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

Abstract

The present invention provides: a fluorine-containing ether compound which has excellent light resistance; a surface treatment agent; a fluorine-containing ether composition; a coating liquid; an article having a surface layer that has excellent light resistance; a method for producing this article; and a compound which is useful as a starting material for a fluorine-containing ether compound that has excellent light resistance. A fluorine-containing ether compound which is represented by general formula (A). Formula (A): (R1R2C=CR3-L1-)n1Q1-Rf-Q2(-T)n2 (In formula (A), the symbols are as defined in the description.)

Description

[Technical Field]

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

[0002] Fluorine-containing ether compounds have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are used in a wide variety of fields, including electrical and electronic materials, semiconductor materials, optical materials, and surface treatment agents. For example, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is suitable for use as a surface treatment agent because it can form a surface layer on the surface of a substrate that exhibits high lubricity, water and oil repellency, etc. Surface treatment agents containing fluorine-containing ether compounds are used in applications where it is required that the performance of the surface layer not easily reduced in water and oil repellency even when rubbed repeatedly with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability) be maintained for a long period of time, such as surface treatment agents for components that constitute the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.

[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] Japanese Patent Application Laid-Open No. 2016-037541 [Patent Document 2] International Publication No. 2017 / 038830 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, fluorinated ether compounds are useful as surface treatment agents for imparting the above-mentioned various physical properties, and there is an increasing demand for fluorinated ether compounds that can be used in a variety of environments. The present inventors have conducted studies with the aim of further improving light resistance.

[0006] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a fluorinated ether compound having excellent light fastness, a surface treatment agent, a fluorinated ether composition, a coating liquid, an article having a surface layer having excellent light fastness and a method for producing the same, and a compound useful as a raw material for a fluorinated ether compound having excellent light fastness. [Means for solving the problem]

[0007] The present invention provides a fluorinated ether compound, a surface treatment agent, a fluorinated ether composition, a coating liquid, an article, a method for producing an article, and a compound having the following structures [1] to [7]. [1] A fluorine-containing ether compound represented by the following general formula (A): (R 1 R 2 C=CR 3 -L 1 -) n1 Q 1 -R f -Q 2 (-T) n2 Formula (A) however, R 1 and R 2 are each independently a hydrogen atom or an alkyl group which may have a substituent, and R 1 and R 2 If there are multiple R 1 and R 2 may be the same or different, R 3 is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 3 If there are multiple R 3 may be the same or different, L 1 is an oxygen atom or CR 4 R 5 And L 1 If there are multiple L 1 may be the same or different, R 4 and R 5 are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 4 and R 5 If there are multiple R 4 and R 5 may be the same or different, R f is a polyfluoropolyether chain, Q 1 is a n1+1 valent linking group, Q 2 is an (n2+1)-valent linking group, T is Si(-R 6 ) 3-a (-R 7 ) a When there is a plurality of T's, the plurality of T's may be the same or different, R 6 is a hydrogen atom or a hydrocarbon group, and R 6 If there are multiple R 6 may be the same or different, R 7 is a hydrolyzable group or a hydroxyl group, and R 7 If there are multiple R 7 may be the same or different, a is an integer from 1 to 3, n1 is an integer from 1 to 20, n2 is an integer from 1 to 20. [2] A surface treatment agent containing the fluorine-containing ether compound of [1] above. [3] A fluorinated ether composition containing the fluorinated ether compound of [1] above and another fluorinated ether compound. [4] A coating liquid containing the fluorinated ether compound of [1] above or the fluorinated ether composition of [3] above, and a liquid medium. [5] An article having a surface layer formed from the fluorinated ether compound of [1] above or the fluorinated ether composition of [3] above. [6] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the fluorinated ether compound of [1] above, the surface treatment agent of [2] above, the fluorinated ether composition of [3] above, or the coating liquid of [4] above. [7] A compound represented by the following general formula (B): (R 1 R 2 C=CR 3 -L 1 -) n1 Q 1 -R f -Q 12 (-L 11 -R 13 C=CR 12 R 11 ) n2 Formula (B) however, R 1 and R 2 are each independently a hydrogen atom or an alkyl group which may have a substituent, and R 1 and R 2 If there are multiple R 1 and R 2 may be the same or different, R 3 is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 3 If there are multiple R 3 may be the same or different, L 1 is an oxygen atom or CR 4 R 5 And L 1 If there are multiple L 1 may be the same or different, R 4 and R 5are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 4 and R 5 If there are multiple R 4 and R 5 may be the same or different, R 11 and R 12 are each independently a hydrogen atom or an alkyl group which may have a substituent, and R 11 and R 12 If there are multiple R 11 and R 12 may be the same or different, R 13 is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 13 If there are multiple R 13 may be the same or different, L 11 is an oxygen atom or CR 14 R 15 And L 11 If there are multiple L 11 may be the same or different, R 14 and R 15 are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 14 and R 15 If there are multiple R 14 and R 15 may be the same or different, R 1 R 2 C=CR 3 -L 1 - and R 11 R 12 C=CR 13 -L 11 - is a different structure, R f is a polyfluoropolyether chain, Q 1 is a n1+1 valent linking group, Q 12is an (n2+1)-valent linking group, n1 is an integer from 1 to 20, n2 is an integer from 1 to 20. [Effects of the Invention]

[0008] The present invention provides a fluorinated ether compound having excellent light resistance, a surface treatment agent, a fluorinated ether composition, a coating liquid, an article having a surface layer having excellent light resistance and a method for producing the same, and a compound useful as a raw material for a fluorinated ether compound having excellent light resistance. [Brief explanation of the drawings]

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

[0010] As used herein, the following terms have the following meanings: In this specification, a compound represented by formula (A) will be referred to as compound (A). Compounds represented by other formulas will also be referred to as compound (A). A perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms. A fluoroalkyl group is a general term that includes partial fluoroalkyl groups and perfluoroalkyl groups. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which also has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group that has one or more fluorine atoms. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. The term "reactive silyl group" is a general term for a hydrolyzable silyl group and a silanol group (Si-OH). The term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "surface layer" refers to a layer formed on the surface of a substrate. The "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 It is the number average molecular weight calculated by F-NMR to determine the number (average value) of oxyfluoroalkylene units based on the terminal groups.

[0011] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the compound") is characterized by being a compound represented by the following general formula (A). (R 1 R 2 C=CR 3 -L 1 -) n1 Q 1 -R f -Q 2 (-T) n2 Formula (A) however, R 1 and R 2 are each independently a hydrogen atom or an alkyl group which may have a substituent, and R 1 and R 2 If there are multiple R 1 and R 2 may be the same or different, R 3 is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 3 If there are multiple R 3 may be the same or different, L 1 is an oxygen atom or CR 4 R 5 And L 1 If there are multiple L 1 may be the same or different, R 4 and R 5 are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 4 and R 5 If there are multiple R 4 and R 5may be the same or different, R f is a polyfluoropolyether chain, Q 1 is a n1+1 valent linking group, Q 2 is an (n2+1)-valent linking group, T is Si(-R 6 ) 3-a (-R 7 ) a When there is a plurality of T's, the plurality of T's may be the same or different, R 6 is a hydrogen atom or a hydrocarbon group, and R 6 If there are multiple R 6 may be the same or different, R 7 is a hydrolyzable group or a hydroxyl group, and R 7 If there are multiple R 7 may be the same or different, a is an integer from 1 to 3, n1 is an integer from 1 to 20, n2 is an integer from 1 to 20.

[0012] This compound roughly has a structure of "olefin-linking group-polyfluoropolyether chain-linking group-reactive silyl group." The reactive silyl group forms a strong chemical bond with the substrate, and therefore the surface layer formed using this compound has excellent abrasion resistance. This compound has a polyfluoropolyether chain "R f ", which provides excellent fingerprint removal properties on the surface layer. Furthermore, in the compound constituting the surface layer, an olefin is disposed near the interface opposite the substrate side. Because the olefin has radical trapping ability, it suppresses the generation of radicals due to ultraviolet rays and the like, and has excellent stability against light. As described above, the present compound is useful as a surface treatment agent capable of forming a surface layer that has excellent light resistance and is excellent in fingerprint removal properties and water and oil repellency. Furthermore, the present compound can be used in combination with other fluorinated ether compounds, and the light resistance of the surface layer is improved compared to when the other fluorinated ether compounds are used alone.

[0013] R 1 and R 2 are each independently a hydrogen atom or an alkyl group which may have a substituent. The alkyl group may be a linear alkyl group or a branched alkyl group. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3. Examples of the substituent which the alkyl group may have include a halogen atom, an alkoxy group, and a hydroxyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom, a chlorine atom, and a bromine atom are preferred. From the viewpoint of water- and oil-repellency and fingerprint removability when formed into a surface layer, a fluorine atom is more preferred. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms which may have a substituent. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the substituent which the alkoxy group may have include a halogen atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. From the viewpoint of water- and oil-repellency and fingerprint removability when formed into a surface layer, a fluorine atom is more preferred. R 1 and R 2 From the viewpoint of ease of synthesis, among others, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms is preferred.

[0014] R 3 R is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. 3 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, and a bromine atom being preferred, and a fluorine atom being more preferred from the viewpoints of water and oil repellency and fingerprint removability when formed into a surface layer. 3 The alkyl group which may have a substituent in R 1 and R2 The same applies to the preferred embodiments.

[0015] L 1 is an oxygen atom or CR 4 R 5 R 4 and R 5 R are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. 4 and R 5 The halogen atom in R 3 The same applies to the preferred embodiments. 4 and R 5 The alkyl group which may have a substituent in R 1 and R 2 The same applies to the preferred embodiments.

[0016] R 1 R 2 C=CR 3 -L 1 Specific examples of - include the following structures: CH2=CH-CH2-, CH2=CH-CF2-, CH2=CF-CF2-, CF2=CF-CF2-, CF3CF=CF-CF2-, (CF3-)2C=CF-CF2-, CF3CF2CF=CF-CF2-, CF3CF2CF2CF=CF-CF2-, CF2=C(-CF3) -CF2-, CF2=CF-C(-CF3)F-, CH2=CH-O-, CH2=CF-O-, CF2=CF-O-, CF3CF=CF-O-, (CF3-)2C=CF-O-, CF3CF2CF=CF-O-, CF3CF2CF2CF=CF-O-, CF2=C(-CF3)-O-.

[0017] R in one molecule of compound (A) 1 R 2 C=CR 3 -L 1 The number n1 of - may be 1 to 20, and n1 is preferably 1 to 12, more preferably 1 to 6, from the viewpoint of ease of synthesis and ease of handling of compound (A). Compound (A) has two or more R 1 R2 C=CR 3 -L 1 -If there is a R 1 R 2 C=CR 3 -L 1 - may have the same structure as each other or may have different structures.

[0018] R f represents a divalent polyfluoropolyether chain. f The polyfluoropolyether chain in the formula (F1) preferably has a structure represented by the following formula (F1). -(O) m0 -[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (F1) however, R f1 is a fluoroalkylene group having one carbon atom, R f2 is a fluoroalkylene group having 2 carbon atoms, R f3 is a fluoroalkylene group having 3 carbon atoms, R f4 is a fluoroalkylene group having 4 carbon atoms, R f5 is a fluoroalkylene group having 5 carbon atoms, R f6 is a fluoroalkylene group having 6 carbon atoms, R f7 is a fluoroalkylene group having 1 to 6 carbon atoms, m0 is 0 or 1, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more; m7 is 0 or 1, and m1+m2+m3+m4+m5+m6 is an integer of 1-200. In addition, (R f1 O)~(R f6 O) can be bonded in any order. m1 to m6 in formula (F1) are respectively (R f1 O)~(R f6 O), not the arrangement. For example, (R f5 O) m5 is (R f5 O) is m5, and (R f5 O) m5 It does not represent the block arrangement structure of (R f1 O)~(R f6 The order of the units does not represent the bonding order of the units. When m7 is 0, R f Q 2 When m7 is 1, R f Q 2 The end of the carbon atom (R f7 When m0 is 1, R f Q 1 The end of the bond to R is -O-. When m0 is 0, R f Q 1 The end of the carbon atom (R f1 ~R f7 (carbon atom at either end of the group, m0 or m7). Note that m0 and m7 each independently represent 0 or 1. 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.

[0019] R f1 Specific examples include -CF2- and -CHF-. R f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF-, etc. R f3Specific examples of the alkyl group include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, - Examples include CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, and -CH(CH2F)-CH2-. R f4 Specific examples of the alkyl group include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2C Examples include HFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, and the like. R f5Specific examples of the group include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, -cycloC5F8-, and the like. R f6 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloCF 10 - and more. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, a specific example of which is perfluorocyclobutane-1,2-diyl, -cycloC5F8- means a perfluorocyclopentanediyl group, a specific example of which is perfluorocyclopentane-1,3-diyl, -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0020] R f Among these, it is preferable that the compound has a structure represented by the following formula (F2) to formula (F4) because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. (R f1 O) m1 -(R f2 O) m2 -(R f7 ) m7 Formula (F2) (R f2 O) m2 -(R f4 O) m4 -(Rf7 ) m7 Formula (F3) (R f3 O) m3 -(R f7 ) m7 Formula (F4) However, the symbols in formulas (F2) to (F4) are the same as those in formula (F1).

[0021] In formula (F2) and formula (F3), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) may be alternated, and (R f1 O) and (R f2 O) may be arranged in blocks or randomly. The same applies to formula (F3). In formula (F2), m1 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (F3), m2 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (F4), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

[0022] The polyfluoropolyether chain R f The proportion of fluorine atoms in the film [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more, in terms of excellent water and oil repellency and fingerprint removability. In addition, the polyfluoropolyether chain R f The molecular weight of the portion is preferably from 200 to 30,000, more preferably from 600 to 25,000, and even more preferably from 1,000 to 20,000, from the viewpoint of abrasion resistance.

[0023] In compound (A), T is Si(-R 6 ) 3-a (-R7 ) a and R 6 is a hydrogen atom or a hydrocarbon group, and R 7 is a hydrolyzable group or a hydroxyl group. R 7 When T is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. The silanol group further reacts with other molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Having a T of 1 or more, this compound (A) exhibits excellent abrasion resistance after the formation of the surface layer.

[0024] Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms. R 7 In terms of ease of production of the present compound, R is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. 7 In terms of the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred because the compound has excellent storage stability and outgassing during the reaction is suppressed, an ethoxy group is particularly preferred from the viewpoint of long-term storage stability, and a methoxy group is particularly preferred from the viewpoint of shortening the hydrolysis reaction time. Furthermore, as the halogen atom, a chlorine atom is particularly preferred.

[0025] R 6 is a hydrogen atom or a monovalent hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group, and from the viewpoint of ease of production, an alkyl group is preferred. From the viewpoint of ease of production, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0026] R within one T7 The number a may be 1 to 3, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the substrate. Specific examples of T include -Si(OCH3)3, -SiCH3(OCH3)2, -Si(OCH2CH3)3, -SiCl3, -Si(OCOCH3)3, -Si(NCO)3, etc. From the viewpoint of ease of handling in production, -Si(OCH3)3 is particularly preferred.

[0027] The number n2 of T in one molecule of compound (A) may be 1 to 20, and from the viewpoints of ease of synthesis and ease of handling of compound (A), n2 is preferably 1 to 12, more preferably 1 to 6. When two or more T's are present in one molecule of compound (A), the T's may have the same structure or different structures.

[0028] Q 1 is R 1 R 2 C=CR 3 -L 1 and R f and Q is an n1+1-valent linking group that links 2 is T and R f Q in compound (A) is a n2+1-valent linking group that links 1 and Q 2 may be the same structure or different structures. 1 and Q 2 Since the specific structure of 1 Q 2 Unless otherwise specified, 1 Same as above.

[0029] Q 1 When the linking group is a trivalent or higher valent linking group, at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and an (n1+1)-valent organopolysiloxane residue is 1 ").

[0030] Branch point P 1As the ring structure constituting the formula (I), one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings is preferred, from the viewpoints of ease of production of the present compound and further superior abrasion resistance, light resistance, and chemical resistance of the surface layer, and the ring structure shown in the following formula is particularly preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (=O).

[0031] [ka]

[0032] Branch point P 1 Examples of the organopolysiloxane residue constituting the formula include the following groups: 25 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 25 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0033] [ka]

[0034] Divalent or higher Q 1 is -C(O)NR 26 -, -C(O)O-, -C(O)-, -O-, -NR 26 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 26 -,-SO2NR 26 -, -Si(R 26 )2-, -OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and at least one bond selected from the group consisting of a divalent organopolysiloxane residue (hereinafter referred to as "bond B 1 "). However, R 26is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 26 The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 or 2, in terms of ease of production of the present compound.

[0035] Examples of the divalent organopolysiloxane residue include groups of the following formula: 27 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 27 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 carbon atom.

[0036] [ka]

[0037] Join B 1 As the compound, -C(O)NR is preferred because it is easy to prepare the compound. 26 -, -C(O)-, -NR 26 At least one bond selected from the group consisting of - and -O- is preferred, and -C(O)NR is preferred in terms of further improving the light resistance and chemical resistance of the surface layer. 26 - or -C(O)- is more preferred.

[0038] Trivalent or higher Q 1 As the divalent hydrocarbon group R 28 and one or more branch points P 1 Combinations with (e.g., {P 1 -(R 28 -) n1+1}), two or more hydrocarbon groups R 28 and one or more branch points P 1 and one or more bonds B 1 Combinations with (e.g., {P 1 -(B 1 -R 28 -) n1+1}) etc. Also, the divalent Q 1 The groups R are single bonds and divalent hydrocarbon groups. 28, one or two divalent hydrocarbon groups R 28 and B 1 Combinations with (e.g., R 28 -B 1 -, -B 1 -R 28 -B 1 -) and others. Examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0039] Q 1 As the group, a group represented by any one of the following formulae (Q1) to (Q7) is preferred in terms of ease of production of the present compound.

[0040] [ka] -A 1 -C(R e2 ) 3-g3 (-Q 22 -) g3 Formula (Q2) -A 2 -N(-Q 23 -)2 equation (Q3) -A 3 -Z 1 (-Q 24 -) g4 Formula (Q4) -A 2 -Si(R e3 ) 3-g3 (-Q 25 -) g3 Formula (Q5) -A 1 -Q 26 - Formula (Q6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-g5 (-Q 25 -) g5 Formula (Q7) However, in formulas (Q1) to (Q7), A1 , A 2 or A 3 side is R of general formula (A) f and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 1 R 2 C=CR 3 -L 1 Or connect to T, A 1 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, A 2 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, A 3 is A 3 Z bonded to 1 If the atom in is a carbon atom, then A 1 and A 3 Z binds to 1 If the atom in is a nitrogen atom, A 2 and Q 11 represents a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, Q 22 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O- containing group, alkylene group R 1 R 2 C=CR 3 -L 1 Or -C(O)NR at the end not connected to T e6 -, -C(O)-, -NR e6A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O- and R 1 R 2 C=CR 3 -L 1 Or -C(O)NR at the end not connected to T e6 -, -C(O)-, -NR e6 - or -O-, and Q 1 Q 22 If there are two or more, there are two or more Q 22 may be the same or different, Q 23 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, and two Q 23 may be the same or different, Q 24 Q 24 Z binds to 1 If the atom in is a carbon atom, then Q 22 and Q 24 Z binds to 1 If the atom in is a nitrogen atom, Q 23 and Q 1 Q 24 If there are two or more, there are two or more Q 24 may be the same or different, Q 25 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6 - or -O-, and Q 1 Q 25 If there are two or more, there are two or more Q 25 may be the same or different, Q 26 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. e6 -, -C(O)-, -NR e6- or -O-, Z 1 is A 3 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having a (g+1)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, R e1 is a hydrogen atom or an alkyl group, and Q 1 R e1 If there are two or more, there are two or more R e1 may be the same or different, R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R e3 is an alkyl group, R e6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, g1 is an integer of 0 to 3, g2 is an integer of 0 to 3, and g1+g2 is an integer of 1 to 6; g3 is an integer from 1 to 3, g4 is an integer equal to or greater than 1, g5 is an integer from 0 to 3. Note that g1+g2=g, g3=g, g4=g, and g5+1=g.

[0041] Q 11 , Q 22 , Q 23 , Q 24 , Q 25 or Q 26 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0042] Z 1 The ring structure in Z includes the ring structures described above, and the preferred embodiments are also the same. 1 The ring structure in 24is directly bonded, for example, an alkylene group is connected to the ring structure, and Q 24 are never connected.

[0043] R e1 , R e2 or R e3 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of the present compound. R e2 The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of compound 1. g4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, in terms of ease of production of the present compound and further excellent abrasion resistance and fingerprint stain removability of the surface layer.

[0044] Q 1 Other examples of the group include groups represented by any of the following formulae (Q11) to (Q17).

[0045] [ka] -A 1 -C(R e2 ) 3-g3 (-Q 22 -G) g3 Formula (Q12) -A 2 -N(-Q 23 -G)2 formula (Q13) -A 3 -Z 1 (-Q 24 -G) g4 Formula (Q14) -A 2 -Si(R e3 ) 3-g3 (-Q 25 -G) g3 Formula (Q15) -A 1 -Q 26 -G formula (Q16) -A 1 -CH(-Q 22-)-Si(R e3 ) 3-g5 (-Q 25 -G) g5 Formula (Q17)

[0046] However, in equations (Q11) to (Q17), A 1 , A 2 or A 3 side is R of general formula (A) f and connect it to Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Side is R 1 R 2 C=CR 3 -L 1 or connected to T. G is the following group g3, and Q 1 The two or more G's may be the same or different. The symbols other than G are the same as those in formulae (Q1) to (Q7). -Si(R 21 ) 3-k (-Q 3 -) k formula g3 However, in equation g3, the Si side is Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Connect to Q 3 Side is R 1 R 2 C=CR 3 -L 1 Or connect to T. R 21 is an alkyl group. 3 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or a group having -O-, or -(OSi(R 22 )2) p -O- and 2 or more Q 3 may be the same or different. k is 2 or 3. R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 22is an alkyl group, a phenyl group, or an alkoxy group, and two R 22 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 22 )2) may be the same or different.

[0047] Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of the present compound and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 21 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of the present compound. R 22 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of the present compound. R 22 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in view of excellent storage stability of the present compound. p is preferably 0 or 1.

[0048] The plurality of present compounds may be one single compound corresponding to formula (A) or a mixture of two or more compounds corresponding to formula (A). The molecular weight of the present compound is preferably 500 to 100,000, and more preferably 1,000 to 20,000. When the present compound is a mixture of two or more compounds, the molecular weight distribution (Mw / Mn) of the compound is preferably 1.0 to 2.0, and more preferably 1.0 to 1.3. When the molecular weight and molecular weight distribution are within the above ranges, the compound has the advantages of low viscosity, few evaporating components, and excellent uniformity when dissolved in a solvent. The molecular weight and molecular weight distribution of the present compound can be measured by gel permeation chromatography, and the measurement conditions can be those described in the examples below. Specific examples of the present compound include the following compounds: The compounds of the following formula are preferred because they are easy to produce industrially, easy to handle, and provide a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light resistance, and chemical resistance, with light resistance being particularly excellent.

[0049] CH2=CF-OR f -C(=O)-NH-CH2-C(CH2CH2CH2-T)3, CH2=CF-OR f -C(=O)-N(CH2CH2CH2-T)2, CH2=CF-OR f -C(=O)-NH-CH2CH2CH2-T, CH2=CF-OR f -C(OH)(-CH2CH2CH2-T)2, CH2=CF-OR f -C(OR 30 )(-CH2CH2CH2-T)2, CH2=CF-OR f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 , CH2=CF-CF2-R f -C(=O)-NH-CH2-C(CH2CH2CH2-T)3, CH2=CF-CF2-R f -C(=O)-N(CH2CH2CH2-T)2, CH2=CF-CF2-R f -C(=O)-NH-CH2CH2CH2-T, CH2=CF-CF2-R f -C(OH)(-CH2CH2CH2-T)2, CH2=CF-CF2-R f -C(OR 30 )(-CH2CH2CH2-T)2, CH2=CF-CF2-R f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 , CH2=CF-CF2CF2-R f-C(=O)-NH-CH2-C(CH2CH2CH2-T)3、 CH2=CF-CF2CF2-R f -C(=O)-N(CH2CH2CH2-T)2、 CH2=CF-CF2CF2-R f -C(=O)-NH-CH2CH2CH2-T、 CH2=CF-CF2CF2-R f -C(OH)(-CH2CH2CH2-T)2、 CH2=CF-CF2CF2-R f -C(OR 30 )(-CH2CH2CH2-T)2、 CH2=CF-CF2CF2-R f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 、 CH2=C(CF3)-O-R f -C(=O)-NH-CH2-C(CH2CH2CH2-T)3、 CH2=C(CF3)-O-R f -C(=O)-N(CH2CH2CH2-T)2、 CH2=C(CF3)-O-R f -C(=O)-NH-CH2CH2CH2-T、 CH2=C(CF3)-O-R f -C(OH)(-CH2CH2CH2-T)2、 CH2=C(CF3)-O-R f -C(OR 30 )(-CH2CH2CH2-T)2、 CH2=C(CF3)-O-R f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 、 CH2=C(CF3)-CF2-R f -C(=O)-NH-CH2-C(CH2CH2CH2-T)3、 CH2=C(CF3)-CF2-R f -C(=O)-N(CH2CH2CH2-T)2、 CH2=C(CF3)-CF2-R f-C(=O)-NH-CH2CH2CH2-T, CH2=C(CF3)-CF2-R f -C(OH)-(CH2CH2CH2-T)2, CH2=C(CF3)-CF2-R f -C(OR 30 )-(CH2CH2CH2-T)2, CH2=C(CF3)-CF2-R f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 , CH2=C(CF3)-CF2CF2-R f -C(=O)-NH-CH2-C(CH2CH2CH2-T)3, CH2=C(CF3)-CF2CF2-R f -C(=O)-N(CH2CH2CH2-T)2, CH2=C(CF3)-CF2CF2-R f -C(=O)-NH-CH2CH2CH2-T, CH2=C(CF3)-CF2CF2-R f -C(OH)-(CH2CH2CH2-T)2, CH2=C(CF3)-CF2CF2-R f -C(OR 30 )-(CH2CH2CH2-T)2, CH2=C(CF3)-CF2CF2-R f -CH2-CHCH2-Q 30 (-CH2CH2-T) n3 , However, R in the formula f and T are as described above, and R 30 is an alkyl group or a fluoroalkyl group, and Q 30 is a 1+n3-valent linking group, where n3 is an integer of 1 to 20. 30 As for Q 2 The same can be mentioned.

[0050] (Method for producing the present compound) An example of a method for producing the present compound will be described below. Although the production method is not limited to the following method, the present compound can be obtained in high yield by the following method.

[0051] The present compound, Compound (A), can be produced, for example, by subjecting the following Compound (B) to a hydrosilylation reaction with the following Compound (C1) or Compound (C2). (R 1 R 2 C=CR 3 -L 1 -) n1 Q 1 -R f -Q 12 (-L 11 -CR 13 =CR 11 R 12 ) n2 Formula (B) HSi(-R 6 ) 3-a (-R 7 ) a Formula (C1) HSi(R 41 ) 3-k [-(OSi(R 42 )2) p1 -O-Si(-R 6 ) 3-a (-R 7 ) a ] k Formula (C2) However, L 11 is an oxygen atom or CR 14 R 15 And L 11 If there are multiple L 11 may be the same or different, R 11 and R 12 are each independently a hydrogen atom or an alkyl group which may have a substituent, and R 11 and R 12 If there are multiple R 11 and R 12 may be the same or different, R 13is a hydrogen atom, a halogen atom, or an alkyl group R 13 If there are multiple R 13 may be the same or different, R 14 and R 15 are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R 14 and R 15 If there are multiple R 14 and R 15 may be the same or different, Q 12 is an (n2+1)-valent linking group, R 41 is an alkyl group, and R 41 If there are multiple R 41 may be the same or different, R 42 is an alkyl group, a phenyl group, or an alkoxy group, and there are multiple R 42 may be the same or different, k is 2 or 3; p1 is an integer of 0 to 5, and when p1 is 2 or more, 2 or more (OSi(R 42 )2) may be the same or different, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , Q 1 , R f , n1, n2 and a are the same as those in the compound (A), and preferred embodiments are also the same. R 1 R 2 C=CR 3 -L 1 - and R 11 R 12 C=CR 13 -L 11 - is a different structure. The compound (C2) can be, for example, , International Publication No. 2019 / 208503 It can be prepared by the method described.

[0052] R 11 , R 12 , R 13 , R 14 , and R 15 The alkyl group which may have a substituent and the halogen atom in 1 ~R 5 The preferred embodiments are the same as those described above. After the above reaction, Q 12 (-L 11 -R 13 CH-CR 12 R 11 ) n2 represents the linking group Q in compound (A). 2 is equivalent to

[0053] The above synthesis method is 1 R 2 C=CR 3 -L 1 and R 11 R 12 C=CR 13 -L 11 and a compound (B) having structures different from each other, 1 R 2 C=CR 3 -L 1 and R 11 R 12 C=CR 13 -L 11 This method utilizes the difference in reactivity between the olefins in compound (B) and the olefins in compound (A) to favor the reaction of one of the olefins in compound (B), thereby increasing the yield of compound (A). For example, when R is an alkyl group, CH2=CH- is more reactive than RCH=CH-. Similarly, when X is a halogen atom, CH2=CH- is more reactive than CH2=CX-. Also, CH2=CH-CH2- is more reactive than CH2=CH-CF2-.

[0054] Specific examples of the compound (B) include the following compounds. CH2=CF-OR f-C(=O)-NH-CH2-C(CH2-CH=CH2)3、 CH2=CF-O-R f -C(=O)-N(CH2-CH=CH2)2、 CH2=CF-O-R f -C(=O)-NH-CH2-CH=CH2、 CH2=CF-O-R f -C(OH)(-CH2-CH=CH2)2、 CH2=CF-O-R f -C(OR 30 )(-CH2-CH=CH2)2、 CH2=CF-O-R f -CH2-CHCH2-Q 32 (-CH2-CH=CH2) n3 、 CH2=CF-CF2-R f -C(=O)-NH-CH2-C(CH2-CH=CH2)3、 CH2=CF-CF2-R f -C(=O)-N(CH2-CH=CH2)2、 CH2=CF-CF2-R f -C(=O)-NH-CH2-CH=CH2T、 CH2=CF-CF2-R f -C(OH)(-CH2-CH=CH2)2、 CH2=CF-CF2-R f -C(OR 30 )(-CH2-CH=CH2)2、 CH2=CF-CF2-R f -CH2-CHCH2-Q 32 (-CH2-CH=CH2) n3 、 CH2=CF-CF2CF2-R f -C(=O)-NH-CH2-C(CH2-CH=CH2)3、 CH2=CF-CF2CF2-R f -C(=O)-N(CH2-CH=CH2)2、 CH2=CF-CF2CF2-R f -C(=O)-NH-CH2-CH=CH2、 CH2=CF-CF2CF2-R f-C(OH)(-CH2-CH=CH2)2、 CH2=CF-CF2CF2-R f -C(OR 30 )(-CH2-CH=CH2)2、 CH2=CF-CF2CF2-R f -CH2-CHCH2-Q 32 (-CH2-CH=CH2) n3 、 CH2=C(CF3)-O-R f -C(=O)-NH-CH2-C(CH2-CH=CH2)3、 CH2=C(CF3)-O-R f -C(=O)-N(CH2-CH=CH2)2、 CH2=C(CF3)-O-R f -C(=O)-NH-CH2-CH=CH2、 CH2=C(CF3)-O-R f -C(OH)(-CH2-CH=CH2)2、 CH2=C(CF3)-O-R f -C(OR 30 )(-CH2-CH=CH2)2、 CH2=C(CF3)-O-R f -CH2-CHCH2-Q 32 (-CH2-CH=CH2) n3 、 CH2=C(CF3)-CF2-R f -C(=O)-NH-CH2-C(CH2-CH=CH2)3、 CH2=C(CF3)-CF2-R f -C(=O)-N(CH2-CH=CH2)2、 CH2=C(CF3)-CF2-R f -C(=O)-NH-CH2-CH=CH2、 CH2=C(CF3)-CF2-R f -C(OH)-(CH2-CH=CH2)2、 CH2=C(CF3)-CF2-R f -C(OR 30 )-(CH2-CH=CH2)2、 CH2=C(CF3)-CF2-R f -CH2-CHCH2-Q32 (-CH2-CH=CH2) n3 , CH2=C(CF3)-CF2CF2-R f -C(=O)-NH-CH2-C(CH2-CH=CH2)3, CH2=C(CF3)-CF2CF2-R f -C(=O)-N(CCH2-CH=CH2)2, CH2=C(CF3)-CF2CF2-R f -C(=O)-NH-CH2-CH=CH2, CH2=C(CF3)-CF2CF2-R f -C(OH)-(CH2-CH=CH2)2, CH2=C(CF3)-CF2CF2-R f -C(OR 30 )-(CH2-CH=CH2)2, CH2=C(CF3)-CF2CF2-R f -CH2-CHCH2-Q 32 (-CH2-CH=CH2) n3 , However, R in the formula f , T, R 30 and n3 are as described above, and Q 32 is a n3+1 valent linking group, and the Q 12 is the same as:

[0055] In the above-mentioned production method, a compound represented by the following formula (D) may be produced as a by-product. In this case, depending on the application of compound (B), compound (B) and compound (D) may be separated by a known column chromatography method or the like, or a mixture of compound (B) and compound (D) may be used as is. (T-) n1 Q 1 -R f -Q 2 (-T) n2 Formula (D) However, each symbol in the formula is the same as in compound (A).

[0056] An example of a method for producing compound (B) is a method in which compound (E) shown below is reacted with compound (F) shown below, and compound (G) is obtained by column chromatography or the like as necessary, and then a highly reactive olefin is introduced into the ester of compound (G). HCO-C(O)-Q 1 -R f -Q 31 -(C(O)OCH3) n4 Formula (E) H2NCH2C(CH2CH=CH2)3 formula (F) HCO-C(O)-Q 1 -R f -Q 31 -(C(O)-NH-CH2-C(CH2-CH=CH2)3) n4 Formula (G) However, Q in the formula 1 and R f is as mentioned above, and Q 31 is a 1+n4-valent linking group, and n4 is an integer of 1 to 20.

[0057] [Fluorine-containing ether composition] The fluorinated ether composition of the present invention (hereinafter also referred to as the present composition) is a composition containing the compound (A), a fluorinated compound other than the present compound, and at least one of the impurities described below. Examples of impurities include compounds that are unavoidable in the production of the compound (A) and other fluorinated compounds (e.g., the compound (B) and the compound (D)). The present composition does not contain a liquid medium, which will be described later.

[0058] Examples of other fluorine-containing compounds include fluorine-containing compounds produced as by-products in the production process of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), and known fluorine-containing compounds used for the same purposes as the present compound. As the other fluorine-containing compound, a compound which is unlikely to deteriorate the properties of the present compound is preferred. The content of other fluorine-containing compounds is preferably less than 50 mass %, more preferably less than 30 mass %, and even more preferably less than 10 mass %, of the total amount of the composition, in order to fully exhibit the properties of the compound.

[0059] Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the present compound. When the present composition contains by-product fluorine-containing compounds, the purification step for removing the by-product fluorine-containing compounds or reducing the amount of the by-product fluorine-containing compounds can be simplified.

[0060] Known fluorine-containing compounds include, for example, those described in the following documents: perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097; perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2008-534696; Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A; Organosilicon compounds described in WO 2011 / 060047 and WO 2011 / 059430; fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in Japanese Patent Application Laid-Open No. 2012-72272; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Application Laid-Open No. 2015-199906, Japanese Patent Application Laid-Open No. 2016-204656, Japanese Patent Application Laid-Open No. 2016-210854, and Japanese Patent Application Laid-Open No. 2016-222859 International Publication No. 2018 / 216630, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 039186, International Publication No. 2019 / 044479, Japanese Patent Application Laid-Open No. 2019-44158 ,country A fluorine-containing ether compound described in International Publication No. 2019 / 163282. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Corporation, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0061] The proportion of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. When the present composition contains other fluorine-containing compounds, the proportion of the other fluorine-containing compounds relative to the total of the present compound and the other fluorine-containing compounds in the present composition is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. The total proportion of the present compound and other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more. When the content of this compound and other fluorine-containing compounds is within the above range, the surface layer has excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0062] [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.

[0063] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a mixture of both.

[0064] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Commercially available products include, for example, C6F 13 H (AGC Corporation, Asahiklin (registered trademark) AC-2000), C6F 13 Examples include C2H5 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (VERTREL (registered trademark) XF, manufactured by Chemours Corporation). Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Commercially available products include, for example, CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The non-fluorine-based organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, or a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. The present coating liquid preferably contains 75 to 99.999 mass %, more preferably 85 to 99.99 mass %, and particularly preferably 90 to 99.9 mass % of the liquid medium.

[0065] The present coating liquid may contain, in addition to the present compound or composition and the liquid medium, other components as long as the effects of the present invention are not impaired. Examples of other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. The content of other components in the present coating liquid is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0066] The total concentration of the present compound and other components or the total concentration of the present composition and other components in the present coating liquid (hereinafter also referred to as solids concentration) is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, even more preferably 0.01 to 10 mass%, and particularly preferably 0.01 to 1 mass%. The solids concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0067] [Goods] FIG. 1 is a schematic cross-sectional view showing an example of an article of the present invention. The first article of the present invention is an article 20 having a substrate 12, an underlayer 14, and a surface layer 22 in this order, The underlayer 14 contains an oxide containing silicon, and the surface layer 22 contains a condensate of the present compound.

[0068] The material and shape of the substrate 12 in the first article may be appropriately selected depending on the intended use of the article 20. Examples of materials for the substrate 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. Examples of substrates 12 that are particularly required to be water- and oil-repellent include substrates for touch panels, display substrates, and substrates that form the housings of electronic devices. Touch panel substrates and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0069] The substrate 12 may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the underlayer 14 is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate 12 and the underlayer 14, and as a result, further improves the abrasion resistance of the surface layer 22. As the surface treatment, corona discharge treatment or plasma treatment is preferred because it further improves the abrasion resistance of the surface layer 22.

[0070] The underlayer 14 is a layer containing at least an oxide containing silicon, and may further contain other elements. When the underlayer 14 contains silicon oxide, T of the present compound undergoes dehydration condensation, forming Si-O-Si bonds between the underlayer 14 and the underlayer 14, thereby forming a surface layer 22 with excellent wear resistance.

[0071] The content of silicon oxide in the underlayer 14 may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the content of silicon oxide is equal to or greater than the lower limit of the above range, Si-O-Si bonds are sufficiently formed in the underlayer 14, and the mechanical properties of the underlayer 14 are sufficiently ensured. The content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of the underlayer 14.

[0072] From the viewpoint of durability of the surface layer 22, it is preferable that the oxide in the underlayer 14 further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. The inclusion of these elements strengthens the bond between the underlayer 14 and the present compound, improving wear resistance.

[0073] When the underlayer 14 contains one or more elements selected from iron, nickel, and chromium, the total content of these elements relative to silicon oxide is preferably 10 to 1100 mass ppm, more preferably 50 to 1100 mass ppm, even more preferably 50 to 500 mass ppm, and particularly preferably 50 to 250 mass ppm. When the underlayer 14 contains one or more elements selected from aluminum and zirconium, the total content thereof is preferably 10 to 2500 mass ppm, more preferably 15 to 2000 mass ppm, and even more preferably 20 to 1000 mass ppm. When the underlayer 14 contains an alkali metal element, the total content thereof is preferably 0.05 to 15 mass %, more preferably 0.1 to 13 mass %, and even more preferably 1.0 to 10 mass %. Examples of the alkali metal element include lithium, sodium, potassium, rubidium, and cesium. When the underlayer 14 contains a platinum group element, the total content thereof is preferably 0.02 mass ppm to 800 mass ppm, more preferably 0.04 mass ppm to 600 mass ppm, and even more preferably 0.7 mass ppm to 200 mass ppm. Examples of the platinum group element include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the underlayer 14 contains one or more elements selected from boron and phosphorus, the total content thereof is, in terms of the abrasion resistance of the surface layer 22, preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, expressed as the ratio of the molar concentration of the sum of boron and phosphorus to the molar concentration of silicon. When the underlayer 14 contains alkaline earth metal elements, the total content thereof, expressed as the ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, from the viewpoint of the wear resistance of the surface layer 22. Examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0074] From the viewpoint of improving the adhesiveness of the compound and improving the water / oil repellency and abrasion resistance of the article 20, the underlayer 14 is preferably a silicon oxide layer containing alkali metal atoms. In particular, in the silicon oxide layer, the average concentration of alkali metal atoms in a region 0.1 to 0.3 nm deep from the surface in contact with the surface layer 22 is preferably 2.0×10 19 atoms / cm 3 On the other hand, in order to ensure sufficient mechanical properties of the silicon oxide layer, the average concentration of the alkali metal atoms is preferably 4.0×10 or more. 22 atoms / cm 3 It is preferable that:

[0075] The thickness of the underlayer 14 is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer 14 is at least the lower limit of the above range, the underlayer 14 is likely to have a sufficient effect of improving adhesion. If the thickness of the underlayer 14 is at most the upper limit of the above range, the underlayer 14 itself will have high abrasion resistance. Methods for measuring the thickness of the underlayer 14 include a method of observing the cross section of the underlayer 14 using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

[0076] The underlayer 14 can be formed, for example, by depositing a deposition material having a desired composition for the underlayer 14 on the surface of the substrate 12 . An example of the vapor deposition method is vacuum deposition, in which a deposition material is evaporated in a vacuum chamber and attached to the surface of the substrate 12. The temperature during vapor deposition (for example, the temperature of the boat where the vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 100 to 3000°C, particularly preferably 500 to 3000°C. The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in a tank in which the vapor deposition material is placed is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less. When the underlayer 14 is formed using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used. Examples of methods for evaporating the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method in which the deposition material is irradiated with an electron beam to directly heat the deposition material, melting and evaporating the surface. The electron gun method is preferred as a method for evaporating the deposition material because it can evaporate high-melting-point substances due to its ability to heat locally, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or contamination with impurities. The deposition material used in the electron gun method is preferably a molten granular or sintered material because it is less likely to scatter even when an air current is generated.

[0077] The surface layer 22 on the underlayer 14 contains a condensate of the present compound. Condensates of the present compound include those in which hydrolyzable silyl groups in the present compound undergo hydrolysis to form silanol groups (Si-OH), which then undergo intermolecular condensation to form Si-O-Si bonds, and those in which silanol groups in the present compound undergo condensation with silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the underlayer 14 to form Si-O-Si bonds. The surface layer 22 may also contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer 22 contains a fluorine-containing compound having reactive silyl groups in a state in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone condensation reaction.

[0078] The thickness of the surface layer 22 is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer 22 is equal to or greater than the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. When the thickness of the surface layer 22 is equal to or less than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer 22 is a thickness obtained by an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 can be calculated from the oscillation period of an interference pattern obtained by an X-ray reflectivity method using the X-ray diffractometer for thin film analysis.

[0079] The second article of the present invention is an article 20 having a substrate 10 with an undercoat layer and a surface layer 22 in this order, the substrate 10 with underlayer contains an oxide containing silicon, The surface layer 22 contains a condensate of the present compound.

[0080] In the second article, the substrate 10 with an undercoat layer has the same composition as the undercoat layer 14 in the first article, and therefore the surface layer 22 has excellent abrasion resistance even when the surface layer 22 is formed directly on the substrate 10 with an undercoat layer. The material of the base layer-attached substrate 10 in the second article may be any material having the composition of the base layer 14, and may be, for example, a glass substrate. Details of the material of the base layer-attached substrate 10 are the same as those of the substrate 12 and the base layer 14, and therefore a description thereof will be omitted here. Furthermore, the configuration of the surface layer 22 is also the same as that of the first article, and therefore a description thereof will be omitted here.

[0081] [Production method] The method for producing an article according to the present invention is a method for forming a surface layer by a dry coating method or a wet coating method using the fluorine-containing compound, the fluorine-containing compound-containing composition, or the coating liquid.

[0082] The present compound and composition can be used directly in a dry coating method. The present compound and composition are suitable for forming a surface layer with excellent adhesion by a dry coating method. Dry coating methods include vacuum deposition, CVD, sputtering, and the like. The vacuum deposition method is suitable for use in terms of suppressing decomposition of the present compound and the simplicity of the equipment. For vacuum deposition, a pellet-shaped material in which the present compound is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped material supporting the present compound can be produced by impregnating a porous metal body with a solution of the present compound and drying it to remove the liquid medium. The solution of the present compound can be the present coating liquid.

[0083] The coating liquid can be suitably used for wet coating methods such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0084] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be carried out as necessary. Such an operation includes heating, humidification, light irradiation, etc. For example, by heating the substrate on which the surface layer has been formed in a humid atmosphere, reactions such as the hydrolysis reaction of the hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of the silanol groups can be promoted. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed by, for example, pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent. [Example]

[0085] 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 "% by mass" unless otherwise specified. Examples 1, 3, and 16 are production examples (examples) of the compound (B), Examples 2, 4, and 17 are production examples (examples) of the compound (A), Examples 5 to 14 and Examples 18 to 20 are examples, and Example 15 is a comparative example.

[0086] (Production Example 1) The following compound 2 was added to 10 g of the following compound 1 and stirred at room temperature for 4 hours. The resulting mixture was purified by column chromatography (silica gel 50 g) to obtain 4.6 g of the following compound 3. Compound 1: H3CO-C(O)-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)OCH3 Compound 2: H2NCH2C(CH2CH=CH2)3 Compound 3: H3CO-C(O)-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2-CH=CH2)3 The average value of n in Compound 1 and Compound 3 is 11.

[0087] (Production Example 2) Sodium borohydride to CF 13 The resulting mixture was added to 10 g of methanol and 10 g of CF 13 The mixture of H and 3 g of the compound 3 was slowly added dropwise. After stirring at room temperature for 4 hours, methanol was slowly added. Then, 1 M aqueous hydrochloric acid solution was slowly added, and 20 g of CF 13 The mixture was extracted with H. The organic phase was dehydrated with magnesium sulfate, filtered, and then concentrated. The resulting mixture was purified by column chromatography (silica gel) to obtain 2.5 g of the following compound 4. Compound 4: HO-CH2-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0088] (Production Example 3) The compound 4 (2 g), triphenylphosphine (1 g), 1,3-bistrifluoromethylbenzene (10 mL), carbon tetrabromide (1 g), and dimethylformamide (2 mL) were added, and the mixture was stirred for 12 hours at 100° C. After filtration, the solvent was distilled off, and the mixture was purified by column chromatography (silica gel) to obtain 1.6 g of the following compound 5. Compound 5:Br-CH2-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0089] (Example 1) The compound 5 (1.5 g), 1,3-bistrifluoromethylbenzene (4 mL), acetic acid (2 mL), and zinc (1 g) were added, and then stirred for 12 hours at 110° C. After filtration, the mixture was concentrated and purified by column chromatography (silica gel) to obtain 1.2 g of the following compound 6. Compound 6: CH2=CF-CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n-OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0090] (Example 2) Compound 6 (1g), CF 13 H, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 5.5 mg), aniline (0.8 mg), and trimethoxysilane (22.7 mg) were added, and the mixture was stirred at 40°C for 5 hours. The solvent was then distilled off under reduced pressure to obtain 1 g of the following compound 7. Compound 7: CH2=CF-CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2CH2CH2-Si(OCH3)3)3

[0091] (Example 3) Compound 4 (500 mg), 1,3-bistrifluoromethylbenzene (1 mL), TBAI (5 mg), 30% aqueous sodium hydroxide solution (25 mg), and 3-Bromo-2-fluoroprop-1-ene (70 mg) were added, and the mixture was stirred at 60° C. for 12 hours. The resulting solution was dissolved in CF 13 After extraction with 10 mL of H, the organic phase was dehydrated with magnesium sulfate, filtered, and concentrated. The resulting mixture was purified by column chromatography (silica gel) to obtain 420 mg of the following compound 8. Compound 8: CH2=CF-CH2-O-CH2-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0092] (Example 4) Compound 8 (400 mg), CF 13H, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 2.2 mg), aniline (0.3 mg), and trimethoxysilane (10.0 mg) were added, and the mixture was stirred at 40°C for 5 hours. The solvent was then distilled off under reduced pressure to obtain 450 mg of compound 9. Compound 9: CH2=CF-CH2-O-CH2-CF2CF2CF2-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2CH2CH2-Si(OCH3)3)3

[0093] The following compounds 10 and 11 were also prepared. Compound 10 was synthesized by the method described in WO 2017 / 038830. Compound 11 was synthesized by the method described in WO 2015 / 166760. Compound 10: CF3-(OCF2CF2-OCF2CF2CF2CF2) n -OCF2CF2-OCF2CF2-CF2-C(O)-NH-CH2-C(CH2CH2CH2-Si(OCH3)3)3 The average value of n in compound 10 is 12.

[0094] [ka]

[0095] (Examples 5 to 14: Preparation of fluorine-containing ether compositions) The compounds 7, 9 and 10 were mixed in the ratios shown in Table 1 below to obtain a fluorine-containing ether composition.

[0096] [Table 1]

[0097] [Production and evaluation of goods] In Examples 5 to 14, the fluorine-containing ether composition obtained was used, and in Example 15, the substrate was surface-treated using the compound 11 to produce an article. The surface treatment used the following dry coating method. A chemically strengthened glass was used as the substrate. The obtained article was evaluated by the following method. The results are shown in Table 2.

[0098] (Dry coating method) The dry coating was performed using a vacuum evaporation apparatus (VTR350M manufactured by ULVAC, vacuum evaporation method). 0.5 g of each of the compositions or compounds of Examples 5 to 15 was filled into a molybdenum boat in the vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1×10 -3 Pa or less. The boat on which the composition or compound was placed was heated at a heating rate of 10 °C / min or less, and when the deposition rate measured by a crystal oscillator type film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached about 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.

[0099] (Evaluation method) <UV irradiation conditions> The surface layer was irradiated with light (650 W / m2, 300 to 700 nm) at a black panel temperature of 63 °C using a desktop xenon arc lamp type accelerated light resistance tester (SUNTEST XLS+ manufactured by Toyo Seiki Co., Ltd.). <Measurement method of contact angle> 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 (DM-500 manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used for calculating the contact angle. The measurements were performed every 30 minutes of UV irradiation time. The results are shown in Table 2. It can be evaluated that the larger the numerical value, the more excellent the water repellency, and the smaller the decrease amount of the numerical value, the more excellent the light resistance.

[0100]

Table 2

[0101] As shown in Table 2, it was revealed that the surface layer formed using the fluorinated ether composition containing the compound (A) was excellent in light resistance.

[0102] (Production Example 4) The following compound 2 was added to 10 g of the following compound 20 and stirred at room temperature for 4 hours. The resulting mixture was purified by column chromatography (silica gel 50 g) to obtain 4.6 g of the following compound 21. Compound 20:H3CO-C(O)-CF2-(OCF2) m -(OCF2CF2) n -OCF2-C(O)OCH3 Compound 2: H2NCH2C(CH2CH=CH2)3 Compound 21: H3CO-C(O)-CF2-(OCF2) m -(OCF2CF2) n -OCF2-C(O)-NH-CH2-C(CH2-CH=CH2)3 The average value of m in Compound 20 and Compound 21 is 21, and the average value of n is 19.

[0103] (Production Example 5) Sodium borohydride to CF 13 The resulting mixture was added to 10 g of methanol and 10 g of CF 13 The mixture of H and 3 g of the compound 21 was slowly added dropwise. After stirring at room temperature for 4 hours, methanol was slowly added. Then, 1 M aqueous hydrochloric acid solution was slowly added, and 20 g of CF 13 The mixture was extracted with H. The organic phase was dehydrated with magnesium sulfate, filtered, and then concentrated. The resulting mixture was purified by column chromatography (silica gel) to obtain 2.5 g of the following compound 22. Compound 22:HO-CH2-CF2-(OCF2) m -(OCF2CF2) n -OCF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0104] (Production Example 6) The compound 22 (2 g), triphenylphosphine (1 g), 1,3-bistrifluoromethylbenzene (10 mL), carbon tetrabromide (1 g), and dimethylformamide (2 mL) were added, and the mixture was stirred for 12 hours at 100° C. After filtration, the solvent was distilled off, and the mixture was purified by column chromatography (silica gel) to obtain 1.6 g of the following compound 23. Compound 23:Br-CH2-CF2-(OCF2) m -(OCF2CF2) n -OCF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0105] (Example 16) The compound 23 (1.5 g), 1,3-bistrifluoromethylbenzene (4 mL), acetic acid (2 mL), and zinc (1 g) were added, and the mixture was stirred for 12 hours at 110° C. After filtration, the mixture was concentrated and purified by column chromatography (silica gel), yielding 1.2 g of the following compound 24. Compound 24: CH2=CF-(OCF2) m -(OCF2CF2) n -OCF2-C(O)-NH-CH2-C(CH2-CH=CH2)3

[0106] (Example 17) (1g) of Compound 24, CF 13 H, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 5.5 mg), aniline (0.8 mg), and trimethoxysilane (22.7 mg) were added, and the mixture was stirred at 40°C for 5 hours. The solvent was then distilled off under reduced pressure to obtain 1 g of the following compound 25. Compound 25: CH2=CF-(OCF2) m -(OCF2CF2) n -OCF2-C(O)-NH-CH2-C(CH2CH2CH2-Si(OCH3)3)3

[0107] (Examples 18 to 20: Preparation of fluorinated ether compositions) The compound 25 and the compound 10 were mixed in the ratio shown in Table 3 below to obtain a fluorine-containing ether composition.

[0108] [Table 3]

[0109] Substrates were surface-treated in the same manner as in Example 5 to produce articles. The surface treatment was performed using the dry coating method described above. Chemically strengthened glass was used as the substrate. The resulting articles were evaluated using the UV irradiation conditions and contact angle measurement method described above. The results are shown in Table 4.

[0110] [Table 4]

[0111] As shown in Table 4, it was revealed that the surface layer formed using the fluorinated ether composition containing the compound (A) was excellent in light resistance.

[0112] This application claims priority based on Japanese Patent Application No. 2021-034907, filed on March 5, 2021, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0113] 10: Base material with undercoat layer, 12: Base material, 14: Undercoat layer, 20: Article, 22: Surface layer

Claims

1. A fluorine-containing ether compound represented by the following general formula (A): (R １ R ２ C═CR ３ -L １ -) ｎ１ Q １ -R ｆ -Q ２ (-T) ｎ２ Formula (A) however, R １ and R ２ are each independently a hydrogen atom or an alkyl group which may have a substituent, and R １ and R ２ If there are multiple R １ and R ２ may be the same or different, R ３ is a halogen atom or an alkyl group which may have a substituent, and R ３ If there are multiple R ３ may be the same or different, L １ is an oxygen atom or CR ４ R ５ And L １ If there are multiple L １ may be the same or different, R ４ and R ５ are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R ４ and R ５ If there are multiple R ４ and R ５ may be the same or different, R ｆ is a polyfluoropolyether chain, Q １ is an n1+1 valent linking group, Q ２ is an (n2+1)-valent linking group, T is Si(-R ６ ) ３－ａ (-R ７ ) ａ When there is a plurality of T's, the plurality of T's may be the same or different, R ６ is a hydrogen atom or a hydrocarbon group, and R ６ If there are multiple R ６ may be the same or different, R ７ is a hydrolyzable group or a hydroxyl group, and R ７ If there are multiple R ７ may be the same or different, a is an integer from 1 to 3, n1 is an integer from 1 to 20, n2 is an integer from 1 to 20.

2. A surface treatment agent comprising the fluorinated ether compound according to claim 1.

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

4. The fluorinated ether compound according to claim 1 or the fluorinated ether composition according to claim 3; A coating liquid comprising a liquid medium.

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

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

7. A compound represented by the following general formula (B): (R １ R ２ C═CR ３ -L １ -) ｎ１ Q １ -R ｆ -Q １２ (-L １１ -R １３ C═CR １２ R １１ ) ｎ２ Formula (B) however, R １ and R ２ are each independently a hydrogen atom or an alkyl group which may have a substituent, and R １ and R ２ If there are multiple R １ and R ２ may be the same or different, R ３ is a halogen atom or an alkyl group which may have a substituent, and R ３ If there are multiple R ３ may be the same or different, L １ is an oxygen atom or CR ４ R ５ And L １ If there are multiple L １ may be the same or different, R ４ and R ５ are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R ４ and R ５ If there are multiple R ４ and R ５ may be the same or different, R １１ and R １２ are each independently a hydrogen atom or an alkyl group which may have a substituent, and R １１ and R １２ If there are multiple R １１ and R １２ may be the same or different, R １３ is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R １３ If there are multiple R １３ may be the same or different, L １１ is an oxygen atom or CR １４ R １５ And L １１ If there are multiple L １１ may be the same or different, R １４ and R １５ are each independently a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, and R １４ and R １５ If there are multiple R １４ and R １５ may be the same or different, R １ R ２ C=CR ３ -L １ - and R １１ R １２ C=CR １３ -L １１ - is a different structure, R ｆ is a polyfluoropolyether chain, Q １ is an n1+1 valent linking group, Q １２ is an (n2+1)-valent linking group, n1 is an integer from 1 to 20, n2 is an integer from 1 to 20.

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