil-repellent layer was measured for its water contact angle after 10,000 strokes of steel wool Bonstar (#0000) at a pressure of 98.07 kPa and a speed of 320 cm / min using a reciprocating traverse tester (manufactured by KNT Corporation) in accordance with JIS L0849:2013 (ISO 105-X12:2001). The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to friction, and the more excellent the abrasion resistance. The evaluation criteria are as follows: ◎ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is less than 1 degree. ○ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is between 1 degree and 2 degrees. □ (Good): The change in water contact angle after 10,000 reciprocating strokes is between 2 and 3 degrees. △ (Acceptable): The change in water contact angle after 10,000 strokes is between 3 and 4 degrees × (unacceptable): The change in water contact angle after 10,000 reciprocating strokes is 4 degrees or more.

[0127] The above-mentioned physical properties were measured and evaluation tests were carried out for each of the above examples. The evaluation results are shown in Tables 1-1 and 1-2. [Table 1-1]

[0128] [Table 1-2]

[0129] As shown in Table 1, Examples 2 to 7, and 12, in which the underlayer contained a specific element and the water- and oil-repellent layer was made of a hydrolysis condensate of compound (A1) (i.e., compound (A-1)) or compound (A2) (i.e., compound (A-3)), all had initial water contact angles of fair or better and abrasion resistances of good or better. Examples 1, 8, and 11, in which the underlayer did not contain a specific element, all had poor abrasion resistance. Examples 9 and 10, in which the underlayer contained a specific element but the water- and oil-repellent layer was formed using a compound other than compound (A1) and compound (A2) (i.e., compound (A-2)), had fair abrasion resistance and were insufficient. Examples 2 to 6, and 12, in which the underlayer contained a Group 1 element (Na) or Group 2 element (Mg) as the specific element, all had excellent or better abrasion resistance. Examples 3, 4, and 12, in which the underlayer contained a Group 1 element (Na) as a specific element and the ratio of the total molar concentration of the specific elements to the molar concentration of silicon in the underlayer was 0.02 to 2.90, had excellent abrasion resistance. Examples 2 to 7, in which the water- and oil-repellent layer was made of a hydrolysis condensate of compound (A1), had excellent initial water contact angles. The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2020-155248, filed on September 16, 2020, are hereby incorporated by reference as the disclosure of the specification of the present invention. [Explanation of symbols]

[0130] 10 Substrate with water- and oil-repellent layer 12 Base material 14 Base layer 16 Water- and oil-repellent layer

Claims

1. A substrate; a base layer formed on the surface of the substrate; a water- and oil-repellent layer formed on the surface of the base layer, the underlayer contains an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, and Group 13 elements of the periodic table; A substrate with a water- and oil-repellent layer, wherein the water- and oil-repellent layer comprises a hydrolysis condensate of a fluorinated ether compound selected from the group consisting of a compound represented by formula (A1) and a compound represented by formula (A2): R ｆ -O-(R ｆ１ O) ｍ -R ｆ２ [-R １ -C(-R ２ -T) ａ (-R ３ ) ３－ａ ] ｂ ・・・(A1) [(T-R ２ -) ａ (R ３ -) ３－ａ C-R １ -] ｂ R ｆ２ -O-(R ｆ１ O) ｍ -R ｆ２ [-R １ -C(-R ２ -T) ａ (-R ３ ) ３－ａ ] ｂ ・・・(A2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ２ is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R １ The carbon atom bonded to R ｆ２ If there are multiple R ｆ２ may be the same or different, R １ is an alkylene group having 1 to 20 carbon atoms, R ２ is an alkylene group having 3 to 20 carbon atoms which may have a fluorine atom, and a plurality of R ２ may be the same or different, R ３ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R ３ If there are multiple R ３ may be the same or different, T is -Si(R) ３－ｃ (L) ｃ where multiple T's may be the same or different, R is an alkyl group, L represents a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different; m is an integer from 1 to 20, a is 3, and a plurality of a's may be the same or different; b is an integer of 1 or more, and when there are multiple b's, the multiple b's may be the same or different, c is 2 or 3, and multiple c's may be the same or different.

2. The R ｆ２ b partial structures "-CQF-* (wherein Q is a hydrogen atom, a fluorine atom or CF ３ and -* is R １ The substrate with a water- and oil-repellent layer according to claim 1 , wherein the hydrocarbon group has a bond (a bond bonded to the water- and oil-repellent layer) and a bond (a bond bonded to the water- and oil-repellent layer).

3. The b is 1, and the R ｆ２ The substrate with a water- and oil-repellent layer according to claim 1 or 2, wherein is a perfluoroalkylene group having 1 to 6 carbon atoms.

4. The substrate with a water- and oil-repellent layer according to any one of claims 1 to 3, wherein the specific element is an element of Group 1 of the periodic table.

5. The substrate with a water- and oil-repellent layer according to any one of claims 1 to 4, wherein b is 1.

6. 6. The substrate with a water- and oil-repellent layer according to claim 1, wherein the ratio of the total molar concentration of the specific elements to the molar concentration of silicon in the underlayer is 0.02 to 2.

90.

7. A method for producing a substrate with a water- and oil-repellent layer, the substrate having a substrate, an undercoat layer, and a water- and oil-repellent layer in this order, comprising: forming an underlayer containing an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, and Group 13 elements of the periodic table on the substrate; Next, a water- and oil-repellent layer comprising a hydrolysis condensate of a fluorinated ether compound selected from the group consisting of a compound represented by formula (A1) and a compound represented by formula (A2) is formed on the underlayer. R ｆ -O-(R ｆ１ O) ｍ -R ｆ２ [-R １ -C(-R ２ -T) ａ (-R ３ ) ３－ａ ] ｂ ・・・(A1) [(T-R ２ -) ａ (R ３ -) ３－ａ C-R １ -] ｂ R ｆ２ -O-(R ｆ１ O) ｍ -R ｆ２ [-R １ -C(-R ２ -T) ａ (-R ３ ) ３－ａ ] ｂ ・・・(A2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ２ is a hydrocarbon group having a fluorine atom with a valence of (1+b), and at least R １ The carbon atom bonded to R ｆ２ If there are multiple R ｆ２ may be the same or different, R １ is an alkylene group having 1 to 20 carbon atoms, R ２ is an alkylene group having 3 to 20 carbon atoms which may have a fluorine atom, and a plurality of R ２ may be the same or different, R ３ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R ３ If there are multiple R ３ may be the same or different, T is -Si(R) ３－ｃ (L) ｃ where multiple T's may be the same or different, R is an alkyl group, L represents a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different; m is an integer from 1 to 20, a is 3, and a plurality of a's may be the same or different; b is an integer of 1 or more, and when there are multiple b's, the multiple b's may be the same or different, c is 2 or 3, and multiple c's may be the same or different.

8. The R ｆ２ b partial structures "-CQF-* (wherein Q is a hydrogen atom, a fluorine atom or CF ３ and -* is R １ The method for producing a substrate with a water and oil repellent layer according to claim 7, wherein the hydrocarbon group has a bond (a bond bonded to the water and oil repellent layer)).

9. The b is 1, and the R ｆ２ The method for producing a substrate with a water- and oil-repellent layer according to claim 7 or 8, wherein is a perfluoroalkylene group having 1 to 6 carbon atoms.

10. The substrate with a water- and oil-repellent layer according to any one of claims 1 to 6, which is used as an optical member.

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