Fluorine-containing ether compound and method of preparing the same, compound and method of preparing the same, fluorine-containing ether composition, coating solution, and article and method of preparing the same

Abstract

The present invention provides a fluorine-containing ether compound, a fluorine-containing ether composition, and a coating solution capable of forming a durable surface layer, and an article having a durable surface layer. It is a fluorine-containing ether compound represented by the following formula (A1) or formula (A2). However, each symbol in the formula is as described in the specification.

Description

Technology Field

[0001] The present invention relates to a fluorine-containing ether compound and a method for manufacturing the same, a novel compound suitable for manufacturing the fluorine-containing ether compound and a method for manufacturing the same, a fluorine-containing ether composition, a coating solution, and an article and a method for manufacturing the same. Background Technology

[0002] Fluorine-containing ether compounds having perfluoropolyether chains and hydrolyzable silyl groups are preferably used as surface treatment agents because they can form a surface layer on the surface of a substrate exhibiting high lubricity, water and oil repellency, etc. Surface treatment agents containing fluorine-containing ether compounds are used as surface treatment agents for applications where performance such as water and oil repellency is not easily reduced even when the surface layer is repeatedly rubbed by a finger (friction resistance) and performance such as fingerprints attached to the surface layer can be easily removed by wiping (fingerprint removal capability) is required to be maintained for a long period of time, for example, as components constituting the surface contacted by a finger of a touch panel, eyeglass lenses, and displays of wearable terminals.

[0003] Fluorine-containing ether compounds capable of forming a surface layer with excellent friction resistance and fingerprint stain removal properties on the surface of a substrate have been proposed, such as fluorine-containing ether compounds having a perfluoropolyether chain and a hydrolyzable silyl group (Patent Documents 1 to 2). Prior art literature

[0004] Japanese Published Patent Application No. 2015-196723 Japanese Published Patent Application No. 2016-204656 The problem to be solved

[0005] The above-mentioned surface treatment agent is required to be applicable not only to display surfaces of, for example, smartphones and tablet terminals, but also to surface treatments of various materials. Further improvement in the durability of the surface treatment agent is required.

[0006] The present invention aims to provide a fluorine-containing ether compound, a fluorine-containing ether composition, and a coating solution capable of forming a durable surface layer, and an article having a durable surface layer. means of solving the problem

[0007] The present invention provides a fluorine-containing ether compound having the compositions of [1] to

[15] below and a method for manufacturing the same, a compound and a method for manufacturing the same, a fluorine-containing composition, a coating solution, and an article and a method for manufacturing the same.

[0008] [1] Fluorine-containing ether compounds represented by the following formula (A1) or formula (A2).

[0009]

[0010]

[0011] step,

[0012] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0013] R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0014] R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0015] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different,

[0016] L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L1 It can be the same or different,

[0017] Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 It can be the same or different,

[0018] T is a close-contacting genitalia, and multiple T may be the same or different,

[0019] m is an integer from 0 to 210, and

[0020] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0021] [2] R 1 Fluorine-containing ether compounds described in [1], having 1 to 6 carbon atoms.

[0022] [3] R 2 Fluorine-containing ether compounds described in [1] or [2], having 1 to 10 carbon atoms.

[0023] [4] -Q 1 (-T) n This, -Q 2 [(-R 3 -T) a (-R 4 ) 3-a A fluorine-containing ether compound described in any one of [1] to [3].

[0024] step,

[0025] Q 2 is a carbon atom or a silicon atom, and Q 2 In cases where there are multiple Qs, the relevant Q 2 It can be the same or different,

[0026] R 3 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 3 In the case of multiple instances, the relevant R 3It can be the same or different,

[0027] R 4 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) b (-R 6 ) 3-b As ], R 4 In cases where there are multiple cases, the relevant R 4 It can be the same or different,

[0028] R 5 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 5 In cases where there are multiple cases, the relevant R 5 It can be the same or different,

[0029] R 6 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 5 -Q 2 [(-R 3 -T) c (-R 7 ) 3-c As ], R 6 In the case of multiple instances, the relevant R 6 It can be the same or different,

[0030] R 7 As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 7 In the case of multiple instances, the relevant R 7 It can be the same or different,

[0031] a is an integer from 0 to 3, and

[0032] b is an integer from 0 to 3, and if there are multiple b, the b may be the same or different, and

[0033] c is an integer from 0 to 3, and if there are multiple cs, said c may be the same or different, and

[0034] The sum of a, b, and c is n.

[0035] [5] R 3 Fluorine-containing ether compounds described in [4], having 2 to 7 carbon atoms.

[0036] [6] T, bromine atom, iodine atom, hydroxyl group, amino group, carboxyl group, aldehyde group, epoxy group, thiol group, phosphate group, phosphonic acid group, unsaturated hydrocarbon group, aryl group, and -Si(R 21 ) 3-d (L 21 ) d A fluorine-containing ether compound described in any one of [1] to [5], which is one or more selected from.

[0037] step,

[0038] R 21 It is an alkyl group, and

[0039] L 21 It is a hydrolytic group or a hydroxyl group, and L has multiple 21 It can be the same or different,

[0040] d is 2 or 3.

[0041] [7] A compound represented by the following formula (B1) or formula (B2).

[0042]

[0043]

[0044] step,

[0045] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0046] R f1Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0047] R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0048] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different,

[0049] L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different,

[0050] Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 It can be the same or different,

[0051] m is an integer from 0 to 210, and

[0052] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0053] [8] -Q 11 (-CH=CH2) n This, -Q 2 [(-R 23 -CH=CH2) a (-R 24 ) 3-a ] Compounds listed in [7].

[0054] step,

[0055] Q 2is a carbon atom or a silicon atom, and Q 2 In cases where there are multiple Qs, the relevant Q 2 It can be the same or different,

[0056] R 23 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 23 In the case of multiple instances, the relevant R 23 It can be the same or different,

[0057] R 24 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 25 -Q 2 [(-R 23 -CH=CH2) b (-R 26 ) 3-b As ], R 24 In cases where there are multiple cases, the relevant R 24 It can be the same or different,

[0058] R 25 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 25 In cases where there are multiple cases, the relevant R 25 It can be the same or different,

[0059] R 26 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 25 -Q 2 [(-R 23 -CH=CH2) c (-R 27 ) 3-c As ], R 26 In the case of multiple instances, the relevant R 26 It can be the same or different,

[0060] R 27As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 27 In the case of multiple instances, the relevant R 27 It can be the same or different,

[0061] a is an integer from 0 to 3, and

[0062] b is an integer from 0 to 3, and if there are multiple b, the b may be the same or different, and

[0063] c is an integer from 0 to 3, and if there are multiple cs, said c may be the same or different, and

[0064] The sum of a, b, and c is n.

[0065] [9] A method for preparing a compound represented by the following formula (B11) or formula (B12), having a process of reacting a compound represented by the following formula (C1) or formula (C2) with a compound represented by the following formula (D1).

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] step,

[0072] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0073] R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0074] R 1As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0075] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, R 11 Silver, as an alkyl group, R 11 In the case of multiple instances, the relevant R 11 It can be the same or different,

[0076] L 11 As -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, L 11 In the case of multiple instances, the relevant L 11 It can be the same or different,

[0077] Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 It can be the same or different,

[0078] X is a halogen atom, and

[0079] m is an integer from 0 to 210, and

[0080] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0081]

[10] A method for preparing a fluorine-containing ether compound represented by the following formula (A11) or formula (A12), having a process of introducing an adhesion group T into a compound represented by the following formula (B11) or formula (B12).

[0082]

[0083]

[0084]

[0085]

[0086] step,

[0087] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0088] R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0089] R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0090] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different,

[0091] L 11 As -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, L 11 In the case of multiple instances, the relevant L 11 It can be the same or different,

[0092] Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 It can be the same or different,

[0093] Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 It can be the same or different,

[0094] m is an integer from 0 to 210, and

[0095] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0096]

[11] A fluorine-containing ether composition containing a fluorine-containing ether compound represented by the following formula (A1) and a fluorine-containing ether compound represented by the following formula (A2).

[0097]

[0098]

[0099] step,

[0100] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0101] R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0102] R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0103] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different,

[0104] L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different,

[0105] Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 It can be the same or different,

[0106] T is a close-contacting genitalia, and multiple T may be the same or different,

[0107] m is an integer from 0 to 210, and

[0108] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0109]

[12] A fluorine-containing ether composition containing one or more of the fluorine-containing ether compounds described in any one of [1] to [6] and other fluorine-containing ether compounds.

[0110]

[13] A fluorine-containing ether compound described in any one of [1] to [6], or a fluorine-containing ether composition described in

[11] or

[12] , and

[0111] A coating solution containing a liquid medium.

[0112]

[14] An article having a surface layer formed of a fluorine-containing ether compound described in any one of [1] to [6], or a fluorine-containing ether composition described in

[11] or

[12] on the surface of the article.

[0113]

[15] A method of manufacturing an article by forming a surface layer by a dry coating method or a wet coating method using a fluorine-containing ether compound described in any one of [1] to [6], a fluorine-containing ether composition described in

[11] or

[12] , or a coating solution described in

[13] . Effects of the invention

[0114] The present invention provides a fluorine-containing ether compound capable of forming a durable surface layer, a fluorine-containing ether composition and a coating solution, an article having a durable surface layer, and a compound useful as a raw material for the fluorine-containing ether compound. Specific details for implementing the invention

[0115] In this specification, a compound represented by formula (A1) is described as compound (A1). Compounds represented by other formulas are also described as such.

[0116] The meanings of the following terms in this specification are as follows.

[0117] "Reactive silyl group" is a general term for hydrolyzable silyl groups and silanol groups (Si-OH). Reactive silyl groups are, for example, T in Formula (A1) or Formula (A2), i.e., -Si(R) 3-c (L) c am.

[0118] "Hydrolytic silyl group" means a group that can form a silanol group through a hydrolysis reaction.

[0119] "Surface layer" means a layer formed on the surface of a substrate.

[0120] In the case where the fluorine-containing ether compound is a mixture of multiple fluorine-containing ether compounds having different chain lengths of polyfluoropolyether chains, 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.

[0121] In the case where the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is a single length, the "molecular weight" of the polyfluoropolyether chain is, 1 H-NMR and 19 R by F-NMR f It is the molecular weight calculated by determining the structure.

[0122] The "∼" indicating a numerical range means that the values ​​listed before and after it are included as lower and upper limits.

[0123] [Fluoride-containing ether compounds]

[0124] 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).

[0125]

[0126]

[0127] step,

[0128] R f is a fluoroalkyl group having 1 to 20 carbon atoms, and

[0129] R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different,

[0130] R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different,

[0131] R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different,

[0132] L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different,

[0133] Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 It can be the same or different,

[0134] T is a close-contacting genitalia, and multiple T may be the same or different,

[0135] m is an integer from 0 to 210, and

[0136] n is an integer from 2 to 20, and if there are multiple n, the n may be the same or different.

[0137] The above-mentioned compound is a polyfluoropolyether chain [R f -O-(R f1 O) m -R 1 ] or [O-(R f1 O) m -R 1 ] and, an admixture [T] and a specific linker [-L connecting the polyfluoropolyether chain and the admixture 1 -R 2 -Q 1 ] has.

[0138] Compound (A1) is a compound having the structure of a “monovalent polyfluoropolyether chain-linker-adhesive group”, and compound (A2) is a compound having the structure of an “adhesive group-linker-divalent polyfluoropolyether chain-linker-adhesive group”.

[0139] The present compound has a polyfluoropolyether chain. The present compound having a polyfluoropolyether chain exhibits excellent fingerprint stain removal properties on the surface layer. Furthermore, the present compound has two or more adhesion groups at at least one end. Since the present compound having two or more adhesion groups at the end forms a strong chemical bond with the substrate, the surface layer exhibits excellent abrasion resistance. Additionally, the present compound, in the above linker, has a polyfluoropolyether chain and a Q having a branched structure. 1 L between 1 , that is, having -CH(OH)-, -C(=O)-, or -CH=CH-. The inventors have the said substituent L 1By possessing [ ], it was discovered that the present compound exhibits excellent durability on the substrate surface, thereby completing the present invention. Although there are still aspects regarding the mechanism by which durability is enhanced by the said substituent that have not yet been elucidated, when the present compound is applied to the substrate surface, said L 1 It is presumed that the interaction between them facilitates the alignment of this compound on the surface layer, and as a result, durability is improved. Also, L 1 Q between the close-contact penis T 1 By interposing, L that can occur through combination 1 It is presumed that the intramolecular reaction of and T is suppressed, and the adhesion group T contributes sufficiently to the adhesion to the substrate.

[0140] As such, the surface layer formed by the present compound has excellent durability, such as friction resistance, chemical resistance, and light resistance, and is characterized by particularly excellent friction resistance.

[0141] R f Since it is a fluoroalkyl group having 1 to 20 carbon atoms, the abrasion resistance and fingerprint stain removal properties of the surface layer are even superior. R f The number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3, in that the friction resistance and fingerprint stain removal properties of the surface layer are more excellent.

[0142] R f As for the fluoroalkyl group, a perfluoroalkyl group is preferred due to its superior abrasion resistance and fingerprint stain removal properties of the surface layer. R f Compound 1A, in which the α is a perfluoroalkyl group, has a CF3- terminal. According to Compound 1A, which has a CF3- terminal, a surface layer with low surface energy can be formed, so the friction resistance and fingerprint removal properties of the surface layer are superior.

[0143] R fExamples of fluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-.

[0144] (R f1 O) m As such, given that the surface layer has superior abrasion resistance and fingerprint stain removal properties, the following formula (R f1 A structure represented as -1) is desirable.

[0145]

[0146] step,

[0147] R f11 It is a fluoroalkylene group having 1 carbon atom, and

[0148] R f12 is a fluoroalkylene group having 2 carbon atoms, and

[0149] R f13 It is a fluoroalkylene group having 3 carbon atoms, and

[0150] R f14 is a fluoroalkylene group having 4 carbon atoms, and

[0151] R f15 is a fluoroalkylene group having 5 carbon atoms, and

[0152] R f16 It is a fluoroalkylene group having 6 carbon atoms, and

[0153] m1, m2, m3, m4, m5, and m6 each independently represent an integer greater than or equal to 0 or 1, and m1 + m2 + m3 + m4 + m5 + m6 is an integer from 1 to 210, and R f11 ~ R f16 In the case of this multiple, the R with the said multiple f11 ~ R f16 It may be the same or different.

[0154] Also, Equation (R f1 (R in -1) f11O) ∼ (R f16 The order of combination of O) is arbitrary. Equation (R f1 -1) m1 ~ m6 are, respectively, (R f11 O) ∼ (R f16 It indicates the number of O), not the arrangement. For example, (R f15 O) m5 is, (R f15 O) indicates that the number of is m5, and (R f5 O) m5 It does not represent the block layout structure of. Likewise, (R f11 O) ∼ (R f16 The order of listing in O) does not indicate the order of combination of each unit.

[0155] Also, the fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or a branched or ring-shaped fluoroalkylene group.

[0156] R f11 Specific examples of this include CHF and CF2. R f12 Specific examples of CF2CF2, CF2CHF, CF2CH2, etc. R f13 Specific examples of include CF2CF2CF2, CF2CF2CHF, CF2CHFCF2, CF2CF2CH2, CF2CH2CF2, CF(CF3)CF2, etc. R f14 Specific examples of include CF2CF2CF2CF2, CF2CF2CF2CH2, CHFCF2CF2CF2, CF2CH2CF2CF2, CF(CF3)CF2CF2, perfluorocyclobutane-1,2-diyl group, etc. R f15 Specific examples of include CF2CF2CF2CF2CF2, CF2CF2CF2CF2CH2, CHFCF2CF2CF2CF2, CF2CF2CH2CF2CF2, etc. R f16Specific examples of the above include CF2CF2CF2CF2CF2CF2, CF2CF2CF2CF2CF2CH2, CF2CF2CF2CF2CF2CF2CHF, etc.

[0157] R 1 It is an alkylene group that may contain silver and fluorine atoms. R 1 Fluoroalkylene groups are preferred in that the surface layer exhibits superior abrasion resistance and fingerprint stain removal properties. R 1 The alkylene group is preferably a straight-chain fluoroalkylene group. Also, R 1 The number of carbon atoms in the alkylene group is preferably 1 to 6.

[0158] R 2 is an alkylene group that may have a single bond or a fluorine atom. R 2 If it is a single bond, L 1 -R 2 -Q 1 y L 1 -Q 1 It can also be expressed as R 2 A single bond or an alkylene group is preferred from the perspective of the synthesis of the present compound. R 2 The alkylene group is preferably a straight-chain fluoroalkylene group. Also, R 2 The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 6.

[0159] Among them, L 1 In the case where this is -CH(OH)-, -C(=O)-, from the perspective of the synthesis of the present compound, R 2 A single bond or an alkylene group having 1 to 10 carbon atoms is preferred, and a single bond or an alkylene group having 1 to 6 carbon atoms is more preferred. Also, L 1 In the case where this is -CH=CH-, from the perspective of the synthesis of the present compound, R 2 A single bond or an alkylene group having 1 to 9 carbon atoms is preferred, and a single bond or an alkylene group having 1 to 5 carbon atoms is more preferred.

[0160] L 1The silver is -CH(OH)-, -C(=O)-, or -CH=CH-, and the durability of the surface layer using this compound is improved.

[0161] Q 1 is a linker of 1 + n and connects n close groups to the polyfluoropolyether chain. Q 1 It is a group having a branching point, and examples of such branching points include tertiary carbon atoms, quaternary carbon atoms, silicon atoms, and ring structures.

[0162] Examples of ring structures constituting the branching point include aliphatic rings of 3 to 8 members, aromatic rings of 6 to 8 members, heterocyclic rings of 3 to 8 members, and condensation rings composed of two or more of these rings, in terms of ease of manufacturing the compound and durability such as friction resistance, chemical resistance, and light resistance of the surface layer. In terms of durability such as friction resistance, chemical resistance, and light resistance of the surface layer, ring structures selected from aliphatic rings of 3 to 8 members, aromatic rings of 6 to 8 members, and condensation rings are preferred. Examples of ring structures constituting the branching point include ring structures shown in the following formula. The following ring structures may be substituted with fluorine atoms. Additionally, as substituents, the ring structures may have alkyl groups, cycloalkyl groups, alkenyl groups, allyl groups, etc., which may have halogen atoms.

[0163] [Chemical Formula 1]

[0164]

[0165] Q in this compound 1 The branching point constituting the compound is preferably a tertiary carbon atom, a quaternary carbon atom, or a silicon atom in terms of ease of synthesis of the compound and durability of the surface layer. Among these, in terms of ease of synthesis and durability of the surface layer, -Q 1 (-T) n This, -Q 2 [(-R3 -T) a (-R 4 ) 3-a It is desirable to have a structure represented as ].

[0166] step,

[0167] Q 2 is a carbon atom or a silicon atom, and Q 2 In cases where there are multiple Qs, the relevant Q 2 It can be the same or different,

[0168] R 3 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 3 In the case of multiple instances, the relevant R 3 It can be the same or different,

[0169] R 4 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) b (-R 6 ) 3-b As ], R 4 In cases where there are multiple cases, the relevant R 4 It can be the same or different,

[0170] R 5 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 5 In cases where there are multiple cases, the relevant R 5 It can be the same or different,

[0171] R 6 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 5 -Q 2 [(-R 3 -T) c (-R7 ) 3-c As ], R 6 In the case of multiple instances, the relevant R 6 It can be the same or different,

[0172] R 7 As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 7 In the case of multiple instances, the relevant R 7 It can be the same or different,

[0173] a is an integer from 0 to 3, and

[0174] b is an integer from 0 to 3, and if there are multiple b, the b may be the same or different, and

[0175] c is an integer from 0 to 3, and if there are multiple cs, said c may be the same or different, and

[0176] The sum of a, b, and c is n.

[0177] Above Q 2 represents a carbon or silicon atom that serves as a branching point.

[0178] R 3 In the case of this single bond, the close bond T is Q 2 Directly coupled to, Q 2 It can also be expressed as -T. R 3 In terms of ease of synthesis, an alkylene group that may have fluorine atoms having 2 to 10 carbon atoms and ether bonds between carbon atoms is preferred.

[0179] R 4 , R 6 and R 7 Examples of alkyl groups include alkyl groups that may have fluorine atoms having 1 to 6 carbon atoms and ether bonds between carbon atoms.

[0180] R 5As for the alkylene group, it is preferable to have a fluorine atom having 2 to 10 carbon atoms and an ether bond between carbon atoms.

[0181] Examples of alkyl groups include alkyl groups that may have fluorine atoms having 1 to 6 carbon atoms and ether bonds between carbon atoms.

[0182] a, b, and c are each independently integers from 0 to 3, and the sum of a, b, and c is n. If there are multiple b and c, the sum of the multiple b and c and a is n. n is an integer from 2 to 20, and 2 to 10 is preferred.

[0183] T is a group that is positioned 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, etc., or may chemically adsorb or physically adsorb onto the substrate surface. In terms of durability, it is preferable for T to chemically bond with the substrate surface.

[0184] As for the cohesive group T, bromine atom, iodine atom, hydroxyl group, amino group, carboxyl group, aldehyde group, epoxy group, thiol group, phosphate group, phosphonic acid group, unsaturated hydrocarbon group, aryl group, -Si(R 21 ) 3-d (L 21 ) d Examples include the above, and it is advisable to select appropriately depending on the material of the applied material.

[0185] As for the amino group in the adhesion group T, -NR 8 R 9 (R 8 , R 9 Each can independently include a hydrogen atom or an alkyl group, and in terms of the durability of the surface layer, -NH2 is preferred among them.

[0186] As for the phosphate group in the close group T, -OP(=O)(OR 10 )2(R10 R, which has multiple hydrogen atoms or alkyl groups. 10 (It may be the same or different) and in terms of the durability of the surface layer, -OP(=O)(OH)2 is preferred among them.

[0187] As for the phosphonic acid group in the adhesion group T, -P(=O)(OR 10 )2(R 10 (It is the same as above) and in terms of the durability of the surface layer, -P(=O)(OH)2 is preferred among them.

[0188] Examples of unsaturated hydrocarbon groups in the adhesive group T include acryloyl groups, methacryloyl groups, vinyl groups, etc.

[0189] Examples of aryl groups in the adhesive group T include phenyl groups, naphthyl groups, anthracenyl groups, etc.

[0190] Also, -Si(R in the adhesion group T 21 ) 3-d (L 21 ) d represents a reactive silyl group.

[0191] A reactive silyl group is a group in which either or both of a hydrolytic group and a hydroxyl group are bonded to a silicon atom.

[0192] A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between molecules to form Si-O-Si bonds. In addition, the silanol group 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).

[0193] Examples of hydrolytic groups include alkoxy groups, halogen atoms, acyl groups, and isocyanate groups. As for the alkoxy groups, alkoxy groups having 1 to 6 carbon atoms are preferred.

[0194] As for the halogen atom, chlorine atoms are preferred.

[0195] As for the hydrolytic group, an alkoxy group or a halogen atom is preferred in that it is easy to manufacture the present compound. As for the hydrolytic group, an alkoxy group having 1 to 4 carbon atoms is preferred in that there is little outgassing during coating and the storage stability of the present compound is excellent; 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.

[0196] R 21 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2, in terms of ease of preparing the compound.

[0197] d is preferably 2 or 3, and more preferably 3, in that the adhesion between the surface layer and the substrate becomes stronger.

[0198] A desirable combination of the adhesive T and the substrate and material is exemplified in the form of "adhesive T-substrate".

[0199] Bromine atom-silicon nitride, hydrogen-terminated silicon nitride,

[0200] Iodine atom-hydrogen termination diamond,

[0201] Hydroxyl-hydrogen terminated silicon, silicon halide, silicon oxide (SiO2), aluminum oxide (Al2O3), diamond-like carbon (DLC),

[0202] Amino group-Indium Tin Oxide (ITO), Mica,

[0203] Carboxyl-Al2O3, silver oxide (AgO), copper oxide (CuO), zirconium-modified aluminum oxide (Zr / Al2O3), amine-terminated oxide (NH2-terminated oxide), tin oxide (SnO2),

[0204] Aldehyde group, epoxy group-hydrogen terminated silicon, halogenated silicon,

[0205] Thiol group-gold (Au),

[0206] Phosphate group, phosphonic acid group-zirconium oxide (ZrO2), titanium oxide (TiO2), Al2O3, tantalum oxide (Ta2O5), Zr / Al2O3,

[0207] Unsaturated hydrocarbon-hydrogen-terminated diamond, hydrogen-terminated silicon, silicon halide, silicon nitride, hydrogen-terminated silicon nitride, polyimide (PI), acrylic,

[0208] Arylgi-Al2O3, DLC,

[0209] Reactive silyl glass, Au, mica, SiO2, tin oxide (SnO2), germanium oxide (GeO2), ZrO2, TiO2, Al2O3, ITO, stainless steel (SUS), lead zirconate titanate (PZT).

[0210] However, the present compound is not limited to these combinations and can be used in combination with various materials.

[0211] Examples of the present compound include, for instance, a compound of the following formula. The compound of the following formula is easy to manufacture industrially and easy to handle, and exhibits superior water and oil repellency, friction resistance, fingerprint stain removal properties, lubricity, chemical resistance, light resistance, and chemical resistance of the surface layer. Furthermore, regarding durability, it is preferable that the weight average molecular weight (Mw) / number average molecular weight (Mn) of the present compound be 1.2 or less.

[0212] [Chemical Formula 2]

[0213]

[0214] n1 to n5 are adjusted so that m in Equation (A1) or Equation (A2) becomes 0 to 210.

[0215] [Compounds represented by the following formula (B1) or formula (B2)]

[0216] The following compounds (B1) and (B2) are compounds in which the adhesive group T in the above compounds corresponds to an unsaturated hydrocarbon group, and are also compounds useful for synthesizing the above compounds (A1) and (A2).

[0217]

[0218]

[0219] step,

[0220] R f , R f1 , R 1 , R 2 , L 1 , m and n are the same as those in the above formulas (A1) and (A2), and the preferred mode is also the same.

[0221] If (-CH=CH2) in equations (B1) and (B2) is the adhesion group T, then Q 11 is Q in the above equations (A1) and (A2). 1 It is identical to. Also, if another adhesion group T is introduced into compound (B1) or compound (B2), Q 11 (-CH=CH2) is, after the reaction Q 1 It is a connector of 1 + n.

[0222] In compounds (B1) and (B2), -Q 11 (-CH=CH2) n This, -Q 2 [(-R 23 -CH=CH2) a (-R 24 ) 3-a It is desirable that ]

[0223] step,

[0224] Q 2 , a, b, and c are identical to those in the above compounds (A1) and (A2), and the preferred embodiments are also identical, and

[0225] R23 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 23 In the case of multiple instances, the relevant R 23 It can be the same or different,

[0226] R 24 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 25 -Q 2 [(-R 23 -CH=CH2) b (-R 26 ) 3-b As ], R 24 In cases where there are multiple cases, the relevant R 24 It can be the same or different,

[0227] R 25 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 25 In cases where there are multiple cases, the relevant R 25 It can be the same or different,

[0228] R 26 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 25 -Q 2 [(-R 23 -CH=CH2) c (-R 27 ) 3-c As ], R 26 In the case of multiple instances, the relevant R 26 It can be the same or different,

[0229] R 27 As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 27 In the case of multiple instances, the relevant R 27It may be the same or different.

[0230] R 23 -CH=CH2 is R in the above compounds (A1) and (A2) after the introduction of the adhesion group. 3 This is the process.

[0231] Also, R 24 , R 25 , R 26 , and R 27 R in the above compounds (A1) and (A2) after the introduction of the adhesion group 4 , R 5 , R 6 , and R 7 This is the process.

[0232] Examples of compounds (B1) and (B2) include compounds of the following formula.

[0233] [Chemical Formula 3]

[0234]

[0235] n6 to n10 are adjusted so that m in Equation (B1) or Equation (B2) becomes 0 to 210.

[0236] (Method for preparing compounds (B1), compounds (B2), etc.)

[0237] As a method for preparing compounds (B11) and (B12) comprising the above compounds (B1) and (B2), a method for preparing compounds may be provided, comprising a process of reacting a compound represented by the following formula (C1) or formula (C2) with a compound represented by the following formula (D1).

[0238]

[0239]

[0240]

[0241]

[0242]

[0243] step,

[0244] R f , R f1 , R 1 , R 2 , Q 11 , m, and n are as described above, and the preferred mode is also the same.

[0245] R 11 Silver is a separator, an alkyl group is preferred, and a methyl group is more preferred. R 11 In the case of multiple instances, the relevant R 11 It may be the same or different.

[0246] L 11 As -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, L 11 In the case of multiple instances, the relevant L 11 It can be the same or different,

[0247] X is a halogen atom, and is preferably a chlorine atom, a bromine atom, or an iodine atom.

[0248] In addition, compounds (B11) and (B12) are L of compounds (B1) and compounds (B2). 1 The part corresponding to (L 11 The only difference is that ) can be -CH2-.

[0249] For example, with respect to an ester of compound (C1) or (C2), by reacting 2 equivalents of compound (D1) and acid treating, L 11 A compound (B11) or (B12) having -CH(OH)- or -C(=O)- is obtained. In the above reaction, as the reaction time is prolonged, L 11 This -CH(OH)- compound is predominantly produced.

[0250] The above L 11 By oxidizing this -CH(OH)- compound (B11) or (B12), L 11A compound (B11) or (B12) that is -C(=O)- is obtained. As the oxidizing agent in the oxidation reaction, known oxidizing agents such as Desmartin reagent may be used.

[0251] Meanwhile, the above L 11 By reducing this -C(=O)- compound (B11) or (B12), L 11 A compound (B11) or (B12) that is -CH(OH)- is obtained. As the reducing agent in the said reduction reaction, known reducing agents such as lithium aluminum hydride may be used.

[0252] The above L 11 By dehydrating the -CH(OH)- compound (B11) or (B12) using triphenylphosphine, etc., L 11 A compound (B11) or (B12) that is -CH=CH- is obtained.

[0253] Also, the above L 11 By deOH-ing the -CH(OH)- compound (B11) or (B12) by a hydride or radical, L 11 A compound (B11) or (B12) that is -CH2- is obtained.

[0254] Compounds (C1) and (C2) can be synthesized by referring, for example, to International Publication No. 2013 / 121984.

[0255] Compound (D1) can be prepared, for example, by a method of reacting the following compound (D2) with metallic magnesium.

[0256]

[0257] However, R in the formula 2 , Q 11 , X and n are identical to compound (D1).

[0258] Preferred specific examples of compound (D2) include the following.

[0259] [Chemical Formula 4]

[0260]

[0261] The above reaction is typically carried out in a solvent. The solvent may be appropriately selected from solvents capable of dissolving the above compounds (C1), (C2), and (D1). The solvent may be a single solvent or a mixed solvent comprising two or more types.

[0262] For example, when compound (C1) or compound (C2) is a compound with a relatively low fluorine atom content (the ratio of fluorine atoms to the molecular weight of the compound molecule), the solvent is not particularly limited as long as it is a solvent inert to the reaction. Among the solvents inert to the reaction, ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane are preferred, and tetrahydrofuran is more preferred.

[0263] In addition, if compound (C1) or compound (C2) is a compound with a relatively high fluorine atom content, a mixed solvent combining the ether-based solvent and the fluorine-based solvent is preferred.

[0264] Fluorinated solvents include, for example, hydrofluorocarbons (1H,4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 2H,3H-perfluoropentane, etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), etc.), hydrofluoroethers (CF3CH2OCF2CF2H (AE3000), (perfluorobutoxy)methane, (perfluorobutoxy)ethane, etc.), and hydrochlorofluoroolefins. Examples include ((Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc (Z) corpus), (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc (E) corpus), (Z)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z) corpus), (E)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (E) corpus), etc.), and fluorinated aromatic compounds (perfluorobenzene, m-bis(trifluoromethyl)benzene (SR-solvent), p-bis(trifluoromethyl)benzene, etc.).

[0265] (Method for preparing compound (A11) and compound (A12))

[0266] As a method for manufacturing compounds (A11) and (A12) comprising the above compounds (A1) and (A2), a method for manufacturing compounds having a process of introducing an adhesion group T into the above compounds (B11) or (B12) may be cited.

[0267]

[0268]

[0269] step,

[0270] R f , R f1 , R 1 , R2 , L 11 , Q 1 , Q 11 , m, and n are as described above, and the preferred mode is also the same.

[0271] Below, we will explain, by way of example, how to introduce each contact device T, but it is not limited to the following methods.

[0272] For example, by applying the following compound (E1) to the double bond of the above compound (B11) or compound (B12) to cause a hydrosilylation reaction, the adhesion group T becomes -Si(R 21 ) 3-d (L 21 ) d A compound (A11) or compound (A12) is obtained.

[0273]

[0274] However, R 21 , L 21 , and d are as described above, and the preferred mode is also the same.

[0275] By reacting a per acid, such as metachloroperbenzoic acid, peracetic acid, or potassium hydrogen persulfate, with the double bond of the above compound (B11) or compound (B12) to epoxidize it, a compound (A11) or compound (A12) in which the adhesive group T is an epoxy group is obtained.

[0276] The double bond of the above compound (B11) or compound (B12) is oxidized by ozone to form an ozonide, and then oxidized by, for example, hydrogen peroxide, etc., so that a compound (A11) or compound (A12) in which the glucose group T is a carboxyl group is obtained.

[0277] In addition, by reducing the above ozonide with a reducing agent such as zinc, dimethyl sulfide, or thiourea, a compound (A11) or compound (A12) in which the adhesion group T is an aldehyde group is obtained.

[0278] Organic boran ((R) in the double bond of the above compound (B11) or compound (B12) 22 )3B ; single R 22 Compound (A11) or compound (A12) in which the admixture group T is a bromine atom or an iodine atom is obtained by adding a hydrogen atom or an organic group to form a hydroboride, and then reacting it with bromine (Br2) or iodine (I2) under basic conditions. Additionally, compound (A11) or compound (A12) in which the admixture group T is a bromine atom or an iodine atom is reacted with a phosphite ester, and then hydrolyzed using hydrochloric acid, etc., to obtain compound (A11) or compound (A12) in which the admixture group T is a phosphonic acid.

[0279] When hydrogen peroxide is reacted with the above hydroboride under basic conditions, a compound (A11) or compound (A12) in which the admixture group T is a hydroxyl group is obtained. Additionally, by reacting an activated phosphoric acid, such as phosphoryl chloride, with the compound (A11) or compound (A12) in which the admixture group T is a hydroxyl group, a compound (A11) or compound (A12) in which the admixture group T is a phosphoric acid is obtained.

[0280] In addition, a compound (A11) or compound (A12) in which the admixture group T is an aldehyde group is reacted with an amine to form an imine or imium ion, and then reduced by hydride to obtain a compound (A11) or compound (A12) in which the admixture group T is an amino group.

[0281] The fluorine-containing compound-containing composition of the present invention (fluorine-containing ether composition, hereinafter also referred to as "the composition") may contain compound (A1) and compound (A2), or may contain one or more selected from compound (A1) and compound (A2) and another fluorine-containing ether compound. In addition, the composition does not include the liquid medium described below.

[0282] Other fluorine-containing ether compounds may include, for example, a fluorine-containing ether compound produced as a byproduct in the manufacturing process of the present compound (hereinafter also referred to as "byproduct fluorine-containing ether compound"), a known fluorine-containing ether compound used for the same purpose as the present compound, and a fluorine-containing oil. As for other fluorine-containing compounds, compounds that are unlikely to degrade the properties of the present compound are preferred.

[0283] Examples of fluorine-containing oils include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE).

[0284] Examples of byproduct fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of the present compound. If the present composition contains byproduct fluorine-containing compounds, the purification process for removing the byproduct fluorine-containing compounds or reducing the amount of the byproduct fluorine-containing compounds can be simplified.

[0285] Known fluorine-containing compounds include, for example, those described in the following literature.

[0286] Perfluoropolyether-modified aminosilane disclosed in Japanese Published Patent Application No. Hei 11-029585,

[0287] Silicon-containing organic fluorine-containing polymer disclosed in Japanese Patent Publication No. 2874715,

[0288] Organosilicon compounds disclosed in Japanese Patent Publication No. 2000-144097,

[0289] Perfluoropolyether-modified aminosilane described in Japanese Patent Publication No. 2000-327772,

[0290] Fluorinated siloxane disclosed in Japanese Patent Publication No. 2002-506887,

[0291] An organic silicon compound described in Japanese Patent Publication No. 2008-534696,

[0292] Fluorinated modified hydrogen-containing polymer disclosed in Japanese Patent Publication No. 4138936

[0293] Compounds described in the specification of U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Publication No. 2014-070163

[0294] Organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0295] Fluorofluoride organosilane compounds described in International Publication No. 2012 / 064649,

[0296] Fluorooxyalkylene group-containing polymer disclosed in Japanese Patent Publication No. 2012-72272,

[0297] Fluorine-containing ether compounds described in International Publication No. 2013 / 042732, International Publication No. 2013 / 121984, International Publication No. 2013 / 121985, International Publication No. 2013 / 121986, International Publication No. 2014 / 163004, Japanese Patent Publication No. 2014-080473, International Publication No. 2015 / 087902, International Publication No. 2017 / 038830, International Publication No. 2017 / 038832, and International Publication No. 2017 / 187775

[0298] Perfluoro(poly)ether-containing silane compounds described in Japanese Patent Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433

[0299] Fluoropolyether group-containing polymer-modified silanes described in Japanese Published Patent Application No. 2015-199906, Japanese Published Patent Application No. 2016-204656, Japanese Published Patent Application No. 2016-210854, and Japanese Published Patent Application No. 2016-222859,

[0300] Fluorine-containing ether compounds described in International Publication No. 2018 / 216630, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 039186, International Publication No. 2019 / 044479, Japanese Patent Publication No. 2019-44158, and International Publication No. 2019 / 163282.

[0301] In addition, 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, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 manufactured by Daikin Industries, etc.

[0302] The proportion of the compound in the composition is less than 100 mass%, preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more.

[0303] When the present composition includes other fluorine-containing compounds, the ratio of the other fluorine-containing compounds to the total of the present compound and 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.

[0304] The ratio of the total of the compound and other fluorine-containing compounds in the composition is preferably 80 mass% or more, and more preferably 85 mass% or more.

[0305] If the content of this compound and other fluorine-containing compounds is within the above range, the water and oil repellency, friction resistance, fingerprint stain removal ability, lubricity, and appearance of the surface layer are excellent.

[0306] [Coating Solution]

[0307] The coating solution of the present invention (hereinafter also referred to as the coating solution) comprises the compound or composition of the present invention and a liquid medium. The coating solution may be in a liquid state, may be a solution, or may be a dispersion.

[0308] The coating solution may contain the compound or the composition, and may also contain impurities such as by-products generated during the manufacturing process of the compound.

[0309] The concentration of the compound or the composition is preferably 0.001 to 40 mass% in the coating solution, preferably 0.01 to 20 mass%, and more preferably 0.1 to 10 mass%.

[0310] As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or include both solvents.

[0311] Examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, etc.

[0312] As for the fluorinated alkanes, compounds having 4 to 8 carbon atoms are preferred. As for commercially available products, for example, C6F 13 H (Manufactured by AGC, Asahi Clean (registered trademark) AC-2000), C6F 13 Examples include C2H5 (manufactured by AGC, Asahi Clean (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours, Butrel (registered trademark) XF), etc.

[0313] Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene, etc.

[0314] As for the fluoroalkyl ether, compounds having 4 to 12 carbon atoms are preferred. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, Asahi Clean (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300), etc.

[0315] Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.

[0316] Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, etc.

[0317] Examples of non-fluorinated organic solvents include compounds composed only of hydrogen atoms and carbon atoms, and compounds composed only of hydrogen atoms, carbon atoms, and oxygen atoms, as well as hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents.

[0318] The coating solution preferably contains 75 to 99.999 mass% of a liquid medium, preferably 85 to 99.99 mass%, and particularly preferably 90 to 99.9 mass%.

[0319] The coating solution may include other components other than the compound or composition and the liquid medium, provided that such inclusion does not impede the effects of the present invention.

[0320] Other components may include known additives, such as acid catalysts or basic catalysts that promote the hydrolysis and condensation reactions of hydrolyzable silyl groups.

[0321] In the coating solution, the content of other components is preferably 10 mass% or less, and more preferably 1 mass% or less.

[0322] The concentration of the total of the compound and other components of the coating solution or the total of the composition and other components (hereinafter also referred to as solid content concentration) is preferably 0.001 to 40 mass%, preferably 0.01 to 20 mass%, more preferably 0.01 to 10 mass%, and more preferably 0.01 to 1 mass%. The solid content concentration of the coating solution is a value calculated from the mass of the coating solution before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0323] [article]

[0324] An article of the present invention (hereinafter also referred to as "the article") has a surface layer formed of the compound or composition of the present invention on the surface of a substrate. The surface layer may be formed on a part of the surface of the substrate or on the entire surface of the substrate. The surface layer may be spread out as a film on the surface of the substrate or may be dotted.

[0325] The surface layer comprises the present compound in a state where some or all of the hydrolyzable silyl groups of the present compound undergo a hydrolysis reaction, and the silanol groups undergo a dehydration condensation reaction.

[0326] The thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. If the thickness of the surface layer is 1 nm or more, it is easy to obtain sufficient effects from the surface treatment. If the thickness of the surface layer is 100 nm or less, the utilization efficiency is high. The thickness of the surface layer can be calculated from the oscillation period of the interference pattern by obtaining the interference pattern of the reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G).

[0327] Examples of materials include materials for which water and oil repellency is required. For instance, materials that are used by contacting other items (e.g., a stylus) or human fingers, materials that are held by human fingers during operation, and materials that are placed on other items (e.g., a stand).

[0328] Examples of materials for the substrate include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. An underlayer, such as a SiO2 film, may be formed on the surface of the substrate. More specifically, reference may be made to the substrate exemplified in the above adhesion member T.

[0329] As for the substrate, a substrate for a touch panel, a substrate for a display, and an eyeglass lens are preferred, and a substrate for a touch panel is particularly preferred. As for the material of the substrate for the touch panel, glass or a transparent resin is preferred.

[0330] In addition, glass or resin film used for the exterior part (excluding the display part) of devices such as mobile phones (e.g., smartphones), portable information terminals (e.g., tablet terminals), game consoles, and remote controls is also preferred.

[0331] [Method of manufacturing the item]

[0332] This article can be manufactured, for example, by the following method.

[0333] A method of forming a surface layer formed of the compound or the composition on the surface of a substrate by treating the surface of the substrate by a dry coating method using the compound or the composition.

[0334] A method of applying the coating solution to the surface of a substrate by a wet coating method and drying it to form a surface layer formed of the compound or composition on the surface of the substrate.

[0335] Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Among dry coating methods, vacuum deposition is preferred due to the suppression of decomposition of compound A1 or compound A2 and the simplicity of the apparatus. When vacuum deposition, a pellet-shaped material in which the compound or the composition is impregnated into a porous metal body such as iron or steel may be used. Alternatively, the coating solution may be impregnated into a porous metal body such as iron or steel, and the liquid medium may be dried to use a pellet-shaped material impregnated with compound A1, compound A2, or the composition.

[0336] Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure coating.

[0337] To improve the friction resistance of the surface layer, operations to promote the reaction between the compound and the substrate may be performed as necessary. Examples of such operations include heating, humidification, and light irradiation.

[0338] For example, by heating a substrate having a surface layer formed in a moist atmosphere, reactions such as the hydrolysis of hydrolyzable groups, the reaction of silanol groups with hydroxyl groups on the surface of the substrate, and the formation of siloxane bonds through the condensation reaction of silanol groups can be promoted.

[0339] After surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, pouring a solvent onto the surface layer or wiping it with a cloth soaked in solvent.

[0340] Examples

[0341] 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, “%” refers to “mass%” unless specifically stated otherwise. Also, Examples 1 to 4, 7 to 9, 11 to 14, and 17 to 19 are examples, and Examples 5 to 6, 10, 15 to 16, and 20 are comparative examples.

[0342] [Synthesization Example 1: Synthesis of Compound (1)]

[0343] Diethyldiallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.45 g), and dimethyl sulfoxide (263 g) were added and stirred at 160 ℃. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic layer, washed with saturated saline solution, and dried with sodium sulfate. After filtration, the solvent was removed by distillation, thereby obtaining 39.5 g of the following compound (1).

[0344] [Chemical Formula 5]

[0345]

[0346] [Synthesization Example 2: Synthesis of Compound (2)]

[0347] After adding THF (260 mL) and diisopropylamine (41.6 mL), the solution was cooled to -78 °C. n-butyllithium hexane solution (2.76 M, 96.6 mL) was added, and the temperature was raised to 0 °C. After stirring, the solution was cooled to -78 °C to prepare a THF solution of lithium diisopropylamide (LDA). Compound (1) (39.5 g) was added to the THF solution and stirred, after which allyl bromide (24.1 mL) was added. The temperature was raised to 0 °C, 1 M hydrochloric acid was added, and the THF was removed by vacuum distillation. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was removed by distillation, and 45.0 g of compound (2) was obtained by performing flash column chromatography using silica gel.

[0348] [Chemical Formula 6]

[0349]

[0350] [Synthesization Example 3: Synthesis of Compound (3)]

[0351] 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 stirred at room temperature, then diluted with dichloromethane. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (3).

[0352] [Chemical Formula 7]

[0353]

[0354] <Other synthesis methods of compound (3)>

[0355] [Synthesization Example 3-1: Synthesis of Compound (2a)]

[0356] After adding THF (260 mL) and diisopropylamine (41.6 mL, 294 mmol), the solution was cooled to -78 °C. n-butyllithium hexane solution (2.76 M, 96.6 mL, 267 mmol) was added, and the temperature was raised to 0 °C to prepare a THF solution of lithium diisopropylamide (LDA).

[0357] THF (50 mL) was added to tert-butyl acetate (9.29 g) and cooled to -78 °C, after which a THF solution of LDA (130 mL) was added. Allyl bromide (10.9 g) was added and the temperature was raised to 0 °C. After 30 minutes, the mixture was cooled to -78 °C, LDA (130 mL) and allyl bromide (10.9 g) were added, and the temperature was raised to 0 °C. After cooling to -78 °C again, LDA (130 mL) and allyl bromide (10.9 g) were added, and the temperature was raised to 0 °C. After stirring for 30 minutes, 1 M hydrochloric acid (100 mL) was added, and the THF was removed by vacuum distillation. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 9.45 g of the following compound (2a).

[0358] [Chemical Formula 8]

[0359]

[0360] [Synthesization Example 3-2: Synthesis of Compound (3)]

[0361] The above compound (2a) (9.45 g) was dissolved in THF (100 mL) and cooled to 0 °C. A THF solution of lithium aluminum hydride (40 mL, 100 mmol) was added and stirred at 50 °C. After adding 1 M hydrochloric acid (100 mL) at 0 °C, the mixture was extracted with dichloromethane. The solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 5.99 g of the above compound (2-3).

[0362] [Synthesization Example 4: Synthesis of Compound (4)]

[0363] Acetonitrile (380 mL), the above compound (3) (31.3 g), triphenylphosphine (64.3 g), and carbon tetrachloride (33.9 g) were added and stirred at 90 °C. After concentration, ethyl acetate / hexane was added and stirred. After filtration and concentration, 28.2 g of the following compound (4) was obtained by distillation (70 °C, 3 hPa).

[0364] [Chemical Formula 9]

[0365]

[0366] [Synthesization Example 5: Synthesis of Compound (5)]

[0367] Magnesium (2.36 g) was mixed with THF (35 mL) and iodine (0.180 g) and stirred at room temperature. A solution of compound (4) (14.0 g) in THF (35 mL) was added and heated to reflux for 2 hours to prepare a solution (0.80 M) of compound (5) below.

[0368] [Chemical Formula 10]

[0369]

[0370] [Synthesization Example 6: Synthesis of Compound (1-1)]

[0371] According to the method described in Example 6 of International Publication No. 2013 / 121984, the following compound (1-1) was obtained.

[0372]

[0373] Average value of unit x1: 14

[0374] [Synthesization Example 7: Synthesis of Compound (1-2)]

[0375] After adding the above compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL), a solution (11.0 mL) of the above compound (5) was added. After stirring at 60 °C for 20 hours, 1 M hydrochloric acid was added. After extraction with AE3000, the mixture was dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 1.15 g of the following compound (1-2).

[0376] [Chemical Formula 11]

[0377]

[0378] Average value of unit x1: 14

[0379] NMR spectrum of compound (1-2);

[0380]

[0381] [Example 1: Synthesis of Fluorine-Containing Ether Compounds (1-3)]

[0382] AC2000 (1.8 g), the above compound (1-2) (0.300 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.291 g of the following fluorine-containing ether compound (1-3).

[0383] [Chemical Formula 12]

[0384]

[0385] Average value of unit x1: 14

[0386] NMR spectrum of fluorine-containing ether compound (1-3);

[0387]

[0388] [Synthesization Example 8: Synthesis of Compound (2-1)]

[0389] Compound (1-2) (0.350 g) obtained in Synthesis Example 7 above, 1,3-bistrifluoromethylbenzene (3 mL), and Desmartin reagent (0.350 g) were added and stirred at 35°C for 2 hours. After adding methanol, extraction was performed with AC6000. The solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 0.280 g of the following compound (2-1).

[0390] [Chemical Formula 13]

[0391]

[0392] Average value of unit x1: 14

[0393] NMR spectrum of compound (2-1);

[0394]

[0395] [Example 2: Synthesis of Fluorofluoride Ether Compound (2-2)]

[0396] AC6000 (2.0 g), the above compound (2-1) (0.280 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 6.7 mg), aniline (2.0 mg), and trimethoxysilane (37.0 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.286 g of the following fluorine-containing ether compound (2-2).

[0397] [Chemical Formula 14]

[0398]

[0399] Average value of unit x1: 14

[0400] NMR spectrum of fluorine-containing ether compound (2-2);

[0401]

[0402] [Synthesization Example 9: Synthesis of Compound (3-1)]

[0403] 1,3-bistrifluoromethylbenzene (7.5 mL), compound (1-2) obtained in Synthesis Example 7 (0.750 g), triphenylphosphine (0.406 g), and carbon tetrachloride (0.310 g) were added, and the mixture was stirred at 100 °C for 2 hours. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 0.524 g of the following compound (3-1).

[0404] [Chemical Formula 15]

[0405]

[0406] Average value of unit x1: 14

[0407] NMR spectrum of compound (3-1);

[0408]

[0409] [Example 3: Synthesis of Fluorofluoride Ether Compounds (3-2)]

[0410] AC2000 (3.1 g), the above compound (3-1) (0.524 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 17.3 mg), aniline (7.0 mg), and trimethoxysilane (69.1 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.514 g of the following fluorine-containing ether compound (3-2).

[0411] [Chemical Formula 16]

[0412]

[0413] Average value of unit x1: 14

[0414] NMR spectrum of fluorine-containing ether compound (3-2);

[0415]

[0416] [Synthesization Example 10: Synthesis of Compound (4-1)]

[0417] Fluorolink D4000 (manufactured by SOLVAY, 15.0 g), 1,3-bistrifluoromethylbenzene (50 ml), and acetonitrile (30 ml) were added, followed by sodium hypochlorite solution (30 ml), TEMPO (1 g), and KBr (1 g). After stirring at 60 ℃ for 5 hours, dilute sulfuric acid was added. After extraction with AE3000, the solvent was removed by distillation to obtain 15.0 g of the following compound (4-1).

[0418] [Chemical Formula 17]

[0419]

[0420] p : 22, q : 25

[0421] [Synthesization Example 11: Synthesis of Compound (4-2)]

[0422] After adding the above compound (4-1) (15.0 g), 1,3-bistrifluoromethylbenzene (50 ml), and methanol (50 ml), 1 g of concentrated sulfuric acid was added. After heating and refluxing, the mixture was concentrated. By purifying the concentrate using flash column chromatography, 14.5 g of the following compound (4-2) was obtained.

[0423] [Chemical Formula 18]

[0424]

[0425] p : 22, q : 25

[0426] NMR spectrum of compound (4-2);

[0427]

[0428] [Synthesization Example 12: Synthesis of Compound (4-3)]

[0429] After adding the above compound (4-2) (6.27 g) and 1,3-bistrifluoromethylbenzene (44 mL), a solution (11.0 mL) of the above compound (5) was added. After stirring at 60 °C for 1 hour, 1 M hydrochloric acid was added. After extraction with AE3000, the mixture was dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 2.95 g of the following compound (4-3).

[0430] [Chemical Formula 19]

[0431]

[0432] p : 22, q : 25

[0433] NMR spectrum of compound (4-3);

[0434]

[0435] [Synthesization Example 13: Synthesis of Compound (4-4)]

[0436] The above compound (4-3) (2.95 g) was dissolved in AE3000 (20 mL) and cooled to 0 °C. A THF solution of lithium aluminum hydride (1.7 mL, 4.3 mmol) was added and stirred. 1 M hydrochloric acid was added, extracted with AE3000, and then dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 0.216 g of the following compound (4-4).

[0437] [Chemical Formula 20]

[0438]

[0439] p : 22, q : 25

[0440] NMR spectrum of compound (4-4);

[0441]

[0442] [Example 4: Synthesis of Fluorinated Ether Compounds (4-5)]

[0443] AC2000 (1.4 g), the above compound (4-4) (0.216 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 13.6 mg), aniline (12.4 mg), and trimethoxysilane (92.7 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.211 g of the following fluorine-containing ether compound (4-5).

[0444] [Chemical Formula 21]

[0445]

[0446] p : 22, q : 25

[0447] NMR spectrum of compound (4-4);

[0448]

[0449] [Synthesization Example 14: Another synthesis example of the above compound (2-1)]

[0450] After adding the above compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL), a solution (11.0 mL) of the above compound (5) was added. After stirring at 60 °C for 3 hours, 1 M hydrochloric acid was added. After extraction with AE3000, the mixture was dried with sodium sulfate. After filtration, the solvent was removed by distillation, and after washing with hexane, flash column chromatography using silica gel was performed to obtain 7.28 g of the above compound (2-1).

[0451] [Synthesizing Example 15: Another synthesis example of the above compound (1-2)]

[0452] The above compound (2-1) (7.15 g) was dissolved in AE3000 (36 mL) and cooled to 0 ℃. A THF solution of lithium aluminum hydride (1.7 mL) was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added and stirred at room temperature. After extraction with AE3000, the solution was dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 5.27 g of the above compound (1-2).

[0453] [Synthesization Example 16: Synthesis of Compound (5-1)]

[0454] After adding the above compound (1-1) (10.0 g) and 1,3-bistrifluoromethylbenzene (31 mL), allyl magnesium bromide (10.0 mL, 0.7 M, 7.0 mmol) was added. After stirring at room temperature for 20 hours, 1 M hydrochloric acid was added. After extraction with AE3000, the mixture was dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 5.57 g of the following compound (5-1).

[0455] [Chemical Formula 22]

[0456]

[0457] Average value of unit x1: 14

[0458] NMR spectrum of compound (5-1);

[0459]

[0460] [Example 5: Synthesis of Compound (5-2)]

[0461] AC2000 (1.8 g), the above compound (5-1) (0.320 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 13.5 mg), aniline (2.8 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.313 g of the following compound (5-2).

[0462] [Chemical Formula 23]

[0463]

[0464] Average value of unit x1: 14

[0465] NMR spectrum of compound (5-2);

[0466]

[0467] [Synthesization Example 17: Synthesis of Compound (6-1)]

[0468] After adding the above compound (5-1) (0.990 g), potassium hydroxide (0.079 g), tetrabutylammonium iodide (0.009 g), and allyl bromide (1.21 g), the mixture was stirred at 80°C for 20 hours. 1 M hydrochloric acid was added, and the mixture was extracted with AE3000 and dried with sodium sulfate. After filtration, the solvent was removed by distillation, and flash column chromatography using silica gel was performed to obtain 0.351 g of the following compound (6-1).

[0469] [Chemical Formula 24]

[0470]

[0471] Average value of unit x1: 14

[0472] NMR spectrum of compound (6-1);

[0473]

[0474] [Example 6: Synthesis of Compound (6-2)]

[0475] AC2000 (1.8 g), the above compound (6-1) (0.351 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 14.5 mg), aniline (3.1 mg), and trimethoxysilane (45.5 mg) were added and stirred at 40°C, after which the solvent was removed by vacuum distillation to obtain 0.333 g of the following compound (6-2).

[0476] [Chemical Formula 25]

[0477]

[0478] Average value of unit x1: 14

[0479] NMR spectrum of compound (6-2);

[0480]

[0481] [Example 7: Preparation of Fluorine-Containing Ether Compositions]

[0482] The above compound (1-2) and the above compound (1-3) were mixed in a ratio of 80:20 (mass ratio) to obtain the fluorine-containing ether composition of Example 7.

[0483] [Example 8: Preparation of Fluorine-Containing Ether Compositions]

[0484] The above compound (2-1) and the above compound (2-2) were mixed in a ratio of 75:25 (mass ratio) to obtain the fluorine-containing ether composition of Example 8.

[0485] [Example 9: Preparation of Fluorine-Containing Ether Compositions]

[0486] The above compound (2-1) and the above compound (2-2) were mixed in a ratio of 85:15 (mass ratio) to obtain the fluorine-containing ether composition of Example 9.

[0487] [Example 10: Preparation of Fluorine-Containing Ether Compositions]

[0488] The above compound (6-1) and the above compound (6-2) were mixed in a ratio of 80:20 (mass ratio) to obtain the fluorine-containing ether composition of Example 10.

[0489] [Examples 11–16: Manufacture and Evaluation of Articles]

[0490] Articles of Examples 11 to 20 were obtained by surface treating a substrate using each compound obtained in Examples 1 to 6 and the compositions obtained in Examples 7 to 10. As a surface treatment method, the following dry coating method and wet coating method were used for each example, respectively. Chemically strengthened glass was used as the substrate. The obtained articles were evaluated by the following methods. The results are shown in Tables 1 and 2.

[0491] (Dry coating method)

[0492] Dry coating was performed using a vacuum deposition apparatus (VTR350M manufactured by ULVAC) (vacuum deposition method). 0.5 g of each compound was loaded into a molybdenum boat inside the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was filled with 1 × 10⁻⁶ -3 The temperature was evacuated to Pa or lower. The boat containing the compound was heated at a heating rate of 10 °C / min or less, and when the deposition rate by a crystal oscillator film thickness gauge exceeded 1 nm / sec, the shutter was opened to begin 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 was deposited was heat-treated at 200 °C for 30 minutes and washed with dichloropentafluoropropane (manufactured by AGC, AK-225) to obtain an article having a surface layer on the surface of the substrate.

[0493] (Wet coating method)

[0494] Each compound was mixed with C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200) as a medium to prepare a coating solution with a solid content concentration of 0.05%. A substrate was dipped into the coating solution, left for 30 minutes, and then lifted (dip coat method). The coating film was dried at 200°C for 30 minutes and cleaned with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0495] (Evaluation Method)

[0496] <Method for Measuring Contact Angle>

[0497] 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 (DM-500 manufactured by Kyowa Kaimen Kagaku Co., Ltd.). 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.

[0498] <Initial Contact Angle>

[0499] For the surface layer, the initial water contact angle and the initial n-hexadecane contact angle were measured using the above measurement method. The evaluation criteria are as follows.

[0500] Initial water contact angle:

[0501] ◎ (Excellent): 115 degrees or higher.

[0502] ○ (Good): 105 degrees or higher and less than 115 degrees.

[0503] × (Not good): Less than 105 degrees.

[0504] <Friction Resistance (Steel Wool)>

[0505] Regarding the surface layer, in accordance with JIS L0849:2013 (ISO 105-X12:2001), a reciprocating traverse tester (manufactured by KNT) was used to reciprocate a steel wool bonster (#0000) 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min, and then the water contact angle was measured by the above method. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the performance degradation due to friction, and the better the friction resistance. The evaluation criteria are as follows.

[0506] ◎ (Excellent): Change in water contact angle after 10,000 cycles is 5 degrees or less.

[0507] ○ (Good): Change in water contact angle after 10,000 cycles is greater than 5 degrees and less than or equal to 8 degrees.

[0508] △ (Good): Change in water contact angle after 10,000 reciprocating cycles is greater than 8 degrees and less than or equal to 10 degrees.

[0509] × (Not good): Change in water contact angle after 10,000 cycles exceeds 10 degrees.

[0510] <Lightfastness>

[0511] For the surface layer, a desktop xenon arc lamp type accelerated lightfastness tester (product name: SUNTEST XLS+, manufactured by Toyo Seiki Co., Ltd.) was used to irradiate light (650 W / m², 300–700 nm) for 500 hours at a black panel temperature of 63 ℃, and then the water contact angle was measured by the above method. The evaluation criteria are as follows.

[0512] ◎ (Excellent): The change in water contact angle after the accelerated lightfastness test is 5 degrees or less.

[0513] ○ (Good): The change in water contact angle after the accelerated lightfastness test is greater than 5 degrees and less than or equal to 10 degrees.

[0514] × (Not good): The change in water contact angle after accelerated lightfastness test is greater than 10 degrees.

[0515]

[0516]

[0517] As shown in Table 1, although the articles of Examples 15 and 16 using the compounds of Examples 5 and 6 had good initial contact angle and light resistance, a decrease in the water contact angle was confirmed, particularly after the friction test. On the other hand, articles of Examples 11 to 14 having a surface layer using the fluorine-containing ether compounds of Examples 1 to 4, which have -CH(OH)-, -C(=O)-, or -CH=CH- between the polyfluoropolyether chain and the branch structure, showed excellent durability, with the decrease in the water contact angle suppressed even after the friction test and the light resistance test.

[0518] In addition, as shown in Table 2, articles having a surface layer using the fluorine-containing ether compositions of Examples 17 to 19, which contain the fluorine-containing ether compounds of Examples 1 to 4, showed excellent durability, with the decrease in the water contact angle suppressed even after the friction test and the light resistance test. Furthermore, according to a comparison of Example 11 and Example 17, it was found that friction resistance was further improved by using a combination of a fluorine-containing ether compound (1-3) having a hydrolyzable silyl group and a fluorine-containing ether compound (1-2) having an unsaturated hydrocarbon group.

[0519] This application claims priority based on Japanese Patent Application No. 2020-39975 filed on March 9, 2020, and incorporates the entire disclosure thereof herein.

Claims

Claim 1 A fluorine-containing ether compound represented by the following formula (A1) or formula (A2). However, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different, R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 may be the same or different, provided that R in Equation (A2) 1 It is a fluoroalkylene group, and R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different, Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 may be the same or different, and T is, as an admixture group, 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 phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R 21 ) 3-d (L 21 ) d One or more types selected from, and R 21 It is an alkyl group, and L 21 It is a hydrolytic group or a hydroxyl group, and L has multiple 21 d may be the same or different, d is 2 or 3, m is an integer from 0 to 210, and n is an integer from 2 to 20, where n is multiple, the n may be the same or different. Claim 2 In claim 1, R 1 Fluorinated ether compounds having 1 to 6 carbon atoms. Claim 3 In claim 1, R 2 Fluorinated ether compounds having 1 to 10 carbon atoms. Claim 4 In Article 1, -Q 1 (-T) n This, -Q 2 [(-R 3 -T) a (-R 4 ) 3-a ] Phosphorus, fluorine-containing ether compound. However, Q 2 is a carbon atom or a silicon atom, and Q 2 In cases where there are multiple Qs, the relevant Q 2 It can be the same or different, R 3 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 3 In the case of multiple instances, the relevant R 3 It can be the same or different, R 4 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 5 -Q 2 [(-R 3 -T) b (-R 6 ) 3-b As ], R 4 In cases where there are multiple cases, the relevant R 4 It can be the same or different, R 5 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 5 In cases where there are multiple cases, the relevant R 5 It can be the same or different, R 6 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 5 -Q 2 [(-R 3 -T) c (-R 7 ) 3-c As ], R 6 In the case of multiple instances, the relevant R 6 It can be the same or different, R 7 As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 7 In the case of multiple instances, the relevant R 7 a and c may be identical or different, a is an integer from 0 to 3, b is an integer from 0 to 3, where b is multiple, b may be identical or different, c is an integer from 0 to 3, where c is multiple, c may be identical or different, and the sum of a, b, and c is n. Claim 5 In Article 4, R 3 Fluorinated ether compounds having 2 to 7 carbon atoms. Claim 6 delete Claim 7 A compound represented by the following formula (B1) or formula (B2). However, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different, R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different, R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different, Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 m may be the same or different, m is an integer from 0 to 210, and n is an integer from 2 to 20. If there are multiple n, the n may be the same or different. Claim 8 In Article 7, -Q 11 (-CH=CH2) n This, -Q 2 [(-R 23 -CH=CH2) a (-R 24 ) 3-a ] Phosphorus, compound. Only, Q 2 is a carbon atom or a silicon atom, and Q 2 In cases where there are multiple Qs, the relevant Q 2 It can be the same or different, R 23 It is an alkylene group that may have single bonds or fluorine atoms, and may have ether bonds between carbon atoms, and R 23 In the case of multiple instances, the relevant R 23 It can be the same or different, R 24 is a hydrogen atom, a fluorine atom, an alkyl group that may have a fluorine atom and an ether bond between carbon atoms, or -R 25 -Q 2 [(-R 23 -CH=CH2) b (-R 26 ) 3-b As ], R 24 In cases where there are multiple cases, the relevant R 24 It can be the same or different, R 25 is an alkylene group that may have a single bond or a fluorine atom, or may have an ether bond between carbon atoms, R 25 In cases where there are multiple cases, the relevant R 25 It can be the same or different, R 26 Silver, hydrogen atoms, fluorine atoms, alkyl groups that may have fluorine atoms and ether bonds between carbon atoms, or, -R 25 -Q 2 [(-R 23 -CH=CH2) c (-R 27 ) 3-c As ], R 26 In the case of multiple instances, the relevant R 26 It can be the same or different, R 27 As an alkyl group that may have silver, hydrogen atoms, fluorine atoms, or fluorine atoms and may have ether bonds between carbon atoms, R 27 In the case of multiple instances, the relevant R 27 a and c may be identical or different, a is an integer from 0 to 3, b is an integer from 0 to 3, where b is multiple, b may be identical or different, c is an integer from 0 to 3, where c is multiple, c may be identical or different, and the sum of a, b, and c is n. Claim 9 A method for preparing a compound represented by the following formula (B11) or formula (B12), having a process of reacting a compound represented by the following formula (C1) or formula (C2) with a compound represented by the following formula (D1). However, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different, R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 It can be the same or different, R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, R 11 Silver, as an alkyl group, R 11 In the case of multiple instances, the relevant R 11 It can be the same or different, L 11 As -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, L 11 In the case of multiple instances, the relevant L 11 It can be the same or different, Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 X may be the same or different, X is a halogen atom, m is an integer from 0 to 210, and n is an integer from 2 to 20, where n is multiple, the n may be the same or different. Claim 10 A method for preparing a fluorine-containing ether compound represented by the following formula (A11) or formula (A12), having a process of introducing an adhesion group T into a compound represented by the following formula (B11) or formula (B12). However, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different, R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 may be the same or different, provided that R in Equation (A12) 1 It is a fluoroalkylene group, and R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, L 11 As -CH(OH)-, -C(=O)-, -CH=CH-, or -CH2-, L 11 In the case of multiple instances, the relevant L 11 It can be the same or different, Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 It can be the same or different, Q 11 is a connector for 1 + n, Q 11 In the case of multiple instances, the relevant Q 11 may be the same or different, and T is a bromine atom, an iodine atom, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, an epoxy group, a thiol group, a phosphate group, a phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R 21 ) 3-d (L 21 ) d One or more types selected from, and R 21 It is an alkyl group, and L 21 It is a hydrolytic group or a hydroxyl group, and L has multiple 21 d may be the same or different, d is 2 or 3, m is an integer from 0 to 210, and n is an integer from 2 to 20, where n is multiple, the n may be the same or different. Claim 11 A fluorine-containing ether composition containing a fluorine-containing ether compound represented by the following formula (A1) and a fluorine-containing ether compound represented by the following formula (A2). However, R f is a fluoroalkyl group having 1 to 20 carbon atoms, and R f1 Silver is a fluoroalkylene group having 1 to 6 carbon atoms, R f1 In the case of multiple instances, the relevant R f1 It can be the same or different, R 1 As an alkylene group that may have silver or fluorine atoms, R 1 In the case of multiple instances, the relevant R 1 may be the same or different, provided that R in Equation (A2) 1 It is a fluoroalkylene group, and R 2 is an alkylene group that may have a single bond or a fluorine atom, R 2 In cases where there are multiple cases, the relevant R 2 It can be the same or different, L 1 As -CH(OH)-, -C(=O)-, or -CH=CH-, L 1 In the case of multiple instances, the relevant L 1 It can be the same or different, Q 1 is a connector for 1 + n, Q 1 In the case of multiple instances, the relevant Q 1 may be the same or different, and T is, as an admixture group, 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 phosphonic acid group, an unsaturated hydrocarbon group, an aryl group, and -Si(R 21 ) 3-d (L 21 ) d One or more types selected from, and R 21 It is an alkyl group, and L 21 It is a hydrolytic group or a hydroxyl group, and L has multiple 21 d may be the same or different, d is 2 or 3, m is an integer from 0 to 210, and n is an integer from 2 to 20, where n is multiple, the n may be the same or different. Claim 12 A fluorine-containing ether composition containing one or more of the fluorine-containing ether compounds described in any one of claims 1 to 5, and another fluorine-containing ether compound. Claim 13 A coating solution comprising a liquid medium and a fluorine-containing ether compound described in any one of claims 1 to 5, a fluorine-containing ether composition described in claim 11, or a fluorine-containing ether composition containing one or more of the fluorine-containing ether compounds and another fluorine-containing ether compound. Claim 14 An article having a surface layer formed on the surface of a substrate, the surface layer being formed of a fluorine-containing ether compound described in any one of claims 1 to 5, a fluorine-containing ether composition described in claim 11, or a fluorine-containing ether composition containing one or more of the fluorine-containing ether compounds and another fluorine-containing ether compound. Claim 15 A method for manufacturing an article, wherein a surface layer is formed by a dry coating method or a wet coating method using a coating solution containing a liquid medium and said fluorine-containing ether compound described in any one of claims 1 to 5, a fluorine-containing ether composition described in claim 11, or said fluorine-containing ether compound or said fluorine-containing ether composition.

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