FLUORINE-CONTAINING ETHER COMPOUND, FLUORINE-CONTAINING ETHER COMPOSITION, COATING LIQUID, ARTICLE, AND METHOD FOR PRODUCING ARTICLE

Abstract

Provided are: a fluoroether compound, a fluoroether composition, and a coating fluid which are able to form surface layers having excellent finger slipperiness and excellent durability; an article having a surface layer which has excellent durability and can retain finger slipperiness and fingerprint removability over a long period; and a method for producing said article.　The fluoroether compound is represented by formula (1).　Formula (1): (T)p1-Q1-A-E1-A-O-Q2-(T)p2 The symbols in the formula are as defined in the description.

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 because they can impart excellent water and oil repellency, abrasion resistance, low fingerprint adhesion, fingerprint stain removability, and lubricity to the surface of a substrate. Since the fluorine-containing ether compounds can form a surface layer exhibiting these properties on the surface of a substrate, they are suitably used in surface treatment agents.

[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 removability 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 fluorine-containing ether compounds and the like described in Patent Document 1 are said to have high abrasion resistance. However, there is an increasing demand for even higher abrasion resistance, and there is a demand for surface treatment agents that exhibit even better abrasion resistance.

[0006] The present invention aims to provide a fluorinated ether compound, a fluorinated ether composition and a coating liquid capable of forming a surface layer having excellent durability, an article having a surface layer having excellent durability and capable of maintaining water / oil repellency, lubricity and fingerprint stain removability for a long period of time, and a method for producing the same. [Means for solving the problem]

[0007] The present invention provides a fluorine-containing compound 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, each having the following configurations [1] to

[12] . [1] A fluorinated ether compound represented by the following formula (1): (T) p1 -Q 1 -A 1 -E 1 -A 2 -OQ 2 -(T) p2 Formula (1) however, A 1 and A 2 are each independently a (poly)oxyfluoroalkylene group consisting of an oxyfluoroalkylene unit having 1 to 4 carbon atoms, 1 and multiple A's 2 may be independently the same or different, E 1 is a (poly)oxyfluoroalkylene group consisting of oxyfluoroalkylene units having 5 to 6 carbon atoms, Q 1 is a (1+p1)-valent linking group, Q 2 is a (1+p2)-valent linking group, T is -Si(R) 3-c (L) c wherein a plurality of T's may be the same or different; R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and a plurality of L's in each T may be the same or different from each other. p1 and p2 each independently represents an integer of 1 or more. [2] A fluorinated ether compound of [1] represented by the following formula (2): (T) p1 -Q 1 -(OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 -OQ 2 -(T) p2 Formula (2) however, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 4 carbon atoms, and R f1 or R f2 If there are multiple, there are multiple R f1 or R f2 may be the same or different, R f3 is a fluoroalkyl group having 5 to 6 carbon atoms, and R f3 If there are multiple, there are multiple R f3 may be the same or different, k1 and k2 each independently represent an integer of 1 to 200, k3 is an integer from 1 to 20. [3] (OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 The fluorine-containing ether compound according to [2], wherein the molecular weight of the moiety is 2,000 to 20,000. [4] The fluorinated ether compound according to [2] or [3], wherein a ratio of k1 to k2 (k1 / k2) is 0.01 to 200. [5] R f1 and R f2 wherein each of said groups independently represents a fluoroalkyl group having 1 to 2 carbon atoms. [6] A fluorinated ether compound of any one of [2] to [5], wherein k3 is 1. [7] A fluorine-containing compound-containing composition comprising any one of the fluorine-containing compounds [1] to [6] and another fluorine-containing compound. [8] A coating liquid comprising a fluorinated ether compound according to any one of [1] to [6] or a fluorinated ether composition according to [7], and a liquid medium. [9] An article having a surface layer formed on the surface of a substrate from any one of the fluorinated ether compounds [1] to [6] or the fluorinated ether composition [7].

[10] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using a fluorinated ether compound of any one of [1] to [6], a fluorinated ether composition of [7], or a coating liquid of [8]. Effect of the Invention

[0008] The present invention can provide a fluorinated ether compound, a fluorinated ether composition and a coating liquid capable of forming a surface layer having excellent durability, an article having a surface layer having excellent durability and capable of maintaining water / oil repellency, lubricity and fingerprint stain removability for a long period of time, and a method for producing the same. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an article of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In this specification, the partial structure represented by formula (1) may be referred to as partial structure (1). Also, the compound represented by formula (4) may be referred to as compound (4). The same applies to other formulas. In this specification, the term "perfluoroalkyl group" refers to a group in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms. In addition, in this specification, the term "fluoroalkyl group" refers to an alkyl group having a fluorine atom, and includes a perfluoroalkyl group. The same applies to a fluoroalkylene group. As used herein, the following terms have the following meanings: The term "reactive silyl group" is a general term for a hydrolyzable silyl group and a silanol group (Si-OH). The term "hydrolyzable silyl group" refers to a group that can form a silanol group by hydrolysis. The term "surface layer" refers to a layer formed on the surface of a substrate. The term "(poly)oxyfluoroalkylene group" is a general term including oxyfluoroalkylene groups and polyoxyfluoroalkylene groups. 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 The number average molecular weight is calculated by determining the number (average value) of oxyfluoro(cyclo)alkylene units based on the terminal groups using F-NMR. The symbol "~" indicating a range of numerical values ​​means that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0011] [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). (T) p1 -Q 1 -A 1 -E 1 -A 2 -OQ 2 -(T) p2 Formula (1) however, A 1 and A 2 are each independently a (poly)oxyfluoroalkylene group consisting of an oxyfluoroalkylene unit having 1 to 4 carbon atoms, 1 and multiple A's 2 may be independently the same or different, E 1 is a (poly)oxyfluoroalkylene group consisting of oxyfluoroalkylene units having 5 to 6 carbon atoms, Q 1is a (1+p1)-valent linking group, Q 2 is a (1+p2)-valent linking group, T is -Si(R) 3-c (L) c wherein a plurality of T's may be the same or different; R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and a plurality of L's in each T may be the same or different from each other. p1 and p2 each independently represents an integer of 1 or more.

[0012] The compound has a polyfluoropolyether chain (A 1 -E 1 -A 2 ), a reactive silyl group, and a specific linking group (Q 1 and Q 2 ) is a compound having the formula:

[0013] This compound has reactive silyl groups at both ends. This compound having reactive silyl groups at the ends is strongly chemically bonded to the substrate, and therefore has excellent abrasion resistance of the surface layer. It also has a polyfluoropolyether chain. This compound having a polyfluoropolyether chain has excellent fingerprint stain removal properties of the surface layer. Furthermore, the polyether chain of this compound contains a (poly)oxyfluoroalkylene group E consisting of an oxyfluoroalkylene unit having 5 to 6 carbon atoms. 1 (Hereinafter, fluoroalkylene E 1 ) is a (poly)oxyfluoroalkylene group A consisting of oxyfluoroalkylene units having 1 to 4 carbon atoms. 1 and A 2 (hereinafter, also referred to as fluoroalkylene A) is linked to a reactive silyl group via a linking group. The fluoroalkylene A has flexibility, and the fluoroalkylene E 1 is estimated to have a more rigid structure than fluoroalkylene A. This compound is similar to fluoroalkylene E. 1The presence of fluoroalkylene E makes it easier for intermolecular interactions to occur between the molecules of the present compound, and the surface layer formed by the present compound 1 As a result, the surface layer formed by this compound has excellent durability. 1 is linked to a reactive silyl group via flexible fluoroalkylene A, it is presumed that the surface layer also has excellent abrasion resistance and finger slipperiness. From the above, the surface layer formed by the present compound is characterized by excellent finger sliding property and excellent durability such as abrasion resistance.

[0014] A 1 and A 2 are each independently a (poly)oxyfluoroalkylene group consisting of oxyfluoroalkylene units having 1 to 4 carbon atoms. 1 and A 2 In view of excellent abrasion resistance, fingerprint stain removability, and finger sliding properties of the surface layer, structures represented by the following formula (A-1) and formula (A-2) are preferred. (OR f1 ) k1 Formula (A-1) (OR f2 ) k2 Formula (A-2) However, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 4 carbon atoms, and R f1 or R f2 If there are multiple, there are multiple R f1 or R f2 may be the same or different, and k1 and k2 each independently represent an integer of 1 to 200.

[0015] k1 and k2 are A 1 and A 2In the present compound, from the viewpoint of durability of the surface layer, the ratio of k1 to k2 (k1 / k2) is preferably within a range of 0.001 to 200, more preferably within a range of 0.01 to 100, further preferably within a range of 0.02 to 50, and particularly preferably within a range of 0.1 to 5.

[0016] Of the structures represented by formula (A-1) and formula (A-2), a structure represented by the following formula (a) is preferred in terms of excellent abrasion resistance, fingerprint removability, and finger sliding properties of the surface layer. (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 Formula (a) however, R f11 is a fluoroalkylene group having one carbon atom, R f12 is a fluoroalkylene group having 2 carbon atoms, R f13 is a fluoroalkylene group having 3 carbon atoms, R f14 is a fluoroalkylene group having 4 carbon atoms, m1, m2, m3, and m4 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4 represents an integer of 1 to 200, and R f11 ~R f14 If there are multiple R f11 ~R f14 may be the same or different. In addition, (R f11 O)~(R f14 The bonding order of m1 to m4 in formula (A-1) is any of (R f11 O)~(R f14 O), not the arrangement. For example, (R f11 O) m1 is (R f11 O) is m1, and (R f1 O)m1 It does not represent the block arrangement structure of (R f12 O)~(R f14 The order of the units does not represent the bonding order of the units. In addition, the fluoroalkylene group having 3 to 4 carbon atoms may be a straight-chain fluoroalkylene group, or a fluoroalkylene group having a branched or cyclic structure.

[0017] R f11 Specific examples of R include -CF2- and -CHF-. f12 Specific examples of R include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, and -CH2CHF-. f13 Specific examples of the compound include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)- CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F) -CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-, and the like. R f14Specific examples of the compound include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHF Examples include CHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -CF(CF3)CF2CF2-, and the like.

[0018] Examples of fluoroalkylene groups having a ring structure include groups of the following formula: In the formula, * indicates a bond, and some of the fluorine atoms in the formula may be replaced with hydrogen atoms.

[0019] [ka]

[0020] In the present compound, among the structures represented by formula (A-1) and formula (A-2), the structure represented by the following formula (a1) is preferred from the viewpoints of excellent abrasion resistance of the surface layer, removability of fingerprint stains, and finger sliding properties. (R f11 O) m1 (R f12 O) m2 Formula (a1) However, R f11 , R f12 is as defined above, m1 and m2 each independently represent an integer of 0 or 1 or more, and m1+m2 is an integer of 1 to 200.

[0021] A of this compound 1 and A 2However, the durability is further improved by using a (poly)oxyfluoroalkylene group consisting of oxyfluoroalkylene units having 1 to 2 carbon atoms. In formula (a1), the ratio of m1 to m2 (m1 / m2) is preferably within the range of 0.02 to 50, more preferably within the range of 0.05 to 30, and even more preferably within the range of 0.1 to 20, from the viewpoint of durability of the surface layer.

[0022] E 1 is a (poly)oxyfluoroalkylene group consisting of oxyfluoroalkylene units having 5 to 6 carbon atoms. 1 is excellent in terms of the abrasion resistance of the surface layer, the removability of fingerprint stains, and the smoothness of fingers, and is determined by the following formula (E 1 The structure represented by -1) is preferred. (OR f3 ) k3 Formula (E 1 -1) However, R f3 is a fluoroalkyl group having 5 to 6 carbon atoms, and R f3 If there are multiple, there are multiple R f3 may be the same or different, and k3 is an integer of 1 to 20.

[0023] k3 is E 1 In the present compound, k3 is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1, from the viewpoints of durability and finger sliding property of the surface layer.

[0024] Furthermore, the formula (E 1 The structure represented by formula (1) is preferably a structure represented by the following formula (b) in terms of excellent abrasion resistance, fingerprint stain removability, and finger sliding properties of the surface layer. (R f15 O) m5 (R f16 O) m6 Formula (b) however, R f15 is a fluoroalkylene group having 5 carbon atoms, R f16is a fluoroalkylene group having 6 carbon atoms, m5 and m6 each independently represent an integer of 0 or 1 or more, m5+m6 represents an integer of 1 to 20, R f15 and R f16 If there are multiple R f15 and R f16 may be the same or different. In addition, (R f15 O) and (R f16 The bond order of m5 and m6 in formula (b) is (R f15 O) and (R f16 O), not the arrangement.

[0025] The fluoroalkylene group having 5 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or a fluoroalkylene group having a branched or cyclic structure. R f15 Specific examples of R include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2-, and -CH2CF2CF2CF2CH2-. f16 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, and the like.

[0026] In this compound, the polyfluoropolyether chain (A 1-E 1 -A 2 ) is preferably a structure represented by the following formula (Rf): (OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 Formula (Rf) Here, each symbol in the formula is as defined above. In addition, (OR f1 ) k1 , (OR f3 ) k3 , and (OR f2 ) k2 Each of these constitutes a block. That is, in this compound, for example, -OR f3 -OR f1 -OR f3 Structures in which fluoroalkylene groups having 1 to 4 carbon atoms are arranged between fluoroalkylene groups having 5 to 6 carbon atoms, such as -, are not included.

[0027] In this compound, the polyfluoropolyether chain (OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 The proportion of fluorine atoms [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and still more preferably 80% or more, in view of excellent water and oil repellency and fingerprint removability.

[0028] In this compound, the polyfluoropolyether chain (OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 The molecular weight of the portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000, from the viewpoint of excellent abrasion resistance, fingerprint stain removability, and finger smoothness of the surface layer.

[0029] Polyfluoropolyether chain (A 1 -E 1 -A 2 Specific examples of the above include the following: -OCF2CF2(OCF2CF2CF2CF2OCF2CF2) m11 -OCF2CF2CF2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2) m12 -OCF2CF2-, -(OCF2) m13 (OCF2CF2) m14 OCF2CF2CF2CF2CF2(OCF2CF2) m15 (OCF2) m16 -, -(OCF2) m17 (OCF2CF2) m18 OCF2CF2CF2CF2CF2CF2(OCF2CF2) m19 (OCF2) m20 -, -(OCF2CF2) m21 OCF2CF2CF2CF2CF2CF2(OCF2CF2) m22 -, -OCF2CF2(OCF2) m23 (OCF2CF2) m24 OCF2CF2CF2CF2CF2CF2(OCF2CF2) m25 (OCF2) m26 OCF2CF2-, -(OCF2) m27 (OCF2CF2) m28 OCF2CH2OCF2CF2CF2-(OCF2) m29 (OCF2CF2) m30 OCF2CF2CF2CF2CF2CF2(OCF2CF2CF2) m31 -, -OCF2CF2(OCF2CF2CF2CF2OCF2CF2) m32 OCF2CF2CF2CF2CF2(OCF2CF2) m33 (OCF2) m34 -, -(OCF2CF2CF2) m35 OCF2CF2CF2CF2CF2CF2(OCF2CF2CF2)m36 -. Here, m11 to m36 are integers of 1 or more, and the upper limit values ​​of m11 to m36 are adjusted according to the upper limit values ​​of k1 and k2.

[0030] Q 1 is a (1+p1)-valent linking group, and Q 2 is a (1+p2)-valent linking group. 1 Q 2 More on this later.

[0031] Q 1 When is trivalent or greater, it preferably has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (1+p1)-valent noruganopolysiloxane residue.

[0032] As the ring structure, from the viewpoints of ease of production of the present compound and of further improving the abrasion resistance, light resistance and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle and a condensed ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is particularly preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an etheric oxygen atom between the carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group or an oxo group (=O).

[0033] [ka]

[0034] Examples of the (1+p1)-valent organopolysiloxane residue include the following groups. 5 R 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.

[0035] [ka]

[0036] Q 1 is an alkylene group, a fluoroalkylene group, a hydroxyalkylene group, an alkoxyalkylene group, a carbonyl group, an amide bond, an ether bond, a thioether bond, a urea bond, a urethane bond, a carbonate bond, an ester bond, -SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue. 6 is 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 of Q is preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the present compound. 1 Each bond or group constituting the 1 -E 1 -A 2 For example, the amide bond may be located on the polyfluoropolyether chain (A 1 -E 1 -A 2 ) side of the nitrogen atom, 1 -E 1 -A 2 ) side. The same applies to other bonds and groups.

[0037] Examples of the divalent organopolysiloxane residue include groups represented by the following formula: 7 R 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.

[0038] [ka]

[0039] Q 1 is preferred because it is easy to prepare this compound. 6 -, -C(O)-, -C(O)OR 6 -, -NR 6 -, -OC(O)OR 6 It is preferable that the surface layer has at least one bond selected from the group consisting of -, -, and O-. In terms of further improving the durability of the surface layer, it is preferable that the surface layer has at least one bond selected from the group consisting of -C(O)NR 6 It is particularly preferred that it has - or C(O)-.

[0040] Q 1 Examples of the alkyl group include a combination of two or more divalent hydrocarbon groups and one or more branch points P, or a combination of two or more hydrocarbon groups, one or more branch points P, and one or more bonds B. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group (such as an alkylene group or a cycloalkylene group) and a divalent aromatic hydrocarbon group (such as a phenylene group). 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.

[0041] Linking group Q is excellent in water and oil repellency, abrasion resistance, and fingerprint stain removal properties. 1 is preferably a group represented by any one of the following formulas (Q1) to (Q9).

[0042] [ka]

[0043] -A 11 -C(R e2 ) 3-e2 (-Q 22 -) e2 Formula (Q2) -A 11 -N(-Q 23 -)2nd formula (Q3) -A 11 -Z 1 (-Q 24 -)h2 Formula (Q4) -A 11 -Si(R e3 ) 3-i2 (-Q 25 -) i2 Formula (Q5) -A 11 -Q 26 - Formula (Q6) -A 11 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 Formula (Q7) -A 11 -[CH2C(R e4 )(-Q 27 -)] i4 -R e5 Formula (Q8) -A 11 -Z a (-Q 28 -) i5 Equation (Q9) However, in formulas (Q1) to (Q9), A 11 side is a polyfluoropolyether chain (A 1 -E 1 -A 2 ) and Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 The side is connected to a reactive silyl group (T).

[0044] A 11 represents a single bond, an alkylene group, or -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 8 -, -C(O)ONR 8 -, -NR 8 C(O)-, -NR 8 C(O)O-, -NR 8 C(O)NR 8 -, -O- or -SONR 8 In each formula, A 11If there are two or more, then there are two or more A 11 may be the same or different. A hydrogen atom of the alkylene group may be substituted with a fluorine atom. 11 The number of carbon atoms is preferably 1 to 6.

[0045] Q 11 is a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 8 -, -NR 8 C(O)NR 8 -, -C(O)-, -C(O)O-, -OC(O)O-, -NR 8 - or a group having O-. 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)- or -NR 8 - or -O-, -C(O)NR at the end of the alkylene group not connected to Si 8 -, -C(O)-, -NR 8 - or -O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms 8 -, -C(O)-, -NR 8 - or -O- and -C(O)NR at the end not connected to Si 8 -, -C(O)-, -NR 8 - or -O-, 22 If there are two or more, then there are two or more Q 22 may be the same or different. Q 23 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 8 -, -C(O)-, -NR 8 - or -O-, and two Q 23 may be the same or different. Q 24 Q 24 Z bonded to 1 If the atom in is a carbon atom, then Q 22 And Q 24 Z bonded to 1 If the atom in is a nitrogen atom, Q23 In each formula, Q 24 If there are two or more, then there are two or more Q 24 may be the same or different. Q 25 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 8 -, -C(O)-, -NR 8 - or -O-, 25 If there are two or more, then there are two or more Q 25 may be the same or different. Q 26 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 8 -, -C(O)-, -NR 8 - or a group having -O-. R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; R 8 If there are multiple, there are multiple R 8 may be the same or different. Q 27 is a single bond or an alkylene group. Q 28 is an alkylene group, or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms in an alkylene group having two or more carbon atoms.

[0046] R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Z 1 A 11 has a carbon atom or nitrogen atom to which Q is directly bonded 24 is a group having a (1+h2)-valent ring structure having a carbon atom or nitrogen atom to which is directly bonded. R e1 is a hydrogen atom or an alkyl group, and in each formula, R e1 If there are two or more, there are two or more R e1 may be the same or different. R e2is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. R e3 is an alkyl group. R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom in terms of ease of production of the compound. e4 If there are two or more, there are two or more R e4 may be the same or different. R e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in terms of ease of production of the compound.

[0047] d2 is an integer of 0 to 3, and preferably 1 or 2. d4 is an integer of 0 to 3, and preferably 2 or 3. d2+d4 is preferably 2 to 5. e2 is 2 or 3. h2 is an integer of 1 or more (preferably 2 or 3). i2 is 2 or 3. i3 is either 2 or 3. i4 is 1 or more (preferably an integer from 1 to 10, and particularly preferably an integer from 1 to 6). i5 is an integer from 2 to 7.

[0048] Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , Q 28 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of the present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, in the case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.

[0049] Z 1 The ring structure in the formula (I) is the same as that described above, and the preferred forms are also the same. 1 The ring structure in 11 Or Q 24is directly bonded to the ring structure, for example, an alkylene group is connected to the alkylene group, and A 11 Or Q 24 are never linked. Z a is an (i5+1)-valent noruganopolysiloxane residue, with the aforementioned groups being preferred.

[0050] Other preferred embodiments of the organic group A include groups represented by any of the following formulae (Q11) to (Q19).

[0051] [ka]

[0052] -A 11 -C(R e2 ) 3-e2 (-Q 22 -G 1 ) e2 Formula (Q12) -A 11 -N(-Q 23 -G 1 )2 formula (Q13) -A 11 -Z 1 (-Q 24 -G 1 ) h2 Formula (Q14) -A 11 -Si(R e3 ) 3-i2 (-Q 25 -G 1 ) i2 Formula (Q15) -A 11 -Q 26 -G 1 Formula (Q16) -A 11 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 Formula (Q17) -A 11 -[CH2C(R e4 )(-Q 27 -G1 )] i4 -R e5 Formula (Q18) -A 11 -Z a (-Q 28 -G 1 ) i5 Formula (Q19) However, in formulas (Q11) to (Q19), A 1 The side is connected to the substructure (1), and G 1 The side connects to the substructure (2).

[0053] G 1 is a group represented by the following formula (G1), and in formulas (Q11) to (Q19), G 1 If there are two or more, there are two or more G 1 may be the same or different. G 1 The symbols other than are the same as those in formulas (Q11) to (Q19). -Si(R 9 ) 3-r1 (-Q 30 -) r1 Formula (G1) However, in formula (G1), the Si side is Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connect to Q 30 The side is connected to a reactive silyl group (T). R 9 is an alkyl group. 30 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 8 -, -C(O)-, -NR 8 - or a group having -O-, or -(OSi(R 10 )2) p11 -O- and 2 or more Q 3 may be the same or different. r1 is 2 or 3. R 8 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 10is an alkyl group, a phenyl group, or an alkoxy group, and two R 10 may be the same or different. p11 is an integer of 0 to 5, and when p is 2 or more, (OSi(R 10 )2) may be the same or different.

[0054] Q 30 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 of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, in the case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2. R 9 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the present compound. R 10 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the present compound. R 10 The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of excellent storage stability of the present compound. p11 is preferably 0 or 1.

[0055] Linking group Q 2 is the linking group Q 1 In the above, except for replacing p1 with p2, 1 In the present compound, the linking group Q 1 and Q 2 From the viewpoint of ease of production of the present compound, etc., the linking group Q 1 and Q 2 are preferably the same.

[0056] Linking group Q 1 and Q 2 A preferred example of the structure is the following:1 are each independently a hydrogen atom or a fluorine atom, and n is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2. Rf in the formula represents (T) in formula (1). p1 -Q 1 -A 1 -E 1 -A 2 -O, T is the same as T in formula (1), and these are Q 2 In the formula below, the linking group Q 2 However, the linking group Q 1 A similar structure can be mentioned for

[0057] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0058] T is -Si(R) 3-c (L) c which is a reactive silyl group. The reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group further 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. As the hydrolyzable group, an alkoxy group or a halogen atom is preferred from the viewpoint of easy production of the present compound. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred from the viewpoint of less outgassing during coating and excellent storage stability of the present compound, an ethoxy group is particularly preferred when the present compound requires long-term storage stability, and a methoxy group is particularly preferred when the reaction time after coating is short. The number of carbon atoms in the alkyl group for R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the present compound. c is preferably 2 or 3, and more preferably 3, in that the adhesion between the surface layer and the substrate is stronger.

[0059] The number of reactive silyl groups T in the present compound may be 2 or more, and is preferably 2 to 18, more preferably 2 to 12, and even more preferably 4 to 8. If the number of reactive silyl groups is equal to or more than the above lower limit, the number of bonds with the substrate increases, resulting in excellent durability. On the other hand, if the number is equal to or less than the above upper limit, the fluorine ratio in the present compound is increased, resulting in excellent water / oil repellency and abrasion resistance. A plurality of T's may be the same or different. From the viewpoint of ease of production of the present compound, it is preferable that T's are the same group.

[0060] Examples of the present compound include compounds of the following formula: The compounds of the following formula are easy to produce industrially, and provide a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removal properties, and lubricity.

[0061] [ka] Here, n1 to n24 are each independently an integer of 1 or more, and the upper limit values ​​of n11 to n24 are adjusted according to the upper limit values ​​of k1 and k2.

[0062] [Method of producing fluorine-containing ether compound] This compound has a polyfluoropolyether chain (A 1 -E 1 -A 2 ) or a precursor chain thereof is used as a raw material, the method of producing the polyfluoropolyether compound can be the same as that of the known fluorine-containing ether compound used as a surface treatment agent. The method of introducing a linking group and a hydrolyzable silyl group into the polyfluoropolyether chain can be, for example, the method described in WO 2017 / 187775, WO 2017 / 038832, etc. Hereinafter, the polyfluoropolyether chain (A 1 -E 1 -A 2 Two examples of methods for synthesizing a compound containing the polyfluoropolyether or its precursor chain are described below, but the method is not limited to these. The precursor chain refers to a chain that becomes a polyfluoropolyether chain when fluorinated by a method such as Synthesis Example 1-3 in the Examples described later.

[0063] Polyfluoropolyether chain (A 1 -E 1 -A 2 A first method for obtaining a compound containing the above-mentioned aryl group or a precursor chain thereof includes reacting a compound represented by the following formula (11) with a compound represented by the following formula (12) to obtain the following compound (13). HO-E 11 -OH formula (11) C(L 11 )2=C(L11 )-A 21 -OH formula (12) HO-{A 21 -C(L 11 )2-CH(L 11 )} n11 -OE 11 -O-{C(L 11 )2-CH(L 11 )-A 21} n12 -OH formula (13) however, E 11 represents a (poly)oxyfluoroalkylene group or (poly)oxyalkylene group having one or more units selected from a fluoroalkylene unit and an alkylene unit having 5 to 6 carbon atoms, or a fluoroalkylene group or alkylene group having 5 to 6 carbon atoms, A 21 is a (poly)oxyfluoroalkylene group or (poly)oxyalkylene group consisting of one or more units selected from an oxyfluoroalkylene unit and an oxyalkylene unit, 11 may be the same or different, L 11 is a hydrogen atom or a fluorine atom, and 11 may be the same or different, n11 and n12 each independently represents an integer of 1 to 200. In addition, in the formula (13), {A 21 -C(L 11 )2-C(L 11 )2} n11 is A in formula (1). 1 or its precursor, {A 21 -C(L 11 )2-C(L 11 )2} n12 A 2 or a precursor thereof. In the first method, the hydroxyl group of compound (11) and the double bond of compound (12) undergo an addition reaction, and then the hydroxyl group derived from compound (12) and the double bond of another compound (12) undergo an addition reaction in sequence to form compound (13).

[0064] In addition, the polyfluoropolyether chain (A 1 -E 1 -A 2 A second method for obtaining a compound containing the above-mentioned aryl group or a precursor chain thereof includes reacting a compound represented by the following formula (21) with a compound represented by the following formula (22) to obtain the following compound (23). XE 11 -X formula (21) OH-A 22 -OH formula (22) H.O.A. 22 -OE 11 -OA 12 -OH formula (23) E 11 is the same as in the above formula (11), A 22 is a (poly)oxyfluoroalkylene group or (poly)oxyalkylene group consisting of one or more units selected from an oxyfluoroalkylene unit and an oxyalkylene unit, 22 may be the same or different, X is a chlorine atom, a bromine atom, an iodine atom, or a sulfonate group. In the second method, X in compound (21) and the hydroxyl group of compound (22) undergo an addition reaction to form compound (23). The sulfonate group in X includes a tosylate group, a mesylate group, a triflate group, etc. X is preferably an iodine atom or a sulfonate group, more preferably an element atom.

[0065] [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 compound, a fluorine-containing compound other than the present compound, and at least one of the following impurities. Examples of impurities include compounds that are unavoidable in the production of the present compound and other fluorine-containing compounds. The present composition does not contain a liquid medium described later.

[0066] Examples of other fluorine-containing compounds include fluorine-containing compounds produced as a by-product during the production of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), and 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 preferable. 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.

[0067] Examples of the by-product fluorine-containing compound include unreacted fluorine-containing compounds during the synthesis of the present compound, etc. When the present composition contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

[0068] Examples of known fluorine-containing compounds include those described in the following documents: Perfluoropolyether-modified aminosilanes described in JP-A-11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP 2000-144097 A; Perfluoropolyether-modified aminosilanes described in 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 as described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A, 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 JP 2012-72272 A; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; Perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, and WO 2019 / 163282. In addition, examples of 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, OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0069] 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 mass % or more, and more preferably 85 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, lubricity and appearance.

[0070] [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.

[0071] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both.

[0072] 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 (ASAHIKLIN (registered trademark) AC-2000, manufactured by AGC), 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 a carbon number of 4 to 12. 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 the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. As the non-fluorinated organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents. The present coating liquid preferably contains 75 to 99.999 mass %, more preferably 85 to 99.99 mass %, and particularly preferably 90 to 99.9 mass %, of the liquid medium.

[0073] The present coating liquid may contain, in addition to the present compound or composition and the liquid medium, other components within the scope of not impairing the effects of the present invention. Examples of other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. 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.

[0074] 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 solid content 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 solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0075] [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 undercoat layer 14, and a surface layer 22 in this order, The underlayer contains an oxide containing silicon, and the surface layer contains a condensate of the present compound.

[0076] The material and shape of the substrate in the first article may be appropriately selected according to the application of the article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. In particular, substrates that require water and oil repellency include substrates for touch panels, substrates for displays, and materials that constitute the housings of electronic devices. Substrates for touch panels and substrates for displays have translucency. "Translucency" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the substrate for touch panels is preferably glass or transparent resin.

[0077] The substrate may be one that has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc., on the surface on which the undercoat layer is to be provided. The surface that has been subjected to the surface treatment has better 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 from the viewpoint of better abrasion resistance of the surface layer.

[0078] 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 to form Si-O-Si bonds between the underlayer and the underlayer, forming a surface layer with excellent wear resistance.

[0079] The content of silicon oxide 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 content of silicon oxide is equal to or more 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 secured. The content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of the underlayer.

[0080] From the viewpoint of durability of the surface layer, it is preferable that the oxide in the underlayer further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bond between the underlayer and the present compound is strengthened, and the wear resistance is improved.

[0081] 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, even 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 further 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 further 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 of the elements 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 elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the underlayer contains one or more elements selected from boron and phosphorus, the total content of these elements is, in terms of the ratio of the molar concentration of boron and phosphorus combined to the molar concentration of silicon, preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, in terms of the abrasion resistance of the surface layer. When the underlayer contains alkaline earth metal elements, the total content of these elements, 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 further preferably 0.007 to 2, from the viewpoint of the wear resistance of the surface layer. Examples of the alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0082] From the viewpoint of improving the adhesiveness of the present compound and improving the water / oil repellency and abrasion resistance of the article, the undercoat layer 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 preferably 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:

[0083] 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 sufficiently improve the adhesiveness. If the thickness of the underlayer is equal to or less than the upper limit of the above range, the underlayer itself is highly resistant to wear. 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 gauge, a spectroscopic ellipsometer, a step gauge, etc.

[0084] The underlayer can be formed, for example, by depositing a deposition material having a desired composition for the underlayer on the surface of the substrate. An example of the deposition method is a vacuum deposition method in which a deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during deposition (for example, the temperature of a boat in which a deposition material is placed when a vacuum deposition apparatus is used) is preferably 100 to 3000°C, particularly preferably 500 to 3000°C. The pressure during deposition (for example, when using a vacuum deposition apparatus, the absolute pressure in a tank in which the deposition material is placed is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less. When the underlayer is formed using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used. Examples of the evaporation method of 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 and directly heated to melt and evaporate the surface of the deposition material. The electron gun method is preferred as the evaporation method of the deposition material because it can evaporate high melting point substances because it can heat locally, and because the areas not irradiated by the electron beam are at low temperature, there is no risk of reaction with the container or contamination with impurities. The deposition material used in the electron gun method is preferably a molten granular body or a sintered body because it is less likely to scatter even when an air current is generated.

[0085] The surface layer on the underlayer contains the condensate of the present compound. The condensate of the present compound includes those in which a hydrolyzable silyl group in the present compound is hydrolyzed to form a silanol group (Si-OH), and the silanol group is condensed between molecules to form a Si-O-Si bond, and those in which a silanol group in the present compound is condensed with a silanol group or a Si-OM group (wherein M is an alkali metal element) on the surface of the underlayer to form a Si-O-Si bond. 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 a reactive silyl group in a state in which a part or all of the reactive silyl group of the fluorine-containing compound is condensed.

[0086] 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 is 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 by an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.

[0087] 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.

[0088] 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, for example, a glass substrate. The details of the substrate material are the same as those of the underlayer, and therefore will not be described here. The configuration of the surface layer is also the same as that of the first article, and therefore will not be described here.

[0089] [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.

[0090] The compound and the composition can be used as is in a dry coating method. The compound and the composition are suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. The vacuum deposition method is suitable for use in terms of suppressing the decomposition of the compound and the simplicity of the device. For vacuum deposition, a pellet-shaped material in which the present compound is supported on a metal porous body made of a metal material such as iron or steel may be used. The pellet-shaped material in which the present compound is supported can be produced by impregnating a metal porous body with a solution of the present compound, and then drying to remove the liquid medium. The present coating liquid can be used as the solution of the present compound.

[0091] The coating liquid can be suitably used in wet coating methods, such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, the Langmuir-Blodgett method, and gravure coating.

[0092] In order to improve the abrasion resistance of the surface layer, if necessary, an operation for promoting the reaction between the present compound and the substrate may be carried out. Such an operation includes heating, humidification, light irradiation, etc. For example, the substrate on which the surface layer is formed can be heated in a humid atmosphere to promote reactions such as hydrolysis reaction of hydrolyzable groups, reaction between hydroxyl groups and silanol groups on the surface of the substrate, and formation of siloxane bonds by condensation reaction of silanol groups. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, pouring a solvent onto the surface layer, wiping it off with a cloth soaked in the solvent, etc. EXAMPLES

[0093] 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 7 and 10 to 12 are examples, and Examples 8 to 9 are comparative examples. In the following, CCl2FCClF2 is R-113, CClF2CF2CCl2CF2CF3 is R-419, CF3CH2OCF2CF2H is AE-3000, and C6F 13 H is referred to as AC-2000 and CF3CF2CHCl2 is referred to as AK-225.

[0094] [Example 1] Synthesis of Compound I (Synthesis Example 1-1) In a 200 mL eggplant flask, 10.0 g of HO-CH2CF2CF2CF2CF2CH2-OH and 11.6 g of potassium carbonate were added and stirred at 120 ° C., and 159.1 g of CF2 = CF-O-CF2CF2CF2CH2-OH was added and stirred at 120 ° C. for 2 hours. The temperature was returned to 25 ° C., and 79.6 g of AC-2000 and 27.6 g of 2N hydrochloric acid were added, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 67 g of the following compound (1-1).

[0095] [ka] The average of x1+y1 is 12.

[0096] (Synthesis Example 1-2) In a 50 mL eggplant flask connected to a reflux condenser, 50 g of the compound (1-1) obtained in Synthesis Example 1-1, 3.2 g of sodium fluoride powder, 50 g of AC-2000, and 40 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and then the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 56.9 g of the following compound (1-2).

[0097] [ka] The average of x1+y1 is 12.

[0098] (Synthesis Example 1-3) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. A CFE-419 solution of compound (1-2) obtained in Synthesis Example 1-2 (concentration: 10% by mass, compound (1-2): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (1-2) (mol / hour) was controlled to be 2:1. After the introduction of compound (1-2) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 28.4 g of compound (1-3).

[0099] [ka] The average of x1+y1 is 12.

[0100] (Synthesis Example 1-4) In a 50 mL eggplant flask, 25 g of the compound (1-3) obtained in Synthesis Example 1-3, 1.8 g of sodium fluoride, and 25 mL of AC-2000 were placed and stirred in an ice bath. 1.6 g of methanol was added and stirred at 25° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 19.6 g of compound (1-4).

[0101] [ka] The average of x1+y1 is 12.

[0102] (Synthesis Example 1-5) 5.5 g of the compound (1-4) obtained in Synthesis Example 1-4 and 0.5 g of H2NCH2CH2CH2Si(OCH3)3 were placed in a 300 mL recovery flask and stirred for 6 hours. Unreacted materials and by-product methanol were removed by vacuum distillation, and the mixture was filtered through a 0.2 μm membrane filter to obtain 5.9 g of the following compound I.

[0103] [ka] The average value of x1+y1 is 12, and the number average molecular weight of compound I is 5,450.

[0104] [Example 2] Synthesis of Compound II (Synthesis Example 2-1) In a 500 mL flask, 10.0 g of HO-CH2CF2CF2CF2CH2-OH, 23.9 g of triethylamine, 0.1 g of N,N-dimethyl-4-aminopyridine, and 150 g of dichloromethane (CH2Cl2) were placed and stirred at 0°C for 10 minutes. Then, 22.5 g of paratoluenesulfonyl chloride dissolved in 100 g of dichloromethane was slowly added. The mixture was sealed with nitrogen and stirred at 0°C for 5 hours. The mixture was extracted with diethyl ether and concentrated under reduced pressure. The mixture was then purified by column chromatography, the solvent was distilled off, and 10.6 g of the following compound (2-1) was obtained.

[0105] [ka] Here, Ts is a tosyl group.

[0106] (Synthesis Example 2-2) In a 500mL flask, 34.4g of the following compound (2a), 6.6g of Cs2CO3, and 5g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 5g of the compound (2-1) obtained in Synthesis Example 2-1 in 30g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Next, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. Then, the mixture was purified by column chromatography, the solvent was distilled off, and 11.9g of the following compound (2-2) was obtained.

[0107] [ka] The average of x2 is 7.2 and the average of y2 is 9.2.

[0108] [ka]

[0109] (Synthesis Example 2-3) In a 50 mL eggplant flask connected to a reflux condenser, 10 g of the compound (2-2) obtained in Synthesis Example 2-2, 0.7 g of sodium fluoride powder, 10 g of AC-2000, and 9.3 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 11.6 g of the following compound (2-3).

[0110] [ka]

[0111] (Synthesis Example 2-4) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. A CFE-419 solution of compound (2-3) obtained in Synthesis Example 2-3 (concentration: 10% by mass, compound (2-3): 20 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (2-3) (mol / hour) was controlled to be 2:1. After the introduction of compound (2-3) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was removed by distillation to obtain 19.8 g of compound (2-4).

[0112] [ka]

[0113] (Synthesis Example 2-5) In a 50 mL recovery flask, 10.0 g of the compound (2-4) obtained in Synthesis Example 2-4 and 0.7 g of CsF were placed, and the temperature was raised to 80° C. to thermally decompose the ester. In order to remove the low-boiling point components as by-products from the system, the pressure was reduced to 10 mmHg while maintaining the temperature at 80° C., and this was maintained for 1 hour to obtain 8.2 g of the following compound (2-5).

[0114] [ka]

[0115] (Synthesis Example 2-6) In a reaction vessel, 1.3 g of tetrahydrofuran and 2.5 g of 1,3-bistrifluoromethylbenzene were mixed, and 0.7 g of 0.7 M allyl magnesium bromide was dropped. Then, 300 g of the compound (2-5) obtained in Synthesis Example 2-5 was slowly dropped, and the mixture was heated at 60°C for 4 hours. After the heating was completed, the mixture was cooled to room temperature, and the solution was dropped into a 1.2 M aqueous hydrochloric acid solution to stop the reaction. The lower layer, the fluorine compound layer, was recovered by a separation operation, and then washed with acetone. The fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure, to obtain 3.8 g of the following compound (2-6).

[0116] [ka]

[0117] (Synthesis Example 2-7) In a 100 mL PFA eggplant flask, 2.0 g of compound (2-6), 0.04 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.28 g of HSi(OCH3)3, 0.02 g of dimethyl sulfoxide, and 2 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 11.9 g of the following compound II.

[0118] [ka] The average of x2+x2 is 14.4, and the average of (y2+1)+(y2+1) is 20.4.

[0119] [Example 3] Synthesis of Compound III (Synthesis Example 3-1) In a 200mL eggplant flask, 49.3g of ethylene glycol, 7g of sodium carbonate, and 56g of water were placed and stirred at 120°C. 30g of CF2=CF-O-CF2CF2CF2CF2CF2CH2-OH was added and stirred at 120°C for 2 hours. The temperature was returned to 25°C, 150g of AC-2000 and 150g of 2N hydrochloric acid were added, the liquids were separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 12.4g of the following compound (3-1).

[0120] [ka]

[0121] (Synthesis Example 3-2) In a 500 mL flask, 10 g of the compound (3-1), 11.5 g of triethylamine, 0.1 g of N,N-dimethyl-4-aminopyridine, and 150 g of dichloromethane (CH2Cl2) were placed and stirred at 0°C for 10 minutes. Then, 10.8 g of paratoluenesulfonyl chloride dissolved in 100 g of dichloromethane was slowly added. The mixture was sealed with nitrogen and stirred at 0°C for 5 hours. The mixture was extracted with diethyl ether and concentrated under reduced pressure. The mixture was then purified by column chromatography, and the solvent was distilled off to obtain 8.2 g of the following compound (3-2).

[0122] [ka] Here, Ts is a tosyl group.

[0123] (Synthesis Example 3-3) In a 500mL flask, 92.3g of the following compound (3a), 7.3g of Cs2CO3, and 8g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 8g of the compound (3-2) obtained in Synthesis Example 3-2 in 30g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Next, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. Then, the mixture was purified by column chromatography, the solvent was distilled off, and 25.6g of the following compound (3-3) was obtained.

[0124] [ka] The average of x3 is 20.1, and the average of y3 is 22.6.

[0125] [ka]

[0126] (Synthesis Example 3-4) In a 50 mL eggplant flask connected to a reflux condenser, 25 g of the compound (3-3), 0.8 g of sodium fluoride powder, 25 g of AC-2000, and 9.6 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 26.3 g of the following compound (3-4).

[0127] [ka]

[0128] (Synthesis Example 3-5) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (3-4) (concentration: 10% by mass, compound (3-4): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (3-4) (mol / hour) was controlled to be 2:1. After the introduction of compound (3-4) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 24.2 g of compound (3-5).

[0129] [ka]

[0130] (Synthesis Example 3-6) In a 50 mL recovery flask, 20.0 g of the compound (3-5), 0.9 g of sodium fluoride, and 20 mL of AC-2000 were placed. Under a nitrogen atmosphere, 0.7 g of methanol was added, and the mixture was stirred at 50° C. for 2 hours and then at room temperature overnight. After removing the sodium fluoride with a pressure filter, the reaction mixture was concentrated with an evaporator to obtain 18.3 g of compound (3-6).

[0131] [ka]

[0132] (Synthesis Example 3-7) In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 120 g of tetrahydrofuran. 16.0 g of compound (3-6) was added to the mixture, and while cooling in an ice bath, a solution of 2.0 g of sodium borohydride dissolved in 120 g of tetrahydrofuran was slowly added dropwise. 240 g of AC-2000 was added, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 14.6 g of compound (3-7).

[0133] [ka]

[0134] (Synthesis Example 3-8) In a 100mL two-necked eggplant flask, 5.5g of compound (3-7), 5.5g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.), 0.2g of CF3SO2Cl (Wako Pure Chemical Industries, Ltd.), and 0.5g of triethylamine were placed and stirred for 4 hours at room temperature under a nitrogen atmosphere. After the reaction was completed, 5.5g of AK-225 was added, washed once each with water and saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 5.6g of compound (3-8).

[0135] [ka]

[0136] (Synthesis Example 3-9) In a 50 mL eggplant flask, 5.0 g of compound (3-8), 5.0 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.), 0.5 g of HN(CH2CH=CH2)2 (Tokyo Chemical Industry Co., Ltd.), and 0.1 g of triethylamine were placed and stirred for 24 hours at 90°C under a nitrogen atmosphere. After the reaction was completed, 10 g of AC-6000 was added, washed once each with water and saturated saline, and the organic phase was recovered and then purified by column chromatography to obtain 3.4 g of compound (3-9).

[0137] [ka]

[0138] (Synthesis Example 3-10) In a 100 mL PFA eggplant flask, 2.0 g of compound (3-9), 0.06 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.12 g of HSi(OCH3)3, 0.01 g of dimethyl sulfoxide, and 2 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.0 g of the following compound III.

[0139] [ka] The average of x3+x3 is 40.2, and the average of (y3+3)+(y3+1) is 49.2.

[0140] [Example 4] Synthesis of compound IV (Synthesis Example 4-1) In a 50 mL eggplant flask, 15.0 g of the compound (1-4) obtained in the above Synthesis Example 1-4, 4.6 g of H2N-CH2-C(CH2CH=CH2)3, 3.5 g of 4-pyrrolidinopyridine, and 7.5 mL of AC-2000 were placed and stirred for 48 hours. Unreacted materials and by-product methanol were distilled off under reduced pressure. The resulting solution was diluted with 10 g of AC-6000 and purified by column chromatography to obtain 10.3 g of compound (4-1).

[0141] [ka] The average of x4+y4 is 14.

[0142] (Synthesis Example 4-2) In a 100 mL PFA eggplant flask, 5.0 g of compound (4-1), 0.15 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.53 g of HSi(OCH3)3, 0.04 g of dimethyl sulfoxide, and 5 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 5.4 g of the following compound IV.

[0143] [ka] The average of x4+y4 is 14.

[0144] [Example 5] Synthesis of compound V (Synthesis Example 5-1) In a 100mL two-necked eggplant flask, 5.0g of the compound (3-7) obtained in the above Synthesis Example 3-7, 0.2g of tetrabutylammonium hydrogen sulfate, 0.2g of BrCH2CH=CH2, and 0.4g of 20% potassium hydroxide aqueous solution were added and stirred at 60°C for 8 hours. After the reaction was completed, 100g of AC-2000 was added, washed once with a dilute hydrochloric acid aqueous solution, and the organic phase was recovered. The recovered organic phase was purified by column chromatography and concentrated to obtain 5g of compound (5-1).

[0145] [ka] The average of x5+x5 is 40.2, and the average of y5a+y5b is 49.2.

[0146] (Synthesis Example 5-2) In a 500mL four-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, 4.5g of compound (5-1), 4.5g of 1,3-bis(trifluoromethyl)benzene, 0.05g of triacetoxymethylsilane, and 0.41g of trichlorosilane were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Then, 0.18ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the temperature was raised to 60°C and stirred at this temperature for 5 hours. Then, volatile matter was distilled off under reduced pressure to obtain 4.4g of compound (5-2).

[0147] [ka]

[0148] (Synthesis Example 5-3) In a 100mL four-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, 4.0g of compound (5-2) and 4g of AC-2000 were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Then, 2.8ml of a diethyl ether solution containing 1mol / L of allylmagnesium bromide was added, the temperature was raised to room temperature, and the mixture was stirred at this temperature for 10 hours. Then, the mixture was cooled to 5°C, 5mL of methanol was added, the temperature was raised to room temperature, and the insoluble matter was filtered. Subsequently, the volatile matter was distilled off under reduced pressure, and the residue was diluted with AC-2000 and purified by column chromatography to obtain 2.6 g of compound (5-3).

[0149] [ka]

[0150] (Synthesis Example 5-4) In a 100 mL PFA eggplant flask, 2.0 g of compound (5-3), 0.12 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.18 g of HSi(OCH3)3, 0.02 g of dimethyl sulfoxide, and 2 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 2.1 g of the following compound V.

[0151] [ka] The average of x5+x5 is 40.2, and the average of y5a+y5b is 49.2.

[0152] [Example 6] Synthesis of compound VI (Synthesis Example 6-1) In a 500 mL flask, 20.0 g of HO-CH2CH2CH2CH2CH2CH2-OH, 85.6 g of triethylamine, 2.1 g of N,N-dimethyl-4-aminopyridine, and 50 g of dichloromethane (CH2Cl2) were placed and stirred at 0°C for 10 minutes. Then, 80.7 g of paratoluenesulfonyl chloride dissolved in 100 g of dichloromethane was slowly added. The mixture was sealed with nitrogen and stirred at 0°C for 5 hours. The mixture was extracted with diethyl ether and concentrated under reduced pressure. The mixture was then purified by column chromatography, the solvent was distilled off, and 27.1 g of the following compound (6-1) was obtained.

[0153] [ka] Here, Ts is a tosyl group.

[0154] (Synthesis Example 6-2) In a 500 mL flask, 79.1 g of the following compound (6a), 7.2 g of Cs2CO3, and 4.5 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 4.5 g of compound (6-1) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Next, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. Then, the mixture was purified by column chromatography, the solvent was distilled off, and 26.4 g of the following compound (6-2) was obtained.

[0155] [ka] The average of x6 is 17.7, and the average of y6 is 19.3.

[0156] [ka]

[0157] (Synthesis Example 6-3) In a 50 mL eggplant flask connected to a reflux condenser, 25 g of compound (6-2), 0.9 g of sodium fluoride powder, 25 g of AC-2000, and 11.5 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 26.6 g of the following compound (6-3).

[0158] [ka] The average of x6+x6 is 35.4, and the average of y6+y6 is 38.6.

[0159] (Synthesis Example 6-4) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (6-3) (concentration: 10% by mass, compound (6-3): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (6-3) (mol / hour) was controlled to be 2:1. After the introduction of compound (6-3) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 28.4 g of compound (6-4).

[0160] [ka]

[0161] (Synthesis Example 6-5) 20 g of compound (6-4), 1 g of sodium fluoride, and 20 mL of AC-2000 were placed in a 50 mL recovery flask and stirred in an ice bath. 0.8 g of methanol was added and stirred at 25° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 18.3 g of compound (6-5).

[0162] [ka]

[0163] (Synthesis Example 6-6) Into a 50 mL recovery flask, 15 g of compound (6-5), 6.6 g of H2N-CH2-C(CH2CH=CH2)3, and 7.5 mL of AC-2000 were placed and stirred for 48 hours. The unreacted material and by-product methanol were distilled off under reduced pressure. The resulting solution was diluted with 10 g of AC-6000 and purified by column chromatography to obtain 11.9 g of compound (6-6).

[0164] [ka]

[0165] (Synthesis Example 6-7) In a 100 mL PFA eggplant flask, 3.0 g of compound (6-6), 0.12 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.3 g of HSi(OCH3)3, 0.01 g of dimethyl sulfoxide, and 3.0 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.1 g of the following compound VI.

[0166] [ka] The average of x6+x6 is 35.4, and the average of (y6+1)+(y6+1) is 40.6.

[0167] [Example 7] Synthesis of Compound VII (Synthesis Example 7-1) In a 50mL flask, 20.0g of HOCH2C(CH2OCH2CH2CH2CH=CH2)3, 60g of AE-3000, and 25.8g of 2,6-lutidine were placed, and 84.8g of (CF3SO2)2O was added dropwise at 0°C under a nitrogen atmosphere. The mixture was heated to room temperature and stirred for 1 hour. After the reaction was completed, the organic phase was recovered by washing with water and concentrated with an evaporator. This was purified by column chromatography to obtain 33.9g of compound (7-1).

[0168] [ka] Here, Tf represents CF3SO2-.

[0169] (Synthesis Example 7-2) In a 100 mL PFA eggplant flask, 27.1 g of the following compound (7a), 2 g of I-CF2CF2CF2CF2CF2CF2-I, 0.9 g of triethylamine, and 10 g of 1,3-bis(trifluoromethyl)benzene were placed and refluxed at 110°C for 24 minutes under a nitrogen atmosphere. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. The mixture was then purified by column chromatography, and the solvent was distilled off to obtain 20.8 g of the following compound (7-2).

[0170] [ka] The average of x7 is 17.7, and the average of y7 is 19.3.

[0171] [ka]

[0172] (Synthesis Example 7-3) In a 50 mL eggplant flask, 10 g of compound (7-2), 2 g of compound (7-1), 10 g of 1,3-bis(trifluoromethyl)benzene, and 1.1 g of cesium carbonate were placed and stirred for 8 hours at 80°C under a nitrogen atmosphere. After the reaction was completed, the organic phase was recovered by washing with water and concentrated with an evaporator. This was purified by column chromatography to obtain 1 g of compound (7-3).

[0173] [ka]

[0174] (Synthesis Example 7-4) In a 100 mL PFA eggplant flask, 2.5 g of compound (7-3), 0.13 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.26 g of HSi(OCH3)3, 0.01 g of dimethyl sulfoxide, and 2.5 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.12.6 g of the following compound VII.

[0175] [ka]

[0176] [Example 8] Synthesis of Compound VIII (Synthesis Example 8-1) 2.0g of ethylene glycol and 9.8g of potassium carbonate were added to a 200mL eggplant flask and stirred at 120°C, then 134.4g of CF2=CF-O-CF2CF2CF2CH2-OH was added and stirred at 120°C for 2 hours. The temperature was returned to 25°C, and 67.2g of AC-2000 and 23.3g of 2N hydrochloric acid were added, separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 54.5g of the following compound (8-1).

[0177] [ka] The average of x8+y8 is 14.

[0178] (Synthesis Example 8-2) In a 50 mL eggplant flask connected to a reflux condenser, 40.0 g of compound (8-1), 2.6 g of sodium fluoride powder, 40 g of AC-2000, and 33.6 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 44.9 g of the following compound (8-2).

[0179] [ka]

[0180] (Synthesis Example 8-3) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (8-2) (concentration: 10% by mass, compound (8-2): 24 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (8-2) (mol / hour) was controlled to be 2:1. After the introduction of compound (8-2) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 26.3 g of compound (8-3).

[0181] [ka]

[0182] (Synthesis Example 8-4) In a 50 mL eggplant flask, 25.0 g of the compound (8-3) obtained in Synthesis Example 1-3, 1.9 g of sodium fluoride, and 25 mL of AC-2000 were placed and stirred in an ice bath. 1.5 g of methanol was added and stirred at 25° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 20.4 g of compound (8-4).

[0183] [ka]

[0184] (Synthesis Example 8-5) Into a 300 mL recovery flask, 3.0 g of compound (8-4) and 1.6 g of H2NCH2CH2CH2Si(OCH3)3 were placed and stirred for 6 hours. The unreacted material and the by-product methanol were distilled off under reduced pressure, and the residue was filtered through a 0.2 μm membrane filter to obtain 3.2 g of the following compound VIII.

[0185] [ka]

[0186] [Example 9] Synthesis of compound IX (Synthesis Example 9-1) The following compound IX was synthesized by the method described in Example 7 of WO 2017 / 038832.

[0187] [ka]

[0188] [Example 10] Synthesis of compound X (Synthesis Example 10-1) In a 500 mL flask, 439.5 g of the following compound (10a), 68.7 g of Cs2CO3, and 500 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 100 g of the above compound (6-1) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Next, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. Then, the mixture was purified by column chromatography, the solvent was distilled off, and 105.8 g of the following compound (10-1) was obtained.

[0189] [ka] The average for x10a is 7.2 and the average for y10a is 9.2.

[0190] [ka]

[0191] (Synthesis Example 10-2) In a 500 mL flask, 136.6 g of the following compound (10b), 12.5 g of Cs2CO3, and 500 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 100 g of the above compound (10-1) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Next, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and then concentrated under reduced pressure at 60°C. Then, the mixture was purified by column chromatography, the solvent was distilled off, and 25.7 g of the following compound (10-2) was obtained.

[0192] [ka] The average of x10b is 17.7 and the average of y10b is 19.3.

[0193] [ka]

[0194] (Synthesis Example 10-3) In a 50 mL eggplant flask connected to a reflux condenser, 25.7 g of the compound (10-2) obtained in Synthesis Example 10-2, 1.3 g of sodium fluoride powder, 25.7 g of AC-2000, and 15.9 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 28.1 g of the following compound (10-3).

[0195] [ka] The average of (x10a+x10b) is 24.9, and the average of (y10a+y10b) is 28.5.

[0196] (Synthesis Example 10-4) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (10-3) (concentration: 10% by mass, compound (10-3): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (10-3) (mol / hour) was controlled to be 2:1. After the introduction of compound (10-3) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 23.9 g of compound (10-4).

[0197] [ka]

[0198] (Synthesis Example 10-5) In a 50 mL recovery flask, 10 g of compound (10-4), 0.7 g of sodium fluoride, and 10 mL of AC-2000 were placed, and 0.8 g of methanol was added under a nitrogen atmosphere and stirred at 50° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 8.8 g of compound (10-5).

[0199] [ka] The average of (x10a+x10b) is 24.9, and the average of (y10a+1)+(y10b+1) is 30.5.

[0200] (Synthesis Example 10-6) In a 50 mL eggplant flask, 15 g of compound (10-5), 6.6 g of H2N-CH2-C(CH2CH=CH2)3, and 7.5 mL of AC-2000 were placed and stirred for 48 hours. Unreacted materials and by-product methanol were distilled off under reduced pressure. The resulting solution was diluted with 10 g of AC-6000 and purified by column chromatography to obtain 11.9 g of compound (10-6).

[0201] [ka]

[0202] (Synthesis Example 10-7) In a 100 mL PFA eggplant flask, 3.0 g of compound (10-6), 0.12 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.4 g of HSi(OCH3)3, 0.02 g of dimethyl sulfoxide, and 3.0 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred at 40°C for 10 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 3.2 g of the following compound X.

[0203] [ka] The average of (x10a+x10b) is 24.9, and the average of (y10a+1)+(y10b+1) is 30.5.

[0204] [Example 11] Synthesis of compound XI (Synthesis Example 11-1) 20g of CF2=CF-O-CF2CF2CF2CH2-OH and 21.9g of potassium carbonate were added to a 200mL eggplant flask and stirred at 120°C, and 80g of CF2=CF-O-CF2CF2CF2CH2-OH was added and stirred at 120°C for 2 hours. The mixture was returned to 25°C, AC-2000 and 2N hydrochloric acid were added, the mixture was separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 29.5g of the following compound (11-1).

[0205] [ka] The average for z11 is 3.0.

[0206] (Synthesis Example 11-2) In a 500 mL flask, 167.8 g of the following compound (11a), 32.1 g of Cs2CO3, and 40 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 20 g of the above compound (6-1) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Then, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and concentrated under reduced pressure at 60°C. The mixture was then purified by column chromatography, the solvent was distilled off, and 53.4 g of the following compound (11-2) was obtained.

[0207] [ka] The average of x11 is 7.2 and the average of y11 is 9.2.

[0208] [ka]

[0209] (Synthesis Example 11-3) In a 500 mL flask, 41.8 g of the compound (11-1), 9.8 g of Cs2CO3, and 500 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 50 g of the compound (11-2) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Then, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and concentrated under reduced pressure at 60°C. The mixture was then purified by column chromatography, the solvent was distilled off, and 25.8 g of the following compound (11-3) was obtained.

[0210] [ka]

[0211] (Synthesis Example 11-4) In a 50 mL eggplant flask connected to a reflux condenser, 25 g of the compound (11-3), 1.0 g of sodium fluoride powder, 25 g of AC-2000, and 13.2 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 26.9 g of the following compound (11-4).

[0212] [ka]

[0213] (Synthesis Example 11-5) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (11-4) (concentration: 10% by mass, compound (11-4): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (11-4) (mol / hour) was controlled to be 2:1. After the introduction of compound (11-4) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 26.5 g of compound (11-5).

[0214] [ka]

[0215] (Synthesis Example 11-6) In a 50 mL recovery flask, 20 g of compound (11-5), 1.2 g of sodium fluoride, and 20 mL of AC-2000 were placed, and 0.9 g of methanol was added under a nitrogen atmosphere and stirred at 50° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 17.8 g of compound (11-6).

[0216] [ka]

[0217] (Synthesis Example 11-7) In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 225 g of tetrahydrofuran. 15.0 g of compound (11-6) was added to the mixture, and while cooling in an ice bath, a solution of 2.65 g of sodium borohydride dissolved in 120 g of tetrahydrofuran was slowly added dropwise. 225 g of AC-2000 was added, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 14 g of compound (11-7).

[0218] [ka]

[0219] (Synthesis Example 11-8) DiethylDiallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.5 g), and dimethylsulfoxide (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 saline and dried with sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (11-8).

[0220] [ka]

[0221] (Synthesis Example 11-9) After adding THF (260 mL) and diisopropylamine (29.8 mL), the solution was cooled to -78°C. n-Butyllithium hexane solution (96.6 mL) was added and the temperature was raised to 0°C. After stirring, the mixture was cooled to -78°C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (11-8) (39.5 g) was added to the THF solution, and after stirring, allyl bromide (24.1 mL) was added. The mixture was heated to 0°C, 1M hydrochloric acid (100 mL) was added, and THF was distilled off under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography was performed to obtain 45.0 g of compound (11-9).

[0222] [ka]

[0223] (Synthesis Example 11-10) The above compound (11-9) (45.0 g) was dissolved in THF (620 mL) and cooled to 0° C. A THF solution (104 mL) of lithium aluminum hydride 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 was performed to obtain 31.3 g of the following compound (11-10).

[0224] [ka]

[0225] (Synthesis Example 11-11) Acetonitrile (380 mL), the compound (11-10) (31.3 g), triphenylphosphine (64.3 g), and carbon tetrachloride (33.9 g) 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 (11-11) was obtained by distillation.

[0226] [ka]

[0227] (Synthesis Examples 11-12) To magnesium (2.36 g), THF (35 mL) and iodine (0.180 g) were added and stirred at room temperature. A solution of the compound (11-11) (14.0 g) in THF (35 mL) was added and heated under reflux for 2 hours to prepare a solution of the following compound (11-12).

[0228] [ka]

[0229] (Synthesis Examples 11-13) 1-Bromo-4-chlorobutane (2.9 g), 1-phenyl-1-propyne (0.20 g), and CuCl2 (0.05 g) were added and stirred at 0°C. The compound (11-12) (24.0 mL) was added and stirred. 1M hydrochloric acid was added, and the mixture was extracted with dichloromethane, and sodium sulfate was added. After filtration and concentration, 3.45 g of the following compound (11-13) was obtained by distillation.

[0230] [ka]

[0231] (Synthesis Examples 11-14) To magnesium (0.17 g), THF (2.6 mL) and iodine (14.0 mg) were added and stirred at room temperature. A solution of the compound (11-13) (1.41 g) in THF (2.6 mL) was added and heated under reflux for 2 hours to prepare a solution (0.74 M) of the following compound (11-14).

[0232] [ka]

[0233] (Synthesis Examples 11-15) 0.2 g of CuCl2, 0.1 g of 1-phenyl-1-propyne, 280 mL of 1,3-bistrifluoromethylbenzene, and 14 g of the compound (11-7) were added, followed by the addition of 12 mL of the compound (11-14). After stirring at room temperature, the mixture was washed with 1 M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, and AC-6000 was added. After washing with DMF and MeOH, flash column chromatography was performed to obtain 1.5 g of the following compound (11-15).

[0234] [ka]

[0235] (Synthesis Examples 11-16) In a 100 mL PFA eggplant flask, 1.0 g of compound (11-15), 0.06 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.12 g of HSi(OCH3)3, 0.01 g of dimethyl sulfoxide, and 1.0 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 40° C. for 10 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 1.1 g of the following compound XI.

[0236] [ka] The average of x11 is 7.2, the average of (Y11+1) is 22.4, and the average of Z11 is 6.0.

[0237] [Example 12] Synthesis of compound XII (Synthesis Example 12-1) 20g of CF2=CF-O-CF2CF2CF2CH2-OH and 21.9g of potassium carbonate were added to a 200mL eggplant flask and stirred at 120°C, and 80g of CF2=CF-O-CF2CF2CF2CH2-OH was added and stirred at 120°C for 2 hours. The mixture was returned to 25°C, AC-2000 and 2N hydrochloric acid were added, the mixture was separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 29.5g of the following compound (12-1).

[0238] [ka] The average for z12 is 3.0.

[0239] (Synthesis Example 11-2) In a 500 mL flask, 419.6 g of the following compound (12a), 80.2 g of Cs2CO3, and 100 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80°C for 30 minutes. Separately, a solution was prepared by dissolving 50 g of the above compound (6-1) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Then, nitrogen sealing was performed and the mixture was stirred at 80°C for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and concentrated under reduced pressure at 60°C. The mixture was then purified by column chromatography, the solvent was distilled off, and 124.3 g of the following compound (12-2) was obtained.

[0240] [ka] The average of x12 is 7.2 and the average of y12 is 9.2.

[0241] [ka]

[0242] (Synthesis Example 12-3) In a 500 mL flask, 100 g of the compound (12-1), 13.1 g of Cs2CO3, and 1000 g of 1,3-bistrifluoromethylbenzene were placed and stirred at 80° C. for 30 minutes. Separately, a solution was prepared by dissolving 100 g of the compound (12-2) in 30 g of a mixed solvent of 1,3-bistrifluoromethylbenzene and chloroform (mass ratio 2:1), and the solution was slowly added. Then, nitrogen sealing was performed and the mixture was stirred at 80° C. for 4 hours. The mixture was returned to room temperature, the reaction was stopped with 2N HCl, washed with AC-2000 and water, extracted, and concentrated under reduced pressure at 60° C. The mixture was then purified by column chromatography, the solvent was distilled off, and 20.8 g of the following compound (12-3) was obtained.

[0243] [ka]

[0244] (Synthesis Example 12-4) In a 50 mL eggplant flask connected to a reflux condenser, 25 g of the compound (12-3), 1.3 g of sodium fluoride powder, 25 g of AC-2000, and 17 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed using a pressure filter, and the excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 27.4 g of the following compound (12-4).

[0245] [ka]

[0246] (Synthesis Example 12-5) 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled through. After the oxygen gas concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through for 1 hour. The CFE-419 solution of the compound (12-4) (concentration: 10% by mass, compound (12-4): 25 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (12-4) (mol / hour) was controlled to be 2:1. After the introduction of compound (12-4) was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through for 1 hour, and finally the inside of the reaction vessel was fully replaced with nitrogen gas. The solvent was distilled off to obtain 26.5 g of compound (12-5).

[0247] [ka]

[0248] (Synthesis Example 12-6) In a 50 mL recovery flask, 20 g of compound (12-5), 1.5 g of sodium fluoride, and 20 mL of AC-2000 were placed, and 1.2 g of methanol was added under a nitrogen atmosphere and stirred at 50° C. for 1 hour. After filtration, the filtrate was purified by column chromatography to obtain 17.5 g of compound (12-6).

[0249] [ka]

[0250] (Synthesis Example 12-7) In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 150 g of tetrahydrofuran. 10 g of compound (12-6) was added to the mixture, and while cooling in an ice bath, a solution of 2.27 g of sodium borohydride dissolved in 120 g of tetrahydrofuran was slowly added dropwise. 150 g of AC-2000 was added, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 9.5 g of compound (12-7).

[0251] [ka]

[0252] (Synthesis Example 12-8) 0.1g of CuCl2, 0.1g of 1-phenyl-1-propyne, 180mL of 1,3-bistrifluoromethylbenzene, and 9g of the compound (12-7) were added, followed by the addition of 9.9mL of the compound (11-14). After stirring at room temperature, the mixture was washed with 1M 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, 1.3g of the following compound (12-8) was obtained by flash column chromatography.

[0253] [ka]

[0254] (Synthesis Example 12-9) In a 100 mL PFA eggplant flask, 1.0 g of compound (12-8), 0.06 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.15 g of HSi(OCH3)3, 0.01 g of dimethyl sulfoxide, and 1.0 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 40° C. for 10 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to obtain 1.1 g of the following compound XII.

[0255] [ka] The average of x12 is 7.2, the average of (Y12+1) is 22.4, and the average of Z12 is 3.0.

[0256] [Production and evaluation of goods] The substrate was surface-treated using each of the compounds obtained in Examples 1 to 12 to obtain an article having a surface layer. The surface treatment method used in each example was the dry coating method and the wet coating method described below. Chemically strengthened glass was used as the substrate. The obtained article was evaluated by the following method. The results are shown in Tables 1 and 2.

[0257] (Dry coating method) Dry coating was performed using a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC Corporation) (vacuum deposition method). 0.5 g of each of the compounds obtained in Examples 1 to 12 was loaded into a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was filled with 1×10 -3 The pressure was evacuated to less than 1 Pa. The boat on which the compound was placed was heated at a rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness gauge exceeded 1 nm / sec, the shutter was opened to start deposition on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to end deposition on the surface of the substrate. The substrate on which the compound was deposited was heat-treated at 200°C for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0258] (Wet coating method) Each compound obtained in Examples 1 to 12 was mixed with C4F9OC2H5 (3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating liquid with a solid content concentration of 0.05%. A substrate was dipped in 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 AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0259] (Evaluation method) <Contact angle measurement method> The contact angle of approximately 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., DMo-701). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.

[0260] <Initial contact angle> The surface layer was measured for the initial water contact angle and the initial n-hexadecane contact angle by the above-mentioned measuring method. The evaluation criteria were as follows. Initial water contact angle: ○(Good): 105 degrees or more △(Acceptable): Between 100 and 105 degrees. ×(Not acceptable): Less than 100 degrees. Initial n-hexadecane contact angle: ○(Good): 63 degrees or more △(Acceptable): Between 60 degrees and 63 degrees. ×(Not acceptable): Less than 60 degrees.

[0261] <Abrasion resistance> For the surface layer, a reciprocating traverse tester (manufactured by KNT Co., Ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to measure the water contact angle every 1000 strokes by reciprocating steel wool Bonstar (#0000) at a pressure of 49 kPa and a speed of 320 cm / min. The water contact angle of the surface layer was measured. The number of strokes at which 90% of the initial contact angle was maintained is shown in Table 1. The measurement was performed up to 15,000 strokes, and if the water contact angle after 15,000 strokes maintained 90% or more of the initial contact angle, it is listed as 15,000 in Table 1.

[0262] [Table 1]

[0263] It has been revealed that a surface layer using this compound, such as compounds I to VII and compounds X to XII, in which a polyfluoropolyether chain has an ABA block consisting of block A consisting of oxyfluoroalkylene units having 1 to 4 carbon atoms and block B consisting of oxyfluoroalkylene units having 5 to 6 carbon atoms, and reactive silyl groups are linked to both ends, has improved abrasion resistance. [Industrial Applicability]

[0264] Articles having a surface layer containing the present compound are useful, for example, as optical articles, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc., used as parts of the following products: Products: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic electroluminescence displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0265] This application claims priority based on Japanese Patent Application No. 2020-23320, filed on February 14, 2020, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0266] 10: substrate with undercoat layer, 12: substrate, 14: undercoat layer, 20: Article, 22: Surface layer

Claims

1. A fluorine-containing ether compound represented by the following formula (2), in which the (OR f1 ) k1 -(OR f3 ) k3 -(OR f2 ) k2 portion in the formula (2) has a molecular weight of 2,000 to 20,000. (T) p1 -Q 1 -(OR f1) k1 -(OR f3) k3 -(OR f2) k2 -O-Q 2 -(T) p2 Formula (2) however, R f1 and R f2 each independently represent a fluoroalkylene group having 1 to 4 carbon atoms, and when there are a plurality of R f1 or R f2 , the plurality of R f1 or R f2 may be the same or different, R f3 is a fluoroalkyl group having 5 to 6 carbon atoms, and when there are a plurality of R f3 s, the plurality of R f3 s may be the same or different, k1 and k2 each independently represent an integer from 1 to 200; k3 is an integer from 1 to 20, Q １ is a (1+p1)-valent linking group, Q ２ is a (1+p2)-valent linking group, T is -Si(R) ３－ｃ (L) ｃ wherein a plurality of T's may be the same or different; R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and a plurality of L in each T may be the same or different. p1 and p2 each independently represent an integer of 1 or more.

2. 2. The fluorine-containing ether compound according to claim 1, wherein the ratio of k1 to k2 (k1 / k2) is 0.01 to 200.

3. R ｆ１ and R ｆ２ The fluorine-containing ether compound according to claim 1 or 2, wherein each of the above is independently a fluoroalkyl group having 1 to 2 carbon atoms.

4. The fluorine-containing ether compound according to any one of claims 1 to 3, wherein k3 is 1.

5. A fluorinated ether composition comprising the fluorinated ether compound according to any one of claims 1 to 4 and another fluorinated ether compound.

6. A coating liquid comprising the fluorinated ether compound according to any one of claims 1 to 4 or the fluorinated ether composition according to claim 5, and a liquid medium.

7. An article having a surface layer formed from the fluorinated ether compound according to any one of claims 1 to 4 or the fluorinated ether composition according to claim 5 on the surface of a substrate.

8. 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 any one of claims 1 to 4, the fluorinated ether composition according to claim 5, or the coating liquid according to claim 6.

Images