Surface treatment agent, coating liquid, article, and method for manufacturing article

Abstract

To provide a surface treatment agent that can form a surface layer having excellent lubricity and rub resistance, a coating liquid, an article and a method for producing an article.SOLUTION: A surface treatment agent comprises a fluorinated ether compound that comprises a fluoro polyether chain comprising a unit represented by (OCF2) and a unit represented by (OCF2CF2) and a reactive silyl group. In a chart obtained by 19F-NMR measurement of the fluorinated ether compound, Y>-0.0062X2+0.1343X+0.1123 holds, X denotes {(a1+a2+a3) / 2} / {(b1+b2) / 4}, Y denotes (a3) / (a1+a2+a3), and a1-a3 and b1-b2 are peak integrals observed in a predetermined chemical shift.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article. [Background technology]

[0002] In order to impart water- and oil-repellency, antifouling properties, etc. to the surface of a substrate, it is known to form a surface layer made of a condensate of a fluorine-containing ether compound on the surface of the substrate by surface treatment using a fluorine-containing ether compound having a fluoropolyether chain and a reactive silyl group (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5761305 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have been increasing. For example, when a surface layer is applied to a member that constitutes a surface that is touched with fingers, the surface layer is required to have excellent lubricity (smoothness when touched with fingers) and excellent abrasion resistance. The present inventors evaluated a surface layer formed using a fluorine-containing ether compound as described in Patent Document 1 and found that there was room for improvement in at least one of the lubricity and abrasion resistance of the surface layer.

[0005] Therefore, an object of the present invention is to provide a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article, which are capable of forming a surface layer having excellent lubricity and abrasion resistance. [Means for solving the problem]

[0006] As a result of intensive research into the above-mentioned problems, the present inventors have discovered that in a surface treatment agent containing a fluorine-containing ether compound having a fluoropolyether chain containing a unit represented by (OCF2) and a unit represented by (OCF2CF2), and a reactive silyl group, 19 The present inventors have found that when the integrated value of the peak corresponding to the fluorine atoms in the units constituting the fluoropolyether chain, obtained by F-NMR measurement, satisfies the formula (A-1) described below, the surface treatment agent can form a surface layer having excellent lubricity and abrasion resistance, and have arrived at the present invention.

[0007] That is, the inventors have found that the above problems can be solved by the following configuration. [1] A surface treatment agent containing a fluorine-containing ether compound having a fluoropolyether chain containing a unit represented by (OCF2) and a unit represented by (OCF2CF2), and a reactive silyl group, The above fluorine-containing ether compound 19 A surface treatment agent characterized by satisfying the following formula (A-1) in a chart obtained by F-NMR measurement. Y>-0.0062X 2 +0.1343X+0.1123 (A-1) X and Y are the values ​​of the above fluorine-containing ether compounds using 1,4-bistrifluoromethylbenzene as an internal standard. 19 This is a value calculated based on a chart obtained by F-NMR measurement. The integral value of the peak observed at chemical shifts of -50.5 to -51.2 ppm is a1, The integral value of the peak observed at chemical shifts of -52.0 to -52.8 ppm is a2, The integral value of the peak observed at chemical shifts of -53.8 to -54.5 ppm is a3, The integral value of the peak observed at chemical shifts of -87.0 to -88.5 ppm is b1, If the integral value of the peak observed at chemical shifts of -88.8 to -90.2 ppm is b2, X means {(a1+a2+a3) / 2} / {(b1+b2) / 4}, Y means (a3) / (a1+a2+a3). [2] The surface treatment agent according to [1], wherein X in the formula (A-1) is 2 to 8. [3] The above fluorine-containing ether compound 19 The surface treatment agent according to [1] or [2], which satisfies the following formula (A-2) in a chart obtained by F-NMR measurement: Y>-0.0056X 2 +0.1231X+0.2119 (A-2) However, X and Y in formula (A-2) are the same as X and Y in formula (A-1) above. [4] A coating liquid comprising the surface treatment agent according to any one of the above [1] to [3] and a liquid medium. [5] An article having a surface layer formed on a substrate using the surface treatment agent according to any one of [1] to [3] above or the coating liquid according to [4] above. [6] The article according to [5], wherein the article is a touch panel and the surface layer is on the surface of a member that constitutes the surface of the touch panel that is touched with a finger. [7] A method for manufacturing an article, comprising forming a surface layer on a substrate by a dry coating method or a wet coating method using the surface treatment agent according to any one of [1] to [3] above or the coating liquid according to [4] above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a surface treatment agent, a coating liquid, an article, and a method for manufacturing an article, which are capable of forming a surface layer having excellent lubricity and abrasion resistance. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a graph in which points given by the values ​​of X and Y of each fluorinated ether compound used in the Examples section are plotted in a Cartesian coordinate system in which the horizontal axis represents the value of X in formula (A-1) and the vertical axis represents the value of Y in formula (A-1). [Figure 2]1 is a chart obtained by measuring 19F-NMR using the mixture 5-1 of fluorine-containing ether compounds used in Example 14 in the Examples section. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, a group represented by formula (g1) may be referred to as group (g1). A structure represented by formula (G1) may be referred to as structure (G1). A compound represented by formula (1-1) may be referred to as compound (1-1). Compounds represented by other formulas may be referred to in the same manner. A fluoroalkyl group is a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group refers to a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which also has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group that has one or more fluorine atoms. The term "reactive silyl group" refers collectively to a hydrolyzable silyl group and a silanol group (Si-OH), and the term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "organic group" refers to a hydrocarbon group which may have a substituent and which may have a heteroatom or other bond in the carbon chain. The term "hydrocarbon group" refers to a group consisting of carbon atoms and hydrogen atoms, and includes aliphatic hydrocarbon groups (for example, divalent aliphatic hydrocarbon groups such as linear alkylene groups, branched alkylene groups, and cycloalkylene groups), aromatic hydrocarbon groups (for example, divalent aromatic hydrocarbon groups such as phenylene groups), and groups consisting of combinations thereof. "Surface layer" means a layer formed on a substrate. The "molecular weight" of the fluoropolyether chain is 1 H-NMR and 19 It is the number average molecular weight calculated by F-NMR to determine the number (average value) of oxyfluoroalkylene units based on the terminal groups. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0011] In this specification, an alkylene structure containing a fluorine atom sandwiched between two oxygen atoms, such as OCF2CH2-O, is interpreted as having a repeating unit consisting of a partial structure sandwiched between two oxygen atoms and an oxygen atom (in the above case, "OCF2CH2").

[0012] [Surface treatment agent] The surface treatment agent of the present invention (hereinafter also referred to as "the present surface treatment agent") is a surface treatment agent containing a fluorine-containing ether compound having a fluoropolyether chain containing a unit represented by (OCF2) and a unit represented by (OCF2CF2), and a reactive silyl group, and 19 In the chart obtained by F-NMR measurement, the formula (A-1) described below is satisfied. By using the present surface treatment agent, a surface layer with excellent lubricity and abrasion resistance can be formed.

[0013] The present surface treatment agent may contain two or more kinds of fluorine-containing ether compounds. In this case, 19 The above chart obtained by F-NMR measurement means a chart obtained by measuring a mixture of two or more fluorine-containing ether compounds.

[0014] <Formula (A-1)> Y>-0.0062X 2 +0.1343X+0.1123 (A-1) In formula (A-1), X and Y are the fluorine-containing ether compounds contained in the present surface treatment agent, determined by using 1,4-bistrifluoromethylbenzene as an internal standard. 19 This is a value calculated based on a chart obtained by F-NMR measurement. The integral value of the peak observed at chemical shifts of -50.5 to -51.2 ppm is a1, The integral value of the peak observed at chemical shifts of -52.0 to -52.8 ppm is a2, The integral value of the peak observed at chemical shifts of -53.8 to -54.5 ppm is a3, The integral value of the peak observed at chemical shifts of -87.0 to -88.5 ppm is b1, If the integral value of the peak observed at chemical shifts of -88.8 to -90.2 ppm is b2, X means {(a1+a2+a3) / 2} / {(b1+b2) / 4}, Y means (a3) / (a1+a2+a3).

[0015] The meanings of the peaks corresponding to a1, a2, a3, b1 and b2 are as follows: Peak corresponding to a1: A peak corresponding to a fluorine atom in (OCF2) located at the center of the sequence represented by -(OCF2CF2)-(OCF2)-(OCF2CF2)- in the sequence of units constituting the fluoropolyether chain in a fluorine-containing ether compound. Peak corresponding to a2: A peak corresponding to the fluorine atom in (OCF2) located at the center of the sequence represented by -(OCF2)-(OCF2)-(OCF2CF2)- in the sequence of units constituting the fluoropolyether chain. Peak corresponding to a3: A peak corresponding to the fluorine atom in (OCF2) located at the center of the sequence represented by -(OCF2)-(OCF2)-(OCF2)- in the sequence of units constituting the fluoropolyether chain. Peaks corresponding to b1 and b2: Peaks corresponding to fluorine atoms in (OCF2CF2)

[0016] X means {(a1+a2+a3) / 2} / {(b1+b2) / 4}, and specifically, is a numerical value indicating the ratio of units represented by (OCF2) to units represented by (OCF2CF2) in the fluoropolyether chain. In other words, a large X means that the ratio of units represented by (OCF2) present in the fluoropolyether chain is high. Here, (a1 + a2 + a3) is multiplied by 1 / 2 and (b1 + b2) is multiplied by 1 / 4 because a1, a2, and a3 are integral values ​​corresponding to two fluorine atoms in (OCF2), and b1 and b2 are integral values ​​corresponding to four fluorine atoms in (OCF2CF2).

[0017] Y means (a3) / (a1+a2+a3), and specifically, is a numerical value that indicates the proportion of structures in which three or more (OCF2) are arranged consecutively in the sequences containing (OCF2) in the fluoropolyether chain. In other words, when Y is large, it means that there are many portions in the fluoropolyether chain in which (OCF2) is arranged consecutively.

[0018] Here, as a method for obtaining a fluorine-containing ether compound having a large Y, for example, there can be mentioned a method in which a raw material M13 obtained by reacting a compound M11 having a high ratio of units represented by (OCF2) to units represented by (OCF2CF2) with a compound M12 having units represented by (OCF2CF2) during the production of a fluorine-containing ether compound is used. Since the compound M11 has a high ratio of (OCF2), (OCF2) tends to be arranged continuously. Therefore, by using the compound M11, it is possible to increase the value of Y. On the other hand, a method for obtaining a fluorine-containing ether compound having a small Y can be exemplified by using a compound M21 having a low ratio of units represented by (OCF2) to units represented by (OCF2CF2) during the production of the fluorine-containing ether compound. Since the compound M21 has a low ratio of (OCF2), it is difficult for (OCF2) to be arranged continuously. Therefore, by using the compound M21, it is possible to reduce the value of Y.

[0019] 19 When calculating the integral value of a peak in an F-NMR spectrum, 19 Two points without significant signals are determined on either side of the relevant peak in the F-NMR spectrum, and each integral value is calculated using the line connecting these two points as the baseline.

[0020] Here, FIG. 1 is a graph in which points given by the values ​​of X and Y of each fluorinated ether compound used in the Examples section described later are plotted in an orthogonal coordinate system in which the horizontal axis represents the value of X (i.e., {(a1+a2+a3) / 2} / {(b1+b2) / 4}) and the vertical axis represents the value of Y (i.e., (a3) / (a1+a2+a3)). Among the points plotted in Fig. 1, the group of points A and B indicate fluorine-containing ether compounds capable of forming a surface layer excellent in abrasion resistance and lubricity, while the group of points C indicates fluorine-containing ether compounds that form a surface layer insufficient in at least one of abrasion resistance and lubricity. Furthermore, when the group of points A and the group of points B are compared, the fluorine-containing ether compounds of the group of points A can form a surface layer with more excellent abrasion resistance and lubricity. The curve A-1 in FIG. 1 is a curve obtained based on the group of points B and the group of points C plotted on the graph. The curve A-1 corresponds to the above formula (A-1), Y=-0.0062X 2 It is expressed as a quadratic function of +0.1343X+0.1123. The points on the positive side of the vertical axis from curve A-1 (in FIG. 1, the group of points A and the group of points B) are fluorine-containing ether compounds that satisfy the above formula (A-1), and the points on curve A-1 and on the negative side of the vertical axis from curve A-1 (in FIG. 1, the group of points C) are fluorine-containing ether compounds that do not satisfy the above formula (A-1). The curve A-2 in FIG. 1 will be described later.

[0021] The present inventors have focused on the parameters X and Y and investigated their relationship with the effects of the present invention, and have found that a predetermined effect can be obtained at the boundary of "Curve A-1." Here, X simply represents the amount of a unit expressed by (OCF2), and Y simply represents the amount of (OCF2) sandwiched between (OCF2). The inventors noticed that when the value of X changes, the value of Y at which a predetermined effect is manifested changes accordingly, and discovered that the parameters X and Y are closely related, leading to the above curve A-1.

[0022] In formula (A-1), X is preferably 0.9 to 8, more preferably 2 to 8, and even more preferably 3 to 6, in that the surface layer has better at least one of abrasion resistance and lubricity.

[0023] Y in formula (A-1) is less than 1.0, and is preferably from 0.10 to 0.90, more preferably from 0.46 to 0.85, and even more preferably from 0.50 to 0.85, in order to improve at least one of the abrasion resistance and lubricity of the surface layer.

[0024] <Formula (A-2)> The fluorine-containing ether compound contained in this surface treatment agent is 19 It is preferable that the following formula (A-2) is satisfied in the chart obtained by F-NMR measurement, whereby at least one of the abrasion resistance and the lubricity of the surface layer is more excellent.

[0025] Y>-0.0056X 2 +0.1231X+0.2119 (A-2) X and Y in formula (A-2) are the same as X and Y in formula (A-1) above.

[0026] Here, the curve A-2 in FIG. 1 is a curve obtained based on the group of points A and the group of points B plotted on the graph. The formula (A-2) corresponds to the curve A-2 in FIG. 1, and the curve A-2 is expressed as Y=-0.0056X 2 It is expressed as a quadratic function of +0.1231X+0.2119. Points located on the positive side of the vertical axis from curve A-2 (a group of points A in FIG. 1) are fluorine-containing ether compounds that satisfy the above formula (A-2), and points located on curve A-2 and on the negative side of the vertical axis from curve A-2 (a group of points B in FIG. 1) are fluorine-containing ether compounds that do not satisfy the above formula (A-2). The inventors have focused on the parameters X and Y and investigated their relationship with the effects of the present invention, and have found that the effects of the present invention are further improved at the boundary of "Curve A-2."

[0027] <Formula (A-3)> The fluorine-containing ether compound contained in this surface treatment agent is 19 In a chart obtained by F-NMR measurement, it is preferable that the above formula (A-1) and the following formula (A-3) are satisfied, and it is more preferable that the above formula (A-2) and the following formula (A-3) are satisfied, whereby at least one of the abrasion resistance and the lubricity of the surface layer is particularly excellent. Y<-0.0045X 2 +0.098X+0.4645 (A-3) X and Y in formula (A-3) are the same as X and Y in formula (A-1) above. The formula (A-3) corresponds to the curve A-3 in FIG. 1, and the curve A-3 is Y=-0.0045X 2 It is expressed as a quadratic function of +0.098X+0.4645.

[0028] <Fluorine-containing ether compounds> The fluorine-containing ether compound contained in the present surface treatment agent has a fluoropolyether chain containing a unit represented by (OCF2) and a unit represented by (OCF2CF2), and a reactive silyl group. Since the fluorine-containing ether compound has a fluoropolyether chain, the surface layer obtained using the fluorine-containing ether compound has excellent water and oil repellency and fingerprint stain removability. The fluorine-containing ether compound has a reactive silyl group, which forms a strong chemical bond with the substrate, and the resulting surface layer has excellent abrasion resistance.

[0029] The fluoropolyether chain preferably has the following structure (G1). (OCF2) m11 (OCF2CF2) m12 ···(G1) however, m11 means the average number of (OCF2) in the fluorinated ether compound and is a positive number of 2 or more, m12 means the average number of (OCF2CF2) in the fluorine-containing ether compound and is a positive number of 2 or more.

[0030] In formula (G1), the bonding order of (OCF2) and (OCF2CF2) is arbitrary. For example, in formula (G1), (OCF2) and (OCF2CF2) may be alternately arranged, or (OCF2) and (OCF2CF2) may be arranged in blocks, or may be random. m11 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60. m12 is a positive number of 2 or more, preferably a positive number of 2 to 100, more preferably a positive number of 3 to 80, and even more preferably a positive number of 4 to 60. The value of m11 / m12 is preferably 0.8-9, more preferably 2-8, and even more preferably 3-7.

[0031] The average number of (OCF2) and the average number of (OCF2CF2) in the fluorine-containing ether compound are 19 Measured by F-NMR.

[0032] The fluoropolyether chain in the fluorine-containing ether compound may contain oxyfluoroalkylene units other than (OCF2) and (OCF2CF2) (hereinafter also referred to as "other oxyfluoroalkylene units"). Other specific examples of oxyfluoroalkylene units include (OG f1 ) m1 , (OG f2 ) m2 , (OG f3 ) m3 , (OG f4 ) m4 , (OG f5 ) m5 , (OG f6 ) m6 Examples include: However, G f1 is a fluoroalkylene group having one carbon atom (wherein G f1 ) except when -CF2- G f2 is a fluoroalkylene group having 2 carbon atoms (wherein G f2 ) except when -CF2CF2- Gf3 is a fluoroalkylene group having 3 carbon atoms, G f4 is a fluoroalkylene group having 4 carbon atoms, G f5 is a fluoroalkylene group having 5 carbon atoms, G f6 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. In addition, the fluoropolyether chain (OG f1 )~(OG f6 ) in which at least one unit selected from (OG f1 )~(OG f6 ) can be joined in any order. m1 to m6 are each f1 )~(OG f6 ) and does not represent the arrangement. For example, (OG f5 ) m5 (OG f5 ) is m5 on average, and (OG f5 ) m5 It does not represent the block placement structure of the f1 )~(OG f6 The order of the units does not represent the order in which they are bonded. 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.

[0033] G f1 A specific example of the group is -CHF-. G f2 Specific examples include -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF-, etc. G f3Specific examples of the alkyl group include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, - CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-C Examples include F2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-, and the like. G f4 Specific examples of the alkyl group include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2C Examples include HFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, and the like. G f5Specific examples of the group include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, -cycloC5F8-, and the like. G f6 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloCF 10 -etc. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, specific examples of which include a perfluorocyclobutane-1,2-diyl group and a perfluorocyclobutane-1,3-diyl group. -cycloC5F8- means a perfluorocyclopentanediyl group, specific examples of which include a perfluorocyclopentane-1,3-diyl group. -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0034] The proportion of fluorine atoms in the fluoropolyether chain [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, in terms of excellent water and oil repellency and fingerprint removability. Furthermore, the molecular weight of the fluoropolyether chain portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000, from the viewpoint of abrasion resistance.

[0035] The ratio of the total number of other oxyfluoroalkylene units to the total number of all units constituting the fluoropolyether chain is preferably 10% or less, more preferably 5% or less.

[0036] The reactive silyl group is preferably the group (g1). -SiR a1 z1 R a2 3-z1 (g1) however, R a1 is a hydroxyl group or a hydrolyzable group, and R a1 If there are multiple R a1 may be the same or different from each other, R a2 is a non-hydrolyzable group, and R a2 If there are multiple R a2 may be the same or different from each other, z1 is an integer of 1 to 3.

[0037] R a1 When is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. A hydrolyzable group is a group that becomes a hydroxyl group (i.e., a silanol group) through a hydrolysis reaction. The silanol group further reacts with other molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate (or underlayer)-OH) on the surface of the substrate (or underlayer) to form a chemical bond (substrate (or underlayer)-O-Si). Having one or more groups (g1) provides the fluorine-containing ether compound with excellent abrasion resistance after the formation of a surface layer.

[0038] R a1 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 (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. 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.

[0039] Ra1 Among these, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred from the viewpoint of ease of production of the fluorine-containing ether compound. a1 In the above, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, since it provides excellent storage stability to the fluorine-containing ether compound and suppresses outgassing during the reaction, and from the viewpoint of long-term storage stability, an ethoxy group is more preferred, and from the viewpoint of shortening the hydrolysis reaction time, a methoxy group is more preferred. Of the halogen atoms, a chlorine atom is preferred.

[0040] R a2 Examples of the non-hydrolyzable group include a hydrogen atom or a monovalent hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group, with an alkyl group being preferred from the standpoint of ease of production. Furthermore, from the standpoint of ease of production, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0041] z1 may be an integer of 1 to 3, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the substrate (or undercoat layer). Specific examples of the group (g1) include -Si(OCH3)3, -SiCH3(OCH3)2, -Si(OCH2CH3)3, -SiCl3, -Si(OCOCH3)3, -Si(NCO)3, etc. From the viewpoint of ease of handling in production, -Si(OCH3)3 is preferred. When there are multiple groups (g1) in one molecule, the multiple groups (g1) may be the same or different.

[0042] In the fluorine-containing ether compound, the fluoropolyether chain and the group (g1) are bonded directly or via a linking group, which may be a divalent or higher organic group. The number of fluoropolyether chains in one molecule of the fluorinated ether compound may be 1 or 2 or more. From the standpoint of ease of synthesis, the number of fluoropolyether chains in one molecule is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The number of groups (g1) in one molecule of the fluorinated ether compound may be 1 or 2 or more. In order to achieve both abrasion resistance and water and oil repellency, the number of groups (g1) is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12. When there are a plurality of fluoropolyether chains, the plurality of fluoropolyether chains may be the same or different, and when there are a plurality of groups (g1), the plurality of groups (g1) may be the same or different.

[0043] The content of the fluorine-containing ether compound is preferably 0.01 to 100 mass%, more preferably 0.10 to 99.99 mass%, and even more preferably 1.00 to 99.00 mass%, based on the total mass of the surface treatment agent. When the content of the fluorine-containing ether compound is within the above range, the surface layer will have better water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0044] The fluorine-containing ether compound may be any compound as long as it satisfies the above-mentioned requirements. In terms of ease of synthesis and ease of handling of the compound, among others, a compound represented by the following formula (1-1), (1-2) or (1-3) is preferred. [R f1 -(OCF2) m11 (OCF2CF2) m12 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 ···(1-1) (T 31 -R 31 ) x3 -L 3 -R 3 -(OCF2) m11 (OCF2CF2) m12 -OR 2 -L 2 -(R 21 -T 21 ) x2 (1-2) Q 1 [-(OCF2) m11 (OCF2CF2)m12 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (1-3) however, R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 If there are multiple R f1 may be the same or different from each other, (OCF2) m11 (OCF2CF2) m12 is as described above, R 1 is an alkylene group or a fluoroalkylene group, and R 1 If there are multiple R 1 may be the same or different (except R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than -CF2- and -CF2CF2-), L 1 is a single bond or a j+x monovalent organic group which may contain N, O, S, or Si and may have a branch point, and R 1 and R 11 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), R 11 L 1 an atom bonded to the group may be an ethereal oxygen atom, or an alkylene group which may have an ethereal oxygen atom between carbon atoms, T 11 -SiR a11 z11 R a12 3-z11 and R a11 is a hydroxyl group or a hydrolyzable group, and R a11 If there are multiple R a11 may be the same or different from each other, R a12is a non-hydrolyzable group, and R a12 If there are multiple R a12 may be the same or different from each other, j is an integer equal to or greater than 1, z11 is an integer from 1 to 3, x1 is an integer greater than or equal to 1, R 2 and R 3 are each independently an alkylene group or a fluoroalkylene group (provided that R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than -CF2- and -CF2CF2-), L 2 is a single bond or a 1+x divalent organic group which may contain N, O, S, or Si and may have a branch point, and R 2 and R 21 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), R 21 L 2 an atom adjacent to the alkylene group may be an ethereal oxygen atom, or an alkylene group having an ethereal oxygen atom between carbon atoms, L 3 is a single bond or a 1+x trivalent organic group which may contain N, O, S, or Si and may have a branch point, and R 3 and R 31 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), R 31 L 3 an atom adjacent to the alkylene group may be an ethereal oxygen atom, or an alkylene group having an ethereal oxygen atom between carbon atoms, T 21 and T 31 are each independently -SiR a21 z21 R a22 3-z21 and R a21 is a hydroxyl group or a hydrolyzable group, and Ra21 If there are multiple R a21 may be the same or different from each other, R a22 is a non-hydrolyzable group, and R a22 If there are multiple R a22 may be the same or different from each other, z21 is an integer from 1 to 3, x2 and x3 each independently represent an integer of 1 or more, Q 1 is an r-valent group having a branch point, R 4 are each independently an alkylene group or a fluoroalkylene group (provided that R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than -CF2- and -CF2CF2-), L 4 is a single bond or a 1+x tetravalent organic group which may contain N, O, S, or Si and may have a branch point, and R 4 and R 41 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O), R 41 L 4 an atom adjacent to the alkylene group may be an ethereal oxygen atom, or an alkylene group having an ethereal oxygen atom between carbon atoms, T 41 -SiR a41 z41 R a42 3-z41 and R a41 is a hydroxyl group or a hydrolyzable group, and R a41 If there are multiple R a41 may be the same or different from each other, R a42 is a non-hydrolyzable group, and R a42 If there are multiple R a42 may be the same or different from each other, z41 is an integer from 1 to 3, x4 is an integer greater than or equal to 1, r1 is 3 or 4. The structure of each compound will be explained below, and symbols having similar structures will be indicated as such and can be read interchangeably for reference as appropriate.

[0045] (Compound (1-1)) The compound (1-1) has a structure represented by the following formula (1-1). [R f1 -(OCF2) m11 (OCF2CF2) m12 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 ···(1-1) However, each symbol in the formula (1-1) is as described above.

[0046] R f1 is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear or may have a branched and / or cyclic structure. From the viewpoint of abrasion resistance, a linear fluoroalkyl group is preferred, and from the viewpoint of ease of synthesis, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, and more preferably 1 to 3.

[0047] (OCF2) m11 (OCF2CF2) m12 is as described above.

[0048] R 1 is an alkylene group or a fluoroalkylene group, provided that R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than -CF2- and -CF2CF2-. R 1The alkylene group and fluoroalkylene group in R may be linear or may have a branched and / or cyclic structure. From the viewpoint of ease of synthesis, linear or branched alkylene or fluoroalkylene groups are preferred, and linear or branched alkylene or fluoroalkylene groups having a methyl group or a fluoromethyl group are more preferred. 1 The number of carbon atoms in R is preferably 1 to 6, and more preferably 1 to 3. 1 L 1 If is a single bond, R 11 In this case, R 1 R in 11 is bonded to at least one fluorine atom or fluoroalkyl group.

[0049] j is the [R f1 -(OCF2) m11 (OCF2CF2) m12 -OR 1 ], which may be an integer of 1 or more, is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

[0050] R 11 L 1 The atom bonded to may be an ethereal oxygen atom, or the alkylene group may have an ethereal oxygen atom between carbon atoms. R 11 The alkylene group in may be linear or may have a branched and / or cyclic structure. In view of the ease with which the present surface treatment agent is densely arranged when forming a surface layer, an alkylene group having a methyl group as a linear or branched chain is preferred, and a linear alkylene group is more preferred. R 11 Specifically, it can be expressed by the following formula (g2). *-(O) a1 -(R g2 O) a2 -R g2 -** ···(g2) however, R g2 is an alkylene group having one or more carbon atoms, and there are multiple R g2may be the same or different from each other, a1 is 0 or 1, a2 is an integer equal to or greater than 0, * is L 1 is a bond that bonds to ** is T 11 is the bond that bonds to

[0051] When a1 is 0, the atom having the bond * is a carbon atom, and when a1 is 1, the atom having the bond * is an oxygen atom. In compound (1-1), a1 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis, etc. a2 is R g2 It is the number of repetitions of O, and is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the viewpoint of durability as a surface layer, etc.

[0052] R 11 is more preferably a group represented by the following formula (g3), in that the surface layer has better water and oil repellency and fingerprint stain removability, and is also excellent in durability such as abrasion resistance. *-(O) a1 -R g3 -** ···(g3) however, R g3 is an alkylene group, a1, *, and ** are the same as in formula (g2).

[0053] R g3 The alkylene group in may be linear or may have a branched and / or cyclic structure. A linear alkylene group is preferred because the compound (1-1) is likely to be densely arranged when forming a surface layer.

[0054] T 11 Ha-SiR a11 z11 R a12 3-z11 and R a11 , R a12 , z11 are R constituting the above group (g1), a1 , R a2, z1, and preferred embodiments are also the same.

[0055] x1 is -R in one molecule 11 -T 11 It is sufficient if it is an integer of 1 or more, and is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12.

[0056] L 1 is a single bond or a j+x monovalent group which may contain N, O, S, or Si and which may have a branch point, and R 1 and R 11 The atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). 1 and R 11 The atoms bonded to may be the same atom or different atoms.

[0057] L 1 When is a single bond, R in formula (1-1) 1 and R 11 is directly bonded, and the compound (1-1) is represented by the following formula (1-1'). R f1 -(OCF2) m11 (OCF2CF2) m12 -OR 1 -R 11 -T 11 (1-1') However, each symbol in the formula (1-1') is the same as in the formula (1-1).

[0058] L 1 When is a trivalent or higher group, L 1 is at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (j+x1)-valent organopolysiloxane residue. 1 ") is also called.

[0059] N is the branch point P 1 If so, the branch point P 1 is expressed as *-N(-**)2 or (*-)2N-**, where * is R1 side bond, and ** is R 11 It is the connecting hand on the side. C is the branch point P 1 If so, the branch point P 1 For example, *-C(-**)3, (*-)2C(-**)2, (*-)3C-**, *-CR 29 (-**)2 or (*-)2CR 29 -**, where * is R 1 side bond, and ** is R 11 side bond, R 29 is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. Si is the branch point P 1 If so, the branch point P 1 For example, *-Si(-**)3, (*-)2Si(-**)2, (*-)3Si-**, *-SiR 29 (-**)2 or (*-)2SiR 29 -**, where * is R 1 side bond, and ** is R 11 side bond, R 29 is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0060] Branch point P 1 From the viewpoints of ease of production of compound (1-1) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer, the ring structure constituting the formula (1-1) is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and more preferably a ring structure shown in the following formula: The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (=O).

[0061] [ka]

[0062] Branch point P 1 Examples of the organopolysiloxane residue constituting the formula include the following groups: 25 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 25 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0063] [ka]

[0064] Divalent or higher L 1 is -C(O)N(R 26 )-, -N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R 26 )-, -SO2N(R 26 )-, -N(R 26 )SO2-, -Si(R 26 )2-, -OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and at least one bond selected from the group consisting of a divalent organopolysiloxane residue (hereinafter referred to as "bond B 1 "). However, R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 26 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1).

[0065] Examples of the divalent organopolysiloxane residue include groups of the following formula: 27 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 27The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0066] [ka]

[0067] Join B 1 As the compound (1-1), —C(O)NR 26 -, -N(R 26 )C(O)—, —C(O)—, and —NR 26 In order to further improve the light resistance and chemical resistance of the surface layer, at least one bond selected from the group consisting of - is preferred, and -C(O)NR 26 -, -N(R 26 )C(O)- or -C(O)- is more preferred.

[0068] Divalent L 1 As for R 1 and R 11 are each independently N, O, S, Si, or a carbon atom having an oxo group (=O). That is, R 1 and R 11 The atoms adjacent to each bond B 1 It is a constituent element of the divalent L 1 Specific examples of B include a single bond, one or more bonds B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**) etc. However, R 28 is a single bond or a divalent organic group, and * is R 1 side bond, and ** is R 11 It is the connecting hand on the side.

[0069] Trivalent or higher L 1 is R 1 and R 11 The atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). 1 and R11 The atoms adjacent to each bond B 1 Or branch point P 1 It is a constituent element of trivalent or higher L 1 A specific example of this is one or more branch points P 1 (for example{(*-) j P 1 (-**) x1}, {(*-) j P 1 -R 28 -P 1 (-**) x1}, etc.), one or more branch points P 1 and one or more bonds B 1 Combination with (for example, {*-B 1 -R 28 -P 1 (-**) x1}, {*-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x1}, etc. However, R 28 is a single bond or a divalent organic group, and * is R 1 side bond, and ** is R 11 It is the connecting hand on the side.

[0070] Above R 28 Examples of the divalent organic group in the formula include hydrocarbon groups such as divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups), and the hydrocarbon groups may have a bond B between carbon atoms. 1 The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0071] The above L 1 As the group, a group represented by any one of the following formulae (L1) to (L7) is preferred in terms of ease of production of the compound (1-1).

[0072] [ka]

[0073] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -) d6 (L2) (-A 2 -) d7 N(-Q 23 -) 3-d7 (L3) (-A 3 -) d8 Z 1 (-Q 24 -) d9 (L4) (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -) d11 ···(L5) -A 1 -Q 26 - (L6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 (L7)

[0074] However, in formulas (L1) to (L7), A 1 , A 2 or A 3 The side is R in formula (1-1). 1 and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 11 Connect to. where A 1 is a single bond, -B 3 -, -B 3 -R 30 - or -B 3 -R 30 -B 2 -wherein R 30is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, B 2 is -C(O)NR e6 -, -C(O)-, -NR e6 - or -O-, and B 3 is -C(O)NR e6 -, -C(O)-, or -NR e6 - and A 2 is a single bond or -B 3 -R 30 - and A 3 is A 3 Z bonded to 1 If the atom in is a carbon atom, then A 1 and A 3 Z bonded to 1 If the atom in is a nitrogen atom, A 2 and Q 11 represents a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, Q 22 is a single bond, -B 3 -, -R 30 -B 3 -or-B 2 -R 30 -B 3 - and Q 23 is a single bond or -R 30 -B 3 - and 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 and Q 25 is a single bond or -R 30-B 3 - and Q 26 is a single bond or -R 30 -B 3 - and Z 1 is A 3 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having a (d8+d9)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, R e1 is a hydrogen atom or an alkyl group, R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R e3 is an alkyl group, R e6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 3; d3 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d3+d4 is an integer of 1 to 3; d1+d3 is an integer between 1 and 5, d2+d4 is an integer between 1 and 5, d5 is an integer of 1 to 3, d6 is an integer of 1 to 3, and d5+d6 is an integer of 2 to 4; d7 is 1 or 2, d8 is an integer greater than or equal to 1, d9 is an integer greater than or equal to 1, d10 is an integer of 1 to 3, d11 is an integer of 1 to 3, and d10+d11 is an integer of 2 to 4; d12 is an integer of 1 to 3. In addition, A 1 If there are multiple A's, 1 may be the same or different. 2 , A 3 , Q 22 , Q 23 , Q 24 , Q 25 , R e1 , R e2 , Re3 The same is true for . Also, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0075] R 30 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of compound (1-1) and further improved abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. Z 1 Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0076] R e1 , R e2 or R e3 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). R e2 The number of carbon atoms in the alkyl group of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, in terms of ease of production of compound (1-1) and further improved abrasion resistance and fingerprint stain removability of the surface layer.

[0077] The above L 1 Other examples of the group include groups represented by any of the following formulae (L11) to (L17).

[0078] [ka]

[0079] (-A 1 -) d5 C(R e2 ) 4-d5―d6 (-Q 22 -G)d6 ···(L12) (-A 2 -) d7 N(-Q 23 -G) 3-d7 ···(L13) (-A 3 -) d8 Z 1 (-Q 24 -G) d9 ···(L14) (-A 2 -) d10 Si(R e3 ) 4-d10-d11 (-Q 25 -G) d11 ···(L15) -A 1 -Q 26 -G (L16) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 ···(L17)

[0080] However, in formulas (L11) to (L17), A 1 , A 2 or A 3 The side is R in formula (1-1). 1 and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 11 G is the following group (G21), and L 1 The two or more G's may be the same or different. The symbols other than G are the same as those in formulae (L1) to (L7). -Si(R 21 ) 3-k (-Q 3 -) k ···(G21) However, in equation (G21), the Si side is Q 22 , Q 23 , Q 24 , Q 25 or Q 26Connect to Q 3 Side is R 11 Connect to R 21 is an alkyl group. 3 is a single bond or -R 31 -B 3 -wherein R 31 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 32 -, -C(O)-, -NR 32 - or a group having -O-, or -(OSi(R 22 )2) p11 -O- and 2 or more Q 3 may be the same or different. k is 2 or 3. R 32 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 22 is an alkyl group, a phenyl group, or an alkoxy group, and two R 22 may be the same or different. p11 is an integer of 0 to 5, and when p11 is 2 or more, 2 or more (OSi(R 22 )2) may be the same or different.

[0081] Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of compound (1-1) and further improved abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 21 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). R 22 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-1). R 22 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of excellent storage stability of the compound (1-1). p11 is preferably 0 or 1.

[0082] Examples of the compound (1-1) include the following: f is [R f1 -(OCF2) m11 (OCF2CF2) m12 -OR 1 ].

[0083] [ka]

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[0096] (Compound (1-2)) The compound (1-2) has a structure represented by the following formula (1-2). (T 31 -R 31 ) x3 -L 3 -R 3 -(OCF2) m11 (OCF2CF2) m12 -OR 2 -L 2 -(R 21 -T 21 ) x2 (1-2) However, each symbol in the formula (1-2) is as described above.

[0097] (OCF2) m11 (OCF2CF2) m12 is as described above.

[0098] R 2 and R 3 are each independently the above R 1 The same applies to the preferred embodiments.

[0099] R 21 and R 31 is the above R 11 The same applies to the preferred embodiments, except that "L 1 "Binds to" is R 21 In the case of "L 2 "Combines with" and R 31 In the case of "L 3 "Binds to" and "T 11 "Binds to" is R 21 In the case of "T 21 "Combines with" and R 31 In the case of "T 31 This should be read as "bonding to L". 2 If is a single bond, R 21 is R 2 It also bonds directly to L 3 If is a single bond, R 31 is R 3 directly binds to

[0100] T 21 and T 31 are each independently -SiR a21 z21 R a22 3-z21 and R a21 , R a22 , z21 are R constituting the above group (g1), a1 , R a2 , z1, and preferred embodiments are also the same.

[0101] x2 and x3 each independently represent the same as x1, and the preferred embodiments are also the same.

[0102] L 2 and L 3 are each independently the above L 1 This is the same as when j is 1. For example, L 2 and L 3 When is a single bond, the compound (1-2) is represented by the following formula (1-2'). T 31 -R 31-R 3 -(OCF2) m11 (OCF2CF2) m12 -OR 2 -L 2 -R 21 -T 21 (1-2') However, each symbol in the formula (1-2') is the same as in the formula (1-2).

[0103] L 2 or L 3 When L is a trivalent or higher valent group, 2 or L 3 is at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (1+x2)- or (1+x3)-valent organopolysiloxane residue. 2 ") is also called.

[0104] N is the branch point P 2 If so, the branch point P 2 is expressed as *-N(-**)2, where * is R 2 or R 3 side bond, and ** is R 21 or R 31 It is the connecting hand on the side. C is the branch point P 2 If so, the branch point P 2 For example, *-C(-**)3 or *-CR 29 It is expressed as (-**)2, where * is R 2 or R 3 side bond, and ** is R 21 or R 31 side bond, R 29 is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group. Si is the branch point P 2 If so, the branch point P 2 is, for example, *-Si(-**)3 or *-SiR 29 It is expressed as (-**)2, where * is R 2 or R 3 side bond, and ** is R 21 or R 31side bond, R 29 is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0105] Branch point P 2 The ring structure and organopolysiloxane residue constituting the above-mentioned branch point P 1 The same applies to the preferred embodiments. In addition, divalent or more L 2 or L 3 Each independently represents the bond B 1 Bond B 1 The embodiments are as described above, and the preferred embodiments are also the same.

[0106] Divalent L 2 or L 3 is R 2 and R 21 , or R 3 and R 31 are each independently N, O, S, Si, or a carbon atom having an oxo group (=O). That is, R 2 and R 21 , or R 3 and R 31 The atoms adjacent to each bond B 1 It is a constituent element of the divalent L 2 or L 3 Specific examples of B include a single bond, one or more bonds B 1 (For example, *-B 1 -**, *-B 1 -R 28 -B 1 -**) etc. However, R 28 is a single bond or a divalent organic group, and * is R 2 or R 3 side bond, and ** is R 21 or R 31 It is the connecting hand on the side.

[0107] Trivalent or higher L 2 or L 3 is R 2 and R 21 , or R 3 and R31 The atoms bonded to R are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (=O). 2 and R 21 , or R 3 and R 31 The atoms adjacent to each bond B 1 Or branch point P 2 It is a constituent element of trivalent or higher L 2 or L 3 A specific example of this is one or more branch points P 2 (e.g., {*-P 2 (-**) x}, {*-P 1 -R 28 -P 1 -** x1 etc.), one or more branch points P 2 and one or more bonds B 1 Combination with (for example, {*-B 1 -R 28 -P 1 (-**) x}, {*-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x}, etc., where x is L 2 In the case of x2, L 3 In the case of R, it is x3. 28 is a single bond or a divalent organic group, and * is R 2 or R 3 side bond, and ** is R 21 or R 31 It is the connecting hand on the side. Above R 28 The embodiments are as described above, and the preferred embodiments are also the same.

[0108] The above L 2 or L 3 As the groups, each independently is preferably a group represented by any one of the following formulae (L21) to (L27), in view of ease of production of the compound (1-2).

[0109] [ka]

[0110] -A 1 -C(R e2 ) 4-d6 (-Q 22 -) d6 ···(L22) -A 2 -N(-Q 23 -)2···(L23) -A 3 -Z 1 (-Q 24 -) d9 ···(L24) -A 2 -Si(R e3 ) 4-d11 (-Q 25 -) d11 ···(L25) -A 1 -Q 26 - (L26) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -) d12 ···(L27)

[0111] However, in formulas (L21) to (L27), A 1 , A 2 or A 3 The side is formula R 2 or R 3 and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 21 or R 31 Connect to. where A 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , R e1, R e2 , R e3 , R e6 is the above L 1 The preferred embodiments are the same as those described above. Z 1 is A 3 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having a (1+d9)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, d2 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d2+d4 is an integer of 1 to 5; d6 is an integer between 1 and 3, d9 is an integer greater than or equal to 1, d11 is an integer between 1 and 3 d12 is an integer of 1 to 3. Note that d2+d4, d6, d9, d11, and 1+d12 are x2 or x3. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, in terms of ease of production of compound (1-2) and further improved abrasion resistance and fingerprint stain removability of the surface layer.

[0112] The above L 2 or L 3 Other examples of the group include groups represented by any of the following formulae (L31) to (L37).

[0113] [ka]

[0114] -A 1 -C(R e2 ) 4-d6 (-Q 22 -G) d6 ···(L32) -A 2 -N(-Q 23 -G)2···(L33) -A 3 -Z 1 (-Q 24 -G) d9 ···(L34) -A2 -Si(R e3 ) 4-d11 (-Q 25 -G) d11 ···(L35) -A 1 -Q 26 -G (L36) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-d12 (-Q 25 -G) d12 ···(L37)

[0115] However, in formulas (L31) to (L37), A 1 , A 2 or A 3 The side of the equation is R 2 or R 3 and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 21 or R 31 G is the above group (G21), and preferred embodiments are also the same. The symbols other than G are the same as the symbols in formulae (L21) to (L27), and preferred embodiments are also the same.

[0116] Examples of the compound (1-2) include the following: f Ha-R 3 -(OCF2) m11 (OCF2CF2) m12 -OR 2 -It is.

[0117] [ka] TIFF0007790182000024.tif61150JPEG0007790182000025.jpg2677JPEG0007790182000026.jpg2984

[0118] [ka]

[0119] [ka]

[0120] (Compound (1-3)) The compound (1-3) has a structure represented by the following formula (1-3). Q 1 [-(OCF2) m11 (OCF2CF2) m12 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (1-3) However, each symbol in the formula (1-3) is as described above.

[0121] (OCF2) m11 (OCF2CF2) m12 is as described above.

[0122] R 4 is the above R 1 The same applies to the preferred embodiments.

[0123] R 41 is the above R 11 The same applies to the preferred embodiments, except that "L 1 "Binding to" is "L 4 "Binds to" and "T 11 "Bind to" is "T 41 This should be read as "bonding to L". 4 If is a single bond, R 41 is R 4 directly binds to

[0124] T 41 -SiR a41 z41 R a42 3-z41 and Ra41 , R a42 , z41 are R constituting the above group (g1), a1 , R a2 , z1, and preferred embodiments are also the same.

[0125] x4 is the same as x1, and the preferred embodiments are also the same. L 4 L 2 or L 3 The same applies to the preferred embodiments.

[0126] Q 1 is an r1-valent group having a branch point, and r1 is 3 or 4.

[0127] Q 1 The branch point P that constitutes 3 Examples of the branch point P include N, C, Si, and a ring structure. 3 There may be one or two or more.

[0128] N is the branch point P 3 If so, the branch point P 1 For example, N(-*)3, NR 29 It is represented as (-*)2. C is the branch point P 3 If so, the branch point P 3 For example, C(-*)4, CR 29 (-*)3, C(R 29 )2(-*)2, etc. Si is the branch point P 3 If so, the branch point P 3 is, for example, Si(-*)4, SiR 29 (-*)3, Si(R 29 )2(-*)2, etc. However, * is (OCF2) m11 (OCF2CF2) m12 side bond, R 29 is a monovalent group. 29 Examples of the alkyl group include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, and R 41 -T 41and the like, for example, a fluoropolyether chain having no such group.

[0129] Branch point P 3 The ring structure that constitutes the 1 The substituents of the ring structure may be the same as those described above, and may further include a fluorine atom, a fluoroalkyl group, R 41 -T 41 It may have a fluoropolyether chain that does not have the formula:

[0130] The above Q 1 As the group, a group represented by any one of the following formulae (Q1) to (Q8) is preferred in terms of ease of production of the compound (1-3).

[0131] [ka]

[0132] C(-A 11 -) d23 (R e12 ) 4-d23 (Q2) N(-A 12 -)3···(Q3) Z 1 (-A 13 -) d24 ···(Q4) Si(-A 12 -) d25 (R e13 ) 4-d25 (Q5) CH(-A 11 -)2-Si(R e13 ) 3-d26 (-A 11 -) d26 ···(Q6)

[0133] [ka]

[0134] [ka]

[0135] However, in formulas (Q1) to (Q8), A 11 , A 12 or A 13 (OCF2) m11 (OCF2CF2) m12 and connect. where A 11 is a single bond, -R 40 -, -B 13 -R 40 -wherein R 40 is an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms, with —C(O)NR e17 -, -C(O)-, -NR e17 - or -O-, B 13 is -C(O)NR e6 -, -C(O)-, -NR e6 - or -O-, A 12 is a single bond or -R 40 - and A 13 is A 13 Z bonded to 1 If the atom in is a carbon atom, then A 11 and A 13 Z bonded to 1 If the atom in is a nitrogen atom, A 12 and Z 1 is A 13 is a group having an r(valent) ring structure having a carbon atom or a nitrogen atom to which is directly bonded, Q 52 represents a single bond, -O-, an alkylene group, a fluoroalkylene group, or an alkylene group or fluoroalkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e17 -, -C(O)-, -NR e17 - or -O-, R e11 is a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, R 41 -T 41or a fluoropolyether chain having no -Q in the range of r1 being 3 to 4. 52 -C(R e11 ) 3-d21 (-A 11 -) d21 is a group having a repeating structure of R e12 is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, or R 41 -T 41 is a fluoropolyether chain that does not have R e13 is an alkyl group or a fluoroalkyl group, R e14 , R e15 , and R e16 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a fluoroalkyl group, R e17 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or a phenyl group which may be substituted with fluorine; d21 is an integer of 0 to 3, d22 is an integer of 0 to 3, and d21+d22 is an integer of 3 to 4; d23 is 3 or 4, d24 is 3 or 4, d25 is 3 or 4, d26 is 1 or 2, d27 is an integer from 1 to 3, d28 is 1 or 2, d29 is an integer from 1 to 3, d30 is an integer from 1 to 3, d31 is 1 or 2, d32 is 1 or 2, d33 is an integer from 1 to 3. In addition, A 11 If there are multiple A's, 1 may be the same or different. 12 , A 13 , R e11 , R e12 , R e13 The same is true for .

[0136] R 40 The number of carbon atoms in the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of compound (1-3) and further improved abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. Z 1 Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0137] R e11 , R e12 , R e13 , R e14 , R e15 and R e16 In the above, the number of carbon atoms in the alkyl group or fluoroalkylene group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound (1-3).

[0138] Examples of the compound (1-3) include the following: f3 (OCF2) m11 (OCF2CF2) m12 -OR 4 is.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] <Other ingredients> The present surface treatment agent may contain at least one of a fluorine-containing compound other than the above-mentioned fluorine-containing ether compound and the following impurities. Examples of the impurities include compounds that are unavoidable in the production of the above-mentioned fluorine-containing ether compound and other fluorine-containing compounds. Note that the present surface treatment agent does not contain a liquid medium described below.

[0144] Examples of other fluorine-containing compounds include fluorine-containing compounds produced as by-products in the production process of the above-mentioned fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing compounds"), and known fluorine-containing compounds used for the same purposes as the above-mentioned fluorine-containing ether compounds. As the other fluorine-containing compound, a compound which is unlikely to deteriorate the properties of the above-mentioned fluorine-containing ether compound is preferred.

[0145] Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the above-mentioned fluorine-containing ether compound. When the present surface treatment agent contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

[0146] Examples of known fluorine-containing compounds include compounds described in the following documents: perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097; perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 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 Japanese Patent Application Laid-Open No. 2012-72272; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Application Laid-Open No. 2015-199906, Japanese Patent Application Laid-Open No. 2016-204656, Japanese Patent Application Laid-Open No. 2016-210854, and Japanese Patent Application Laid-Open No. 2016-222859 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, WO 2019 / 044479, and WO 2019 / 163282. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., the SURECO AF series such as SURECO (registered trademark) 2101S manufactured by AGC Corporation, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0147] When the present surface treatment agent contains the other fluorine-containing compound described above, the content of the other fluorine-containing compound is preferably less than 50 mass%, more preferably less than 30 mass%, and even more preferably less than 10 mass%, relative to the total mass of the present surface treatment agent, in order to fully exhibit the properties of the fluorine-containing ether compound.

[0148] [Coating liquid] The coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains the present surface treatment agent and a liquid medium. The present coating liquid may be in any liquid form, and may be a solution or a dispersion. The present coating liquid is only required to contain the present surface treatment agent, and may contain impurities such as by-products produced in the production process of the fluorinated ether compound.

[0149] The content of the present surface treatment agent is preferably 0.001 to 40 mass %, more preferably 0.01 to 20 mass %, and more preferably 0.1 to 10 mass %, relative to the total mass of the present coating liquid.

[0150] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a mixture of both.

[0151] Specific examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. Specific examples of fluorinated alkanes are preferably compounds having 4 to 8 carbon atoms. Commercially available products include C6F 13H (AGC Corporation, Asahiklin (registered trademark) AC-2000), C6F 13 Examples include C2H5 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (VERTREL (registered trademark) XF, manufactured by Chemours Corporation). Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). 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. The non-fluorinated organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, or a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents.

[0152] The present coating liquid preferably contains 60 to 99.999 mass %, more preferably 85 to 99.99 mass %, and even more preferably 90 to 99.9 mass % of the liquid medium.

[0153] The present coating liquid may contain, in addition to the present surface treatment agent and the liquid medium, other components as long as the effects of the present invention are not impaired. 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. The content of other components in the present coating liquid is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0154] The total concentration of the present surface treatment agent and other components (hereinafter also referred to as "solids concentration") is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, even more preferably 0.01 to 10 mass%, and particularly preferably 0.01 to 1 mass%. The solids concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0155] [Goods] The article of the present invention (hereinafter also referred to as "the article") has a substrate and a surface layer disposed on the substrate, and preferably has an underlayer between the substrate and the surface layer. The surface layer is a layer formed from the present surface treatment agent or the present coating liquid, and contains a condensate of the above-mentioned fluorine-containing ether compound.

[0156] The material and shape of the substrate may be appropriately selected depending on the intended use of the article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. Substrates that require water and oil repellency in particular include substrates for touch panels, display substrates, and substrates that constitute the housings of electronic devices. Touch panel substrates and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0157] The substrate may be one that has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the undercoat layer is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate and the undercoat layer, and as a result, the abrasion resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferred in terms of further improving the abrasion resistance of the surface layer.

[0158] The underlayer is preferably a layer containing a silicon-containing oxide (preferably silicon oxide), and may further contain other elements. When the underlayer contains silicon oxide, the reactive silyl groups of the fluorine-containing ether compound undergo dehydration condensation to form Si-O-Si bonds with the underlayer, resulting in the formation of a surface layer with excellent abrasion resistance.

[0159] The content of silicon oxide in the underlayer is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more. When the content of silicon oxide is equal to or greater than the lower limit, Si-O-Si bonds are sufficiently formed in the underlayer, and the mechanical properties of the underlayer are sufficiently ensured. The content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted to oxide) from the mass of the underlayer.

[0160] From the viewpoint of durability of the surface layer, it is preferable that the oxide in the underlayer further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bond between the underlayer and the fluorine-containing ether compound is strengthened, and the abrasion resistance is improved.

[0161] The thickness of the underlayer is preferably 1 to 200 nm, more preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the lower limit, the underlayer is likely to have a sufficient effect of improving adhesion. If the thickness of the underlayer is equal to or less than the upper limit, the abrasion resistance of the underlayer itself is increased. Methods for measuring the thickness of the underlayer include a method of observing the cross section of the underlayer using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

[0162] The underlayer can be formed, for example, by depositing a deposition material having a desired composition for the underlayer on the surface of the substrate. An example of the vapor deposition method is vacuum deposition, in which a 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 a boat in which a vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 100 to 3000°C, more preferably 250 to 3000°C. The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in a tank in which the vapor deposition material is placed is preferably 1 Pa or less, more 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. Examples of methods for evaporating 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 a method for evaporating the deposition material because it can evaporate high-melting-point substances due to its ability to heat locally, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or contamination with impurities. The deposition material used in the electron gun method is preferably a molten granular or sintered material because it is less likely to scatter even when an air current is generated.

[0163] The surface layer contains a condensate of the above-mentioned fluorine-containing ether compound. The condensate of the fluorine-containing ether compound includes a structure in which a hydrolyzable silyl group in the fluorine-containing ether compound is hydrolyzed to form a silanol group (Si-OH), and the silanol group undergoes a condensation reaction between molecules to form a Si-O-Si bond, and a structure in which a silanol group in the fluorine-containing ether compound undergoes a condensation reaction with a silanol group or a Si-OM group (wherein M is an alkali metal element) on the surface of the substrate or underlayer to form a Si-O-Si bond. The surface layer may also contain a condensate of a fluorine-containing compound other than the fluorine-containing ether compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone a condensation reaction.

[0164] The thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency is high. The thickness of the surface layer is the thickness obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity analysis using an X-ray diffractometer for thin film analysis.

[0165] The article is preferably a touch panel. In this case, the surface layer is preferably formed on the surface of a member that constitutes the surface of the touch panel that is touched by a finger.

[0166] [Production method] The method for producing the present article is a method for forming a surface layer on a substrate by a dry coating method or a wet coating method using the present surface treatment agent or the present coating liquid.

[0167] The present surface treatment agent can be used directly in a dry coating method. The present surface treatment agent is suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of dry coating methods include vacuum deposition, CVD, and sputtering. The vacuum deposition method is suitable from the viewpoints of suppressing decomposition of the fluorinated ether compound and simplicity of the equipment. For vacuum deposition, a pellet-shaped material in which the present surface treatment agent is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped material supporting the present surface treatment agent can be produced by impregnating a porous metal body with a solution of the present surface treatment agent and then drying it to remove the liquid medium. The present coating liquid can be used as the solution of the present surface treatment agent.

[0168] The coating liquid can be suitably used for wet coating methods such as 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.

[0169] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the fluorine-containing ether compound and the substrate (or the undercoat layer) may be carried out as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate on which the surface layer has been formed can be heated in a moist atmosphere to promote reactions such as the hydrolysis reaction of hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed, for example, by pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent. [Example]

[0170] The present invention will be described in detail below with reference to examples. Examples 2, 3, 5, 6, 8, 9, 11, 12, 14, 15, 17, and 18 are working examples, and Examples 1, 4, 7, 10, 13, and 16 are comparative examples. However, the present invention is not limited to these examples.

[0171] [Synthesis of fluorine-containing ether compound X1-1] <Synthesis of compound a-2> A 500 mL three-neck flask was charged with 2.9 g of 20% aqueous KOH solution, 33 g of tert-butyl alcohol, 110 g of 1,3-bis(trifluoromethyl)benzene, 220 g of compound a-1, and 14.6 g of perfluoropropyl vinyl ether. The mixture was then stirred at 40°C for 20 hours under a nitrogen atmosphere. After stirring, the mixture was washed once with dilute aqueous hydrochloric acid, and the organic layer was concentrated using an evaporator to obtain 233 g of crude product. The obtained crude product was separated and purified using silica gel column chromatography to obtain 100 g of compound a-2.

[0172] HO-CH2CF2{(OCF2) m (OCF2CF2) n}-OCF2CH2-OH (a-1) m≒14, n≒13

[0173] CF3CF2CF2OCHFCF2OCH2CF2{(OCF2) m (OCF2CF2) n}-OCF2CH2-OH (a-2) m≒14, n≒13

[0174] <Synthesis of compound a-3> A 100 mL recovery flask was charged with 30.0 g of compound a-2, 0.9 g of sodium fluoride powder, and 30 g of dichloropentafluoropropane (AGC, Asahiklin (registered trademark) AK-225), and 3.5 g of CF3CF2CF2OCF(CF3)COF was added. The mixture was then stirred at 50°C for 24 hours under a nitrogen atmosphere. The sodium fluoride powder was removed using a pressure filter, followed by evaporation under reduced pressure. The resulting crude product was diluted with AC-2000 (AGC, Asahiklin (registered trademark) AC-2000) and passed through a silica gel column. The recovered solution was concentrated using an evaporator to obtain 31.8 g of compound a-3.

[0175] CF3CF2CF2OCHFCF2OCH2CF2{(OCF2) m (OCF2CF2) n}OCF2CH2OC(=O)CF(CF3)OCF2CF2CF3...(a-3) m≒14, n≒13

[0176] <Synthesis of compound a-4> An autoclave (made of nickel, internal volume 1 L) was prepared, and a condenser maintained at 20°C, a NaF pellet packed bed, and another condenser maintained at 0°C were installed in series at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the coagulated liquid from the condenser maintained at 0°C to the autoclave. 750 g of ClCF2CFClCF2OCF2CF2Cl (hereinafter also referred to as "CFE-419") was charged into an autoclave and stirred while maintaining the temperature at 25°C. Nitrogen gas was blown into the autoclave at 25°C for 1 hour, and then 20% fluorine gas was blown into it at a flow rate of 2.0 L / hour for 1 hour at 25°C. Next, while blowing 20% ​​fluorine gas at the same flow rate, a solution prepared by dissolving 31.0 g of compound a-3 in 124 g of CFE-419 was injected into the autoclave over 4.3 hours. Next, while blowing in 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was injected into the autoclave while heating from 25 to 40°C, and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, another 4 mL of the benzene solution was injected while maintaining the temperature at 40°C, and the inlet was closed. The same procedure was repeated three more times. The total amount of benzene injected was 0.17 g. Stirring was continued for another hour while blowing in 20% fluorine gas at the same flow rate. The pressure inside the autoclave was then adjusted to atmospheric pressure, and nitrogen gas was blown in for another hour. The contents of the autoclave were concentrated using an evaporator to obtain 31.1 g of compound a-4.

[0177] CF3CF2CF2OCF2CF2OCF2CF2O{(CF2O) m (CF2CF2O) n}CF2CF2OC(=O)CF(CF3)OCF2CF2CF3...(a-4) m≒14, n≒13

[0178] <Synthesis of compound a-5> 30.0 g of compound a-4 and 60 g of AK-225 were placed in a PFA round-bottom flask. The mixture was stirred while cooled in an ice bath, and 2.0 g of methanol was slowly added dropwise from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated using an evaporator to obtain 27.6 g of compound a-5.

[0179] CF3CF2CF2OCF2CF2OCF2CF2{(OCF2) m (OCF2CF2) n}OCF2C(=O)OCH3···(a-5) m≒14, n≒13

[0180] <Synthesis of compound a-6> In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.3 g of ethanol. 25.0 g of compound a-5 was added to the mixture, and while cooling in an ice bath, a solution of 0.75 g of sodium borohydride in 22.5 g of ethanol was slowly added dropwise. The ice bath was then removed, and the mixture was allowed to warm slowly to room temperature (23 °C) while stirring. After stirring at room temperature (23 °C) for 12 hours, aqueous hydrochloric acid was added dropwise until the solution became acidic. 20 mL of AC-2000 was added to the solution containing the aqueous hydrochloric acid, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated using an evaporator and purified using a column to obtain 24.6 g of compound a-6.

[0181] CF3CF2CF2OCF2CF2OCF2CF2{(OCF2) m (OCF2CF2) n}OCF2CH2OH (a-6) m≒14, n≒13

[0182] <Synthesis of compound a-7> In a 100 mL two-necked recovery flask, 20.0 g of compound a-6, 0.21 g of tetrabutylammonium hydrogen sulfate, 1.76 g of allyl bromide, and 2.6 g of 30% aqueous sodium hydroxide solution were added and stirred at 60 °C for 8 hours. After the reaction was completed, 20 g of AC-2000 was added, washed once with dilute aqueous hydrochloric acid, and the organic phase was recovered. The recovered organic phase was passed through a silica gel column, and the recovered solution was concentrated using an evaporator to obtain 19.8 g of compound a-7.

[0183] CF3CF2CF2OCF2CF2OCF2CF2{(OCF2) m (OCF2CF2) n}OCF2CH2-OCH2CH=CH2...(a-7) m≒14, n≒13

[0184] <Synthesis of compound a-8> A 30 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 6 g of compound a-7, 6 g of 1,3-bis(trifluoromethyl)benzene, 0.018 g of triacetoxymethylsilane, and 0.41 g of trichlorosilane, and the mixture was stirred at 5°C for 30 minutes under a nitrogen stream. Subsequently, a xylene solution (0.028 ml) containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated to 60°C and stirred at this temperature for 5 hours. The volatiles were then distilled off, and the mixture was purified using a column to obtain 5.7 g of compound a-8.

[0185] CF3CF2CF2OCF2CF2OCF2CF2{(OCF2) m (OCF2CF2) n}OCF2CH2-OCH2CH2CH2SiCl3...(a-8) m≒14, n≒13

[0186] <Synthesis of compound a-9> 5 g of compound a-8 and 5 g of 1,3-bis(trifluoromethyl)benzene were placed in a 30 ml four-neck flask equipped with a reflux condenser, thermometer, and stirrer, and stirred at 5 ° C for 30 minutes under a nitrogen stream. Subsequently, a diethyl ether solution (6.91 ml) containing 0.9 mol / L allylmagnesium bromide was added, and the mixture was heated to room temperature (23 ° C) and stirred at this temperature for 10 hours. After that, the mixture was cooled to 5 ° C, and methanol (2 ml) was added. The mixture was then heated to room temperature (23 ° C) and filtered to remove insoluble matter. The volatiles were then distilled off, and the nonvolatiles were diluted with perfluorohexane and washed with methanol in a separatory funnel. Subsequently, the volatiles were distilled off to obtain 5 g of compound a-9.

[0187] CF3CF2CF2OCF2CF2OCF2CF2{(OCF2) m (OCF2CF2) n}OCF2CH2-OCH2CH2CH2Si(CH2CH=CH2)3...(a-9) m≒14, n≒13

[0188] <Synthesis of Compound X1-1> 5.0 g of compound a-9, 0.03 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% by mass), 0.36 g of trimethoxysilane, 0.01 g of aniline, and 2.0 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at room temperature (23° C.) for 8 hours. The solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.5 μm to obtain 5.2 g of compound X1-1.

[0189] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3...(X1-1) Average number of m11: 13.9, average number of m12: 15.4

[0190] The average number of (OCF2) and (OCF2CF2) in the compound X1-1 is 19 The average number of (OCF2) and (OCF2CF2) of each fluorine ether compound described below was also determined in the same manner as for compound X1-1.

[0191] [Synthesis of fluorine-containing ether compound X1-2] <Synthesis of compound b-1> 5 g of ethylene glycol, 7.5 g of 48% KOH aqueous solution, 6 g of water, and tert-butyl alcohol were mixed in a 100 ml four-neck flask, and 5 g of perfluoropropyl vinyl ether was added dropwise from a dropping funnel. The mixture was then stirred at 40°C for 20 hours under a nitrogen atmosphere. After stirring, the mixture was washed once with dilute hydrochloric acid aqueous solution, and the organic layer was concentrated using an evaporator. After column purification, 22 g of compound b-1 was obtained.

[0192] CF3CF2CF2OCHFCF2OCH2CH2OH (b-1)

[0193] <Synthesis of compound b-2> A 100 ml four-neck flask was charged with 20 g of compound b-1, 10 g of triethylamine, and 200 g of AC-2000, to which 15 g of tosyl chloride was added. The mixture was mixed at 40°C for 8 hours, filtered, concentrated, and purified with a column to obtain 18 g of compound b-2.

[0194] CF3CF2CF2OCHFCF2OCH2CH2O-Ts...(b-2)

[0195] <Synthesis of compound b-4> A 100 ml four-neck flask was charged with 23 g of the following compound b-3, 23 g of 1,3-bis(trifluoromethyl)benzene, 2 g of cesium carbonate, and 3 g of b-2. The mixture was stirred at 70°C for 20 hours under a nitrogen atmosphere. The mixture was washed with a dilute hydrochloric acid solution, washed three times with water, concentrated, and purified using a column to obtain 24 g of compound b-4.

[0196] HO-CH2CF2{(OCF2) m (OCF2CF2) n}-OCF2CH2-OH b-3 m≒14, n≒12

[0197] CF3CF2CF2OCHFCF2OCH2CH2O-CH2CF2{(OCF2) m (OCF2CF2) n}-OCF2CH2-OH (b-4) m≒14, n≒12

[0198] <Synthesis of Fluorine-Containing Ether Compound X1-2> Fluorine-containing ether compound X1-2 was synthesized in the same manner as in the synthesis of fluorine-containing ether compound X1-1, except that compound b-4 was used instead of compound a-2. The fluorine-containing ether compound X1-2 differs from the fluorine-containing ether compound X1-1 in the arrangement of (OCF2) and (OCF2CF2).

[0199] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X1-2) Average number of m11: 13.9, average number of m12: 15.4

[0200] [Synthesis of fluorinated ether compound X2-1] With reference to the synthesis of fluorine-containing ether compound X1-1, fluorine-containing ether compound X2-1 was obtained.

[0201] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X2-1) Average number of m11: 22.3, average number of m12: 10.6

[0202] [Synthesis of fluorinated ether compound X2-2] Fluorinated ether compound X2-2 was obtained in the same manner as in the synthesis of fluorinated ether compound X1-2, except that a compound obtained by using diethylene glycol instead of ethylene glycol in the synthesis of compound b-1 was used. The fluorine-containing ether compound X2-2 differs from the fluorine-containing ether compound X2-1 in the arrangement of (OCF2) and (OCF2CF2).

[0203] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X2-2) Average number of m11: 22.3, average number of m12: 10.6

[0204] [Synthesis of fluorinated ether compound X3-1] With reference to the synthesis of fluorine-containing ether compound X1-1, fluorine-containing ether compound X3-1 was obtained.

[0205] CF3CF2CF2-{(OCF2) m11(OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X3-1) Average number of m11: 25.9, average number of m12: 8.6

[0206] [Synthesis of fluorinated ether compound X3-2] Fluorinated ether compound X3-2 was obtained in the same manner as in the synthesis of fluorinated ether compound X1-2, except that a compound obtained by using diethylene glycol instead of ethylene glycol in the synthesis of compound b-1 was used. The fluorine-containing ether compound X3-2 differs from the fluorine-containing ether compound X3-1 in the arrangement of (OCF2) and (OCF2CF2).

[0207] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X3-2) Average number of m11: 25.9, average number of m12: 8.6

[0208] [Synthesis of fluorinated ether compound X4-1] With reference to the synthesis of fluorinated ether compound X1-1, fluorinated ether compound X4-1 was obtained.

[0209] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X4-1) Average number of m11: 28.5, average number of m12: 7.1

[0210] [Synthesis of fluorinated ether compound X4-2] Fluorinated ether compound X4-2 was obtained in the same manner as in the synthesis of fluorinated ether compound X1-2, except that a compound obtained by using diethylene glycol instead of ethylene glycol in the synthesis of compound b-1 was used. The fluorine-containing ether compound X4-2 differs from the fluorine-containing ether compound X4-1 in the arrangement of (OCF2) and (OCF2CF2).

[0211] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X4-2) Average number of m11: 28.5, average number of m12: 7.1

[0212] [Synthesis of fluorinated ether compound X5-1] With reference to the synthesis of fluorinated ether compound X1-1, fluorinated ether compound X5-1 was obtained.

[0213] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X5-1) Average number of m11: 31.6, average number of m12: 5.4

[0214] [Synthesis of fluorinated ether compound X5-2] With reference to the synthesis of the fluorinated ether compound X1-2, a fluorinated ether compound X5-2 was obtained. The fluorine-containing ether compound X5-2 differs from the fluorine-containing ether compound X5-1 in the arrangement of (OCF2) and (OCF2CF2).

[0215] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X5-2) Average number of m11: 31.6, average number of m12: 5.4

[0216] [Synthesis of fluorinated ether compound X6-1] With reference to the synthesis of fluorinated ether compound X1-1, fluorinated ether compound X6-1 was obtained.

[0217] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X6-1) Average number of m11: 33.6, average number of m12: 4.2

[0218] [Synthesis of fluorinated ether compound X6-2] With reference to the synthesis of the fluorinated ether compound X1-2, a fluorinated ether compound X6-2 was obtained. The fluorine-containing ether compound X6-2 differs from the fluorine-containing ether compound X6-1 in the arrangement of (OCF2) and (OCF2CF2).

[0219] CF3CF2CF2-{(OCF2) m11 (OCF2CF2) m12}-OCF2CH2-OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3(X6-2) Average number of m11: 33.6, average number of m12: 4.2

[0220] [Preparation of the mixture] Mixtures 1-1, 1-2, 2-1, 2-2, 3-1, 3-2, 4-1, 4-2, 5-1, 5-2, 6-1, and 6-2 were obtained by mixing the fluorinated ether compounds listed in Table 1. In preparing each mixture, the fluorinated ether compounds were mixed in such a ratio that the value of Y in formula (A-1) was the value shown in Table 1.

[0221] [Values ​​of X and Y in formula (A-1)] The obtained fluorine-containing ether compound or mixture was used to 19Based on the chart obtained by F-NMR measurement, the values ​​of X and Y in formula (A-1) were calculated. In addition, based on the values ​​of X and Y, the sufficiency of formula (A-1) and formula (A-2) was judged, and if the formula was satisfied, it was marked as "○", and if it was not satisfied, it was marked as "×". The results are shown in Table 1. 19 F-NMR measurements were carried out under the following measurement conditions. Measuring device: “JNM-ECZ 400” manufactured by JEOL Internal standard: 1,4-bistrifluoromethylbenzene

[0222] 19 A typical chart obtained by F-NMR measurement is shown in Figure 2. Figure 2 shows the results of the 400 MHz test using mixture 5-1. 19 This is a chart obtained by F-NMR measurement. As shown in Figure 2, peaks were observed at chemical shifts of -50.5 to -51.2 ppm, -52.0 to -52.8 ppm, -53.8 to -54.5 ppm, -87.0 to -88.5 ppm, and -88.8 to -90.2 ppm. The peak at chemical shift -63.5 ppm in Figure 2 corresponds to 1,4-bistrifluoromethylbenzene. Although not shown in the chart, peaks were observed in the above chemical shift range for other fluorine-containing ether compounds and mixtures.

[0223] [Example 1 to Example 18] A substrate (alkali-free glass (Eagle XG: product name, Corning, 50 mm x 50 mm, thickness 0.5 mm)) was placed in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 5 × 10 -3The atmosphere was evacuated to a pressure of 100 Pa or less. A deposition vessel containing each fluorinated ether compound or mixture of each example listed in Table 1 was heated to 300°C by resistance heating, positioned 1000 mm away from one main surface of the substrate, and the fluorinated ether compound or mixture was vacuum-deposited. Film formation was terminated when the thickness of the fluorinated ether compound or mixture on the substrate reached 10 nm. Thereafter, the substrate on which the fluorinated ether compound or mixture had been deposited was heated at 200°C for 30 minutes (post-treatment) to obtain a substrate (article) with a surface layer.

[0224] [Evaluation test] The substrates with surface layers of Examples 1 to 18 were subjected to the following evaluation tests.

[0225] <Abrasion resistance (steel wool)> For the surface layer, a reciprocating traverse tester (manufactured by KNT Corporation) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to measure the number of reciprocating strokes required to reduce the water contact angle to less than 100 degrees by rubbing steel wool Bonstar (#0000) at a pressure of 98.07 kPa and a speed of 320 cm / min. The greater the number of reciprocating strokes, the less the deterioration in performance due to friction, and the better the abrasion resistance. The evaluation criteria are as follows: A (Excellent): 7,001 or more round trips B (Good): Number of round trips is between 6,001 and 7,000 C (Acceptable): Number of round trips is between 4001 and 6000 D (Not acceptable): 4000 or fewer round trips (Method for measuring water contact angle) The contact angle of approximately 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated to determine the water contact angle. The 2θ method was used to calculate the contact angle.

[0226] <Lubricity> The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a load-varying friction and wear testing system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under conditions of contact area: 3cm x 3cm, load: 0.98N. The smaller the dynamic friction coefficient, the better the lubricity. The evaluation criteria are as follows: A (Excellent): Dynamic friction coefficient less than 0.02 B (Good): Dynamic friction coefficient is 0.02 or more and less than 0.03 C (Acceptable): Coefficient of dynamic friction is 0.03 or more and less than 0.04 D (unacceptable): Dynamic friction coefficient is 0.04 or more

[0227] [Table 1]

[0228] As shown in Table 1, it was confirmed that a surface layer excellent in lubricity and abrasion resistance could be formed by using a fluorine-containing ether compound satisfying formula (A-1) (Examples 2, 3, 5, 6, 8, 9, 11, 12, 14, 15, 17, and 18). Furthermore, as shown in Table 1, it was confirmed that by using a fluorine-containing ether compound satisfying formula (A-2), a surface layer having at least one of superior lubricity and superior abrasion resistance could be formed (Examples 3, 6, 9, 12, 15, and 18).

Claims

1. (OCF ２ ) and units represented by (OCF ２ CF ２ and a reactive silyl group, The fluorine-containing ether compound has a structure represented by the following formula (1-1): The mixture of fluorine-containing ether compounds １９ A surface treatment agent characterized by satisfying the following formula (A-1) in a chart obtained by F-NMR measurement: Y>-0.0062X ２ +0.1343X+0.1123 ・・・(A-1) In this case, X and Y are the values ​​of the fluorine-containing ether compound using 1,4-bistrifluoromethylbenzene as an internal standard. １９ It is a value determined based on a chart obtained by F-NMR measurement, Chemical shift: a1, the integral value of the peak observed at −50.5 to −51.2 ppm The integral value of the peak observed at chemical shifts of −52.0 to −52.8 ppm is a2, The integral value of the peak observed at chemical shifts of −53.8 to −54.5 ppm is a3, The integral value of the peak observed at chemical shifts of −87.0 to −88.5 ppm is designated as b1, When the integral value of the peak observed at chemical shifts of −88.8 to −90.2 ppm is defined as b2, X means {(a1+a2+a3) / 2} / {(b1+b2) / 4}, Y means (a3) / (a1+a2+a3). [R f1 -(OCF 2 ) m11 ・(OCF 2 CF 2 ) m12 -O-R 1 ] j -L 1 -(R 11 -T 11 ) x1...(1-1) however, R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and when there are a plurality of R f1 s, the plurality of R f1 s may be the same or different from each other; m11 is a positive number equal to or greater than 2, m12 is a positive number equal to or greater than 2, R 1 is an alkylene group or a fluoroalkylene group, and when there are a plurality of R 1 s, the plurality of R 1 s may be the same or different (however, when R 1 is a fluoroalkylene group, R 1 is a fluoroalkylene group other than —CF 2 — and —CF 2 CF 2 —); j is an integer of 1 or greater, L 1 is a single bond or a j+x monovalent organic group which may have N, O, S or Si and which may have a branch point, and atoms bonding to R 1 and R 11 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having an oxo group (═O); R 11 is an alkylene group in which the atom bonded to L 1 may be an ethereal oxygen atom or which may have an ethereal oxygen atom between carbon atoms; T 11 is —SiR a11 z11 R a12 3-z11 , R a11 is a hydroxyl group or a hydrolyzable group, and when there are multiple R a11 s, the multiple R a11 s may be the same or different, R a12 is a non-hydrolyzable group, and when there are multiple R a12 s, the multiple R a12 s may be the same or different, and z11 is an integer of 1 to 3, x1 is an integer of 1 or more.

2. 2. The surface treatment agent according to claim 1, wherein X in formula (A-1) is 2 to 8.

3. of the fluorine-containing ether compound １９ 3. The surface treatment agent according to claim 1, wherein the following formula (A-2) is satisfied in a chart obtained by F-NMR measurement: Y>-0.0056X ２ +0.1231X+0.2119 ・・・(A-2) However, X and Y in formula (A-2) are the same as X and Y in formula (A-1).

4. A coating liquid comprising the surface treatment agent according to any one of claims 1 to 3 and a liquid medium.

5. An article, comprising a substrate and a surface layer formed from the surface treatment agent according to any one of claims 1 to 3 or the coating liquid according to claim 4.

6. The article according to claim 5 , wherein the article is a touch panel, and the surface layer is provided on a surface of a member that constitutes a surface of the touch panel that is touched with a finger.

7. A method for producing an article, comprising forming a surface layer on a substrate by a dry coating method or a wet coating method using the surface treatment agent according to any one of claims 1 to 3 or the coating liquid according to claim 4.

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