Fluorine-containing ether compound and method for producing the same, compound and method for producing the same, fluorine-containing ether composition, coating liquid, and article and method for producing the same

Abstract

Provided are: a fluorine-containing ether compound, a fluorine-containing ether composition, and a coating liquid that are capable of forming a surface layer having excellent durability; and an article that has a surface layer having excellent durability.　The present invention provides a fluorine-containing ether compound represented by formula (A1) or formula (A2).　Formula (A1): RfO-(Rf1O)m-R1-L1-R2-Q1(-T)n Formula (A2): (T-)nQ1-R2-L1-R1-O-(Rf1O)m-R1-L1-R2-Q1(-T)n In the formulae, each symbol is as defined in the description.

Description

[Technical field]

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

[0002] A fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is suitable for use as a surface treatment agent since it can form a surface layer on the surface of a substrate that exhibits high lubricity, water repellency, oil repellency, etc. The surface treatment agent containing the fluorine-containing ether compound is used as a surface treatment agent for applications requiring a long-term maintenance of the performance that the water and oil repellency is not likely to decrease even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance that allows fingerprints attached to the surface layer to be easily removed by wiping (fingerprint stain removability), for example, as a member constituting the surface of a touch panel that is touched by fingers, a spectacle lens, and a display of a wearable terminal.

[0003] As a fluorine-containing ether compound capable of forming a surface layer having excellent abrasion resistance and fingerprint stain removability on the surface of a substrate, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group has been proposed (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-196723 A [Patent Document 2] JP 2016-204656 A Summary of the Invention [Problem to be solved by the invention]

[0005] The above-mentioned surface treatment agent is required to be applicable not only to the display surfaces of smartphones, tablet terminals, etc. but also to the surface treatment of various materials. There is a demand for further improvement in the durability of the surface treatment agent.

[0006] An object of the present invention is to provide a fluorinated ether compound, a fluorinated ether composition and a coating liquid which are capable of forming a surface layer having excellent durability, and an article having a surface layer having excellent durability. [Means for solving the problem]

[0007] The present invention provides a fluorinated ether compound and a method for producing the same, a compound and a method for producing the same, a fluorinated composition, a coating liquid, and an article and a method for producing the same, each having the following structures [1] to

[15] . [1] A fluorinated ether compound represented by the following formula (A1) or formula (A2): R f O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A1) (T-) n Q 1 -R 2 -L 1 -R 1 -O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1 may be the same or different, R 1is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2 is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 1 is -CH(OH)-, -C(=O)-, or -CH=CH-, and L 1 If there are multiple L 1 may be the same or different, Q 1 is a linking group having a valence of 1+n, and Q 1 If there are multiple Qs, 1 may be the same or different, T is an adhesive group, and a plurality of T may be the same or different; m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different. [2] R 1 The fluorine-containing ether compound according to [1], wherein the carbon number is 1 to 6. [3] R 2 The fluorine-containing ether compound according to [1] or [2], wherein the carbon number is 1 to 10. [4] -Q 1 (-T) n But -Q 2 [(-R 3 -T) a (-R 4 ) 3-a The fluorine-containing ether compound according to any one of [1] to [3], wherein however, Q 2 is a carbon or silicon atom, and Q 2 If there are multiple Qs, 2 may be the same or different, R 3is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 3 If there are multiple R 3 may be the same or different, R 4 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) b (-R 6 ) 3-b ], where R 4 If there are multiple R 4 may be the same or different, R 5 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 5 If there are multiple R 5 may be the same or different, R 6 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) c (-R 7 ) 3-c ], where R 6 If there are multiple R 6 may be the same or different, R 7 is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, and R 7 If there are multiple R 7 may be the same or different, a is an integer from 0 to 3; b is an integer of 0 to 3, and when there are multiple b's, the b's may be the same or different; c is an integer of 0 to 3, and when there are multiple c's, the c's may be the same or different; The sum of a, b, and c is n. [5] R 3 The fluorine-containing ether compound according to [4], wherein the carbon number is 2 to 7. [6] T is a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, or -Si(R 21 ) 3-d (L 21 ) d The fluorinated ether compound according to any one of [1] to [5], which is one or more selected from the following. however, R 21 is an alkyl group, L 21 is a hydrolyzable group or a hydroxyl group, and there are multiple L 21 may be the same or different, d is 2 or 3. [7] A compound represented by the following formula (B1) or formula (B2): R f O-(R f1 O) m -R 1 -L 1 -R 2 -Q 11 (-CH=CH2) n Formula (B1) (CH2=CH-) n Q 11 -R 2 -L 1 -R 1 -O-(R f1 O) m -R 1 -L 1 -R 2 -Q 11 (-CH=CH2) n Formula (B2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1may be the same or different, R 1 is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2 is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 1 is -CH(OH)-, -C(=O)-, or -CH=CH-, and L 1 If there are multiple L 1 may be the same or different, Q 11 is a linking group having a valence of 1+n, and Q 11 If there are multiple Qs, 11 may be the same or different, m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different. [8] -Q 11 (-CH=CH2) n But -Q 2 [(-R 3 -CH=CH2) a (-R 4 ) 3-a The compound according to [7], wherein however, Q 2 is a carbon or silicon atom, and Q 2 If there are multiple Qs, 2 may be the same or different, R 3 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 3 If there are multiple R 3 may be the same or different, R 4represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -CH=CH2) b (-R 6 ) 3-b ], where R 4 If there are multiple R 4 may be the same or different, R 5 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 5 If there are multiple R 5 may be the same or different, R 6 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -CH=CH2) c (-R 7 ) 3-c ], where R 6 If there are multiple R 6 may be the same or different, R 7 is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, and R 7 If there are multiple R 7 may be the same or different, a is an integer from 0 to 3; b is an integer of 0 to 3, and when there are multiple b's, the b's may be the same or different; c is an integer of 0 to 3, and when there are multiple c's, the c's may be the same or different; The sum of a, b, and c is n. [9] A method for producing a compound represented by the following formula (B11) or formula (B12), comprising a step of reacting a compound represented by the following formula (C1) or formula (C2) with a compound represented by the following formula (D1): R f O-(R f1 O) m -R 1 -C(=O)-OR 11 Formula (C1) R 11 OC(=O)-R 1 -O-(R f1 O) m -R 1 -C(=O)-OR 11 Formula (C2) (CH2=CH-) n Q 11 -R 2 -MgX formula (D1) R f O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B11) (CH2=CH-) n Q 11 -R 2 -L 11 -R 1 -O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B12) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1 may be the same or different, R 1 is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 11 is -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, and L 11 If there are multiple L 11 may be the same or different, Q 11 is a linking group having a valence of 1+n, and Q 11 If there are multiple Qs, 11 may be the same or different, X is a halogen atom; m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different.

[10] A method for producing a fluorinated ether compound represented by the following formula (A11) or formula (A12), comprising a step of introducing an adhesive group T into a compound represented by the following formula (B11) or formula (B12): R f O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B11) (CH2=CH-) n Q 11 -R 2 -L 11 -R 1 -O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B12) R f O-(R f1 O) m -R 1 -L 11 -R 2 -Q 1(-T) n Formula (A11) (T-) n Q 1 -R 2 -L 11 -R 1 -O-(R f1 O) m -R 1 -L 11 -R 2 -Q 1 (-T) n Formula (A12) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1 may be the same or different, R 1 is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2 is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 11 is -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, and L 11 If there are multiple L 11 may be the same or different, Q 1 is a linking group having a valence of 1+n, and Q 1 If there are multiple Qs, 1 may be the same or different, Q 11 is a linking group having a valence of 1+n, and Q 11 If there are multiple Qs, 11 may be the same or different, m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different.

[11] A fluorinated ether composition comprising a fluorinated ether compound represented by the following formula (A1) and a fluorinated ether compound represented by the following formula (A2): R f O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A1) (T-) n Q 1 -R 2 -L 1 -R 1 -O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1 may be the same or different, R 1 is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2 is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 1 is -CH(OH)-, -C(=O)-, or -CH=CH-, and L 1 If there are multiple L 1 may be the same or different, Q 1 is a linking group having a valence of 1+n, and Q 1 If there are multiple Qs, 1 may be the same or different, T is an adhesive group, and a plurality of T may be the same or different; m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different.

[12] A fluorinated ether composition comprising one or more fluorinated ether compounds according to any one of [1] to [6] and another fluorinated ether compound.

[13] A fluorinated ether compound according to any one of [1] to [6] or a fluorinated ether composition according to

[11] or

[12] , A coating liquid comprising a liquid medium.

[14] An article having a surface layer formed on the surface of a substrate from the fluorinated ether compound according to any one of [1] to [6], or the fluorinated ether composition according to

[11] or

[12] .

[15] 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 [1] to [6], the fluorinated ether composition according to

[11] or

[12] , or the coating liquid according to

[13] . Effect of the Invention

[0008] The present invention provides a fluorinated ether compound capable of forming a surface layer having excellent durability, a fluorinated ether composition and a coating liquid, an article having a surface layer having excellent durability, and a compound useful as a raw material for the fluorinated ether compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, the compound represented by formula (A1) will be referred to as compound (A1). Compounds represented by other formulae will be referred to in the same manner. As used herein, the following terms have the following meanings: The term "reactive silyl group" is a general term for hydrolyzable silyl groups and silanol groups (Si-OH). The reactive silyl group is, for example, T in formula (A1) or formula (A2), i.e., -Si(R) 3-c (L) c It is. 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. When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 It is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units by F-NMR. When the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is the same, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 F-NMR f The molecular weight is calculated by determining the structure of the compound. The symbol "~" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0010] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the compound") is a fluorine-containing ether compound represented by the following formula (A1) or formula (A2). R f O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A1) (T-) n Q 1 -R 2 -L 1 -R 1-O-(R f1 O) m -R 1 -L 1 -R 2 -Q 1 (-T) n Formula (A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 If there are multiple R f1 may be the same or different, R 1 is an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different, R 2 is a single bond or an alkylene group which may have a fluorine atom, and R 2 If there are multiple R 2 may be the same or different, L 1 is -CH(OH)-, -C(=O)-, or -CH=CH-, and L 1 If there are multiple L 1 may be the same or different, Q 1 is a linking group having a valence of 1+n, and Q 1 If there are multiple Qs, 1 may be the same or different, T is an adhesive group, and a plurality of T may be the same or different; m is an integer from 0 to 210; n is an integer of 2 to 20, and when there are multiple ns, the ns may be the same or different.

[0011] The compound has a polyfluoropolyether chain [R f -O-(R f1 O) m -R 1 ] or [O-(Rf1 O) m -R 1 ], an adhesive group [T], and a specific linking group [-L 1 -R 2 -Q 1 ]. Compound (A1) is a compound having a structure of "monovalent polyfluoropolyether chain-linking group-adhesive group", and compound (A2) is a compound having a structure of "adhesive group-linking group-divalent polyfluoropolyether chain-linking group-adhesive group".

[0012] The compound has a polyfluoropolyether chain. The compound having a polyfluoropolyether chain has excellent fingerprint stain removal properties on the surface layer. The compound also has two or more adhesive groups at at least one end. The compound having two or more adhesive groups at the end is strongly chemically bonded to the substrate, so that the surface layer has excellent abrasion resistance. Furthermore, the compound has a polyfluoropolyether chain and a Q having a branched structure in the linking group. 1 Between 1 That is, -CH(OH)-, -C(=O)-, or -CH=CH-. 1 The present invention was completed by finding that the compound has excellent durability on the substrate surface by having the substituent. Although the effect of improving durability by the substituent is not fully understood, when the compound is applied to the substrate surface, the L 1 It is speculated that the interaction between the two compounds facilitates the alignment of the compounds on the surface layer, resulting in improved durability. 1 Between the adhesive group T and Q 1 By using the combination of 1 It is presumed that the intramolecular reaction between and T is suppressed, and the adhesive group T contributes sufficiently to the adhesion to the substrate. Thus, the surface layer formed by the present compound is characterized by excellent durability such as abrasion resistance, chemical resistance, and light resistance, and is particularly excellent in abrasion resistance.

[0013] Rf R is a fluoroalkyl group having 1 to 20 carbon atoms, which provides the surface layer with even better abrasion resistance and fingerprint removability. f The number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3, in that the surface layer has better abrasion resistance and fingerprint stain removability. R f As the fluoroalkyl group of R, a perfluoroalkyl group is preferable because it provides the surface layer with even better abrasion resistance and fingerprint stain removability. f Compound 1A in which the terminal is a perfluoroalkyl group has a CF3- terminal. Compound 1A having a CF3- terminal can form a surface layer with low surface energy, and therefore the abrasion resistance and fingerprint stain removability of the surface layer are further improved. R f Examples of the fluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0014] (R f1 O) m In order to further improve the abrasion resistance and fingerprint stain removability of the surface layer, f1 The structure represented by -1) is preferred. (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having one carbon atom, R f12 is a fluoroalkylene group having 2 carbon atoms, R f13 is a fluoroalkylene group having 3 carbon atoms, R f14 is a fluoroalkylene group having 4 carbon atoms, R f15 is a fluoroalkylene group having 5 carbon atoms, R f16 is a fluoroalkylene group having 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 represents an integer of 1 to 210, and R f11 ~R f16 If there are multiple R f11 ~R f16 may be the same or different. In addition, the formula (R f1 -1) in (R f11 O)~(R f16 The bonding order of m1 to m6 in formula (R-1) is f11 O)~(R f16 O), not the arrangement. For example, (R f15 O) m5 is (R f15 O) is m5, and (R f5 O) m5 It does not represent the block arrangement structure of (R f11 O)~(R f16 The order of the units does not represent the bonding order of the units.

[0015] In addition, the fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or may be a fluoroalkylene group having a branched or cyclic structure. R f11 Specific examples of R include CHF and CF2. f12 Specific examples of R include CF2CF2, CF2CHF, and CF2CH2. f13 Specific examples of R include CF2CF2CF2, CF2CF2CHF, CF2CHFCF2, CF2CF2CH2, CF2CH2CF2, and CF(CF3)CF2. f14Specific examples of R include CF2CF2CF2CF2, CF2CF2CF2CH2, CHFCF2CF2CF2, CF2CH2CF2CF2, CF(CF3)CF2CF2, and perfluorocyclobutane-1,2-diyl group. f15 Specific examples of R include CF2CF2CF2CF2CF2, CF2CF2CF2CF2CH2, CHFCF2CF2CF2CF2, and CF2CF2CH2CF2CF2. f16 Specific examples include CF2CF2CF2CF2CF2CF2, CF2CF2CF2CF2CF2CH2, and CF2CF2CF2CF2CF2CHF.

[0016] R 1 R is an alkylene group which may have a fluorine atom. 1 R is preferably a fluoroalkylene group, since the abrasion resistance and fingerprint stain removability of the surface layer are further improved. 1 The alkylene group of R is preferably a linear fluoroalkylene group. 1 The alkylene group preferably has 1 to 6 carbon atoms.

[0017] R 2 R is a single bond or an alkylene group which may have a fluorine atom. 2 If is a single bond, L 1 -R 2 -Q 1 L 1 -Q 1 It can also be expressed as R 2 From the viewpoint of synthesis of the present compound, R is preferably a single bond or an alkylene group. 2 The alkylene group of R is preferably a linear fluoroalkylene group. 2 The alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. Among them, L 1 When -CH(OH)- or -C(=O)-, from the viewpoint of synthesis of the present compound, R 2 is preferably a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 6 carbon atoms. 1In the case where -CH=CH-, from the viewpoint of the synthesis of this compound, R 2 is preferably a single bond or an alkylene group having 1 to 9 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 5 carbon atoms.

[0018] L 1 is -CH(OH)-, -C(=O)-, or -CH=CH-, and the durability of the surface layer using this compound is improved.

[0019] Q 1 Q is a linking group with a valence of 1+n, which links n adhesive groups to the polyfluoropolyether chain. 1 is a group having a branching point, and examples of the branching point include a tertiary carbon atom, a quaternary carbon atom, a silicon atom, and a ring structure.

[0020] Examples of the ring structure constituting the branching point include a 3- to 8-membered aliphatic ring, a 6- to 8-membered aromatic ring, a 3- to 8-membered heterocyclic ring, and a condensed ring consisting of two or more of these rings, from the viewpoint of ease of production of the present compound and durability of the surface layer such as abrasion resistance, chemical resistance, and light resistance. From the viewpoint of durability of the surface layer such as abrasion resistance, chemical resistance, and light resistance, a ring structure selected from a 3- to 8-membered aliphatic ring, a 6- to 8-membered aromatic ring, and a condensed ring thereof is preferable. Examples of the ring structure constituting the branching point include the ring structure shown in the following formula. The following ring structure may be substituted with a fluorine atom. The ring structure may also have an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group, or the like, which may have a halogen atom, as a substituent.

[0021] [ka]

[0022] In this compound, Q 1 From the viewpoint of ease of synthesis of the present compound and durability of the surface layer, the branching point constituting -Q is preferably a tertiary carbon atom, a quaternary carbon atom, or a silicon atom. 1 (-T) n But -Q2 [(-R 3 -T) a (-R 4 ) 3-a It is preferable that the structure is represented by the formula: however, Q 2 is a carbon or silicon atom, and Q 2 If there are multiple Qs, 2 may be the same or different, R 3 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 3 If there are multiple R 3 may be the same or different, R 4 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) b (-R 6 ) 3-b ], where R 4 If there are multiple R 4 may be the same or different, R 5 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 5 If there are multiple R 5 may be the same or different, R 6 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) c (-R 7 ) 3-c ], where R 6 If there are multiple R 6 may be the same or different, R 7is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, and R 7 If there are multiple R 7 may be the same or different, a is an integer from 0 to 3; b is an integer of 0 to 3, and when there are multiple b's, the b's may be the same or different; c is an integer of 0 to 3, and when there are multiple c's, the c's may be the same or different; The sum of a, b, and c is n.

[0023] Above Q 2 represents a carbon atom or silicon atom that is a branch point. R 3 When is a single bond, the adhesive group T is Q 2 Binds directly to Q 2 -T. 3 From the viewpoint of ease of synthesis, an alkylene group having 2 to 10 carbon atoms which may have a fluorine atom and which may have an ether bond between carbon atoms is preferred. R 4 , R 6 and R 7 The alkyl group in the formula (I) may be an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom and which may have an ether bond between carbon atoms. R 5 The alkylene group in is preferably an alkylene group having 2 to 10 carbon atoms which may have a fluorine atom and which may have an ether bond between the carbon atoms. The alkyl group in the formula (I) may be an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom and which may have an ether bond between carbon atoms. a, b, and c each independently represent an integer of 0 to 3, and the sum of a, b, and c is n. When there are multiple b's and multiple c's, the sum of the multiple b's and multiple c's and a is n. n is an integer of 2 to 20, and preferably 2 to 10.

[0024] T is a group that is arranged on the substrate surface side during the formation of the surface layer and exhibits adhesion to the substrate. T may form a chemical bond with the substrate surface or the like, or may be chemically or physically adsorbed to the substrate surface. From the viewpoint of durability, T is preferably one that chemically bonds with the substrate surface.

[0025] The adhesive group T is a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, -Si(R 21 ) 3-d (L 21 ) d It is preferable to select an appropriate one according to the material of the substrate to be used. The amino group in the adhesive group T is -NR 8 R 9 (R 8 , R 9 each independently represents a hydrogen atom or an alkyl group), and from the viewpoint of durability of the surface layer, -NH2 is preferred. The phosphate group in the adhesive group T is -OP(=O)(OR 10 )2(R 10 R is a hydrogen atom or an alkyl group. 10 may be the same or different), and among them, -OP(=O)(OH)2 is preferred from the viewpoint of durability of the surface layer. The phosphonic acid group in the adhesive group T is -P(=O)(OR 10 )2(R 10 is the same as above), and among them, -P(=O)(OH)2 is preferred from the viewpoint of durability of the surface layer. Examples of the unsaturated hydrocarbon group in the adhesive group T include an acryloyl group, a methacryloyl group, and a vinyl group. Examples of the aryl group in the adhesive group T include a phenyl group, a naphthyl group, and an anthracenyl group. In addition, -Si(R 21 ) 3-d (L 21 ) d represents 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 ease of 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. R 21 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the present compound. d is preferably 2 or 3, and more preferably 3, in that the adhesion between the surface layer and the substrate is stronger.

[0026] Preferred combinations of the adhesive group T, substrate and material are shown in the form of "adhesive group T-substrate". Bromine-silicon nitride, hydrogen-terminated silicon nitride, Iodine-hydrogen terminated diamond, Hydroxyl-hydrogen terminated silicon, silicon halides, silicon oxide (SiO2), aluminum oxide (Al2O3), diamond-like carbon (DLC), Amino group-indium tin oxide (ITO), mica, Carboxylic-Al2O3, silver oxide (AgO), copper oxide (CuO), zirconium-modified aluminum oxide (Zr / Al2O3), amine-terminated oxide (NH2-terminated oxide), tin oxide (SnO2), Aldehyde group, epoxy group-hydrogen terminated silicon, halogenated silicon, Thiol group-gold (Au), Phosphate group, phosphonate group - zirconium oxide (ZrO2), titanium oxide (TiO2), Al2O3, tantalum oxide (Ta2O5), Zr / Al2O3, Unsaturated hydrocarbon group - hydrogen-terminated diamond, hydrogen-terminated silicon, silicon halide, silicon nitride, hydrogen-terminated silicon nitride, polyimide (PI), acrylic, Aryl groups - Al2O3, DLC, Reactive silyl groups - glass, Au, mica, SiO2, tin oxide (SnO2), germanium oxide (GeO2), ZrO2, TiO2, Al2O3, ITO, stainless steel (SUS), lead zirconate titanate (PZT). However, the present compound is not limited to these combinations, and can be used in combination with various substrates.

[0027] Examples of the present compound include compounds of the following formula. The compounds of the following formula are easy to produce industrially, easy to handle, and have excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light resistance, and chemical resistance of the surface layer. In addition, from the viewpoint of durability, the present compound preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.2 or less.

[0028] [ka] n1 to n5 are adjusted so that m in formula (A1) or formula (A2) is 0 to 210.

[0029] [Compound represented by the following formula (B1) or (B2)] The following compounds (B1) and (B2) are compounds in which the adhesive group T in the present compound is an unsaturated hydrocarbon group, and are also useful for synthesizing the compounds (A1) and (A2). R f O-(R f1 O) m -R 1 -L 1 -R 2 -Q 11 (-CH=CH2) n Formula (B1) (CH2=CH-) n Q 11 -R 2 -L 1 -R 1 -O-(R f1 O) m -R 1 -L 1 -R 2 -Q 11 (-CH=CH2) n Formula (B2) however, R f , R f1 , R 1 , R 2 , L 1 , m and n are the same as those in the formulae (A1) and (A2), and preferred embodiments are also the same. When (-CH=CH2) in formula (B1) and formula (B2) is the adhesive group T, Q 11 Q in the formula (A1) and the formula (A2) 1 In addition, when another adhesive group T is introduced into the compound (B1) or the compound (B2), Q 11 (-CH=CH2) is Q after reaction 1 It is a linking group having a valence of 1+n.

[0030] In the compounds (B1) and (B2), -Q 11 (-CH=CH2) n But -Q 2 [(-R 23 -CH=CH2) a (-R 24 ) 3-a ] is preferable. however, Q 2 a, b, and c are the same as those in the compound (A1) and the compound (A2), and preferred embodiments are also the same. R 23 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 23 If there are multiple R 23 may be the same or different, R 24 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 25 -Q 2 [(-R 23 -CH=CH2) b (-R 26 ) 3-b ], where R 24 If there are multiple R 24 may be the same or different, R 25 is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R 25 If there are multiple R 25 may be the same or different, R 26 represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R 25 -Q 2 [(-R 23 -CH=CH2) c (-R 27 ) 3-c ], where R 26 If there are multiple R 26 may be the same or different, R 27 is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, and R 27 If there are multiple R 27 may be the same or different.

[0031] R 23 -CH=CH2 is R in the compound (A1) and the compound (A2) after the introduction of the adhesive group. 3 This is a group. Also, R 24 , R 25 , R 26 , and R 27 After the introduction of the adhesive group, R in the compound (A1) and the compound (A2) 4 , R 5 , R 6 , and R 7 This is a group.

[0032] Examples of the compound (B1) and the compound (B2) include compounds represented by the following formulae.

[0033] [ka] n6 to n10 are adjusted so that m in formula (B1) or formula (B2) is 0 to 210.

[0034] (Method for producing compound (B1), compound (B2), etc.) An example of a method for producing the compounds (B11) and (B12) including the compounds (B1) and (B2) includes a method for producing the compounds comprising a step of reacting a compound represented by the following formula (C1) or (C2) with a compound represented by the following formula (D1). R f O-(R f1 O) m -R 1 -C(=O)-OR 11 Formula (C1) R 11 OC(=O)-R 1 -O-(R f1 O) m -R 1 -C(=O)-OR 11 Formula (C2) (CH2=CH-) n Q 11 -R 2 -MgX formula (D1) R f O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B11) (CH2=CH-) n Q 11 -R 2 -L 11 -R 1 -O-(R f1 O) m -R 1 -L 11 -R 2 -Q 11 (-CH=CH2) n Formula (B12) however, R f , R f1 , R 1 , R 2 , Q 11 , m, and n are as described above, and the preferred embodiments are also the same. R 11 R is a leaving group, preferably an alkyl group, more preferably a methyl group. 11 If there are multiple R 11 may be the same or different. L 11 is -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, and L 11 If there are multiple L 11 may be the same or different, X is a halogen atom, and is preferably a chlorine atom, a bromine atom, or an iodine atom. Compound (B11) and compound (B12) are the same as compounds (B1) and (B2). 1 The part corresponding to (L 11 The only difference is that ) can also be -CH-.

[0035] For example, an ester of compound (C1) or (C2) can be reacted with 2 equivalents of compound (D1) and treated with an acid to obtain L 11In the above reaction, the compound (B11) or (B12) in which L is -CH(OH)- or -C(=O)- is obtained as the reaction time is increased. 11 The compound -CH(OH)- is predominantly produced.

[0036] Said L 11 By oxidizing the compound (B11) or (B12) of -CH(OH)-, L 11 In the oxidation reaction, a compound (B11) or (B12) having a formula -C(=O)- can be obtained. As the oxidizing agent in the oxidation reaction, a known oxidizing agent such as a Dess-Martin reagent can be used.

[0037] On the other hand, the L 11 By reducing the compound (B11) or (B12) having -C(=O)-, L 11 As the reducing agent in the reduction reaction, a known reducing agent such as lithium aluminum hydride can be used.

[0038] Said L 11 Compound (B11) or (B12) in which L is -CH(OH)- is dehydrated using triphenylphosphine or the like to obtain L 11 The compound (B11) or (B12) having the formula -CH=CH- is obtained.

[0039] In addition, the above-mentioned L 11 Compound (B11) or (B12) having -CH(OH)- is dehydroxylated by a hydride or radical to obtain L 11 Compound (B11) or (B12) in which is —CH2— is obtained.

[0040] Compound (C1) and compound (C2) can be synthesized by referring to, for example, International Publication No. 2013 / 121984. The compound (D1) can be produced, for example, by reacting the following compound (D2) with metallic magnesium. ((CH2=CH-) n Q 11 -R 2 -X formula (D2) However, R in the formula 2 , Q 11 , X and n are the same as in compound (D1).

[0041] Specific preferred examples of the compound (D2) include the following:

[0042] [ka]

[0043] The above reaction is usually carried out in a solvent. The solvent can be appropriately selected from those capable of dissolving the compound (C1), the compound (C2) and the compound (D1). The solvent may be a single type alone or a mixed solvent of two or more types. For example, when the compound (C1) or the compound (C2) is a compound having a relatively low fluorine atom content (the ratio of fluorine atoms to the molecular weight of the compound molecule), the solvent is not particularly limited as long as it is a solvent inert to the reaction. As the solvent inert to the reaction, among them, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane are preferable, and tetrahydrofuran is more preferable. When the compound (C1) or the compound (C2) has a relatively high fluorine atom content, a mixed solvent of the above-mentioned ether solvent and a fluorine-based solvent is preferred. Examples of fluorine-based solvents include hydrofluorocarbons (1H,4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 2H,3H-perfluoropentane, etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), etc.), hydrofluoroethers (CF3CH2OCF2CF2H(AE3000), (perfluorobutoxy)methane, (perfluorobutoxy)ethane, etc.), hydrochlorofluorocarbons (1H,4H-perfluorohexane, ... olefins ((Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z) form), (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(E) form), (Z)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z) form), (E)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E) form), etc.), fluorine-containing aromatic compounds (perfluorobenzene, m-bis(trifluoromethyl)benzene (SR-solvent), p-bis(trifluoromethyl)benzene, etc.).

[0044] (Method for producing compound (A11) and compound (A12)) As a method for producing the compound (A11) and the compound (A12) including the compound (A1) and the compound (A2), there may be mentioned a method for producing the compound, which comprises a step of introducing an adhesive group T into the compound (B11) or the compound (B12). R f O-(R f1 O) m -R 1 -L 11 -R 2 -Q 1 (-T) n Formula (A11) (T-) n Q 1 -R 2 -L 11 -R1 -O-(R f1 O) m -R 1 -L 11 -R 2 -Q 1 (-T) n Formula (A12) however, R f , R f1 , R 1 , R 2 , L 11 , Q 1 , Q 11 , m, and n are as described above, and the preferred embodiments are also the same.

[0045] Hereinafter, the method for introducing each adhesive group T will be described by way of example, but is not limited to the following methods. For example, the double bond of the compound (B11) or the compound (B12) is reacted with the following compound (E1) to cause a hydrosilylation reaction, whereby the adhesive group T is converted to -Si(R 21 ) 3-d (L 21 ) d Compound (A11) or compound (A12) of the formula (A11) or (A12) is obtained. HSi(R 21 ) 3-d (L 21 ) d Formula (E1) However, R 21 , L 21 and d are as described above, and the preferred embodiments are also the same.

[0046] The double bond of the compound (B11) or the compound (B12) is epoxidized by the action of a peracid such as metachloroperbenzoic acid, peracetic acid, or potassium hydrogen persulfate to obtain the compound (A11) or the compound (A12) in which the adhesive group T is an epoxy group.

[0047] The double bond of the compound (B11) or the compound (B12) is oxidized with ozone to form an ozonide, and then the compound is oxidized with, for example, hydrogen peroxide to obtain the compound (A11) or the compound (A12) in which the adhesive group T is a carboxy group. Furthermore, by subjecting the ozonide to a reduction treatment with a reducing agent such as zinc, dimethylsulfide, or thiourea, a compound (A11) or compound (A12) in which the adhesive group T is an aldehyde group can be obtained.

[0048] The compound (B11) or the compound (B12) has a double bond, and an organoborane ((R 22 )3B; but R 22 is a hydrogen atom or an organic group) to form a hydroboronate, which is then reacted with bromine (Br2) or iodine (I2) under basic conditions to obtain compound (A11) or compound (A12) in which the adhesive group T is a bromine atom or an iodine atom. Furthermore, compound (A11) or compound (A12) in which the adhesive group T is a bromine atom or an iodine atom is reacted with a phosphite ester, and then hydrolysis is performed using hydrochloric acid or the like to obtain compound (A11) or compound (A12) in which the adhesive group T is a phosphonic acid. When the hydroboration product is reacted with hydrogen peroxide under basic conditions, a compound (A11) or compound (A12) in which the adhesive group T is a hydroxy group is obtained. Furthermore, when an activated phosphoric acid such as phosphoryl chloride is reacted with the compound (A11) or compound (A12) in which the adhesive group T is a hydroxy group, a compound (A11) or compound (A12) in which the adhesive group T is a phosphoric acid is obtained.

[0049] Furthermore, the compound (A11) or compound (A12) in which the adhesive group T is an aldehyde group can be reacted with an amine to form an imine or iminium ion, followed by hydride reduction to obtain the compound (A11) or compound (A12) in which the adhesive group T is an amino group.

[0050] The fluorine-containing compound-containing composition of the present invention (fluorine-containing ether composition, hereinafter also referred to as "the composition") may contain compound (A1) and compound (A2), or may contain one or more compounds selected from compound (A1) and compound (A2) and other fluorine-containing ether compounds. Note that the composition does not include a liquid medium described later.

[0051] Examples of the other fluorine-containing ether compounds include fluorine-containing ether compounds produced as a by-product in the production process of the present compound (hereinafter also referred to as "by-product fluorine-containing ether compounds"), known fluorine-containing ether compounds used for the same purpose as the present compound, and fluorine-containing oils. As the other fluorine-containing compounds, compounds that are unlikely to deteriorate the properties of the present compound are preferred.

[0052] Examples of fluorine-containing oils include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE).

[0053] 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.

[0054] Examples of known fluorine-containing compounds include those described in the following documents: Perfluoropolyether-modified aminosilanes described in JP-A-11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP 2000-144097 A; Perfluoropolyether-modified aminosilanes described in JP 2000-327772 A; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Publication No. 2008-534696; Fluorinated modified hydrogen-containing polymers as described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A, Organosilicon compounds described in WO 2011 / 060047 and WO 2011 / 059430; Fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in JP 2012-72272 A; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A; Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, 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.

[0055] 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, 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.

[0056] [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.

[0057] 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.

[0058] 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 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 preferable, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents. The present coating liquid preferably contains the liquid medium in an amount of 75 to 99.999 mass %, more preferably 85 to 99.99 mass %, and particularly preferably 90 to 99.9 mass %.

[0059] 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.

[0060] 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.

[0061] [Goods] The article of the present invention (hereinafter also referred to as "the article") has a surface layer formed from the compound or composition on the surface of a substrate. The surface layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. The surface layer may extend in the form of a film on the surface of the substrate, or may be scattered in the form of dots. The surface layer contains the present compound in a state in which a part or all of the hydrolyzable silyl groups of the present compound have undergone hydrolysis reaction and the silanol groups have undergone dehydration condensation reaction.

[0062] The thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. If the thickness of the surface layer is 1 nm or more, the effect of the surface treatment is easily obtained sufficiently. If the thickness of the surface layer is 100 nm or less, the utilization efficiency is high. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G).

[0063] The substrate may be a substrate to which water and oil repellency is required, such as a substrate that may be used by contacting with other articles (e.g., a stylus) or human fingers, a substrate that may be held by human fingers during operation, or a substrate that may be placed on top of other articles (e.g., a mounting table). The substrate material may be metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof. The glass may be chemically strengthened. A base film such as a SiO2 film may be formed on the surface of the substrate. More specifically, the substrates listed in the adhesive group T may be referred to. The substrate is preferably a substrate for a touch panel, a substrate for a display, or a lens for glasses, and is particularly preferably a substrate for a touch panel. The material of the substrate for a touch panel is preferably glass or a transparent resin. Further, the substrate is preferably glass or a resin film used for the exterior parts (excluding the display parts) of devices such as mobile phones (for example, smartphones), personal digital assistants (for example, tablet terminals), game consoles, and remote controls.

[0064] [Production method] The present article can be produced, for example, by the following method. A method for forming a surface layer formed from the present compound or composition on the surface of a substrate by treating the surface of the substrate by a dry coating method using the present compound or composition. A method in which the coating liquid is applied to the surface of a substrate by a wet coating method, and then dried to form a surface layer formed from the compound or composition on the surface of the substrate.

[0065] Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. As the dry coating method, the vacuum deposition method is preferred from the viewpoint of suppressing the decomposition of compound A1 or compound A2 and from the viewpoint of the simplicity of the device. During vacuum deposition, a pellet-like material in which a metal porous body such as iron or steel is impregnated with the present compound or the present composition may be used. The present coating liquid may be impregnated into a metal porous body such as iron or steel, the liquid medium may be dried, and a pellet-like material in which compound A1 or compound A2 or the present composition is impregnated may be used.

[0066] Examples of the wet coating method include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0067] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be carried out, if necessary. Such an operation may include heating, humidification, light irradiation, etc. For example, by heating a substrate on which a surface layer has been formed in an atmosphere containing moisture, it is possible to promote reactions such as the hydrolysis reaction of hydrolyzable groups, the reaction of hydroxyl groups and the like on the surface of the substrate with silanol groups, and the formation of siloxane bonds through condensation reactions 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

[0068] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following, "%" means "mass %" unless otherwise specified. Examples 1 to 4, 7 to 9, 11 to 14, and 17 to 19 are examples, and Examples 5 to 6, 10, 15 to 16, and 20 are comparative examples.

[0069] [Synthesis Example 1: Synthesis of Compound (1)] DiethylDiallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.45 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 (1).

[0070] [ka]

[0071] [Synthesis Example 2: Synthesis of Compound (2)] After adding THF (260 mL) and diisopropylamine (41.6 mL), the solution was cooled to -78°C. n-Butyllithium hexane solution (2.76 M, 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 (1) (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, 1 M hydrochloric acid 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 using silica gel was performed to obtain 45.0 g of compound (2).

[0072] [ka]

[0073] [Synthesis Example 3: Synthesis of compound (3)] The above compound (2) (45.0 g) was dissolved in THF and cooled to 0° C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, stirred at room temperature, and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (3).

[0074] [ka]

[0075] <Another synthesis method for compound (3)> [Synthesis Example 3-1: Synthesis of compound (2a)] After adding THF (260 mL) and diisopropylamine (41.6 mL, 294 mmol), the solution was cooled to −78° C. A n-butyllithium hexane solution (2.76 M, 96.6 mL, 267 mmol) was added and the temperature was raised to 0° C. to prepare a THF solution of lithium diisopropylamide (LDA). THF (50 mL) was added to tert-Butyl Acetate (9.29 g), cooled to -78 ° C, and then a THF solution of LDA (130 mL) was added. Allyl bromide (10.9 g) was added, and the temperature was raised to 0 ° C. After 30 minutes, the mixture was cooled to -78 ° C, and then LDA (130 mL) and allyl bromide (10.9 g) were added, and the temperature was raised to 0 ° C. After cooling to -78 ° C again, LDA (130 mL) and allyl bromide (10.9 g) were added, and the temperature was raised to 0 ° C. After stirring for 30 minutes, 1 M 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 using silica gel was performed to obtain 9.45 g of the following compound (2a).

[0076] [ka]

[0077] [Synthesis Example 3-2: Synthesis of compound (3)] The compound (2a) (9.45 g) was dissolved in THF (100 mL) and cooled to 0° C. A solution of lithium aluminum hydride in THF (40 mL, 100 mmol) was added and stirred at 50° C. 1 M hydrochloric acid (100 mL) was added at 0° C., and then extracted with dichloromethane. The solvent was removed, and flash column chromatography using silica gel was performed to obtain 5.99 g of the compound (2-3).

[0078] [Synthesis Example 4: Synthesis of compound (4)] Acetonitrile (380 mL), the compound (3) (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 (4) was obtained by distillation (70° C., 3 hPa).

[0079] [ka]

[0080] [Synthesis Example 5: Synthesis of compound (5)] 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 (4) (14.0 g) in THF (35 mL) was added and heated under reflux for 2 hours to prepare a solution (0.80 M) of the following compound (5).

[0081] [ka]

[0082] [Synthesis Example 6: Synthesis of compound (1-1)] According to the method described in Example 6 of WO 2013 / 121984, the following compound (1-1) was obtained. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x1 (CF2CF2O)-CF2CF2CF2-C(O)OCH3...Formula (1-1) Units x 1 average: 14

[0083] [Synthesis Example 7: Synthesis of compound (1-2)] The compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL) were added, and then the compound (5) solution (11.0 mL) was added. After stirring at 60° C. for 20 hours, 1M hydrochloric acid was added. After extraction with AE3000, the mixture was dried over sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 1.15 g of the following compound (1-2).

[0084] [ka] Units x 1 average: 14

[0085] NMR spectrum of compound (1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.92~5.74(m,3H),5.13~4.97(m,6H),4.40(s,1H),2.24~2.02(m,6H) ,1.90(d,J=7.7Hz,1H),1.77(d,J=15.2Hz,1H),1.61(dd,J=15.3,10.1Hz,1H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-55.24,-82.81,-87.63~-88.38(m),-89.99~-90.36(m),-117.61~-117.84(m),-118. 35~-118.58(m),-123.13~-123.30(m),-124.49~-124.66(m),-125.24,-127.57~-127.77(m).

[0086] [Example 1: Synthesis of fluorine-containing ether compound (1-3)] AC2000 (1.8 g), the above compound (1-2) (0.300 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure to obtain 0.291 g of the following fluorine-containing ether compound (1-3).

[0087] [ka] Units x 1 average: 14

[0088] NMR spectrum of fluorine-containing ether compound (1-3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):4.82~4.65(m,1H),3.70~3.51(m,27H),2.02~1.13(m,15H),0.85~0.59(m,6H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-55.27,-82.85,-88.07,-90.19,-117.56,-122.25~-122.86(m),-125.26.

[0089] [Synthesis Example 8: Synthesis of compound (2-1)] The compound (1-2) (0.350 g) obtained in Synthesis Example 7, 1,3-bistrifluoromethylbenzene (3 mL), and Dess-Martin reagent (0.350 g) were added and stirred at 35° C. for 2 hours. Methanol was added, and the mixture was extracted with AC6000. The solvent was removed, and flash column chromatography using silica gel was performed to obtain 0.280 g of the following compound (2-1).

[0090] [ka] Units x 1 average: 14

[0091] NMR spectrum of compound (2-1); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.99~5.80(m,3H),5.22~5.11(m,6H),2.81(s,2H),2.32(d,J=7.6Hz,6H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.74,-81.50~-81.67(m),-82.19,-87.15~-87.71(m),-89.56,-118.50,-124.35,-124.59.

[0092] [Example 2: Synthesis of fluorine-containing ether compound (2-2)] AC6000 (2.0 g), the above compound (2-1) (0.280 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 6.7 mg), aniline (2.0 mg), and trimethoxysilane (37.0 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure, thereby obtaining 0.286 g of the following fluorine-containing ether compound (2-2).

[0093] [ka] Units x 1 average: 14

[0094] NMR spectrum of fluorine-containing ether compound (2-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):3.58(s,27H),2.70(s,2H),1.56~1.41(m,12H),0.61(t,J=7.5Hz,6H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-55.12,-81.96,-82.61,-87.51~-87.97(m),-89.98,-119.04,-124.72,-125.03.

[0095] [Synthesis Example 9: Synthesis of compound (3-1)] 1,3-Bistrifluoromethylbenzene (7.5 mL), the compound (1-2) (0.750 g) obtained in Synthesis Example 7, triphenylphosphine (0.406 g), and carbon tetrachloride (0.310 g) were added and stirred for 2 hours at 100° C. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 0.524 g of the following compound (3-1).

[0096] [ka] Units x 1 average: 14

[0097] NMR spectrum of compound (3-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):6.34(dt,J=16.3,2.1Hz,1H),5.68(ddt,J=17.7,10.4,7.4Hz,3H),5.59~5.44(m,1H),5.07~4.97(m,6H),2.13(d,J=7.3Hz,6H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-55.31,-81.79~-82.03(m),-82.92,-87.75~-88.40(m),-90.24(q,J=8.2,7.8Hz),-110.96(q,J=9.9Hz),-125.35,-126.26.

[0098] [Example 3: Synthesis of fluorine-containing ether compound (3-2)] AC2000 (3.1 g), the compound (3-1) (0.524 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 17.3 mg), aniline (7.0 mg), and trimethoxysilane (69.1 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure, thereby obtaining 0.514 g of the following fluorine-containing ether compound (3-2).

[0099] [ka] Units x 1 average: 14

[0100] NMR spectrum of fluorine-containing ether compound (3-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):6.34(dd,J=16.3,2.0Hz,1H),5.61(dt,J=16.3,11.7Hz,1H),3.59(s,27H),1.57~1.30(m,12H),0.66(t,J=7.5Hz,6H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-55.27,-81.64~-81.91(m),-82.85,-87.66~-88.31(m),-90.18(q,J=8.7Hz),-110.50(q,J=10.2Hz),-125.26,-125.96.

[0101] [Synthesis Example 10: Synthesis of compound (4-1)] Fluorolink D4000 (SOLVAY, 15.0 g), 1,3-bistrifluoromethylbenzene (50 ml), and acetonitrile (30 ml) were added, followed by sodium hypochlorite solution (30 ml), TEMPO (1 g), and KBr (1 g) in that order. After stirring at 60°C for 5 hours, dilute sulfuric acid was added. After extraction with AE3000, the solvent was distilled off to obtain 15.0 g of the following compound (4-1).

[0102] [ka] p:22, q:25

[0103] [Synthesis Example 11: Synthesis of compound (4-2)] The compound (4-1) (15.0 g), 1,3-bistrifluoromethylbenzene (50 ml), and methanol (50 ml) were added, and then 1 g of concentrated sulfuric acid was added. The mixture was heated under reflux and then concentrated. The concentrate was purified by flash column chromatography to obtain 14.5 g of the following compound (4-2).

[0104] [ka] p:22, q:25

[0105] NMR spectrum of compound (4-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):3.84(s,6H).

[0106] [Synthesis Example 12: Synthesis of compound (4-3)] The compound (4-2) (6.27 g) and 1,3-bistrifluoromethylbenzene (44 mL) were added, and then the compound (5) solution (11.0 mL) was added. After stirring at 60° C. for 1 hour, 1M hydrochloric acid was added. After extraction with AE3000, the mixture was dried over sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 2.95 g of the following compound (4-3).

[0107] [ka] p:22, q:25

[0108] NMR spectrum of compound (4-3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.82~5.69(m,6H),5.13~5.03(m,12H),2.64(s,4H),2.19(d,J=7.6Hz,12H).

[0109] [Synthesis Example 13: Synthesis of compound (4-4)] The compound (4-3) (2.95 g) was dissolved in AE3000 (20 mL) and cooled to 0° C. A solution of lithium aluminum hydride in THF (1.7 mL, 4.3 mmol) was added and stirred. 1 M hydrochloric acid was added, extracted with AE3000, and then dried with sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 0.216 g of the following compound (4-4).

[0110] [ka] p:22, q:25

[0111] NMR spectrum of compound (4-4); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.75(m,6H),5.13~5.01(m,12H),4.27~4.07(m,2H),2.34~1.60(m,16H).

[0112] [Example 4: Synthesis of fluorine-containing ether compound (4-5)] AC2000 (1.4 g), the compound (4-4) (0.216 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 13.6 mg), aniline (12.4 mg), and trimethoxysilane (92.7 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure, obtaining 0.211 g of the following fluorine-containing ether compound (4-5).

[0113] [ka] p:22, q:25

[0114] NMR spectrum of compound (4-4); 1H-NMR(400MHz,Chloroform-d) δ(ppm):4.67~4.44(m,2H),3.72~3.54(m,54H),2.06~1.35(m,30H),0.78~0.57(m,12H).

[0115] [Synthesis Example 14: Another synthesis example of the compound (2-1)] The compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL) were added, and then the solution of the compound (5) (11.0 mL) was added. After stirring at 60° C. for 3 hours, 1M hydrochloric acid was added. After extraction with AE3000, the mixture was dried over sodium sulfate. After filtration, the solvent was distilled off, and the mixture was washed with hexane, followed by flash column chromatography using silica gel to obtain 7.28 g of the compound (2-1).

[0116] [Synthesis Example 15: Another synthesis example of the compound (1-2)] The compound (2-1) (7.15 g) was dissolved in AE3000 (36 mL) and cooled to 0° C. A solution of lithium aluminum hydride in THF (1.7 mL) was added and stirred. Water and a 15% aqueous solution of sodium hydroxide were added and stirred at room temperature. After extraction with AE3000, the mixture was dried over sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 5.27 g of the compound (1-2).

[0117] [Synthesis Example 16: Synthesis of compound (5-1)] The compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL) were added, and then allylmagnesium bromide (10.0 mL, 0.7 M, 7.0 mmol) was added. After stirring at room temperature for 20 hours, 1 M hydrochloric acid was added. After extraction with AE3000, the mixture was dried over sodium sulfate. After filtration, the solvent was removed, and flash column chromatography using silica gel was performed to obtain 5.57 g of the following compound (5-1).

[0118] [ka] Units x 1 average: 14

[0119] NMR spectrum of compound (5-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):6.03~5.87(m,2H),5.40~5.21(m,4H),2.71~2.50(m,4H),2.39(s,1H). 19 F-NMRf(376MHz,Chloroform-d) δ(ppm):-54.87(t,J=9.2Hz),-82.17(p,J=7.9Hz),-86.90~-87.67(m),-8 9.57(q,J=9.1Hz),-115.83~-116.17(m),-121.47(q,J=6.5Hz),-124.52f.

[0120] [Example 5: Synthesis of compound (5-2)] AC2000 (1.8 g), the above compound (5-1) (0.320 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 13.5 mg), aniline (2.8 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure to obtain 0.313 g of the following compound (5-2).

[0121] [ka] Units x 1 average: 14

[0122] NMR spectrum of compound (5-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):3.68~3.56(m,18H),2.27~1.11(m,9H),0.87~0.60(m,4H). 19F-NMR (376MHz, Chloroform-d) δ(ppm):-54.84(t,J=9.1Hz),-82.15(dd,J=18.3,9.3Hz),-86.20,-87.09~-87.5 9(m),-89.55(q,J=9.4Hz),-114.46~-116.39(m),-120.82~-120.99(m),-124.50.

[0123] [Synthesis Example 17: Synthesis of compound (6-1)] The above compound (5-1) (0.990 g), potassium hydroxide (0.079 g), tetrabutylammonium iodide (0.009 g), and allyl bromide (1.21 g) were added, and the mixture was stirred at 80° C. for 20 hours. 1M hydrochloric acid was added, and the mixture was extracted with AE3000 and then dried with sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 0.351 g of the following compound (6-1).

[0124] [ka] Units x 1 average: 14

[0125] NMR spectrum of compound (6-1); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.95~5.78(m,3H),5.33~5.03(m,6H),4.17(d,J=5.0Hz,2H),2.82~2.42(m,4H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-54.88(t,J=9.2Hz),-82.19,-87.00~-87.83(m),-89.59(q,J=9.5Hz),-109.82~-111.37(m),-121.70~-122.53(m),-124.55.

[0126] [Example 6: Synthesis of compound (6-2)] AC2000 (1.8 g), the above compound (6-1) (0.351 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 14.5 mg), aniline (3.1 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40° C., and the solvent was then distilled off under reduced pressure to obtain 0.333 g of the following compound (6-2).

[0127] [ka] Units x 1 average: 14

[0128] NMR spectrum of compound (6-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):3.78~3.31(m,29H),2.07~1.21(m,10H),0.90~0.55(m,6H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-54.97(t,J=9.1Hz),-82.22,-87.14~-87.99(m),-89.64(q,J=9.5Hz),-109.89~-111.67(m),-121.87~-122.73(m),-124.75.

[0129] [Example 7: Preparation of fluorinated ether composition] The compound (1-2) and the compound (1-3) were mixed in a ratio of 80:20 (mass ratio) to obtain a fluorinated ether composition of Example 7.

[0130] [Example 8: Preparation of fluorine-containing ether composition] The compound (2-1) and the compound (2-2) were mixed in a ratio of 75:25 (mass ratio) to obtain a fluorinated ether composition of Example 8.

[0131] [Example 9: Preparation of fluorinated ether composition] The compound (2-1) and the compound (2-2) were mixed in a ratio of 85:15 (mass ratio) to obtain a fluorinated ether composition of Example 9.

[0132] [Example 10: Preparation of fluorine-containing ether composition] The compound (6-1) and the compound (6-2) were mixed in a ratio of 80:20 (mass ratio) to obtain a fluorinated ether composition of Example 10.

[0133] [Examples 11 to 16: Manufacturing and evaluation of articles] Substrates were surface-treated using the compounds obtained in Examples 1 to 6 and the compositions obtained in Examples 7 to 10 to obtain articles in Examples 11 to 20. 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 articles were evaluated by the following method. The results are shown in Tables 1 and 2.

[0134] (Dry coating method) Dry coating was performed using a vacuum deposition apparatus (ULVAC, VTR350M) (vacuum deposition method). 0.5 g of each compound 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 film formation on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to end film formation 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 dichloropentafluoropropane (AK-225, manufactured by AGC) to obtain an article having a surface layer on the surface of the substrate.

[0135] (Wet coating method) Each compound was mixed with C4F9OC2H5 (3M, Novec (registered trademark) 7200) as a medium to prepare a coating solution with a solid content concentration of 0.05%. A substrate was dipped in the coating solution, 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.

[0136] (Evaluation method) <Contact angle measurement method> The contact angle of about 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., DM-500). 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.

[0137] <Initial contact angle> The initial water contact angle and the initial n-hexadecane contact angle of the surface layer were measured by the above-mentioned measuring method. The evaluation criteria were as follows. Initial water contact angle: ◎ (Excellent): Over 115 degrees. ○ (Good): Between 105 degrees and 115 degrees. ×(Not acceptable): Less than 105 degrees.

[0138] <Abrasion resistance (steel wool)> 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 by the above-mentioned method after steel wool Bonstar (#0000) was reciprocated 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the decrease in performance due to friction and the more excellent the friction resistance. The evaluation criteria are as follows. ◎ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is 5 degrees or less. ◯ (Good): The change in water contact angle after 10,000 reciprocating strokes is more than 5 degrees and less than 8 degrees. △ (Acceptable): The change in water contact angle after 10,000 reciprocating strokes is more than 8 degrees and less than 10 degrees. × (Fail): The change in water contact angle after 10,000 strokes exceeds 10 degrees.

[0139] <Light resistance> The surface layer was subjected to accelerated light fastness testing using a tabletop xenon arc lamp type accelerated light fastness tester (product name: SUNTEST XLS+, manufactured by Toyo Seiki Co., Ltd.) at a black panel temperature of 63°C and light (650 W / m 2After irradiation with light of 300 to 700 nm for 500 hours, the water contact angle was measured by the above-mentioned method. The evaluation criteria are as follows. ⊚ (Excellent): The change in water contact angle after the accelerated light resistance test is 5 degrees or less. ◯ (Good): The change in water contact angle after the accelerated light resistance test is more than 5 degrees and 10 degrees or less. × (unacceptable): The change in water contact angle after the accelerated light resistance test is more than 10 degrees.

[0140] [Table 1]

[0141] [Table 2]

[0142] As shown in Table 1, the articles of Examples 15 and 16 using the compounds of Examples 5 and 6 had good initial contact angles and light resistance, but a decrease in water contact angle was confirmed, especially after the friction test. On the other hand, the articles of Examples 11 to 14 having surface layers using the fluorinated ether compounds of Examples 1 to 4 having -CH(OH)-, -C(=O)-, or -CH=CH- between the polyfluoropolyether chain and the branched structure showed suppressed decrease in water contact angle even after the friction test and light resistance test, demonstrating excellent durability. Moreover, as shown in Table 2, the articles having a surface layer using the fluorine-containing ether compositions of Examples 17 to 19 containing the fluorine-containing ether compounds of Examples 1 to 4 showed suppressed decrease in water contact angle even after the friction test and the light resistance test, and were shown to have excellent durability. Furthermore, a comparison between Examples 11 and 17 showed that the friction resistance was further improved by using a combination of the fluorine-containing ether compound (1-3) having a hydrolyzable silyl group and the fluorine-containing ether compound (1-2) having an unsaturated hydrocarbon group.

[0143] This application claims priority based on Japanese Patent Application No. 2020-39975, filed on March 9, 2020, the disclosure of which is incorporated herein in its entirety.

Claims

1. A fluorine-containing ether compound represented by the following formula (A1) or formula (A2): R ｆ O-(R ｆ１ O) ｍ -R １ -L １ -R ２ -Q １ (-T) ｎ Formula (A1) (T-) ｎ Q １ -R ２ -L １ -R １ -O-(R ｆ１ O) ｍ -R １ -L １ -R ２ -Q １ (-T) ｎ Formula (A2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１ If there are multiple R ｆ１ may be the same or different, R １ is an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different, R ２ is a single bond or an alkylene group which may have a fluorine atom, and R ２ If there are multiple R ２ may be the same or different, L １ is -CH(OH)-, -C(=O)-, or -CH=CH-, and L １ If there are multiple L １ may be the same or different, Q １ is a 1+n valent linking group, and Q １ If there are multiple Q １ may be the same or different, T is at least one selected from a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R21)3-d(L21)d; R 21 is an alkyl group; L 21 represents a hydrolyzable group or a hydroxyl group, and a plurality of L 21 may be the same or different; d is 2 or 3; n is an integer from 2 to 20, and when there are multiple n's, the n's may be the same or different; (R f1 O) m is a structure represented by the following formula (R f1 -1). (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having 1 carbon atom; R f12 is a fluoroalkylene group having 2 carbon atoms; R f13 is a fluoroalkylene group having 3 carbon atoms; R f14 is a fluoroalkylene group having 4 carbon atoms; R f15 is a fluoroalkylene group having 5 carbon atoms; R f16 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 210, and when there are multiple R f11 to R f16 , the multiple R f11 to R f16 may be the same or different.

2. R １ The fluorine-containing ether compound according to claim 1, wherein the carbon number of the formula is 1 to 6.

3. R ２ 3. The fluorine-containing ether compound according to claim 1, wherein the carbon number of the formula is 1 to 10.

4. -Q １ (-T) ｎ But, -Q ２ [(-R ３ -T) ａ (-R ４ ) ３－ａ The fluorine-containing ether compound according to any one of claims 1 to 3, wherein however, Q ２ is a carbon atom or a silicon atom, and Q ２ If there are multiple Q ２ may be the same or different, R ３ is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R ３ If there are multiple R ３ may be the same or different, R ４ represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R ５ -Q ２ [(-R ３ -T) ｂ (-R ６ ) ３－ｂ ], where R ４ If there are multiple R ４ may be the same or different, R ５ is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R ５ If there are multiple R ５ may be the same or different, R ６ represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R ５ -Q ２ [(-R ３ -T) ｃ (-R ７ ) ３－ｃ ], where R ６ If there are multiple R ６ may be the same or different, R ７ is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, R ７ If there are multiple R ７ may be the same or different, a is an integer from 0 to 3; b is an integer of 0 to 3, and when there are multiple b's, the b's may be the same or different; c is an integer of 0 to 3, and when there are multiple c's, the c's may be the same or different; The sum of a, b, and c is n.

5. R ３ The fluorine-containing ether compound according to claim 4, wherein the carbon number of the formula is 2 to 7.

6. A compound represented by the following formula (B1) or formula (B2): R ｆ O-(R ｆ１ O) ｍ -R １ -L １ -R ２ -Q １１ (-CH=CH ２ ) ｎ Formula (B1) (CH ２ =CH - ) ｎ Q １１ -R ２ -L １ -R １ -O-(R ｆ１ O) ｍ -R １ -L １ -R ２ -Q １１ (-CH=CH ２ ) ｎ Formula (B2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１ If there are multiple R ｆ１ may be the same or different, R １ is an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different, R ２ is a single bond or an alkylene group which may have a fluorine atom, and R ２ If there are multiple R ２ may be the same or different, L １ is -CH(OH)-, -C(=O)-, or -CH=CH-, and L １ If there are multiple L １ may be the same or different, Q １１ is a 1+n valent linking group, and Q １１ If there are multiple Q １１ may be the same or different, n is an integer from 2 to 20, and when there are multiple n's, the n's may be the same or different; (R f1 O) m is a structure represented by the following formula (R f1 -1). (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having 1 carbon atom; R f12 is a fluoroalkylene group having 2 carbon atoms; R f13 is a fluoroalkylene group having 3 carbon atoms; R f14 is a fluoroalkylene group having 4 carbon atoms; R f15 is a fluoroalkylene group having 5 carbon atoms; R f16 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 210, and when there are multiple R f11 to R f16 , the multiple R f11 to R f16 may be the same or different.

7. -Q １１ (-CH=CH ２ ) ｎ But, -Q ２ [(-R ２３ -CH=CH ２ ) ａ (-R ２４ ) ３－ａ 7. The compound according to claim 6, wherein however, Q ２ is a carbon atom or a silicon atom, and Q ２ If there are multiple Q ２ may be the same or different, R ２３ is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R ２３ If there are multiple R ２３ may be the same or different, R ２４ represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R ２５ -Q ２ [(-R ２３ -CH=CH ２ ) ｂ (-R ２６ ) ３－ｂ ], where R ２４ If there are multiple R ２４ may be the same or different, R ２５ is a single bond or an alkylene group which may have a fluorine atom and may have an ether bond between carbon atoms, R ２５ If there are multiple R ２５ may be the same or different, R ２６ represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom and which may have an ether bond between carbon atoms, or -R ２５ -Q ２ [(-R ２３ -CH=CH ２ ) ｃ (-R ２７ ) ３－ｃ ], where R ２６ If there are multiple R ２６ may be the same or different, R ２７ is a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom and may have an ether bond between carbon atoms, R ２７ If there are multiple R ２７ may be the same or different, a is an integer from 0 to 3; b is an integer of 0 to 3, and when there are multiple b's, the b's may be the same or different; c is an integer of 0 to 3, and when there are multiple c's, the c's may be the same or different; The sum of a, b, and c is n.

8. A method for producing a compound represented by the following formula (B11) or (B12), comprising a step of reacting a compound represented by the following formula (C1) or (C2) with a compound represented by the following formula (D1). R ｆ O-(R ｆ１ O) ｍ -R １ -C(=O)-OR １１ Formula (C1) R １１ O−C(=O)−R １ −O−(R ｆ１ O) ｍ −R １ −C(=O)−OR １１ Formula (C2) (CH ２ =CH - ) ｎ Q １１ -R ２ -MgX Formula (D1) R ｆ O-(R ｆ１ O) ｍ -R １ -L １１ -R ２ -Q １１ (-CH = CH ２ ) ｎ Formula (B11) (CH ２ =CH - ) ｎ Q １１ -R ２ -L １１ -R １ -O-(R ｆ１ O) ｍ -R １ -L １１ -R ２ -Q １１ (-CH=CH ２ ) ｎ Formula (B12) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１ If there are multiple R ｆ１ may be the same or different, R １ is an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different, R ２ is a single bond or an alkylene group which may have a fluorine atom, and R ２ If there are multiple R ２ may be the same or different, R １１ is an alkyl group, R １１ If there are multiple R １１ may be the same or different, L １１ is -CH(OH)-, -C(=O)-, -CH=CH-, or -CH ２ - and L １１ If there are multiple L １１ may be the same or different, Q １１ is a 1+n valent linking group, and Q １１ If there are multiple Q １１ may be the same or different, X is a halogen atom; n is an integer from 2 to 20, and when there are multiple n's, the n's may be the same or different; (R f1 O) m is a structure represented by the following formula (R f1 -1). (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having 1 carbon atom; R f12 is a fluoroalkylene group having 2 carbon atoms; R f13 is a fluoroalkylene group having 3 carbon atoms; R f14 is a fluoroalkylene group having 4 carbon atoms; R f15 is a fluoroalkylene group having 5 carbon atoms; R f16 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 210, and when there are multiple R f11 to R f16 , the multiple R f11 to R f16 may be the same or different.

9. A method for producing a fluorinated ether compound represented by the following formula (A11) or (A12), comprising a step of introducing an adhesive group T into a compound represented by the following formula (B11) or (B12). R ｆ O-(R ｆ１ O) ｍ -R １ -L １１ -R ２ -Q １１ (-CH = CH ２ ) ｎ Formula (B11) (CH ２ =CH−) ｎ Q １１ −R ２ −L １１ −R １ −O−(R ｆ１ O) ｍ −R １ −L １１ −R ２ −Q １１ (−CH=CH ２ ) ｎ Formula (B12) R ｆ O-(R ｆ１ O) ｍ -R １ -L １１ -R ２ -Q １ (-T) ｎ Formula (A11) (T−) ｎ Q １ −R ２ −L １１ −R １ −O−(R ｆ１ O) ｍ −R １ −L １１ −R ２ −Q １ (−T) ｎ Formula (A12) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１ If there are multiple R ｆ１ may be the same or different, R １ is an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different, R ２ is a single bond or an alkylene group which may have a fluorine atom, and R ２ If there are multiple R ２ may be the same or different, L １１ is -CH(OH)-, -C(=O)-, -CH=CH-, or -CH ２ - and L １１ If there are multiple L １１ may be the same or different, Q １ is a 1+n valent linking group, and Q １ If there are multiple Q １ may be the same or different, Q １１ is a 1+n valent linking group, and Q １１ If there are multiple Q １１ may be the same or different, T is at least one selected from a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R21)3-d(L21)d; R 21 is an alkyl group; L 21 represents a hydrolyzable group or a hydroxyl group, and a plurality of L 21 may be the same or different; d is 2 or 3; n is an integer from 2 to 20, and when there are multiple n's, the n's may be the same or different; (R f1 O) m is a structure represented by the following formula (R f1 -1). (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having 1 carbon atom; R f12 is a fluoroalkylene group having 2 carbon atoms; R f13 is a fluoroalkylene group having 3 carbon atoms; R f14 is a fluoroalkylene group having 4 carbon atoms; R f15 is a fluoroalkylene group having 5 carbon atoms; R f16 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 210, and when there are multiple R f11 to R f16 , the multiple R f11 to R f16 may be the same or different.

10. A fluorinated ether composition comprising a fluorinated ether compound represented by the following formula (A1) and a fluorinated ether compound represented by the following formula (A2): R ｆ O-(R ｆ１ O) ｍ -R １ -L １ -R ２ -Q １ (-T) ｎ Formula (A1) (T−) ｎ Q １ −R ２ −L １ −R １ −O−(R ｆ１ O) ｍ −R １ −L １ −R ２ −Q １ (−T) ｎ Formula (A2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１ If there are multiple R ｆ１ may be the same or different, R １ is an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different, R ２ is a single bond or an alkylene group which may have a fluorine atom, and R ２ If there are multiple R ２ may be the same or different, L １ is -CH(OH)-, -C(=O)-, or -CH=CH-, and L １ If there are multiple L １ may be the same or different, Q １ is a 1+n valent linking group, and Q １ If there are multiple Q １ may be the same or different, T is at least one selected from a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R21)3-d(L21)d; R 21 is an alkyl group; L 21 represents a hydrolyzable group or a hydroxyl group, and a plurality of L 21 may be the same or different; d is 2 or 3; n is an integer from 2 to 20, and when there are multiple n's, the n's may be the same or different; (R f1 O) m is a structure represented by the following formula (R f1 -1). (R f11 O) m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 Formula (R f1 -1) however, R f11 is a fluoroalkylene group having 1 carbon atom; R f12 is a fluoroalkylene group having 2 carbon atoms; R f13 is a fluoroalkylene group having 3 carbon atoms; R f14 is a fluoroalkylene group having 4 carbon atoms; R f15 is a fluoroalkylene group having 5 carbon atoms; R f16 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, m1+m2+m3+m4+m5+m6 is an integer of 1 to 210, and when there are multiple R f11 to R f16 , the multiple R f11 to R f16 may be the same or different.

11. A fluorinated ether composition comprising at least one of the fluorinated ether compounds according to any one of claims 1 to 5 and another fluorinated ether compound.

12. A fluorinated ether compound according to any one of claims 1 to 5 or a fluorinated ether composition according to claim 10, A coating liquid comprising a liquid medium.

13. An article having a surface layer formed from the fluorinated ether compound according to any one of claims 1 to 5, or the fluorinated ether composition according to claim 10, on the surface of a substrate.

14. 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 5, the fluorinated ether composition according to claim 10, or the coating liquid according to claim 12.

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