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

Abstract

To provide: a surface treatment agent which enables formation of a surface layer excellent in lubricity; a coating liquid; an article; and an article manufacturing method.SOLUTION: A surface treatment agent comprises a fluorine-containing ether compound having a fluoropolyether chain(s) and a reactive group(s), and satisfies the following requirement 1. Requirement 1: in a mass spectrum showing a relationship between mass / charge ratios of product ions and area intensities, the mass spectrum being acquired from product ions using a second mass spectrometer, IB / IA, which is a ratio of IB, a total of area intensities of peaks corresponding, respectively, to product ions having mass / charge ratios 66 u, 166 u, 182 u and 282 u, to IA, a total of area intensities of peaks corresponding, respectively, to product ions having mass charge ratios of 116 u and 232 u, is 0.025 or more, where the product ions are generated by generating negative secondary ions by irradiating a surface layer, formed on a base material using the surface treatment agent, with pulsed primary ions, separating the generated negative secondary ions on the basis of a mass / charge ratio using a first time-of-flight mass spectrometer, selecting the negative secondary ions having a mass charge ratio of 348 u as precursor ions from the separated negative secondary ions using an ion selection device, and introducing the selected precursor ions into a collision cell and cleaving the precursor ions by high energy collision-induced dissociation.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 producing an article. [Background technology]

[0002] In order to impart water repellency, oil repellency, stain resistance, and the like 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 the surface layer is applied to a member that constitutes a surface that is touched by fingers, the surface layer is required to have excellent lubricity (smoothness when touched with fingers). 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 the lubricity 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 with excellent lubricity. [Means for solving the problem]

[0006] As a result of intensive investigations into the above-mentioned problems, the inventors have found that when a surface layer formed on a substrate using a surface treatment agent satisfies specific requirements regarding the ratio of peak area intensities of product ions obtained by analyzing the surface layer using a tandem mass spectrometer capable of time-of-flight mass spectrometry, the surface treatment agent is capable of forming a surface layer with excellent lubricity, and have arrived at the present invention.

[0007] That is, the inventors discovered that the above problems can be solved by the following configuration. [1] A surface treatment agent comprising a fluorinated ether compound having a fluoropolyether chain and a reactive group, and satisfying Requirement 1 described below. [2] Ratio I, described below B / I A The surface treatment agent according to [1], wherein [3] The surface treatment agent according to [1] or [2], wherein the reactive group is a reactive silyl group. [4] The fluoropolyether chain is (OCF 2 ) and (OC 2 F 4 ) and (OC 3 F 6 The surface treatment agent according to any one of [1] to [3], which contains a unit represented by the following formula: [5] A coating liquid comprising the surface treatment agent according to any one of [1] to [4] and a liquid medium. [6] An article having a surface layer formed on a substrate using the surface treatment agent according to any one of [1] to [4] or the coating liquid according to [5]. [7] An article having a substrate and a surface layer containing a fluoropolyether chain, and satisfying requirement 2 described below. [8] Ratio I, described below B / I A The article according to [7], wherein the n-th order number is 0.025 to 0.112. [9] The fluoropolyether chain is (OCF 2 ) and (OC 2 F 4) and (OC 3 F 6 ) and a unit represented by the formula: [7] or [8].

[10] The article according to any one of [6] to [9], wherein the article is a touch panel and has the surface layer on a surface of a member constituting a surface of the touch panel that is touched with a finger.

[11] 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 [1] to [4] or the coating liquid according to [5]. Effect 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 with excellent lubricity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, the group represented by formula (g1) may be referred to as group (g1). Also, the compound represented by formula (A1) may be referred to as compound (A1). Compounds represented by other formulas may be similarly described. The term "fluoroalkyl group" refers to a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups. The term "perfluoroalkyl group" refers to a group in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms. The term "partial fluoroalkyl group" refers to an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms. In other words, the term "fluoroalkyl group" refers to an alkyl group that has one or more fluorine atoms. The term "reactive silyl group" is a general term for a hydrolyzable silyl group and a silanol group (Si-OH), and the term "hydrolyzable silyl group" refers to a group that can form a silanol group by hydrolysis. 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 combinations thereof. "Surface layer" means a layer formed on a substrate. The "molecular weight" of the fluoropolyether chain and compound is 1 H-NMR and 19 It is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal groups using F-NMR. The symbol "~" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0010] [Surface treatment agent] The surface treatment agent of the present invention (hereinafter also referred to as "the present treatment agent") contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group, and satisfies the following requirement 1.

[0011] Requirement 1: generating negative secondary ions by irradiating a surface layer formed on a substrate using a surface treatment agent with pulsed primary ions; separating the generated negative secondary ions based on their mass-to-charge ratio using a first time-of-flight secondary ion mass spectrometer; From the separated negative secondary ions, a negative secondary ion having a mass-to-charge ratio of 348 u was selected as a precursor ion using an ion selection device; introducing the selected precursor ions into a collision cell and fragmenting them by high-energy collision-induced dissociation to generate product ions; A mass spectrum showing a relationship between the mass-to-charge ratio and the area intensity of the product ions, which is obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities of the peaks corresponding to the product ions with mass-to-charge ratios of 116 u and 232 u, I AThe sum of the area intensities of the peaks corresponding to the product ions with mass-to-charge ratios of 66u, 166u, 182u, and 282u, I B Ratio I B / I A is greater than or equal to 0.025.

[0012] According to the present treatment agent that satisfies the above requirement 1, a surface layer with excellent lubricity can be formed. The present treatment agent is also suitable as a surface treatment agent for forming a surface layer on a substrate that imparts water and oil repellency, abrasion resistance, and fingerprint stain removability. The evaluation method for Requirement 1 is explained in detail below.

[0013] <Requirement 1> Requirement 1 is determined based on the results of a surface analysis performed by forming a surface layer on a substrate using a surface treatment agent and analyzing the surface layer using a mass spectrometer described below. Examples of the method for forming a surface layer on a substrate using a surface treatment agent include a method for forming the surface treatment agent by a dry coating method, and a method for forming a coating liquid containing the surface treatment agent and a liquid medium by a wet coating method. Examples of the method for forming a surface layer on a substrate include the methods described in [Production method of an article] below. Examples of the substrate include the substrates described in [Article] below.

[0014] To analyze the surface layer, a tandem mass spectrometer is used that includes a primary ion source, a first time-of-flight mass spectrometer for detecting secondary ions (hereinafter also referred to as the "first mass spectrometer"), an ion selection device, a collision cell, and a second mass spectrometer for detecting product ions. The primary ion source irradiates the surface layer with pulsed primary ions. More specifically, the ion source irradiates Bi as the primary ions. 3 ++ The surface layer is irradiated with light, which generates negative secondary ions derived from the compound that constitutes the surface layer. The first mass spectrometer includes, for example, a separation unit that spatially separates the negative secondary ions based on their mass-to-charge ratios, and a detection unit that detects the separated negative secondary ions. The separation unit of the first mass spectrometer spatially separates the negative secondary ions generated from the surface layer and taken into the separation unit based on their mass-to-charge ratios.

[0015] The ion selection device selects negative secondary ions with a mass-to-charge ratio of 348 u as precursor ions from the negative secondary ions separated by the first mass spectrometer, and guides the selected ions to the collision cell. The ion selection device is disposed, for example, between a separation unit and a detection unit of the first mass spectrometer, and includes a plurality of electrodes. When a voltage is applied between the electrodes at the timing when the precursor ions enter the ion selection device, the traveling direction of the precursor ions attempting to pass between the electrodes is changed to a direction toward the collision cell. On the other hand, when no voltage is applied between the electrodes, the negative secondary ions that have entered the ion selection device pass between the electrodes without changing their traveling direction, and reach the detection unit of the first mass spectrometer.

[0016] The collision cell includes, for example, a chamber and a collision gas contained in the chamber. When precursor ions enter the collision cell, they collide with the collision gas in the chamber, and high-energy collision-induced organic dissociation (CID) occurs, in which product ions are generated by fragmenting the precursor ions. More specifically, Ar is selected as the collision gas.

[0017] The second mass spectrometer detects the product ions generated in the collision cell, and a mass spectrum showing the relationship between the mass-to-charge ratio of the product ions and the amount of detection is obtained from the detection results. By determining the peak area intensity of each product ion in the obtained mass spectrum, mass information on the partial structure of the negative secondary ion with a mass-to-charge ratio of 348 u among the negative secondary ions derived from the components constituting the surface layer is obtained. Examples of the second mass spectrometer include a time-of-flight mass spectrometer, a quadrupole mass spectrometer, and an ion trap mass spectrometer. Here, a time-of-flight mass spectrometer is selected. Further specific examples of the surface layer analyzing apparatus and method are described in JP-T-2015-514300.

[0018] To confirm whether Requirement 1 is satisfied, the peak area intensities of the product ions having mass-to-charge ratios of 66 u, 116 u, 166 u, 182 u, 232 u, and 282 u are obtained from the mass spectrum obtained by the second mass spectrometer. Next, the sum I of the peak area intensities corresponding to the product ions having mass-to-charge ratios of 116 u and 232 u is calculated. A (Hereinafter referred to as “total area intensity I A "), and the sum of the peak area intensities I corresponding to the product ions with mass-to-charge ratios of 66u, 166u, 182u, and 282u B (Hereinafter referred to as “total area intensity I B " is also called ". ) and calculate the ratio I B / I A Request. In addition, the total area intensity I A and I B When calculating the total area intensity I A is 100,000 counts or more, or the total area intensity I B The mass spectrum obtained by the above analysis method is continuously accumulated until the count reaches 1000 or more. As a result of the above calculation, ratio I B / I A If the ratio is 0.025 or more, the surface treatment agent satisfies requirement 1 and the ratio I B / I A If it is less than 0.025, the surface treatment agent does not satisfy requirement 1.

[0019] Here, the precursor ion has a mass-to-charge ratio of 348 u, the product ion has a mass-to-charge ratio of either 116 u or 232 u (hereinafter also referred to as “product ion A”), the product ion has a mass-to-charge ratio of either 66 u, 166 u, 182 u, or 282 u (hereinafter also referred to as “product ion B”), and the product ion having a mass-to-charge ratio of either 116 u, 166 u, 182 u, or 282 u (hereinafter also referred to as “product ion B”) is a product ion having a mass-to-charge ratio of 116 u or 232 u. B / I A The relationship between these two will be explained. The precursor ion with a mass-to-charge ratio of 348 u is derived from the fluoropolyether chain that constitutes part of the surface treatment agent and has the formula "C 6 F 12 O 3 - This precursor ion can have a structure represented by the following structural formulas (1) to (4), and thus, by fragmentation in the collision cell, the ether bond of the precursor ion is broken, resulting in the generation of a total of six product ions with mass-to-charge ratios of at least 66 u, 116 u, 166 u, 182 u, 232 u, and 282 u.

[0020] [ka]

[0021] Among the above structural parts, (C 2 F 4 In the structural portion (1) consisting of only (CF O) units, product ions A with mass-to-charge ratios of 116 u or 232 u are generated. On the other hand, in the structural portions (2) to (4), 2 O) units, (C 2 F 4 O) units, and (C 3 F 6 O) unit, product ions B having mass-to-charge ratios of 66 u, 166 u, 182 u, or 282 u are also generated in addition to product ions A having mass-to-charge ratios of 116 u or 232 u. Therefore, the total area intensity I corresponding to the product ion A obtained by fragmenting the precursor ion with a mass-to-charge ratio of 348 u is A Total area intensity I of product ion B B Ratio I B / I A It can be said that this is a parameter that indicates the continuity of the same unit. That is, the ratio I obtained by the above method B / I A It means that the higher the value, the lower the continuity of the same units in the fluoropolyether chain contained in the surface layer.

[0022] Above ratio I B / I A Although the details of why a treatment agent having a lubricity of 0.025 or more can form a surface layer with excellent lubricity are not clear, it is presumed to be due to the following reasons. When a surface layer is formed using the present treatment agent that contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group and satisfies requirement 1, the continuity of the fluoroalkylene unit having 1 or 2 carbon atoms in the fluoropolyether chain contained in the surface layer tends to decrease, and the packing property of the fluoropolyether chain in the surface layer tends to decrease. As a result, it is presumed that the degree of freedom of the fluoropolyether chain is improved, and the lubricity of the surface layer is increased.

[0023] The above ratio I B / I A is preferably 0.040 or more, more preferably 0.050 or more, and even more preferably 0.060 or more. B / I A The upper limit of is 0.224 or less, preferably 0.168 or less, and more preferably 0.112 or less.

[0024] ratio I B / I A For example, in the preparation of a fluorine-containing ether compound containing a fluoropolyether chain described later, (OC 3 F 6 This can be adjusted by controlling the molecular weight of the perfluoropolyether compound (PFPE) reacted during the introduction reaction of the skeleton corresponding to the ) structure.

[0025] <Fluorine-containing ether compounds> The fluorine-containing ether compound has a fluoropolyether chain and a reactive group.

[0026] Since the fluorine-containing ether compound contained in the present treatment agent has a fluoropolyether chain, the surface layer obtained by using the present treatment agent has excellent water and oil repellency and fingerprint stain removal properties. In addition, the fluorine-containing ether compound has a reactive group, which is strongly chemically bonded to the substrate, and therefore the resulting surface layer has excellent durability, such as abrasion resistance.

[0027] The fluoropolyether chain is a group having two or more oxyfluoroalkylene units. The fluoropolyether chain may have a hydrogen atom. From the viewpoint of superior abrasion resistance and fingerprint stain removability of the surface layer, the ratio of fluorine atoms in the fluoropolyether chain represented by the following formula (I) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, that is, a perfluoropolyether chain. If the fluorine atoms are 60% or more, the amount of fluorine in the fluoropolyether chain increases, and lubricity and fingerprint removability are further improved. Formula (I): Percentage of fluorine atoms (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} x 100

[0028] The molecular weight of each fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000, from the viewpoint of achieving both fingerprint stain removability and lubricity of the surface layer. If the molecular weight of the fluoropolyether chain is 2,000 or more, the flexibility of the fluoropolyether chain is improved, and the amount of fluorine in the molecule is increased, so that the lubricity and fingerprint removability are further improved. On the other hand, if the molecular weight of the fluoropolyether chain is 20,000 or less, the abrasion resistance of the surface layer is more excellent.

[0029] The fluoropolyether chain preferably has the structure (f1). (OR f ) y (f1)

[0030] R f is a fluoroalkylene group having 1 to 6 carbon atoms, f may be the same or different from each other. The value of y may be an integer of 2 or more, and is preferably 2-200.

[0031] (ORf ) y preferably has a structure represented by the following formula (f2). -[(OG f1 ) m1 (O.G. f2 ) m2 (O.G. f3 ) m3 (O.G. f4 ) m4 (O.G. f5 ) m5 (O.G. f6 ) m6 ]- ···(f2) however, G f1 is a fluoroalkylene group having one carbon atom, G f2 is a fluoroalkylene group having 2 carbon atoms, G f3 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; m1+m2+m3+m4+m5+m6 is preferably an integer of 2 to 200. In addition, in formula (f2), (OG f1 )~(OG f6 The order of bonds in the formula (f2) is arbitrary. f1 )~(OG f6 ) and does not represent the arrangement. For example, (OG f5 ) m5 (O.G. f5 ) is m5, and (OG f5 ) m5 It does not represent the block arrangement structure of (OG f1 )~(OG f6 The order of the units does not represent the order of bonding of the units. The fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or a fluoroalkylene group having a branched or cyclic structure.

[0032] G f1 A specific example of this is -CF 2 -, -CHF-. G f2 A specific example of this is -CF 2 CF 2 -,-CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, -CH 2 CHF-, etc. G f3 A specific example of this is -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -,-CHFCF 2 CF 2 -,-CHFCHFCF 2 -, -CHFCHFCHF-, -CHFCH 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CH 2 CHFCF 2 -, -CH 2 CH 2 CF 2 -, -CH 2 CF 2 CHF-, -CH 2 CHFCHF-, -CH 2 CH 2 CHF-, -CF(CF 3 )-CF 2 -, -CF(CHF 2 )-CF 2 -, -CF(CH 2 F)-CF 2 -, -CF(CH 3 )-CF 2 -, -CF(CF3 )-CHF-, -CF(CHF 2 )-CHF-, -CF(CH 2 F)-CHF-, -CF(CH 3 )-CHF-, -CF(CF 3 )-CH 2 -, -CF(CHF 2 )-CH 2 -, -CF(CH 2 F)-CH 2 -, -CF(CH 3 )-CH 2 -, -CH(CF 3 )-CF 2 -, -CH(CHF 2 )-CF 2 -, -CH(CH 2 F)-CF 2 -, -CH(CH 3 )-CF 2 -, -CH(CF 3 )-CHF-, -CH(CHF 2 )-CHF-, -CH(CH 2 F)-CHF-, -CH(CH 3 )-CHF-, -CH(CF 3 )-CH 2 -, -CH(CHF 2 )-CH 2 -, -CH(CH 2 F)-CH 2 - etc. can be mentioned. G f4 As specific examples of, -CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CHFCHFCF 2 CF 2 -, -CH 2 CHFCF 2 CF 2 -, -CF2 CH 2 CF 2 CF 2 -,-CHFCH 2 CF 2 CF 2 -,-CH 2 CH 2 CF 2 CF 2 -,-CHFCF 2 CHFCF 2 -,-CH 2 CF 2 CHFCF 2 -,-CF 2 CHFCHFCF 2 -,-CHFCHFCHFCF 2 -,-CH 2 CHFCHFCF 2 -,-CF 2 CH 2 CHFCF 2 -,-CHFCH 2 CHFCF 2 -,-CH 2 CH 2 CHFCF 2 -,-CF 2 CH 2 CH 2 CF 2 -,-CHFCH 2 CH 2 CF 2 -,-CH 2 CH 2 CH 2 CF 2 -,-CHFCH 2 CH 2 CHF-,-CH 2 CH 2 CH 2 CHF-,-cycloC 4 F 6 - etc. can be mentioned. G f5 As specific examples of,-CF 2 CF 2 CF 2 CF 2 CF 2 -,-CHFCF 2 CF 2 CF 2 CF 2 -,-CH2 CHFCF 2 CF 2 CF 2 -、-CF 2 CHFCF 2 CF 2 CF 2 -、-CHFCHFCF 2 CF 2 CF 2 -、-CF 2 CH 2 CF 2 CF 2 CF 2 -、-CHFCH 2 CF 2 CF 2 CF 2 -、-CH 2 CH 2 CF 2 CF 2 CF 2 -、-CF 2 CF 2 CHFCF 2 CF 2 -、-CHFCF 2 CHFCF 2 CF 2 -、-CH 2 CF 2 CHFCF 2 CF 2 -、-CH 2 CF 2 CF 2 CF 2 CH 2 -、-cycloC 5 F 8 -According to this. G f6 of the singular and -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -、-CF 2 CF 2 CHFCHFCF 2 CF 2 -、-CHFCF 2 CF 2 CF 2 CF 2 CF 2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF 2 CF 2 CF 2 CF 2 CH 2 -, -CH 2 CF 2 CF 2 CF 2 CF 2 CH 2 -,-cycloC 6 F 10 --etc. Where -cycloC 4 F 6 - means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. 5 F 8 - means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. 6 F 10 "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0033] (OR f ) y In view of being more excellent in water and oil repellency, abrasion resistance, and fingerprint stain removability, it is preferable for the compound to have any of the structures represented by the following formulae (f3) to (f6), and in view of being more excellent in lubricity, the compound represented by the following formulae (f3) and (F4) is more preferable, and the compound represented by the following formula (f4) is even more preferable. (O.G. f1 ) m1 ·(OG f2 ) m2 (f3) (O.G. f1 ) m1 ·(OG f2 ) m2 ·(OG f3 ) m3 (f4) (O.G. f2 ) m2 ·(OG f4 )m4 (f5) (O.G. f3 ) m3 (f6) However, the symbols in formulas (f3) to (f6) are the same as those in formula (f2) above.

[0034] In formulas (f3) to (f5), (OG f1 ) and (OG f2 ), (O.G. f1 ) and (OG f2 ) and (OG f3 ), (O.G. f2 ) and (OG f4 The order of bonds in (OG f1 ) and (OG f2 ) may be arranged alternately, and (OG f1 ) and (OG f2 ) may be arranged in blocks or randomly. The same applies to formula (f6). In formula (f3), m1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (f4), m1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (f5), m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (f6), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

[0035] The fluoropolyether chain is (OCF 2 ) and (OC 2 F 4 ) and (OC 3 F 6 ) and a unit represented by the formula (I). The fluoropolyether chain preferably contains a structure represented by the following formula (f7). (OCF 2) m21 ·(OC 2 F 4 ) m22 ·(OC 3 F 6 ) m23 (f7) In formula (f7), m21 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m22 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m23 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

[0036] In formula (f6), (OCF 2 ), (O.C. 2 F 4 ) and (OC 3 F 6 ) can be bonded in any order. For example, in formula (f6), 2 ), (O.C. 2 F 4 ) and (OC 3 F 6 ) may be randomly arranged, and (OCF 2 ), (O.C. 2 F 4 ) and (OC 3 F 6 ) may be arranged in blocks, and (OCF 2 ) and (OC 2 F 4 ) are arranged alternately, and (OC 3 F 6 ) blocks may be placed.

[0037] (OC 2 F 4 A specific example of the unit represented by (OCF 2 CF 2 ), (OCF(CF 3 )) and (OCF 2 CF 2 ) is preferred. (OC 3 F 6 A specific example of the unit represented by (OCF 2 CF 2 CF 2 ), (OCF(CF 3)CF 2 ) and (OCF 2 CF 2 CF 2 ) is preferred. The fluoropolyether chain is (OCF 2 ), (O.C. 2 F 4 ) and (OC 3 F 6 ) (hereinafter also referred to as "other oxyfluoroalkylene units"). Specific examples of other oxyfluoroalkylene units include (OG f1 ) m1 (However, G f1 Ga-CF 2 -Unless otherwise specified. f2 ) m2 (However, G f2 Ga-CF 2 CF 2 -Unless otherwise specified. f3 ) m3 (However, G f3 Ga-CF 2 CF 2 CF 2 -Unless otherwise specified. f4 ) m4 , (O.G. f5 ) m5 , (O.G. f6 ) m6 Examples include:

[0038] The fluoropolyether chain (OR f ) y The ratio of fluorine atoms in the composition [{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, from the viewpoint of excellent water and oil repellency and fingerprint removability. The upper limit of the ratio is usually 100%. In addition, the fluoropolyether chain (OR f ) yFrom the viewpoint of abrasion resistance, the molecular weight of the 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.

[0039] The reactive group of the fluorine-containing ether compound is a general term for a group having a functional group that chemically bonds with the material constituting the base material. Examples of the reactive group include a reactive silyl group, an ethylenically unsaturated group (e.g., a (meth)acryloyl group, an allyl group, a styryl group, etc.), a cyclic ether group (e.g., an epoxy group, an oxetanyl group, etc.), an isocyanate group, a carboxy group, a hydroxyl group, a mercapto group, an amino group, etc. From the viewpoint of adhesion to a substrate, a reactive silyl group or a polymerizable unsaturated group is preferred, and a reactive silyl group is more preferred.

[0040] 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, R a1 If there are multiple, there are multiple R a1 may be the same or different, R a2 is a non-hydrolyzable group, and R a2 If there are multiple, there are multiple R a2 may be the same or different, z1 is an integer from 1 to 3.

[0041] R a1is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. The hydrolyzable group is a group that becomes a hydroxyl group (i.e., a silanol group) by hydrolysis. 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 undercoat)-OH) on the surface of the substrate (or undercoat) to form a chemical bond (substrate (or undercoat)-O-Si). The fluorine-containing ether compound has one or more groups (g1) and thus has excellent abrasion resistance after the formation of the surface layer.

[0042] 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.

[0043] R a1 Of 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, from the viewpoint of excellent storage stability of the fluorine-containing ether compound and suppression of outgassing during the reaction, more preferably an ethoxy group from the viewpoint of long-term storage stability, and more preferably a methoxy group from the viewpoint of shortening the hydrolysis reaction time. As the halogen atom, a chlorine atom is preferable.

[0044] R a2 The non-hydrolyzable group may be 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. From the viewpoint of ease of production, an alkyl group is preferred. From the viewpoint 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.

[0045] z1 may be an integer of 1 to 3, and is preferably 2 or 3, and more preferably 3, from the viewpoint of adhesion to the substrate (or undercoat layer). Specific examples of the group (g1) include -Si(OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si(OCH 2 CH 3 ) 3 , -SiCl 3 , -Si(OCOCH 3 ) 3 , -Si(NCO) 3 From the viewpoint of ease of handling in manufacturing, -Si(OCH 3 ) 3 is preferred. When there are multiple groups (g1) in one molecule, the multiple groups (g1) may be the same or different.

[0046] In the fluorine-containing ether compound, the fluoropolyether chain and the reactive group are bonded directly or through a linking group. In the fluorine-containing ether compound, the fluoropolyether chain and the group (g1) are preferably bonded directly or through a linking group. The linking group may be an organic group having a valence of 2 or more. The number of fluoropolyether chains in one molecule of the fluorinated ether compound may be 1 or 2 or more. From the viewpoint of ease of synthesis, etc., 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 reactive groups in one molecule of the fluorinated ether compound may be 1 or more. When the reactive group is group (g1), the number of groups (g1) is preferably 1 to 32, more preferably 1 to 18, and even more preferably 2 to 12, from the viewpoint of achieving both abrasion resistance and water / oil repellency. 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 reactive groups, the respective reactive groups may be the same or different.

[0047] The fluorine-containing ether compound may be any compound as long as it satisfies the above-mentioned requirements. From the viewpoints of ease of synthesis and ease of handling of the compound, among others, it is preferable to use a compound represented by the following formula (A1), (A2) or (A3). [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T 11 ) x1 (A1) (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 (A2) Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (A3) however, R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 If there are multiple, there are multiple R f1 may be the same or different, R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and R f11 If there are multiple, there are multiple R f11 may be the same or different, R 1 is an alkylene group or a fluoroalkylene group, R 1 If there are multiple, there are multiple R 1 may be the same or different, L1 is a single bond or a j+x1-valent organic group which may have N, O, S, or Si and may have a branch point; R 1 and R 11 each atom bonded to is 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, R a11 If there are multiple, there are multiple R a11 may be the same or different, R a12 is a non-hydrolyzable group, and R a12 If there are multiple, there are multiple R a12 may be the same or different, j is an integer equal to or greater than 1, z11 is an integer from 1 to 3; x1 is an integer equal to or greater than 1, y1 is an integer of 1 or more, and when there are multiple y1, the multiple y1 may be the same or different. R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and R f12 If there are multiple, there are multiple R f12 may be the same or different, R 2 and R 3 each independently represents an alkylene group or a fluoroalkylene group, L 2 is a single bond or a 1+x2-valent organic group which may have N, O, S, or Si and may have a branch point; R 2 and R 21each atom bonded to is 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+x3-valent organic group which may have N, O, S, or Si and may have a branch point; R 3 and R 31 each atom bonded to is 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 each independently represents -SiR a21 z21 R a22 3-z21 and R a21 is a hydroxyl group or a hydrolyzable group, R a21 If there are multiple, there are multiple R a21 may be the same or different, R a22 is a non-hydrolyzable group, and R a22 If there are multiple, there are multiple R a22 may be the same or different, z21 is an integer from 1 to 3; x2 and x3 each independently represent an integer of 1 or more; y2 is an integer equal to or greater than 1; Q 1 is a valent group having a branch point, R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and R f13 If there are multiple, there are multiple R f13 may be the same or different, R4 each independently represents an alkylene group or a fluoroalkylene group, L 4 is a single bond or a 1+x4-valent organic group which may have N, O, S, or Si and may have a branch point; R 4 and R 41 each atom bonded to is 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, R a41 If there are multiple, there are multiple R a41 may be the same or different, R a42 is a non-hydrolyzable group, and R a42 If there are multiple, there are multiple R a42 may be the same or different, z41 is an integer from 1 to 3, x41 is an integer equal to or greater than 1, y3 is an integer equal to or greater than 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 as appropriate for reference.

[0048] (Compound (A1)) The compound (A1) has a structure represented by the following formula (A1). [R f1 -(OR f11 ) y1 -OR 1 ] j -L 1 -(R 11 -T11 ) x1 (A1) Here, each symbol in the formula (A1) is as defined above.

[0049] 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.

[0050] (OR f11 ) y1 R f11 , y1 are R in the above formula (f1), f , y, and preferred embodiments are also the same.

[0051] R 1 is an alkylene group or a fluoroalkylene group. 1 The alkylene group and fluoroalkylene group in 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 a fluoroalkyl group.

[0052] j is the [R f1 -(OR f11 ) y1 -OR 1 ], which may be an integer of 1 or more, is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 4.

[0053] R 11 L 1 The atom bonded to may be an ethereal oxygen atom, or it is an alkylene group which 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 order that the compound (A1) is easily arranged densely 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 g2 may be the same or different, 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 a bond that bonds to

[0054] 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 (A1), 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 further preferably 0 to 1, from the viewpoint of durability as a surface layer, etc.

[0055] R 11 is more preferably a group represented by the following formula (g3) in that the surface layer has excellent water and oil repellency and fingerprint stain removability, and also has excellent 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).

[0056] R g3 The alkylene group in may be linear or may have a branched and / or cyclic structure. A linear alkylene group is preferred in that the compound (A1) is easily arranged densely when forming a surface layer.

[0057] T 11 Ha-SiR a11 z11 R a12 3-z11 and R a11 , R a12 , z11 are each R constituting the above group (g1). a1 , R a2 , z1, and preferred embodiments are also the same.

[0058] x1 is R in one molecule 11 -T 11 It is sufficient that the number is an integer of 1 or more, and is preferably 1 to 32, more preferably 1 to 18, and further preferably 2 to 12.

[0059] L 1 is a single bond or a j+x1-valent group which may have N, O, S, or Si and 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.

[0060] L 1 When is a single bond, R in formula (A1) 1 and R 11 is directly bonded, and compound (A1) is represented by the following formula (A1'). R f1 -(OR f11 ) y1 -OR 1 -R 11 -T 11 (A1') However, each symbol in formula (A1') is the same as in formula (A1).

[0061] 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 ").

[0062] N is the branch point P 1 If so, the branch point P 1 For example, *-N(-**) 2 or (*-) 2 It is represented as N-**, where * is R 1 side bond, and ** is R 11 It is the connecting part on the side. C is the branch point P 1 If so, the branch point P 1 For example, *-C(-**) 3 , (*-) 2 C(-**) 2 , (*-) 3 C-**, *-CR 29 (-**) 2 , or (*-) 2 CR 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 , (*-) 2 Si(-**) 2 , (*-) 3 Si-**, *-SiR29 (-**) 2 , or (*-) 2 SiR 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.

[0063] Branch point P 1 As the ring structure constituting the above, from the viewpoints of ease of production of the fluorine-containing ether compound and of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer, 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 condensed ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is more preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an etheric oxygen atom between the carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group or an oxo group (=O).

[0064] [ka]

[0065] Branch point P 1 Examples of the organopolysiloxane residue constituting the above formula include the following groups. 25 R 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.

[0066] [ka]

[0067] 2 or more valences of 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 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -,-OSi(R 26 ) 2 -, -Si(CH 3 ) 2 -Ph-Si(CH 3 ) 2 - and at least one bond selected from the group consisting of divalent organopolysiloxane residues (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 alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the fluorinated ether compound.

[0068] Examples of the divalent organopolysiloxane residue include groups represented by the following formula: 27 R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 27 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0069] [ka]

[0070] Join B 1 As for the fluorine-containing ether compound, -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)-, and -NR 26In view of further improving the light resistance and chemical resistance of the surface layer, at least one bond selected from the group consisting of -C(O)NR 26 -, -N(R 26 )C(O)- or -C(O)- is more preferred.

[0071] Divalent L 1 As for R 1 and R 11 Each atom bonded to R is independently N, O, S, Si, or a carbon atom having an oxo group (=O). That is, R 1 and R 11 Each atom adjacent to 1 It is a constituent element of the divalent L 1 Specific examples of the bond include a single bond and 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 part on the side.

[0072] 3 or more valences of 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). That is, R 1 and R 11 Each atom adjacent to 1 Or branch point P 1 It is a constituent element of L with a valence of 3 or more. 1 A specific example of the 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 B1 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 part on the side.

[0073] Above R 28 Examples of the divalent organic group in the formula include hydrocarbon groups such as divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.), and the hydrocarbon groups 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 further preferably 1 to 4 carbon atoms.

[0074] The above L 1 As the group, a group represented by any one of the following formulae (L1) to (L7) is preferred from the viewpoint of ease of production of the fluorinated ether compound.

[0075] [ka]

[0076] (-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 (-Q24 -) 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)

[0077] However, in formulas (L1) to (L7), A 1 , A 2 Or A 3 The side is R of formula (A1). 1 and Q 22 , Q 23 , Q 24 , Q 25 Or Q 26 Side is R 11 Connect to. Here, A 1 is a single bond, -B 3 -, -B 3 -R 30 - or -B 3 -R 30 -B 2 -wherein R 30 is 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-, B 3 -C(O)NR e6 -, -C(O)-, or -NR e6 - and A 2 is a single bond or -B 3 -R 30 - and A 3 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 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 e2is 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 from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 3; d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3+d4 is an integer from 1 to 3; d1+d3 is an integer from 1 to 5, d2+d4 is an integer from 1 to 5, d5 is an integer from 1 to 3, d6 is an integer from 1 to 3, and d5+d6 is an integer from 2 to 4; d7 is 1 or 2, d8 is an integer equal to or greater than 1, d9 is an integer equal to or greater than 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 from 1 to 3. In addition, A 1 If there are multiple A's, 1 may be the same or different. A 2 , A 3 , Q 22 , Q 23 , Q 24 , Q 25 , R e1 , R e2 , R e3 The same applies to. Also, d1+d3, d5, d7, d8, and d10 are j, and d2+d4, d6, 3-d7, d9, d11, and 1+d12 are x1.

[0078] R 30From the viewpoints of ease of production of the fluorinated ether compound and of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. However, in the case where an alkylene group has a specific bond 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.

[0079] R e1 , R e2 or R e3 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the fluorinated ether compound. 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 compound 1. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of ease of production of the fluorinated ether compound and of further improving the abrasion resistance and fingerprint stain removability of the surface layer.

[0080] The above L 1 Other examples of the substituent include groups represented by any of the following formulae (L11) to (L17).

[0081] [ka] (-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 (-Q24 -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)

[0082] In the formulas (L11) to (L17), A 1 , A 2 Or A 3 The side is R of formula (A1). 1 and 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 in formula (L11) to formula (L17) may be the same or different. -Si(R 21 ) 3-k (-Q 3 -) k (G21) However, in formula (G21), the Si side is Q 22 , Q 23 , Q 24 , Q 25 Or Q 26 Connect 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 31represents 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 R 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, (OSi(R 22 ) 2 ) may be the same or different.

[0083] Q 3 From the viewpoints of ease of production of the fluorinated ether compound and of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. However, in the case where an alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 21 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the fluorinated ether compound. R 22 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the fluorinated ether compound. 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, from the viewpoint of excellent storage stability of the fluorinated ether compound. p11 is preferably 0 or 1.

[0084] Examples of the compound (A1) include the following, where R f [R f1 -(ORf11 ) y1 -OR 1 ].

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

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[0098] (Compound (A2)) The compound (A2) has a structure represented by the following formula (A2). (T 31 -R 31 ) x3 -L 3 -R 3 -(OR f12 ) y2 -OR 2 -L 2 -(R 21 -T 21 ) x2 (A2) Here, each symbol in formula (A2) is as defined above.

[0099] R f12 , and (OR f12 ) y2 is the above R f11 OR f11 ) y1 The same applies to the preferred embodiments. R 2 and R 3 are each independently the above R 1 The same applies to the preferred embodiments.

[0100] R 21 and R 31is the above R 11 The same applies to the preferred embodiment, except that "L 1 "Binds to" is R 21 In the case of "L 2 "Join to" and R 31 In the case of "L 3 "Binds to" shall be read as "T 11 "Bind to" is R 21 In the case of "T 21 "Join to" 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

[0101] 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.

[0102] x2 and x3 each independently have the same meaning as x1, and the preferred embodiments are also the same.

[0103] 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 (A2) is represented by the following formula (A2'). T 31 -R 31 -R 3 -(OR f12 ) y2 -OR2 -L 2 -R 21 -T 21 (A2') However, each symbol in formula (A2') is the same as in formula (A2).

[0104] L 2 Or L 3 When L is a trivalent or higher 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 ").

[0105] N is the branch point P 2 If so, the branch point P 2 For example, *-N(-**) 2 where * is R 2 or R 3 side bond, and ** is R 21 or R 31 It is the connecting part on the side. C is the branch point P 2 If so, the branch point P 2 For example, *-C(-**) 3 , or *-CR 29 (-**) 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 For example, *-Si(-**) 3 , or *-SiR 29 (-**) 2 where * is R 2 or R 3 side bond, and ** is R 21 or R 31 side bond, R29 is a monovalent group, examples of which include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0106] 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, L with 2 or more valences 2 Or L 3 Each independently represents the bond B 1 Bond B may be 1 The embodiments are as described above, and the preferred embodiments are also the same.

[0107] Divalent L 2 Or L 3 is R 2 and R 21 , or R 3 and R 31 Each atom bonded to R is 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 Each atom adjacent to 1 It is a constituent element of the divalent L 2 Or L 3 Specific examples of the bond include a single bond and 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 part on the side.

[0108] 3 or more valences of L 2 Or L 3 is R 2 and R 21 , or R 3 and R 31The 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). That is, R 2 and R 21 , or R 3 and R 31 Each atom adjacent to 1 Or branch point P 2 It is a constituent element of L with a valence of 3 or more. 2 Or L 3 A specific example of the 2 (For example, {*-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 x3, 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 part on the side. Above R 28 The embodiments are as described above, and the preferred embodiments are also the same.

[0109] The above L 2 Or L 3 As each of these, a group represented by any one of the following formulae (L21) to (L27) is preferred from the viewpoint of ease of production of the fluorinated ether compound.

[0110] [ka]

[0111] -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)

[0112] However, in formulas (L21) to (L27), A 1 , A 2 Or A 3 The side is formula R 2 or R 3 and Q 22 , Q 23 , Q 24 , Q 25 Or Q 26 Side is R 21 or R 31 Connect to. Here, A 1 , A 2 , A 3 , Q 11 , Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Re1 , R e2 R e3 , R e6 is the above L 1 The preferred embodiments are the same as those described above. Z 1 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 from 0 to 3, d4 is an integer from 0 to 3, and d2+d4 is an integer from 1 to 5; d6 is an integer between 1 and 3, d9 is an integer equal to or greater than 1, d11 is an integer between 1 and 3 d12 is an integer from 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, from the viewpoints of ease of production of the fluorinated ether compound and of further improving the abrasion resistance and fingerprint stain removability of the surface layer.

[0113] The above L 2 Or L 3 Other examples of the above include groups represented by any of the following formulae (L31) to (L37).

[0114] [ka]

[0115] -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) -A 2 -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)

[0116] In the formulas (L31) to (L37), A 1 , A 2 Or A 3 The side of the formula is R 2 or R 3 and 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.

[0117] Examples of the compound (A2) include the following: f -R 3 -(OR f12 ) y2 -OR 2 -It is.

[0118] [ka] TIFF2025038262000025.tif61150 JPEG2025038262000026.jpg2677 JPEG2025038262000027.jpg2984

[0119] [ka]

[0120] [ka]

[0121] (Compound (A3)) The compound (A3) has a structure represented by the following formula (A3). Q 1 [-(OR f13 ) y3 -OR 4 -L 4 -(R 41 -T 41 ) x4 ] r1 (A3) Here, each symbol in formula (A3) is as defined above.

[0122] R f13 , and (OR f13 ) y3 is the above R f11 OR f11 ) y1 The same applies to the preferred embodiments. 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 embodiment, except that "L 1 "Binding to" is "L 4 "Binds to" shall be read as "T 11 "Binding to 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 R a41 , 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, or a ring structure. 3 may be one or may have two or more.

[0128] N is the branch point P 3 If so, the branch point P 1 For example, N(-*) 3 , N.R. 29 (-*) 2 It is expressed as: C is the branch point P 3 If so, the branch point P 3 For example, C(-*) 4 , C.R. 29 (-*) 3 , C(R 29 ) 2 (-*) 2 etc. Si is the branch point P 3 If so, the branch point P 3 For example, Si(-*) 4 , SiR 29 (-*) 3 , Si(R 29 ) 2 (-*) 2However, * indicates OR. f13 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 41 and the like.

[0129] Branch point P 3 The ring structure constituting the 1 The substituents of the ring structure include, in addition to the above-mentioned substituents, a fluorine atom, a fluoroalkyl group, R 41 -T 41 Alternatively, the fluoropolyether chain may have no fluoropolyether chain.

[0130] Above Q 1 As the group, a group represented by any one of the following formulae (Q1) to (Q6) is preferred from the viewpoint of ease of production of the fluorinated ether compound.

[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 OR f13 ) and connect it. Here, 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 a 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 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 A 13 is a group having an r1-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 -C(O)NR between carbon atoms of an alkylene group or a fluoroalkylene group having two or more 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 41 or a fluoropolyether chain having no -Q 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, 1may be the same or different. A 12 , A 13 , R e11 , R e12 , R e13 The same applies to.

[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 the fluorinated ether compound and of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer. However, in the case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms 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 fluorinated ether compound.

[0138] Examples of the compound (A3) include the following: f3 is (OR f13 ) y3 -OR 4 It is.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] The treating agent may contain one type of fluorine-containing ether compound or two or more types of fluorine-containing ether compounds. This treatment agent is (OCF 2 ), (O.C. 2 F 4 ) and (OC 3 F 6 ), and one or more fluorine-containing ether compounds having a fluoropolyether chain containing (OCF 2 ) and (OC 2 F 4 ), and (OC 3 F 6 and one or more fluorine-containing ether compounds having a fluoropolyether chain not containing fluoropolyether.

[0144] The present treatment agent contains a fluorine-containing ether compound, and may further contain at least one of a fluorine-containing compound other than the fluorine-containing ether compound and the following impurities. Examples of the impurities include compounds that are unavoidable in the production of the fluorine-containing ether compound and other fluorine-containing compounds. The present treatment agent does not contain a liquid medium described later.

[0145] Examples of the other fluorine-containing compounds include fluorine-containing compounds produced as a by-product in the production process of 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 fluorine-containing ether compounds.

[0146] As the other fluorine-containing compound, a compound which is unlikely to deteriorate the properties of the fluorine-containing ether compound is preferred. In order to fully exhibit the properties of the fluorinated ether compound, the content of the other fluorinated compounds is preferably less than 50 mass %, more preferably less than 30 mass %, and even more preferably less than 10 mass %, of the total amount of the treatment agent.

[0147] Examples of the by-product fluorine-containing compound include unreacted fluorine-containing compounds during the synthesis of a fluorine-containing ether compound, etc. When the present 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.

[0148] Examples of known fluorine-containing compounds include those described in the following documents: Perfluoropolyether-modified aminosilanes described in JP-A-11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP 2000-144097 A; Perfluoropolyether-modified aminosilanes described in JP 2000-327772 A; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Publication No. 2008-534696; Fluorinated modified hydrogen-containing polymers as 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 JP 2012-72272 A; 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 JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A; Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, 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, OPTOOL (registered trademark) UD509, etc. manufactured by Daikin Industries, Ltd.

[0149] The content of the fluorine-containing ether compound is 100% by mass or less, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the present treatment agent. When the present treatment agent contains other fluorine-containing compounds, the content of the other fluorine-containing compounds relative to the total content of the fluorine-containing ether compound and the other fluorine-containing compounds in the present treatment agent is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. The total content of the fluorinated ether compound and the other fluorinated compounds in the present treatment agent is preferably 80 mass % or more, more preferably 85 mass % or more. When the content of the fluorine-containing ether compound and other fluorine-containing compounds is within the above range, the surface layer has excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity and appearance. The present treating agent is suitable as a surface treating agent for forming a surface layer that imparts water and oil repellency, abrasion resistance, and fingerprint stain removability to the surface of a substrate.

[0150] [Coating liquid] The coating liquid of the present invention (hereinafter also referred to as "the present coating liquid") contains the present treatment agent and a liquid medium. The present coating liquid may be in a liquid state, and may be a solution or a dispersion. The present coating liquid is only required to contain the present treatment agent, and may contain impurities such as by-products produced in the production process of the fluorinated ether compound. The concentration of the fluorine-containing ether compound or the present treatment agent in the present coating liquid is preferably from 0.001 to 40% by mass, more preferably from 0.01 to 20% by mass, and more preferably from 0.1 to 10% by mass.

[0151] 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 may contain both.

[0152] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. 6 F 13 H (ASAHIKLIN (registered trademark) AC-2000, manufactured by AGC), C6 F 13 C 2 H 5 (AGC Corporation, Asahiklin (registered trademark) AC-6000), C 2 F 5 CHFCHFCF 3 (Bertrel (registered trademark) XF, manufactured by Chemours) and the like. Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. 3 CH 2 OCF 2 CF 2 H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M, Novec (registered trademark) 7100), C 4 F 9 O.C. 2 H 5 (3M, Novec (registered trademark) 7200), C 2 F 5 CF(OCH 3 ) C 3 F 7 (Novec (registered trademark) 7300, manufactured by 3M Corporation) and the like. 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. As the non-fluorinated organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents. 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 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 fluorinated ether compound and other components or the total concentration of the treatment agent and other components in the coating liquid (hereinafter also referred to as "solid content concentration") is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, further preferably 0.01 to 10 mass%, particularly preferably 0.01 to 1 mass%. The solid content 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 present article") has a substrate and a surface layer disposed on the substrate. The surface layer is a layer formed from the present treatment agent or the present coating liquid, and contains the above-mentioned fluoropolyether chains.

[0156] In a preferred embodiment, the article satisfies the following requirement 2. generating negative secondary ions by irradiating a surface layer of an article with pulsed primary ions; separating the generated negative secondary ions based on their mass-to-charge ratio using a first time-of-flight secondary ion mass spectrometer; From the separated negative secondary ions, a negative secondary ion having a mass-to-charge ratio of 348 u was selected as a precursor ion using an ion selection device; introducing the selected precursor ions into a collision cell and fragmenting them by high-energy collision-induced dissociation to generate product ions; A mass spectrum showing a relationship between the mass-to-charge ratio and the area intensity of the product ions, which is obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities of the peaks corresponding to the product ions with mass-to-charge ratios of 116 u and 232 u, I A The sum of the area intensities of the peaks corresponding to the product ions with mass-to-charge ratios of 66u, 166u, 182u, and 282u, I B Ratio I B / I A is greater than or equal to 0.025.

[0157] The surface layer of the present article that satisfies the above requirement 2 has excellent lubricity. In addition, the surface layer of the article is provided with water and oil repellency, abrasion resistance, and fingerprint stain removability. Evaluation method for requirement 2 of goods, preferred ratio I B / I A range, ratio I in the surface layer B / I A The adjustment method etc. shall conform to requirement 1 above.

[0158] The material and shape of the substrate may be appropriately selected depending on the application of the present article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. In particular, substrates that require water and oil repellency include substrates for touch panels, substrates for displays, and substrates that constitute the housings of electronic devices. Substrates for touch panels and substrates for displays have translucency. "Translucency" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the substrate for touch panels is preferably glass or transparent resin.

[0159] The surface layer is formed from the present treatment agent which contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group, or from a coating liquid which contains the present treatment agent. The fluoropolyether chain contained in the surface layer, including preferred embodiments, is the same as the fluoropolyether chain contained in the fluorine-containing ether compound contained in the above surface treatment agent.

[0160] In the surface layer, the reactive group of the fluorine-containing ether compound reacts with and bonds to the reactive group on the surface of the substrate or undercoat layer, thereby obtaining a substrate having excellent adhesion to the substrate or undercoat layer. The fluorine-containing ether compound may also form a condensate or polymer with other compounds. When the reactive group of the fluorine-containing ether compound is a reactive silyl group, the surface layer includes a structure in which a silanol group (Si-OH) is formed by hydrolysis of the reactive silyl group, 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 undercoat layer 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 may contain a fluorine-containing compound having a reactive group in a state in which a part or all of the reactive groups of the fluorine-containing compound are reacted. On the other hand, the fluoropolyether chain structure of the fluorine-containing ether compound is usually maintained even after the surface layer is formed.

[0161] 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 by an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.

[0162] 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.

[0163] [Production method] The method for producing the present article is a method in which a surface layer is formed on a substrate by a dry coating method or a wet coating method using the present treatment agent or the present coating liquid.

[0164] This treatment agent can be used as it is in the dry coating method. This treatment agent is suitable for forming a surface layer with excellent adhesion by the dry coating method. Examples of the dry coating method include vacuum deposition, CVD, sputtering, etc. The vacuum deposition method is preferably used from the viewpoint of suppressing decomposition of the fluorine-containing ether compound and the simplicity of the device. For vacuum deposition, a pellet-like material in which a fluorine-containing ether compound is supported on a metal porous body made of a metal material such as iron or steel may be used. The pellet-like material in which a fluorine-containing ether compound is supported can be produced by impregnating a metal porous body with a solution of the present treatment agent, and then drying to remove the liquid medium. The present coating liquid can be used as the solution of the present treatment agent.

[0165] The coating liquid can be suitably used in wet coating methods, such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, the Langmuir-Blodgett method, and gravure coating.

[0166] In order to improve the abrasion resistance of the surface layer, the reaction between the fluorine-containing ether compound and the substrate (or undercoat layer) may be promoted as necessary. Examples of the operation for promoting the reaction include heating, humidification, and light irradiation. For example, the substrate on which the surface layer is formed can be heated in a humid atmosphere to promote reactions such as hydrolysis reaction of hydrolyzable groups, reaction between hydroxyl groups and silanol groups on the surface of the substrate, and condensation reaction of silanol groups to form siloxane bonds. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific examples of the method include a method of pouring a solvent onto the surface layer, a method of wiping off with a cloth soaked in the solvent, etc. EXAMPLES

[0167] The present invention will be described in detail below with reference to examples. Examples 2 to 4 are working examples, and Example 1 is a comparative example. However, the present invention is not limited to these examples. The blending amount of each component in the table below is based on mass.

[0168] [Preparation Example 1: Preparation of Surface Treatment Agent 1] According to the method described in Example 16 of WO 2017 / 038830, the following compound X1 was synthesized using "Fomblin D4000" manufactured by Solvay as a starting material, and a surface treatment agent 1 consisting of compound X1 was obtained. CF 3 CF 2 CF 2 -(OCF 2 CF 2 )(OCF 2 CF 2 ){(OCF 2 ) x1 (OCF 2 CF 2 ) x2 (OCF 2 CF 2 CF 2 ) x3}-OCF 2 C(O)NH-CH 2 -C[CH 2 CH 2 CH 2 -Si(OCH 3) 3 ] 3 (X1) 1 H-NMR and 19 As a result of measuring compound X1 by F-NMR, the molecular weight of compound X1 was found to be about 4700. 2 The average value of the number of units x1 of (OCF 2 CF 2 The average of the number of units x2 of (OCF 2 CF 2 CF 2 ) the average value for number of units x 3 was 1.0.

[0169] [Preparation Example 2: Preparation of Surface Treatment Agent 2] <Synthesis of compound a1> According to the method described in Journal of the American Chemical Society (2009), 131(49), 17980, the following compound a1 was obtained. CF 3 -SO 2 -O-CH 2 CH 2 CH 2 -O-SO 2 -CF 3 (a1)

[0170] <Synthesis of compound b1> A fluorine-containing ether compound (manufactured by Solvay, "Fomblin D2") was subjected to molecular weight fractionation by silica gel column chromatography to obtain the following compound b1 having a molecular weight of 1,500. HO-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -OH (b1) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b1, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0171] <Synthesis of compound b2> In a 200 mL eggplant flask, 20 g of the above compound b1, 8.3 g of cesium carbonate, and 20 g of SR Solvent (AGC Seimi Chemical) were placed and stirred under ice cooling. Then, 3.2 g of the above compound a1 was slowly added, and the mixture was stirred at 80°C for 8 hours. After the reaction was completed, the resulting mixture was washed with water, and the organic phase was collected and concentrated with an evaporator. The concentrated organic phase was purified by silica gel column chromatography to obtain 21 g of compound b2. HO-CH 2 CF 2 -{(OCF 2 O) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -OH (b2) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b2, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0172] <Synthesis of compound b3> In a 200 mL eggplant flask, 4.4 g of 20% KOH aqueous solution, 3.2 g of tert-butyl alcohol, 10 g of SR solvent, and 21 g of compound b2 were placed, and CF 3 CF 2 CF 2 -O-CF=CF 21.4 g of was added. The mixture was stirred at 40° C. for 20 hours under a nitrogen atmosphere. The resulting mixture was washed once with a dilute hydrochloric acid aqueous solution, the organic phase was recovered, and the recovered organic phase was concentrated using an evaporator, and the concentrated organic phase was purified by silica gel column chromatography to obtain 11 g of compound b3. CF 3 CF 2 CF 2 -O-CHF-CF 2 -O-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -OH (b3) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b3, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0173] <Synthesis of compound b4> In a 100 mL eggplant flask, 11 g of the above compound b3, 0.4 g of sodium fluoride powder, and C 6 F 13 After adding 11g of H (AGC, AC-2000), CF 3 CF 2 CF 2 OCF(CF 3 )COF (1.8 g) was further added. The mixture was stirred at 50°C for 24 hours under nitrogen atmosphere. After removing the sodium fluoride powder with a pressure filter, the excess CF 3 CF 2 CF 2 OCF(CF3 ) COF and AC-2000 were distilled off under reduced pressure. The resulting crude product was purified using a silica gel column, and the collected solution was concentrated using an evaporator to obtain 11.5 g of compound b4. CF 3 CF 2 CF 2 -O-CHF-CF 2 -O-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -OC(O)-CF(CF 3 )OCF 2 CF 2 CF 3 (b4) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b4, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0174] <Synthesis of compound b5> An autoclave (made of nickel, internal volume 0.5 L) was prepared, and a cooler maintained at 20°C, a NaF pellet packed bed, and a cooler maintained at 0°C were installed in series in this order at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the coagulated liquid from the cooler maintained at 0°C to the autoclave. Autoclave ClCF 2 CFClCF 2 OCF 2 CF 2Cl (hereinafter, referred to as "CFE-419"), 400 g, was added 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 in at 25°C and a flow rate of 2.0 L / hour for 1 hour. Next, while blowing in 20% fluorine gas at the same flow rate, a solution in which 11.5 g of the above compound b4 was dissolved in 104 g of CFE-419 was injected into the autoclave over 2 hours. Into the autoclave, 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was injected while heating from 25°C to 40°C, and the benzene solution injection port of the autoclave was closed. After stirring for 15 minutes, 4 mL of the benzene solution was again injected while maintaining the temperature at 40°C, and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.17 g. Further, stirring was continued for 1 hour while blowing in 20% fluorine gas at a constant flow rate. Then, nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator to obtain 11.6 g of compound b5. CF 3 CF 2 CF 2 -O-CF 2 CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CF 2 -O-CF 2 CF 2 CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CF 2 -OC(O)-CF(CF 3 )OCF 2 CF 2 CF 3 (b5) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b5, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0175] <Synthesis of compound b6> In a 100 mL eggplant flask, 11.6 g of the above compound b5 and 11 g of dichloropentafluoropropane (AK-225, manufactured by AGC) were placed. The mixture was stirred while cooled in an ice bath, and 3.0 g of methanol was slowly added dropwise to the mixture from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 10.8 g of the following compound b6. CF 3 CF 2 CF 2 -O-CF 2 -CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CF 2 -O-CF 2 CF 2 CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 C(O)-OCH 3 (b6) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b6, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0176] <Synthesis of compound b7> In a 100 mL eggplant flask, add 10 g of the above compound b6 and H 2 N-CH 2 -C(CH2 CH=CH 2 ) 3 The mixture was stirred for 12 hours. The crude product was then subjected to molecular weight fractionation by silica gel column chromatography to obtain 3.5 g of the following compound b7 having a molecular weight of 4,300. CF 3 CF 2 CF 2 -O-CF 2 -CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CF 2 -O-CF 2 CF 2 CF 2 -O-CF 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 C(O)NH-CH 2 -C(CH 2 CH=CH 2 ) 3 (b7) 1 H-NMR and 19 As a result of F-NMR measurement, in compound b7, the average ratio x1 / x2 of the number of units x1 to the number of units x2 was 1.1.

[0177] <Synthesis of compound X2> In a 20 mL sample tube, 2.0 g of the above compound b7, 0.03 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), and HSi(OCH 3 ) 30.25 g of the above, 0.01 g of aniline, and 1.0 g of SR Solvent (manufactured by AGC Seimi Chemical) were added, and the mixture was stirred for 10 hours at 40° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 1.0 μm to obtain 2.2 g of the following compound X2 as surface treatment agent 2. [CF 3 CF 2 CF 2 -(OCF 2 ) y1 (OCF 2 CF 2 ) y2 (OCF 2 CF 2 CF 2 ) y3 ]-OCF 2 C(O)NH-CH 2 -C[CH 2 CH 2 CH 2 -Si(OCH 3 ) 3 ] 3 (X2) 1 H-NMR and 19 As a result of F-NMR measurement, the molecular weight of compound X2 was 4600, the ratio y1 / y2 of the number of units y1 to the number of units y2 in compound X2 was 0.9, and the average value of the number of units y3 was 2.8.

[0178] [Preparation Example 3: Preparation of Surface Treatment Agent 3] <Synthesis of compound c1> A fluorine-containing ether compound (manufactured by Solvay, "Fomblin D2") was subjected to molecular weight fractionation by silica gel column chromatography to obtain a compound c1 having a molecular weight of 2,300. HO-CH 2 CF 2 -{(OCF 2 ) x1 (OCF 2 CF 2 ) x2}-OCF 2 CH 2 -OH (c1) 1 H-NMR and 19As a result of F-NMR measurement, the ratio x1 / x2 of the number of units x1 to the number of units x2 in compound c1 was 1.1.

[0179] <Synthesis of compound X3> The following compound X3 having a molecular weight of 4600 was synthesized in the same manner as in Preparation Example 2 above, except that compound b1 was changed to compound c1 above, and surface treatment agent 3 consisting of compound X3 was obtained. [CF 3 CF 2 CF 2 -(OCF 2 ) y1 (OCF 2 CF 2 ) y2 (OCF 2 CF 2 CF 2 ) y3 ]-OCF 2 C(O)NH-CH 2 -C[CH 2 CH 2 CH 2 -Si(OCH 3 ) 3 ] 3 (X3) 1 H-NMR and 19 As a result of measuring compound X3 by F-NMR, the molecular weight of compound X3 was 4600, the ratio y1 / y2 of the number of units y1 to the number of units y2 was 0.9, and the average value of the number of units y3 was 2.0.

[0180] [Preparation Example 4: Preparation of Surface Treatment Agent 4] 1.0 g of the above surface treatment agent 1 and 0.8 g of the surface treatment agent 3 were each dissolved in 10 g of SR solvent and then mixed together. The SR solvent was then distilled off to obtain a surface treatment agent 4 containing the compound X1 and the compound X3.

[0181] [Example 1 to Example 4] 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 pressure was evacuated to a pressure of 10 Pa or less. A deposition vessel containing a surface treatment agent was heated to 300° C. by resistance heating at a distance of 1000 mm so as to face one of the main surfaces of the substrate, and the surface treatment agent was vacuum-deposited. When the thickness of the surface treatment agent on the substrate reached 10 nm, film formation was terminated. Thereafter, the substrate on which the surface treatment agent had been deposited was heated at a temperature of 200° C. for 30 minutes (post-treatment) to obtain a substrate (article) with a surface layer.

[0182] [Evaluation test] The substrates with surface layers of Examples 1 to 4 were used to carry out the following evaluation tests.

[0183] <Requirement 1> The surface layer of the obtained substrate with a surface layer was analyzed using a tandem mass spectrometer equipped with a primary ion source, a first mass spectrometer (time-of-flight mass spectrometer), an ion selection device, a collision cell, and a second mass spectrometer (time-of-flight mass spectrometer) according to the method described above. The analysis conditions in this example are as follows. - Tandem mass spectrometer: ULVAC-PHI "PHI nanoTOF II" Primary ion: Bi 3 ++ Primary ion acceleration voltage: 30kV Raster size: 500×500μm 2 Bunching: Yes Static neutralization: Yes Secondary ion polarity: negative Collision gas (MS / MS): Ar Collision energy: 1.5keV

[0184] The surface layer was irradiated with pulsed primary ions to generate negative secondary ions, which were then separated based on their mass-to-charge ratio using a first mass spectrometer. A precursor ion with a mass-to-charge ratio of 348 u was selected from the separated negative secondary ions using an ion selection device, and the selected precursor ion was introduced into a collision cell to generate product ions. The generated product ions were analyzed by a second mass spectrometer to obtain a mass spectrum showing the relationship between the mass-to-charge ratio of the product ions and the area intensity. The obtained mass spectrum was divided into two groups, i.e., the total area intensity I corresponding to the product ion A with a mass-to-charge ratio of 116 u or 232 u, A is 100,000 counts or more, or the total area intensity I corresponding to product ion B having a mass-to-charge ratio of 66 u, 166 u, 182 u, or 282 u B The total area intensity I was then calculated by integrating the total area intensity I A Total area intensity I B Ratio I B / I A was calculated. The total area intensity I obtained for each example A , total area intensity I B , and ratio I B / I A are shown in Table 1 below. As a result of the above mass spectrometry, the ratio of surface treatment agent 1 I B / I A is 0.016, and the ratio of surface treatment agent 2 I B / I A is 0.112, and the ratio of surface treatment agent 3 I B / I A is 0.061, and the ratio of surface treatment agent 4 I B / I A was 0.025.

[0185] <Lubricity> The dynamic friction coefficient of the surface layer against artificial skin (Idemitsu Technofine, PBZ13001) was measured using a variable load friction and wear test system (Shinto Scientific, HHS2000) 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: The dynamic friction coefficient of the surface layer is 0.017 or less. B: The dynamic friction coefficient of the surface layer is greater than 0.017 and less than 0.019. C: The dynamic friction coefficient of the surface layer is greater than 0.019 and less than 0.021. D: The dynamic friction coefficient of the surface layer is greater than 0.021.

[0186] [Table 1]

[0187] As shown in Table 1, it was confirmed that when the surface treatment agent satisfies Requirement 1, a surface layer with excellent lubricity can be formed (Examples 2 to 4). Moreover, it was confirmed that the surface layer satisfying requirement 2 had excellent lubricity (Examples 2 to 4).

Claims

1. The composition contains a fluorine-containing ether compound having a fluoropolyether chain and a reactive group, A surface treatment agent that satisfies the following requirement 1. Requirement 1: generating negative secondary ions by irradiating a surface layer formed on a substrate using the surface treatment agent with pulsed primary ions; separating the generated negative secondary ions based on their mass to charge ratio using a first time-of-flight mass analyzer; a negative secondary ion having a mass-to-charge ratio of 348 u is selected as a precursor ion from the separated negative secondary ions using an ion selection device; introducing the selected precursor ions into a collision cell to fragment them by high energy collision induced dissociation to generate product ions; A mass spectrum showing a relationship between the mass-to-charge ratio and the area intensity of the product ions, the mass spectrum being obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities I of the peaks corresponding to the product ions having mass-to-charge ratios of 116 u and 232 u Ａ The sum of the area intensities I of the peaks corresponding to the product ions having mass-to-charge ratios of 66 u, 166 u, 182 u, and 282 u, Ｂ Ratio I Ｂ / I Ａ is 0.025 or more.

2. The ratio I Ｂ / I Ａ The surface treatment agent according to claim 1, wherein the viscosity is 0.025 to 0.

112.

3. The surface treatment agent according to claim 1 or 2, wherein the reactive group is a reactive silyl group.

4. The fluoropolyether chain is (OCF ２ ) and the unit represented by (OC ２ F ４ ) and the unit represented by (OC ３ F ６ The surface treatment agent according to any one of claims 1 to 3, comprising a unit represented by the following formula:

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

6. An article having a surface layer formed on a substrate using the surface treatment agent according to any one of claims 1 to 4 or the coating liquid according to claim 5.

7. An article having a substrate and a surface layer comprising fluoropolyether chains, An item that meets requirement 2 below. Requirement 2: irradiating the surface layer with pulsed primary ions to generate negative secondary ions; separating the generated negative secondary ions based on their mass to charge ratio using a first time-of-flight mass analyzer; a negative secondary ion having a mass-to-charge ratio of 348 u is selected as a precursor ion from the separated negative secondary ions using an ion selection device; introducing the selected precursor ions into a collision cell to fragment them by high energy collision induced dissociation to generate product ions; A mass spectrum showing a relationship between the mass-to-charge ratio and the area intensity of the product ions, the mass spectrum being obtained from the generated product ions using a second mass spectrometer, The sum of the area intensities I of the peaks corresponding to the product ions having mass-to-charge ratios of 116 u and 232 u Ａ The sum of the area intensities I of the peaks corresponding to the product ions having mass-to-charge ratios of 66 u, 166 u, 182 u, and 282 u, Ｂ Ratio I Ｂ / I Ａ is 0.025 or more.

8. The ratio I Ｂ / I Ａ The article of claim 7, wherein the σ is 0.025 to 0.

112.

9. The fluoropolyether chain is (OCF ２ ) and the unit represented by (OC ２ F ４ ) and the unit represented by (OC ３ F ６ 9. The article according to claim 7 or 8, comprising a unit represented by the formula:

10. The article according to any one of claims 6 to 9, wherein the article is a touch panel, and the surface layer is provided on a surface of a member constituting a surface of the touch panel that is touched by a finger.

11. 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 4 or the coating liquid according to claim 5.

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