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

Abstract

To provide a fluorine-containing ether compound, a fluorine-containing ether composition and a coating liquid excellent in chemical resistance, an article having a surface layer excellent in chemical resistance and a method for producing the same, and a method for producing a fluorine-containing ether compound excellent in chemical resistance.SOLUTION: Provided is a fluorine-containing ether compound that has a first partial structure represented by the following formula (1) and a second partial structure represented by the following formula (2), and that has at least five first partial structures, or has at least two second partial structures: -ORf12- (1), -ORf13- (2), wherein Rf12 is a C1-6 fluoroalkylene group, and Rf13 is a group having a fluorine-containing cyclic structure which may have a hetero atom.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Fluorine-containing ether compounds have a variety of excellent properties, including a 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 can form a surface layer on the surface of a substrate that exhibits high lubricity, water- and oil-repellency, etc., and is therefore suitable for use as a surface treatment agent. 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 repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability) are maintained for a long period of time, such as the surface treatment agents for members constituting the surface of a touch panel that is touched by fingers, eyeglass lenses, and displays of wearable terminals.

[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 2016-037541 A [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 various environments, and therefore there is a demand for fluorinated ether compounds having further excellent chemical resistance.

[0006] The present invention aims to provide a fluorinated ether compound having excellent chemical resistance, a fluorinated ether composition and coating liquid capable of forming a surface layer having excellent chemical resistance, an article having a surface layer having excellent chemical resistance and a method for producing the same, and a method for producing a fluorinated compound useful as a raw material for the fluorinated ether compound. [Means for solving the problem]

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

[25] . [1] A fluorinated ether compound having a first partial structure represented by the following formula (1) and a second partial structure represented by the following formula (2): A fluorine-containing ether compound having five or more of the first partial structures or having two or more of the second partial structures. -OR f12 - (1) -OR f13 - (2) however, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, R f13 is a group having a fluorine-containing ring structure which may have a heteroatom.

[0008] [2] A fluorinated ether compound of [1], which is a compound represented by the following formula (1A): [R f -] a1 Q 1[-T] b1 (1A) however, R f has the first partial structure and the second partial structure, and R is a monovalent group having five or more of the first partial structures or two or more of the second partial structures, the bonding end of which is a carbon atom; f If there are two or more, two or more R f may be the same or different, Q 1 represents a single bond or a linking group having a valence of a1+b1, T is -R f6 , -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 )2, -N + (R 10 )3X 3 , -C≡N, -C(=NR 10 )-R 10 , -N + ≡N, -N=NR 10 , -C(=O)OR 10 , -C(=O)OX 2 , -C(=O)OX 4 , -C(=O)OC(=O)R 10 , -SO2R 10 , -SO3H, -SO3X 2 ,-OP(=O)(-OR 10 )2, -OP(=O)(-OR 10 )(-OX 2 ), -N=C=O, -Si(R) 3-c (L) c , -C(R 10 )=C(R 10 )2, -C≡C(R 10 ), -C(=O)N(R 10 )2, -N(R 10 )C(=O)R 10 , -Si(R 10 )2-O-Si(R 10 )3, -NH-C(=O)R 10 , -C(=O)NHR 10 , -I, [ka] R f6 is a fluoroalkyl group having 1 to 6 carbon atoms, R 10 is a hydrogen atom, an alkyl group or a fluoroalkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent, and R 10 If there are 2 or more, R is 2 or more 10 may be the same or different, Ar is an optionally substituted aryl group, X 2 is an alkali metal ion or an ammonium ion, X 3 is a halide ion, X 4 is a halogen atom, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. a1 is an integer of 1 or more, b1 is an integer equal to or greater than 1, c is 2 or 3; When there are two or more T's, the two or more T's may be the same or different.

[0009] [3] R f is a group represented by the following formula (g1a): R f1 -(OR f2 ) m (OR f3 ) n - (g1a) however, R f1 represents a fluoroalkyl group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having a fluorine-containing ring structure, R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q 1 R binds to f2 Q1 At least one fluorine atom is bonded to the terminal carbon atom of the R f3 is a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q 1 R binds to f3 Q 1 At least one fluorine atom is bonded to the terminal carbon atom of the n is R f1 When R has a fluorine-containing ring structure, it is an integer of 0 to 500. f1 is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR f3 ) n OR of two or more types f3 It may consist of When n is 0, m is an integer from 5 to 500; When n is 1 or more, m is an integer of 2 to 500, If m is 2 or more, (OR f2 ) m OR of two or more types f2 It may consist of m (OR f2 ) and n (OR f3 ) may be joined in any order.

[0010] [4] Q. 1 is a group represented by formula (g2-1) (provided that a1=d1+d3 and b1=d2+d4), a group represented by formula (g2-2) (provided that a1=e1 and b1=e2), a group represented by formula (g2-3) (provided that a1=1 and b1=2), a group represented by formula (g2-4) (provided that a1=h1 and b1=h2), a group represented by formula (g2-5) (provided that a1=i1 and b1=i2), a group represented by formula (g2-6) (provided that a1=1 and b1=1), or a group represented by formula (g2-7) (provided that a1=1 and b1=i3). [ka] (-AQ12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -) e2 (g2-2) -AQ 13 -N(-Q 23 -)2(g2-3) (-AQ 14 -) h1 Z(-Q 24 -) h2 (g2-4) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -) i2 (g2-5) -AQ 26 - (g2-6) -AQ 12 -CH(-Q 22 -)-Si(R 3 ) 3-i3 (-Q 25 -) i3 (g2-7) however, In formulas (g2-1) to (g2-7), the A side is R f Connect to Q 22 , Q 23 , Q 24 , Q 25 and Q 26 side connects to T, A is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O- or -SO2NR 6 - 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. 6 -, -C(O)-, -NR 6 - or -O-, Q 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6-, -C(O)-, -NR 6 - or -O-, Q 1 Q 12 If you have two or more, you need two or more Q 12 may be the same or different, Q 13 represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 a group having - or -O-, or a group having -C(O)- at the N-terminal of the alkylene group, Q 14 Q 14 If the atom in Z to which is bonded is a carbon atom, Q 12 And Q 14 If the atom in Z to which is bonded is a nitrogen atom, Q 13 And Q 1 Q 14 If you have two or more, you need two or more Q 14 may be the same or different, Q 15 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Q 15 If you have two or more, you need two or more Q 15 may be the same or different, Q 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the end of the alkylene group not connected to T 6 -, -C(O)-, -NR 6 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to T 6-, -C(O)-, -NR 6 - or -O-, Q 1 Q 22 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different, Q 24 Q 24 If the atom in Z to which is bonded is a carbon atom, Q 22 And Q 24 If the atom in Z to which is bonded is a nitrogen atom, Q 23 And Q 1 Q 24 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Q 25 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, Z is Q 14 has a carbon atom or nitrogen atom to which Q is directly bonded 24 is a group having a ring structure with a valence of a1+b1 and having a carbon atom or a nitrogen atom to which is directly bonded, R 1 is a hydrogen atom or an alkyl group, and Q 1 R 1 If there are two or more, two or more R1 may be the same or different, R 2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R 3 is an alkyl group, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 3; d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3+d4 is an integer from 1 to 3; d1+d3 is Q 1 is an integer from 1 to 5, d2+d4 is Q 1 is an integer from 1 to 5, e1+e2 is 3 or 4, e1 is Q 1 is an integer from 1 to 3, e2 is Q 1 is an integer from 1 to 3, h1 is Q 1 is an integer equal to or greater than 1, h2 is an integer equal to or greater than 1, i1+i2 is 3 or 4, i1 is Q 1 is an integer from 1 to 3, i2 is Q 1 is an integer from 1 to 3, i3 is 2 or 3.

[0011] [5] A fluorinated ether compound of [1], which is a compound represented by the following formula (1B): [T-] b2 Q 2 -Q f -Q 2 [-T] b2 (1B) however, Q f has the first partial structure and the second partial structure, and a divalent group having five or more of the first partial structures or two or more of the second partial structures, both bonding terminals of which are carbon atoms, Q 2 is a single bond or a b2+1 valent linking group, and two Q 2 may be the same or different, T is -R f6 , -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 )2, -N + (R 10 )3X 3 , -C≡N, -C(=NR 10 )-R 10 , -N + ≡N, -N=NR 10 , -C(=O)OR 10 , -C(=O)OX 2 , -C(=O)OX 4 , -C(=O)OC(=O)R 10 , -SO2R 10 , -SO3H, -SO3X 2 ,-OP(=O)(-OR 10 )2, -OP(=O)(-OR 10 )(-OX 2 ), -N=C=O, -Si(R) 3-c (L) c , -C(R 10 )=C(R 10 )2, -C≡C(R 10 ), -C(=O)N(R 10 )2, -N(R 10 )C(=O)R 10 , -Si(R 10 )2-O-Si(R 10 )3, -NH-C(=O)R 10 , -C(=O)NHR 10 , -I, [ka] R f6 is a fluoroalkyl group having 1 to 6 carbon atoms, R 10is a hydrogen atom, an alkyl group or a fluoroalkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent, and R 10 If there are 2 or more, R is 2 or more 10 may be the same or different, Ar is an optionally substituted aryl group, X 2 is an alkali metal ion or an ammonium ion, X 3 is a halide ion, X 4 is a halogen atom, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. b2 is an integer of 1 or more, and two b2's may be the same or different. c is 2 or 3; When there are two or more T's, the two or more T's may be the same or different.

[0012] [6] Q. f is a group represented by the following formula (g1b): [5] A fluorine-containing ether compound. -R f4 -(OR f2 ) m (OR f3 ) n - (g1b) however, R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q 2 R binds to f2 Q 2 At least one fluorine atom is bonded to the terminal carbon atom of the R f3 is a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q 2 R binds to f3 Q 2 At least one fluorine atom is bonded to the terminal carbon atom of the Rf4 represents a fluoroalkylene group having 1 to 6 carbon atoms, or a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein R f4 Q 2 At least one fluorine atom is bonded to the terminal carbon atom of the n is R f4 When R has a fluorine-containing ring structure, it is an integer of 0 to 500. f4 is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR f3 ) n OR of two or more types f3 It may consist of When n is 0, m is an integer from 5 to 500; When n is 1 or more, m is an integer of 2 to 500, If m is 2 or more, (OR f2 ) m OR of two or more types f2 It may consist of m (OR f2 ) and n (OR f3 ) may be joined in any order.

[0013] [7] Q. 2 is a group represented by formula (g2-1) (with the proviso that b2=d2+d4), a group represented by formula (g2-2) (with the proviso that b2=e2), a group represented by formula (g2-3) (with the proviso that b2=2), a group represented by formula (g2-4) (with the proviso that b2=h2), a group represented by formula (g2-5) (with the proviso that b2=i2), a group represented by formula (g2-6) (with the proviso that b2=1), or a group represented by formula (g2-7) (with the proviso that b2=i3). [ka] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -) e2 (g2-2) -AQ13 -N(-Q 23 -)2(g2-3) (-AQ 14 -) h1 Z(-Q 24 -) h2 (g2-4) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -) i2 (g2-5) -AQ 26 - (g2-6) -AQ 12 -CH(-Q 22 -)-Si(R 3 ) 3-i3 (-Q 25 -) i3 (g2-7) however, In formulas (g2-1) to (g2-7), side A is Q f Connect to Q 22 , Q 23 , Q 24 , Q 25 and Q 26 side connects to T, A is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O- or -SO2NR 6 - 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. 6 -, -C(O)-, -NR 6 - or -O-, Q 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 2 Q 12 If you have two or more, you need two or more Q 12may be the same or different, and Q 13 represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 a group having - or -O-, or a group having -C(O)- at the N-terminal of the alkylene group, Q 14 Q 14 If the atom in Z to which is bonded is a carbon atom, Q 12 And Q 14 If the atom in Z to which is bonded is a nitrogen atom, Q 13 And Q 2 Q 14 If you have two or more, you need two or more Q 14 may be the same or different, Q 15 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 2 Q 15 If you have two or more, you need two or more Q 15 may be the same or different, Q 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the end of the alkylene group not connected to T 6 -, -C(O)-, -NR 6 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to T 6 -, -C(O)-, -NR 6 - or -O-, Q 2 Q 22 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different, Q 24 Q 24 If the atom in Z to which is bonded is a carbon atom, Q 22 And Q 24 If the atom in Z to which is bonded is a nitrogen atom, Q 23 And Q 2 Q 24 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, Q 2 Q 25 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, Z is Q 14 has a carbon atom or nitrogen atom to which Q is directly bonded 24 is a group having a b2+1 valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, R 1 is a hydrogen atom or an alkyl group, and Q 2 R 1 If there are two or more, two or more R 1 may be the same or different, R 2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R 3 is an alkyl group, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 3; d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3+d4 is an integer from 1 to 3; d1+d3 is Q 2 is 1 in d2+d4 is Q 2 is an integer from 3 to 5, e1+e2 is 3 or 4, e1 is Q 2 is 1 in e2 is Q 2 is 2 or 3, h1 is Q 2 is 1 in h2 is an integer equal to or greater than 1, i1+i2 is 3 or 4, i1 is Q 2 is 1 in i2 is Q 2 is 2 or 3, i3 is 2 or 3.

[0014] [8] The fluorine-containing ether compound according to any one of [1] to [7], wherein the fluorine-containing ring structure is a four-membered ring. [9] Any of the fluorinated ether compounds according to [1] to [8], having a number average molecular weight of 2,500 or more.

[10] T is -Si(R) 3-c (L) c The fluorine-containing ether compound according to any one of [2] to [9], however, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. c is 2 or 3.

[0015]

[11] A fluorinated ether composition comprising at least one of the fluorinated ether compounds according to any one of [1] to

[10] and another fluorinated ether compound.

[12] A coating liquid comprising the fluorinated ether compound according to any one of [1] to

[10] or the fluorinated ether composition according to

[11] , and a liquid medium.

[13] An article having a surface layer formed on the surface of a substrate from a fluorinated ether compound of any one of [1] to

[10] or the fluorinated ether composition of

[11] .

[14] The article according to

[13] , having the surface layer on a surface of a member constituting a surface of a touch panel that is touched by a finger.

[15] A method for producing an article, comprising treating a surface of a substrate by a dry coating method using a fluorinated ether compound of any one of [1] to

[10] or the fluorinated ether composition of

[11] , and forming a surface layer made from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.

[16] A method for producing an article, comprising applying the coating liquid of

[12] to a surface of a substrate by a wet coating method, and drying the coating liquid to form a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.

[0016]

[17] A fluorine-containing ether compound represented by the following formula (2A): [R f -] a1 Q 10 [-CH=CH2] b1 (2A) however, R f is a monovalent polyfluoropolyether chain having at least one of a monovalent fluorine-containing ring structure at a free end and a divalent fluorine-containing ring structure in the main chain, and the bonding end being a carbon atom (with the proviso that at least one fluorine atom is bonded to the carbon atom at the bonding end), R f If there are two or more, two or more R f may be the same or different, Q 10is a linking group having a valence of a1+b1, a1 is an integer of 1 or more, b1 is an integer of 1 or greater.

[18] A fluorine-containing ether compound represented by the following formula (2B): [CH2=CH-] b2 Q 20 -Q f -Q 20 [-CH=CH2] b2 (2B) however, Q f is a divalent polyfluoropolyether chain having a divalent fluorine-containing ring structure in the main chain and both bonding terminals being carbon atoms (provided that at least one fluorine atom is bonded to each of the carbon atoms at both bonding terminals), Q 20 is a b2+1 valent linking group, and two Q 20 may be the same or different, b2 is an integer of 1 or more, and two b2's may be the same or different.

[0017]

[19] A method for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (12) to obtain a compound represented by the following formula (21): [ka] however, R 11 is an alkylene group, a group having -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH2), or a group having -O- between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH2), R 12 is a halogen atom, a perfluoroalkyl group, or a group having -O- between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, q is 0 or 1; E is -OH, -OR14 , -SR 14 , -C(O)OR 14 , -C(O)NHR 14 , -C(O)NR 14 R 15 , -NH2, -NHR 14 , -NR 14 R 15 , -SO2X 1 , -C(O)X 1 or a halogen atom, R 14 and R 15 are each independently an alkyl group, X 1 is a halogen atom.

[0018]

[20] A method for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (22): [ka] however, R 11 is an alkylene group, a group having -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH2), or a group having -O- between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH2), R 13 is a fluoroalkylene group, a group having -O- at both terminals of a fluoroalkylene group, or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, q is 0 or 1; E is -OH, -OR 14 , -SR 14 , -C(O)OR 14 , -C(O)NHR 14 , -C(O)NR 14 R 15 , -NH2, -NHR 14 , -NR 14 R 15 , -SO2X1 , -C(O)X 1 or a halogen atom, R 14 and R 15 are each independently an alkyl group, X 1 is a halogen atom, There are multiple R in equation (22) 11 , q and E may be the same or different.

[0019]

[21] A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (11) with each other to obtain a compound represented by the following formula (23): [ka] however, R 11 is an alkylene group, a group having -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH2), or a group having -O- between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH2), q is 0 or 1; E is -OH, -OR 14 , -SR 14 , -C(O)OR 14 , -C(O)NHR 14 , -C(O)NR 14 R 15 , -NH2, -NHR 14 , -NR 14 R 15 , -SO2X 1 , -C(O)X 1 or a halogen atom, R 14 and R 15 are each independently an alkyl group, X 1 is a halogen atom, There are multiple R in equation (23) 11 , q and E may be the same or different.

[0020]

[22] A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (13) with each other to obtain a compound represented by the following formula (24): [ka] however, R 13 is a fluoroalkylene group, a group having -O- at both terminals of a fluoroalkylene group, or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, r is an integer equal to or greater than 1, There are multiple R in equation (24) 13 may be the same or different.

[0021]

[23] A method for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (25): [ka] however, R 11 is an alkylene group, a group having -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH2), or a group having -O- between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH2), R 13 is a fluoroalkylene group, a group having -O- at both terminals of a fluoroalkylene group, or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, q is 0 or 1; r is an integer equal to or greater than 1; E is -OH, -OR 14 , -SR 14 , -C(O)OR 14 , -C(O)NHR 14 , -C(O)NR 14 R 15, -NH2, -NHR 14 , -NR 14 R 15 , -SO2X 1 , -C(O)X 1 or a halogen atom, R 14 and R 15 are each independently an alkyl group, X 1 is a halogen atom, There are multiple R in equation (25) 13 may be the same or different.

[0022]

[24] A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (12) with each other to obtain a compound represented by the following formula (26): [ka] however, R 12 represents a halogen atom, a perfluoroalkyl group, or a group having -O- between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, There are multiple R in equation (26) 12 may be the same or different.

[0023]

[25] A method for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (12) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (27): [ka] however, R 12 is a halogen atom, a perfluoroalkyl group, or a group having -O- between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, R 13 is a fluoroalkylene group, a group having -O- at both terminals of a fluoroalkylene group, or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, r2 is an integer equal to or greater than 1, There are multiple R in equation (27) 13 may be the same or different. Effect of the Invention

[0024] The present invention provides a fluorine-containing ether compound having excellent chemical resistance, a fluorine-containing ether composition and coating liquid capable of forming a surface layer having excellent chemical resistance, an article having a surface layer having excellent chemical resistance and a method for producing the same, and a method for producing a fluorine-containing compound useful as a raw material for the fluorine-containing ether compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] In this specification, the compound represented by formula (1A) is referred to as compound (1A). Compounds represented by other formulas are also referred to in the same manner. In addition, the group represented by formula (g1a) will be referred to as group (g1a). Groups represented by other formulae will be similarly referred to. "Oxyfluoro(cyclo)alkylene" is a general term for oxyfluoroalkylene and oxyfluorocycloalkylene. The formula of an oxyfluoro(cyclo)alkylene unit is intended to be represented with the oxygen atom to the left of the fluoro(cyclo)alkylene group.

[0026] As used herein, the following terms have the following meanings: The term "free end" means an end of the polyfluoropolyether chain that is not bonded to a reactive silyl group via a linking group. The term "terminal region" refers to a range constituted by oxyfluoro(cyclo)alkylene units including the above-mentioned "free end". The "fluorine-containing ring structure" refers to a group containing a group in which at least a part of the hydrogen atoms bonded to carbon atoms constituting an aliphatic ring or an aromatic ring are substituted with fluorine atoms, and may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in the carbon chain. Examples of the "fluorine-containing ring structure" include groups containing a fluoroaryl group, a fluoroarylene group, a fluorocycloalkyl group, a fluorocycloalkylene group, and the like. The term "monovalent fluorine-containing ring structure at a free end" refers to a ring structure in which one of the carbon atoms constituting the fluorine-containing ring is a carbon atom at the end of the main chain of the polyfluoropolyether chain that is not bonded to a linking group, and refers to a fluorine-containing ring structure constituting a terminal region. Examples of the "monovalent fluorine-containing ring structure at a free end" include monovalent groups including fluorocycloalkyl groups, fluoroaryl groups, etc. The term "divalent fluorine-containing ring structure in the middle of the main chain" means a ring structure in which one or more of the carbon atoms constituting the fluorine-containing ring are carbon atoms constituting the main chain of the polyfluoropolyether chain. Examples of the "divalent fluorine-containing ring structure in the middle of the main chain" include divalent groups including fluorocycloalkylene groups, fluoroarylene groups, etc. The "fluorine-containing aliphatic ring structure" is a group in which at least a part of the hydrogen atoms bonded to the carbon atoms constituting the aliphatic ring are substituted with fluorine atoms, and the atoms constituting the fluorine-containing aliphatic ring may contain oxygen atoms, nitrogen atoms, etc. in addition to carbon atoms, and preferably consist of only carbon atoms or carbon atoms and oxygen atoms. Examples of the "fluorine-containing aliphatic ring structure" include groups containing a fluorocycloalkyl group, a fluorocycloalkylene group, etc.

[0027] The term "reactive silyl group" refers collectively to hydrolyzable silyl groups and silanol groups (Si-OH). The reactive silyl group is, for example, -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. The fluorine-containing ether compound has a polyfluoropolyether chain (R f Or Q f In the case where the polyfluoropolyether chain (R f Or Q f The "molecular weight" of 1 H-NMR and 19The number average molecular weight is calculated by F-NMR to determine the number (average value) of oxyfluoro(cyclo)alkylene units based on the terminal group. The terminal group is, for example, R f1 Or T in formula (1A) or formula (1B). The fluorine-containing ether compound has a polyfluoropolyether chain (R f Or Q f When the chain length of the polyfluoropolyether chain (R f Or Q f The "molecular weight" of 1 H-NMR and 19 F-NMR f The molecular weight is calculated by determining the structure of the compound.

[0028] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the compound") is a compound having a polyfluoropolyether chain, and the polyfluoropolyether chain has a fluorine-containing ring structure. The fluorine-containing ring structure may have one or more heteroatoms. When the polyfluoropolyether chain has the specific fluorine-containing ring structure, the compound has excellent chemical resistance. In the present compound, when the polyfluoropolyether chain has one fluorine-containing ring structure, the polyfluoropolyether chain has five or more oxyfluoroalkylene units, which provides flexibility to the polyfluoropolyether chain and ensures a sufficient amount of fluorine to provide various properties of the fluorine-containing ether compound. In addition, in the present compound, when the polyfluoropolyether chain has two or more fluorine-containing ring structures, the polyfluoropolyether chain has two or more (preferably five or more) oxyfluoroalkylene units, which gives flexibility to the polyfluoropolyether chain and ensures a sufficient amount of fluorine to give various properties of the fluorine-containing ether compound. The fluorine-containing ring structure is an OR f13 (second partial structure). The oxyfluoroalkylene group is an ORf12 (First partial structure). The polyfluoropolyether chain is preferably a perfluoropolyether chain because of the excellent effect of imparting various properties by fluorine. Also, because of the excellent effect of imparting various properties by fluorine, the molecular weight of the present compound is preferably 2,500 or more, more preferably 2,500 to 100,000, and even more preferably 3,000 to 10,000.

[0029] The present compound preferably has a structure in which a polyfluoropolyether chain and a group that imparts various functions to the present compound (T in formula (1A) and formula (1B) described below (hereinafter, also referred to as a functionality-imparting group T)) are linked directly or via a linking group.

[0030] The polyfluoropolyether chain in the present invention has a fluorine-containing ring structure which may have a heteroatom. In the case of a monovalent polyfluoropolyether chain, it has at least one of a monovalent fluorine-containing ring structure at a free end and a divalent fluorine-containing ring structure in the main chain. In the case of a divalent polyfluoropolyether chain, it has a divalent fluorine-containing ring structure in the main chain. The polyfluoropolyether chain has a fluorine-containing ring structure, which provides excellent chemical resistance and various durability properties such as light resistance. As the fluorine-containing ring structure, a 3- to 8-membered ring is preferable from the viewpoint of ease of production of the present compound, and a 4- to 6-membered ring is more preferable, a 4- or 5-membered ring is even more preferable, and a 4-membered ring is particularly preferable from the viewpoint of further improving the abrasion resistance and slip resistance of the surface layer.

[0031] The compound is a fluorine-containing ether compound having a first partial structure represented by the following formula (1) (hereinafter also referred to as "partial structure 1") and a second partial structure represented by the following formula (2) (hereinafter also referred to as "partial structure 2"), The partial structure 1 has 5 or more, or The compound is characterized by having two or more of the partial structure 2. -OR f12 - (1) -ORf13 - (2) however, R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, R f13 is a group having a fluorine-containing ring structure which may have a heteroatom. The present compound preferably has one partial structure 2 and five or more partial structures 1 in terms of high fingerprint stain removal properties.

[0032] In the partial structure 1, R f12 Since the fluoroalkylene group has 1 to 6 carbon atoms, flexibility is imparted to the polyfluoropolyether chain, and the surface layer formed has excellent abrasion resistance and fingerprint stain removability. R f12 As the fluoroalkylene group, a straight-chain fluoroalkylene group is preferred since it provides the surface layer with even better abrasion resistance and fingerprint stain removability. R f12 The fluoroalkylene group is preferably a perfluoroalkylene group, since this provides a surface layer with even better abrasion resistance and fingerprint removability. All R f12 The proportion of perfluoroalkylene groups among these is preferably 60 mol % or more, more preferably 80 mol % or more, and particularly preferably 100 mol %, in order to provide a surface layer with even better abrasion resistance and fingerprint stain removability.

[0033] In the substructure 2, R f13Examples of the group having a fluorine-containing ring structure which may have a heteroatom include a fluorocycloalkylene group which may have a heteroatom and may have a substituent. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like, and an oxygen atom is preferred. The number of members of the ring containing a heteroatom is preferably 3 to 8 in terms of ease of production of the present compound, and more preferably 4 to 6, further preferably 4 to 5, and particularly preferably 4 in terms of further excellent abrasion resistance and slip resistance of the surface layer. In addition, in terms of excellent chemical resistance, the fluorine-containing ring structure is preferably a fluorine-containing ring structure without a heteroatom. In addition, the fluorine-containing ring structure is preferably a fluorine-containing aliphatic ring structure. The fluorocycloalkylene group, which is a divalent fluorine-containing aliphatic ring structure, is preferably a perfluorocycloalkylene group, since the surface layer has better abrasion resistance and fingerprint stain removability. The fluorocycloalkylene group may have, for example, a fluoroalkylene group as a substituent. The carbon number of the fluoroalkylene group is preferably 1 to 6, more preferably 1 to 4. The fluoroalkylene group is preferably a perfluoroalkylene group.

[0034] Furthermore, a fluoroalkylene group as a substituent may be bonded to the oxygen atom of the above formula (2). In this case, the above formula (2) is represented by the following formula (2a). -OR f14 R f15 - (2a) however, R f14 is a fluoroalkylene group having 1 to 6 carbon atoms, R f15 is a fluorine-containing ring structure which may have a heteroatom. f14 R f15 is R f13 Represents. The polyfluoropolyether chain may have the partial structure 2 at its terminal region. In this case, the terminal region is represented by the following formula (2b). -OR f13 R f16 (2b) However, R f13 is as mentioned above, and Rf16 is a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. f13 R f16 is sometimes referred to as a monovalent fluorine-containing ring structure. Examples of the monovalent fluorine-containing ring structure include groups of the following formulae: In the formulae, * represents a bond.

[0035] [ka]

[0036] Examples of the divalent fluorine-containing ring structure include a fluorocycloalkylene group and a group having -O- between carbon atoms of the fluorocycloalkylene group. The number of carbon atoms in the fluorocycloalkylene group is preferably 3 to 8 in terms of ease of production of the present compound, more preferably 4 to 6, and particularly preferably 4, in terms of further improving the abrasion resistance and slip resistance of the surface layer. The fluorocycloalkylene group is preferably a perfluorocycloalkylene group, since the surface layer has better abrasion resistance and fingerprint stain removability. The fluorocycloalkylene group may have, for example, a fluoroalkyl group as a substituent. Examples of the divalent fluorine-containing ring structure include groups of the following formula: In the formula, * represents a bond.

[0037] [ka]

[0038] The molecular weight of the polyfluoropolyether chain is preferably 100 to 6000, more preferably 500 to 5000, and particularly preferably 1000 to 4000, from the viewpoint of achieving both fingerprint removability and slip resistance of the surface layer, and from the viewpoint of chemical resistance. If the molecular weight of the polyfluoropolyether chain is equal to or higher than the lower limit of the above range, the fingerprint removability of the surface layer is further excellent. If the molecular weight of the polyfluoropolyether chain is equal to or lower than the upper limit of the above range, the slip resistance of the surface layer is further excellent. The molecular weight of the polyfluoropolyether chain is preferably 1500 to 10000, more preferably 2000 to 8000, and particularly preferably 2500 to 6000, from the viewpoint of further excellent abrasion resistance and fingerprint removability of the surface layer, and from the viewpoint of chemical resistance. If the molecular weight of the polyfluoropolyether chain is equal to or higher than the lower limit of the above range, the abrasion resistance and fingerprint removability of the surface layer are further excellent. If the molecular weight of the polyfluoropolyether chain is equal to or lower than the upper limit of the above range, the abrasion resistance of the surface layer is further excellent.

[0039] (Compound (1A) and Compound (1B)) As the present compound, the compounds (1A) and (1B) are preferred in that they provide a surface layer with even better abrasion resistance and fingerprint stain removability. [R f -] a1 Q 1 [-T] b1 (1A) [T-] b2 Q 2 -Q f -Q 2 [-T] b2 (1B) However, R f is a monovalent group having the partial structure 1 and the partial structure 2, and having 5 or more of the partial structure 1 or 2 or more of the partial structure 2, the bonding end of which is a carbon atom, and R f If there are two or more, two or more R f may be the same or different. Q f represents a divalent group having the partial structure 1 and the partial structure 2, and having 5 or more of the partial structure 1 or 2 or more of the partial structure 2, both bonding terminals of which are carbon atoms. In particular, the compound (1B) preferably has only one of the partial structure 2 and five or more of the partial structure 1, from the viewpoint of high fingerprint stain removability. In particular, the total molecular weight of the partial structure 1 is preferably 1,000 to 10,000, and more preferably 2,000 to 6,000. Q 1 Q is a single bond or a linking group having a valence of a1+b1. 2is a single bond or a b2+1 valent linking group, and two Q 2 may be the same or different. T is -R f6 , -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 )2, -N + (R 10 )3X 3 , -C≡N, -C(=NR 10 )-R 10 , -N + ≡N, -N=NR 10 , -C(=O)OR 10 , -C(=O)OX 2 , -C(=O)OX 4 , -C(=O)OC(=O)R 10 , -SO2R 10 , -SO3H, -SO3X 2 ,-OP(=O)(-OR 10 )2, -OP(=O)(-OR 10 )(-OX 2 ), -N=C=O, -Si(R) 3-c (L) c , -C(R 10 )=C(R 10 )2, -C≡C(R 10 ), -C(=O)N(R 10 )2, -N(R 10 )C(=O)R 10 , -Si(R 10 )2-O-Si(R 10 )3, -NH-C(=O)R 10 , -C(=O)NHR 10 , -I, [ka] R f6 is a fluoroalkyl group having 1 to 6 carbon atoms, R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 10If there are 2 or more, R is 2 or more 10 may be the same or different, Ar is an optionally substituted aryl group, X 2 is an alkali metal ion or an ammonium ion, X 3 is a halide ion, X 4 is a halogen atom, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. b2 is an integer of 1 or more, and two b2's may be the same or different. c is 2 or 3; When there are two or more T's, the two or more T's may be the same or different.

[0040] Compound (1A) has R at the end f It has R at the end. f Compound (1A) having Q has excellent chemical resistance and excellent fingerprint stain removal properties on the surface layer. f Q f The compound (1B) having the formula (1B) has excellent chemical resistance and excellent ability to remove fingerprint stains from the surface layer. Compound (1A) and compound (1B) have the specific functionality-imparting group T at their terminals. Compound (1A) and compound (1B) having the functionality-imparting group T at their terminals are strongly chemically bonded to the substrate, and various functions are imparted to the compounds, such as excellent abrasion resistance of the surface layer. a1 is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2, from the viewpoints of ease of production of compound (1A), excellent chemical resistance, and further excellent abrasion resistance and fingerprint stain removability of the surface layer. From the viewpoints of ease of production of compound (1A), excellent chemical resistance, and further excellent abrasion resistance and fingerprint stain removability of the surface layer, b1 is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and particularly preferably 2 to 4. From the viewpoints of ease of production of compound (1B), excellent chemical resistance, and further excellent abrasion resistance and fingerprint stain removability of the surface layer, b2 is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and particularly preferably 2 to 4.

[0041] R f R is a monovalent polyfluoropolyether chain whose binding end is a carbon atom. f As the perfluoropolyether chain, a monovalent perfluoropolyether chain is more preferred from the viewpoints of excellent chemical resistance, and further excellent abrasion resistance and fingerprint stain removability of the surface layer. Q f is a divalent polyfluoropolyether chain whose both bond ends are carbon atoms. f As the perfluoropolyether chain, a divalent perfluoropolyether chain is more preferred from the viewpoints of excellent chemical resistance, and further excellent abrasion resistance and fingerprint stain removability of the surface layer. R f and Q f The preferred range of the molecular weight of the polyfluoropolyether chain is the same as the preferred range of the molecular weight of the polyfluoropolyether chain described above.

[0042] R f Examples of the group (g1a) include the group (g1a): The group (g1a) has one or more fluorine-containing ring structures. R f1 -(OR f2 ) m (OR f3 ) n - (g1a) However, R f1 R is a fluoroalkyl group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having a fluorine-containing ring structure. f2 is a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q 1 R binds to f2 Q 1At least one fluorine atom is bonded to the terminal carbon atom of the R f3 is a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q 1 R binds to f3 Q 1 At least one fluorine atom is bonded to the terminal carbon atom on the side. n is R f1 When R has a fluorine-containing ring structure, it is an integer of 0 to 500. f1 is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR f3 ) n OR of two or more types f3 It may consist of: When n is 0, m is an integer of 5 to 500. When n is 1 or more, m is an integer of 2 to 500. When m is 2 or more, (OR f2 ) m OR of two or more types f2 and m (OR f2 ) and n (OR f3 ) may be joined in any order.

[0043] Q f Examples of the group (g1b) include a group having a group (g1b). The group (g1b) has one or more fluorine-containing ring structures. -R f4 -(OR f2 ) m (OR f3 ) n - (g1b) However, R f2 is a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q 2 R binds to f2 Q 2 At least one fluorine atom is bonded to the terminal carbon atom of the R f3 is a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q 2 R binds to f3 Q 2 At least one fluorine atom is bonded to the terminal carbon atom of the R f4represents a fluoroalkylene group having 1 to 6 carbon atoms, or a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein R f4 Q 2 At least one fluorine atom is bonded to the terminal carbon atom on the side. n is R f4 When R has a fluorine-containing ring structure, it is an integer of 0 to 500. f4 is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR f3 ) n OR of two or more types f3 It may consist of: When n is 0, m is an integer of 5 to 500. When n is 1 or more, m is an integer of 2 to 500. When m is 2 or more, (OR f2 ) m OR of two or more types f2 and m (OR f2 ) and n (OR f3 ) may be joined in any order. Further Q f As the group (g1b1), the group (g1b1) is particularly preferred. -R f4 -(OR f2 ) mm1 -(OR f3 )-(OR f2 ) mm2 - (g1b1) However, mm1+mm2=m and n=1. In the group (g1b1), it is preferable that (mm1+1) and (mm2) are almost equal in terms of abrasion resistance. Here, "almost equal" means that the ratio of (mm1+1) / mm2 is 0.5 to 2, preferably 0.75 to 1.33.

[0044] R f1 When the carbon number of the fluoroalkyl group is 1 to 20, the chemical resistance is excellent, and the abrasion resistance and fingerprint stain removability of the surface layer are further excellent. f1 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 terms of excellent chemical resistance and further excellent abrasion resistance and fingerprint stain removability of the surface layer. Rf1 As the fluoroalkyl group of R, a perfluoroalkyl group is preferable because it has excellent chemical resistance and further excellent abrasion resistance and fingerprint stain removability of the surface layer. f1 In the compound (1A) in which the terminal is a perfluoroalkyl group, the terminal is CF3-. The compound (1A) in which the terminal is CF3- 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 f1 Examples of the fluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)-, and (CF3CF2)2CF-.

[0045] R f1 The number of carbon atoms in the monovalent fluorinated hydrocarbon group having a fluorine-containing ring structure is preferably from 3 to 20, more preferably from 4 to 8, and particularly preferably from 4 to 6. When the number of carbon atoms in the fluorinated hydrocarbon group is within the above range, the chemical resistance is excellent, and the abrasion resistance and fingerprint stain removability of the surface layer are even more excellent. R f1 As the fluorinated hydrocarbon group, a fluorocycloalkyl group is preferred from the viewpoints of excellent chemical resistance and further excellent slip resistance of the surface layer. R f1 The fluorinated hydrocarbon group is preferably a fully fluorinated hydrocarbon group, since it has excellent chemical resistance and is further excellent in the abrasion resistance and removability of fingerprint stains of the surface layer. R f1 Examples of the fluorinated hydrocarbon group include the monovalent fluorine-containing ring structures exemplified in the above formula.

[0046] R f2 or R f4 When the fluoroalkylene group has 1 to 6 carbon atoms, the chemical resistance is excellent, and the surface layer has even better abrasion resistance and fingerprint stain removability. R f2 or R f4As the fluoroalkylene group, a straight-chain fluoroalkylene group is preferred since it has excellent chemical resistance and further excellent abrasion resistance and fingerprint stain removability of the surface layer. R f2 or R f4 The fluoroalkylene group is preferably a perfluoroalkylene group, since it has excellent chemical resistance and further excellent abrasion resistance and fingerprint stain removability of the surface layer. All R f2 The proportion of perfluoroalkylene groups in the above is preferably 60 mol % or more, more preferably 80 mol % or more, and particularly preferably 100 mol %, in terms of excellent chemical resistance and even better abrasion resistance and fingerprint stain removability of the surface layer.

[0047] R f3 or R f4 The number of carbon atoms in the divalent fluorinated hydrocarbon group having a fluorine-containing ring structure is preferably from 3 to 20, more preferably from 4 to 8, and particularly preferably from 4 to 6. When the number of carbon atoms in the fluorinated hydrocarbon group is within the above range, the chemical resistance is excellent, and the abrasion resistance and fingerprint stain removability of the surface layer are even more excellent. R f3 or R f4 As the fluorinated hydrocarbon group, a fluorocycloalkylene group is preferred because it has excellent chemical resistance and further excellent slip resistance of the surface layer. R f3 or R f4 The fluorinated hydrocarbon group is preferably a fully fluorinated hydrocarbon group, since it has excellent chemical resistance and is further excellent in the abrasion resistance and removability of fingerprint stains of the surface layer. R f3 or R f4 Examples of the fluorinated hydrocarbon group include the divalent fluorine-containing ring structures exemplified in the above formula.

[0048] When sufficient slip resistance is required for the surface layer, m is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and particularly preferably an integer of 1 to 10. When m is equal to or less than the upper limit of the above range, the surface layer has even better slip resistance. When sufficient abrasion resistance and fingerprint stain removability are required for the surface layer, m is preferably an integer of 2-200, more preferably an integer of 5-150, and particularly preferably an integer of 10-100. When m is equal to or greater than the lower limit of the above range, the chemical resistance is excellent, and the abrasion resistance and fingerprint stain removability of the surface layer are even more excellent. When m is equal to or less than the upper limit of the above range, the abrasion resistance of the surface layer is even more excellent. That is, when the number average molecular weights of the compounds (1A) and (1B) are too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases. When sufficient slip resistance is required for the surface layer, n is preferably an integer from 1 to 200, more preferably an integer from 1 to 150, and particularly preferably an integer from 1 to 100. When n is equal to or less than the upper limit of the above range, the chemical resistance is excellent and the slip resistance of the surface layer is further excellent.

[0049] In addition, in terms of excellent chemical resistance and excellent slip resistance of the surface layer, when n is 0, R f1 or R f4 It is preferable that the ring structure has a fluorine-containing ring structure. When n is 1, R f1 or R f4 When does not have a fluorine-containing ring structure or n is 0, m is preferably an integer of 5 to 30, more preferably an integer of 6 to 20, and particularly preferably an integer of 7 to 10, in terms of excellent chemical resistance and excellent slip resistance of the surface layer. When n is 1, R f1 or R f4 When has a fluorine-containing ring structure or when n is an integer of 2 or more, m is preferably an integer of 1 to 30, more preferably an integer of 2 to 20, and particularly preferably an integer of 3 to 10, in terms of excellent chemical resistance and excellent slip resistance of the surface layer.

[0050] OR f2, that is, examples of oxyfluoroalkylene units include OCHF, OCF2CHF, OCHFCF2, OCF2CH2, OCH2CF2, OCF2CF2CHF, OCHFCF2CF2, OCF2CF2CH2, OCH2CF2CF2, OCF2CF2CF2CH2, OCH2CF2CF2CF2, OCF2CF2CF2CF2CH2, OCH2CF2CF2CF2, OCF2CF2CF2CF2CH2, OCH2CF2CF2CF2CF2, OCF2CF2CF2CF2CH2, OCH2CF2CF2CF2CF2, OCF2, OCF2CF2, OCF2CF2CF2CF2, OCF(CF3)CF2, OCF2CF2CF2CF2, OCF(CF3)CF2CF2, OCF2CF2CF2CF2CF2, and OCF2CF2CF2CF2CF2CF2.

[0051] OR f3 Examples of the oxyfluorocycloalkylene unit include the following formula: In the formula, * represents a bond.

[0052] [ka]

[0053] (OR f2 ) m (OR f3 ) n In the above, when two or more kinds of oxyfluoro(cyclo)alkylene units are present, the bonding order of each oxyfluoro(cyclo)alkylene unit is not limited. For example, when OCF2CF2 and OCF2CF2CF2CF2 are present, OCF2CF2 and OCF2CF2CF2CF2 may be arranged randomly, alternately, or in blocks. When OCF2 and OCF2CF2 are present, it is preferable that both are arranged randomly. The presence of two or more types of oxyfluoro(cyclo)alkylene units means that there are two or more types of oxyfluoro(cyclo)alkylene units with different numbers of carbon atoms, there are two or more types of oxyfluoro(cyclo)alkylene units with different numbers of hydrogen atoms, there are two or more types of oxyfluoro(cyclo)alkylene units with different positions of hydrogen atoms, and there are two or more types of oxyfluoro(cyclo)alkylene units that have the same number of carbon atoms but differ in the presence or absence of side chains or the type of side chain (the number of side chains, the number of carbon atoms in the side chain, etc.). The arrangement of two or more oxyfluoro(cyclo)alkylene units is, for example, {(OCF2) m1 (OCF2CF2) m2 The structure represented by} indicates that m1 (OCF2) and m2 (OCF2CF2) are randomly arranged. m5 The structure represented by the formula (1) represents m5 (OCF2CF2) and m5 (OCF2CF2CF2CF2) arranged alternately.

[0054] If n is 0, then (OR f2 ) m (OR f3 ) n As the polyimide, those having the following structure in at least a part thereof are preferred. {(OCF2) m1 (OCF2CF2) m2}, (OCF2CF2) m3 , (OCF2CF2CF2) m4 , (OCF2CF2-OCF2CF2CF2CF2) m5 , (OCF2CF2CF2CF2CF2) m6 (OCF2) m7 , (OCF2CF2CF2CF2CF2) m6 (OCF2CF2) m7 , (OCF2CF2CF2CF2CF2CF2) m6 (OCF2) m7 , (OCF2CF2CF2CF2CF2CF2) m6 (OCF2CF2) m7 , (OCF2CF2CF2CF2CF2-OCF2) m8 , (OCF2CF2CF2CF2CF2-OCF2CF2) m8 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m8 , (OCF2CF2CF2CF2CF2CF2-OCF2CF2) m8 , (OCF2-OCF2CF2CF2CF2CF2) m8 , (OCF2-OCF2CF2CF2CF2CF2CF2) m8 , (OCF2CF2-OCF2CF2CF2CF2CF2) m8 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m8 , (OCF(CF3)CF2) m9 . Here, m1, m2, m3, m4, m5, m6, m7, m8, and m9 are integers equal to or greater than 1. The upper limit values ​​of m1, m2, m3, m4, m5, m6, m7, m8, and m9 are adjusted according to the upper limit value of m.

[0055] If n is 0, then (OR f2 ) m (OR f3 ) n As the compound (1A) and the compound (1B), the following are preferable from the viewpoint of ease of production. {(OCF2) m1 (OCF2CF2) m2}OCF2, (OCF2CF2) m3 OCF2, (OCF2CF2CF2) m4 OCF2CF2, (OCF2CF2)2{(OCF2) m1 (OCF2CF2) m2}OCF2, (OCF2CF2-OCF2CF2CF2CF2) m5 OCF2CF2OCF2CF2CF2, (OCF2-OCF2CF2CF2CF2CF2) m8 OCF2OCF2CF2CF2CF2, (OCF2-OCF2CF2CF2CF2CF2CF2) m8 OCF2OCF2CF2CF2CF2CF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2) m8 OCF2CF2OCF2CF2CF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m8 OCF2CF2OCF2CF2CF2CF2CF2CF2, (OCF(CF3)CF2) m9 OCF(CF3).

[0056] (OR if n is 1 or more f2 ) m (OR f3 ) n As the polyimide, those having the following structure in at least a part thereof are preferred. (OCF2CF2-OCF2CF2CF2CF2) m11 -O(c-C4F6)-(OCF2CF2CF2CF2-OCF2CF2) m12 , (OCF2CF2CF2CF2-O(c-C4F6)) m13 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m14 -O(c-C4F6)-(OCF2CF2CF2CF2CF2CF2-OCF2CF2) m15 . Here, c-C4F6 is a perfluoro-1,2-cyclobutylene group, and m11, m12, m13, m14, and m15 are integers of 1 or more. The upper limits of m11, m12, m13, m14, and m15 are adjusted according to the upper limits of m and n.

[0057] (OR if n is 1 or moref2 ) m (OR f3 ) n As the compound (1A) and the compound (1B), the following are preferable from the viewpoint of ease of production. OCF2CF2CF2(OCF2CF2-OCF2CF2CF2CF2) m11 -O(c-C4F6)-(OCF2CF2CF2CF2-OCF2CF2) m12 OCF2CF2CF2, OCF2CF2(OCF2CF2CF2CF2-O(c-C4F6)) m13 OCF2CF2CF2, O(c-C4F6)(OCF2CF2CF2CF2-O(c-C4F6)) m13 OCF2CF2CF2, OCF2CF2CF2(OCF2CF2-OCF2CF2CF2CF2CF2CF2) m11 -O(c-C4F6)-(OCF2CF2CF2CF2CF2CF2-OCF2CF2) m12 OCF2CF2CF2.

[0058] Q 1 Q is a single bond or a linear or branched linking group having a valence of a1+b1. 2 is a single bond or a b2+1 valent linear or branched linking group. The linking group is a divalent or higher organic group. Q 1 Or Q 2 When R is a single bond, the compound has a polyfluoroalkylene chain (R f Or Q f ) to which the functionality-imparting group T is directly bonded. Q 1 When a1+b1 is 3 or more, it is preferable that Q further has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and an a1+b1 valent organopolysiloxane residue. 2 When b2+1 is 3 or more, it is preferable that the copolymer has at least one branch point (hereinafter referred to as "branch point P'") selected from the group consisting of C, N, Si, a ring structure, and a b2+1-valent organopolysiloxane residue.

[0059] As the ring structure, from the viewpoints of ease of production of compound (1A) and compound (1B) and further superior abrasion resistance, light resistance and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle and a condensed ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is particularly preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an etheric oxygen atom between the carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (=O), etc.

[0060] [ka]

[0061] Examples of the a1+b1-valent organopolysiloxane residue or the b2+1-valent organopolysiloxane residue include the following groups. 5 R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0062] [ka]

[0063] Q 1 and Q 2 is -C(O)NR 6 -, -C(O)O-, -C(O)-, -O-, -NR 6 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -,-SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6It may further have at least one bond (hereinafter referred to as "bond B") selected from the group consisting of -Si(CH3)2-, -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue. 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 6 The number of carbon atoms in the alkyl group is preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (1A) and compound (1B).

[0064] Examples of the divalent organopolysiloxane residue include groups represented by the following formula: 7 R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0065] [ka]

[0066] As the bond B, -C(O)NR is preferably used because it is easy to produce the compound (1A) and the compound (1B). 6 -, -C(O)-, -NR 6 At least one bond selected from the group consisting of - and -O- is preferred, and from the viewpoint of further improving the light resistance and chemical resistance of the surface layer, -C(O)NR 6 - or -C(O)- is particularly preferred.

[0067] Q 1 Examples of the alkyl group include a combination of two or more divalent hydrocarbon groups and one or more branch points P, or a combination of two or more hydrocarbon groups, one or more branch points P, and one or more bonds B. Q 2 Examples of the alkyl group include a combination of two or more divalent hydrocarbon groups and one or more branching points P', or a combination of two or more hydrocarbon groups, one or more branching points P', and one or more bonds B. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group (such as an alkylene group or a cycloalkylene group) and a divalent aromatic hydrocarbon group (such as a phenylene group). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0068] Q of the above combination 1 As the group, from the viewpoint of ease of production of compound (1A), the group (g2-1) (wherein a1=d1+d3 and b1=d2+d4), the group (g2-2) (wherein a1=e1 and b1=e2), the group (g2-3) (wherein a1=1 and b1=2), the group (g2-4) (wherein a1=h1 and b1=h2), the group (g2-5) (wherein a1=i1 and b1=i2), the group (g2-6) (wherein a1=1 and b1=1), and the group (g2-7) (wherein a1=1 and b1=i3) are preferred. Q of the above combination 2 As the group g2, from the viewpoint of ease of production of compound (1B), the group (g2-1) (wherein b2=d2+d4), the group (g2-2) (wherein b2=e2), the group (g2-3) (wherein b2=2), the group (g2-4) (wherein b2=h2), the group (g2-5) (wherein b2=i2), the group (g2-6) (wherein b2=1), and the group (g2-7) (wherein b2=i3) are preferred.

[0069] [ka]

[0070] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -) e2 (g2-2) -AQ 13 -N(-Q 23 -)2(g2-3) (-AQ 14 -) h1 Z(-Q 24-) h2 (g2-4) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -) i2 (g2-5) -AQ 26 - (g2-6) -AQ 12 -CH(-Q 22 -)-Si(R 3 ) 3-i3 (-Q 25 -) i3 (g2-7)

[0071] However, in formulas (g2-1) to (g2-7), the A side is R f Or Q f Connect to Q 22 , Q 23 , Q 24 , Q 25 Or Q 26 The side connects to T. A is a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O- or -SO2NR 6 -It is. 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. 6 -, -C(O)-, -NR 6 Q is a group having - or -O-. 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Or Q 2 Q 12 If you have two or more, you need two or more Q 12 may be the same or different. Q 13 represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6-, -C(O)-, -NR 6 Q is a group having - or -O-, or a group having -C(O)- at the N-terminus of the alkylene group. 14 Q 14 If the atom in Z to which is bonded is a carbon atom, Q 12 And Q 14 If the atom in Z to which is bonded is a nitrogen atom, Q 13 And Q 1 Or Q 2 Q 14 If you have two or more, you need two or more Q 14 may be the same or different. Q 15 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Or Q 2 Q 15 If you have two or more, you need two or more Q 15 may be the same or different. Q 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the end of the alkylene group not connected to T 6 -, -C(O)-, -NR 6 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to T 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Or Q 2 Q 22 If you have two or more, you need 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. 6 -, -C(O)-, -NR6 - or -O-, and two Q 23 may be the same or different. Q 24 Q 24 If the atom in Z to which is bonded is a carbon atom, Q 22 And Q 24 If the atom in Z to which is bonded is a nitrogen atom, Q 23 And Q 1 Or Q 2 Q 24 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or -O-, Q 1 Or Q 2 Q 25 If you have two or more, you need 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. 6 -, -C(O)-, -NR 6 - or a group having -O-. Z is Q 14 has a carbon atom or nitrogen atom to which Q is directly bonded 24 is a group having a ring structure with a valence of a1+b1 or b2+1 and having a carbon atom or a nitrogen atom to which R is directly bonded. 1 is a hydrogen atom or an alkyl group, and Q 1 Or Q 2 R 1 If there are two or more, two or more R 1 may be the same or different. 2 R is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. 3 is an alkyl group. 6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. d1 represents an integer of 0 to 3, and is preferably 1 or 2. d2 is an integer of 0 to 3, and preferably 1 or 2. d1+d2 is an integer of 1 to 3. d3 is an integer of 0 to 3, and preferably 0 or 1. d4 is an integer of 0 to 3, and preferably 2 or 3. d3+d4 is an integer of 1 to 3. d1+d3 is Q 1 is an integer of 1 to 5, preferably 1 or 2; Q 2 In Q, d2+d4 is 1. 1 is an integer of 1 to 5, preferably 4 or 5; Q 2 is an integer of 3 to 5, preferably 4 or 5. e1+e2 is 3 or 4. e1 is Q 1 is an integer of 1 to 3, preferably 1 or 2; Q 2 e2 is 1 in Q 1 is an integer of 1 to 3, preferably 2 or 3; Q 2 In the case of Q, h1 is 2 or 3. 1 is an integer of 1 or more, preferably 1 or 2; Q 2 In this case, the value is 1. h2 is an integer of 1 or more, preferably 2 or 3. i1+i2 is 3 or 4. i1 is Q 1 is an integer of 1 to 3, preferably 1 or 2; Q 2 In Q, i2 is 1. 1 is an integer of 1 to 3, preferably 2 or 3; Q 2 In i3, it is either 2 or 3.

[0072] Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22 , Q 23 , Q 24 , Q 25 and Q 26The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of compound (1A) and compound (1B) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, in the case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0073] Examples of the ring structure in Z include the ring structures described above, and the preferred forms are also the same. In addition, the ring structure in Z is Q 14 Or Q 24 is directly bonded, so that, for example, an alkylene group is linked to the ring structure, and Q 14 Or Q 24 are never linked.

[0074] R 1 , R 2 and R 3 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 compound (1A) and compound (1B). R 2 The number of carbon atoms in the alkyl group of the acyloxy 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 compound 1. h1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of production of compound (1A) and compound (1B) and of further improving the abrasion resistance and fingerprint stain removability of the surface layer. h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoints of ease of production of compound (1A) and compound (1B) and of further improving the abrasion resistance and fingerprint stain removability of the surface layer.

[0075] Q 1Other forms of include the group (g2-8) (wherein a1=d1+d3 and b1=k), the group (g2-9) (wherein a1=e1 and b1=e2), the group (g2-10) (wherein a1=1 and b1=k), the group (g2-11) (wherein a1=h1 and b1=k), the group (g2-12) (wherein a1=i1 and b1=k), the group (g2-13) (wherein a1=1 and b1=k), and the group (g2-14) (wherein a1=1 and b1=k). Q 2 Other forms of include the group (g2-8) (with the proviso that b2=k in total), the group (g2-9) (with the proviso that b2=e2), the group (g2-10) (with the proviso that b2=k in total), the group (g2-11) (with the proviso that b2=k in total), the group (g2-12) (with the proviso that b2=k in total), the group (g2-13) (with the proviso that b2=k), and the group (g2-14) (with the proviso that b2=k in total).

[0076] [ka]

[0077] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -G) e2 (g2-9) -AQ 13 -N(-Q 23 -G)2(g2-10) (-AQ 14 -) h1 Z(-Q 24 -G) h2 (g2-11) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -G) i2 (g2-12) -AQ 26 -G (g2-13) -AQ 12 -CH(-Q 22 -G)-Si(R 3 ) 3-i3 (-Q 25 -G) i3 (g2-14)

[0078] However, in formulas (g2-8) to (g2-14), the A side is R f Or Q f The G side is connected to T. G is a group (g3), and Q 1 Or Q 2 The two or more G's in formula (g2-1) to formula (g2-7) may be the same or different. -Si(R 8 ) 3-k (-Q 3 -) k (g3) However, in formula (g3), the Si side is Q 22 , Q 23 , Q 24 , Q 25 Or Q 26 Connect to Q 3 The side connects to the T. 8 is an alkyl group. 3 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-, or -(OSi(R 9 )2) p -O- and 2 or more Q 3 may be the same or different. k is 2 or 3. R 6 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 9 )2) may be the same or different.

[0079] Q3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of compound (1A) and compound (1B) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, in the case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 8 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (1A) and compound (1B). R 9 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (1A) and compound (1B). R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of excellent storage stability of compound (1A) and compound (1B). p is preferably 0 or 1.

[0080] T is a functionality-imparting group that imparts various functions to the compound, such as a function to improve adhesion to a substrate surface, a function to impart photocurability or thermosetting property to the compound, a function to impart acidity / alkalinity to the compound, a function to adjust the solubility of the compound in a specific solvent, and a function as a reactive group when synthesizing other compounds using the compound as a raw material. R f6 and R 10 The fluoroalkyl group in the formula (I) preferably has 1 to 6 carbon atoms. The fluoroalkyl group may have other substituents. The present compound having a fluoroalkyl group as T is a compound with a high fluorine content, and is excellent in various properties such as a low refractive index, a low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency. Examples of the substituent that the fluoroalkyl group may have include a fluorine atom, a halogen atom such as a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and the same as those exemplified as the functionality-imparting group T. Ar and R 10The aryl group in the formula (I) may be a phenyl group, a naphthyl group, or the like, and may further have a substituent. The substituent that the aryl group may have may be a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group having 1 to 6 carbon atoms, or the same as those exemplified as the functionality-imparting group T. R 10 The alkyl group in the formula (I) preferably has 1 to 6 carbon atoms. The alkyl group may have another substituent. Examples of the substituent that the alkyl group may have include a halogen atom such as a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and the same as those exemplified as the functionality-imparting group T.

[0081] The compound having a hydroxy group, N-hydroxy group, aldehyde group, ketone group, amino group, quaternary ammonium group, nitrile group, imino group, diazo group, carboxy group, carboxylate, acid anhydride group, sulfo group, sulfonate, phosphoric acid group, or phosphate as T is endowed with various properties such as acidity, alkalinity, and hydrophilicity by the functionality-imparting group T, and imparts functions such as improved solubility in a specific solvent and improved adhesion to a specific substrate. Examples of counter ions of quaternary ammonium salts include halide ions. Examples of counter ions of carboxylates, sulfonates, and phosphates include alkali metal ions and ammonium ions. Examples of the group having a carbon-carbon double bond include a vinyl group, an acryloyloxy group, a methacryloyloxy group, an olefin, etc. The compound having a carbon-carbon double bond can be combined with a photoinitiator to prepare a photocurable composition, and the cured coating film obtained from the composition has both water and oil repellency and hard coat properties. Furthermore, the present compound having an isocyanate group, an epoxy group, a glycidyl group, an oxetanyl group, or a mercapto group can be combined with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating film obtained from the composition has both water and oil repellency and hard coat properties. The amide bond, ester bond, ether bond, thioether bond, siloxane bond, and urea bond in T are bonds that connect the alkyl group, fluoroalkyl group, aryl group, heteroaryl group, and the like contained in T. Other functionality-imparting groups may be further provided via these bonds.

[0082] The functionality-imparting group T of the present compound is preferably a hydroxyl group, an amino group, or a group having a carbon-carbon double bond in terms of synthesis, chemical stability, adhesion to a substrate, etc. Among groups having a carbon-carbon double bond, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an olefin is preferred.

[0083] In addition, when the present compound is used as a surface treatment agent for forming a surface layer having excellent durability such as abrasion resistance, T is preferably a group having a reactive silyl group. Examples of the group having a reactive silyl group include -Si(R) 3-c (L) c In the above formula, a1 is an integer of 1 or more, b1 is an integer of 1 or more, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, two or more Ls in T may be the same or different, and c is 2 or 3. The number of carbon atoms in the alkyl group for R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (1A) and compound (1B). Examples of the hydrolyzable group for L include the same as the hydrolyzable group described above, and the preferred forms are also the same. c is particularly preferably 3, since this provides stronger adhesion between the surface layer and the substrate. The multiple T's in the compound (1A) and the compound (1B) may be the same or different, and are preferably the same group from the viewpoint of ease of production of the compound (1A) and the compound (1B).

[0084] Specific examples of T include the following structures: a represents an alkyl group, a fluoroalkyl group, or an aryl group which may have a substituent; R brepresents an optionally substituted fluoroalkyl group or an aryl group, and * represents a bond.

[0085] [ka]

[0086] Examples of compound (1A) and compound (1B) include compounds of the following formulae. The compounds of the following formulae are preferred because they 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, and are particularly excellent in light resistance. f , Q f and T is R in the above formula (1A). f Or Q in formula 2A f The same applies to the preferred embodiments.

[0087] Q 1 Examples of compound (1A) in which is a group (g2-1) include compounds of the following formula:

[0088] [ka]

[0089] Q 1 Examples of compound (1A) in which is a group (g2-2) include compounds of the following formula:

[0090] [ka]

[0091] Q 1 Examples of compound (1A) in which is a group (g2-3) include compounds of the following formula:

[0092] [ka]

[0093] Q 1 Examples of compound (1A) in which is a group (g2-4) include compounds of the following formula:

[0094] [ka]

[0095] Q 1 Examples of compound (1A) in which is a group (g2-5) include compounds of the following formula:

[0096] [ka]

[0097] Q 1 Examples of compound (1A) in which is a group (g2-6) include compounds of the following formula:

[0098] [ka]

[0099] Q 1 Examples of compound (1A) in which is a group (g2-7) include compounds of the following formula:

[0100] [ka]

[0101] Q 1 Examples of compound (1A) in which is a group (g2-8) include compounds of the following formula:

[0102] [ka]

[0103] Q 1Examples of compound (1A) in which is a group (g2-9) include compounds of the following formula:

[0104] [ka]

[0105] Q 1 Examples of compound (1A) in which is a group (g2-10) include compounds of the following formula:

[0106] [ka]

[0107] Q 1 Examples of compound (1A) in which is a group (g2-11) include compounds of the following formula:

[0108] [ka]

[0109] Q 1 Examples of compound (1A) in which is a group (g2-12) include compounds of the following formula:

[0110] [ka]

[0111] Q 1 Examples of compound (1A) in which is a group (g2-13) include compounds of the following formula:

[0112] [ka]

[0113] Q 1 Examples of compound (1A) in which is a group (g2-14) include compounds of the following formula:

[0114] [ka]

[0115] Q 2 Examples of compound (1B) in which is a group (g2-1) include compounds of the following formula:

[0116] [ka]

[0117] Q 2 Examples of compound (1B) in which is a group (g2-2) include compounds of the following formula:

[0118] [ka]

[0119] Q 2 Examples of compound (1B) in which is a group (g2-3) include compounds of the following formula:

[0120] [ka]

[0121] Q 2 Examples of compound (1B) in which is a group (g2-4) include compounds of the following formula:

[0122] [ka]

[0123] Q 2 Examples of compound (1B) in which is a group (g2-5) include compounds of the following formula:

[0124] [ka]

[0125] Q 2 Examples of compound (1B) in which is a group (g2-6) include compounds of the following formula:

[0126] [ka]

[0127] Q 2 Examples of compound (1B) in which is a group (g2-7) include compounds of the following formula:

[0128] [ka]

[0129] Q 2 Examples of compound (1B) in which is a group (g2-9) include compounds of the following formula:

[0130] [ka]

[0131] In one embodiment of the present invention, T is -Si(R) 3-c (L) c The present compound (hereinafter also referred to as the present compound having a reactive silyl group) can form a surface layer that is excellent in fingerprint stain removal properties, abrasion resistance, and slip resistance. The present compound having a reactive silyl group has a polyfluoropolyether chain, a reactive silyl group, and a specific linking group that links the polyfluoropolyether chain and the reactive silyl group. The polyfluoropolyether chain is preferably monovalent or divalent. That is, the present compound may be a compound having a structure of "monovalent polyfluoropolyether chain-linking group-reactive silyl group", or may be a compound having a structure of "reactive silyl group-linking group-divalent polyfluoropolyether chain-linking group-reactive silyl group".

[0132] The present compound having a reactive silyl group has a polyfluoropolyether chain. The present compound having a polyfluoropolyether chain has an excellent ability to remove fingerprint stains from the surface layer. The present compound having a reactive silyl group has a reactive silyl group at at least one end. The present compound having a reactive silyl group at the end is strongly chemically bonded to the substrate, and therefore the surface layer has excellent abrasion resistance. In addition, as the compound having reactive silyl group, the compound having reactive silyl group only at one end is preferable. The compound having reactive silyl group only at one end is difficult to aggregate, so that the appearance of the surface layer is excellent. In addition, the surface layer has excellent abrasion resistance and fingerprint stain removability.

[0133] 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.

[0134] The structure of the present compound having a reactive silyl group other than T is the same as that explained for the present compound above, and the preferred structures are also the same. Specific examples of the present compound having a reactive silyl group are given below.

[0135] Q 1 Examples of compound (1A) in which is a group (g2-1) include compounds of the following formula:

[0136] [ka]

[0137] Q 1 Examples of compound (1A) in which is a group (g2-2) include compounds of the following formula:

[0138] [ka]

[0139] Q 1 Examples of compound (1A) in which is a group (g2-3) include compounds of the following formula:

[0140] [ka]

[0141] Q 1 Examples of compound (1A) in which is a group (g2-4) include compounds of the following formula:

[0142] [ka]

[0143] Q 1 Examples of compound (1A) in which is a group (g2-5) include compounds of the following formula:

[0144] [ka]

[0145] Q 1 Examples of compound (1A) in which is a group (g2-6) include compounds of the following formula:

[0146] [ka]

[0147] Q 1 Examples of compound (1A) in which is a group (g2-7) include compounds of the following formula:

[0148] [ka]

[0149] Q 1 Examples of compound (1A) in which is a group (g2-8) include compounds of the following formula:

[0150] [ka]

[0151] Q 1 Examples of compound (1A) in which is a group (g2-9) include compounds of the following formula:

[0152] [ka]

[0153] Q 1 Examples of compound (1A) in which is a group (g2-10) include compounds of the following formula:

[0154] [ka]

[0155] Q 1 Examples of compound (1A) in which is a group (g2-11) include compounds of the following formula:

[0156] [ka]

[0157] Q 1 Examples of compound (1A) in which is a group (g2-12) include compounds of the following formula:

[0158] [ka]

[0159] Q 1 Examples of compound (1A) in which is a group (g2-13) include compounds of the following formula:

[0160] [ka]

[0161] Q 1 Examples of compound (1A) in which is a group (g2-14) include compounds of the following formula:

[0162] [ka]

[0163] Q 2 Examples of compound (1B) in which is a group (g2-1) include compounds of the following formula:

[0164] [ka]

[0165] Q 2Examples of compound (1B) in which is a group (g2-2) include compounds of the following formula:

[0166] [ka]

[0167] Q 2 Examples of compound (1B) in which is a group (g2-3) include compounds of the following formula:

[0168] [ka]

[0169] Q 2 Examples of compound (1B) in which is a group (g2-4) include compounds of the following formula:

[0170] [ka]

[0171] Q 2 Examples of compound (1B) in which is a group (g2-5) include compounds of the following formula:

[0172] [ka]

[0173] Q 2 Examples of compound (1B) in which is a group (g2-6) include compounds of the following formula:

[0174] [ka]

[0175] Q 2 Examples of compound (1B) in which is a group (g2-7) include compounds of the following formula:

[0176] [ka]

[0177] Q 2 Examples of compound (1B) in which is a group (g2-9) include compounds of the following formula:

[0178] [ka]

[0179] Specific examples of the present compound include the following compounds, where n1 to n12 represent the number of repeating units and are appropriately adjusted within the range of 1 to 200.

[0180] [ka]

[0181] (Method for producing compound (1A) and compound (1B)) In the following, as an example of a method for producing compound (1A) and compound (1B), a method for producing compound (1A) and compound (1B) having a reactive silyl group will be described. When a functionality-imparting group T other than a reactive silyl group is to be introduced, a compound having a desired functionality-imparting group and a substituent capable of undergoing an addition reaction with a double bond may be used in place of compound (3a) in the following production method. In addition, although the following reaction is an addition reaction to a double bond, the functionality-imparting group T may be introduced by utilizing a known reaction such as esterification or amidation.

[0182] Compound (1A) can be produced, for example, by a method of subjecting compound (2A) to a hydrosilylation reaction with compound (3a) or compound (3b). Compound (1B) can be produced, for example, by a method of subjecting compound (2B) to a hydrosilylation reaction with compound (3a) or compound (3b). [R f -] a1 Q 10 [-CH=CH2] b1(2A) [CH2=CH-] b2 Q 20 -Q f -Q 20 [-CH=CH2] b2 (2B) In the formula (2A), Q 10 is a linking group having a valence of a1+b1, and Q 10 The symbols other than are the same as those in formula (1A). In formula (2B), Q 20 is a b2+1 valent linking group, and two Q 20 may be the same or different, and Q 20 The symbols other than are the same as those in formula (1B). Q 10 [-CH=CH2] b1 is the Q in compound (1A) after hydrosilylation. 1 Q 10 As for Q 1 The same groups as those shown in and preferred embodiments are also the same. 20 [-CH=CH2] b2 is the Q in compound (1B) after hydrosilylation. 2 Q 20 As for Q 2 The same groups as those shown above can be mentioned, and preferred embodiments are also the same.

[0183] HSi(R) 3-c (L) c (3a) HSi(R 8 ) 3-k [-(OSi(R 9 )2) p -O-Si(R) 3-c (L) c ] k (3b) However, the symbols in formula (3a) and formula (3b) are the same as the symbols in formula (1A), formula (1B) and formula (g3). Compound (3b) can be produced, for example, by the method described in the specification of Japanese Patent Application No. 2018-085493.

[0184] Q 10 [-CH=CH2] b1As the group (g4-1), a1=d1+d3 and b1=d2+d4, a1=e1 and b1=e2, a1=g4-3, a1=1 and b1=2, a1=h1 and b1=h2, a1=g4-5, a1=i1 and b1=i2, a1=i1 and b1=i2, a1=g4-6, a1=1 and b1=1, or a1=g4-7 is preferably a group (g4-1) (a1=d1+d3 and b1=d2+d4), a1=e1 and b1=e2, a1=g4-3, a1=1 and b1=2, a1=h1 and b1=h2, a1=g4-5, a1=i1 and b1=i2, a1=g4-6, a1=1 and b1=1, or a group (g4-7) (a1=1 and b1=i3). Q 20 [-CH=CH2] b2 As the group g4, from the viewpoint of ease of production of compound (1B), the group (g4-1) (wherein b2=d2+d4), the group (g4-2) (wherein b2=e2), the group (g4-3) (wherein b2=2), the group (g4-4) (wherein b2=h2), the group (g4-5) (wherein b2=i2), the group (g4-6) (wherein b2=1), and the group (g4-7) (wherein b2=i3) are preferred.

[0185] [ka]

[0186] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 220 -CH=CH2) e2 (g4-2) -AQ 13 -N(-Q 230 -CH=CH2)2(g4-3) (-AQ 14 -) h1 Z(-Q 240 -CH=CH2) h2 (g4-4) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 250 -CH=CH2) i2 (g4-5) -AQ 260 -CH=CH2(g4-6) -AQ 12 -CH(-Q 220 -CH=CH2)-Si(R 3 ) 3-i3 (-Q 250 -CH=CH2) i3 (g4-7)

[0187] However, Q 220 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 a group having - or -O-, -C(O)NR at the end of the alkylene group not connected to -CH=CH2 6 -, -C(O)-, -NR 6 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to -CH=CH2 6 -, -C(O)-, -NR 6 - or -O-, Q 10 Or Q 20 Q 220 If you have two or more, you need two or more Q 220 may be the same or different. Q 230 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two or more Q 230 may be the same or different. Q 240 Q 240 If the atom in Z to which is bonded is a carbon atom, Q 220 And Q 240 If the atom in Z to which is bonded is a nitrogen atom, Q 230 And Q 10 Or Q 20 Q 240 If you have two or more, you need two or more Q 240may be the same or different. Q 250 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, Q 10 Or Q 20 Q 250 If you have two or more, you need two or more Q 250 may be the same or different. Q 260 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 Q is a group having - or -O-. 220 , Q 230 , Q 240 , Q 250 and Q 260 The symbols other than are the same as those in formulas (g2-1) to (g2-7).

[0188] Q 220 -CH=CH2 is Q in compound (1A) and compound (1B) after hydrosilylation. 22 Q 220 As for Q 22 The same groups as those shown above can be mentioned, and preferred embodiments are also the same. Q 230 -CH=CH2 is Q in compound (1A) and compound (1B) after hydrosilylation. 23 Q 230 As for Q 23 The same groups as those shown above can be mentioned, and preferred embodiments are also the same. Q 240 -CH=CH2 is Q in compound (1A) and compound (1B) after hydrosilylation. 24 Q 240 As for Q 24 The same groups as those shown above can be mentioned, and preferred embodiments are also the same. Q 250 -CH=CH2 is Q in compound (1A) and compound (1B) after hydrosilylation. 25 Q 250 As for Q 25The same groups as those shown above can be mentioned, and preferred embodiments are also the same. Q 260 -CH=CH2 is Q in compound (1A) and compound (1B) after hydrosilylation. 26 Q 260 As for Q 26 The same groups as those shown above can be mentioned, and preferred embodiments are also the same.

[0189] Q 10 [-CH=CH2] b1 Other forms of include the group (g4-8) (wherein a1=d1+d3 and b1=k), the group (g4-9) (wherein a1=e1 and b1=k), the group (g4-10) (wherein a1=1 and b1=k), the group (g4-11) (wherein a1=h1 and b1=k), the group (g4-12) (wherein a1=i1 and b1=k), the group (g4-13) (wherein a1=1 and b1=k), or the group (g4-14) (wherein a1=1 and b1=k). Q 20 [-CH=CH2] b2 Other forms include the group (g4-8) (with the proviso that b2=k in total), the group (g4-9) (with the proviso that b2=k in total), the group (g4-10) (with the proviso that b2=k in total), the group (g4-11) (with the proviso that b2=k in total), the group (g4-12) (with the proviso that b2=k in total), the group (g4-13) (with the proviso that b2=k in total), and the group (g4-14) (with the proviso that b2=k in total).

[0190] [ka]

[0191] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 (g4-9) -AQ13 -N(-Q 23 -G 1 )2(g4-10) (-AQ 14 -) h1 Z(-Q 24 -G 1 ) h2 Formula (g4-11) (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 (g4-12) -AQ 26 -G 1 (g4-13) -AQ 12 -CH(-Q 22 -G 1 )-Si(R 3 ) 3-i3 (-Q 25 -G 1 ) i3 (g4-14)

[0192] However, G 1 is group (g5), and Q 10 [-CH=CH2] b1 Or Q 20 [-CH=CH2] b2 Two or more Gs 1 may be the same or different, and G 1 The symbols other than are the same as those in formulas (g2-1) to (g2-7). -Si(R 8 ) 3-k (-Q 30 -CH=CH2) k (g5) However, Q 30 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two or more Q 30 may be the same or different, and Q 30 The symbols other than are the same as those in formula (g3). Q 30 -CH=CH2 is the Q in group (g3) after hydrosilylation. 3 Q 30 As for Q 3 (wherein, -(OSi(R 9 )2) p -O- is excluded.) The same applies to the preferred forms.

[0193] (Method for producing compound (2A) and compound (2B)) Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-1), 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-1) can be, for example, R f Precursor of the part of Q f Except for changing the method for producing the precursor of the portion, it can be produced by the method described in WO 2017 / 187775. Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-2), 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-2) can be, for example, R f Precursor of the part of Q f Except for changing the manufacturing method of the precursor of the part, it can be manufactured by the method described in JP 2015-199906 A, the method described in Patent Document 1, the method described in JP 2016-204656 A, the method described in JP 2016-222859 A, the method described in Patent Document 2, the method described in WO 2017 / 187775, or the method described in WO 2019 / 039226. Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-3), 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-3) can be, for example, R f Precursor of the part of Q fExcept for changing the method for producing the precursor of the portion, it can be produced by the method described in WO 2017 / 038832. Q 10 [-CH=CH2] b1 Compound (2A) in which is a group (g4-4), and Q 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-4) can be, for example, R f Precursor of the part of Q f Except for changing the manufacturing method of the precursor of the part, it can be manufactured by the method described in WO 2019 / 039186. Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-5), 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-5) can be, for example, R f Precursor of the part of Q f Except for changing the method for producing the precursor of the portion, the compound can be produced by the method described in Patent Document 1 or the method described in International Publication No. 2016 / 121211. Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-6), 20 [-CH=CH2] b2 The compound (2B) in which is a group (g4-6) can be, for example, R f Precursor of the part of Q f Except for changing the method for producing the precursor of the portion, the compound can be produced by the methods described in JP 2012-072272 A, WO 2013 / 121984 A, or WO 2013 / 121986 A. Q 10 [-CH=CH2] b1 Compound (2A), in which Q is a group (g4-7), 20 [-CH=CH2] b2 Compound (2B) in which is a group (g4-7) can be, for example, R f Precursor of the part of Q f Except for changing the method for producing the precursor of the portion, it can be produced by the method described in WO 2019 / 163282. Q 10 [-CH=CH2] b1 Compound (2A) in which is a group (g4-8) to a group (g4-14), and Q 20 [-CH=CH2] b2 Compound (2B) in which is a group (g4-8) to a group (g4-14) can be, for example, R f Precursor of the part of Q f Except for changing the method for producing the precursor of the portion, it can be produced by the method described in WO 2019 / 163282.

[0194] R of compound (2A) f An example of the precursor of the moiety is compound (4A). Q of compound (2B) f An example of the precursor of the moiety is compound (4B). R f -E 1 (4A) E 1 -Q f -E 1 (4B) However, E 1 are -CH2-OH, -C(O)-X, -I, -OC(O)R f5 , -SO2F, -CH2-SO2R f5 , -CH2-NH2, or -CH2-O-CH2CH=CH2. X is a halogen atom, an alkoxy group, a hydroxyl group, or an amino group. R f5 is a perfluoroalkyl group or a group having -O- between carbon atoms of a perfluoroalkyl group having 2 or more carbon atoms. 1 , X and R f5 The symbols other than are the same as those in formula (2A) and formula (2B).

[0195] As the compound (4A) and the compound (4B), for example, a fluorine-containing compound (A) described later has a plurality of -O- between carbon atoms and has E at the terminal. 1When the fluorine-containing compound (A) described later does not have a plurality of -O- between carbon atoms, the compounds (4A) and (4B) are prepared by using the fluorine-containing compound (A) as a starting material, introducing one or more oxyfluoroalkylene units by a known addition reaction or the like to form a polyfluoropolyether chain, and then, if necessary, adding E to the end of the polyfluoropolyether chain by a known method or the like. 1 It can be produced by introducing

[0196] E at the end of the polyfluoropolyether chain 1 Examples of the method for introducing the above include the method described in International Publication No. WO 2009 / 008380, the method described in International Publication No. WO 2013 / 121984, the method described in International Publication No. WO 2013 / 121986, the method described in International Publication No. WO 2015 / 087902, the method described in Patent Document 1, the method described in International Publication No. WO 2017 / 038832, the method described in International Publication No. WO 2018 / 143433, and the method described in International Publication No. WO 2018 / 216630.

[0197] The present compound described above has a monovalent or divalent polyfluoropolyether chain, and therefore can form a surface layer that is excellent in terms of fingerprint stain removal properties. Furthermore, since the compound has a reactive silyl group, a surface layer having excellent abrasion resistance can be formed. In addition, in the present compound, the monovalent polyfluoropolyether chain has at least one of a monovalent fluorine-containing ring structure at a free end and a divalent fluorine-containing ring structure in the main chain, or the divalent polyfluoropolyether chain has a divalent fluorine-containing ring structure in the main chain, so that a surface layer with excellent slip resistance can be formed without reducing abrasion resistance and fingerprint stain removability.

[0198] [Method of producing fluorine-containing compounds] Hereinafter, a method for producing a fluorine-containing compound useful as a raw material for the present compound having a silyl group will be described. However, some of the following fluorine-containing compounds may correspond to the present compound having a functionality-imparting group T other than a silyl group.

[0199] A first embodiment of the method for producing a fluorine-containing compound having at least one of a monovalent 4-membered fluorine-containing ring structure and a divalent 4-membered fluorine-containing ring structure (hereinafter also referred to as "fluorine-containing compound (A)") includes a method of reacting compound (11) with compound (12) to obtain compound (21).

[0200] [ka]

[0201] However, R 11 is an alkylene group, a group having -O- between carbon atoms of an alkylene group having 2 or more carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH2), or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH2). R 12 is a halogen atom, a perfluoroalkyl group, or a group having -O- between carbon atoms of a perfluoroalkyl group having 2 or more carbon atoms. q is 0 or 1. E is -OH, -OR 14 , -SR 14 , -C(O)OR 14 , -C(O)NHR 14 , -C(O)NR 14 R 15 , -SO2X 1 , -C(O)X 1 or a halogen atom. 14 and R 15 Each of X is independently an alkyl group. 1 is a halogen atom.

[0202] R 11 From the viewpoint of ease of production of the fluorine-containing compound (A), the number of carbon atoms in the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 2 to 6. However, when an -O- is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group or fluoroalkylene group is 2. R 11Examples of such groups include -CH2-, -CH2CH2-, -CHF-, -CF2CH2-, -CF2CF2CF2CH2-, -CF2-, -CF2CF2-, -CF2CF2OCF2-, -CF(CF3)CF2OCF(CF3)-, and -CF2CF2CF2CF2CF2CH2-.

[0203] Examples of compound (11) include the following compounds: CF2 = CFOCF3, CF2 = CFOCF2CF3, CF2=CFFOCF2CF2CF3, CF2=CFOCF2CF(CF3)OCF2CF2CF3, CF2=CFOCF2CF(CF3)OCF2CF(CF3)OCF2CF2CF3, CF2=CFOCF2CF(CF3)OCF2CF2SO2F, CF2 = CFOCF2CFCF2CONH2, CF2=CFOCF2CF2CF2CH2OCF2CHFOCF3, CF2=CFOCF2CF2CF2CH2OCF2CHFOCF2CF3, CF2=CFOCF2CF2CF2CH2OCF2CHFOCF2CF2CF3, CF2=CFOCF2CF2CF2CF2CF2CH2OCF2CHFOCF3, CF2=CFOCF2CF2CF2CF2CF2CH2OCF2CHFOCF2CF3, CF2=CFOCF2CF2CF2CF2CF2CH2OCF2CHFOCF2CF2CF3, CF2=CFOCF2CF2CF2OCHFCF2OCH3, CF2=CFOCF2CF2CF2OCHFCF2OCH2CH3, CF2=CFOCF2CF2CF2OCHFCF2OCH2CH2CH3, CF2=CFOCF2CF2CF2OCHFCF2OCH2CH2CH2CH3, CF2=CFOCF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH3, CF2=CFOCF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH2CH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH2CH2CH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH2CH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CF2OCHFCF2OCH2CH2CH2CH2CH2CH3、 CF2=CFOCF2CF2CF2CF2CF2CH2OH、 CF2=CFOCF2CF2CF2CF2CF2COOCH3、 CF2=CFOCF2CF2CF2CF2CF2CONHCH3、 CF2=CFOCF2CF2CF2CF2CF2CONH2、 CF2=CFOCF2CF2CF2CF2CF2SO2F、 CF2=CFOCF2C(CF2OCF2CF2SO2F)FOCF2CF2SO2F、 CF2=CFOCF2CF2SO2F、 CF2=CFOCF2CF2CF2CF2SO2F、 CF2=CF-O-CF2CF2CF2CH2-OH、 CF2=CF-O-CF2CF2CF2-C(O)OCH3、 CF2=CF-O-CF2CF2CF2-C(O)NHCH3、 CF2=CF-O-CF2CF2CF2-C(O)N(CH3)2、 CF2=CF-O-CF2CF2CF2-SO2F、 CF2=CF-O-CF2CF2CF2CF2-F、 CF2=CF-O-CF2CF2CF2CF2-Cl、 CF2=CF-O-CF2CF2CF2CF2-Br、 CF2=CF-O-CF2CF2CF2CF2-I、 CF2=CF-O-CF2CF2CF2CH2-OCH3、 CF2=CF-O-CF2CF2CF2-C(O)F、 CF2=CF-O-CF2CF2CF2CF2OCHFCF2-OCH3。

[0204] R 12From the viewpoint of easiness in producing the fluorine-containing compound (A), the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 6. However, the lower limit of the number of carbon atoms in the perfluoroalkyl group in the case where it has -O- between carbon atoms is 2. R 12 As the halogen atom, a fluorine atom or a chlorine atom is preferred from the viewpoint of ease of production of the fluorine-containing compound (A). R 12 Examples of such groups include -F, -Cl, -CF3, -CF2CF3, -CF2CF2OCF3, and -CF(CF3)CF2CF3. Examples of compound (12) include CF2=CF2, CF2=CF-CF3, CF2=CF-CF2CF3, and CF2=CF-CF(CF3)2.

[0205] R 14 or R 15 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms, from the viewpoint of ease of production of the fluorine-containing compound A. X 1 As the alkyl group, a fluorine atom or a chlorine atom is preferred from the viewpoint of ease of production of the fluorine-containing compound (A).

[0206] Compound (21) can be produced, for example, by charging compound (11) and compound (12) into a reaction vessel and heating the mixture. The reaction vessel may be, for example, a vessel made of metal (stainless steel, etc.). The reaction temperature is, for example, 150 to 250°C. The reaction time is, for example, 50 to 300 hours. The reaction pressure is, for example, from atmospheric pressure to 2.0 MPa (gauge), preferably 0.2 MPa or less.

[0207] A second embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compound (11) is reacted with compound (13) to give compound (22).

[0208] [ka]

[0209] However, R 13 R is a fluoroalkylene group, a group having -O- at both ends of a fluoroalkylene group, or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms. 13 The symbols other than are the same as those in formula (11), and the preferred forms are also the same. 11 In the case where compound (11) is a single compound, the compound (22) obtained is a compound having a structure in which a plurality of R 11 On the other hand, when compound (11) is a combination of multiple compounds, the resulting compound (22) has multiple R 11 , E and q are different compounds.

[0210] R 13 From the viewpoint of easiness in producing the fluorine-containing compound (A), the number of carbon atoms in the fluoroalkylene group is preferably 0 to 10, more preferably 1 to 8, and particularly preferably 1 to 6. However, in the case where the fluoroalkylene group has -O- between carbon atoms, the lower limit of the number of carbon atoms in the fluoroalkylene group is 2. R 13 Examples of such groups include -CF2-, -CF2CF2-, -CF(CF3)CF2-, -CF2CH2CF2-, -OCF2CF2CF2O-, and -CF2OCF2CF2OCF2-.

[0211] Examples of compound (13) include CF2=CF-OCF2CF2CF2O-CF=CF2, CF2=CF-OCF2-CF=CF2, CF2=CF-OCF2CF2CF2CF2O-CF=CF2, CF2=CFOCF2CF2OCF=CF2, CF2=CFOCF2CF2CF2CF2CF2CF2OCF=CF2, CF2=CFOCF2CF2CF2CF2CF2CF2OCF=CF2, CF2=CFOCF2OCF2OCF=CF2, CF2=CFOCF2CF2CF2CF2OCF=CF2, CF2=CFOCF2CF2OCF2CF2OCF=CF2. Compound (22) can be produced in the same manner as compound (21).

[0212] A third embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compounds (11) are reacted with each other to give compound (23).

[0213] [ka]

[0214] However, the symbols in formula (23) are the same as those in formula (11), and the preferred embodiments are also the same. Compound (23) can be produced in the same manner as compound (21). Compound (11) may be a single compound or a combination of multiple compounds corresponding to formula (11). When compound (11) is a single compound, the resulting compound (23) can be produced by combining multiple R 11 On the other hand, when compound (11) is a combination of a plurality of compounds, the obtained compound (23) has a structure in which a plurality of R 11 , E and q are different compounds.

[0215] A fourth embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compounds (13) are reacted with each other to give compound (24).

[0216] [ka]

[0217] Here, r is an integer of 1 or more. The symbols other than r are the same as the symbols in formula (13), and the preferred embodiments are also the same. r is preferably an integer of 1 to 100, and particularly preferably an integer of 2 to 20. Compound (24) can be produced in the same manner as compound (21). Compound (13) may be a single compound or a combination of multiple compounds corresponding to formula (13). When compound (13) is a single compound, the resulting compound (24) can be produced by combining multiple R 13 On the other hand, when compound (13) is a combination of multiple compounds, the resulting compound (24) has multiple R 13 It includes compounds in which

[0218] A fifth embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compound (11) and compound (13) are reacted to give compound (25).

[0219] [ka] However, the symbols in formula (25) are the same as those in formulas (11), (13) and (24), and the preferred embodiments are also the same. Compound (25) can be produced in the same manner as compound (21).

[0220] A sixth embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compound (12) is reacted with itself to give compound (26).

[0221] [ka] However, the symbols in formula (26) are the same as those in formula (12), and the preferred embodiments are also the same. Compound (26) can be produced in the same manner as compound (21). Compound (12) may be a single compound or a combination of multiple compounds corresponding to formula (12). When compound (12) is a single compound, the resulting compound (26) can be produced by combining multiple R 12 On the other hand, when compound (12) is a combination of multiple compounds, the resulting compound (23) has multiple R 12 It includes compounds in which

[0222] A seventh embodiment of the process for producing the fluorine-containing compound (A) includes a process in which compound (12) and compound (13) are reacted to give compound (27).

[0223] [ka] Here, r2 is an integer of 1 or more. The symbols other than r2 are the same as the symbols in formula (12) and formula (13), and the preferred embodiments are also the same. r2 is preferably an integer of 1 to 100, particularly preferably an integer of 2 to 20. Compound (27) can be produced in the same manner as compound (21).

[0224] [Fluorine-containing compound-containing composition] The fluorine-containing compound-containing composition of the present invention (hereinafter also referred to as "the composition") contains one or more fluorine-containing ether compounds which are the present compound, and a fluorine-containing ether compound other than the present compound. The composition may contain, for example, both compound (1A) and compound (1B) as the present compound. The composition does not contain a liquid medium described later.

[0225] The other fluorine-containing ether compounds include both compounds which are inevitably contained and compounds which are used in combination depending on the application, etc.

[0226] Compounds that can be used in combination with the present compound include known fluorine-containing ether compounds and fluorine-containing oils.

[0227] Examples of fluorine-containing oils include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE).

[0228] In addition, examples of known fluorine-containing ether compounds include fluorine-containing ether compounds commercially available as surface treatment agents. When the present composition contains a known fluorine-containing ether compound, new effects such as compensating for the properties of the present compound may be exhibited. Examples of known fluorine-containing ether compounds include those described in the following documents: Perfluoropolyether-modified aminosilanes described in JP-A-11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in JP 2000-144097 A; Perfluoropolyether-modified aminosilanes described in JP 2000-327772 A; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Publication No. 2008-534696; Fluorinated modified hydrogen-containing polymers as described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A, Organosilicon compounds described in WO 2011 / 060047 and WO 2011 / 059430; Fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in JP 2012-72272 A; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; Fluoropolyether group-containing polymer-modified silanes described in JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A Fluorine-containing ether compounds described in WO 2018 / 216630, WO 2019 / 039226, WO 2019 / 039341, WO 2019 / 039186, WO 2019 / 044479, JP 2019-44158 A, WO 2019 / 044479, and WO 2019 / 163282. 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.

[0229] In the present composition, when the present compound is combined with a known fluorine-containing ether compound, the content ratio may be appropriately adjusted depending on the application, etc. The content ratio of the present compound in the present composition is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 25 to 75 mass%. By setting it within the above range, the properties of the present compound are fully exhibited, and the properties of the fluorine-containing ether compound used in combination are also fully obtained.

[0230] Examples of compounds that are inevitably contained include fluorine-containing ether compounds that are by-produced in the production process of the present compound (hereinafter, also referred to as "by-produced fluorine-containing ether compounds"). Examples of the by-produced fluorine-containing ether compound include unreacted fluorine-containing compounds (e.g., compound (2A) or compound (2B)) and fluorine-containing ether compounds in which a part of the allyl group has been isomerized to an inner olefin during hydrosilylation in the production of the present compound.

[0231] When the present composition contains a by-produced fluorinated ether compound, the by-produced fluorinated ether compound can be removed by purification, but may be contained in the present composition to the extent that the properties of the present compound can be fully exhibited, thereby simplifying the purification step of the by-produced fluorinated ether compound. When a known fluorinated ether compound is not combined, the content of the present compound in the present composition is preferably from 60 mass% to less than 100 mass%, more preferably from 70 mass% to less than 100 mass%, and particularly preferably from 80 mass% to less than 100 mass%, of the present composition. The content of the by-produced fluorinated ether compound in the present composition is preferably more than 0 mass % and not more than 40 mass %, more preferably more than 0 mass % and not more than 30 mass %, particularly preferably more than 0 mass % and not more than 20 mass %. When the content of the present compound and the content of the by-produced fluorine-containing ether compound are within the above ranges, the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light fastness and chemical resistance of the surface layer are further improved.

[0232] In addition, compounds inevitably contained include additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. Examples of acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of base catalysts include sodium hydroxide, potassium hydroxide, and ammonia. The content of these in the present composition is preferably 0 to 9.999 mass %, particularly preferably 0 to 0.99 mass %.

[0233] [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 a solution or a dispersion.

[0234] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-containing organic solvent or a non-fluorine-containing organic solvent, or may contain both. Examples of the fluorine-containing 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 fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The non-fluorine-containing organic solvent is preferably a compound consisting of only hydrogen atoms and carbon atoms, or a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms, and examples of such organic solvents include hydrocarbons, alcohols, ketones, ethers and esters. The liquid medium may be a mixed medium in which two or more types are mixed.

[0235] The content of the present compound or the present composition in the present coating liquid is preferably from 0.001 to 10 mass %, particularly preferably from 0.01 to 1 mass %. The content of the liquid medium in the present coating liquid is preferably 90 to 99.999 mass %, and particularly preferably 99 to 99.99 mass %.

[0236] [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. When the present compound having a silyl group is used, 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.

[0237] 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).

[0238] 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. The substrate is preferably a substrate for a touch panel, a substrate for a display, or a spectacle lens, and is particularly preferably a substrate for a touch panel. As the material for the substrate for a touch panel, glass and transparent resin are preferred. Further, as the substrate, glass and resin films 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 are also preferred.

[0239] [Production method] The present article can be produced, for example, by the following method. A method for forming a surface layer formed from compound (1A) or compound (1B) or this composition on the surface of a substrate by treating the surface of the substrate by a dry coating method using the present compound or this 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.

[0240] 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 decomposition of the present compound and 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 the present compound or the present composition is impregnated may be used.

[0241] 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. EXAMPLES

[0242] 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 10, and 13 to 16 are examples related to the present compound having a reactive silyl group, and Examples 5, 6, 11, and 12 are comparative examples. More specifically, Examples 1-3 to 1-8, Examples 2-2 to 2-7, Examples 3-2 to 3-7, Examples 4-1 to 4-6, Examples 14-2 to 14-7, and Examples 15-2 to 15-7 are examples showing the synthesis method of the fluorinated ether compound according to the present invention.

[0243] [Example 1] (Example 1-1) Compound (11-1) was obtained according to the method described in Example 1-1 of the Examples of WO 2013-121984. CF2=CF-O-CF2CF2CF2CH2-OH (11-1)

[0244] (Example 1-2) In a 100 mL metal reactor, 10 g of the compound (11-1) obtained in Example 1-1 was placed and stirred for 200 hours at 175° C. The obtained organic phase was concentrated to obtain 6 g of the compound (23-1).

[0245] [ka]

[0246] NMR spectrum of compound (23-1); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: tetramethylsilane (TMS)) δ (ppm): 4.1 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -85 (2F), -123 (4F), -126 (4F), -128 (2F), -131 (2F), -137 (1F), -139 (1F).

[0247] (Example 1-3) In a 200 mL recovery flask, 5 g of the compound (23-1) obtained in Example 1-2 and 1.2 g of potassium carbonate were placed and stirred at 120° C., and 25 g of the compound (11-1) was added and stirred at 120° C. for 2 hours. The temperature in the recovery flask was brought to 25° C., and 30 g each of AC-2000 and hydrochloric acid were added, followed by separation and concentration of the organic phase. The resulting reaction crude liquid was purified by column chromatography to obtain 21 g of the compound (4-1).

[0248] [ka]

[0249] NMR spectrum of compound (4-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 4.6 (20H), 4.1 (4H). 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -85 (22F), -91 (20F), -120 (20F), -123 (4F), -126 (24F), -128 (2F), -131 (2F), -137 (1F), -139 (1F), -144 (10F). Average of x1+x2: 10.

[0250] (Example 1-4) In a 50 mL eggplant flask, 20 g of the compound (4-1) obtained in Example 1-3, 7.1 g of sodium fluoride powder, 20 g of AC-2000, and 20 g of CF3CF2CF2OCF(CF3)COF were added. The mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After the temperature inside the eggplant flask was brought to 25°C, the sodium fluoride powder was removed by filtration. Excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of compound (4-2).

[0251] [ka]

[0252] NMR spectrum of compound (4-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 5.0 (4H), 4.6 (20H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -80 (2F), -81 (6F), -82 (6F), -85 (22F), -91 (20F), -119 (4F), -120 (20F), -126 (24F), -128 (2F), -129 (4F), -131 (2F), -131 (2F), -137 (1F), -139 (1F), -144 (10F). Average of x1+x2: 10.

[0253] (Example 1-5) 250 mL of ClCF2CFClCF2OCF2CF2Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL metal reactor, and nitrogen gas was bubbled through, followed by 20 volume % fluorine gas diluted with nitrogen gas. A CFE-419 solution of compound (4-2) obtained in Example 1-4 (concentration: 10%, compound (4-2): 20 g) was added over 3 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (4-2) (mol / hour) was controlled to be 2:1. After the introduction of compound (4-2) was completed, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled through, and finally the inside of the reactor was fully replaced with nitrogen gas. The solvent was distilled off, and 21 g of compound (4-3) was obtained.

[0254] [ka]

[0255] NMR spectrum of compound (4-3); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -80 (2F), -81 (6F), -82 (6F), -83 (46F), -87 (40F), -124 (48F), -128 (2F), -129 (4F), -131 (2F), -131 (2F), -137 (1F), -139 (1F). Average of x1+x2: 10.

[0256] (Example 1-6) In a 50 mL eggplant flask, 20 g of the compound (4-3) obtained in Example 1-5, 1.8 g of sodium fluoride, and 20 mL of AC-2000 were placed and stirred in an ice bath. 1.4 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 14 g of compound (4-4) was obtained.

[0257] [ka]

[0258] NMR spectrum of compound (4-4); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (42F), -87 (40F), -119 (4F), -124 (44F), -128 (2F), -131 (2F), -137 (1F), -139 (1F). Average of x1+x2: 10.

[0259] (Example 1-7) In a 50 mL recovery flask, 12 g of the compound (4-4) obtained in Example 1-6, 1.5 g of H2NCH2C(CH2CH=CH2)3, and 12 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography. 9 g of compound (2-1) was obtained.

[0260] [ka]

[0261] NMR spectrum of compound (2-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (42F), -87 (40F), -120 (4F), -124 (44F), -128 (2F), -131 (2F), -137 (1F), -139 (1F). Average of x1+x2: 10.

[0262] (Example 1-8) In a 50 mL recovery flask, 1 g of the compound (2-1) obtained in Example 1-7, 0.21 g of trimethoxysilane, 0.001 g of aniline, 1.0 g of AC-6000, and 0.0033 g of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed and stirred overnight at 25° C. The solvent and the like were distilled off under reduced pressure to obtain 1.2 g of compound (1-1).

[0263] [ka]

[0264] NMR spectrum of compound (1-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (42F), -87 (40F), -120 (4F), -124 (44F), -128 (2F), -131 (2F), -137 (1F), -139 (1F). Average of x1+x2: 10.

[0265] [Example 2] (Example 2-1) In a 100 mL metal reactor, 20 g of the compound (11-1) obtained in Example 1-1 and 7.2 g of CF2=CF2 were added, and the mixture was stirred for 300 hours at 180° C. The obtained organic phase was concentrated to obtain 8 g of compound (21-1).

[0266] [ka]

[0267] NMR spectrum of compound (21-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.1 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -123 (2F), -126 (2F), -128 (2F), -130 (4F), -137 (1F).

[0268] (Example 2-2) The same procedure as in Example 1-3 was repeated, except that the compound (23-1) was changed to 3.4 g of the compound (21-1) obtained in Example 2-1 and the potassium carbonate was changed to 0.6 g, to obtain 20 g of the compound (4-5).

[0269] [ka]

[0270] NMR spectrum of compound (4-5); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 4.6 (20H), 4.1 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -85 (20F), -91 (20F), -120 (20F), -123 (2F), -126 (22F), -128 (2F), -130 (4F), -137 (1F), -144 (10F). Average value of x:10.

[0271] (Example 2-3) Compound (4-1) was changed to 16 g of compound (4-5) obtained in Example 2-2, the amount of sodium fluoride powder was changed to 3.5 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 10 g, and the same procedure as in Example 1-4 was performed to obtain 18 g of compound (4-6).

[0272] [ka]

[0273] NMR spectrum of compound (4-6); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 5.0 (2H), 4.6 (20H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (2F), -80 (2F), -81 (3F), -82 (3F), -85 (20F), -91 (20F), -119 (2F), -120 (20F), -126 (22F), -128 (2F), -129 (2F), -130 (4F), -131 (1F), -137 (1F), -144 (10F). Average value of x:10.

[0274] (Example 2-4) The same procedure as in Example 1-5 was repeated, except that compound (4-2) was changed to 18 g of compound (4-6) obtained in Example 2-3, to obtain 19 g of compound (4-7).

[0275] [ka]

[0276] NMR spectrum of compound (4-7); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (2F), -80 (2F), -81 (3F), -82 (3F), -83 (42F), -87 (40F), -124 (44F), -128 (2F), -129 (2F), -130 (4F), -131 (1F), -137 (1F). Average value of x:10.

[0277] (Example 2-5) The same procedure as in Example 1-6 was repeated, except that compound (4-3) was changed to 19 g of compound (4-7) obtained in Example 2-4, to obtain 14 g of compound (4-8).

[0278] [ka]

[0279] NMR spectrum of compound (4-8); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (40F), -87 (40F), -119 (2F), -124 (42F), -128 (2F), -130 (4F), -137 (1F). Average value of x:10.

[0280] (Example 2-6) The same procedure as in Example 1-7 was repeated, except that the compound (4-4) was changed to 14 g of the compound (4-8) obtained in Example 2-5, to obtain 10 g of the compound (2-2).

[0281] [ka]

[0282] NMR spectrum of compound (2-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (40F), -87 (40F), -120 (2F), -124 (42F), -128 (2F), -130 (4F), -137 (1F). Average value of x:10.

[0283] (Example 2-7) The same procedure as in Example 1-8 was repeated, except that compound (2-1) was changed to 1 g of compound (2-2) obtained in Example 2-6, to obtain 1.1 g of compound (1-2).

[0284] [ka]

[0285] NMR spectrum of compound (1-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (27), 3.4 (2H), 1.3 (12H), 0.9 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -80 (2F), -83 (40F), -87 (40F), -120 (2F), -124 (42F), -128 (2F), -130 (4F), -137 (1F). Average value of x:10.

[0286] [Example 3] (Example 3-1) 39.4 g of CF2=CFOCF2CF2CF2CF2OCF=CF2, 3.2 g of methanol, and 13.8 g of potassium carbonate were placed in a 500 mL eggplant flask and stirred at 40°C for 2 hours. Hydrochloric acid was added, and the organic phase obtained by separation was dehydrated with magnesium sulfate. The magnesium sulfate was filtered off, and the crude liquid was distilled to obtain 17.0 g of compound (11-2).

[0287] [ka]

[0288] NMR spectrum of compound (11-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (1H), 3.4 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (4F), -90 (2F), -114 (1F), -122 (1F), -124 (4F), -135 (1F), -144 (1F).

[0289] (Example 3-2) In a 200 mL metal reactor, 15 g of the compound (11-2) obtained in Example 3-1 was placed, and 138 g of CF2=CFOCF2CF2CF2CF2OCF=CF2 was placed, and the mixture was stirred at 160° C. for 300 hours. The temperature inside the reactor was set to 25° C., and 9.8 g of the compound (11-1) obtained in Example 1-1 was placed, and the mixture was stirred at 180° C. for 100 hours. The temperature inside the reactor was set to 25° C., and the resulting reaction crude liquid was purified by column chromatography to obtain 9.8 g of compound (4-9).

[0290] [ka]

[0291] NMR spectrum of compound (4-9); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (1H), 4.0 (2H), 3.4 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (44F), -85 (2F), -90 (2F), -123 (2F), -124 (44F), -126 (2F), -128 (22F), -131 (22F), -137 (11F), -139 (11F), -144 (1F). Average value of x: 11.

[0292] (Example 3-3) Compound (4-1) was changed to 9 g of compound (4-9) obtained in Example 3-2, the amount of sodium fluoride powder was changed to 0.4 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 3.2 g, and the same procedure as in Example 1-4 was performed to obtain 10 g of compound (4-10).

[0293] [ka]

[0294] NMR spectrum of compound (4-10); 1H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (1H), 5.0 (2H), 3.4 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (2F), -81 (3F), -82 (47F), -85 (2F), -90 (2F), -119 (2F), -124 (44F), -126 (2F), -128 (22F), -129 (2F), -131 (23F), -137 (11F), -139 (11F), -144 (1F). Average value of x: 11.

[0295] (Example 3-4) Compound (4-2) was changed to 10 g of compound (4-10) obtained in Example 3-3, and the addition time of the CFE-419 solution of compound (4-10) was changed to 2 hours, and the same procedure as in Example 1-5 was repeated to obtain 9.2 g of compound (4-11).

[0296] [ka]

[0297] NMR spectrum of compound (4-11); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (3F), -79 (2F), -81 (3F), -82 (51F), -87 (4F), -124 (48F), -128 (22F), -129 (2F), -131 (23F), -137 (11F), -139 (11F). Average value of x: 11.

[0298] (Example 3-5) In a 50 mL eggplant flask, 9 g of the compound (4-11) obtained in Example 3-4, 0.4 g of sodium fluoride, and 10 mL of AC-2000 were placed and stirred in an ice bath. 0.3 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 6.7 g of compound (4-12) was obtained.

[0299] [ka]

[0300] NMR spectrum of compound (4-12); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (3F), -82 (46F), -87 (4F), -119 (2F), -124 (46F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x: 11.

[0301] (Example 3-6) In a 50 mL recovery flask, 6 g of the compound (4-12) obtained in Example 3-5, 0.4 g of H2NCH2C(CH2CH=CH2)3, and 6 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography. 4.3 g of compound (2-3) was obtained.

[0302] [ka]

[0303] NMR spectrum of compound (2-3); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (3F), -82 (46F), -87 (4F), -120 (2F), -124 (46F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x: 11.

[0304] (Example 3-7) The same procedure as in Example 1-8 was repeated, except that compound (2-1) was changed to 1 g of compound (2-3) obtained in Example 3-6, to obtain 1.2 g of compound (1-3).

[0305] [ka]

[0306] NMR spectrum of compound (1-3); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (27H), 3.4 (2H), 1.3 (12H), 0.9 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (3F), -82 (46F), -87 (4F), -120 (2F), -124 (46F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x: 11.

[0307] [Example 4] (Example 4-1) 394 g of CF2=CFOCF2CF2CF2CF2OCF=CF2 was placed in a 500 mL metal reactor and stirred at 180° C. for 200 hours. The temperature inside the reactor was set to 25° C., and 55.6 g of compound (11-1) obtained in Example 1-1 was placed in the reactor and stirred at 180° C. for 100 hours. The temperature inside the reactor was set to 25° C., and the resulting reaction crude liquid was purified by column chromatography to obtain 45.0 g of compound (4-13).

[0308] [ka]

[0309] NMR spectrum of compound (4-13); 1H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.0 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (40F), -85 (4F), -123 (4F), -124 (40F), -126 (4F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x:10.

[0310] (Example 4-2) Compound (4-1) was changed to 20 g of compound (4-13) obtained in Example 4-1, the amount of sodium fluoride powder was changed to 1.7 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 14.8 g, and the same procedure as in Example 1-4 was performed to obtain 22.8 g of compound (4-14).

[0311] [ka]

[0312] NMR spectrum of compound (4-14); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 5.0 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (46F), -85 (4F), -119 (4F), -124 (40F), -126 (4F), -128 (22F), -129 (4F), -131 (24F), -137 (11F), -139 (11F). Average value of x:10.

[0313] (Example 4-3) Compound (4-15) (19.3 g) was obtained in the same manner as in Example 1-5, except that compound (4-2) was changed to 19.3 g of compound (4-14) obtained in Example 4-2 and the addition time of the CFE-419 solution of compound (4-14) was changed to 5 hours.

[0314] [ka]

[0315] NMR spectrum of compound (4-15); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (54F), -124 (48F), -128 (22F), -129 (4F), -131 (24F), -137 (11F), -139 (11F). Average value of x:10.

[0316] (Example 4-4) In a 50 mL eggplant flask, 19.3 g of the compound (4-15) obtained in Example 4-3, 1.6 g of sodium fluoride, and 20 mL of AC-2000 were placed and stirred in an ice bath. 1.2 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 13.5 g of compound (4-16) was obtained.

[0317] [ka]

[0318] NMR spectrum of compound (4-16); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (44F), -119 (4F), -124 (44F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x:10.

[0319] (Example 4-5) In a 50 mL recovery flask, 10.0 g of the compound (4-16) obtained in Example 4-4, 1.5 g of H2NCH2C(CH2CH=CH2)3, and 10 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography. 7.4 g of compound (2-4) was obtained.

[0320] [ka]

[0321] NMR spectrum of compound (2-4); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (44F), -120 (4F), -124 (44F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x:10.

[0322] (Example 4-6) The same procedure as in Example 1-8 was repeated, except that compound (2-1) was changed to 1 g of compound (2-4) obtained in Example 4-5, to obtain 1.2 g of compound (1-4).

[0323] [ka]

[0324] NMR spectrum of compound (1-4); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H). 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (44F), -120 (4F), -124 (44F), -128 (22F), -131 (22F), -137 (11F), -139 (11F). Average value of x:10.

[0325] [Example 5] Compound (10-1) was obtained according to the method described in Example 11 of Patent Document 2. Average value of x: 11.

[0326] [ka]

[0327] [Example 6] (Example 6-1) In a 200 mL eggplant flask, 16.2 g of HOCH2CF2CF2CH2OH and 13.8 g of potassium carbonate were placed and stirred at 120° C., and 278 g of compound (11-1) obtained in Example 1-1 was added and stirred at 120° C. for 2 hours. The eggplant flask was brought to 25° C., and 50 g each of AC-2000 and hydrochloric acid were added, followed by separation and concentration of the organic phase. The resulting reaction crude liquid was purified by column chromatography to obtain 117.7 g of compound (5-1).

[0328] [ka]

[0329] NMR spectrum of compound (5-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (12H), 4.6 (20H), 4.2 (4H), 4.1 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -85 (24F), -90 (24F), -120 (20F), -122 (4F), -123 (4F), -126 (24F), -144 (12F). Average of x1+x2: 10.

[0330] (Example 6-2) Compound (4-1) was changed to 20 g of compound (5-1) obtained in Example 6-1, the amount of sodium fluoride powder was changed to 2.4 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 18.8 g, and the same procedure as in Example 1-4 was performed to obtain 24 g of compound (5-2).

[0331] [ka]

[0332] NMR spectrum of compound (5-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (12H), 5.0 (4H), 4.6 (20H), 4.2 (4H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -85 (24F), -90 (24F), -119 (4F), -120 (20F), -122 (4F), -126 (24F), -129 (4F), -131 (2F), -144 (12F). Average of x1+x2: 10.

[0333] (Example 6-3) Compound (4-2) was changed to 24 g of compound (5-2) obtained in Example 6-2, and the addition time of the CFE-419 solution of compound (5-2) was changed to 6 hours, but the same procedure as in Example 1-5 was repeated to obtain 25.3 g of compound (5-3).

[0334] [ka]

[0335] NMR spectrum of compound (5-3); 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -83 (52F), -87 (48F), -124 (52F), -129 (4F), -131 (2F). Average value of x: 11.

[0336] (Example 6-4) In a 50 mL eggplant flask, 25.3 g of the compound (5-3) obtained in Example 6-3, 2.2 g of sodium fluoride, and 25 mL of AC-2000 were placed and stirred in an ice bath. 1.7 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 15 g of compound (5-4) was obtained.

[0337] [ka]

[0338] NMR spectrum of compound (5-4); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (48F), -87 (48F), -119 (4F), -124 (48F). Average value of x: 11.

[0339] (Example 6-5) In a 50 mL recovery flask, 15 g of the compound (5-4) obtained in Example 6-4, 3.2 g of H2NCH2C(CH2CH=CH2)3, and 15 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography. 11.2 g of compound (20-2) was obtained.

[0340] [ka]

[0341] NMR spectrum of compound (20-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (48F), -87 (48F), -120 (4F), -124 (48F). Average value of x: 11.

[0342] (Example 6-6) The same procedure as in Example 1-8 was repeated, except that the compound (2-1) was changed to 1 g of the compound (20-2) obtained in Example 6-5, to obtain 1.2 g of the compound (10-2).

[0343] [ka]

[0344] NMR spectrum of compound (10-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -83 (48F), -87 (48F), -120 (4F), -124 (48F). Average value of x: 11.

[0345] [Examples 7-13: Manufacturing and evaluation of products] Substrates were surface-treated with compositions prepared by mixing each of the compounds obtained in Examples 1 to 6 and the compounds obtained in Examples 1 and 5 (compound (1-1) and compound (10-1)) in a mass ratio of 1:1 to obtain articles of Examples 7 to 13. As the surface treatment method, the following dry coating method and wet coating method were used in each example. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following method. The results are shown in Table 1.

[0346] (Dry coating method) Dry coating was performed using a vacuum deposition apparatus (VTR350M, manufactured by ULVAC Corporation) (vacuum deposition method). 0.5 g of each of the compounds obtained in Examples 1 to 6 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.

[0347] (Wet coating method) Each compound obtained in Examples 1 to 6 was mixed with C4F9OC2H5 (3M, Novec (registered trademark) 7200) as a medium to prepare a coating liquid with a solid concentration of 0.05%. A substrate was dipped in the coating liquid, left for 30 minutes, and then pulled out (dip coating method). The coating film was dried at 200°C for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0348] (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.

[0349] <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 110 degrees and 115 degrees. △(Acceptable): Between 100 and 110 degrees. ×(Not acceptable): Less than 100 degrees. Initial n-hexadecane contact angle: ◎ (Excellent): Over 66 degrees. ○ (Good): Between 65 degrees and 66 degrees. △(Acceptable): Between 63 degrees and 65 degrees. ×(Not acceptable): Less than 63 degrees.

[0350] <Light resistance> The surface layer was subjected to accelerated light fastness testing using a tabletop xenon arc lamp type accelerated light fastness tester (SUNTEST XLS+, manufactured by Toyo Seiki Co., Ltd.) at a black panel temperature of 63°C and light (650 W / m 2 After 1,000 hours of exposure to UV light (300 to 700 nm), the water contact angle was measured. The smaller the decrease in water contact angle after the accelerated light resistance test, the smaller the decrease in performance due to light and the better the light resistance. The evaluation criteria are as follows: ⊚ (Excellent): The change in water contact angle after accelerated light resistance test is 2 degrees or less. ○ (Good): The change in water contact angle after the accelerated light resistance test is more than 2 degrees and not more than 5 degrees. △ (Acceptable): The change in water contact angle after accelerated light resistance test is more than 5 degrees and less than 10 degrees. × (Fail): The change in water contact angle after accelerated light resistance test is more than 10 degrees.

[0351] <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 15,000 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 15,000 reciprocating strokes is less than 2 degrees. ○ (Good): The change in water contact angle after 15,000 reciprocating strokes is more than 2 degrees and less than 5 degrees. △ (Acceptable): The change in water contact angle after 15,000 reciprocating strokes is more than 5 degrees and less than 10 degrees. × (Fail): The change in water contact angle after 15,000 cycles exceeds 10 degrees.

[0352] <Chemical resistance (alkali resistance)> The article was immersed in a 1N aqueous solution of sodium hydroxide (pH=14) for 5 hours, then washed with water, air-dried, and the water contact angle was measured using the method described above. The smaller the decrease in the water contact angle after the test, the smaller the decrease in performance due to alkali and the more excellent the alkali resistance. The evaluation criteria are as follows. ◎ (Excellent): The change in water contact angle after the alkali resistance test is 2 degrees or less. ◯ (Good): The change in water contact angle after the alkali resistance test is more than 2 degrees and less than 5 degrees. △ (Acceptable): The change in water contact angle after the alkali resistance test is more than 5 degrees and less than 10 degrees. × (Fail): The change in water contact angle after the alkali resistance test is more than 10 degrees.

[0353] <Chemical resistance (salt water resistance)> A salt spray test was conducted in accordance with JIS H8502. That is, the article was exposed to a salt water atmosphere for 300 hours in a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.), and then the water contact angle was measured by the above method. The smaller the decrease in the water contact angle after the test, the smaller the decrease in performance due to salt water and the more excellent the salt water resistance. The evaluation criteria are as follows. ◎ (Excellent): The change in water contact angle after the salt spray test is 2 degrees or less. ○ (Good): The change in water contact angle after the salt spray test is more than 2 degrees and not more than 5 degrees. △ (Acceptable): The change in water contact angle after the salt spray test is more than 5 degrees and less than 10 degrees. × (Fail): The change in water contact angle after the salt spray test is more than 10 degrees.

[0354] <Slip resistance> The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a variable load friction and wear test system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under the conditions of contact area: 3 cm x 3 cm, load: 0.98 N. The higher the dynamic friction coefficient, the better the slip resistance. The evaluation criteria are as follows: ◎ (Excellent): Dynamic friction coefficient is 0.6 or more. ○ (Good): The dynamic friction coefficient is 0.5 or more and less than 0.6. △(Acceptable): Coefficient of dynamic friction is 0.4 or more and less than 0.5. × (Not possible): The dynamic friction coefficient is less than 0.4.

[0355] <Fingerprint removal> After applying artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of a silicone rubber stopper, excess oil was wiped off with a nonwoven fabric (Bencotto (registered trademark) M-3, manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed with a load of 9.8 N for 10 seconds. The haze of the area where the fingerprint was attached was measured with a haze meter and set as the initial value. The area where the fingerprint was attached was wiped off with a load of 4.9 N using a reciprocating traverse tester (manufactured by KNT Corporation) equipped with tissue paper. The haze value was measured for each reciprocating wipe, and the number of wipes required to reduce the haze to 10% or less from the initial value was measured. The fewer the number of wipes, the easier it is to remove fingerprint stains, and the better the fingerprint stain wiping ability. The evaluation criteria are as follows. ◎ (Excellent): Wiping required 3 times or less. ○ (Good): Wipe off 4 to 5 times. △(Acceptable): Wipe 6 to 8 times. × (Not acceptable): Wipe more than 9 times.

[0356] [Table 1]

[0357] It was confirmed that Examples 7 to 10 using this compound were excellent in initial water and oil repellency, light resistance, abrasion resistance, chemical resistance, slip resistance, and fingerprint stain removability. Examples 11 and 12, which used a conventional fluorinated ether compound, were inferior in abrasion resistance, lubricity, light resistance and chemical resistance. On the other hand, Example 13, which used the present composition combining the present compound with a conventional fluorinated ether compound, showed improved slip resistance and chemical resistance compared to Example 11, demonstrating the full effect of the present compound.

[0358] Furthermore, various fluorine-containing ether compounds (present compounds) were synthesized. Synthesis examples are shown below. [Example 14] (Example 14-1) In a 100 mL metal reactor, 20 g of the compound (11-1) obtained in Example 1-1 and 19.1 g of CF2=CFOCF2CF2CF3 were placed, and the mixture was stirred for 300 hours at 180° C. The resulting organic phase was concentrated and purified by distillation to obtain 5.9 g of compound (33-1).

[0359] [ka]

[0360] NMR spectrum of compound (33-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.1 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (3F), -82 (4F), -123 (2F), -126 (2F), -128 (4F), -129 (2F), -137 (2F).

[0361] (Example 14-2) Compound (23-1) was changed to 4.9 g of compound (33-1) obtained in Example 14-1, and potassium carbonate was changed to 0.5 g, and the same procedure as in Example 1-3 was repeated to obtain 12 g of compound (33-2).

[0362] [ka]

[0363] NMR spectrum of compound (33-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 4.6 (20H), 4.1 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (3F), -82 (24F), -90 (20F), -120 (20F), -123 (2F), -126 (22F), -128 (4F), -129 (2F), -137 (2F), -144 (10F). Average value of n+1: 10.

[0364] (Example 14-3) Compound (4-1) was changed to 10 g of compound (33-2) obtained in Example 14-2, the amount of sodium fluoride powder was changed to 0.6 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 5 g, and the same procedure as in Example 1-4 was performed to obtain 11 g of compound (33-3).

[0365] [ka]

[0366] NMR spectrum of compound (33-3); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 5.0 (2H), 4.6 (20H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (6F), -82 (26F), -83 (3F), -90 (20F), -119 (2F), -120 (20F), -126 (22F), -128 (4F), -129 (4F), -132 (1F), -137 (2F), -144 (10F). Average value of n+1: 10.

[0367] (Example 14-4) The same procedure as in Example 1-5 was repeated, except that compound (4-2) was changed to 10 g of compound (33-3) obtained in Example 14-3, to obtain 12 g of compound (33-4).

[0368] [ka]

[0369] NMR spectrum of compound (33-4); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (6F), -82 (6F), -83 (3F), -84 (42F), -90 (40F), 124 (44F), -128 (4F), -129 (4F), -132 (1F), -137 (2F). Average value of n+1: 10.

[0370] (Example 14-5) The same procedure as in Example 1-6 was repeated, except that the compound (4-3) was changed to 12 g of the compound (33-4) obtained in Example 14-4, to obtain 11 g of the compound (33-5).

[0371] [ka]

[0372] NMR spectrum of compound (33-5); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (3F), -82 (4F), -84 (40F), -90 (40F), -118 (2F), 124 (42F), -128 (4F), -129 (2F), -137 (2F). Mean value of n:9.

[0373] (Example 14-6) 12 g of compound (33-6) was obtained in the same manner as in Example 1-7, except that compound (4-4) was changed to 12 g of compound (33-5) obtained in Example 14-5.

[0374] [ka]

[0375] NMR spectrum of compound (33-6); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (3F), -82 (4F), -84 (40F), -90 (40F), -120 (2F), 124 (42F), -128 (4F), -129 (2F), -137 (2F). Mean value of n:9.

[0376] (Example 14-7) The same procedure as in Example 1-8 was repeated, except that the compound (2-1) was changed to 1 g of the compound (33-6) obtained in Example 14-6, to obtain 1.1 g of the compound (33-7).

[0377] [ka]

[0378] NMR spectrum of compound (33-7); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (27), 3.4 (2H), 1.3 (12H), 0.9 (6H). 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (3F), -82 (4F), -84 (40F), -90 (40F), -120 (2F), 124 (42F), -128 (4F), -129 (2F), -137 (2F). Mean value of n:9.

[0379] [Example 15] (Example 15-1) In a 50 mL recovery flask, 10 g of the compound (33-1) obtained in Example 14-1, 15.6 g of trifluoromethanesulfonic anhydride, 5.6 g of triethylamine, and 10 g of 1,3-bistrifluoromethylbenzene were mixed and reacted at 40° C. for 3 hours. Water was added to the crude liquid after the reaction to wash, and the organic layer was recovered. The solvent and the like were distilled off under reduced pressure to obtain 9.9 g of compound (34-1).

[0380] [ka] In the formula, OTf represents —OSO2CF3.

[0381] NMR spectrum of compound (34-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 5.0 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -74 (3F), -81 (3F), -82 (4F), -119 (2F), -126 (2F), -128 (4F), -129 (2F), -137 (2F).

[0382] (Example 15-2) In a 50 mL recovery flask, 10 g of the compound (34-1) obtained in Example 15-1, 13.1 g of cesium carbonate, 59 g of 1,3-bistrifluoromethylbenzene, and 59 g of FLUOROLINK (registered trademark) D4000 manufactured by Solvay Solexis were mixed and reacted at 80° C. for 6 hours. After the reaction, the crude liquid was washed with an aqueous hydrochloric acid solution, and the organic layer was recovered. The solvent and the like were distilled off under reduced pressure, and the mixture was purified by column chromatography to obtain 20 g of compound (34-2). In the following compounds (34-2) to (34-7), -[CF2O] C1 -[CF2CF2O] C2 - represents a random copolymer chain of C1 (CF2O) and C2 (CF2CF2O).

[0383] [ka]

[0384] NMR spectrum of compound (34-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 5.0 (2H), 4.2 (2H), 3.9 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -80 (2F), -81 (5F), -82 (4F), -90 (96F), -119 (2F), -126 (2F), -128 (4F), -129 (2F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0385] (Example 15-3) The same procedure as in Example 1-5 was repeated, except that compound (4-2) was changed to 20 g of compound (34-2) obtained in Example 15-2, to obtain 12 g of compound (34-3).

[0386] [ka]

[0387] NMR spectrum of compound (34-3); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 5.0 (2H), 4.7 (2H), 4.2 (2H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -80 (2F), -81 (8F), -82 (6F), -83 (3F), -90 (96F), -119 (2F), -126 (2F), -128 (4F), -129 (4F), -132 (1F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0388] (Example 15-4) 12 g of compound (34-4) was obtained in the same manner as in Example 1-5, except that compound (4-2) was changed to 12 g of compound (34-3) obtained in Example 15-3.

[0389] [ka]

[0390] NMR spectrum of compound (34-4); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -81 (6F), -82 (8F), -83 (3F), -90 (104F), -124 (4F), -128 (4F), -129 (4F), -132 (1F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0391] (Example 15-5) The same procedure as in Example 1-6 was repeated, except that compound (4-3) was changed to 20 g of compound (34-4) obtained in Example 15-4, to obtain 19 g of compound (34-5).

[0392] [ka]

[0393] NMR spectrum of compound (34-5); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (3H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -80 (2F), -81 (3F), -82 (6F), -90 (100F), -124 (4F), -128 (4F), -129 (2F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0394] (Example 15-6) The same procedure as in Example 1-7 was repeated, except that the compound (4-4) was changed to 19 g of the compound (34-5) obtained in Example 15-5, to obtain 15 g of the compound (34-6).

[0395] [ka]

[0396] NMR spectrum of compound (34-6); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -79 (2F), -81 (3F), -82 (6F), -90 (100F), -124 (4F), -128 (4F), -129 (2F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0397] (Example 15-7) The same procedure as in Example 1-8 was repeated, except that the compound (2-1) was changed to 1 g of the compound (34-6) obtained in Example 15-6, to obtain 1.1 g of the compound (34-7).

[0398] [ka]

[0399] NMR spectrum of compound (34-7); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (27), 3.4 (2H), 1.3 (12H), 0.9 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55 (44F), -79 (2F), -81 (3F), -82 (6F), -90 (100F), -124 (4F), -128 (4F), -129 (2F), -137 (2F). Average value of C1: 22. Average value of C2: 24.

[0400] [Example 16] (Example 16-1) In a 200 mL eggplant flask, 10.0 g of 1,4-cyclohexanedimethanol and 19.2 g of potassium carbonate were added and stirred at 120° C., and 192.8 g of the compound (11-1) obtained in Example 1-1 was added and stirred at 120° C. for 2 hours. The temperature in the eggplant flask was brought to 25° C., and 100 g each of AC-2000 and hydrochloric acid were added, and the liquids were separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by column chromatography to obtain 96.6 g of compound (35-1).

[0401] [ka]

[0402] NMR spectrum of compound (35-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 4.6 (16H), 4.1 (4H), 3.3 (4H), 1.9 (2H), 1,5 (8H). 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -82 (20F), -90 (20F), -120 (16F), -123 (4F), -126 (20F), -144 (10F). Average of (m+1)+(n+1):10.

[0403] (Example 16-2) Compound (4-1) was changed to 90 g of compound (35-1) obtained in Example 16-1, the amount of sodium fluoride powder was changed to 5.4 g, and the amount of CF3CF2CF2OCF(CF3)COF was changed to 85.8 g, and the same procedure as in Example 1-4 was performed to obtain 100.8 g of compound (35-2).

[0404] [ka]

[0405] NMR spectrum of compound (35-2); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.0 (10H), 5.0 (4H), 4.6 (16H), 3.3 (4H), 1.9 (2H), 1,5 (8H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (6F), -82 (24F), -83 (6F), -90 (20F), -119 (4F), -120 (16F), -126 (20F), -129 (4F), -132 (2F), -144 (10F). Average of (m+1)+(n+1):10.

[0406] (Example 16-3) Compound (4-2) was changed to 40 g of compound (35-2) obtained in Example 16-2, and the addition time of the CFE-419 solution of compound (35-2) was changed to 8 hours, and the same procedure as in Example 1-5 was repeated to obtain 45.3 g of compound (35-3).

[0407] [ka]

[0408] NMR spectrum of compound (35-3); 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -81 (6F), -82 (4F), -83 (6F), -84 (40F), -90 (40F), -93 (4F), -124 (40F), -127 (8F), -129 (4F), -132 (2F), -184 (2F). Average of (m+1)+(n+1):10.

[0409] (Example 16-4) In a 50 mL eggplant flask, 40.0 g of the compound (35-3) obtained in Example 16-3, 3.4 g of sodium fluoride, and 40 mL of AC-2000 were placed and stirred in an ice bath. 2.6 g of methanol was added and stirred at 25°C for 1 hour. After filtration, the filtrate was purified by column chromatography. 31.3 g of compound (35-4) was obtained.

[0410] [ka]

[0411] NMR spectrum of compound (35-4); 1 H-NMR (300.4 MHz, solvent: CDCl3, standard: TMS) δ (ppm): 4.2 (6H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -84 (36F), -90 (40F), -93 (4F), -118 (4F), -124 (36F), -127 (8F), -184 (2F). Average value of m+n:8.

[0412] (Example 16-5) In a 50 mL recovery flask, 20 g of the compound (35-4) obtained in Example 16-4, 2.3 g of H2NCH2C(CH2CH=CH2)3, and 15 mL of AC-2000 were placed and stirred at 0°C for 24 hours. The reaction crude liquid was purified by column chromatography. 12.7 g of compound (35-5) was obtained.

[0413] [ka]

[0414] NMR spectrum of compound (35-5); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -84 (36F), -90 (40F), -93 (4F), -120 (4F), -124 (36F), -127 (8F), -184 (2F). Average value of m+n:8.

[0415] (Example 16-6) The same procedure as in Example 1-8 was repeated, except that the compound (2-1) was changed to 1 g of the compound (35-5) obtained in Example 16-5, to obtain 1.1 g of the compound (35-6).

[0416] [ka]

[0417] NMR spectrum of compound (35-6); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H). 19F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -84 (36F), -90 (40F), -93 (4F), -120 (4F), -124 (36F), -127 (8F), -184 (2F). Average value of m+n:8. [Industrial Applicability]

[0418] The fluorine-containing ether compound of the present invention can be used in various applications requiring lubricity or water- and oil-repellency. For example, it can be used as a surface protective coating for display input devices such as touch panels, transparent glass or plastic members, an antifouling coating for kitchens, a water- and moisture-proof or antifouling coating for electronic devices, heat exchangers, batteries, etc., an antifouling coating for toiletries, a coating for members that need to be conductive and liquid-repellent, a water-repellent, waterproof, or water-slip coating for heat exchangers, a surface low-friction coating for the inside of vibrating sieves and cylinders, etc. More specific examples of use include front protective plates, anti-reflection plates, polarizing plates, anti-glare plates for displays, or those with their surfaces treated with an anti-reflection film, various devices with display input devices that allow operations on the screen with human fingers or palms, such as touch panel sheets and touch panel displays for devices such as mobile phones and personal digital assistants, decorative building materials for wet areas such as toilets, baths, washrooms, and kitchens, waterproof coatings for wiring boards, water-repellent and waterproof coatings for heat exchangers, water-repellent coatings for solar cells, waterproof and water-repellent coatings for printed wiring boards, waterproof and water-repellent coatings for electronic device housings and electronic components, coatings to improve the insulation of power transmission lines, waterproof and water-repellent coatings for various filters, waterproof coatings for radio wave absorbing materials and sound absorbing materials, anti-fouling coatings for baths, kitchen equipment, and toiletries, water-repellent, waterproof, and water-slip coatings for heat exchangers, low-friction surface coatings for vibrating sieves and the inside of cylinders, and surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools, etc. The entire contents of the specifications, claims and abstracts of Japanese Patent Application No. 2019-022079 filed on February 8, 2019 and Japanese Patent Application No. 2019-220995 filed on December 6, 2019 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A first partial structure represented by the following formula (1), A fluorine-containing ether compound having a second partial structure represented by the following formula (2): The compound has five or more of the first partial structures, or A fluorine-containing ether compound having two or more of the second partial structures. -OR ｆ１２ - (1) -OR ｆ１３ - (2) however, R ｆ１２ is a fluoroalkylene group having 1 to 6 carbon atoms, R ｆ１３ is a group having a fluorine-containing ring structure which may have a heteroatom.

2. The fluorine-containing ether compound according to claim 1, which is a compound represented by the following formula (1A): [R ｆ -] ａ１ Q １ [-T] ｂ１ (1A) however, R ｆ has the first partial structure and the second partial structure, and R is a monovalent group having five or more of the first partial structures or two or more of the second partial structures, the bonding end of which is a carbon atom; ｆ When the group has two or more, two or more R ｆ may be the same or different, Q １ represents a single bond or a linking group having a valence of a1+b1, Tは、-R ｆ６ 、-Ar、-OR １０ 、-SR １０ 、-NOR １０ 、-C(=O)R １０ 、-N(R １０ ) ２ 、-N ＋ (R １０ ) ３ X ３ 、-C≡N、-C(=NR １０ )-R １０ 、-N ＋ ≡N、-N=NR １０ 、-C(=O)OR １０ 、-C(=O)OX ２ 、-C(=O)OX ４ 、-C(=O)OC(=O)R １０ 、-SO ２ R １０ 、-SO ３ H、-SO ３ X ２ 、-O-P(=O)(-OR １０ ) ２ 、-O-P(=O)(-OR １０ )(-OX ２ )、-N=C=O、-Si(R) ３－ｃ (L) ｃ 、-C(R １０ )=C(R １０ ) ２ 、-C≡C(R １０ )、-C(=O)N(R １０ ) ２ 、-N(R １０ )C(=O)R １０ 、-Si(R １０ ) ２ -O-Si(R １０ ) ３ 、-NH-C(=O)R １０ 、-C(=O)NHR １０ 、-I、 【Chemistry 1】 R ｆ６ is a fluoroalkyl group having 1 to 6 carbon atoms, R １０ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or an aryl group which may have a substituent, R １０ If there are two or more, two or more R １０ may be the same or different, Ar is an optionally substituted aryl group, X ２ is an alkali metal ion or an ammonium ion, X ３ is a halide ion, X ４ is a halogen atom, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. a1 is an integer of 1 or more, b1 is an integer of 1 or more, c is 2 or 3, When there are two or more T's, the two or more T's may be the same or different.

3. The R ｆ The fluorine-containing ether compound according to claim 2 , wherein R ｆ１ -(OR ｆ２ ) ｍ (OR ｆ３ ) ｎ - (g1a) however, R ｆ１ represents a fluoroalkyl group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having a fluorine-containing ring structure, R ｆ２ represents a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q １ R bonded to ｆ２ Q １ At least one fluorine atom is bonded to the terminal carbon atom of the R ｆ３ represents a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q １ R bonded to ｆ３ Q １ At least one fluorine atom is bonded to the terminal carbon atom of the n is R ｆ１ When R has a fluorine-containing ring structure, it is an integer of 0 to 500; ｆ１ is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR ｆ３ ) ｎ OR of two or more ｆ３ It may consist of When n is 0, m is an integer from 5 to 500; When n is 1 or more, m is an integer from 2 to 500, When m is 2 or more, (OR ｆ２ ) ｍ OR of two or more ｆ２ It may consist of m (OR ｆ２ ) and n (OR ｆ３ ) may be bonded in any order.

4. Q １ is a group represented by formula (g2-1) (provided that a1=d1+d3 and b1=d2+d4), a group represented by formula (g2-2) (provided that a1=e1 and b1=e2), a group represented by formula (g2-3) (provided that a1=1 and b1=2), a group represented by formula (g2-4) (provided that a1=h1 and b1=h2), a group represented by formula (g2-5) (provided that a1=i1 and b1=i2), a group represented by formula (g2-6) (provided that a1=1 and b1=1), or a group represented by formula (g2-7) (provided that a1=1 and b1=i3). 【Chemistry 2】 (-A-Q １２ -) ｅ１ C(R ２ ) ４－ｅ１－ｅ２ (-Q ２２ -) ｅ２ (g2-2) -A-Q １３ -N(-Q ２３ -) ２ (g2-3) (-A-Q １４ -) ｈ１ Z(-Q ２４ -) ｈ２ (g2-4) (-A-Q １５ -) ｉ１ Si(R ３ ) ４－ｉ１－ｉ２ (-Q ２５ -) ｉ２ (g2-5) -A-Q ２６ - (g2-6) -A-Q １２ -CH(-Q ２２ -)-Si(R ３ ) ３－ｉ３ (-Q ２５ -) ｉ３ (g2-7) however, In formulae (g2-1) to (g2-7), the A side is R ｆ Connect to Q ２２ , Q ２３ , Q ２４ , Q ２５ and Q. ２６ The side connects to the T. A is a single bond, -C(O)NR ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O- or -SO ２ N.R. ６ - and Q １１ represents a single bond, —O—, an alkylene group, or a —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, Q １２ represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, and Q １ Q １２ If there are two or more, there are two or more Q １２ may be the same or different, Q １３ represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ a group having - or -O-, or a group having -C(O)- at the N-terminal of the alkylene group, Q １４ Is, Q １４ When the atom in Z to which is bonded is a carbon atom, Q １２ And Q １４ When the atom in Z to which is bonded is a nitrogen atom, Q １３ And Q １ Q １４ If there are two or more, there are two or more Q １４ may be the same or different, Q １５ represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, and Q １ Q １５ If there are two or more, there are two or more Q １５ may be the same or different, Q ２２ represents an alkylene group, an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ a group having - or -O-, -C(O)NR at the end of the alkylene group not connected to T; ６ -, -C(O)-, -NR ６ A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O- and -C(O)NR at the end not connected to T ６ -, -C(O)-, -NR ６ - 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. ６ -, -C(O)-, -NR ６ - or -O-, and two Q ２３ may be the same or different, Q ２４ Is, Q ２４ When the atom in Z to which is bonded is a carbon atom, Q ２２ And Q ２４ When the atom in Z to which is bonded 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. ６ -, -C(O)-, -NR ６ - 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. ６ -, -C(O)-, -NR ６ - or -O-, Z is Q １４ has a carbon atom or a nitrogen atom to which Q is directly bonded, ２４ is a group having a ring structure with a valence of a1+b1, which has a carbon atom or a nitrogen atom to which is directly bonded, R １ is a hydrogen atom or an alkyl group, and Q １ R １ When the group has two or more, two or more R １ may be the same or different, R ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R ３ is an alkyl group, R ６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 3; d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3+d4 is an integer from 1 to 3; d1+d3 is Q １ is an integer from 1 to 5, d2+d4 is Q １ is an integer from 1 to 5, e1 + e2 is 3 or 4, e1 is Q １ is an integer from 1 to 3, e2 is Q １ is an integer from 1 to 3, h1 is Q １ is an integer of 1 or more, h2 is an integer of 1 or more, i1 + i2 is 3 or 4, i1 is Q １ is an integer from 1 to 3, i2 is Q １ is an integer from 1 to 3, i3 is 2 or 3.

5. The fluorine-containing ether compound according to claim 1, which is a compound represented by the following formula (1B): [T-] ｂ２ Q ２ -Q ｆ -Q ２ [-T] ｂ２ (1B) however, Q ｆ has the first partial structure and the second partial structure, and a divalent group having five or more of the first partial structures or two or more of the second partial structures, both bonding terminals of which are carbon atoms, Q ２ is a single bond or a b2+1 valent linking group, and two Q ２ may be the same or different, Tは、-R ｆ６ 、-Ar、-OR １０ 、-SR １０ 、-NOR １０ 、-C(=O)R １０ 、-N(R １０ ) ２ 、-N ＋ (R １０ ) ３ X ３ 、-C≡N、-C(=NR １０ )-R １０ 、-N ＋ ≡N、-N=NR １０ 、-C(=O)OR １０ 、-C(=O)OX ２ 、-C(=O)OX ４ 、-C(=O)OC(=O)R １０ 、-SO ２ R １０ 、-SO ３ H、-SO ３ X ２ 、-O-P(=O)(-OR １０ ) ２ 、-O-P(=O)(-OR １０ )(-OX ２ )、-N=C=O、-Si(R) ３－ｃ (L) ｃ 、-C(R １０ )=C(R １０ ) ２ 、-C≡C(R １０ )、-C(=O)N(R １０ ) ２ 、-N(R １０ )C(=O)R １０ 、-Si(R １０ ) ２ -O-Si(R １０ ) ３ 、-NH-C(=O)R １０ 、-C(=O)NHR １０ 、-I、 【Chemistry 3】 R ｆ６ is a fluoroalkyl group having 1 to 6 carbon atoms, R １０ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or an aryl group which may have a substituent, R １０ If there are two or more, two or more R １０ may be the same or different, Ar is an optionally substituted aryl group, X ２ is an alkali metal ion or an ammonium ion, X ３ is a halide ion, X ４ is a halogen atom, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. b2 is an integer of 1 or more, and two b2's may be the same or different. c is 2 or 3, When there are two or more T's, the two or more T's may be the same or different.

6. Q ｆ The fluorine-containing ether compound according to claim 5 , wherein -R ｆ４ -(OR ｆ２ ) ｍ (OR ｆ３ ) ｎ - (g1b) however, R ｆ２ represents a fluoroalkylene group having 1 to 6 carbon atoms (wherein Q ２ R bonded to ｆ２ Q ２ At least one fluorine atom is bonded to the terminal carbon atom of the R ｆ３ represents a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein Q ２ R bonded to ｆ３ Q ２ At least one fluorine atom is bonded to the terminal carbon atom of the R ｆ４ represents a fluoroalkylene group having 1 to 6 carbon atoms, or a divalent fluorinated hydrocarbon group having a fluorine-containing ring structure (wherein R ｆ４ Q ２ At least one fluorine atom is bonded to the terminal carbon atom of the n is R ｆ４ When R has a fluorine-containing ring structure, it is an integer of 0 to 500; ｆ４ is an integer of 1 to 500 when n does not have a fluorine-containing ring structure, and when n is 2 or more, (OR ｆ３ ) ｎ OR of two or more ｆ３ It may consist of When n is 0, m is an integer from 5 to 500; When n is 1 or more, m is an integer from 2 to 500, When m is 2 or more, (OR ｆ２ ) ｍ OR of two or more ｆ２ It may consist of m (OR ｆ２ ) and n (OR ｆ３ ) may be bonded in any order.

7. Q ２ is a group represented by formula (g2-1) (with the proviso that b2=d2+d4), a group represented by formula (g2-2) (with the proviso that b2=e2), a group represented by formula (g2-3) (with the proviso that b2=2), a group represented by formula (g2-4) (with the proviso that b2=h2), a group represented by formula (g2-5) (with the proviso that b2=i2), a group represented by formula (g2-6) (with the proviso that b2=1), or a group represented by formula (g2-7) (with the proviso that b2=i3). 【Chemistry 4】 (-A-Q １２ -) ｅ１ C(R ２ ) ４－ｅ１－ｅ２ (-Q ２２ -) ｅ２ (g2-2) -A-Q １３ -N(-Q ２３ -) ２ (g2-3) (-A-Q １４ -) ｈ１ Z(-Q ２４ -) ｈ２ (g2-4) (-A-Q １５ -) ｉ１ Si(R ３ ) ４－ｉ１－ｉ２ (-Q ２５ -) ｉ２ (g2-5) -A-Q ２６ - (g2-6) -A-Q １２ -CH(-Q ２２ -)-Si(R ３ ) ３－ｉ３ (-Q ２５ -) ｉ３ (g2-7) however, In formulae (g2-1) to (g2-7), the A side is Q ｆ Connect to Q ２２ , Q ２３ , Q ２４ , Q ２５ and Q. ２６ The side connects to the T. A is a single bond, -C(O)NR ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O- or -SO ２ N.R. ６ - and Q １１ represents a single bond, —O—, an alkylene group, or a —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, Q １２ represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, and Q ２ Q １２ If there are two or more, there are two or more Q １２ may be the same or different, Q １３ represents a single bond (where A is -C(O)-), an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ a group having - or -O-, or a group having -C(O)- at the N-terminal of the alkylene group, Q １４ Is, Q １４ When the atom in Z to which is bonded is a carbon atom, Q １２ And Q １４ When the atom in Z to which is bonded is a nitrogen atom, Q １３ And Q ２ Q １４ If there are two or more, there are two or more Q １４ may be the same or different, Q １５ represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O-, and Q ２ Q １５ If there are two or more, there are two or more Q １５ may be the same or different, Q ２２ represents an alkylene group, an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ a group having - or -O-, -C(O)NR at the end of the alkylene group not connected to T; ６ -, -C(O)-, -NR ６ A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O- and -C(O)NR at the end not connected to T ６ -, -C(O)-, -NR ６ - or -O-, and Q ２ 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. ６ -, -C(O)-, -NR ６ - or -O-, and two Q ２３ may be the same or different, Q ２４ Is, Q ２４ When the atom in Z to which is bonded is a carbon atom, Q ２２ And Q ２４ When the atom in Z to which is bonded is a nitrogen atom, Q ２３ And Q ２ 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. ６ -, -C(O)-, -NR ６ - or -O-, and Q ２ 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. ６ -, -C(O)-, -NR ６ - or -O-, Z is Q １４ has a carbon atom or a nitrogen atom to which Q is directly bonded, ２４ is a group having a b2+1 valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, R １ is a hydrogen atom or an alkyl group, and Q ２ R １ When the group has two or more, two or more R １ may be the same or different, R ２ is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, R ３ is an alkyl group, R ６ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 3; d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, and d3+d4 is an integer from 1 to 3; d1+d3 is Q ２ is 1 in d2+d4 is Q ２ is an integer from 3 to 5, e1 + e2 is 3 or 4, e1 is Q ２ is 1 in e2 is Q ２ is 2 or 3, h1 is Q ２ is 1 in h2 is an integer of 1 or more, i1 + i2 is 3 or 4, i1 is Q ２ is 1 in i2 is Q ２ is 2 or 3, i3 is 2 or 3.

8. The fluorine-containing ether compound according to any one of claims 1 to 7, wherein the fluorine-containing ring structure is a four-membered ring.

9. The fluorine-containing ether compound according to any one of claims 1 to 8, having a number average molecular weight of 2,500 or more.

10. T is -Si(R) ３－ｃ (L) ｃ The fluorine-containing ether compound according to any one of claims 2 to 9, however, R is an alkyl group; L is a hydrolyzable group or a hydroxyl group, and two or more L in T may be the same or different. c is 2 or 3.

11. 11. A fluorine-containing ether composition comprising at least one of the fluorine-containing ether compounds according to claim 1 and another fluorine-containing ether compound.

12. The fluorine-containing ether compound according to any one of claims 1 to 10 or the fluorine-containing ether composition according to claim 11, A coating liquid comprising a liquid medium.

13. 12. An article comprising a substrate having a surface layer formed from the fluorinated ether compound according to any one of claims 1 to 10 or the fluorinated ether composition according to claim 11 on the surface of the substrate.

14. The article according to claim 13 , comprising the surface layer on a surface of a member that constitutes a surface of a touch panel that is touched by a finger.

15. A method for producing an article, comprising treating a surface of a substrate by a dry coating method using the fluorinated ether compound according to any one of claims 1 to 10 or the fluorinated ether composition according to claim 11, and forming a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.

16. A method for producing an article, comprising applying the coating liquid according to claim 12 to a surface of a substrate by a wet coating method, and drying the coating liquid to form a surface layer formed from the fluorinated ether compound or the fluorinated ether composition on the surface of the substrate.

17. A fluorine-containing ether compound represented by the following formula (2A): [R ｆ -] ａ１ Q １０ [-CH=CH ２ ] ｂ１ (2A) however, R ｆ is a monovalent polyfluoropolyether chain having at least one of a monovalent fluorine-containing ring structure at a free end and a divalent fluorine-containing ring structure in the main chain, and a bonding end being a carbon atom (with the proviso that at least one fluorine atom is bonded to the carbon atom at the bonding end), R ｆ When the group has two or more, two or more R ｆ may be the same or different, Q １０ is a linking group having a valence of a1+b1, a1 is an integer of 1 or more, b1 is an integer of 1 or more.

18. A fluorine-containing ether compound represented by the following formula (2B): [CH ２ =CH-] ｂ２ Q ２０ -Q ｆ -Q ２０ [-CH=CH ２ ] ｂ２ (2B) however, Q ｆ is a divalent polyfluoropolyether chain having a divalent fluorine-containing ring structure in the main chain and both bonding terminals being carbon atoms (provided that at least one fluorine atom is bonded to each of the carbon atoms at both bonding terminals), Q ２０ is a b2+1-valent linking group, and two Q ２０ may be the same or different, b2 is an integer of 1 or more, and two b2's may be the same or different.

19. A process for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (12) to obtain a compound represented by the following formula (21): 【Chemistry 5】 however, R １１ represents an alkylene group, an alkylene group having 2 or more carbon atoms and having -O- between carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH ２ ), or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH ２ ) and R １２ is a halogen atom, a perfluoroalkyl group, or a group having —O— between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, q is 0 or 1; E is -OH, -OR １４ , -SR １４ , -C(O)OR １４ , -C(O)NHR １４ , -C(O)NR １４ R １５ , -NH ２ , -NHR １４ , -NR １４ R １５ , -SO ２ X １ , -C(O)X １ or a halogen atom, R １４ and R １５ are each independently an alkyl group, X １ is a halogen atom.

20. A process for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (22): 【Chemistry 6】 however, R １１ represents an alkylene group, an alkylene group having 2 or more carbon atoms and having -O- between carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH ２ ), or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH ２ ) and R １３ is a fluoroalkylene group, a group having —O— at both terminals of a fluoroalkylene group, or a group having —O— between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, q is 0 or 1; E is -OH, -OR １４ , -SR １４ , -C(O)OR １４ , -C(O)NHR １４ , -C(O)NR １４ R １５ , -NH ２ , -NHR １４ , -NR １４ R １５ , -SO ２ X １ , -C(O)X １ or a halogen atom, R １４ and R １５ are each independently an alkyl group, X １ is a halogen atom, There are multiple R in formula (22) １１ , q and E may be the same or different.

21. A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (11) with each other to obtain a compound represented by the following formula (23): 【Chemistry 7】 however, R １１ represents an alkylene group, an alkylene group having 2 or more carbon atoms and having -O- between carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH ２ ), or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH ２ ) and q is 0 or 1; E is -OH, -OR １４ , -SR １４ , -C(O)OR １４ , -C(O)NHR １４ , -C(O)NR １４ R １５ , -NH ２ , -NHR １４ , -NR １４ R １５ , -SO ２ X １ , -C(O)X １ or a halogen atom, R １４ and R １５ are each independently an alkyl group, X １ is a halogen atom, There are multiple R in formula (23) １１ , q and E may be the same or different.

22. A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (13) with each other to obtain a compound represented by the following formula (24): 【Chemistry 8】 however, R １３ is a fluoroalkylene group, a group having —O— at both terminals of a fluoroalkylene group, or a group having —O— between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, r is an integer of 1 or more, There are multiple R in formula (24) １３ may be the same or different.

23. A process for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (25): 【Chemistry 9】 however, R １１ represents an alkylene group, an alkylene group having 2 or more carbon atoms and having -O- between carbon atoms, a fluoroalkylene group (provided that when E is -OH, the terminal on the E side is CH ２ ), or a group having -O- between carbon atoms of a fluoroalkylene group having 2 or more carbon atoms (provided that when E is -OH, the terminal on the E side is CH ２ ) and R １３ is a fluoroalkylene group, a group having —O— at both terminals of a fluoroalkylene group, or a group having —O— between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, q is 0 or 1; r is an integer of 1 or more, E is -OH, -OR １４ , -SR １４ , -C(O)OR １４ , -C(O)NHR １４ , -C(O)NR １４ R １５ , -NH ２ , -NHR １４ , -NR １４ R １５ , -SO ２ X １ , -C(O)X １ or a halogen atom, R １４ and R １５ are each independently an alkyl group, X １ is a halogen atom, There are multiple R in formula (25) １３ may be the same or different.

24. A method for producing a fluorine-containing compound, comprising reacting compounds represented by the following formula (12) with each other to obtain a compound represented by the following formula (26): 【Chemistry 10】 however, R １２ represents a halogen atom, a perfluoroalkyl group, or a group having -O- between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, There are multiple R in formula (26) １２ may be the same or different.

25. A process for producing a fluorine-containing compound, comprising reacting a compound represented by the following formula (12) with a compound represented by the following formula (13) to obtain a compound represented by the following formula (27): 【Chemistry 11】 however, R １２ is a halogen atom, a perfluoroalkyl group, or a group having —O— between carbon atoms of a perfluoroalkyl group having two or more carbon atoms, R １３ is a fluoroalkylene group, a group having —O— at both terminals of a fluoroalkylene group, or a group having —O— between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms, r2 is an integer of 1 or more, There are multiple R in formula (27) １３ may be the same or different.

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