Fluorine-containing ether compound and method of manufacturing the same, compound and method of manufacturing the same, fluorine-containing ether composition, coating liquid, and article and method of manufacturing the same

Abstract

To provide a fluorine-containing ether compound that can form a surface layer that excels in durability and a method of manufacturing the same, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer that excels in durability and a method of manufacturing the same.SOLUTION: A fluorine-containing ether compound is expressed by the following formula (A1) or (A2). Formula (A1): {RfO-(Rf1O)m1-(R1)m2-(CHF)m3-O-(CHF)m4}n1-Q1(-T1)n2. Formula (A2): (T2)n3-Q2-(CHF)m5-O-(CHF)m6-(R2)m7-O-(Rf2O)m8-(R3)m9-(CHF)m10-O-(CHF)m11-Q3(-T3)n4, provided that the symbols in the formulas are as described in the specification.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Fluorine-containing ether compounds having a perfluoropolyether chain and a hydrolyzable silyl group are suitable for use as surface treatment agents because they can form a surface layer on the surface of a substrate that exhibits high lubricity, water and oil repellency, etc. Surface treatment agents containing fluorine-containing ether compounds are used in applications where the performance of the surface layer not easily reduced in water and oil repellency even when rubbed repeatedly with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability) must be maintained for a long period of time, such as for components that constitute the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.

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

[0004] [Patent Document 1] International Publication No. 2017 / 022437 Summary of the Invention [Problem to be solved by the invention]

[0005] The surface treatment agent is required to be applicable to the surface treatment of various materials, not just the display surfaces of smartphones, tablet terminals, etc. Further improvement in durability of the surface treatment agent is required.

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

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

[10] . [1] A fluorine-containing ether compound represented by the following formula (A1) or (A2): {R f O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1) (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2) however, R fis a fluoroalkyl group having 1 to 20 carbon atoms, and R f If there are multiple R f may be the same or different from each other, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R f1 or R f2 If there are multiple R f1 or R f2 may be the same or different from each other, R 1 , R 2 and R 3 are each independently an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different from each other, Q 1 is an n1+n2-valent linking group, Q 2 is a 1+n trivalent linking group, Q 3 is a 1+n4-valent linking group, T 1 , T 2 and T 3 are each independently an adhesive group, and T 1 , T 2 or T 3 If there are multiple T 1 , T 2 or T 3 may be the same or different from each other, m1 and m8 each independently represent an integer of 0 to 210, and when there are multiple m1s, the m1s may be the same or different from each other; m2, m7, and m9 each independently represent 0 or 1, and when there are multiple m2s, the m2s may be the same or different from each other; m3 and m4 each independently represent 0 or 1, and m3 + m4 represents 1 or 2; (CHF) m3 -O-(CHF) m4When there are a plurality of combinations of m3 and m4, the combinations of m3 and m4 may be the same or different from each other, m1+m2 is equal to or greater than 1, m7+m8+m9 is greater than or equal to 1, m5 and m6 each independently represent 0 or 1, and m5 + m6 represents 1 or 2; m10 and m11 each independently represent 0 or 1, and m10 + m11 represents 1 or 2; n1 is an integer from 1 to 10, n2, n3, and n4 each independently represent an integer of 1 to 20. [2] The fluorine-containing ether compound according to [1], wherein m3, m6 or m10 is 1. [3] The fluorine-containing ether compound according to [1] or [2], wherein m4, m5 or m11 is 0. [4] A compound represented by the following formula (B1) or formula (B2): R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R f1 or R f2 If there are multiple R f1 or R f2 may be the same or different from each other, R 1 , R 2 and R 3 each independently represents an alkylene group optionally having a fluorine atom, m1 and m8 each independently represent an integer of 0 to 210, m2, m7 and m9 each independently represent 0 or 1. [5] A method for producing a fluorinated ether compound, comprising reacting a compound represented by the following formula (B1) or (B2) with a compound represented by the following formula (C1): R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2) (CH2=CH-) n5 -Q 4 (-OH) n6 Formula (C1) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R f1 or R f2 If there are multiple R f1 or R f2 may be the same or different from each other, R 1 , R 2 and R 3 each independently represents an alkylene group optionally having a fluorine atom, Q 4 is an n5+n6 valent linking group, m1 and m8 each independently represent an integer of 0 to 210, m2, m7, and m9 each independently represent 0 or 1; n5 is an integer from 1 to 20, n6 is an integer from 1 to 10. [6] A compound represented by the following formula (D1) or formula (D2) is reacted with a silicon hydride compound in the presence of a Lewis acid compound to obtain a compound represented by the following formula (E1) or formula (E2): From the compound represented by the following formula (E1) or formula (E2), Si(R 16 )3 to obtain a compound represented by the following formula (F1) or (F2): Heating a compound represented by the following formula (F1) or formula (F2): A method for producing a compound represented by the following formula (B1) or (B2): R f O-(R f1 O) m1 -(R 1 ) m2 -C(=O)OR 11 Formula (D1) R 11 OC(=O)-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -C(=O)OR 11 Formula (D2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 12 )2 formula (E1) (R 12 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 13 )2 formula (E2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 14 )2 formula (F1) (R 14 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 15 )2 formula (F2) R f O-(Rf1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R f1 or R f2 If there are multiple R f1 or R f2 may be the same or different from each other, R 1 , R 2 and R 3 each independently represents an alkylene group optionally having a fluorine atom, R 11 is a hydrogen atom or an alkyl group which may have a substituent, and R 11 If there are multiple R 11 may be the same or different from each other, R 12 and R 13 are each independently Si(R 16 )3 or R 11 and there are multiple R 12 and R 13 At least one of each of 16 )3, R 14 and R 15 are each independently a hydrogen atom or R 11 and there are multiple R 14 and R 15 at least one of each is a hydrogen atom, R 16 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an alkoxy group, and there are multiple R 16may be the same or different from each other, m1 and m8 each independently represent an integer of 0 to 210, m2, m7 and m9 each independently represent 0 or 1. [7] A fluorinated ether composition comprising at least one fluorinated ether compound according to any one of [1] to [3] and another fluorinated ether compound. [8] A fluorinated ether compound according to any one of [1] to [3] or a fluorinated ether composition according to [7], A coating liquid containing a liquid medium. [9] An article having a surface layer formed from the fluorinated ether compound of any one of [1] to [3] or the fluorinated ether composition of [7].

[10] A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the fluorinated ether compound of any one of [1] to [3], the fluorinated ether composition of [7], or the coating liquid of [8]. [Effects of the Invention]

[0008] The present invention provides a fluorinated ether compound capable of forming a surface layer having excellent durability, a fluorinated ether composition and coating liquid, an article having a surface layer having excellent durability, and a compound useful as a raw material for the fluorinated ether compound. [Brief explanation of the drawings]

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

[0010] In this specification, the compound represented by formula (A1) will be referred to as compound (A1), and the same applies to compounds represented by other formulas. As used herein, the following terms have the following meanings: The term "reactive silyl group" is a general term for a hydrolyzable silyl group and a silanol group (Si-OH). The term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "surface layer" refers to a layer formed on the surface of a substrate. When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 It is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units by F-NMR. When the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is uniform, the "molecular weight" of the polyfluoropolyether chain is 1 H-NMR and 19 It is the molecular weight calculated by determining the structure of the polyfluoropolyether chain by F-NMR. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0011] [Fluorine-containing ether compounds] The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the compound") is a fluorine-containing ether compound represented by the following formula (A1) or formula (A2). {R f O-(R f1 O) m1 -(R 1 ) m2 -(CHF) m3 -O-(CHF) m4} n1 -Q 1 (-T 1 ) n2 Formula (A1) (T 2 ) n3 -Q 2 -(CHF) m5 -O-(CHF) m6 -(R 2 ) m7 -O-(R f2 O) m8-(R 3 ) m9 -(CHF) m10 -O-(CHF) m11 -Q 3 (-T 3 ) n4 Formula (A2) however, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f If there are multiple R f may be the same or different from each other, R f1 and R f2 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R f1 or R f2 If there are multiple R f1 or R f2 may be the same or different from each other, R 1 , R 2 and R 3 are each independently an alkylene group which may have a fluorine atom, and R 1 If there are multiple R 1 may be the same or different from each other, Q 1 is an n1+n2-valent linking group, Q 2 is a 1+n trivalent linking group, Q 3 is a 1+n4-valent linking group, T 1 , T 2 and T 3 are each independently an adhesive group, and T 1 , T 2 or T 3 If there are multiple T 1 , T 2 or T 3 may be the same or different from each other, m1 and m8 each independently represent an integer of 0 to 210, and when there are multiple m1s, the m1s may be the same or different from each other; m2, m7, and m9 each independently represent 0 or 1, and when there are multiple m2s, the m2s may be the same or different from each other; m3 and m4 each independently represent 0 or 1, and m3 + m4 represents 1 or 2; (CHF) m3 -O-(CHF) m4 When there are a plurality of combinations of m3 and m4, the combinations of m3 and m4 may be the same or different from each other, m1+m2 is equal to or greater than 1, m7+m8+m9 is greater than or equal to 1, m5 and m6 each independently represent 0 or 1, and m5 + m6 represents 1 or 2; m10 and m11 each independently represent 0 or 1, and m10 + m11 represents 1 or 2; n1 is an integer from 1 to 10, n2, n3, and n4 each independently represent an integer of 1 to 20.

[0012] The compound has a polyfluoropolyether chain [R f O-(R f1 O) m1 -(R 1 ) m2 ] or [(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 ], an adhesive group [T], and a specific linking portion [-(CHF) p1 -O-(CHF) p2 -Q p3 ] (wherein p1 is m3, m6 or m10, p2 is m4, m5 or m11, and p3 is 1, 2 or 3). Compound (A1) is a compound having a structure of "n1 monovalent polyfluoropolyether chains-linking group-adhesive group", and compound (A2) is a compound having a structure of "adhesive group-linking group-divalent polyfluoropolyether chain-linking group-adhesive group".

[0013] The present compound has a polyfluoropolyether chain. The present compound having a polyfluoropolyether chain has excellent fingerprint stain removal properties on the surface layer. The present compound also has two or more adhesive groups at at least one end. The present compound having two or more adhesive groups at the end is strongly chemically bonded to the substrate, and therefore has excellent abrasion resistance on the surface layer. Furthermore, the present compound has a polyfluoropolyether chain and a linking group Q in the linking group. p3 The present inventors have found that the substituent -O-CHF- has at least one -O-CHF- between them. p3 The present invention was completed based on the discovery that the durability of this compound to the substrate surface is excellent by arranging the substituent adjacent to the substituent. Although the mechanism by which durability is improved by this substituent is still unclear, it is presumed that the hydrogen atom of -O-CHF- is positively charged compared to the hydrogen atom of -O-CH2- due to the action of the oxygen atom and fluorine atom. It is presumed that this hydrogen atom forms a hydrogen bond with the fluorine atom of -O-CHF- in an adjacent molecule, forming a hydrogen bond network such as FCH...FCH...FCH, thereby improving the adhesion of the film and achieving high durability. Note that "..." represents a hydrogen bond. Furthermore, when the substituent -O-CHF- is connected to the linking group Q, p3 By arranging the fluorocarbons adjacent to the polyfluoropolyether chain, the flexibility of the polyfluoropolyether chain after the surface layer is formed is maintained compared to when the fluorocarbons are arranged within the polyfluoropolyether chain, which is presumably why a surface layer with a large water contact angle can be obtained. Thus, the surface layer formed by the present compound has a large water contact angle, which allows for excellent removability of fingerprints and other stains, and is characterized by excellent durability in terms of abrasion resistance, chemical resistance, light resistance, and the like.

[0014] R f R is a fluoroalkyl group having 1 to 20 carbon atoms, which provides the surface layer with even better abrasion resistance and fingerprint removability. f The number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3, in order to further improve the abrasion resistance and fingerprint stain removability of the surface layer. R fThe fluoroalkyl group R is preferably a perfluoroalkyl group, since it provides the surface layer with even better abrasion resistance and fingerprint removability. f In the compound (A1) in which is a perfluoroalkyl group, the terminal is CF3-. The compound (A1) in which is a CF3- terminal can form a surface layer with low surface energy, and therefore the abrasion resistance and fingerprint removability of the surface layer are further improved. R f Examples of the fluoroalkyl group include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0015] (R f1 O) m1 and (R f2 O) m8 In order to further improve the abrasion resistance and fingerprint stain removability of the surface layer, f The structure represented by -1) is preferred. (R f11 O) k1 (R f12 O) k2 (R f13 O) k3 (R f14 O) k4 (R f15 O) k5 (R f16 O) k6 Formula (R f -1) however, R f11 is a fluoroalkylene group having one carbon atom, R f12 is a fluoroalkylene group having 2 carbon atoms, R f13 is a fluoroalkylene group having 3 carbon atoms, R f14 is a fluoroalkylene group having 4 carbon atoms, R f15 is a fluoroalkylene group having 5 carbon atoms, R f16 is a fluoroalkylene group having 6 carbon atoms, k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or 1 or more, and k1+k2+k3+k4+k5+k6 is an integer of 0 to 210; R f11 ~R f16 If there are multiple R f11 ~R f16 may be the same or different from each other. In addition, the formula (R f -1) in (R f11 O)~(R f16 O) may be bonded in any order. k1 to k6 in formula (R-1) are each f11 O)~(R f16 O), not the arrangement. For example, (R f15 O) k5 is (R f15 O) is k5, and (R f5 O) k5 It does not represent the block arrangement structure of (R f11 O)~(R f16 The order of the units does not represent the bonding order of the units.

[0016] The fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or may be a fluoroalkylene group having a branched or cyclic structure. R f11 Specific examples of R include CHF and CF2. f12 Specific examples of R include CF2CF2, CF2CHF, and CF2CH2. f13 Specific examples of R include CF2CF2CF2, CF2CF2CHF, CF2CHFCF2, CF2CF2CH2, CF2CH2CF2, and CF(CF3)CF2. f14 Specific examples of R include CF2CF2CF2CF2, CF2CF2CF2CH2, CHFCF2CF2CF2, CF2CH2CF2CF2, CF(CF3)CF2CF2, and perfluorocyclobutane-1,2-diyl group. f15Specific examples of R include CF2CF2CF2CF2CF2, CF2CF2CF2CF2CH2, CHFCF2CF2CF2CF2, and CF2CF2CH2CF2CF2. f16 Specific examples include CF2CF2CF2CF2CF2CF2, CF2CF2CF2CF2CF2CH2, and CF2CF2CF2CF2CF2CHF.

[0017] (R f1 O) m1 and (R f2 O) m8 It is preferable that at least a part of the compound has the following structure: {(OCF2) k11 (OCF2CF2) k12}, (OCF2CF2) k13 , (OCF2CF2CF2) k14 , (OCF2CF2-OCF2CF2CF2CF2) k15 , (OCF2CF2CF2) k16 (OCF2CF2) k17 , (OCF2CF2CF2CF2CF2) k16 (OCF2) k17 , (OCF2CF2CF2CF2CF2) k16 (OCF2CF2) k17 , (OCF2CF2CF2CF2CF2CF2) k16 (OCF2) k17 , (OCF2CF2CF2CF2CF2CF2) k16 (OCF2CF2) k17 , (OCF2CF2CF2CF2CF2CF2-OCF2) k18 , (OCF2CF2CF2CF2CF2-OCF2CF2) k18 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) k18 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2CF2) k18 , (OCF2-OCF2CF2CF2CF2CF2) k18 , (OCF2-OCF2CF2CF2CF2CF2CF2) k18 , (OCF2CF2-OCF2CF2CF2CF2CF2) k18 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) k18 , (OCF(CF3)CF2) k19 (OCF2CF(CF3)) k20 (OCF2CF2CF2) k21 (OCF2CF2) k22 . Here, k11, k12, k13, k14, k15, k16, k17, k18, k19, k20, k21, and k22 are integers of 1 or greater, and their upper limits are adjusted according to the upper limit of m1 or m8. Note that {(OCF2) k11 (OCF2CF2) k12} indicates that k11 (OCF2) and k12 (OCF2CF2) are randomly arranged.

[0018] m1 and m8 each independently represent 0 to 210. When m1 is 0, (R f1 O) m1 represents a single bond. Also, when m8 is 0 (R f2 O) m8 represents a single bond. m1 and m8 are preferably an integer of 1 to 210, more preferably an integer of 2 to 210, from the viewpoint of the water repellency of the resulting surface layer.

[0019] (R f1 O) m1 and (R f2 O) m8In particular, from the viewpoint of various properties of fluorinated ether compounds such as chemical resistance and low refractive index, the fluorination rate represented by the following mathematical formula (1) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., perfluoropolyether. Formula (1): Fluorination rate (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} × 100

[0020] R 1 , R 2 and R 3 R are each independently an alkylene group which may have a fluorine atom. 1 ~R 3 R is preferably a fluoroalkylene group, since it provides the surface layer with even better abrasion resistance and fingerprint removability. 1 ~R 3 The alkylene group in R is preferably a linear fluoroalkylene group. 1 ~R 3 The alkylene group preferably has 1 to 6 carbon atoms.

[0021] m2, m7, and m9 each independently represent 0 or 1. When m2 is 0, (R 1 ) m2 represents a single bond. When m7 is 0 (R 2 ) m7 represents a single bond. When m9 is 0, (R 3 ) m9 represents a single bond. In terms of ease of synthesis of the present compound, m2, m7 and m9 are preferably 1.

[0022] This compound has a linking moiety [-(CHF) p1 -O-(CHF) p2 -Q p3] (wherein p1 is m3, m6 or m10, p2 is m4, m5 or m11, and p3 is 1, 2 or 3). When p1+p2 is 1 or 2, the aforementioned hydrogen bond network can be formed. From the viewpoint of the water repellency and durability of the obtained surface layer, it is preferable that p1 (m3, m6 or m10) is 1. Furthermore, from the viewpoint of ease of synthesis of the present compound, it is preferable that p2 (m4, m5 or m11) is 0.

[0023] Q 1 is a n1+n2-valent linking group, which connects n2 adhesive groups to n1 polyfluoropolyether chains. 2 is a 1+n trivalent linking group, and Q 3 is a 1+n4 valent linking group, which connects n3 adhesive groups to one end of the polyfluoropolyether chain and n4 adhesive groups to the other end. 1 , Q 2 and Q 3 (These are collectively referred to as Q p3 When Q is a divalent linking group, p3 Q may be a single bond or a linear linking group. The linear linking group may be an alkylene group which may have a substituent. p3 The alkylene group in the formula (I) is preferably an alkylene group having a carbon number of 1 to 6. Examples of the substituent that the alkylene group may have include a fluorine atom and an alkyl group. Q p3 When is a trivalent or higher valent linking group, the linking group is a group having a branch point P. Examples of the branch point P include C, N, Si, a ring structure, and an organopolysiloxane residue.

[0024] From the viewpoints of ease of production of the present compound and durability of the surface layer formed from the present compound, the ring structure constituting the branching point is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and particularly preferably a ring structure shown in the following formula: The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (=O).

[0025] [ka]

[0026] Examples of organopolysiloxane residues that constitute branching points include the following groups: 5 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0027] [ka]

[0028] Q p3 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 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue. In terms of ease of production of the present compound, it is preferred to use -C(O)NR 6 -, -C(O)-, -NR 6At least one bond selected from the group consisting of - and -O- is preferred, and -C(O)NR is preferred in terms of excellent light resistance and chemical resistance of the surface layer. 6 - or -C(O)- is more preferred. 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, in terms of ease of production of the present compound.

[0029] Examples of the divalent organopolysiloxane residue include groups of the following formula: 7 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. R 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0030] [ka]

[0031] Q p3 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 divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0032] Q p3 As the group, a group represented by any one of the following formulae (Q1) to (Q7) is preferred in terms of ease of production of the present compound.

[0033] [ka] (-A 1 -)e1 C(R 22 ) 4-e1-e2 (-Q 22 -) e2 Formula (Q2) -A 2 -N(-Q 23 -)2 equation (Q3) (-A 3 -) h1 Z 1 (-Q 24 -) h2 Formula (Q4) (-A 2 -) i1 Si(R 23 ) 4-i1-i2 (-Q 25 -) i2 Formula (Q5) -A 1 -Q 26 - Formula (Q6) -A 1 -CH(-Q 22 -)-Si(R 23 ) 3-i3 (-Q 25 -) i3 Formula (Q7)

[0034] However, in formulas (Q1) to (Q7), A 1 , A 2 or A 3 The Q side is connected to the polyfluoropolyether chain side. 22 , Q 23 , Q 24 , Q 25 or Q 26 The adhesive side is T 1 , T 2 or T 3 Connect to A 1 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, A 2 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, A 3 is A 3 Z binds to 1 If the atom in is a carbon atom, then A 1 and A 3 Z binds to 1 If the atom in is a nitrogen atom, A 2 and Q 11 represents a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, Q 22 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 a group having - or -O-, and -C(O)NR at the end of the alkylene group not connected to the adhesive group T 26 -, -C(O)-, -NR 26 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O- and -C(O)NR at the end not connected to the adhesive group T 26 -, -C(O)-, -NR 26 - or -O-, and Q p3 Q 22 If there are two or more, there are two or more Q 22 may be the same or different from each other, Q 23 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, and two Q 23 may be the same or different from each other, Q 24 Q 24 Z binds to 1 If the atom in is a carbon atom, Q 22 and Q 24 Z binds to1 If the atom in is a nitrogen atom, Q 23 and Q p3 Q 24 If there are two or more, there are two or more Q 24 may be the same or different from each other, Q 25 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, and Q p3 Q 25 If there are two or more, there are two or more Q 25 may be the same or different from each other, Q 26 represents an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 26 -, -C(O)-, -NR 26 - or -O-, Z 1 is A 3 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having a (h1+h2)-valent ring structure having a carbon atom or a nitrogen atom to which is directly bonded, R 21 is a hydrogen atom or an alkyl group, and Q p3 R 21 If there are two or more, there are two or more R 21 may be the same or different from each other, R 22 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, and Q p3 R 22 If there are two or more, there are two or more R 22 may be the same or different from each other, R 23 is an alkyl group, and Q p3 R 23 If there are two or more, there are two or more R 23 may be the same or different from each other, R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1+d2 is an integer of 1 to 3; d3 is an integer of 0 to 3, d4 is an integer of 0 to 3, and d3+d4 is an integer of 1 to 3, d1+d3 is Q 1 is an integer between 1 and 5, and Q 2 and Q 3 is 1 in d2+d4 is an integer between 1 and 5 e1 is Q 1 is an integer between 1 and 3, and Q 2 and Q 3 is 1 in e2 is an integer from 1 to 3, e1+e2 is an integer from 2 to 4, h1 is Q 1 is an integer greater than or equal to 1, and Q 2 and Q 3 is 1 in h2 is an integer equal to or greater than 1, i1 is Q 1 is an integer between 1 and 3, and Q 2 and Q 3 is 1 in i2 is an integer from 1 to 3, i1+i2 is an integer from 2 to 4, i3 is an integer from 1 to 3.

[0035] Q 11 , Q 22 , Q 23 , Q 24 , Q 25 or Q 26 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of the present compound and further improvement in the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0036] Z 1Examples of the ring structure in the formula (I) include the ring structures described above, and the preferred forms are also the same.

[0037] R 21 , R 22 or R 23 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. R 22 The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. h1+h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, in terms of ease of production of the present compound and further improved abrasion resistance and fingerprint stain removability of the surface layer.

[0038] Q p3 Other examples of the group include groups represented by any of the following formulae (Q11) to (Q17).

[0039] [ka] (-A 1 -) e1 C(R 22 ) 4-e1-e2 (-Q 22 -G) e2 Formula (Q12) -A 2 -N(-Q 23 -G)2 formula (Q13) (-A 3 -) h1 Z 1 (-Q 24 -G) h2 Formula (Q14) (-A 2 -) i1 Si(R 23 ) 4-i1-i2 (-Q 25 -G) i2 Formula (Q15) -A 1 -Q 26 -G formula (Q16) -A1 -CH(-Q 22 -)-Si(R 23 ) 3-i3 (-Q 25 -G) i3 Formula (Q17)

[0040] However, in equations (Q11) to (Q17), A 1 , A 2 or A 3 The G side is connected to the polyfluoropolyether chain side, and the T side is the adhesive group. 1 , T 2 or T 3 G is a group represented by the following formula (G1), and Q p3 The two or more G's may be the same or different. The symbols other than G are the same as those in formulae (Q1) to (Q7). -Si(R 27 ) 3-j1 (-Q 27 -) j1 Formula (G1) However, in formula (G1), the Si side is Q 22 , Q 23 , Q 24 , Q 25 or Q 26 Connect to Q 27 The R side connects to the adhesive group T. 27 is an alkyl group. 27 is an alkylene group, an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 28 -, -C(O)-, -NR 28 - or a group having -O-, or -(OSi(R 29 )2) j2 -O- and 2 or more Q 27 may be the same or different. j1 is 2 or 3. R 28 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 29 is an alkyl group, a phenyl group, or an alkoxy group, and two R 29 may be the same or different. j2 is an integer of 0 to 5, and when j2 is 2 or more, 2 or more (OSi(R29 )2) may be the same or different from each other.

[0041] Q 27 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoints of ease of production of the present compound and further improvement in the abrasion resistance, light resistance, and chemical resistance of the surface layer. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 28 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. R 29 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. j2 is preferably 0 or 1.

[0042] T 1 , T 2 and T 3 (These may be collectively referred to as T) is a group that is arranged on the substrate surface side during the formation of the surface layer and exhibits adhesion to the substrate. T may form a chemical bond with the substrate surface, or may be chemically or physically adsorbed to the substrate surface. From the viewpoint of durability, it is preferable that T chemically bonds with the surface of the substrate.

[0043] Examples of the adhesive group T include a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphate group, a phosphonate group, an unsaturated hydrocarbon group, an aryl group, and a reactive silyl group, and it is preferable to select an appropriate group depending on the material of the substrate to which the adhesive group T is applied. The amino group in the adhesive group T is -NR 32 R 33 (R 32 , R 33 are each independently a hydrogen atom or an alkyl group), and from the viewpoint of durability of the surface layer, -NH2 is preferred. The phosphate group in the adhesive group T is -OP(=O)(OR34 )2(R 34 is a hydrogen atom or an alkyl group, and there are multiple R 34 may be the same or different), and among them, -OP(=O)(OH)2 is preferred from the viewpoint of durability of the surface layer. The phosphonic acid group in the adhesive group T is -P(=O)(OR 35 )2(R 35 is the above R 34 Among these, -P(=O)(OH)2 is preferred from the viewpoint of durability of the surface layer. Examples of the unsaturated hydrocarbon group in the adhesive group T include an acryloyl group, a methacryloyl group, and a vinyl group. Examples of the aryl group in the adhesive group T include a phenyl group, a naphthyl group, and an anthracenyl group. The reactive silyl group in the adhesive group T is -Si(R 31 ) 3-c (L 31 ) c Examples of the group include a group represented by the following formula: L 31 is a hydrolyzable group or a hydroxyl group, and the reactive silyl group is a group in which at least one of a hydrolyzable group and a hydroxyl group is bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group then undergoes a dehydration condensation reaction between molecules to form a Si-O-Si bond. The silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanate groups. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms. L 31Among these, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred. The hydrolyzable group is preferably an alkoxy group or a halogen atom in view of ease of production of the present compound. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred in view of less outgassing during coating and excellent storage stability of the present compound, an ethoxy group is particularly preferred when long-term storage stability of the present compound is required, and a methoxy group is particularly preferred when the reaction time after coating is short. R 31 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the present compound. c is preferably 2 or 3, more preferably 3, in that the adhesion between the surface layer and the substrate is stronger.

[0044] Suitable combinations of adhesive group T, substrate and material are exemplified in the form of "adhesive group T-substrate". Bromine atom-silicon nitride, hydrogen-terminated silicon nitride, Iodine atom-hydrogen terminated diamond, Hydroxyl-hydrogen terminated silicon, silicon halide, silicon oxide (SiO2), aluminum oxide (Al2O3), diamond-like carbon (DLC), Amino group-indium tin oxide (ITO), mica, Carboxylic acid-Al2O3, silver oxide (AgO), copper oxide (CuO), zirconium-modified aluminum oxide (Zr / Al2O3), amine-terminated oxide (NH2-terminated oxide), tin oxide (SnO2), Aldehyde group, epoxy group-hydrogen terminated silicon, halogenated silicon, Thiol group-gold (Au), Phosphate group, phosphonate group - zirconium oxide (ZrO2), titanium oxide (TiO2), Al2O3, tantalum oxide (Ta2O5), Zr / Al2O3, Unsaturated hydrocarbon group - hydrogen-terminated diamond, hydrogen-terminated silicon, silicon halide, silicon nitride, hydrogen-terminated silicon nitride, polyimide (PI), acrylic, Aryl groups - Al2O3, DLC, Reactive silyl groups - glass, Au, mica, SiO2, tin oxide (SnO2), germanium oxide (GeO2), ZrO2, TiO2, Al2O3, ITO, stainless steel (SUS), lead zirconate titanate (PZT). However, the present compound is not limited to these combinations, and can be used in combination with various substrates.

[0045] Specific examples of the present compound include compounds of the following formula: The compounds of the following formula are preferred because they are easy to produce industrially, easy to handle, and provide a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, light fastness, and chemical resistance, with the chemical resistance being particularly excellent.

[0046] [ka] [ka] [ka] n11 to n33 are integers from 0 to 210.

[0047] (Method for producing the present compound) Although the method for producing the present compound is not limited to the following method, the present compound can be obtained in high yield by the following production method. That is, the method for producing a fluorinated ether compound according to the present invention (hereinafter also referred to as the present production method) is a method for producing a fluorinated ether compound represented by formula (A1) or formula (A2), which comprises reacting a compound represented by formula (B1) or formula (B2) below with a compound represented by formula (C1) below. R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O)m8 -(R 3 ) m9 -CHO Formula (B2) (CH2=CH-) n5 -Q 4 (-OH) n6 Formula (C1) However, R f , R f1 , R f2 , R 1 , R 2 , R 3 , m1, m2, m7, m8, and m9 are the same as those in the compounds (A1) and (A2), and preferred embodiments are also the same. Q 4 is an n5+n6 valent linking group, n5 is an integer from 1 to 20, n6 is an integer from 1 to 10.

[0048] Q 4 is Q in compound (A1) 1 or Q in compound (A2) 2 or Q 3 In a preferred embodiment, the Q p3 is the same as: n5 is the moiety that corresponds to n2 in compound (A1) or n3 or n4 in compound (A2), and the same applies to preferred embodiments. n6 is the moiety that corresponds to n1 in compound (A1), and the same applies to the preferred embodiments. When compound (B2) is reacted with compound (C1), a compound in which n6 is 1 is selected. CH2=CH- in compound (C1) corresponds to the adhesive group T in compounds (A1) and (A2). If necessary, another adhesive group may be introduced by reacting with a compound having another adhesive group.

[0049] For example, when compound (B1) is reacted with compound (C1) where n6 is 1, R f O-(R f1 O) m1 -(R 1 ) m2-CH(OH)-OQ 4 -(CH=CH2) n5 By fluorinating the compound with a fluorinating agent, R f O-(R f1 O) m1 -(R 1 ) m2 -CHF-OQ 4 -(CH=CH2) n5 is obtained.

[0050] Examples of the fluorinating agent include bis(2-methoxyethyl)aminosulfur trifluoride, diethylaminosulfur trifluoride, perfluoro-1-butanesulfonyl fluoride, 1,1,2,2-tetrafluoro-N,N-dimethylethylamine, (diethylamino)difluorosulfonium tetrafluoroborate, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride, 2-chloro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazolium chloride-cesium fluoride, and pyridine-2-sulfonyl fluoride.

[0051] -(CH=CH2) n5 For example, when a reactive silyl group is introduced into the compound, the compound can be produced by a method of subjecting the compound to a hydrosilylation reaction with the following compound 3a. HSi(R 31 ) 3-c (L 31 ) c formula 3a However, the symbols in formula 3a are the same as those in the present compound, and the preferred embodiments are also the same. Compound 3a may be synthesized, or a commercially available product may be used.

[0052] The compounds (B1) and (B2) are novel compounds suitable for this production method. The production method for compounds (B1) and (B2) is not limited to the following method, but the following production method allows compounds (B1) and (B2) to be obtained in high yield. That is, the method for producing the compound (B1) or the compound (B2) according to the present invention is as follows: A compound represented by the following formula (D1) or (D2) is reacted with a silicon hydride compound HSi(R 16 )3 to obtain a compound represented by the following formula (E1) or (E2): From the compound represented by the following formula (E1) or formula (E2), Si(R 16 )3 to obtain a compound represented by the following formula (F1) or (F2): The method for producing a compound represented by the following formula (B1) or (B2) comprises heating a compound represented by the following formula (F1) or (F2). R f O-(R f1 O) m1 -(R 1 ) m2 -C(=O)OR 11 Formula (D1) R 11 OC(=O)-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -C(=O)OR 11 Formula (D2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 12 )2 formula (E1) (R 12 O)2CH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CH(OR 13 )2 formula (E2) R f O-(R f1 O) m1 -(R 1 ) m2 -CH(OR 14 )2 formula (F1) (R 14 O)2CH-(R 2 ) m7 -O-(R f2 O)m8 -(R 3 ) m9 -CH(OR 15 )2 formula (F2) R f O-(R f1 O) m1 -(R 1 ) m2 -CHO formula (B1) OHC-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO Formula (B2) where: R f , R f1 , R f2 , R 1 , R 2 , R 3 , m1, m2, m7, m8, and m9 are the same as those in the present compound, and preferred embodiments are also the same. R 11 is a hydrogen atom or an alkyl group which may have a substituent, and R 11 If there are multiple R 11 may be the same or different from each other, R 12 and R 13 are each independently Si(R 16 )3 or R 11 and there are multiple R 12 and R 13 At least one of each of 16 )3, R 14 and R 15 are each independently a hydrogen atom or R 11 and there are multiple R 14 and R 15 at least one of each is a hydrogen atom, R 16 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an alkoxy group, and there are multiple R 16 may be the same or different from each other.

[0053] R11 ~R 16 is a moiety that does not remain in compound (B1), compound (B2) or the present compound, and therefore may be appropriately selected in terms of reactivity and availability. R 11 The alkyl group in is preferably a methyl group or an ethyl group, and more preferably a methyl group from the viewpoint of reactivity. R 16 As the alkyl group, an alkyl group is preferable, and an ethyl group is more preferable.

[0054] Another method for producing the present compound is characterized by comprising a step of reacting a compound represented by the following formula (B3) or (B4) with a compound represented by the following formula (C2): R f O-(R f1 O) m1 -(R 1 ) m2 -OH formula (B3) OH-(R 2 ) m7 -O-(R f2 O) m8 -(R 3 ) m9 -CHO expression (B4) (CH2=CH-) n5 -Q 4 (-CHO) n6 Formula (C2) However, the symbols in the formula are the same as those in the compounds (B1), (B2) and (C1), and the preferred embodiments are also the same.

[0055] [Fluorine-containing ether composition] The fluorine-containing ether composition of the present invention (hereinafter also referred to as the present composition) is a composition containing the fluorine-containing compound of the present invention, fluorine-containing compounds other than the present compound, and at least one of the impurities described below. Examples of impurities include compounds that are unavoidable in the production of the present compound and other fluorine-containing compounds. Note that the present composition does not contain a liquid medium described below.

[0056] Examples of other fluorine-containing compounds include fluorine-containing compounds produced as by-products in the production process of the present compound (hereinafter also referred to as by-product fluorine-containing compounds), and known fluorine-containing compounds used for the same purposes as the present compound. As the other fluorine-containing compound, a compound which is unlikely to deteriorate the properties of the present compound is preferred. In order to fully exhibit the properties of the present compound, the content of the other fluorine-containing compound is preferably less than 50 mass %, more preferably less than 30 mass %, and even more preferably less than 10 mass % of the total amount of the present composition.

[0057] Examples of by-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the present compound. When the present composition contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound or reducing the amount of the by-product fluorine-containing compound can be simplified.

[0058] Known fluorine-containing compounds include, for example, those described in the following documents: perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 11-029585; Silicon-containing organic fluorine-containing polymers described in Japanese Patent No. 2874715; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097; perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772; Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887; Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2008-534696; Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936; Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, WO 2014 / 126064, and JP 2014-070163 A; Organosilicon compounds described in WO 2011 / 060047 and WO 2011 / 059430; fluorine-containing organosilane compounds described in WO 2012 / 064649; Fluorooxyalkylene group-containing polymers described in Japanese Patent Application Laid-Open No. 2012-72272; fluorine-containing ether compounds described in WO 2013 / 042732, WO 2013 / 121984, WO 2013 / 121985, WO 2013 / 121986, WO 2014 / 163004, JP 2014-080473 A, WO 2015 / 087902, WO 2017 / 038830, WO 2017 / 038832, and WO 2017 / 187775; perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017 / 022437 A, WO 2018 / 079743 A, and WO 2018 / 143433 A; fluoropolyether group-containing polymer-modified silanes described in 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. Commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Corporation, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

[0059] The proportion of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. When the present composition contains other fluorine-containing compounds, the proportion of the other fluorine-containing compounds relative to the total of the present compound and the other fluorine-containing compounds in the present composition is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. The total proportion of the present compound and other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more. When the content of this compound and other fluorine-containing compounds is within the above range, the surface layer has excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0060] [Coating liquid] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound or the present composition and a liquid medium. The present coating liquid may be in a liquid state, and may be a solution or a dispersion. The present coating liquid is only required to contain the present compound or the present composition, and may contain impurities such as by-products produced in the manufacturing process of the present compound. The concentration of the present compound or the present composition in the present coating liquid is preferably from 0.001 to 40% by mass, more preferably from 0.01 to 20% by mass, and even more preferably from 0.1 to 10% by mass.

[0061] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a mixture of both.

[0062] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Commercially available products include, for example, C6F 13 H (AGC Corporation, Asahiklin (registered trademark) AC-2000), C6F 13 Examples include C2H5 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (VERTREL (registered trademark) XF, manufactured by Chemours Corporation). Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Commercially available products include, for example, CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The non-fluorine-based organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, or a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. The present coating liquid preferably contains 75 to 99.999 mass % of the liquid medium, more preferably 85 to 99.99 mass %, and particularly preferably 90 to 99.9 mass %.

[0063] The present coating liquid may contain, in addition to the present compound or composition and the liquid medium, other components as long as the effects of the present invention are not impaired. Examples of other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. The content of other components in the present coating liquid is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0064] The total concentration of the present compound and other components or the total concentration of the present composition and other components in the present coating liquid (hereinafter also referred to as solids concentration) is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, even more preferably 0.01 to 10 mass%, and particularly preferably 0.01 to 1 mass%. The solids concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

[0065] [Goods] FIG. 1 is a schematic cross-sectional view showing an example of an article of the present invention. The first article of the present invention is an article 20 having a substrate 12, an underlayer 14, and a surface layer 22 in this order, The underlayer contains a silicon-containing oxide, and the surface layer contains a condensate of the present compound.

[0066] The material and shape of the substrate in the first article may be appropriately selected depending on the intended use of the article. Examples of the substrate material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. Substrates that require water and oil repellency in particular include touch panel substrates, display substrates, and materials constituting the housings of electronic devices. Touch panel substrates and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the touch panel substrate.

[0067] The substrate may be one that has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment on the surface on which the undercoat layer is to be formed. The surface that has been subjected to the surface treatment further improves the adhesion between the substrate and the undercoat layer, and as a result, the abrasion resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferred in terms of further improving the abrasion resistance of the surface layer.

[0068] The underlayer is a layer containing at least an oxide containing silicon, and may further contain other elements. When the underlayer contains silicon oxide, the partial structure (2) of the present compound undergoes dehydration condensation, forming Si-O-Si bonds between the underlayer and the underlayer, resulting in the formation of a surface layer with excellent wear resistance.

[0069] The silicon oxide content in the underlayer may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the silicon oxide content is equal to or greater than the lower limit of the above range, Si-O-Si bonds are sufficiently formed in the underlayer, and the mechanical properties of the underlayer are sufficiently ensured. The silicon oxide content is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of the underlayer.

[0070] From the viewpoint of durability of the surface layer, it is preferable that the oxide in the underlayer further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten, which strengthens the bond between the underlayer and the present compound and improves wear resistance.

[0071] When the underlayer contains one or more elements selected from iron, nickel, and chromium, the total content of these elements relative to silicon oxide is preferably 10 to 1100 ppm by mass, more preferably 50 to 1100 ppm by mass, still more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass. When the underlayer contains one or more elements selected from aluminum and zirconium, the total content thereof is preferably from 10 to 2500 ppm by mass, more preferably from 15 to 2000 ppm by mass, and even more preferably from 20 to 1000 ppm by mass. When the underlayer contains an alkali metal element, the total content thereof is preferably 0.05 to 15 mass %, more preferably 0.1 to 13 mass %, and even more preferably 1.0 to 10 mass %. Examples of the alkali metal element include lithium, sodium, potassium, rubidium, and cesium. When the underlayer contains a platinum group element, the total content thereof is preferably 0.02 mass ppm to 800 mass ppm, more preferably 0.04 mass ppm to 600 mass ppm, and even more preferably 0.7 mass ppm to 200 mass ppm. Examples of the platinum group element include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the underlayer contains one or more elements selected from boron and phosphorus, the total content thereof is, in terms of the abrasion resistance of the surface layer, preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, expressed as the ratio of the molar concentration of the sum of boron and phosphorus to the molar concentration of silicon. When the underlayer contains alkaline earth metal elements, the total content thereof, expressed as the ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, from the viewpoint of the abrasion resistance of the surface layer. Examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0072] From the viewpoint of improving the adhesiveness of the present compound and improving the water / oil repellency and abrasion resistance of the article, the underlayer is preferably a silicon oxide layer containing alkali metal atoms. In particular, in the silicon oxide layer, the average concentration of alkali metal atoms in a region 0.1 to 0.3 nm deep from the surface in contact with the surface layer is 2.0 × 10 19 atoms / cm 3 On the other hand, in order to ensure sufficient mechanical properties of the silicon oxide layer, the average concentration of the alkali metal atoms is preferably 4.0×10 or more. 22 atoms / cm 3 It is preferable that:

[0073] The thickness of the underlayer is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer is equal to or greater than the lower limit of the above range, the underlayer is likely to have a sufficient effect of improving adhesion. If the thickness of the underlayer is equal to or less than the upper limit of the above range, the abrasion resistance of the underlayer itself is increased. Methods for measuring the thickness of the underlayer include a method of observing the cross section of the underlayer using an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

[0074] The underlayer may be formed, for example, by depositing a deposition material having a desired composition for the underlayer on the surface of the substrate. An example of the vapor deposition method is vacuum deposition, in which a deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during vapor deposition (for example, the temperature of the boat where the vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 100 to 3000°C, particularly preferably 500 to 3000°C. The pressure during vapor deposition (for example, the absolute pressure in a tank in which a vapor deposition material is placed when a vacuum vapor deposition device is used) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less. When the underlayer is formed using a deposition material, one deposition material may be used, or two or more deposition materials containing different elements may be used. Examples of methods for evaporating the deposition material include a resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method in which the deposition material is irradiated with an electron beam to directly heat the deposition material, melting and evaporating the surface. The electron gun method is preferred as a method for evaporating the deposition material because it can evaporate high-melting-point substances due to its ability to heat locally, and because areas not irradiated by the electron beam are at low temperatures, there is no risk of reaction with the container or contamination with impurities. The deposition material used in the electron gun method is preferably a molten granular or sintered material because it is less likely to scatter even when an air current is generated.

[0075] The surface layer on the underlayer contains a condensate of the present compound. Condensates of the present compound include those in which hydrolyzable silyl groups in the present compound undergo hydrolysis to form silanol groups (Si-OH), which then undergo intermolecular condensation to form Si-O-Si bonds, and those in which silanol groups in the present compound undergo condensation with silanol groups or Si-OM groups (wherein M is an alkali metal element) on the surface of the underlayer to form Si-O-Si bonds. The surface layer may also contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer contains a fluorine-containing compound having reactive silyl groups in a state in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone condensation reaction.

[0076] The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit of the above range, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is equal to or less than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer is the thickness obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity analysis using an X-ray diffractometer for thin film analysis.

[0077] A second article of the present invention is an article 20 having a substrate 12 and a surface layer 22 in this order, the substrate contains an oxide containing silicon, The surface layer contains a condensate of the present compound.

[0078] In the second article, the substrate has the same composition as the undercoat layer in the first article, and therefore the surface layer has excellent abrasion resistance even when the surface layer is formed directly on the substrate. The material of the substrate in the second article may be any material having the composition of the underlayer, such as a glass substrate. Details of the material of the substrate are the same as those of the underlayer, and therefore a detailed description thereof will be omitted. Furthermore, the configuration of the surface layer is also the same as that of the first article, and therefore a detailed description thereof will be omitted.

[0079] [Production method] The method for producing an article according to the present invention is a method for forming a surface layer by a dry coating method or a wet coating method using the fluorine-containing compound, the fluorine-containing compound-containing composition, or the coating liquid.

[0080] The present compound and composition can be used directly in a dry coating method. The present compound and composition are suitable for forming a surface layer with excellent adhesion by a dry coating method. Dry coating methods include vacuum deposition, CVD, sputtering, and the like. The vacuum deposition method is suitable for use in terms of suppressing decomposition of the present compound and the simplicity of the equipment. For vacuum deposition, a pellet-shaped material in which the present compound is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-shaped material supporting the present compound can be produced by impregnating a porous metal body with a solution of the present compound and drying it to remove the liquid medium. The solution of the present compound can be the present coating liquid.

[0081] The coating liquid can be suitably used for wet coating methods such as spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0082] In order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be carried out as necessary. Such an operation includes heating, humidification, light irradiation, etc. For example, by heating the substrate on which the surface layer has been formed in a humid atmosphere, reactions such as the hydrolysis reaction of the hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of the silanol groups can be promoted. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed, for example, by pouring a solvent over the surface layer or wiping it off with a cloth soaked in the solvent. [Example]

[0083] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following, "%" means "% by mass" unless otherwise specified. Examples 1 to 4 and 8 to 11 are working examples, and Examples 5 to 7 and 12 to 14 are comparative examples.

[0084] [Synthesis Example 1: Synthesis of Compound (1)] Diethyldiallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.45 g), and dimethyl sulfoxide (263 g) were added and stirred at 160°C. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic phase, which was washed with saturated saline and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (1).

[0085] [ka]

[0086] NMR spectrum of compound (1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):(ddt,J=17.1,10.1,7.0Hz,2H),5.06~4.94(m,4H),4.09(q,J=7.1Hz,2H),2.47(ddd,J=14.0 ,8.0,6.1Hz,1H),2.33(dt,J=14.9,7.5Hz,2H),2.22(dt,J=14.1,6.5Hz,2H),1.21(t,J=7.1Hz,3H).

[0087] [Synthesis Example 2: Synthesis of Compound (2)] After adding THF (260 mL) and diisopropylamine (41.6 mL), the solution was cooled to -78°C. A hexane solution of n-butyllithium (2.76 M, 96.6 mL) was added, and the mixture was heated to 0°C. After stirring, the mixture was cooled to -78°C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (1) (39.5 g) was added to the THF solution, and after stirring, allyl bromide (24.1 mL) was added. The mixture was heated to 0°C, 1 M hydrochloric acid was added, and the THF was evaporated under reduced pressure. Extraction with dichloromethane was performed, followed by the addition of sodium sulfate. After filtration, the solvent was evaporated, and the mixture was subjected to flash column chromatography using silica gel to obtain 45.0 g of the following compound (2).

[0088] [ka]

[0089] NMR spectrum of compound (2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.74~5.62(m,3H),5.04(dd,J=13.6,1.9Hz,6H),4.10(q,J=7.1Hz,2H),2.29(d,J=7.4Hz,6H),1.22(t,J=7.1Hz,3H).

[0090] [Synthesis Example 3: Synthesis of Compound (3)] The above compound (2) (45.0 g) was dissolved in THF and cooled to 0°C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (3).

[0091] [ka]

[0092] NMR spectrum of compound (3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.76(m,3H),5.10~5.02(m,6H),3.38(s,2H),2.03(dt,J=7.5,1.2Hz,6H),1.45(s,1H).

[0093] [Synthesis Example 4: Synthesis of Compound (4)] The above compound (1) (8.4 g) was dissolved in THF and cooled to 0°C. A THF solution of lithium aluminum hydride (21 mL, 52 mmol) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 5.4 g of the following compound (4).

[0094] [ka]

[0095] NMR spectrum of compound (4); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.79 (m,2H),5.07~4.97(m,4H),3.55(t,J=5.5Hz,2H),2.10(m,4H),1.76~1.64(m,1H).

[0096] [Synthesis Example 5: Synthesis of Compound (5)] The above compound (4) (2.5 g) was dissolved in dichloromethane and cooled to 0 °C. Dess-Martin reagent (10 g) was added and stirred. After filtration, the solvent was distilled off and the mixture was subjected to flash column chromatography using silica gel to obtain 2.1 g of the following compound (5).

[0097] [ka] NMR spectrum of compound (5); 1H-NMR(400MHz,Chloroform-d) δ(ppm):9.65(d,J=1.9Hz,1H),5.74(m,2H),5.16~5.02(m,4H),2.53~2.34(m,3H),2.32~2.19(m,2H).

[0098] [Synthesis Example 6: Synthesis of Compound (6)] The above compound (5) (2.1 g) was dissolved in THF and cooled to 0°C. An ethyl ether solution of allylmagnesium bromide (30 ml, 21 mmol) was added and stirred. 1 M hydrochloric acid was added, and the THF was evaporated under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was evaporated, and flash column chromatography using silica gel was performed to obtain 1.8 g of the following compound (6).

[0099] [ka]

[0100] NMR spectrum of compound (6); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.89~5.72(m,3H),5.18~4.98(m,6H),3.66(s,1H),2.37~2.01(m,6H),1.71~1.57(m,1H).

[0101] [Synthesis Example 7: Synthesis of Compound (1-1)] According to the method described in Example 6 of WO 2013 / 121984, the following compound (1-1) was obtained. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x1 (CF2CF2O)-CF2CF2CF2-C(O)OCH3...Formula (1-1) Average number of units x 1: 14

[0102] [Synthesis Example 8: Synthesis of Compounds (1-2) and (1-3)] To the compound (1-1) (10.0 g), 1,3-bistrifluoromethylbenzene (10 g) was added, followed by the addition of triethylsilane (450 mg) and trispentafluorophenylborane (10 mg). After stirring at room temperature for 2 hours, the low-boiling components were distilled off to obtain 10.3 g of a mixture of the following compounds (1-2) and (1-3).

[0103] [ka] Average number of units x 1: 14

[0104] NMR spectrum of compound (1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.12~5.02(1H),3.46(s,3H),1.02~0.90(9H),0.75~0.58(6H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.32,-86.23,-87.56,-89.70,-124.15,-124.73.

[0105] NMR spectrum of compound (1-3); 1 H-NMR (400MHz, Chloroform-d) δ(ppm): 5.57~5.52(1H), 1.02~0.90(18H), 0.75~0.58(12H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.32,-86.23,-87.56,-89.70,-124.15,-124.73.

[0106] [Synthesis Example 9: Synthesis of Compounds (1-4) and (1-5)] To a mixture (5.0 g) of the above (1-2) and (1-3), 1,3-bistrifluoromethylbenzene (10 g) was added, followed by methanol (5.0 g) and concentrated sulfuric acid (2.5 g). After stirring at 60°C for 3 hours, the mixture was extracted with AC-6000. The solvent was distilled off to obtain 4.9 g of a mixture of the following compounds (1-4) and (1-5).

[0107] [ka] Average number of units x 1: 14

[0108] NMR spectrum of compound (1-4); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):4.89~4.73(1H),3.45(s,3H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.84,-82.31,-86.22,-87.54,-89.69,-124.70,-125.25,-128.63.

[0109] NMR spectrum of compound (1-5); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.34~5.21(1H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.84,-82.31,-86.22,-87.54,-89.69,-124.70,-125.25,-128.63.

[0110] [Synthesis Example 10: Synthesis of Compound (1-6)] A mixture (4.9 g) of the above (1-4) and (1-5) was placed in a vacuum constant temperature dryer and concentrated under reduced pressure at 100° C. for 16 hours to obtain 4.8 g of the following compound (1-6).

[0111] [ka] Average number of units x 1: 14

[0112] NMR spectrum of compound (1-6); 1 H-NMR(400MHz,Chloroform-d) δ(ppm): 9.42(t,J=3.3Hz,1H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.32,-86.24,-87.56,-89.68,-124.73,-125.27,-126.50.

[0113] [Synthesis Example 11: Synthesis of Compound (1-7)] 1,3-bistrifluoromethylbenzene (1.0 g) was added to the above compound (1-6) (1.0 g), followed by the above compound (3) (60 mg). After stirring at room temperature for 1 hour, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80°C and stirring for 1 hour, methanol was added and the mixture was extracted with AC-6000. The solvent was distilled off, and column chromatography using silica gel was performed to obtain 0.85 g of the following compound (1-7).

[0114] [ka] Average number of units x 1: 14

[0115] NMR spectrum of compound (1-7); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.83~5.67(3H),5.56~5.30(1H),5.14~4.96(6H),3.79~3.69(1H),3.43~3.34(1H),2.07~1.96(6H). 19F-NMR (376MHz, Chloroform-d) δ(ppm):-54.85,-82.32,-86.23,-87.56,-89.70,-124.73,-125.0,-125.21,-125.43,-125.98,-126.15,-141.30~-141.80.

[0116] [Example 1: Synthesis of fluorine-containing ether compound (1-8)] AC-6000 (1.0 g), the above compound (1-7) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (125 mg) were added and stirred at 40°C, and then the solvent was distilled off under reduced pressure, yielding 0.51 g of the following fluorine-containing ether compound (1-8).

[0117] [ka] Average number of units x 1: 14

[0118] NMR spectrum of compound (1-8); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.61~5.25(1H),3.80~3.68(1H),3.64~3.45(27H),3.44~3.31(1H),1.57~1.29(12H),0.75~0.47(6H). 19 F-NMR (376MHz, Chloroform-d) δ(ppm):-54.85,-82.32,-86.23,-87.56,-89.70,-124.73,-125.0,-125.21,-125.43,-125.98,-126.15,-141.30~-141.80.

[0119] [Synthesis Example 12: Synthesis of Compound (2-1)] To the above compound (1-6) (1.0 g), 1,3-bistrifluoromethylbenzene (1.0 g) was added, followed by 1,6-Heptadien-4-ol (40 mg). After stirring at room temperature for 5 hours, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80°C and stirring for 1 hour, methanol was added and the mixture was extracted with AC-6000. The solvent was distilled off, and column chromatography using silica gel was performed to obtain 0.65 g of the following compound (2-1).

[0120] [ka] Average number of units x 1: 14

[0121] NMR spectrum of compound (2-1); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.85~5.50(3H),5.13~4.93(4H),3.88~3.78(1H),2.42~2.19(4H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.33,-86.24,-87.57,-89.71,-124.74,-124.94,-125.18,-136.79~-137.11.

[0122] [Example 2: Synthesis of fluorine-containing ether compound (2-2)] AC-6000 (1.0 g), the above compound (2-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (83 mg) were added and stirred at 40°C, and then the solvent was distilled off under reduced pressure, thereby obtaining 0.5 g of the following fluorine-containing ether compound (2-2).

[0123] [ka] Average number of units x 1: 14

[0124] NMR spectrum of compound (2-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.77~5.51(1H),3.98~3.75(1H),3.65~3.43(18H),1.78~1.49(8H),0.88~0.71(4H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.33,-86.24,-87.57,-89.71,-124.74,-124.94,-125.18,-136.79~-137.11.

[0125] [Synthesis Example 13: Synthesis of Compound (3-1)] 1,3-bistrifluoromethylbenzene (1.0 g) was added to the above compound (1-6) (1.0 g), followed by the addition of the above compound (6) (60 mg). After stirring at room temperature for 72 hours, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80°C and stirring for 1 hour, methanol was added and the mixture was extracted with AC-6000. The solvent was distilled off, and column chromatography using silica gel was performed to obtain 0.55 g of the following compound (3-1).

[0126] [ka] Average number of units x 1: 14

[0127] NMR spectrum of compound (3-1); 1 H-NMR (400MHz, Chloroform-d) δ (ppm): 5.77~5.33 (4H), 5.08~4.62 (6H), 3.93~3.66 (1H), 2.36~1.46 (7H). 19F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-124.75,-125.26,-133.46~―133.84,-136.50~-136.89.

[0128] [Example 3: Synthesis of fluorine-containing ether compound (3-2)] AC-6000 (1.0 g), the above compound (3-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.3 mg), aniline (2.6 mg), and trimethoxysilane (125 mg) were added and stirred at 40°C, and then the solvent was distilled off under reduced pressure, yielding 0.51 g of the following fluorine-containing ether compound (3-2).

[0129] [ka] Average number of units x 1: 14

[0130] NMR spectrum of compound (3-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.80~5.50(1H),4.01~3.86(1H),3.78~3.30(27H),1.86~1.37(13H),0.85~0.45(6H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-124.75,-125.26,-133.46~-133.84,-136.50~-136.89.

[0131] [Synthesis Example 14: Synthesis of Compound (4-1)] To the compound (1-6) (1.0 g) was added 1,3-bistrifluoromethylbenzene (1.0 g), followed by the addition of allyl alcohol (20 mg). After stirring at room temperature for 1 hour, bis(2-methoxyethyl)aminosulfur trifluoride (300 mg) was added. After heating to 80°C and stirring for 1 hour, methanol was added and the mixture was extracted with AC-6000. The solvent was removed by distillation, and column chromatography using silica gel was performed to obtain 0.77 g of the following compound (4-1).

[0132] [ka]

[0133] NMR spectrum of compound (4-1); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.73(1H),5.68~5.43(1H),5.35~5.13(2H),4.41~4.13(2H) 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-124.67,-125.14~-125.29,-126.16,-142.64~-143.30

[0134] [Example 4: Synthesis of fluorine-containing ether compound (4-2)] AC-6000 (1.0 g), the above compound (4-1) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.0 mg), aniline (2.8 mg), and trimethoxysilane (50 mg) were added and stirred at 40°C, and then the solvent was distilled off under reduced pressure, thereby obtaining 0.51 g of the following fluorine-containing ether compound (4-2).

[0135] [ka]

[0136] NMR spectrum of compound (4-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.65~5.36(1H),3.77~3.39(13H),1.87~1.71(2H),0.76~0.63(2H) 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-124.67,-125.14~-125.29,-126.16,-142.64~-143.30

[0137] [Example 5: Synthesis of compound (5-1)] The following compound (5-1) was obtained according to the methods described in Synthesis Examples 1 to 3 of WO 2017 / 022437.

[0138] [ka] The average value of the number of repeating units x 2 is 21, and the average value of the number of repeating units x 3 is 19.

[0139] [Example 6: Synthesis of compound (6-1)] The following compound (6-1) was obtained according to the method described in Example 5 of WO 2017 / 038830.

[0140] [ka] The average value of the number of repeating units x 2 is 21, and the average value of the number of repeating units x 3 is 19.

[0141] [Synthesis of compound (7-1)] The following compound (7-1) was obtained according to the method described in Example 7 of WO 2013 / 121984. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) X1 (CF2CF2O)-CF2CF2CF2-CH2OH...Formula (7-1) Average number of units x 1: 14

[0142] [Synthesis of compound (7-2)] 1,3-bistrifluoromethylbenzene (1.0 g) was added to the above compound (7-1) (1.0 g), followed by the addition of cesium carbonate (5.0 g) and allyl bromide (200 mg). After stirring overnight at 60°C, hydrochloric acid was added for extraction. The solvent was distilled off, and column chromatography using silica gel was performed to obtain 0.83 g of the following compound (7-2).

[0143] [ka]

[0144] NMR spectrum of compound (7-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.85~5.69(1H),5.29~5.04(2H),4.08~3.98(2H),3.94~3.81(2H) 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-118.86,-124.67,-125.97

[0145] [Example 7: Synthesis of compound (7-3)] AC-6000 (1.0 g), the above compound (7-2) (0.5 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 8.0 mg), aniline (2.8 mg), and trimethoxysilane (50 mg) were added and stirred at 40°C, and then the solvent was distilled off under reduced pressure, thereby obtaining 0.51 g of the following fluorine-containing ether compound (7-3).

[0146] [ka]

[0147] NMR spectrum of compound (7-3); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):3.98~3.81(2H),3.65~3.47(11H),1.79~1.63(2H),0.73~0.59(2H) 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-54.85,-82.34,-86.24,-87.57,-89.70,-118.86,-124.67,-125.97

[0148] [Examples 8-14: Manufacture and evaluation of articles] Substrates were surface-treated using the compounds obtained in Examples 1 to 7, to obtain articles in Examples 8 to 14. The surface treatment method used in each example was the dry coating method or wet coating method described below. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following methods. The results are shown in Table 1.

[0149] (Dry coating method) Dry coating was carried out using a vacuum deposition apparatus (VTR350M, manufactured by ULVAC) (vacuum deposition method). 0.5 g of each compound was placed in a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 1 × 10 -3 The boat containing the compound was heated at a rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness meter exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached approximately 50 nm, the shutter was closed to terminate film formation on the surface of the substrate. The substrate on which the compound had been deposited was heat-treated at 200°C for 30 minutes and washed with dichloropentafluoropropane (AK-225, manufactured by AGC Corporation), yielding an article having a surface layer on the surface of the substrate.

[0150] (Evaluation method) <Contact angle measurement method> The contact angle of approximately 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., 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.

[0151] <Initial contact angle> The surface layer was measured for the initial water contact angle and the initial n-hexadecane contact angle by the above-mentioned measurement method. The evaluation criteria were as follows. Initial water contact angle: 〇 (Good): 115 degrees or higher. × (Not acceptable): Less than 115 degrees.

[0152] <Abrasion resistance (steel wool)> The surface layer was measured for its water contact angle using a reciprocating traverse tester (KNT Corporation) in accordance with JIS L0849:2013 (ISO 105-X12:2001) by rubbing steel wool Bonstar (#0000) back and forth 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min. The water contact angle was then measured using the method described above. The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to friction, and the more excellent the abrasion resistance. The evaluation criteria are as follows: ◎ (Excellent): The change in water contact angle after 10,000 reciprocating strokes is 4 degrees or less. ◯ (Good): The change in the water contact angle after 10,000 reciprocating strokes is more than 4 degrees and 8 degrees or less. × (unacceptable): The change in the water contact angle after 10,000 reciprocating strokes is more than 8 degrees.

[0153] <Light resistance> The surface layer was subjected to a tabletop xenon arc lamp accelerated light resistance test (product name: SUNTEST XLS+, manufactured by Toyo Seiki Co., Ltd.) at a black panel temperature of 63°C and exposed to light (650 W / m 2 After irradiating the film with light (300 to 700 nm) for 500 hours, the water contact angle was measured by the above method. The evaluation criteria are as follows. ⊚ (Excellent): The change in water contact angle after the accelerated light resistance test is 5 degrees or less. ◯ (Good): The change in water contact angle after the accelerated light resistance test is more than 5 degrees and 10 degrees or less. × (unacceptable): The change in water contact angle after the accelerated light resistance test is more than 10 degrees.

[0154] [Table 1]

[0155] As shown in Table 1, the articles of Examples 12 and 14, which used the compounds of Examples 5 and 7, also had good initial contact angles and light resistance, but a decrease in water contact angle was confirmed, especially after the friction test. Furthermore, the article using the compound of Example 6, in which the O-CHF group was located away from the adhesion group, had insufficient initial water repellency. On the other hand, the articles of Examples 8 to 11, which used the fluorine-containing ether compounds of Examples 1 to 4 having an O-CHF group at the linkage between the polyfluoropolyether chain and the adhesive group, showed suppressed reduction in water contact angle even after the friction test and light resistance test, demonstrating excellent durability. [Industrial Applicability]

[0156] Articles having a surface layer containing the present compound are useful as, for example, optical articles used as parts of the following products, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc. Products: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic light-emitting diode (OLED) displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0157] This application claims priority based on Japanese Patent Application No. 2020-102409, filed on June 12, 2020, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0158] 10: Base material with undercoat layer, 12: Base material, 14: Undercoat layer, 20: Article, 22: Surface layer

Claims

1. A fluorine-containing ether compound represented by the following formula (A1) or (A2): {R １ , ｎ１ , １ , ｎ２ O-(R ｆ１ O) ｍ１ -(R １ ) ｍ２ -(CHF) ｍ３ -O-(CHF) ｍ４} ｎ１ -Q １ (-T １ ) ｎ２ Formula (A1) (T ２ ) ｎ３ -Q ２ -(CHF) ｍ５ -O-(CHF) ｍ６ -(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ -(R ３ ) ｍ９ -(CHF) ｍ１０ -O-(CHF) ｍ１１ -Q ３ (-T ３ ) ｎ４ Formula (A2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, and R ｆ If there are multiple R ｆ may be the same or different from each other, R ｆ１ and R ｆ２ are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１ or R ｆ２ If there are multiple R ｆ１ or R ｆ２ may be the same or different from each other, R １ , R ２ and R ３ are each independently an alkylene group which may have a fluorine atom, and R １ If there are multiple R １ may be the same or different from each other, Q １ is an n1+n2-valent linking group, Q ２ is a 1+n3-valent linking group, Q ３ is a 1+n4-valent linking group, T １ , T ２ and T ３ are each independently an adhesive group, and T １ , T ２ or T ３ If there are multiple T １ , T ２ or T ３ may be the same or different from each other, m1 and m8 each independently represent an integer of 0 to 210, and when there are multiple m1s, the m1s may be the same or different from each other; m2, m7, and m9 each independently represent 0 or 1, and when there are multiple m2s, the m2s may be the same or different from each other, m3 and m4 each independently represent 0 or 1, and m3 + m4 represents 1 or 2; (CHF) ｍ３ —O—(CHF) ｍ４ When there are a plurality of combinations of m3 and m4, the combinations of m3 and m4 may be the same or different from each other, m1+m2 is 1 or more, m7+m8+m9 is 1 or more, m5 and m6 each independently represent 0 or 1, and m5 + m6 represents 1 or 2; m10 and m11 each independently represent 0 or 1, and m10 + m11 represents 1 or 2; n1 is an integer from 1 to 10, n2, n3 and n4 each independently represent an integer of 1 to 20.

2. The fluorine-containing ether compound according to claim 1, wherein m3, m6, or m10 is 1.

3. The fluorine-containing ether compound according to claim 1 or 2, wherein m4, m5 or m11 is 0.

4. A compound represented by the following formula (B1) or formula (B2): R ｆ O-(R ｆ１ O) ｍ１ - (R １ ) ｍ２ -CHO Formula (B1) OHC-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ - (R ３ ) ｍ９ -CHO Formula (B2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ and R ｆ２ are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１ or R ｆ２ If there are multiple R ｆ１ or R ｆ２ may be the same or different from each other, R １ , R ２ and R ３ each independently represents an alkylene group optionally having a fluorine atom, m1 and m8 each independently represent an integer of 0 to 210; m2, m7 and m9 each independently represent 0 or 1.

5. A method for producing a fluorinated ether compound, comprising reacting a compound represented by the following formula (B1) or (B2) with a compound represented by the following formula (C1): R ｆ O-(R ｆ１ O) ｍ１ - (R １ ) ｍ２ -CHO Formula (B1) OHC-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ - (R ３ ) ｍ９ -CHO Formula (B2) (CH ２ =CH−) ｎ５ −Q ４ (−OH) ｎ６ Formula (C1) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ and R ｆ２ are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１ or R ｆ２ If there are multiple R ｆ１ or R ｆ２ may be the same or different from each other, R １ , R ２ and R ３ each independently represents an alkylene group optionally having a fluorine atom, Q ４ is an n5+n6 valent linking group, m1 and m8 each independently represent an integer of 0 to 210; m2, m7, and m9 each independently represent 0 or 1; n5 is an integer from 1 to 20, n6 is an integer from 1 to 10.

6. A compound represented by the following formula (D1) or formula (D2) is reacted with a silicon hydride compound in the presence of a Lewis acid compound to obtain a compound represented by the following formula (E1) or formula (E2): From the compound represented by the following formula (E1) or formula (E2), Si(R １６ ) ３ to obtain a compound represented by the following formula (F1) or (F2): Heating a compound represented by the following formula (F1) or formula (F2): A method for producing a compound represented by the following formula (B1) or (B2): R ｆ O-(R ｆ１ O) ｍ１ -(R １ ) ｍ２ -C(=O)OR １１ Formula (D1) R １１ OC(=O)-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ -(R ３ ) ｍ９ -C(=O)OR １１ Formula (D2) R ｆ O-(R ｆ１ O) ｍ１ -(R １ ) ｍ２ -CH(OR １２ ) ２ Formula (E1) (R １２ O) ２ CH-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ -(R ３ ) ｍ９ -CH(OR １３ ) ２ Formula (E2) R ｆ O-(R ｆ１ O) ｍ１ -(R １ ) ｍ２ -CH(OR １４ ) ２ Formula (F1) (R １４ O) ２ CH-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ -(R ３ ) ｍ９ -CH(OR １５ ) ２ Formula (F2) R ｆ O-(R ｆ１ O) ｍ１ - (R １ ) ｍ２ -CHO Formula (B1) OHC-(R ２ ) ｍ７ -O-(R ｆ２ O) ｍ８ - (R ３ ) ｍ９ -CHO Formula (B2) however, R ｆ is a fluoroalkyl group having 1 to 20 carbon atoms, R ｆ１ and R ｆ２ are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１ or R ｆ２ If there are multiple R ｆ１ or R ｆ２ may be the same or different from each other, R １ , R ２ and R ３ each independently represents an alkylene group optionally having a fluorine atom, R １１ is a hydrogen atom or an alkyl group which may have a substituent, and R １１ If there are multiple R １１ may be the same or different from each other, R １２ and R １３ are each independently Si(R １６ ) ３ or R １１ where there are multiple R １２ and R １３ At least one of each is Si(R １６ ) ３ and R １４ and R １５ are each independently a hydrogen atom or R １１ where there are multiple R １４ and R １５ at least one of each is a hydrogen atom, R １６ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an alkoxy group, and there are a plurality of R １６ may be the same or different from each other, m1 and m8 each independently represent an integer of 0 to 210; m2, m7 and m9 each independently represent 0 or 1.

7. A fluorinated ether composition comprising one or more fluorinated ether compounds according to any one of claims 1 to 3 and other fluorinated ether compounds.

8. The fluorinated ether compound according to any one of claims 1 to 3 or the fluorinated ether composition according to claim 7, A coating liquid containing a liquid medium.

9. An article having a surface layer formed from the fluorinated ether compound according to any one of claims 1 to 3 or the fluorinated ether composition according to claim 7.

10. A method for producing an article, comprising forming a surface layer by a dry coating method or a wet coating method using the fluorinated ether compound according to any one of claims 1 to 3, the fluorinated ether composition according to claim 7, or the coating liquid according to claim 8.

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