Fluorinated ether compound, fluorinated ether composition, coating liquid, article, and method for producing article

Abstract

The objective of the present invention is to provide: a fluorine-containing ether compound from which a surface layer having an excellent fingerprint stain removing property and finger slipperiness can be formed; a fluorine-containing ether composition; a coating liquid; an article having a surface layer having an excellent fingerprint stain removing property and finger slipperiness; and a method for producing said article. The fluorine-containing ether compound is represented by formula (1) or formula (2).　Formula (1): {(Rf1-A1-)p1Si(-R1)3-p1}q1-Q1(-T)n1(-Rf2)r1 Formula (2): {(Rf1-A1-)p2Si(-R1)3-p2}q2-Q2(-T)n2-Rf3-Q3(-T)n3{-Si(-R2)3-p3(-A2-Rf1)p3}q3 Each symbol in the formulas is same as described in the specification.

Description

[Technical Field]

[0001] The present invention relates to a fluorinated ether compound, a fluorinated ether composition, a coating liquid, an article, and a method for producing an article. [Background technology]

[0002] Fluorine-containing ether compounds having a fluoropolyether chain and a hydrolyzable silyl group have attracted attention as they can impart excellent water and oil repellency, abrasion resistance, low fingerprint adhesion, fingerprint stain removability, and finger slipperiness to the surface of a substrate. They are suitable for use in surface treatment agents because they can form a surface layer exhibiting the above properties on the surface of a substrate.

[0003] For example, Patent Document 1 proposes a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group as a fluorine-containing ether compound that has excellent fingerprint stain removal properties and can form a durable surface layer on the surface of a substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 038832 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide a fluorinated ether compound, a fluorinated ether composition, and a coating liquid capable of forming a surface layer excellent in fingerprint stain removability and finger smoothness, an article having a surface layer excellent in fingerprint stain removability and finger smoothness, and a method for producing the same. [Means for solving the problem]

[0006] The present invention provides a fluorine-containing compound having the following constitutions [1] to [9] and a method for producing the same, a fluorine-containing compound-containing composition, a coating liquid, an article and a method for producing the same. [1] A fluorine-containing ether compound represented by the following formula (1) or (2): {(R f1 -A 1 -) p1 Si(-R 1 ) 3-p1} q1 -Q 1 (-T) n1 (-R f2 ) r1 Formula (1) {(R f1 -A 1 -) p2 Si(-R 1 ) 3-p2} q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si(-R 2 ) 3-p3 (-A 2 -R f1 ) p3} q3 Formula (2) however, R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and there are a plurality of R f1 may be the same or different from each other, R f2 is a monovalent polyfluoropolyether chain, and there are multiple R f2 may be the same or different from each other, R f3 is a divalent polyfluoropolyether chain, A 1 and A 2 are each independently -O- or C(=O)-O-, and a plurality of A 1 and A 2 may each independently be the same or different, R 1 and R 2 is an alkyl group, a hydrolyzable group, or a hydroxyl group, and there are multiple R 1 and R 2 may be the same or different, Q 1 is a linking group with a valence of q1+n1+r1, Q 2 is a q2+n2+1 valent linking group, Q 3 is a q+n+1 valent linking group, T is -Si(-R) 3-a (-L) a When there are two or more T's, the two or more T's may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different; a is 2 or 3, q1 is an integer of 1 or more, When q1 is 1, p1 is 1 or 2; when q1 is 2 or more, p1 is an integer of 0 to 3, at least one of the multiple p1 is 1 or 2, and the multiple p1 may be the same or different from each other; n1 is an integer equal to or greater than 0, and r1 is an integer equal to or greater than 1, q2 is an integer of 1 or more, When q2 is 1, p2 is 1 or 2; when q2 is 2 or more, p2 is an integer of 0 to 3, and at least one of the multiple p2 is 1 or 2, and the multiple p2 may be the same or different from each other; n2 is an integer equal to or greater than 0, q3 is an integer equal to or greater than 0, When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are multiple p3, each p3 may be the same or different, n3 is an integer of 0 or greater, and q3+n3 is an integer of 1 or greater. [2] R f1 The fluorine-containing ether compound [1] is represented by the following formula (3A): L 1 -R f11a -(OR f12 ) m1 -(CH2) s1- Formula (3A) L 1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, -C(O)X, or -C(O)OR 10 , -C(O)N(R 10 )2, X is a hydrogen atom or a halogen atom, R 10 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom, or a phenyl group which may have a fluorine atom, and R 10 If there are multiple R 10 may be the same or different from each other, R f11a is a fluoroalkylene group having 1 to 20 carbon atoms, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12 may be the same or different, s1 is an integer from 0 to 20. [3] R f2 The fluorine-containing ether compound of [1] or [2] is represented by the following formula (3): R f11 -(OR f12 ) m1 - Equation (3) however, R f11 is a fluoroalkyl group having 1 to 20 carbon atoms, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12 may be the same or different. [4] R f3 The fluorine-containing ether compounds [1] to [3] are represented by the following formula (4): -R f13 -(OR f13 ) m2 - Formula (4) however, R f13is a fluoroalkylene group having 1 to 6 carbon atoms, and multiple R f13 may be the same or different, m2 is an integer of 0 to 500. [5] Q 1 , Q 2 , and Q 3 Fluorine-containing ether compounds [1] to [4], each of which is independently represented by any one of the following formulas (5-1) to (5-7): [ka] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -)(-Q 22 -) d3 Formula (5-2) (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -) Formula (5-3) (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -) d4 Formula (5-4) (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -) d5 Formula (5-5) -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -) d6 Formula (5-6) -A 11 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q 25 -) d7Formula (5-7) However, in formulas (5-1) to (5-7), A 11 Side is R f2 or R f3 Connect to Q 22 , Q 23 , Q 24 , or Q 25 The side connects to T, and the Q 32 , Q 33 , Q 34 , or Q 35 through Si to R f1 Connect to A 11 is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 SO2-, Q 11 is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 SO2-, alkylene group, or alkylene group with 2 or more carbon atoms with -C(O)NR between carbon atoms 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 13 represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms.6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 a group having SO2- or a group having -C(O)- at the N-terminal of the alkylene group, Q 14 Q 14 If the atom in Z to which is bonded is a carbon atom, Q 12 and Q 14 If the atom in Z to which is bonded is a nitrogen atom, Q 13 and Q 15 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 22 and Q 32 each independently represents an alkylene group, an alkylene group having 2 or more carbon atoms, and a —C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 A group having SO2-, -C(O)NR at the end of the alkylene group not connected to Si 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 or a group having —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 It has SO2- and -C(O)NR at the end not connected to Si 6-, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, and Q 22 If there are multiple Qs, 22 may be the same or different, Q 23 and Q 33 each independently represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms; 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 24 and Q 34 are each independently, Q 24 or Q 34 If the atom in Z to which is bonded is a carbon atom, Q 22 or Q 32 and Q 24 or Q 34 If the atom in Z to which is bonded is a nitrogen atom, Q 23 or Q 33 and Q 24 If there are multiple Qs, 24 may be the same or different, Q 25 and Q 35 Each of the represents independently an alkylene group or an alkylene group having two or more carbon atoms, and represents —C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, and Q 25 If there are multiple Qs, 25 may be the same or different, Z is Q 14 , Q 24 and Q 34is a group having a d4+2-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, and R 1 If there are multiple R 1 may be the same or different, R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R e3 is an alkyl group, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 6, d3 is 1 or 2, d4 is an integer equal to or greater than 1, d5 is 1 or 2, d6 is an integer from 1 to 3, d7 is 1 or 2. [6] A fluorinated ether composition comprising the fluorinated ether compound of any one of [1] to [5] and another fluorinated ether compound. [7] A coating liquid comprising the fluorinated ether compound of any one of [1] to [5] or the fluorinated ether composition of [6], and a liquid medium. [8] An article having a surface layer formed on the surface of a substrate from the fluorinated ether compound of any one of [1] to [5] or the fluorinated ether composition of [6]. [9] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the fluorinated ether compound of [1] to [5], the fluorinated ether composition of [6], or the coating liquid of [7]. [Effects of the Invention]

[0007] The present invention provides a fluorine-containing ether compound, a fluorine-containing ether composition, and a coating liquid capable of forming a surface layer excellent in fingerprint stain removability and finger smoothness, an article having a surface layer excellent in fingerprint stain removability and finger smoothness, and a method for producing the same. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a schematic cross-sectional view showing an example of an article of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, the compound represented by formula (1) will be referred to as compound (1). Compounds represented by other formulas will also be referred to as compound (1). As used herein, the following terms have the following meanings: The term "reactive silyl group" refers collectively to a hydrolyzable silyl group and a silanol group (Si-OH). The reactive silyl group is, for example, -Si(-R) in formula (1) or formula (2). 3-a (-L) a , and -Si(-R 1 ) or Si(-R 2 ) in R 1 or R 2 is a hydrolyzable group or a hydroxyl group. The term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "surface layer" refers to a layer formed on the surface of a substrate. When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 It is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units by F-NMR. When the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is uniform, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 F-NMR f The molecular weight is calculated by determining the structure of the molecule. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0010] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the compound") is a compound represented by the following formula (1) or (2). {(R f1 -A 1 -) p1 Si(-R 1 ) 3-p1} q1 -Q 1 (-T) n1 (-R f2 ) r1 Formula (1) {(R f1 -A 1 -) p2 Si(-R 1 ) 3-p2} q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si(-R 2 ) 3-p3 (-A 2 -R f1 ) p3} q3 Formula (2) however, R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and there are a plurality of R f1 may be the same or different from each other, R f2 is a monovalent polyfluoropolyether chain, and there are multiple R f2 may be the same or different from each other, R f3 is a divalent polyfluoropolyether chain, A 1 and A 2 are each independently -O- or C(=O)-O-, and a plurality of A 1 and A 2 may each independently be the same or different, R 1 and R 2is an alkyl group, a hydrolyzable group, or a hydroxyl group, and there are multiple R 1 and R 2 may be the same or different, Q 1 is a linking group with a valence of q1+n1+r1, Q 2 is a q2+n2+1 valent linking group, Q 3 is a q+n+1 valent linking group, T is -Si(-R) 3-a (-L) a When there are two or more T's, the two or more T's may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different; a is 2 or 3, q1 is an integer of 1 or more, When q1 is 1, p1 is 1 or 2; when q1 is 2 or more, p1 is an integer of 0 to 3, at least one of the multiple p1 is 1 or 2, and the multiple p1 may be the same or different from each other; n1 is an integer equal to or greater than 0, and r1 is an integer equal to or greater than 1, q2 is an integer of 1 or more, When q2 is 1, p2 is 1 or 2; when q2 is 2 or more, p2 is an integer of 0 to 3, and at least one of the multiple p2 is 1 or 2, and the multiple p2 may be the same or different from each other; n2 is an integer equal to or greater than 0, q3 is an integer equal to or greater than 0, When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are multiple p3, each p3 may be the same or different, n3 is an integer of 0 or greater, and q3+n3 is an integer of 1 or greater.

[0011] The compound (1) comprises two polyfluoropolyether chains, a reactive silyl group, and a specific linking group [A 1 -Si(R 1 )-Q 1 ] and The compound (2) also comprises three polyfluoropolyether chains, a reactive silyl group, and a specific linking group [A 1 -Si(R 1 )-Q 2 ] and [Q 3 -Si(R 2 )-A 2 ] and

[0012] The compound has a polyfluoropolyether chain. The compound having a polyfluoropolyether chain has excellent fingerprint stain removal properties on the surface layer. The compound also has at least one reactive silyl group [T] and a linking group [Si(R 1 )] and [Si(R 2 )] can also function as a reactive silyl group. This compound is composed of a reactive silyl group [T] and a [Si(R 1 )] and [Si(R 2 )] are each strongly chemically bonded to the substrate. At this time, in compound (1), two polyfluoropolyether chains [R f1 ] and [R f2 ], whereas in compound (2), two polyfluoropolyether chains [R f1 ] and [R f1 As a result, a surface layer is formed that is excellent in abrasion resistance, fingerprint removal properties, and finger sliding properties. Furthermore, this compound can be produced by the production method described below, in which two polyfluoropolyether chains [R f1 ] and [R f2 ], and compound (2) has two polyfluoropolyether chains [R f1 ] and [R f3], it is easy to introduce different polyfluoropolyether chains into the polyfluoropolyether chain, which increases the degree of freedom in molecular design. Therefore, this compound has the advantage of being easy to design a molecular structure according to the physical properties required for the surface layer of an article. In addition, examples of different polyfluoropolyether chains include those in which the oxyfluoroalkyl groups constituting the polyfluoropolyether chain have different carbon numbers, and polyfluoropolyether chains with different molecular weights.

[0013] R f1 and R f2 is a monovalent polyfluoropolyether chain. R f1 In order to further improve the abrasion resistance and fingerprint removability of the surface layer, the fluorination rate of the polyfluoropolyether chain is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, as represented by the following mathematical formula (1): If the fluorination rate is equal to or higher than the above lower limit, the amount of fluorine in the polyfluoropolyether chain increases, improving the smoothness and fingerprint removability. Formula (1): Fluorination rate (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100 Polyfluoropolyether chain (R f1 , or R f2 ) is preferably 1,000 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 removability and anti-slip properties of the surface layer. When the molecular weight of the polyfluoropolyether chain is equal to or greater than the above lower limit, the flexibility of the polyfluoropolyether chain is improved and the amount of fluorine in the molecule is increased, thereby improving finger slipperiness and fingerprint removability. On the other hand, when the molecular weight of the polyfluoropolyether chain is equal to or less than the above upper limit, the surface layer has excellent abrasion resistance. However, R f1 A 1 or A 2 The terminal carbon atom bonded to R may have a fluorine atom bonded thereto. f2 No, Q 1 At least one fluorine atom is bonded to the terminal carbon atom bonded to

[0014] R f1 The polyfluoropolyether chain in may have a substituent. The substituent imparts adhesiveness to the polyfluoroether chain, and other compounds such as polyfluoropolyether chains can be introduced from the substituent. The substituent is preferably located at the end of the polyfluoropolyether chain. That is, R f1 is preferably a structure represented by the following formula (3A). L 1 -R f11a -(OR f12 ) m1 -(CH2) s1 - Formula (3A) however, L 1 represents a hydrogen atom, a fluorine atom, a hydroxyl group, -C(O)X, or -C(O)OR 10 , -C(O)N(R 10 )2, X is a hydrogen atom or a halogen atom, R 10 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom, or a phenyl group which may have a fluorine atom, and R 10 If there are multiple R 10 may be the same or different from each other, R f11a is a fluoroalkylene group having 1 to 20 carbon atoms, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12 may be the same or different, s1 is an integer from 0 to 20. In addition, L 1 When is a hydrogen atom or a fluorine atom, L 1 -R f11a is R in equation (3) described later. f11 The same applies to the preferred embodiments.

[0015] Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 10 Among these, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom is preferred. In addition, s1 is preferably an integer of 1 to 6 from the viewpoint of ease of synthesis of the present compound.

[0016] R f2 In terms of fingerprint removability and finger smoothness, the polyfluoropolyether chain in the above formula (3) preferably has a structure represented by the following formula (3): R f11 -(OR f12 ) m1 - Equation (3) however, R f11 is a fluoroalkyl group having 1 to 20 carbon atoms, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12 may be the same or different.

[0017] R f11 is a fluoroalkyl group constituting the end of a polyfluoropolyether chain, and has 1 to 20 carbon atoms in order to provide excellent abrasion resistance and fingerprint removability to the surface layer. R f11 The fluoroalkyl group preferably has a fluorination rate of 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., a perfluoroalkyl group, in order to provide a surface layer with even better abrasion resistance and fingerprint removability.

[0018] R f11 The fluoroalkyl group may be linear, branched, or have a ring structure. The linear or branched fluoroalkyl group may have 1 to 20 carbon atoms, preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3, in terms of excellent abrasion resistance and fingerprint removability of the surface layer. Examples of straight-chain or branched fluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)-, and the like.

[0019] R f11 The number of carbon atoms in the fluoroalkyl group (also called a fluorocycloalkyl group) having the above ring structure is preferably 3 to 20, more preferably 4 to 8, and particularly preferably 4 to 6. If it is within the above range, the surface layer will have excellent abrasion resistance and fingerprint removability. Examples of fluoroalkyl groups having a ring structure include groups of the following formula: wherein * indicates a bond.

[0020] [ka] However, some of the fluorine atoms in the formula may be replaced with hydrogen atoms.

[0021] R f12 is a fluoroalkylene group having 1 to 6 carbon atoms in order to provide a surface layer with excellent abrasion resistance and fingerprint removability. R f12 In order to further improve the abrasion resistance and fingerprint removability of the surface layer, the fluorination rate of the fluoroalkylene group represented by the formula (1) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., a perfluoroalkylene group. If the fluorination rate is equal to or higher than the lower limit, the amount of fluorine in the polyfluoropolyether chain increases, improving the smoothness and fingerprint removability.

[0022] R f12 The fluoroalkylene group may be linear, branched, or have a ring structure. Examples of straight-chain or branched fluoroalkylene groups include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2CF2-, -CF2CF(CF3)-, and the like. Examples of the fluoroalkylene group having a ring structure include groups of the following formula: wherein * indicates a bond.

[0023] [ka] However, some of the fluorine atoms in the formula may be replaced with hydrogen atoms.

[0024] m1 is an oxyfluoroalkylene group OR f12 m1 is an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of superior water and oil repellency, abrasion resistance, and fingerprint stain removability.

[0025] (OR) of formula (3) and formula (3A) f12 ) m1 is preferably a structure represented by the following formula (3B): [(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 ] Formula (3B) however, R 11 is a fluoroalkylene group having one carbon atom, R 12 is a fluoroalkylene group having 2 carbon atoms, R 13 is a fluoroalkylene group having 3 carbon atoms, R 14 is a fluoroalkylene group having 4 carbon atoms, R 15 is a fluoroalkylene group having 5 carbon atoms, R 16 is a fluoroalkylene group having 6 carbon atoms, m11, m12, m13, m14, m15, and m16 each represent an integer of 0 or 1 or more, and m11+m12+m13+m14+m15+m16 is an integer of 1-500. In addition, (OR 11 )~(OR 16 The bonding order of m11 to m16 in formula (3B) is arbitrary. 11 )~(OR 16 ) and does not represent the arrangement. For example, (OR 15 ) m5 is (OR 15 ) is m5, and (OR 15 ) m5 Similarly, (OR 11 )~(OR 16 The order of the units does not represent the order in which they are bonded. R 11 ~R 16 Specific examples of R f12 You can refer to the specific examples below.

[0026] Due to its excellent water and oil repellency, abrasion resistance, and fingerprint removal properties, (OR f12 ) m1 Among the formula (3B), a structure represented by any one of the following formulas (3C) to (3F) is preferred. (OR 11 ) m11 -(OR 12 ) m12 (3C) (OR 12 ) m12 -(OR 14 ) m14 (3D) (OR 13 ) m13 (3F) However, the symbols in formulas (3C) to (3F) are the same as those in formula (3A).

[0027] In the above formula (3C) and formula (3D), (OR 11 ) and (OR 12 ), (OR 12 ) and (OR 14 The order of bonding of (OR ) is arbitrary. For example, in formula (3C), 11 ) and (OR 12 ) may be alternated, and (OR f1 ) and (OR f2 ) may be arranged in blocks or randomly. The same applies to formula (3D). In formula (3C), m11 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m12 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (3D), m12 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m14 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (3F), m13 is preferably 1 to 30, and more preferably 1 to 20.

[0028] In addition, the polyfluoropolyether chain of formula (3B) is preferably (OR 11 Specifically, the ratio represented by the following mathematical formula (2) is preferably 0.2 or more, more preferably 0.5 or more, more preferably 1.0 or more, and more preferably 2.0 or more. Formula (2): m11 / (m12+m13+m14+m15+m16)

[0029] R f3 is a divalent polyfluoropolyether chain. The presence of the polyfluoropolyether chain gives the compound excellent fingerprint removal properties and finger slipperiness on the surface layer. R f3 In order to further improve the abrasion resistance and fingerprint removability of the surface layer, the fluorination rate of the polyfluoropolyether chain is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%. If the fluorination rate is equal to or more than the lower limit, the amount of fluorine in the polyfluoropolyether chain increases, improving the smoothness and fingerprint removability. R f3 The molecular weight of R is preferably from 1,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000, from the viewpoint of achieving both fingerprint removability and slip resistance of the surface layer. f3 If the molecular weight of R is equal to or greater than the lower limit, the flexibility of the polyfluoropolyether chain is improved and the amount of fluorine in the molecule is increased, improving finger sliding properties and fingerprint removability. f3 When the molecular weight is equal to or less than the upper limit, the surface layer has excellent abrasion resistance. However, R f3 No, Q 2 and Q 3 A fluorine atom is bonded to the terminal carbon atom bonded to

[0030] In terms of fingerprint removal and finger sliding, R f3 is preferably a structure represented by the following formula (4). -R f13 -(OR f13 ) m2 - Formula (4) however, R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, m2 is an integer from 0 to 500, and when m2 is 1 or more, there are multiple R f13 may be the same or different.

[0031] R f13 In the formula, the fluoroalkylene group having 1 to 6 carbon atoms is f12 and preferred embodiments are similar. m2 is an oxyfluoroalkylene group OR f13 m2 is an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of superior water and oil repellency, abrasion resistance, and fingerprint stain removability.

[0032] (OR f13 ) m2 is preferably a structure represented by the following formula (4A). [(OR 11 ) m11(OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 ] Formula (4A) However, each symbol in the formula (4A) is the same as in the formula (3B), and the preferred embodiments are also the same as in the formula (3B).

[0033] T in formula (1) and formula (2) is -Si(R) 3-a (L) a where R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, two or more Ls in each T may be the same or different, and a is 2 or 3. The reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group then undergoes a dehydration condensation reaction between molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a chlorine atom. The hydrolyzable group is preferably an alkoxy group or a halogen atom in view of ease of production of the present compound. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred in view of less outgassing during coating and excellent storage stability of the present compound, an ethoxy group is particularly preferred when long-term storage stability of the present compound is required, and a methoxy group is particularly preferred when the reaction time after coating is short. The alkyl group may be an alkyl group having 1 to 6 carbon atoms.

[0034] Si(-R 1 ) 3-p1 , Si(-R 1 ) 3-p2 and -Si(-R 2 ) 3-p3 is a structure that constitutes a part of the linking group that links the polyfluoropolyether chain and the reactive silyl group. R 1 and R 2 are each independently an alkyl group, a hydrolyzable group, or a hydroxyl group, and there are multiple R 1 and R 2 may be the same or different. 1 and R 2 The alkyl group and hydrolyzable group may be the same as those in the reactive silyl group, and preferred embodiments are also the same. Among them, there are several R 1 It is preferable that at least one of R is a hydrolyzable group or a hydroxyl group. 2 At least one of the groups is preferably a hydrolyzable group or a hydroxyl group. 1 and SiR 2 As with the above-mentioned T, the compound undergoes a dehydration condensation reaction with the hydroxyl groups (substrate-OH) on the surface of the substrate, further improving the adhesion.

[0035] Q in equation (1) 1 is a linking group with a valence of q1+n1+r1. Q 1 has at least one branch point (P1) selected from the group consisting of C, N, Si, a ring structure, and a q1+n1+r1 valent organopolysiloxane residue. The ring structure is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, in terms of ease of production of the compound and excellent abrasion resistance, light resistance, and chemical resistance of the surface layer, and is particularly preferably a ring structure shown in the following formula: The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (=O).

[0036] [ka]

[0037] Examples of the q1+n1+r1-valent organopolysiloxane residue include the following groups: 5 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0038] [ka]

[0039] The compound (1) is a compound in which Si, T or R in formula (1) is directly attached to the branch point (P1). f2 may be bonded, and -C(O)NR 6 -, -C(O)O-, -C(O)-, -O-, -NR 6 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -,-SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and divalent organopolysiloxane residues. 6is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 6 The number of carbon atoms in the alkyl group is preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound.

[0040] Examples of the divalent organopolysiloxane residue include groups of the following formula: 7 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0041] [ka]

[0042] As the bond (P2), -C(O)NR is used because it is easy to prepare this compound. 6 -, -C(O)-, -NR 6 At least one bond selected from the group consisting of - and -O- is preferred, and -C(O)NR 6 -, -C(O)-, and -O- are particularly preferred.

[0043] Q 1 Examples of the alkyl group include a combination of two or more divalent hydrocarbon groups and one or more branch points (P1), or a combination of two or more hydrocarbon groups, one or more branch points (P1), and one or more bonds (P2). Examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0044] Among them, Q 1 However, it is preferable that the compound has a structure represented by any one of the following formulae (5-1) to (5-7) in terms of ease of production of the present compound.

[0045] [ka] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -)(-Q 22 -) d3 Formula (5-2) (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -) Formula (5-3) (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -) d4 Formula (5-4) (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -) d5 Formula (5-5) -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -) d6 Formula (5-6) -A 11 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q 25 -) d7 Formula (5-7) However, in formulas (5-1) to (5-7), A 11 Side is R f2 or R f3 Connect to Q 22 , Q 23 , Q 24 , or Q 25 The side connects to T, and the Q 32 , Q 33 , Q 34 , or Q 35through Si to R f1 Connect to A 11 is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 SO2-, Q 11 is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 SO2-, alkylene group, or alkylene group with 2 or more carbon atoms with -C(O)NR between carbon atoms 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 13 represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 a group having SO2- or a group having -C(O)- at the N-terminal of the alkylene group, Q 14 Q 14 If the atom in Z to which is bonded is a carbon atom, Q 12and Q 14 If the atom in Z to which is bonded is a nitrogen atom, Q 13 and Q 15 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 22 and Q 32 each independently represents an alkylene group, an alkylene group having 2 or more carbon atoms, and a —C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 A group having SO2-, -C(O)NR at the end of the alkylene group not connected to Si 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 or a group having —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 It has SO2- and -C(O)NR at the end not connected to Si 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, and Q 22 If there are multiple Qs, 22 may be the same or different, Q 23 and Q 33each independently represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms; 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, Q 24 and Q 34 are each independently, Q 24 or Q 34 If the atom in Z to which is bonded is a carbon atom, Q 22 or Q 32 and Q 24 or Q 34 If the atom in Z to which is bonded is a nitrogen atom, Q 23 or Q 33 and Q 24 If there are multiple Qs, 24 may be the same or different, Q 25 and Q 35 Each of the represents independently an alkylene group or an alkylene group having two or more carbon atoms, and represents —C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-NR 6 is a group having SO2-, and Q 25 If there are multiple Qs, 25 may be the same or different, Z is Q 14 , Q 24 and Q 34 is a group having a d4+2-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, and R 1 If there are multiple R 1 may be the same or different, R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R e3is an alkyl group, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 6, d3 is 1 or 2, d4 is an integer equal to or greater than 1, d5 is 1 or 2, d6 is an integer from 1 to 3, d7 is 1 or 2.

[0046] Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22 , Q 23 , Q 24 , Q 25 , Q 32 , Q 33 , Q 34 , and Q 35 In terms of ease of production of the present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer, the alkylene group in the formula (I) is preferably a linear alkylene group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0047] Examples of the ring structure in Z include the ring structure at the branch point (P1) described above, and the preferred forms are also the same. 14 , Q 24 and Q 34 is directly bonded.

[0048] R e1 , R e2 and R e3 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms, in view of ease of production of the present compound. R e2The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of the present compound. d4 is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound and excellent abrasion resistance and fingerprint stain removability of the surface layer.

[0049] Q 1 Other examples of the compound include those having a structure represented by any one of the following formulas (6-1) to (6-7).

[0050] [ka] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -)(-Q 22 -G) d3 Formula (6-2) (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -G) Formula (6-3) (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -G) d4 Formula (6-4) (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -G) d5 Formula (6-5) -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -G) d6 Formula (6-6) -A 11 -Q 12 -CH(-Q 22-G)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q 25 -G) d7 Formula (6-7) However, in formulas (6-1) to (6-7), A 11 R f2 connects to , G connects to T, Q 32 , Q 33 , Q 34 , or Q 35 through Si to R f1 Connect to. G is a group represented by the following formula (6-8), and the symbols other than G are the same as the symbols in formulas (5-1) to (5-7).

[0051] -Si(R 8 ) 3-k (-Q 41 -) k Formula (6-8) However, in equation (6-8), Si is Q 22 , Q 23 , Q 24 , or Q 25 or Q 26 Connect to Q 41 connects to T. R 8 is an alkyl group. 41 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-, or -(OSi(R 9 )2) p -O- and 2 or more Q 41 may be the same or different. k is 2 or 3. R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 9 )2) may be the same or different.

[0052] Q 41 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of the present compound and further improvement in the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 8 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. R 9 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of excellent storage stability of the present compound. p is preferably 0 or 1.

[0053] Q 2 is a q2+n2+1 valent linking group, and Q 3 is a q3+n3+1 valent linking group. Q 2 and Q 3 Q 1 The same applies to the preferred embodiments. 1 In the description of the compound (1), compound (2) is R f2 is R f3 In the above, n1 is replaced by n2 or n3, q1 is replaced by q2 or q3, and r1 is replaced by 1. Here, q1 and q2 are each independently an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3. q3 may be 0 or an integer of 1 or more. q3 is preferably 0 to 6, and more preferably 0 to 3. Furthermore, n1, n2, and n3 may each independently be 0 or an integer of 1 or more. n1 to n3 are each independently preferably 0 to 6, more preferably 0 to 3, and even more preferably 1 to 3.

[0054] Specific examples of the present compound include the following compounds. [ka] [ka] [ka] [ka] [ka] [ka] [ka] However, m21 to m121 each independently represent the number of repetitions, and the bonding order of OCF2 and OCF2CF2 in the formula is arbitrary. f represents a fluoroalkylene group or a polyfluoropolyether chain. m21 to m121 each independently represent an integer of 1 to 500, and m1 is adjusted within the range of 1 to 500 as appropriate.

[0055] <Method of manufacturing the present compound> An example of a method for synthesizing compound (1) is method (A) in which the following compound (1A) is reacted with the following compound (1B) or the following compound (2B). R f2 -Q 1 (-T) n1+1 Formula (1A) R f1 -OH formula (1B) R f1 -COOH formula (2B) However, each symbol is the same as in formula (1), and the preferred embodiments are also the same.

[0056] An example of a method for synthesizing compound (2) is method (B) in which the following compound (2A) is reacted with the following compound (1B) or the following compound (2B). (T-) n2+1 Q 2-R f3 -Q 3 (-T) n3+1 Formula (2A) R f1 -OH formula (1B) R f1 -COOH formula (2B) However, each symbol is the same as in formula (2), and the preferred embodiments are also the same.

[0057] In all of the above synthesis methods, L in T is reacted with compound (1B) or compound (2B). f1 and R f2 , R in compound (2) f1 and R f3 It is easy to change the chain to a different polyfluoropolyether chain, which increases the degree of freedom in molecular design.

[0058] When compound (1A) and compound (2A) have a plurality of L's, the plurality of L's react with compound (1B) or compound (2B) to form a plurality of R's. f1 may be introduced (for example, the following compound (1C) or the following compound (2C)). {R f1 -A 1 -Si(R 1 )2}2-Q 1 (-T) n1-1 -R f2 Formula (1C) {R f1 -A 1 -Si(R 1 )2}2-Q 2 (-T) n2-1 -R f3 -Q 3 (-T) n3-1 {-Si(R 2 )2-A 2 -R f1}2 formula (2C) However, each symbol is the same as in formula (1) or formula (2), and the preferred embodiments are also the same.

[0059] However, it has been confirmed that compound (1) is predominantly produced by method (A), and compound (2) is predominantly produced by method (B). Compounds (1C) and (2C), which exist as by-products, can also function as coating agents that exhibit fingerprint removal properties and finger slipperiness, and as described below, they can be used as a coating agent as they are mixed with this compound.

[0060] Compound (1A) and compound (2A) can be synthesized with reference to, for example, International Publication No. 2017 / 038832, International Publication No. 2017 / 038830, International Publication No. 2018 / 216630, etc. Compound (1B) can be synthesized with reference to, for example, International Publication No. 2017 / 038832, etc. Compound (2B) can be synthesized with reference to, for example, International Publication No. 2017 / 038832, etc. Commercially available products may also be used.

[0061] [Fluorine-containing compound-containing composition] The fluorine-containing compound-containing composition of the present invention (hereinafter also referred to as the present composition) is a composition containing the fluorine-containing compound of the present invention, a fluorine-containing compound other than the present compound, and at least one of the impurities described below. Examples of impurities include compounds that are unavoidable in the production of the present compound and other fluorine-containing compounds. Note that the present composition does not contain a liquid medium, which will be described later.

[0062] Examples of other fluorine-containing compounds include fluorine-containing compounds produced as by-products in the production process of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), known fluorine-containing compounds used for the same purposes as the present compound, etc. Compounds (1A) and (2A) used as raw materials in the above synthesis method correspond to known fluorine-containing compounds used for the same purposes as the present compound. As the other fluorine-containing compound, a compound which is unlikely to deteriorate the properties of the present compound is preferred. In order to fully exhibit the properties of the present compound, the content of the other fluorine-containing 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 present composition.

[0063] Examples of by-produced fluorine-containing compounds include fluorine-containing compounds produced during the synthesis of the present compound. Examples include the above-mentioned compounds (1C) and (2C) which are replicated by the above-mentioned synthesis method. Since the compounds (1C) and (2C) can also function as coating agents that exhibit fingerprint removal properties and finger-smoothing properties, when the present composition contains by-produced fluorine-containing compounds, the purification step for removing the by-produced fluorine-containing compounds or reducing the amount of the by-produced fluorine-containing compounds can be simplified.

[0064] Known fluorine-containing compounds include, for example, those described in the following documents: perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097; perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Publication No. 2008-534696; Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A; Nolganosilicon compounds described in International Publication Nos. 2011 / 060047 and 2011 / 059430; fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in Japanese Patent Application Laid-Open No. 2012-72272; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Application Laid-Open No. 2015-199906, Japanese Patent Application Laid-Open No. 2016-204656, Japanese Patent Application Laid-Open No. 2016-210854, and Japanese Patent Application Laid-Open No. 2016-222859 Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, and WO 2019 / 163282 A. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Corporation, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0065] The proportion of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. When the present composition contains other fluorine-containing compounds, the proportion of the other fluorine-containing compounds relative to the total of the present compound and the other fluorine-containing compounds in the present composition is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. The total proportion of the present compound and other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more. When the content of this 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, finger slipperiness, and appearance.

[0066] [Coating liquid] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound or the present composition 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 compound or the present composition, and may contain impurities such as by-products produced in the manufacturing process of the present compound. The concentration of the present compound or the present composition 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.

[0067] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a mixture of both.

[0068] 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. Commercially available products include, for example, C6F 13 H (AGC Corporation, Asahiklin (registered trademark) AC-2000), C6F 13 Examples include C2H5 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (VERTREL (registered trademark) XF, manufactured by Chemours Corporation). Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The non-fluorine-based organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, or a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, and ester-based organic solvents. The present coating liquid preferably contains 75 to 99.999 mass %, more preferably 85 to 99.99 mass %, and particularly preferably 90 to 99.9 mass % of the liquid medium.

[0069] The present coating liquid may contain, in addition to the present compound or composition 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.

[0070] The total concentration of the present compound and other components or the total concentration of the present composition and other components in the present coating liquid (hereinafter also referred to as solids concentration) is preferably 0.001 to 40 mass%, preferably 0.01 to 20 mass%, more preferably 0.01 to 10 mass%, and more preferably 0.01 to 1 mass%. The solids concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0071] [Goods] FIG. 1 is a schematic cross-sectional view showing an example of an article of the present invention. The first article of the present invention is an article 20 having a substrate 12, an underlayer 14, and a surface layer 22 in this order, The underlayer contains a silicon-containing oxide, and the surface layer contains a condensate of the present compound.

[0072] The material and shape of the substrate in the first article may be appropriately selected depending on the intended use of the article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. Substrates that require water and oil repellency in particular include touch panel substrates, display substrates, and materials constituting the housings of electronic devices. Touch panel substrates and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0073] The substrate may be one that has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the undercoat layer is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate and the undercoat layer, and as a result, the abrasion resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferred in terms of further improving the abrasion resistance of the surface layer.

[0074] The underlayer is a layer containing at least an oxide containing silicon, and may further contain other elements. When the underlayer contains silicon oxide, the partial structure (2) of the present compound undergoes dehydration condensation, forming Si-O-Si bonds between the underlayer and the underlayer, resulting in the formation of a surface layer with excellent wear resistance.

[0075] The silicon oxide content in the underlayer may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the silicon oxide content is equal to or greater than the lower limit of the above range, Si-O-Si bonds are sufficiently formed in the underlayer, and the mechanical properties of the underlayer are sufficiently ensured. The silicon oxide content is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of the underlayer.

[0076] From the viewpoint of durability of the surface layer, it is preferable that the oxide in the underlayer further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten, which strengthens the bond between the underlayer and the present compound and improves wear resistance.

[0077] When the underlayer contains one or more elements selected from iron, nickel, and chromium, the total content of these elements relative to silicon oxide is preferably 10 to 1100 ppm by mass, more preferably 50 to 1100 ppm by mass, still more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass. When the underlayer contains one or more elements selected from aluminum and zirconium, the total content thereof is preferably from 10 to 2500 ppm by mass, more preferably from 15 to 2000 ppm by mass, and even more preferably from 20 to 1000 ppm by mass. When the underlayer contains an alkali metal element, the total content thereof is preferably 0.05 to 15 mass %, more preferably 0.1 to 13 mass %, and even more preferably 1.0 to 10 mass %. Examples of the alkali metal element include lithium, sodium, potassium, rubidium, and cesium. When the underlayer contains a platinum group element, the total content thereof is preferably 0.02 mass ppm to 800 mass ppm, more preferably 0.04 mass ppm to 600 mass ppm, and even more preferably 0.7 mass ppm to 200 mass ppm. Examples of the platinum group element include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the underlayer contains one or more elements selected from boron and phosphorus, the total content thereof is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, in terms of the ratio of the molar concentration of the sum of boron and phosphorus to the molar concentration of silicon, from the viewpoint of the wear resistance of the surface layer. When the underlayer contains alkaline earth metal elements, the total content thereof, expressed as the ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, from the viewpoint of the abrasion resistance of the surface layer. Examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0078] From the viewpoint of improving the adhesiveness of the present compound and improving the water / oil repellency and abrasion resistance of the article, the underlayer is preferably a silicon oxide layer containing alkali metal atoms. In particular, in the silicon oxide layer, the average concentration of alkali metal atoms in a region 0.1 to 0.3 nm deep from the surface in contact with the surface layer is 2.0 × 10 19 atoms / cm 3 On the other hand, in order to ensure sufficient mechanical properties of the silicon oxide layer, the average concentration of the alkali metal atoms is preferably 4.0×10 or more. 22 atoms / cm 3 It is preferable that:

[0079] The thickness of the underlayer is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the lower limit of the above range, the underlayer is likely to have a sufficient effect of improving adhesion. If the thickness of the underlayer is equal to or less than the upper limit of the above range, the abrasion resistance of the underlayer itself is increased. Methods for measuring the thickness of the underlayer include a method of observing the cross section of the underlayer using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

[0080] The underlayer may be formed, for example, by depositing a deposition material having a desired composition for the underlayer on the surface of the substrate. An example of the vapor deposition method is vacuum deposition, in which a deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 100 to 3000°C, particularly preferably 500 to 3000°C. The pressure during vapor deposition (for example, the absolute pressure in a tank in which a vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less. When the underlayer is formed using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used. Examples of evaporation methods for the deposition material include the resistance heating method, in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and the electron gun method, in which the deposition material is irradiated with an electron beam to directly heat the deposition material and melt and evaporate the surface. The electron gun method is preferred as an evaporation method for the deposition material because it can evaporate high-melting-point substances due to its ability to heat locally, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or the inclusion of impurities. The deposition material used in the electron gun method is preferably a molten granular or sintered body because it is less likely to scatter even when an air current is generated.

[0081] The surface layer on the underlayer contains a condensate of the present compound. Condensates of the present compound include those in which hydrolyzable silyl groups in the present compound undergo hydrolysis to form silanol groups (Si-OH), which then undergo intermolecular condensation to form Si-O-Si bonds, and those in which silanol groups in the present compound undergo condensation with silanol groups or Si-OM groups (wherein M is an alkali metal element) on the surface of the underlayer to form Si-O-Si bonds. The surface layer may also contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer contains a fluorine-containing compound having reactive silyl groups in a state in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone condensation reaction.

[0082] The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit of the above range, 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 of the above range, the utilization efficiency is high. The thickness of the surface layer is the thickness obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity analysis using an X-ray diffractometer for thin film analysis.

[0083] A second article of the present invention is an article 20 having a substrate 12 and a surface layer 22 in this order, the substrate contains an oxide containing silicon, The surface layer contains a condensate of the present compound.

[0084] In the second article, the substrate has the same composition as the undercoat layer in the first article, and therefore the surface layer has excellent abrasion resistance even when the surface layer is formed directly on the substrate. The material of the substrate in the second article may be any material having the composition of the underlayer, such as a glass substrate. Details of the material of the substrate are the same as those of the underlayer, and therefore a detailed description thereof will be omitted. Furthermore, the configuration of the surface layer is also the same as that of the first article, and therefore a detailed description thereof will be omitted.

[0085] [Production method] The method for producing an article according to the present invention is a method for forming a surface layer by a dry coating method or a wet coating method using the fluorine-containing compound, the fluorine-containing compound-containing composition, or the coating liquid.

[0086] The present compound and composition can be used directly in a dry coating method. The present compound and composition are suitable for forming a surface layer with excellent adhesion by a dry coating method. Dry coating methods include vacuum deposition, CVD, sputtering, and the like. The vacuum deposition method is suitable for use in terms of suppressing decomposition of the present compound and the simplicity of the equipment. For vacuum deposition, a pellet-shaped material in which the present compound is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped material supporting the present compound can be produced by impregnating a porous metal body with a solution of the present compound and drying it to remove the liquid medium. The solution of the present compound can be the present coating liquid.

[0087] The coating liquid can be suitably used for wet coating methods such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0088] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be carried out as necessary. Such an operation includes heating, humidification, light irradiation, etc. For example, by heating the substrate on which the surface layer has been formed in a humid atmosphere, reactions such as the hydrolysis reaction of the hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of the silanol groups can be promoted. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed, for example, by pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent. [Example]

[0089] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Examples 1 to 12 are working examples, and Examples 11 and 13 are comparative examples. In the following, CCl2FCClF2 is referred to as R-113, CClF2CF2CCl2CF2CF3 is referred to as R-419, CF3CH2OCF2CF2H is referred to as AE-3000, and CF 13 H is written as AC-2000, CF3CF2CHCl2 as AK-225, and C4F9OC2H5 as HFE-7200.

[0090] [Example 1] Synthesis of Compound I (Synthesis Example 1-1) The following compound (1a) was synthesized according to the method described in Example 3-4 of WO 2017 / 038832.

[0091] [ka] However, the average of x1 is 13.

[0092] (Synthesis Example 1-2) The following compound (1b) was synthesized according to the method described in Examples 1-5 of WO 2017 / 038832.

[0093] [ka] However, the average of y1 is 21 and the average of z1 is 20.

[0094] (Synthesis Example 1-3) In a 50 mL flask under a N2 atmosphere, 20.0 g of HFE-7200, 5.0 g of compound (1a), and an equimolar amount of compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (I). Si-NMR confirmed that a bond was formed between Si in compound (1a) and OH in compound (1b). The product was also confirmed by F-NMR.

[0095] [ka] However, the average of x1 is 13, the average of y1 is 21, and the average of z1 is 20.

[0096] [Example 2] Synthesis of Compound II (Synthesis Example 2-1) The following compound (2b) was synthesized according to the method described in Example 7 of WO 2013 / 121984.

[0097] [ka] However, the average of x2 is 13.

[0098] (Synthesis Example 2-2) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 2.0 g of compound (1a), and an equal mole of compound (2b) were added, heated to 60°C, and stirred to obtain the following compound (II). Si-NMR confirmed that a bond was formed between Si in compound (1a) and OH in compound (2b). The product was also confirmed by F-NMR.

[0099] [ka] However, the average of x2 is 13 and the average of y2 is 13.

[0100] [Example 3] Synthesis of Compound III (Synthesis Example 3-1) FLUOROL INK (registered trademark) D4000 (compound (3b) below) manufactured by Solvay Solexis was prepared. In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of compound (1a), and an equal mole of compound (3b) were added, heated to 60°C, and stirred to obtain the following compound (III). Si-NMR confirmed that a bond was formed between Si in compound (1a) and OH in compound (3b). The product was also confirmed by F-NMR.

[0101] [ka] However, the average of y3 is 21 and the average of z3 is 20.

[0102] [ka] However, the average of x3 is 13, the average of y3 is 21, and the average of z3 is 20.

[0103] [Example 4] Synthesis of Compound IV (Synthesis Example 4-1) The following compound (4a) was synthesized according to the method described in Example 11-3 of WO 2017 / 038830.

[0104] [ka] However, the average of x4 is 13.

[0105] (Synthesis Example 4-2) The following compound (4b) was synthesized according to the method described in Example 1-1 of WO 2017 / 038832.

[0106] [ka] However, the average of y4 is 21 and the average of z4 is 20.

[0107] (Synthesis Example 4-3) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 2.0 g of compound (4a), and an equimolar amount of compound (4b) were added, heated to 60°C, and stirred to obtain the following compound (IV). Si-NMR confirmed that a bond was formed between Si in compound (4a) and OH in compound (4b). The product was also confirmed by F-NMR.

[0108] [ka] However, the average of x4 is 13, the average of y4 is 21, and the average of z4 is 20.

[0109] [Example 5] Synthesis of Compound V (Synthesis Example 5-1) The following compound (5a) was synthesized according to the method described in Example 5-8 of WO 2018 / 216630.

[0110] [ka] However, the average of x5 is 9.

[0111] (Synthesis Example 5-2) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (5a), and an equal mole of the compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (V). The product was confirmed by NMR. Si-NMR confirmed that a bond was formed between Si in compound (5a) and OH in compound (1b). The product was also confirmed by F-NMR.

[0112] [ka] However, the average of x5 is 9, the average of y5 is 21, and the average of z5 is 20.

[0113] [Example 6] Synthesis of Compound VI (Synthesis Example 6-1) The following compound (6-1) was synthesized according to the method of Example 1 of WO 2013 / 121984, except that a fraction in which the average of x6 in the following formula (6-1) was 5 was collected by silica gel chromatography.

[0114] [ka] However, the average of x6 is 5.

[0115] (Synthesis Example 6-2) 9.0 g of compound (6-1), 50 g of Asahiklin AK-225 (product name, manufactured by AGC Corporation), and 7.5 g of 2.0 M ammonia-methanol solution were placed in a 100 cc pressure reactor and stirred at room temperature for 6 hours. Thereafter, the solvent was distilled off to obtain the following compound (6-2).

[0116] [ka]

[0117] (Synthesis Example 6-3) 9.0 g of compound (6-2), 75 g of AK-225, and 30 g of diethyl ether were added to a 300 cc recovery flask and stirred in an ice bath. Then, 0.31 g of lithium aluminum hydride was slowly added and stirred at room temperature. Then, 0.3 cc of saturated aqueous sodium sulfate solution was added, and the precipitated solid was removed by filtration through Celite. The resulting filtrate was concentrated and purified by silica gel column chromatography to obtain the following compound (6-3).

[0118] [ka]

[0119] (Synthesis Example 6-4) 0.2 g of HO(C=O)C(CH2CH=CH2)3, 10 mL of dichloromethane, and 0.2 mL of oxalyl chloride were added to a 50 cc recovery flask and stirred under ice cooling, followed by the addition of 0.02 g of DMF (N,N-dimethylformamide). After stirring at room temperature, the mixture was concentrated to obtain 0.18 g of Cl(C=O)C(CH2CH=CH2)3. Separately, 1.8 g of compound (6-3) and 0.35 mL of triethylamine were added to a 50 cc recovery flask, and the above Cl(C=O)C(CHCH=CH) and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was distilled off. The resulting crude product was purified by silica gel column chromatography to obtain the following compound (6-4).

[0120] [ka]

[0121] (Synthesis Example 6-5) A 50 cc recovery flask purged with nitrogen was charged with 0.6 g of compound (6-4), 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0009 g of aniline, and 1.0 g of AC-6000 (product name, manufactured by AGC Corporation), followed by the addition of 0.11 g of trimethoxysilane and stirring at 40° C. The same amounts of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were then added and stirred for 7 hours, after which the solvent was distilled off to obtain compound (6a) below.

[0122] [ka]

[0123] (Synthesis Example 6-6) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 0.5 g of the compound (6a), and an equimolar amount of the compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (VI). Si-NMR confirmed that a bond was formed between Si in compound (6a) and OH in compound (1b). The product was also confirmed by F-NMR.

[0124] [ka] However, the average of x6 is 5, the average of y6 is 21, and the average of z6 is 20.

[0125] [Example 7] Synthesis of Compound VII (Synthesis Example 7-1) 3.0 g of the following compound (7-1), 0.55 g of HO-CHC(CHCH=CH) , 0.14 g of NaF, and 3.0 g of AC-2000 were placed in a 50 ml recovery flask and stirred for 5 hours at 30° C. The obtained crude product was purified by silica gel chromatography to obtain the following compound (7-2).

[0126] [ka] However, the average of x7 is 13.

[0127] [ka]

[0128] (Synthesis Example 7-2) A 50 cc recovery flask purged with nitrogen was charged with 1.0 g of compound (7-2), 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0009 g of aniline, and 1.0 g of AC-6000, followed by the addition of 0.11 g of trimethoxysilane and stirring at 40° C. Then, the same amounts of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were added and stirred, and the solvent was then distilled off to obtain compound (7a).

[0129] [ka]

[0130] (Synthesis Example 7-3) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.5 g of the compound (7a), and an equal mole of the compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (VII). Si-NMR confirmed that a bond was formed between Si in compound (7a) and OH in compound (1b). The product was also confirmed by F-NMR.

[0131] [ka] However, the average of x7 is 13, the average of y7 is 21, and the average of z7 is 20.

[0132] [Example 8] Synthesis of Compound VIII (Synthesis Example 8-1) Compound (8-1) was synthesized by the same synthesis method as that described in Synthesis Examples 1 to 4 of Japanese Patent No. 6024816. CH3OCOCF2-(OCF2) x8 -(OCF2CF2) y8 -OCF2CO2CH3 formula (8-1) However, the average of x8 is 26 and the average of y8 is 22.

[0133] (Synthesis Example 8-2) Compound (8-2) was synthesized according to the method described in (Example 13-1) to (Example 13-2) of WO 2018 / 216630. CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2OTs Formula (8-2) (OTs represents -O-SO2-Ph-CH3, where Ph represents a phenylene group.)

[0134] (Synthesis Example 8-3) A 300 mL three-neck flask was charged with 4 g of compound (8-2), 30 g of compound (8-1), and 160 g of 1,3-bis(trifluoromethyl)benzene, followed by the addition of 12 g of cesium carbonate. The mixture was stirred at 70°C under a nitrogen atmosphere. The solid was filtered and washed with water, and the organic phase was recovered. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 12 g of compound (8-3). CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CH2-OH Formula (8-3)

[0135] (Synthesis Example 8-4) In a 100 mL recovery flask, 12 g of compound (8-3) and 2.3 g of sodium fluoride powder were placed, and 11 g of CFCFCFOCF(CF)C(O)F was added. The mixture was stirred under a nitrogen atmosphere. After removing the sodium fluoride powder by filtration, the excess CFCFCFOCF(CF)C(O)F was distilled off under reduced pressure to obtain 12 g of compound (8-4). CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CH2-OC(O)CF(CF3)OCF2CF2CF3 formula (8-4)

[0136] (Synthesis Example 8-5) A condenser maintained at 20°C, a packed bed of NaF pellets, and another condenser maintained at 0°C were installed in series at the gas outlet of a 1-liter nickel autoclave. A liquid return line was installed to return the condensed liquid from the condenser maintained at 0°C to the autoclave. 750 g of CFE-419 was placed in an autoclave and stirred while maintaining the temperature at 25°C. Nitrogen gas was bubbled into the autoclave at 25°C for 1 hour, followed by 20% fluorine gas bubbled in at a flow rate of 2.0 L / h for 1 hour at 25°C. While the 20% fluorine gas was bubbled in at the same flow rate, a solution of 6.0 g of compound (8-4) dissolved in 54 g of CFE-419 was injected into the autoclave over 1 hour. While the 20% fluorine gas was bubbled in at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was bubbled into the autoclave while heating from 25°C to 40°C, and the benzene solution inlet on the autoclave was closed. After stirring, 4 mL of the benzene solution was again bubbled in while maintaining the temperature at 40°C, and the inlet was closed. The same procedure was repeated. The total amount of benzene injected was 0.17 g. Stirring was continued while blowing in 20% fluorine gas at the same flow rate. The pressure inside the autoclave was adjusted to atmospheric pressure, and nitrogen gas was blown in. The contents of the autoclave were concentrated using an evaporator to obtain 6.1 g of compound (8-5). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CF2-OC(O)CF(CF3)OCF2CF2CF3 formula (8-5)

[0137] (Synthesis Example 8-6) 6.1 g of compound (8-5) and 10 g of AK-225 were placed in a PFA round-bottom flask. While stirring in an ice bath, 10 g of methanol was slowly added dropwise from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours. The reaction mixture was concentrated using an evaporator to obtain 5.5 g of compound (8-6). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-C(O)OCH3 Formula (8-6)

[0138] (Synthesis Example 8-7) A 300 cc three-necked round-bottom flask was charged with 2.4 g of sodium borohydride powder and 15 g of AC-2000. The mixture was cooled in an ice bath while stirring, and under a nitrogen atmosphere, a solution containing 30 g of compound (8-6), 4 g of methanol, and 60 g of AC-2000 was slowly added dropwise from the dropping funnel so that the internal temperature did not exceed 10°C. After the entire amount had been added, an additional 4 g of methanol was added dropwise. The mixture was then stirred at 10°C. The mixture was again cooled in an ice bath, and aqueous hydrochloric acid solution was added dropwise. After the reaction was completed, the mixture was washed with hydrochloric acid and then with water to recover the organic phase, which was then concentrated and evaporated under reduced pressure to obtain compound (8-7). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CH2-OH Formula (8-7)

[0139] (Synthesis Example 8-8) 0.67 g of HO(C=O)C(CH2CH=CH2)3, 33 mL of dichloromethane, and 0.67 mL of oxalyl chloride were added to a 200 cc recovery flask and stirred under ice cooling, followed by the addition of 0.0393 g of DMF (N,N-dimethylformamide). After stirring at room temperature, the mixture was concentrated to obtain 0.6 g of Cl(C=O)C(CH2CH=CH2)3. Separately, 7 g of compound (8-7), 7 g of AC-6000, 0.4 g of triethylamine, 0.2 g of N,N-dimethyl-4-aminopyridine were added to a 50 cc recovery flask, and 0.6 g of the above Cl(C=O)C(CHCH=CH) was added, followed by stirring at 30° C. The resulting reaction solution was purified by silica gel chromatography to obtain compound (8-8). CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CH2-O(C=O)C(CH2CH=CH2)3 formula (8-8)

[0140] (Synthesis Examples 8-9) A nitrogen-purged 50 cc recovery flask was charged with 1.0 g of compound (8-8), 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0009 g of aniline, and 1.0 g of AC-6000, followed by 0.11 g of trimethoxysilane and stirring for 4 hours at 40° C. Then, 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were added and stirred, and the solvent was then distilled off to obtain 1.1 g of compound (8a).

[0141] [ka] However, the average of x8 is 26 and the average of y8 is 22.

[0142] (Synthesis Examples 8-10) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (8a), and an equimolar amount of the compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (VIII). Si-NMR confirmed that a bond was formed between Si in compound (8a) and OH in compound (1b). The product was also confirmed by F-NMR.

[0143] [ka] However, the average of x8 is 26, the average of y8 is 22, the average of z8 is 21, and the average of w8 is 20.

[0144] [Example 9] Synthesis of Compound IX (Synthesis Example 9-1) According to the method described in Example 7 of WO 2013 / 121984, the following compound (9-1) was obtained. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x9 (CF2CF2O)-CF2CF2CF2-CH2OH...Formula (9-1) However, the average for x9 is 14.

[0145] (Synthesis Example 9-2) The compound (9-1) (6.8 g, 1.5 mmol), 2,6-lutidine (0.76 g, 7.1 mmol), and AE-3000 (28.0 g) were added and stirred at 0°C. Trifluoromethanesulfonic anhydride (0.99 g, 3.5 mol) was added, and the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 6.8 g of the following compound (9-2). CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x9 (CF2CF2O)-CF2CF2CF2-CH2OTf...Formula (9-2) Here, OTf is triflate: -OS(=O)2(-CF3).

[0146] (Synthesis Example 9-3) Diethyldiallylmalonate (60.0 g, 250 mmol), lithium chloride (23.7 g, 559 mmol), water (6.5 g, 360 mmol), and dimethyl sulfoxide (263 g) were added and stirred at 160°C. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic layer, which was washed with saturated brine and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (9-3).

[0147] [ka]

[0148] (Synthesis Example 9-4) After adding THF (260 mL) and diisopropylamine (29.8 mL, 294 mmol), the solution was cooled to -78 °C. A n-butyllithium hexane solution (2.76 M, 96.6 mL, 294 mmol) was added, and the mixture was heated to 0 °C. After stirring, the mixture was cooled to -78 °C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (9-3) (39.5 g, 235 mmol) was added to the THF solution, and after stirring, allyl bromide (24.1 mL, 278 mmol) was added. The mixture was heated to 0 °C, 1 M hydrochloric acid (100 mL) was added, and the THF was evaporated under reduced pressure. Extraction with dichloromethane was followed by the addition of sodium sulfate. After filtration, the solvent was evaporated, and the mixture was subjected to flash column chromatography using silica gel to obtain 45.0 g of compound (9-4).

[0149] [ka]

[0150] (Synthesis Example 9-5) The above compound (9-4) (45.0 g, 216 mmol) was dissolved in THF (620 mL) and cooled to 0°C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (9-5).

[0151] [ka]

[0152] (Synthesis Example 9-6) Acetonitrile (380 mL), the compound (9-5) (31.3 g, 188 mmol), triphenylphosphine (64.3 g, 245 mmol), and carbon tetrachloride (33.9 g, 221 mmol) were added and stirred at 90°C. After concentration, ethyl acetate / hexane was added and stirred. After filtration and concentration, 28.2 g of the following compound (9-6) was obtained by distillation (70°C, 3 hPa).

[0153] [ka]

[0154] (Synthesis Example 9-7) To magnesium (2.36 g, 97.2 mmol), THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added and stirred at room temperature. A solution of the compound (9-6) (14.0 g, 75.9 mmol) in THF (35 mL) was added, and the mixture was heated under reflux for 2 hours to prepare a solution (0.80 M) of the following compound (9-7).

[0155] [ka]

[0156] (Synthesis Example 9-8) 1-Bromo-4-chlorobutane (2.9 g, 16.8 mmol), 1-phenyl-1-propyne (0.20 g, 1.7 mmol), and CuCl (0.05 g, 0.36 mmol) were added and stirred at 0°C. Compound (9-7) (0.80 M, 24.0 mL, 19.3 mmol) was added and stirred. 1 M hydrochloric acid was added, and the mixture was extracted with dichloromethane, followed by addition of sodium sulfate. After filtration and concentration, the mixture was distilled (120°C, 3 hPa) to obtain 3.45 g of the following compound (9-8).

[0157] [ka]

[0158] (Synthesis Example 9-9) To magnesium (0.17 g, 6.9 mmol), THF (2.6 mL) and iodine (14.0 mg, 0.055 mmol) were added and stirred at room temperature. A solution of the compound (9-8) (1.41 g, 5.9 mmol) in THF (2.6 mL) was added, and the mixture was heated under reflux for 2 hours to prepare a solution (0.74 M) of the following compound (9-9).

[0159] [ka]

[0160] (Synthesis Examples 9-10) CuCl2 (9.9 mg, 0.074 mmol), 1-phenyl-1-propyne (0.019 g, 0.16 mmol), 1,3-bistrifluoromethylbenzene (23 mL), and the compound (9-2) (1.5 g, 0.32 mmol) were added, followed by the compound (9-9) (4.5 mL, 1.0 M, 3.3 mmol). After stirring at room temperature, the mixture was washed with 1 M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was removed by distillation, and AC-6000 was added. After washing with DMF and MeOH, flash column chromatography using silica gel was performed to obtain 0.25 g of the following compound (9-10).

[0161] [ka]

[0162] (Synthesis Examples 9-11) AC2000 (1.5 g), the above compound (9-10) (0.25 g, 0.048 mmol), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 8.9 mg), aniline (1.3 mg), and trimethoxysilane (26.9 mg, 0.221 mmol) were added and stirred at 40°C. The solvent was then distilled off under reduced pressure to obtain 0.25 g of the fluorine-containing ether compound (9a) shown below. The Mw / Mn of compound (9a) determined by the above GPC method was 1.06.

[0163] [ka]

[0164] (Synthesis Examples 9-12) A 100 mL PFA recovery flask was charged with 25 g of the following compound (9-12), 0.93 g of 20% aqueous KBr solution, 0.2 g of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), and 25 g of acetonitrile to obtain a mixture. The resulting mixture was stirred, and a mixture of 18 g of 25% by mass aqueous sodium hypochlorite solution and 2.5 g of sodium bicarbonate was slowly added. The mixture was heated at 40 °C for approximately 48 hours to obtain a reaction mixture. After cooling, the resulting reaction mixture was acidified by adding 30 g of 10% aqueous sulfuric acid solution and 30 g of AC-2000. The mixture was washed three times each with water and saturated brine, and the organic phase was recovered. The organic phase was then mixed with 10.0 g of silica gel and filtered. The recovered organic phase was concentrated using an evaporator to obtain the following compound (9b). CF3-O-(CF2CF2OCF2CF2CF2CF2O) y9 CF2CF2OCF2CF2CF2-CH2OH Formula (9-12) However, the average for y9 is 13.

[0165] [ka]

[0166] (Synthesis Examples 9-13) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of compound (9a), and an equimolar amount of compound (9b) were added, heated to 60°C, and stirred to obtain the following compound (IX). Si-NMR confirmed that a bond was formed between Si in compound (9a) and OH in compound (9b). The product was also confirmed by F-NMR.

[0167] [ka] However, the average of x9 is 14 and the average of y9 is 13.

[0168] [Example 10] Synthesis of Compound X (Synthesis Example 10-1) In a 50 mL flask under a N atmosphere, 10.0 g of HFE-7200, 2.0 g of the compound (9a), and an equal mole of the compound (1b) were added, and the mixture was heated and stirred at 60° C. to obtain the following compound (X). The product was confirmed by NMR.

[0169] [ka] However, the average of x10 is 14, the average of y10 is 21, and the average of z10 is 20.

[0170] [Example 11] Synthesis of Compound XI (Synthesis Example 11-1) The following compound (XI) was obtained according to Example 6 of WO 2013 / 121084.

[0171] [ka] However, the average of x11 is 13.

[0172] [Example 12] Synthesis of Compound XII (Synthesis Example 12-1) The following compound (12a) was obtained in Synthesis Example 1 and Synthesis Example 2 of WO 2019 / 151445.

[0173] [ka] However, the average of x12 is 22.

[0174] (Synthesis Example 12-2) In a 50 mL flask under a N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (12a), and an equimolar amount of the compound (1b) were added, heated to 60°C, and stirred to obtain the following compound (XII). Si-NMR confirmed that a bond was formed between Si in the compound (12a) and OH in the compound (1b). The product was also confirmed by F-NMR.

[0175] [ka] However, the average of x12 is 22, the average of y12 is 21, and the average of z12 is 20.

[0176] [Production and evaluation of goods] The surface of the substrate was treated with each of the compounds obtained in Examples 1 to 12, and a mixture XIII (referred to as Example 13) of the compound (1a) and the compound (1b), to obtain an article having a surface layer. For each example, the surface layer was formed by surface treatment using the following dry coating method and wet coating method (this process is also referred to as Process A). Furthermore, the surface layer of each article after Process A in each example was wiped with a Bemcot wetted with isopropyl alcohol while a sufficient load was applied (also referred to as Process B). Chemically strengthened glass was used as the substrate. The resulting articles were evaluated by the following methods. The results are shown in Table 1.

[0177] (Dry coating method) Dry coating was carried out using a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC Corporation) (vacuum deposition method). 0.5 g of each of the compounds or mixtures obtained in Examples 1 to 13 was placed in a molybdenum boat in the vacuum deposition apparatus, and the interior of the vacuum deposition apparatus was heated to 1×10 -3The boat containing the compound was heated at a rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the substrate. The substrate on which the compound had been deposited was heat-treated at 200°C for 30 minutes and washed with isopropyl alcohol to obtain an article having a surface layer on the surface of the substrate.

[0178] (wet coating method) Each compound or mixture obtained in Examples 1 to 13 was mixed with C4F9OC2H5 (3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating liquid with a solids concentration of 0.05%. A substrate was dipped into the coating liquid, left for 30 minutes, and then pulled out (dip coating method). The coating film was dried at 200°C for 30 minutes and washed with isopropyl alcohol to obtain an article having a surface layer on the surface of the substrate.

[0179] (Evaluation method) <Finger smoothness> The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a variable load friction wear test system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under conditions of contact area: 3 cm x 3 cm, load: 0.98 N. The smaller the dynamic friction coefficient, the better the finger sliding. The evaluation criteria are as follows: ◎ (Excellent): Coefficient of dynamic friction is less than 0.15. ○ (Good): Coefficient of dynamic friction is 0.15 or more and less than 0.20. △ (Acceptable): Coefficient of dynamic friction is 0.20 or more and less than 0.25. × (Not acceptable): Coefficient of dynamic friction is 0.25 or more.

[0180] <Fingerprint removability> A fingerprint stamp was prepared by applying artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of a silicone rubber stopper and then wiping off excess oil with a nonwoven fabric (Bencotto (registered trademark) M-3, manufactured by Asahi Kasei Corporation). The fingerprint stamp was placed on the surface layer and pressed with a load of 9.8 N for 10 seconds. The haze of the fingerprint-adhered area was measured with a haze meter and recorded as the initial value. The fingerprint-adhered area was wiped with a reciprocating traverse tester (manufactured by KNT Corporation) equipped with tissue paper at a load of 4.9 N. The haze value was measured after each wiping stroke, and the number of wiping strokes required to reduce the haze to 10% or less of the initial value was counted. The fewer the wiping strokes, the easier it was to remove fingerprint stains and the better the fingerprint stain wiping ability. The evaluation criteria are as follows. ◎ (Excellent): Wiping required 3 times or less. ○ (Good): Wiping was performed 4 to 6 times. △ (Acceptable): Wipe 6 to 8 times. × (Not acceptable): Wiping more than 9 times.

[0181] [Table 1]

[0182] Compound I to compound X, R f1 -A 1 -Si(R 1 It was revealed that the surface layer using this compound having the structure of (I)2- has excellent finger smoothness and fingerprint removability. From a comparison with the results of Example 13 in which Compound (1a) and Compound (1b), which are raw materials for Compound I, were mixed, it was revealed that this compound has significantly better finger smoothness and fingerprint removability than the mixture of raw materials. [Industrial Applicability]

[0183] Articles having a surface layer containing the present compound are useful as, for example, optical articles used as parts of the following products, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc. Products: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic light-emitting diode (OLED) displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0184] This application claims priority based on Japanese Patent Application No. 2020-137440, filed on August 17, 2020, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0185] 10: Base material with undercoat layer, 12: Base material, 14: Undercoat layer, 20: Article, 22: Surface layer

Claims

1. A fluorine-containing ether compound represented by the following formula (1): {(R ｆ１ -A １ -) ｐ１ Si(-R １ ) ３－ｐ１} ｑ１ -Q １ (-T) ｎ１ (-R ｆ２ ) ｒ１ Formula (1) however, R ｆ１ is a monovalent polyfluoropolyether chain represented by the following formula (3A), and a plurality of R ｆ１ may be the same or different from each other, R ｆ２ is a monovalent polyfluoropolyether chain, and there are multiple R ｆ２ may be the same or different from each other, Each A 1 is independently —O— or C(═O)—O—, and a plurality of A 1 s may be the same or different from each other; R １ represents an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 s may be the same or different; Q １ is a linking group with a valence of q1+n1+r1, T is -Si(-R) ３－ａ (-L) ａ When two or more T's are present, the two or more T's may be the same or different, R is an alkyl group, L represents a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different; a is 2 or 3; q1 is an integer of 1 or more, When q1 is 1, p1 is 1 or 2; when q1 is 2 or more, p1 is an integer from 0 to 3, at least one of the multiple p1s is 1 or 2, and the multiple p1s may be the same or different; n1 is an integer of 0 or more, r1 is an integer of 1 or more, L １ -R ｆ１１ａ -(OR ｆ１２ ) ｍ１ -(CH ２ ) ｓ１ - Formula (3A) L １ represents a hydrogen atom, a fluorine atom, a hydroxyl group, —C(O)X, —C(O)OR １０ , -C(O)N(R １０ ) ２ and X is a hydrogen atom or a halogen atom; R １０ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom, or a phenyl group which may have a fluorine atom, and R １０ If there are multiple R １０ may be the same or different from each other, R ｆ１１ａ is a fluoroalkylene group having 1 to 20 carbon atoms, R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, there are multiple R ｆ１２ may be the same or different, s1 is an integer from 0 to 20, Q １ , Q ２ , and Q ３ are each independently represented by any one of the following formulas (5-1) to (5-7): 【Chemistry 1】 (-A １１ -Q １２ -)C(-R ｅ２ ) ２－ｄ３ (-Q ３２ -) (-Q ２２ -) ｄ３ Formula (5-2) (-A １１ -Q １３ -)N(-Q ３３ -) (-Q ２３ -) Formula (5-3) (-A １１ -Q １４ -)Z(-Q ３４ -)(-Q ２４ -) ｄ４ Formula (5-4) (-A １１ -Q １５ -)Yes(-R ｅ３ ) ２－ｄ５ (-Q ３５ -)(-Q ２５ -) ｄ５ formula (5-5) -A １１ -Q １２ -\H(-Q ３２ -)-Yes(R ｅ３ ) ３－ｄ６ (-Q ２５ -) ｄ６ formula (5-6) -A １１ -Q １２ -\H(-Q ２２ -)-Yes(R ｅ３ ) ２－ｄ７ (-Q ３５ -)(-Q ２５ -) ｄ７ formula (5-7) However, in the formulas (5-1) to (5-7), A １１ The side is connected to Rf2, and the Q ２２ , Q ２３ , Q ２４ , or Q ２５ The side connects to T, and Q ３２ , Q ３３ , Q ３４ , or Q ３５ is connected to R via Si ｆ１ Connect to A １１ represents a single bond, -C(O)NR ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - and Q １１ represents a single bond, -C(O)NR ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ -, an alkylene group, or an alkylene group having two or more carbon atoms, with -C(O)NR between carbon atoms. ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - is a group having Q １２ represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - is a group having Q １３ is a single bond (where A １１ is —C(O)—), an alkylene group, an alkylene group having 2 or more carbon atoms having —C(O)NR between carbon atoms. ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ or a group having —C(O)— at the N-terminal of the alkylene group, Q １４ Is, Q １４ When the atom in Z to which is bonded is a carbon atom, Q １２ and Q １４ When the atom in Z to which is bonded is a nitrogen atom, Q １３ and Q １５ represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - is a group having Q ２２ and Q ３２ each independently represents an alkylene group, an alkylene group having 2 or more carbon atoms with —C(O)NR between carbon atoms; ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ a group having -, -C(O)NR at the end of the alkylene group not connected to Si; ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ or a group having —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - and -C(O)NR at the end not connected to Si ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ -, and Q ２２ If there are multiple Qs, ２２ may be the same or different, Q ２３ and Q ３３ each independently represents an alkylene group or an alkylene group having 2 or more carbon atoms with —C(O)NR between carbon atoms; ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ - is a group having Q ２４ and Q ３４ are each independently ２４ or Q ３４ When the atom in Z to which is bonded is a carbon atom, Q ２２ or Q ３２ and Q ２４ or Q ３４ When the atom in Z to which is bonded is a nitrogen atom, Q ２３ or Q ３３ and Q ２４ If there are multiple Qs, ２４ may be the same or different, Q ２５ and Q ３５ each independently represents an alkylene group or an alkylene group having 2 or more carbon atoms with —C(O)NR between carbon atoms; ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, -SO ２ NR ６ -or-NR ６ SO ２ -, and Q ２５ If there are multiple Qs, ２５ may be the same or different, Z is Q １４ , Q ２４ and Q ３４ is a group having a d4+2-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, and R １ If there are multiple R １ may be the same or different, R ｅ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R ｅ３ is an alkyl group, R ６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 6; d3 is 1 or 2; d4 is an integer of 1 or more, d5 is 1 or 2, d6 is an integer from 1 to 3, d7 is 1 or 2, The hydrolyzable group is an alkoxy group, a halogen atom, an acyl group, or an isocyanate group.

2. The R ｆ２ The fluorine-containing ether compound according to claim 1, wherein the fluorine-containing ether compound is represented by the following formula (3): R ｆ１１ -(OR ｆ１２ ) ｍ１ - Formula (3) however, R ｆ１１ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, m1 is an integer from 0 to 500, and when m1 is 2 or more, there are multiple R ｆ１２ may be the same or different.

3. A fluorinated ether composition comprising the fluorinated ether compound according to claim 1 or 2 and another fluorinated ether compound.

4. A coating liquid comprising the fluorinated ether compound according to claim 1 or 2 or the fluorinated ether composition according to claim 3, and a liquid medium.

5. An article having a surface layer formed from the fluorinated ether compound according to claim 1 or 2 or the fluorinated ether composition according to claim 3 on the surface of a substrate.

6. 10. A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the fluorinated ether compound according to claim 1 or 2, the fluorinated ether composition according to claim 3, or the coating liquid according to claim 4.

7. An article as described in claim 5, which is an optical article.

8. The article described in claim 5, which is a touch panel.

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