Liquid composition for surface treatment

Abstract

A liquid composition for surface treatment, comprising a fluorinated polyether group-containing silane compound, a fluorinated alkyl group-containing silane compound and a solvent, wherein the average hydrodynamic particle size of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound in the liquid composition obtained by a dynamic light scattering method is 1 to 1500 nm, and the average hydrodynamic particle size is a value obtained by mixing a liquid mixture containing 50% by mass of the fluorinated polyether group-containing silane compound in the solvent and the fluorinated alkyl group-containing silane compound in the same ratio as the ratio of the fluorinated polyether group-containing silane compound to the fluorinated alkyl group-containing silane compound in the liquid composition, and then allowing the mixture to stand at 25° C. for measurement.

Description

Technical Field

[0001] The present invention relates to a liquid composition for surface treatment containing a fluorinated polyether group-containing silane compound. Background Art

[0002] It is known that certain types of fluorinated polyether group-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of substrates. The layer obtained from the surface treatment liquid composition containing the fluorinated polyether group-containing silane compound (hereinafter also referred to as "surface treatment layer") is applied to various substrates such as glass, plastic, fiber, building materials, etc. as a so-called functional film.

[0003] As such a fluorinated polyether group-containing silane compound, there are known perfluoropolyether group-containing silane compounds having a perfluoropolyether group in the main chain of the molecule and a hydrolyzable group bonded to a Si atom at the molecular terminal or at the terminal portion (Patent Documents 1 and 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2008-534696

[0007] Patent Document 2: International Publication No. 97 / 07155 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] The surface treatment layer formed from the surface treatment liquid composition containing the fluorinated polyether group-containing silane compound as described above is required to have further improved friction durability.

[0010] Technical solutions for solving technical problems

[0011] The present invention provides the following [1] to

[16] .

[0012] [1] A liquid composition for surface treatment, comprising a fluorinated polyether group-containing silane compound, a fluorinated alkyl group-containing silane compound and a solvent, wherein the average hydrodynamic particle size of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound in the liquid composition as measured by a dynamic light scattering method is 1 to 1500 nm, and the average hydrodynamic particle size is a value obtained by mixing a liquid mixture containing 50% by mass of the fluorinated polyether group-containing silane compound in the solvent and the fluorinated alkyl group-containing silane compound in the same ratio as the ratio of the fluorinated polyether group-containing silane compound to the fluorinated alkyl group-containing silane compound in the liquid composition, and then allowing the mixture to stand at 25° C.

[0013] The above-mentioned fluorinated alkyl-containing silane compound has a group represented by the following formula:

[0014] -SiR 31 n3 R 32 3-n3

[0015] In the formula,

[0016] R 31 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0017] R 32 Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0018] n3 is independently an integer from 0 to 3 at each occurrence;

[0019] In the above-mentioned fluorinated alkyl group-containing silane compound, at least one n3 is 1 or more.

[0020] [2] A liquid composition for surface treatment as described in [1], wherein the 60% cumulative distribution particle size in the particle size distribution based on the scattering intensity obtained by a dynamic light scattering method is 1 to 700 nm, wherein the measurement conditions of the above-mentioned particle size distribution are the same as the measurement conditions of the above-mentioned average hydrodynamic particle size.

[0021] [3] The surface treatment liquid composition according to [1] or [2], wherein the solvent is at least one selected from the group consisting of perfluorobutyl methyl ether, perfluorobutyl ethyl ether and perfluorohexyl methyl ether.

[0022] [4] The surface treatment liquid composition according to any one of [1] to [3], wherein the ratio of the number of moles of the fluorinated alkyl group-containing silane compound to the number of moles of the fluorinated polyether group-containing silane compound is 0.001 to 1.5.

[0023] [5] The surface treatment liquid composition according to any one of [1] to [4], wherein the fluorinated polyether group-containing silane compound is represented by the following formula (1) or (2):

[0024] R F1 α -X A -R Si β (1)

[0025] R Si γ -X A -R F2 -X A -R Siγ (2)

[0026] In the formula,

[0027] R F1 Rf 1 -R F -O q -;

[0028] R F2 Rf 2 p -R F -O q -;

[0029] R 1 is C which may be substituted by one or more fluorine atoms 1－16 alkyl;

[0030] R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene;

[0031] R F Each time it occurs, it is independently of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - the group shown;

[0032] a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary;

[0033] R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom;

[0034] p is independently 0 or 1 at each occurrence;

[0035] q is independently 0 or 1 at each occurrence;

[0036] R Si Each occurrence is independently a monovalent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded;

[0037] At least 1 RSi It is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded;

[0038] X A Each is independently a single bond or a 2- to 10-valent organic group;

[0039] α is an integer from 1 to 9;

[0040] β is an integer from 1 to 9;

[0041] γ is an integer of 1-9 respectively independently.

[0042] [6] The surface treatment liquid composition according to [5], wherein

[0043] X A It is expressed by the following formula:

[0044]

[0045] α, β and γ are 1,

[0046] R Si Each occurrence is independently any one of the following groups represented by formula (S1) to (S2),

[0047] -SiR a1 k1 R b1 l1 R c1 m1 (S1)

[0048] -CR d1 k2 R e1 l2 R f1 m2 (S2)

[0049] In the formula,

[0050] R n Each time it occurs, it is independently -X 1 -R Si The groups shown, hydrogen atoms, phenyl groups or C 1－6 alkyl;

[0051] X 1 Each occurrence is independently a single bond or a divalent organic group;

[0052] R a1 Each time it occurs, it is independently -Z 1 -SiR 41 r1 R 42r2 R 43 r3 ;

[0053] Z 1 Each occurrence is independently an oxygen atom or a divalent organic group;

[0054] R 41 Each time it occurs, it is independently -Z 1′ -SiR 41′ r1′ R 42′ r2′ R 43′ r3′ ;

[0055] Z 1′ Each occurrence is independently an oxygen atom or a divalent organic group;

[0056] R 41′ Each time it occurs, it is independently -Z 1″ -SiR 41″ r1″ R 42″ r2 ″;

[0057] Z 1″ Each occurrence is independently an oxygen atom or a divalent organic group;

[0058] R 41″ Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0059] R 42″ Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0060] r1″ is independently an integer from 0 to 3 at each occurrence;

[0061] r2″ is independently an integer from 0 to 3 at each occurrence;

[0062] R 42′ Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0063] R 43′ Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0064] r1′ is independently an integer from 0 to 3 at each occurrence;

[0065] r2′ is independently an integer from 0 to 3 at each occurrence;

[0066] r3′ is independently an integer from 0 to 3 at each occurrence;

[0067] R 42 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0068] R 43 Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0069] r1 is independently an integer from 0 to 3 at each occurrence;

[0070] r2 is independently an integer from 0 to 3 at each occurrence;

[0071] r3 is independently an integer from 0 to 3 at each occurrence;

[0072] R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0073] R c1 Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0074] k1 is independently an integer from 0 to 3 at each occurrence;

[0075] l1 is independently an integer from 0 to 3 each time it appears;

[0076] m1 is independently an integer from 0 to 3 at each occurrence;

[0077] Wherein, in formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group;

[0078] R d1 Each time it occurs, it is independently -Z 2 -CR 51 s1 R 52 s2 R 53 s3 ;

[0079] Z 2 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group;

[0080] R 51 Each time it occurs, it is independently -Z 2′ -CR 51′ s1′ R 52′ s2′ ;

[0081] Z 2′ Each occurrence is independently a single bond, an oxygen atom or a divalent organic group;

[0082] R 51′ Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ;

[0083] Z 3 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group;

[0084] R 51″ Each occurrence is independently a hydroxyl group or a hydrolyzable group;

[0085] R 52″ Each occurrence is independently a hydrogen atom or a monovalent organic group;

[0086] m1″ is independently an integer from 0 to 3 at each occurrence;

[0087] R 52′ Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

[0088] s1′ is independently an integer from 0 to 3 at each occurrence;

[0089] s2′ is independently an integer from 0 to 3 at each occurrence;

[0090] R 52 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ;

[0091] R 53 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

[0092] s1 is independently an integer from 0 to 3 each time it appears;

[0093] s2 is independently an integer from 0 to 3 at each occurrence;

[0094] s3 is independently an integer from 0 to 3 at each occurrence;

[0095] R e1 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ;

[0096] R f1 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

[0097] k2 is independently an integer from 0 to 3 at each occurrence;

[0098] l2 is independently an integer from 0 to 3 at each occurrence;

[0099] m2 is independently an integer from 0 to 3 at each occurrence;

[0100] In formula (S2), there is at least one -SiR 51″ m1″ R 52″ 3－m1″ .

[0101] [7] The surface treatment liquid composition according to any one of [1] to [6], wherein the silane compound containing a fluorinated alkyl group is represented by the formula (B1),

[0102] R 3 -X 31 -SiR 31 n3 R 32 3-n3 (B1)

[0103] R 3 C is substituted with one or more fluorine atoms 1－6 alkyl,

[0104] X 31 is a single bond, an oxygen atom or a divalent organic group;

[0105] R 31 are independently a hydroxyl group or a hydrolyzable group;

[0106] R 32 are each independently a hydrogen atom or a monovalent organic group;

[0107] n3 is an integer from 1 to 3.

[0108] [8] The surface treatment liquid composition according to [7], wherein Rf 3 C 1－6 Perfluoroalkyl.

[0109] [9] The surface treatment liquid composition according to [7] or [8], wherein

[0110] X 31 By - (X 311 ) z11 -(Z3 ) z12 -express,

[0111] X 311 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0112] Z 3 are independently an oxygen atom or a sulfur atom,

[0113] z11 is an integer from 1 to 3,

[0114] z12 is an integer from 0 to 2,

[0115] The order of existence of the repeating units enclosed in brackets is X 31 is arbitrary.

[0116]

[10] The surface treatment liquid composition according to any one of [1] to [9], further comprising a fluorinated oil.

[0117]

[11] The surface treatment liquid composition according to

[10] , wherein

[0118] The above fluorinated oil is represented by the formula: Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 express,

[0119] R 5 and Rf 6 are each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with 1 or more fluorine atoms,

[0120] a′ and b′ are each independently an integer from 0 to 30, c′ and d′ are each independently an integer from 1 to 200, the sum of a′, b′, c′ and d′ is at least 5, and the order of existence of the repeating units marked with subscripts a′, b′, c′ or d′ and enclosed in brackets in the formula is arbitrary.

[0121]

[12] The surface treatment liquid composition according to

[10] or

[11] , wherein the fluorinated oil is contained in an amount of 0.001 to 50 mol % based on the total amount of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound.

[0122]

[13] A liquid composition for surface treatment as described in any one of [5] to

[12] , wherein the silane compound containing a fluorinated polyether group comprises a silane compound containing a fluorinated polyether group represented by formula (1) and a silane compound containing a fluorinated polyether group represented by formula (2), and the liquid composition further contains a fluorinated oil.

[0123]

[14] The surface treatment liquid composition according to any one of [1] to

[13] , which does not contain an oligomer of a compound selected from the fluorinated alkyl group-containing silane compound.

[0124]

[15] The surface treatment liquid composition according to

[14] , wherein the liquid composition is used for wet coating.

[0125]

[16] An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment liquid composition according to any one of [1] to

[15] .

[0126] Effects of the Invention

[0127] The present invention can provide a surface treatment agent that helps form a surface treatment layer having better friction durability. DETAILED DESCRIPTION

[0128] When used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, meaning a group in which one hydrogen atom is separated from a hydrocarbon. Such a hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms that may be substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon group" may be any of linear, branched or cyclic, and may be any of saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. Furthermore, the hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its end or in the molecular chain.

[0129] As used in this specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include halogen atoms; C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0130] When used in this specification, "organic group" means a group containing carbon. The organic group is not particularly limited, and may be a hydrocarbon group. In addition, "2- to 10-valent organic group" means a 2- to 10-valent group containing carbon. The 2- to 10-valent organic group is not particularly limited, and examples include 2- to 10-valent groups in which 1 to 9 hydrogen atoms are further separated from the hydrocarbon group. For example, as a divalent organic group, there is no particular limitation, and examples include a divalent group in which 1 hydrogen atom is further separated from the hydrocarbon group.

[0131] In this specification, when used in this specification, "a hydrolyzable group" means a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR h1 , -OCOR h1 、-O-N=CR h1 2. -NR h1 2. -NHR h1 , -NCO, halogen (in these formulas, R h1 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR h1 (i.e. alkoxy). h1 Examples include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, alkyl groups, particularly non-substituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, the hydrolyzable group is a methoxy group. In another embodiment, the hydrolyzable group is an ethoxy group.

[0132] (Surface treatment liquid composition)

[0133] The surface treatment liquid composition of the present invention (hereinafter sometimes referred to as "liquid composition") contains a fluorinated polyether group-containing silane compound, a fluorinated alkyl group-containing silane compound and a solvent. The fluorinated alkyl group-containing silane compound has a group represented by the following formula.

[0134] -SiR 31 n3 R 32 3-n3

[0135] In the present invention, the liquid composition refers to a mixture of a liquid solvent, a silane compound containing a fluorinated polyether group, and a silane compound containing a fluorinated alkyl group, including a solution, a suspension, and an emulsion.

[0136] The average hydrodynamic particle size of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound in the liquid composition of the present invention is 1 to 1500 nm. Here, the average hydrodynamic particle size refers to the value obtained when a liquid mixture containing 50% by mass of the fluorinated polyether group-containing silane compound in a solvent and a fluorinated alkyl group-containing silane compound are mixed in the same ratio as the ratio of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound in the liquid composition, and then allowed to stand at 25° C. for measurement. The above average hydrodynamic particle size is preferably 1 to 1400 nm, more preferably 1 to 1000 nm, for example, 1 to 600 nm.

[0137] In addition, a composition of a liquid mixture containing 50% by mass of a fluorinated polyether group-containing silane compound and a fluorinated alkyl group-containing silane compound in a mixed solvent (hereinafter sometimes referred to as a "liquid mixture") in the same ratio as the ratio of the fluorinated polyether group-containing silane compound to the fluorinated alkyl group-containing silane compound in the liquid composition is sometimes referred to as a measuring composition.

[0138] The liquid mixture can be obtained, for example, by concentrating a mixture containing a fluorinated polyether group-containing silane compound.

[0139] It can be considered that in the composition for measuring the average hydrodynamic particle size, the silane compound containing a fluorinated polyether group forms micelles, and it can be considered that the diameter of the micelle is detected as the average hydrodynamic particle size. When the average hydrodynamic particle size is in the above range, the surface treatment layer formed using the liquid composition shows good friction durability. This is considered to be able to improve the leveling of the liquid composition when having such an average hydrodynamic particle size as described above. As a result, the surface of the formed surface treatment layer becomes flatter, which can suppress the reduction of friction durability. In addition, the composition for measuring refers to a mixture of a liquid solvent, a silane compound containing a fluorinated polyether group and a silane compound containing a fluoroalkyl group, including a solution, a suspension, and an emulsion.

[0140] In one embodiment, the lower limit of the average hydrodynamic particle size may be 10 nm or 25 nm.

[0141] The average hydrodynamic particle size is measured by a dynamic light scattering method. The measurement is performed after the composition for measurement is allowed to stand until it reaches 25° C. The standing time is, for example, 2 minutes.

[0142] The liquid mixture preferably contains at least one selected from the group consisting of perfluorobutyl methyl ether, perfluorobutyl ethyl ether and perfluorohexyl methyl ether as a solvent.

[0143] In the composition for measurement, in the particle size distribution based on the scattering intensity by the dynamic light scattering method, the 60% cumulative distribution particle size is preferably 1 to 700 nm, more preferably 1 to 500 nm, and even more preferably 1 to 100 nm. Here, the measurement conditions of the particle size distribution are the same as the measurement conditions of the mean hydrodynamic particle size. The above-mentioned 60% cumulative distribution particle size refers to the diameter when the proportion of all particles 100% reaches 60% when accumulated sequentially from the smaller particle size in the particle size distribution obtained by the dynamic light scattering method.

[0144] By setting the 60% cumulative distribution particle size to be within the above range, the formation of micelles in the liquid composition of the present invention can be further suppressed.

[0145] (Fluorinated polyether group-containing silane compound)

[0146] The fluorinated polyether group-containing silane compound is represented by, for example, the following formula (1) or (2).

[0147] R F1 α -X A -R Si β (1)

[0148] R Si γ -X A -R F2 -X A -R Si γ (2)

[0149] In the above formula (1), R F1 Rf 1 -R F -O q -

[0150] In the above formula (2), R F2 Rf 2 p -R F -O q -

[0151] In the above formula, Rf 1 Each occurrence is independently C which may be substituted with one or more fluorine atoms. 1－16 alkyl.

[0152] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkyl groups, especially C 1－3Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0153] The above Rf 1 Preferably, C may be substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0154] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0155] In the above formula, Rf 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene.

[0156] The above C may be substituted with one or more fluorine atoms 1－6 The "C" in the alkylene 1－6 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkylene, more preferably a straight chain C 1－3 Alkylene.

[0157] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene.

[0158] C 1－6 The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Perfluoroalkylene, more preferably linear C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0159] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0160] In the above formula, q is independently 0 or 1 at each occurrence. In one embodiment, q is 0. In another embodiment, q is 1.

[0161] In the above formula, R F Each occurrence of is independently a divalent fluoropolyether group. F Each time it occurs, it is independently of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f In this specification, it is recorded as R F The left side of the group is Rf 1 or Rf 2 Bonding, the right side is O (when q is 0, it is X A ) bonding.

[0162] In the above formula, R Fa Each occurrence of is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0163] In the above formula, a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer from 0 to 100. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less. The order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary.

[0164] These repeating units may be straight-chain or branched, preferably straight-chain. 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, and the like, preferably -(OCF2CF2CF2CF2CF2CF2CF2)-. -(OC5F 10)- can be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc., and is preferably -(OCF2CF2CF2CF2CF2)-. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-, and is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- (that is, in the above formula, R Fa The -(OCF2CF2CF2)- may be any of -(OCF(CF3)CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-, and is preferably -(OCF2CF2CF2)-. In addition, -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-, and is preferably -(OCF2CF2)-.

[0165] In one approach, R F Each occurrence is independently a group represented by the following formula (f1), (f2), (f3), (f4) or (f5).

[0166] -(OC3F6) d -(OC2F4) e - (f1)

[0167] [In formula (f1), d is an integer of 1 to 200, and e is 0 or 1.]

[0168] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0169] [In formula (f2), c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

[0170] The sum of c, d, e and f is greater than 2,

[0171] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0172] -(R 6 -R 7 ) g - (f3)

[0173] [In formula (f3), R 6 For OCF2 or OC2F4,

[0174] R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0175] g is an integer from 2 to 100.]

[0176] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4)

[0177] [In formula (f4), e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary.]

[0178] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5)

[0179] [In formula (f5), f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary.]

[0180] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, 25 to 35. (OC3F6) in the above formula (f1) is preferably a group represented by (OCF2CF2CF2) or (OCF(CF3)CF2), and more preferably a group represented by (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably a group represented by (OCF2CF2) or (OCF(CF3)), and more preferably a group represented by (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0181] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably 10 to 200. In addition, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) may be -(OC2F4) e -(OCF2) f - the group shown.

[0182] In the above formula (f3), R 6 Preferably, it is OC2F4. In the above (f3), R 7It is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It may be either a straight chain or a branched chain, preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or - (OC2F4 - OC4F8) g -

[0183] In the above formula (f4), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0184] In the above formula (f5), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0185] In one embodiment, the above R F It is a group represented by the above formula (f1).

[0186] In one embodiment, the above R F It is a group represented by the above formula (f2).

[0187] In one embodiment, the above R F It is a group represented by the above formula (f3).

[0188] In one embodiment, the above R F It is a group represented by the above formula (f4).

[0189] In one embodiment, the above R F It is a group represented by the above formula (f5).

[0190] In a preferred embodiment, R F Formula (f2): -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -. In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200, preferably from 5 to 200, more preferably from 10 to 200, and the order of existence of each repeating unit marked with a subscript e or f and enclosed in parentheses is arbitrary in the formula. R F More specifically - (OC2F4) e -(OCF2) f - the group shown.

[0191] In R F In the embodiment of the present invention, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, and further preferably 0.2 to 0.85. By making the e / f ratio less than 10, the sliding property, friction durability and chemical resistance (for example, durability to artificial sweat) of the cured layer (for example, the surface treatment layer) obtained from the liquid composition can be further improved. The smaller the e / f ratio, the more the sliding property and friction durability of the cured layer are improved. On the other hand, by making the e / f ratio greater than 0.1, the stability of the compound can be further improved. The larger the e / f ratio, the more the stability of the silane compound containing the fluorinated polyether group is improved. In this case, the value of f is greater than 1.

[0192] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0193] In one embodiment, the e / f ratio is lower than 0.9, preferably lower than 0.8, lower than 0.7, and may be lower than 0.65. The e / f ratio is, for example, greater than 0.2, greater than 0.3, greater than 0.4, greater than 0.5, or greater than 0.55. The e / f ratio may be, for example, greater than 0.2 and less than 0.9, specifically greater than 0.4 and less than 0.8, and more specifically greater than 0.5 and less than 0.8. By having such an e / f ratio, the liquid composition of the present invention can form a surface treatment layer having better sliding properties.

[0194] In one embodiment, the e / f ratio may be 0.4 or more and 0.7 or less, 0.5 or more and 0.7 or less, 0.55 or more and 0.7 or less, or 0.55 or more and 0.65 or less.

[0195] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, and more preferably 1.0 or more and 2.0 or less.

[0196] -R F The number average molecular weight of the - part is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. 19 The value measured by F-NMR.

[0197] In another way, -R F The number average molecular weight of the moiety may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0198] In another way, -R F The number average molecular weight of the moiety may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0199] R Si Each occurrence is independently a monovalent group comprising a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded, and at least one R Si It is a monovalent group including a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0200] R Si For example, each occurrence is independently any group represented by the following formulae (S1) to (S3).

[0201] -SiR a1 kl R b1 l1 R c1 m1 (S1)

[0202] -CR d1 k2 R e1 l2 R f1 m2 (S2)

[0203]

[0204] In one approach, R Si It is represented by formula (S1).

[0205] In one approach, R Si It is expressed by formula (S2).

[0206] In one approach, R Si It is expressed by formula (S3).

[0207] In formula (S1), the above R a1 Each time it occurs, it is independently -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 .

[0208] The above Z 1 Each occurrence is independently an oxygen atom or a divalent organic group. 1 The right side of the structure is 41 r1 R 42 r2 R 43 r3 ) bonding.

[0209] In a preferred embodiment, Z 1 It is a divalent organic group.

[0210] In a preferred embodiment, Z 1 Not including Z 1 The bonded Si atoms form siloxane bonds. That is, in formula (S1), (Si—Z 1 -Si) does not contain siloxane bonds.

[0211] The above Z 1 Preferably C 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be a straight chain or a branched chain, preferably a straight chain. 1－6 Alkyl, C2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0212] In a preferred embodiment, Z 1 C 1－6 Alkylene or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -. In Z 1 In the case of the above groups, higher light resistance, particularly ultraviolet resistance, can be obtained.

[0213] In another preferred embodiment, Z 1 C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 1 It can be -CH2CH2CH2-. In another embodiment, Z 1 It can be -CH2CH2-.

[0214] The above R 41 Each time it occurs, it is independently -Z 1′ -SiR 41′ r1′ R 42′ r2′ R 43′ r3′ .

[0215] The above Z 1′ Each occurrence is independently an oxygen atom or a divalent organic group. 1′ The right side of the structure is 41′ r1′ R 42′ r2′ R 43′ r3′ ) bonding.

[0216] In a preferred embodiment, Z 1′ It is a divalent organic group.

[0217] In a preferred embodiment, Z 1′ Not including Z 1′ The bonded Si atoms form siloxane bonds. That is, in formula (S1), (Si—Z 1′ -Si) does not contain siloxane bonds.

[0218] The above Z 1′ Preferably C 1－6 Alkylene, -(CH2) z1′ -O-(CH2)z2′ -(wherein z1′ is an integer of 0 to 6, for example, an integer of 1 to 6, and z2′ is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z3′ -phenylene-(CH2) z4′ - (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be straight chain or branched, preferably straight chain. These groups may be selected from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0219] In a preferred embodiment, Z 1′ C 1－6 Alkylene or -(CH2) z3′ -phenylene-(CH2) z4′ -, preferably -phenylene-(CH2) z4′ -. In Z 1′ In the case of the above groups, light resistance, particularly ultraviolet resistance, is further improved.

[0220] In another preferred embodiment, the above Z 1′ C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 1′ It can be -CH2CH2CH2-. In another embodiment, Z 1′ It can be -CH2CH2-.

[0221] The above R 41′ Each time it occurs, it is independently -Z 1″ -SiR 41″ r1″ R 42″ r2″ .

[0222] The above Z 1″ Each occurrence is independently an oxygen atom or a divalent organic group.

[0223] Z 1″ Each occurrence is independently an oxygen atom or a divalent organic group. 1″ The right side of the structure is 41″ r1″ R 42″ r2″ ) bonding.

[0224] In a preferred embodiment, Z 1″It is a divalent organic group.

[0225] In a preferred embodiment, Z 1″ Not including Z 1″ The bonded Si atoms form siloxane bonds. That is, in formula (S1), (Si—Z 1″ -Si) does not contain siloxane bonds.

[0226] The above Z 1″ Preferably C 1－6 Alkylene, -(CH2) z1″ -O-(CH2) z2″ -(wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z3″ -phenylene-(CH2) z4 ″—(wherein z3″ is an integer of 0 to 6, for example, an integer of 1 to 6, and z4″ is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be straight chain or branched, preferably straight chain. These groups may be selected from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0227] In a preferred embodiment, Z 1″ C 1－6 Alkylene or -(CH2) z3″ -phenylene-(CH2) z4″ -, preferably -phenylene-(CH2) z4″ -. In Z 1″ In the case of the above groups, light resistance, particularly ultraviolet resistance, is further improved.

[0228] In another preferred embodiment, the above Z 1″ C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 1″ It can be -CH2CH2CH2-. In another embodiment, Z 1″ It can be -CH2CH2-.

[0229] The above R 41″ Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0230] R 41″ Preferably, each occurrence is independently a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0231] The above R 42″ Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0232] In the above R 42″ The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0233] The above r1″ is independently an integer of 0 to 3 at each occurrence; the above r2″ is independently an integer of 0 to 3 at each occurrence. In addition, the sum of r1″ and r2″ is (SiR 41″ r1″ R 42″ r2″ ) unit is 3.

[0234] r1″ in each (SiR 41″ r1″ R 42″ r2″ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0235] The above R 42′ Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0236] R 42′ Preferably, each occurrence is independently a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0237] The above R 43′ Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0238] In the above R 43′ The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0239] The above r1′ is independently an integer of 0 to 3 at each occurrence; the above r2′ is independently an integer of 0 to 3 at each occurrence; and the above r3′ is independently an integer of 0 to 3 at each occurrence. In addition, the sum of r1′, r2′ and r3′ is (SiR 41′ r1′ R 42′ r2′ R 43′ r3′ ) unit is 3.

[0240] In one embodiment, r1′ is zero.

[0241] In one embodiment, r1′ is 0, r2′ is an integer from 0 to 3, and r3′ is also an integer from 0 to 3.

[0242] In one embodiment, r1′ is 41′ r1′ R 42′ r2′ R 43′ r3′ ) units are each independently an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, r1′ is 3.

[0243] In one embodiment, r2′ is 41′ r1′ R 42′ r2′ R 43′ r3′ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0244] In one embodiment, at each (SiR 41′ r1′ R 42′ r2′ R 43′ r3′ ) units, r1′ is independently 0, r2′ is an integer from 1 to 3, and r3′ is an integer from 0 to 2. Preferably, r1′ is 0, r2′ is an integer from 2 to 3, and r3′ is an integer from 0 to 1. More preferably, r2′ is 3.

[0245] In one embodiment, r2′ is 0 and r3′ is 41′ r1′ R 42′ r2′ R 43′ r3′ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0246] The above R 42 Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0247] R 42 Preferably, each occurrence is independently a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0248] The above R 43Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0249] In the above R 43 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0250] The above r1 is independently an integer of 0 to 3 at each occurrence; the above r2 is independently an integer of 0 to 3 at each occurrence; and the above r3 is independently an integer of 0 to 3 at each occurrence. In addition, the sum of r1, r2 and r3 is (SiR 41 r1 R 42 r2 R 43 r3 ) unit is 3.

[0251] In one embodiment, r1 is zero.

[0252] In one embodiment, r1 is 0, r2 is an integer of 0-3, and r3 is an integer of 0-3.

[0253] In one embodiment, r1 is 41 r1 R 42 r2 R 43 r3 ) units are each independently an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, r1 is 3.

[0254] In one embodiment, at each (SiR 41 r1 R 42 r2 R 43 r3 ) units are independently, r1 is an integer from 1 to 3, r2 is an integer from 0 to 2, and r3 is an integer from 0 to 2; in another embodiment, r1 is an integer from 2 to 3, r2 is 0 or 1, and r3 is 0 or 1.

[0255] In one embodiment, r2 is 41 r1 R 42 r2 R 43 r3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0256] In one embodiment, at each (SiR41 r1 R 42 r2 R 43 r3 ) units are independent of each other, r1 is an integer from 0 to 2, r2 is an integer from 1 to 3, and r3 is an integer from 0 to 2; in another embodiment, r1 is 0 or 1, r2 is 2 or 3, and r3 is 0 or 1; in another embodiment, r2 is 3.

[0257] In one embodiment, r1 is 0 and r2 is 41 r1 R 42 r2 R 43 r3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0258] In one embodiment, r1 is 0, r2 is an integer of 1 to 3, and r3 is an integer of 0 to 2. Preferably, r1 is 0, r2 is 2 or 3, and r3 is 0 or 1. More preferably, r1 and r3 are 0, and r2 is 3.

[0259] In the above formula, R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0260] The above R b1 Preferably, each occurrence is independently a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0261] In the above formula, R c1 Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0262] In the above R c1 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0263] The above k1 is independently an integer of 0 to 3 at each occurrence; the above l1 is independently an integer of 0 to 3 at each occurrence; and the above m1 is independently an integer of 0 to 3 at each occurrence. In addition, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3.

[0264] In one embodiment, k1 is a1 k1 R b1 l1 R c1 m1 ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0265] In one embodiment, at each (SiR a1 k1 R b1 l1 R c1 m1 ) units, respectively and independently, k1 is an integer from 1 to 3, l1 is an integer from 0 to 2, and m1 is an integer from 0 to 2; in another embodiment, k1 is 2 or 3, l1 is 0 or 1, and m1 is 0 or 1; in another embodiment, k1 is 3.

[0266] In one embodiment, at each (SiR a1 k1 R b1 l1 R c1 m1 ) units, respectively and independently, k1 is 1 or 2, l1 is 2 or 1, and m1 is 0.

[0267] In one embodiment, at each (SiR a1 k1 R b1 l1 R c1 m1 ) units, respectively and independently, k1 is 1 or 2, l1 is 0, and m1 is 2 or 1.

[0268] In one embodiment, k1 is 0. In other words, -SiR a1 k1 R b1 l1 R c1 m1 The group shown is -SiR b1 l1 R c1 m1 , and the sum of l1 and m1 is 3. However, in this embodiment, R at the end of formula (1) and formula (2) Si In the moiety (hereinafter sometimes referred to as the "terminal moiety" of formula (1) and formula (2)), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.

[0269] The above l1 is preferably an integer of 1 to 3, more preferably 2 or 3, and further preferably 3, each time it appears.

[0270] In one embodiment, k1 is 0, and l1 is preferably 2 or 3, and more preferably k1 is 0, and l1 is 3.

[0271] In formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group. That is, the group represented by formula (S1) has -SiR b1 l1 R c1 m1 (wherein, l1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and the total of l1 and m1 is 3), -SiR 42 r2 R 43 r3 (wherein r2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the sum of r2 and r3 is 3), -SiR 42′ r2′ R 43′ r3′ (wherein r2′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the total of r2′ and r3′ is 3), or -SiR 41″ r1″ R 42″ r2″ (wherein r1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the total of r1″ and r2″ is 3).

[0272] In a preferred embodiment, at the terminal part of formula (1) and formula (2), when R Si When represented by (S1), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group.

[0273] In a preferred embodiment, in formula (S1), there is R a1 In the case of at least 1 R a1 In all R a1 In the above formula, r2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0274] In a preferred embodiment, in formula (S1), there is R a1 In the case of at least 1 R a1 In all R a1 In the above, r1 is an integer of 0 to 2, r2 is an integer of 1 to 3, and r3 is an integer of 0 to 2. Preferably, r1 is 0 or 1, r2 is 2 or 3, and r3 is 0 or 1. More preferably, r2 is 3.

[0275] In a preferred embodiment, in formula (S1), there is R 41 In the case of at least 1 R 41 In all R41 In the formula (a), r2′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0276] In a preferred embodiment, in formula (S1), there is R 41 In the case of at least 1 R 41 In all R 41 wherein r1′ is an integer of 0 to 2, r2′ is an integer of 1 to 3, and r3′ is an integer of 0 to 2. Preferably, r1′ is 0 or 1, r2′ is 2 or 3, and r3′ is 0 or 1. More preferably, r2′ is 3.

[0277] In a preferred embodiment, in formula (S1), there is R 41′ In the case of at least 1 R 41′ In all R 41′ In the above, r1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0278] In a preferred embodiment, in formula (S1), k1 is 2 or 3, preferably 3, r1 is 0, and r2 is 2 or 3, preferably 3.

[0279] In a preferred embodiment, in formula (S1), k1 is 2 or 3, l1 is 0 or 1, m1 is 0 or 1, r1 is 0, r2 is 2 or 3, and r3 is 0 or 1; preferably, k1 is 3, r1 is 0, r2 is 2 or 3, and r3 is 0 or 1; more preferably, k1 is 3 and r2 is 3.

[0280] In formula (S2), the above R d1 Each time it occurs, it is independently -Z 2 -CR 51 s1 R 52 s2 R 53 s3 .

[0281] The above Z 2 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 2 The right side of the structure is the same as (CR 51 s1 R 52 s2 R 53 s3 ) bonding.

[0282] In a preferred embodiment, Z 2 It is a divalent organic group.

[0283] The above Z 2 Preferably C 1－6 Alkylene, -(CH2) z5-O-(CH2) z6 -(wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z7 -phenylene-(CH2) z8 - (wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be a straight chain or a branched chain, preferably a straight chain. 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0284] In a preferred embodiment, Z 2 C 1－6 Alkylene or -(CH2) z7 -phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 -. In Z 2 In the case of the above groups, light resistance, particularly ultraviolet resistance, is further improved.

[0285] In another preferred embodiment, Z 2 C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 2 It can be -CH2CH2CH2-. In another embodiment, Z 2 It can be -CH2CH2-.

[0286] The above R 51 Each time it occurs, it is independently -Z 2′ -CR 51′ s1′ R 52′ s2′ .

[0287] The above Z 2′ Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 2′ The right side of the structure is the same as (CR 51′ s1′ R 52′ s2′ ) bonding.

[0288] Z 2′ Preferably C 1－6 Alkylene, -(CH2) z5′ -O-(CH2) z6′-(wherein z5′ is an integer of 0 to 6, for example, an integer of 1 to 6, and z6′ is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z7′ -phenylene-(CH2) z8′ - (wherein z7' is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be a straight chain or a branched chain, preferably a straight chain. 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0289] In a preferred embodiment, Z 2′ C 1－6 Alkylene or -(CH2) z7′ -phenylene-(CH2) z8 '-, preferably -phenylene-(CH2) z8′ -. In Z 2′ In the case of the above groups, light resistance, particularly ultraviolet resistance, is further improved.

[0290] In another preferred embodiment, the above Z 2′ C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 2′ It can be -CH2CH2CH2-. In another embodiment, Z 2′ It can be -CH2CH2-.

[0291] The above R 51′ Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ .

[0292] The above Z 3 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 3 The right side of the structure is 51″ m1″ R 52″ 3－m1″ ) bonding.

[0293] In one approach, Z 3 For oxygen atoms.

[0294] In one approach, Z 3 It is a divalent organic group.

[0295] The above Z 3 Preferably C 1－6 Alkylene, -(CH2) z5″ -O-(CH2) z6″ -(wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z7″ -phenylene-(CH2) z8″ - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be a straight chain or a branched chain, preferably a straight chain. 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0296] In a preferred embodiment, Z 3 C 1－6 Alkylene or -(CH2) z7″ -phenylene-(CH2) z8″ -, preferably -phenylene-(CH2) z8″ -. In Z 3 In the case of the above groups, light resistance, particularly ultraviolet resistance, is further improved.

[0297] In another preferred embodiment, the above Z 3 C 1－6 Alkylene, preferably C 1－3 In one embodiment, Z 3 It can be -CH2CH2CH2-. In another embodiment, Z 3 It can be -CH2CH2-.

[0298] The above R 51″ Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0299] R 51″ Preferably, each occurrence is independently a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0300] The above R 52″ Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0301] In the above R 52″ The monovalent organic group is preferably C1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0302] The above m1″ is in each (SiR 51″ m1″ R 52″ 3－m1″ ) units are each independently an integer of 0 to 3. In formula (S2), there is at least one -SiR 51″ m1″ R 52″ 3－m1″ That is, at the terminal part, all m1″ are not set to 0. In other words, at the terminal part of formulae (1) and (2), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.

[0303] m1″ in each (SiR 51″ m1″ R 52″ 3－m1″ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0304] The above R 52′ Each occurrence of is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0305] In R 52′ The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0306] In one approach, R 52′ It is hydroxyl.

[0307] In another approach, R 52′ is a monovalent organic group, preferably C 1－20 Alkyl, more preferably C 1－6 alkyl.

[0308] The above s1′ is independently an integer of 0 to 3 at each occurrence; the above s2′ is independently an integer of 0 to 3 at each occurrence. In addition, the sum of s1′ and s2′ is (CR 51′ s1′ R 52′ s2′ ) unit is 3.

[0309] s1′ in each (CR 51′ s1′ R 52′ s2′) units are each independently preferably an integer of 1 to 3, more preferably an integer of 2 to 3, and even more preferably 3.

[0310] The above R 52 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ . The -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ The meaning is the same as above R 51′ -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ same.

[0311] The above R 53 Each occurrence of is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0312] In the above R 53 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0313] In one approach, R 53 It is hydroxyl.

[0314] In another approach, R 53 is a monovalent organic group, preferably C 1－20 Alkyl, more preferably C 1－6 alkyl.

[0315] The above s1 is independently an integer of 0 to 3 at each occurrence; the above s2 is independently an integer of 0 to 3 at each occurrence; the above s3 is independently an integer of 0 to 3 at each occurrence. In addition, the sum of s1, s2 and s3 is (CR 51 s1 R 52 s2 R 53 s3 ) unit is 3.

[0316] In one embodiment, s1 is zero.

[0317] In one embodiment, s1 is 0, s2 is an integer of 0 to 3, and s3 is an integer of 0 to 3. In one embodiment, s1 is 0, s2 is an integer of 2 to 3, and s3 is an integer of 0 to 1. In another embodiment, s1 is 0, s2 is an integer of 3, and s3 is 0.

[0318] In one embodiment, s1 is 51 s1 R 52 s2 R 53 s3 ) units are each independently an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, s1 is 3.

[0319] In one embodiment, s2 is 51 s1 R 52 s2 R 53 s3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0320] In one embodiment, s1 is 0 and s2 is 51 s1 R 52 s2 R 53 s3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0321] The above R e1 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ . The -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ The meaning is the same as above R 51′ -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ same.

[0322] The above R f1 Each occurrence of is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0323] In the above Rf1 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0324] In one approach, R f1 It is hydroxyl.

[0325] In other ways, R f1 For -O(R f11 O) n1 R f12 The group shown. f11 C 1－6 Alkylene, preferably C 1－3 Alkylene, n1 is an integer of 1 to 10, preferably an integer of 1 to 6, R f12 C 1－10 Alkyl, preferably C 1－3 The alkyl group is, for example, a methyl group.

[0326] The above k2 is independently an integer from 0 to 3 at each occurrence, l2 is independently an integer from 0 to 3 at each occurrence, and m2 is independently an integer from 0 to 3 at each occurrence. In addition, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3.

[0327] In one approach, in R Si In the case of a group represented by formula (S2), m1″ is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 51″ m1″ R 52″ 3－m1″ ) units exist in each terminal portion of formula (1) and formula (2) in 2 or more numbers, for example, 2 to 27 numbers, preferably 2 to 9 numbers, more preferably 2 to 6 numbers, even more preferably 2 to 3 numbers, and particularly preferably 3 numbers.

[0328] In a preferred embodiment, in formula (S2) there is R 51′ In the case of at least 1 R 51′ In all R 51′ In the formula, m1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0329] In a preferred embodiment, in formula (S2) there is R 52 In the case of at least 1 R 52 In all R 52In the formula, m1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0330] In a preferred embodiment, in formula (S2) there is R e1 In the case of at least 1 R e1 In all R e1 In the formula, m1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0331] In a preferred embodiment, in formula (S2), k2 is 0, l2 is 2 or 3, preferably 3, and m1″ is 2 or 3, preferably 3.

[0332] In a preferred embodiment, in formula (S2), k2 is 0, l2 is 2 or 3, m2 is 0 or 1, and preferably l2 is 3. In this embodiment, m1″ is 2 or 3, and preferably 3.

[0333] In one embodiment, in formula (S2), k2 is 0, m2 is 1, l2 is 2, and m1″ is 2 or 3, preferably 3. For example, R f For -O(R f11 O) n1 R f12 The group shown. f11 、n1、R f12 The meaning is the same as above.

[0334] In formula (S3), in the above formula, R 11 Each occurrence is independently a hydroxyl group or a hydrolyzable group.

[0335] R 11 Preferably, each occurrence is independently a hydrolyzable group.

[0336] R 11 Preferably, each occurrence is independently -OR h , -OCOR h 、-O-N=CR h 2. -NR h 2. -NHR h or halogen (in these formulas, R h Indicates substituted or unsubstituted C 1－4 alkyl), more preferably -OR h (i.e., alkoxy). h , non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc., and substituted alkyl groups such as chloromethyl, etc. are listed. Among them, alkyl groups, especially non-substituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is methyl, in another embodiment, R h It is ethyl.

[0337] In the above formula, R 12 Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0338] In R 12 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0339] In the above formula, n1 is in each (SiR 11 n1 R 12 3－n1 ) units are independently an integer of 0 to 3. Si In the case of a group represented by formula (S3), at least one (SiR 11 n1 R 12 3－n1 ) unit. That is, at the terminal portion, not all n1 are simultaneously 0. In other words, at the terminal portion of formula (1) and formula (2), there is at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

[0340] n1 in each (SiR 11 n1 R 12 3－n1 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0341] In the above formula, X 11 Each occurrence is independently a single bond or a divalent organic group. The divalent organic group is preferably C 1－20 Alkylene. 1－20 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain.

[0342] In a preferred embodiment, X 11 Each occurrence is independently a single bond or a linear C 1－6 Alkylene, preferably a single bond or straight chain C 1－3 Alkylene, more preferably a single bond or straight chain C 1－2 Alkylene, more preferably a straight chain C 1－2 Alkylene.

[0343] In the above formula, R 13 Each occurrence is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably C 1－20 Alkyl.1－20 The alkyl group may be a straight chain or a branched chain, and is preferably a straight chain.

[0344] In a preferred embodiment, R 13 Each occurrence is independently a hydrogen atom or a linear C 1－6 Alkyl, preferably a hydrogen atom or a straight-chain C 1－3 The alkyl group is preferably a hydrogen atom or a methyl group.

[0345] In the above formula, t is independently an integer of 2 to 10 at each occurrence.

[0346] In a preferred embodiment, t is independently an integer from 2 to 6 at each occurrence.

[0347] In the above formula, R 14 Each occurrence of is independently a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 A hydrogen atom.

[0348] In one approach, R 14 Each time it occurs, it is independently -X 11 -SiR 11 n1 R 12 3－n1 .

[0349] In the above formula, R 15 Each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

[0350] In one approach, R 15 Each occurrence is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

[0351] In a preferred embodiment, R 15 For a single key.

[0352] In one embodiment, formula (S3) is the following formula (S3-a).

[0353]

[0354] [Wherein,

[0355] R 11 , R 12 , R 13 , X 11 and n1 have the same meanings as those in the above formula (S3);

[0356] Each occurrence of t1 and t2 is independently an integer greater than 1. The sum of t1 and t2 is t.]

[0357] In a preferred embodiment, formula (S3) is the following formula (S3-b).

[0358]

[0359] [Where R 11 , R 12 , R 13 , X 11 , n1 and t have the same meanings as those described in the above formula (S3).]

[0360] In the above formulas (1) and (2), X A It can be understood that the fluoropolyether portion (R F1 and R F2 ) and the part providing the ability to bind to the substrate (R Si ) is connected to a linker. Therefore, the X A As long as the compounds represented by formulae (1) and (2) can be stably present, the residue may be a single bond or any group.

[0361] In the above formula (1), α is an integer of 1 to 9, and β is an integer of 1 to 9. These α and β can be determined according to X A The sum of α and β is equal to X A For example, in X A When X is a devalent organic group, the sum of α and β is 10, for example, α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9. A When it is a divalent organic group, α and β are 1.

[0362] In the above formula (2), γ is an integer from 1 to 9. γ can be calculated based on X A That is, γ is the value of X A The value obtained by subtracting 1 from the valence of .

[0363] X A Each independently represents a single bond or a di- to decavalent organic group.

[0364] The above X A The 2- to 10-valent organic group is preferably a 2- to 8-valent organic group. In one embodiment, the 2- to 10-valent organic group is preferably a 2- to 4-valent organic group, and more preferably a 2-valent organic group. In another embodiment, the 2- to 10-valent organic group is preferably a 3- to 8-valent organic group, and more preferably a 3- to 6-valent organic group.

[0365] In one approach, XA is a single bond or a divalent organic group, α is 1, and β is 1.

[0366] In one approach, X A is a single bond or a divalent organic group, and γ is 1.

[0367] In one approach, X A It is a tri- to hexavalent organic group, wherein α is 1 and β is 2-5.

[0368] In one approach, X A It is a tri- to hexavalent organic group, and γ is 2-5.

[0369] In one approach, X A It is a trivalent organic group, α is 1, and β is 2.

[0370] In one approach, X A It is a trivalent organic group, and γ is 2.

[0371] In one approach, X A For a single key.

[0372] In one approach, X A It is a divalent organic group.

[0373] In X A In the case of a single bond or a divalent organic group, formulae (1) and (2) are represented by the following formulae (1') and (2').

[0374] R Fl -X A -R Si (1')

[0375] R Si -X A -R F2 -X A -R Si (2')

[0376] X A Examples include single bonds or the following formula: -(R 201 ) p0 -(X a0 ) q0 - The divalent organic group shown.

[0377] R 201 is a single bond, -(CH2) p10 - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) p10 -

[0378] p10 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, further preferably 1 or 2.

[0379] X a0 Indicates - (X b0 ) q10 -

[0380] X b0 Each occurrence independently represents a group selected from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -(OR 305 ) n40 -、-C(O)O-、-Si(R 303 )2-、-(Si(R 303 )2O) m0′ -Si(R 303 )2-,-CONR 304 -、-O-CONR 304 -, -NR 304 - and -(CH2) n0′ - in the group,

[0381] R 303 Each occurrence independently represents phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl,

[0382] R 304 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl (preferably methyl),

[0383] R 305 Each time it occurs, it is independently C 1－6 Alkylene,

[0384] n40 is independently an integer from 1 to 5 at each occurrence,

[0385] m0′ is independently an integer of 1 to 100 at each occurrence, preferably an integer of 1 to 20,

[0386] n0′ is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3,

[0387] q10 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3,

[0388] p0 is 0 or 1,

[0389] q0 is 0 or 1,

[0390] The order of presence of the repeating units indicated as p0 or q0 and enclosed in brackets is arbitrary.

[0391] Here, at least one of p0 and q0 is 1.

[0392] Among them, X A (Typically X A The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, X A Not substituted by these groups.

[0393] In a preferred embodiment, the above X A Each independently is -(R 201 ) p0 -(X a0 ) q0 -R 202 -. R 202 Represents a single bond, -(CH2) p11 - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) p11 p11 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. 202 (Typically R 202 The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, R 202 is not substituted by these groups. 201 , p0, X a0 , q0 has the same meaning as above.

[0394] In one approach, X A It is a group represented by the following formula.

[0395]

[0396] X 1 Each occurrence is independently a single bond or a divalent organic group.

[0397] As the above X 1 , for example, a single bond or the following formula can be cited: -(R 21 ) p1 -(X a ) q1 - The divalent organic group shown.

[0398] R 21 is a single bond, -(CH2)p2 - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) p2 -

[0399] p2 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, further preferably 1 or 2,

[0400] X a Indicates - (X b ) q2 -

[0401] X b Each occurrence independently represents a group selected from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -(OR 35 ) n4 -、-C(O)O-、-Si(R 33 )2-、-(Si(R 33 )2O) m′ -Si(R 33 )2-,-CONR 34 -、-O-CONR 34 -, -NR 34 - and -(CH2) n′ - in the group,

[0402] R 33 Each occurrence independently represents phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl,

[0403] R 34 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl (preferably methyl),

[0404] R 35 Each time it occurs, it is independently C 1－6 Alkylene,

[0405] n4 is independently an integer from 1 to 5 at each occurrence,

[0406] m' is independently an integer of 1 to 100 at each occurrence, preferably an integer of 1 to 20,

[0407] n' is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

[0408] q2 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3,

[0409] p1 is 0 or 1,

[0410] q1 is 0 or 1,

[0411] The order of presence of the individual repeating units denoted p1 or q1 and enclosed in brackets is arbitrary.

[0412] Here, at least one of p1 and q1 is 1.

[0413] Here, X 1 (Typically X 1 The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, X 1 Not substituted by these groups.

[0414] In a preferred embodiment, the above X 1 can be independently -(R 21 ) p1 -(X a ) q1 -R 22 -. R 22 Represents a single bond, -(CH2) p3 - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) p3 p3 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. 22 (Typically R 22 The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, R 22 is not substituted by these groups. 21 , p1, X a , q1 has the same meaning as above.

[0415] Preferably the above X 1 Each independently may be a single bond, C 1－20 Alkylene, -R 21 -X a -R 22 -or-X a1 -R 22 -

[0416] [Where R 21 and R 22 The meaning is the same as above.

[0417] X a express:

[0418] -O-,

[0419] -S-,

[0420] -C(O)O-,

[0421] -CONR 34 -

[0422] -O-CONR 34 -

[0423] -Si(R 33 )2-、

[0424] -(Si(R 33 )2O) m′ -Si(R 33 )2-、

[0425] -O-(CH2) u5 -(Si(R 33 )2O) m′ -Si(R 33 )2-、

[0426] -O-(CH2) u5 -Si(R 33 )2-O-Si(R 33 )2-CH2CH2-Si(R 33 )2-O-Si(R 33 )2-、

[0427] -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-,

[0428] -CONR 34 -(CH2) u5 -(Si(R 33 )2O) m′ -Si(R 33 )2-、

[0429] -CONR 34 -(CH2) u5 -N(R 34 )-,or

[0430] -CONR 34 -(o-phenylene, m-phenylene or p-phenylene)-Si(R 33 )2-

[0431] (Where R 33 , R 34and m' has the same meaning as above, u5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3),

[0432] X a1 Indicates -S-, -C(O)O-, or -O-CONR 34 -(In the formula, the meanings of the symbols are the same as above).]

[0433] In one approach, X 1 are independently a single bond or C 1－6 Alkylene, preferably C 1－6 Alkylene, more preferably C 1－3 The alkylene group is, for example, a methylene group.

[0434] The above X 1 can be independently selected from fluorine atoms, C 1－3 Alkyl and C 1－3 Fluorinated alkyl (preferably C 1－3 In one embodiment, X 1 For non-substitution.

[0435] As X 1 Specific examples include:

[0436] single bond,

[0437] -CH2OCH2-,

[0438] -CH2O(CH2)2-,

[0439] -CH2O(CH2)3-,

[0440] -CH2O(CH2)4-,

[0441] -CH2O(CH2)5-,

[0442] -CH2O(CH2)6-,

[0443] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0444] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0445] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0446] <h2 style=";text-align:left;direction:ltr">-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0447] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0448] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 20 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0449] <h2 style=";text-align:left;direction:ltr"> CH2OCF2CHFOCF2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0450] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0451] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0452] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0453] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0454] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0455] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0456] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0457] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0458] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0459] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0460] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0461] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0462] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0463] <h2 style=";text-align:left;direction:ltr">-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0464] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0465] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0466] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0467] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0468] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0469] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0470] <h2 style=";text-align:left;direction:ltr"> -(CH2)2-Si(CH3)2-(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0471] <h2 style=";text-align:left;direction:ltr"> CH2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0472] <h2 style=";text-align:left;direction:ltr"> (CH2)2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0473] <h2 style=";text-align:left;direction:ltr"> (CH2)3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0474] <h2 style=";text-align:left;direction:ltr"> (CH2)4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0475] <h2 style=";text-align:left;direction:ltr"> (CH2)5<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0476] <h2 style=";text-align:left;direction:ltr"> (CH2)6<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0477] <h2 style=";text-align:left;direction:ltr"> CO<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0478] <h2 style=";text-align:left;direction:ltr"> -S-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0479] <h2 style=";text-align:left;direction:ltr"> (CH2)2S(CH2)3)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0480] <h2 style=";text-align:left;direction:ltr"> -C(O)O-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0481] <h2 style=";text-align:left;direction:ltr"> -C(O)O-(CH2)6-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0482] <h2 style=";text-align:left;direction:ltr"> -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、

[0483] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,

[0484] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-,

[0485] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[0486] -OCH2-,

[0487] -O(CH2)3-,

[0488] -OCFHCF2-,

[0489] wait.

[0490] The above R n Each time it occurs, it is independently -X 1 -R Si The groups shown, hydrogen atoms, phenyl groups or C 1－6 alkyl.

[0491] In one approach, R n is a hydrogen atom, a phenyl group or a C 1－6 The alkyl group is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0492] In one approach, R n is a hydrogen atom. In one embodiment, R n In one embodiment, R n C 1－6 alkyl.

[0493] In one approach, R n For -X 1 -R Si Here, X 1 The meaning is the same as above, R Si It is a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded.

[0494] In one approach, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si It is a group represented by formula (S1).

[0495] In formula (S1), k1 is preferably 2 or 3, l1 is 0 or 1, and m1 is 0 or 1 (wherein the total of k1, l1, and m1 is 3), and k1 is more preferably 3. Here, r2 is 2 or 3, preferably 3. In addition, the total of r1, r2, and r3 is 3.

[0496] In one approach, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si It is a group represented by formula (S2).

[0497] In formula (S2), preferably l2 is 2 or 3, m2 is 0 or 1 (wherein the total of l2 and m2 is 3), and more preferably l2 is 3. Here, m1″ is 2 or 3, and preferably 3.

[0498] In one approach, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si It is a group represented by formula (S2).

[0499] In formula (S2), preferably, l2 is 2 and m2 is 1. Here, m1″ is 2 or 3, preferably 3.

[0500] In one approach, R n For -X 1 -R Si The group shown, R Si It is a group represented by formula (S1).

[0501] In formula (S1), k1 is preferably 2 or 3, l1 is 0 or 1, and m1 is 0 or 1 (wherein the total of k1, l1, and m1 is 3), and k1 is more preferably 3. Here, r2 is 2 or 3, preferably 3. In addition, the total of r1, r2, and r3 is 3.

[0502] In one approach, R n For -X 1 -R Si The group shown, R Si It is a group represented by formula (S2).

[0503] In formula (S2), preferably l2 is 2 or 3, m2 is 0 or 1 (wherein the total of l2 and m2 is 3), and more preferably l2 is 3. Here, m1″ is 2 or 3, and preferably 3.

[0504] In one approach, R n For -X 1 -R Si The group shown, R Si It is a group represented by formula (S3).

[0505] In one approach, R n For -X1 -R Si The group shown in formula (1) or (2) is Si is a group represented by formula (S1), k1 is 0. Preferably l1 is 2 or 3, and more preferably l1 is 3.

[0506] In one embodiment, in the liquid composition of the present invention, the fluorinated polyether group-containing silane compound is a compound represented by formula (1).

[0507] In another embodiment, in the liquid composition of the present invention, the fluorinated polyether group-containing silane compound is a compound represented by formula (2).

[0508] The fluorinated polyether group-containing silane compound represented by the above formula (1) or formula (2) is not particularly limited and may have a 5×10 2 ~1×10 5 In this range, from the viewpoint of friction durability, it is preferably 2,000 to 32,000, more preferably 2,500 to 12,000. Here, the "average molecular weight" refers to the number average molecular weight, and the "average molecular weight" is calculated by 19 The value measured by F-NMR.

[0509] The content of the silane compound containing the fluorinated polyether group can be, for example, 10% by mass or less, or 3% by mass or less relative to the liquid composition. The above content can be, for example, 0.5% by mass or more, or 0.01% by mass or more. In the liquid composition, by containing the above content, the micelle formation of the silane compound containing the fluorinated alkyl group is suppressed, and it can be considered that, as a result, the surface of the formed surface treatment layer becomes flatter and the friction durability becomes better.

[0510] In addition, the suppression of micelle formation in the liquid composition means, for example, that when the average hydrodynamic particle size of the solute in the liquid composition of the present invention is measured by a dynamic light scattering method, there is no peak of scattering intensity at an average hydrodynamic particle size of 100 nm or more. Specifically, it means that there is no scattering intensity at an average hydrodynamic particle size of 100 nm or more.

[0511] (Fluorinated alkyl-containing silane compound)

[0512] The silane compound containing a fluorinated alkyl group has a group represented by the following formula: The molecular weight of the silane compound containing a fluorinated alkyl group is, for example, 300 to 500.

[0513] -SiR 31 n3 R 32 3-n3

[0514] The fluorinated alkyl group-containing silane compound is preferably represented by formula (B1).

[0515] RF 3 -X 31 -SiR 31 n3 R 32 3-n3 (B1)

[0516] The above R 31 Each occurrence of is independently a hydroxyl group or a hydrolyzable group. The hydrolyzable group has the same meaning as above.

[0517] The above R 32 Each occurrence of is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0518] In R 32 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0519] Each occurrence of n3 is independently an integer of 0 to 3. In the fluorinated alkyl group-containing silane compound, at least one n3 is 1 or more.

[0520] n3 is preferably an integer of 1 to 3, more preferably 2 or 3, and further preferably 3.

[0521] The above Rf 3 C substituted with one or more fluorine atoms 1－6 Alkyl, preferably C 1－6 Perfluoroalkyl, more preferably C 2－6 Perfluoroalkyl.

[0522] In one embodiment, Rf 3 C 2－5 In one embodiment, Rf 3 C 3－5 Perfluoroalkyl.

[0523] The above X 31 It is a single bond, an oxygen atom or a divalent organic group.

[0524] In one approach, X 31 For a single key.

[0525] In one approach, X 31 For oxygen atoms.

[0526] In one approach, X 31 It is a divalent organic group.

[0527] X 31 Preferably -(X 311 ) z11 -(Z 31 ) z12 -. The order of existence of the repeating units enclosed in brackets is 31 In addition, in X 31 Center left and Rf 3 Bonding.

[0528] The above X 311 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene, preferably C 1－3 Alkylene.

[0529] The above Z 31 Each is independently an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

[0530] The above z11 is an integer of 1 to 3. In one embodiment, z11 is 1. In one embodiment, z11 is 2. In one embodiment, z11 is 3.

[0531] The above z12 is an integer of 0 to 2. In one embodiment, z12 is 0. In one embodiment, z12 is 1.

[0532] X 31 Preferably -X 311 -Z 31 -X 311 -, or -X 311 In one embodiment, C 1－5 Alkylene-O-C 1－5 Alkylene, C 1－5 Alkylene.

[0533] X 31 Specifically, the following structures can be cited.

[0534] -CH2-,

[0535] -(CH2)2-,

[0536] -(CH2)3-,

[0537] -(CH2)4-,

[0538] -CH2-O-(CH2)2-,

[0539] -CH2-O-(CH2)3-,

[0540] -CH2-O-(CH2)4-

[0541] Examples of the fluorinated alkyl group-containing silane compound include the following structures.

[0542] C2F5CH2O(CH2)3Si(OCH3)3,

[0543] C4F9(CH2)2Si(OCH3)3,

[0544] C4F9CH2O(CH2)2Si(OCH3)3,

[0545] C4F9CH2O(CH2)3Si(OCH3)3,

[0546] C5F 11 (CH2)2Si(OCH3)3,

[0547] C5F 11 CH2O(CH2)2Si(OCH3)3,

[0548] C5F 11 CH2O(CH2)3Si(OCH3)3,

[0549] C6F 13 (CH2)2Si(OCH3)3,

[0550] C6F 13 CH2O(CH2)2Si(OCH3)3,

[0551] C6F 13 CH2O(CH2)3Si(OCH3)3

[0552] The content of the fluorinated alkyl-containing silane compound relative to the fluorinated polyether group-containing silane compound is preferably 0.001 to 1.5 in terms of molar ratio ([number of moles of the fluorinated alkyl-containing silane compound] / [number of moles of the fluorinated polyether group-containing silane compound]), more preferably 0.001 to 0.5, further preferably 0.001 to 0.1, and particularly preferably 0.001 to 0.02.

[0553] The content of the silane compound containing a fluorinated alkyl group may be, for example, 0.2 mass % or less, 0.1 mass % or less, 0.02 mass % or less, or 0.0002 mass % or less relative to the liquid composition. The above content may be, for example, 0.00002 mass % or more, or 0.000002 mass % or more.

[0554] In one embodiment, the content of the fluorinated alkyl group-containing silane compound may be, for example, 0.0002 mass % or more, or 0.002 mass % or more, based on the liquid composition.

[0555] In one embodiment, the liquid composition of the present invention does not contain an oligomer of a fluoroalkyl group-containing silane compound.

[0556] (Solvent)

[0557] The solvent is preferably a fluorinated solvent, more preferably a hydrofluoroether, further preferably at least one selected from perfluorobutyl methyl ether (C4F9OCH3) (for example, Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (for example, Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.) and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.), and particularly preferably perfluorobutyl methyl ether and / or perfluorobutyl ethyl ether.

[0558] In addition, the solvent may also contain the following solvents. For example, aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, etc.; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, lactic acid esters such as ethyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl aminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono butyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether and other glycol ethers; methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, tert-pentanol and other alcohols; ethylene glycol, propylene glycol and other glycols; tetrahydrofuran, tetrahydropyran, dioxane and other cyclic ethers; N,N-dimethylformamide, N,N-dimethylacetamide and other amides; methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve Fiber agents, ether alcohols such as diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by ZEON Corporation of Japan) and other fluorinated solvents, etc. Or a mixed solvent of two or more thereof may be contained.

[0559] The solvent may be contained in an amount of 50 to 99.8% by mass, or 90 to 99.8% by mass, based on the liquid composition of the present invention.

[0560] (Other compounds)

[0561] The liquid composition of the present invention may further contain a (non-reactive) fluorinated polyether compound that can be understood as a fluorinated oil, preferably a perfluoro (poly) ether compound (hereinafter collectively referred to as "fluorinated oil"), a (non-reactive) organosilicon compound that can be understood as a silicone oil (hereinafter also referred to as "silicone oil"), a catalyst, a surfactant, an inhibitor, a sensitizer, and the like.

[0562] The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (3) (perfluoro (poly) ether compound).

[0563] R 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 …(3)

[0564] In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1―16 Perfluoroalkyl), Rf 6 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1―16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0565] a', b', c' and d' respectively represent the number of four repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 to 300, and the sum of a', b', c' and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of existence of each repeating unit marked with subscript a', b', c' or d' and enclosed in parentheses is arbitrary in the formula. In these repeating units, -(OC4F8)- may be any one of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, and is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, and is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be any of -(OCF2CF2)- and (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0566] Examples of the perfluoro(poly)ether compound represented by the general formula (3) include compounds represented by any one of the following general formulas (3a) and (3b) (the compounds may be one or a mixture of two or more).

[0567] R 5 -(OCF2CF2CF2) b″ -Rf 6 …(3a)

[0568] R 5 -(OCF2CF2CF2CF2) a″ -(OCF2CF2CF2) b″ -(OCF2CF2) c″ -(OCF2) d″ -Rf 6 …(3b)

[0569] In these formulas, Rf 5 and Rf 6As described above; in formula (3a), b″ is an integer greater than 1 and less than 100; in formula (3b), a″ and b″ are each independently an integer greater than 0 and less than 30, and c″ and d″ are each independently an integer greater than 1 and less than 300. The order of existence of each repeating unit marked with subscripts a″, b″, c″, d″ and enclosed in brackets in the formula is arbitrary.

[0570] In addition, from another point of view, the fluorinated oil can be of the general formula Rf 4 -F(where Rf 4 C 5－16 A compound represented by a perfluoroalkyl group. In addition, it may be a chlorotrifluoroethylene oligomer.

[0571] The fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0572] The liquid composition of the present invention may contain, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass of fluorinated oil. In one embodiment, the liquid composition of the present invention contains substantially no fluorinated oil. Substantially containing no fluorinated oil means that the liquid composition contains no fluorinated oil at all, or may contain a very small amount of fluorinated oil.

[0573] In one embodiment, the average molecular weight of the fluorinated oil can be greater than the average molecular weight of the fluorinated polyether group-containing silane compound. By designing the average molecular weight in this way, better friction durability and surface sliding properties can be obtained, especially when the surface treatment layer is formed by vacuum deposition.

[0574] In one embodiment, the molecular weight of the fluorinated oil can be made smaller than the molecular weight of the silane compound containing the fluorinated polyether group. By designing the molecular weight, the transparency of the surface treatment layer obtained by the compound can be suppressed to decrease, and a cured product with high friction durability and high surface slip can be formed.

[0575] The fluorine-containing oil contributes to improving the surface slip properties of the layer formed from the liquid composition of the present invention.

[0576] In one embodiment, the fluorinated oil may be contained in an amount of 0.001 to 50 mol %, for example, 0.01 to 40 mol %, based on the total amount of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound.

[0577] In one embodiment, the liquid composition of the present invention contains a compound represented by formula (1) and a compound represented by formula (2) as a fluorinated polyether group-containing silane compound, and further contains a fluorinated oil.

[0578] In one embodiment, the compound represented by formula (1), the compound represented by formula (2), the silane compound containing a fluorinated alkyl group, and the fluorinated oil preferably contain 0.001 to 70 mol% of the compound represented by formula (2) and 0.001 to 50 mol% of the fluorinated oil, more preferably contain 0.01 to 60 mol% of the compound represented by formula (2) and 0.01 to 40 mol% of the fluorinated oil, and further preferably contain 0.1 to 50 mol% of the compound represented by formula (2) and 0.1 to 30 mol% of the fluorinated oil. The ratio of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of the silane compound containing a fluorinated polyether group is 0.001 to 1.5.

[0579] In one embodiment, the compound represented by formula (1), the compound represented by formula (2), the silane compound containing a fluorinated alkyl group, and the fluorinated oil preferably contain 0.001 to 70 mol% of the compound represented by formula (1) and 0.001 to 50 mol% of the fluorinated oil, more preferably contain 0.01 to 60 mol% of the compound represented by formula (1) and 0.01 to 40 mol% of the fluorinated oil, and further preferably contain 0.1 to 50 mol% of the compound represented by formula (1) and 0.1 to 30 mol% of the fluorinated oil. The ratio of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of the silane compound containing a fluorinated polyether group is 0.001 to 1.5.

[0580] As the above-mentioned silicone oil, for example, a straight-chain or cyclic silicone oil with a siloxane bond of 2,000 or less can be used. The straight-chain silicone oil can be the so-called ordinary silicone oil (Straight silicone) and modified silicone oil. As ordinary silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil can be listed. As modified silicone oil, silicone oil obtained by modifying ordinary silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. can be listed. Cyclic silicone oil, for example, cyclic dimethylsiloxane oil can be listed.

[0581] In the liquid composition (e.g., surface treatment agent) of the present invention, the silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass (the total when two or more types are used, and the same applies hereinafter) of the fluorinated polyether group-containing silane compound of the present invention.

[0582] Silicone oil helps to improve the surface slip properties of the surface treatment layer.

[0583] Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), and transition metals (eg, Ti, Ni, Sn, etc.).

[0584] The catalyst promotes the hydrolysis and dehydration condensation of the fluorinated polyether group-containing silane compound of the present invention, and promotes the formation of a layer formed from the liquid composition of the present invention (eg, surface treatment agent).

[0585] Examples of other components include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane in addition to the above components.

[0586] (Surface treatment agent)

[0587] The liquid composition of the present invention is used as a surface treating agent for treating the surface of a substrate.

[0588] In one embodiment, the surface treatment agent of the present invention can be impregnated into a porous material, such as a porous ceramic material, a metal fiber, such as a product obtained by fixing steel wool in a cotton-like shape, to form a pellet. The pellet can be used, for example, for vacuum deposition.

[0589] In one embodiment, the surface treatment agent of the present invention is used for wet coating.

[0590] (thing)

[0591] Next, the article of the present invention will be described.

[0592] The article of the present invention comprises a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the liquid composition of the present invention.

[0593] The substrate that can be used in the present invention can be composed of any appropriate material, such as glass, resin (natural or synthetic resin, such as general plastic material, in the form of plate, film, or other forms), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building components, etc.

[0594] For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material for optical components, such as glass or transparent plastic. In addition, when the article to be manufactured is an optical component, a certain layer (or film), such as a hard coating or an anti-reflection layer, can also be formed on the surface (outermost layer) of the substrate. The anti-reflection layer can use any of a single-layer anti-reflection layer and a multi-layer anti-reflection layer. As examples of inorganic substances that can be used for anti-reflection layers, SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. can be cited. These inorganic substances can be used alone or in combination with two or more of these (for example, as a mixture). When a multi-layer anti-reflection layer is used, SiO2 and / or SiO are preferably used in its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode can be provided on a portion of the surface of the substrate (glass), such as a thin film of indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film and a liquid crystal display module, etc. according to its specific specifications.

[0595] The shape of the substrate is not particularly limited. In addition, the surface area of ​​the substrate on which the surface treatment layer is to be formed may be at least a portion of the substrate surface, and can be appropriately determined according to the purpose and specific specifications of the article to be manufactured.

[0596] As the substrate, at least part of its surface can be composed of a material that originally has hydroxyl groups. As such materials, glass can be cited, and metals (especially base metals), ceramics, semiconductors, etc., with natural oxide films or thermal oxide films formed on the surface can also be cited. Alternatively, in the case where the substrate has hydroxyl groups but not enough, or does not originally have hydroxyl groups, hydroxyl groups can be introduced or increased on the substrate surface by subjecting the substrate to certain pretreatments. Examples of such pretreatments include plasma treatment (such as corona discharge) or ion beam irradiation. Plasma treatment is not only used to introduce hydroxyl groups or increase hydroxyl groups on the substrate surface, but is also suitable for cleaning the substrate surface (removing foreign matter, etc.). In addition, as other examples of such pretreatments, there can be cited: using the LB method (Langmuir-Blodgett method, Langmuir-Blodgett method) or chemical adsorption method, etc., to form a film of an interface adsorbent having a carbon-carbon unsaturated bond group in the form of a monomolecular film on the substrate surface in advance, and then, the unsaturated bond is disconnected in an atmosphere containing oxygen or nitrogen.

[0597] Alternatively, the substrate may be composed of a material having at least a surface portion thereof that contains an organic silicon compound having one or more other reactive groups, for example, a Si—H group, or an alkoxysilane.

[0598] Thereafter, a layer of the liquid composition of the present invention is formed on the surface of the substrate, and the layer is subjected to post-treatment as necessary, thereby forming a layer of the liquid composition of the present invention.

[0599] The liquid composition can be applied to the surface of the substrate in a manner that covers the surface, thereby implementing the layer formation of the liquid composition of the present invention. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

[0600] As examples of the wet coating method, dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and the like can be cited.

[0601] Examples of dry coating methods include evaporation (usually vacuum evaporation), sputtering, CVD, and similar methods. Specific examples of evaporation methods (usually vacuum evaporation) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0602] Alternatively, coating may be performed using a normal pressure plasma method.

[0603] In the case of a wet coating method, the liquid composition of the present invention can be diluted with a solvent and applied to the surface of the substrate. From the viewpoint of the stability of the liquid composition of the present invention and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F 13CH2CH3 (e.g. ASAHIKLIN (registered trademark) AC-6000 produced by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g. ZEORORA (registered trademark) H produced by ZEON Corporation of Japan); hydrofluoroether (HFE) (e.g. perfluoropropyl methyl ether (C3F7OCH3) (e.g. Novec (registered trademark) 7000 produced by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g. Novec (registered trademark) )7100), perfluorobutyl ethyl ether (C4F9OC2H5) (for example, Novec (trademark) 7200 produced by Sumitomo 3M Co., Ltd.), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (for example, Novec (trademark) 7300 produced by Sumitomo 3M Co., Ltd.), or CF3CH2OCF2CHF2 (for example, ASAHIKLIN (registered trademark) AE-3000 produced by Asahi Glass Co., Ltd.)). These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0604] As the solvent used in the wet coating method, it is preferable to use the same solvent as the solvent of the liquid composition of the present invention.

[0605] When the dry coating method is used, the liquid composition of the present invention can be used for the dry coating method directly, or can be used for the dry coating method after being diluted with the above-mentioned solvent.

[0606] Since the liquid composition of the present invention has good dispersibility, it can be effectively used in a wet coating method, particularly spray coating.

[0607] The layer formation of the liquid composition is preferably implemented in a manner that the liquid composition of the present invention and the catalyst for hydrolysis and dehydration condensation coexist in the layer. For simplicity, in the case of utilizing the wet coating method, after diluting the liquid composition of the present invention with a solvent, a catalyst is added to the diluent of the liquid composition of the present invention before being applied to the substrate surface. In the case of utilizing the dry coating method, the liquid composition of the present invention to which the catalyst is added can be directly subjected to vapor deposition (usually vacuum deposition) treatment, or a granular material formed by impregnating the liquid composition of the present invention to which the catalyst is added in a metal porous body such as iron or copper is used for vapor deposition (usually vacuum deposition) treatment.

[0608] Any appropriate acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. In addition, as the base catalyst, for example, ammonia, organic amines, etc. can be used.

[0609] As mentioned above, a layer from the liquid composition of the present invention is formed on the surface of the substrate to manufacture the article of the present invention. The above-mentioned layer thus obtained has both high surface slip and high friction durability. In addition, the above-mentioned layer, in addition to having high friction durability, although also depending on the composition of the liquid composition used, can also have water repellency, oil repellency, antifouling (for example, preventing dirt such as fingerprints from adhering), waterproofness (preventing water from immersing electronic components, etc.), surface slip (or lubricity, such as the wiping off of dirt such as fingerprints, excellent touch for fingers), etc., and is suitable for use as a functional film.

[0610] That is, the present invention also relates to an optical material having the above-mentioned surface treatment layer as the outermost layer.

[0611] As optical materials, in addition to optical materials related to displays such as those exemplified below, it is also preferred to cite a variety of optical materials, for example: cathode ray tubes (CRT, such as computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED, Field Emission Display) and other displays or protective plates of these displays, or materials with anti-reflection film treatment applied to their surfaces.

[0612] The article having the layer obtained by the present invention may be an optical component, but is not particularly limited. Examples of optical components include the following articles: lenses of glasses, etc.; front protection plates, anti-reflection plates, polarizing plates, anti-glare plates of displays such as PDP and LCD; touch panel sheets of devices such as mobile phones and portable information terminals; disc surfaces of Blu-ray (registered trademark) discs, DVD discs, CD-R, MO, etc.; optical fibers; display surfaces of clocks, etc.

[0613] Furthermore, the article having the layer obtained by the present invention may be a medical device or a medical material.

[0614] In addition, the article having the layer obtained by the present invention can also be an interior and exterior component of an automobile. Examples of exterior components include windows, lampshades, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.

[0615] The thickness of the layer is not particularly limited. In the case of an optical component, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and more preferably 1 to 15 nm from the viewpoint of optical performance, surface slip, friction durability, and antifouling properties.

[0616] The articles obtained by using the liquid composition (eg, surface treatment agent) of the present invention have been described in detail above. In addition, the uses, methods of use, and methods of producing articles of the liquid composition of the present invention are not limited to the above examples.

[0617] Although the embodiments have been described above, it will be appreciated that various modifications may be made to the embodiments and details without departing from the spirit and scope of the claims.

[0618] Example

[0619] The liquid composition of the present invention is described in more detail by the following examples, but the present invention is not limited to these examples. In addition, in the present example, the chemical formulas shown below all represent average compositions. In the present example, the order of existence of the repeating units constituting the perfluoropolyether is arbitrary. In addition, Me refers to a methyl group.

[0620] (Examples 1 to 7)

[0621] A silane compound containing a fluorinated polyether group (Compound A1) was dissolved in a hydrofluoroether (manufactured by 3M, Novec HFE-7200) in a solid content concentration of 0.06 mass %. Then, a silane compound containing a fluorinated alkyl group (Compounds B1 to B3) was added to the solution in the proportions described in Table 1 to prepare a liquid composition. In addition, the numerical value described as "molar ratio" in the table means the ratio (molar ratio) of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of Compound A1.

[0622] Compound A1:

[0623]

[0624] (m≈21, n≈35)

[0625] Compound B1:

[0626] C2F5CH2OCH2CH2CH2Si(OCH3)3

[0627] Compound B2:

[0628] C4F9CH2CH2Si(OCH3)3

[0629] Compound B3:

[0630] C6F13 CH2CH2Si(OCH3)3

[0631] (Examples 8 to 14)

[0632] A silane compound containing a fluorinated polyether group (Compound A2) was dissolved in a hydrofluoroether (3M, Novec HFE-7200) in a solid content concentration of 0.06 mass %. Then, a silane compound containing a fluorinated alkyl group (Compounds B1 to B3) was added to the solution in the ratios described in Table 2 to prepare a liquid composition. In addition, the numerical value described as "molar ratio" in the table means the ratio (molar ratio) of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of Compound A2.

[0633] Compound A2:

[0634]

[0635] (m≈21, n≈35)

[0636] (Examples 15-16)

[0637] A silane compound containing a fluorinated polyether group (Compound A3) was dissolved in a hydrofluoroether (3M, Novec HFE-7200) in a solid content concentration of 0.06 mass %. Then, a silane compound containing a fluorinated alkyl group (Compound B2) was added to the solution in the ratio described in Table 3 to prepare a liquid composition. In addition, the numerical value described as "molar ratio" in the table means the ratio (molar ratio) of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of Compound A3.

[0638] Compound A3:

[0639]

[0640] (m≈27, n≈29)

[0641] (Examples 17-18)

[0642] A silane compound containing a fluorinated polyether group (Compound A4) was dissolved in a hydrofluoroether (3M, Novec HFE-7200) in a solid content concentration of 0.06 mass %. Then, a silane compound containing a fluorinated alkyl group (Compound B2) was added to the solution in the ratio described in Table 3 to prepare a liquid composition. In addition, the numerical value described as "molar ratio" in the table means the ratio (molar ratio) of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of Compound A4.

[0643] Compound A4:

[0644]

[0645] (n≈13)

[0646] (Comparative Example 1)

[0647] A fluorinated polyether group-containing silane compound (Compound A1) was dissolved in hydrofluoroether (Novec HFE-7200 manufactured by 3M Company) so as to have a solid content concentration of 0.06% by mass to prepare a liquid composition.

[0648] (Comparative Example 2)

[0649] A fluorinated polyether group-containing silane compound (Compound A1) was dissolved in hydrofluoroether (3M Company, Novec HFE-7200) to a solid content concentration of 0.06 mass %. Then, a fluorinated alkyl group-containing silane compound (Compound B2) in an amount shown in Table 1 was added to the solution to prepare a surface treatment agent.

[0650] (Comparative Example 3)

[0651] A fluorinated polyether group-containing silane compound (Compound A2) was dissolved in hydrofluoroether (Novec HFE-7200 manufactured by 3M Company) so as to have a solid content concentration of 0.06% by mass to prepare a liquid composition.

[0652] (Comparative Example 4)

[0653] A fluorinated polyether group-containing silane compound (Compound A2) was dissolved in hydrofluoroether (Novec HFE-7200 manufactured by 3M) to a solid content concentration of 0.06 mass %. Then, a fluorinated alkyl group-containing silane compound (Compound B2) in an amount shown in Table 2 was added to the solution to prepare a surface treatment agent.

[0654] (Comparative Example 5)

[0655] A fluorinated polyether group-containing silane compound (Compound A3) was dissolved in hydrofluoroether (Novec HFE-7200 manufactured by 3M Co.) so as to have a solid content concentration of 0.06% by mass to prepare a liquid composition.

[0656] (Comparative Example 6)

[0657] A fluorinated polyether group-containing silane compound (Compound A4) was dissolved in hydrofluoroether (Novec HFE-7200 manufactured by 3M Co.) so as to have a solid content concentration of 0.06% by mass to prepare a liquid composition.

[0658] (Formation of Surface Treatment Layer)

[0659] The liquid composition prepared above was uniformly sprayed onto the surface of a substrate (chemically strengthened glass (Gorilla glass manufactured by Corning Incorporated, thickness 0.7 mm) using a spray coating device equipped with a two-fluid nozzle (manufactured by Toho Chemical Co., Ltd.). The coating amount of the liquid composition was set to 48 g / m 2 The coated substrate was heated at 150° C. for 30 minutes to form a cured film.

[0660] (Determination of mean hydrodynamic particle size)

[0661] A silane compound containing a fluorinated polyether group adjusted to a concentration of 50% is mixed with a silane compound containing a fluorinated alkyl group, and the mixture is stirred for 3 minutes using a test tube stirrer at 25±2°C, and then placed in a dedicated container. The container is placed in a dynamic light scattering (DLS) measuring device (Malvern, Zetasizer Nano S), and the measurement is started after standing for 2 minutes to obtain particle size distribution data. The operation is performed 3 times for one sample, and the average value is taken as the average hydrodynamic particle size and 60% cumulative distribution particle size.

[0662] (evaluate)

[0663] The abrasion durability of the cured films obtained in Examples 1 to 18 and Comparative Examples 1 to 6 was measured.

[0664] (Rubber friction durability test)

[0665] The water contact angle was measured by rubbing 2500 times using a Rubbing Tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions. The test was continued until the contact angle reached less than 100°. The test environment conditions were 25°C and 40% RH. The number of rubbing times when the contact angle reached less than 100° is shown in Tables 1 to 3 as the results of the rubber rubbing durability test.

[0666] Eraser: Raber Eraser (Minoan Company);

[0667] Ground contact area:

[0668] Moving distance (one way): 30mm;

[0669] Moving speed: 40 round trips / minute;

[0670] load:

[0671] [Table 1]

[0672]

[0673] [Table 2]

[0674]

[0675] [Table 3]

[0676]

[0677] Industrial Applicability

[0678] The liquid composition of the present invention is suitable for use on a variety of substrates, and is particularly suitable for forming a surface treatment layer on the surface of an optical component that requires transparency.

Claims

1. A liquid composition for surface treatment, characterized in that: Contains a fluorinated polyether group-containing silane compound represented by the following formula (1) or (2), a fluorinated alkyl group-containing silane compound represented by the formula (B1), and a solvent, The average hydrodynamic particle size of the silane compound containing a fluorinated polyether group and the silane compound containing a fluorinated alkyl group in the liquid composition obtained by a dynamic light scattering method is 10 to 1500 nm. The average hydrodynamic particle size is a value obtained by mixing a liquid mixture containing 50% by mass of the fluorinated polyether group-containing silane compound in the solvent with the fluorinated alkyl group-containing silane compound in the same ratio as the ratio of the fluorinated polyether group-containing silane compound to the fluorinated alkyl group-containing silane compound in the liquid composition, and then allowing the mixture to stand at 25° C. for measurement. R F1 α -X A -R Si β (1) R Si γ -X A -R F2 -X A -R Si γ (2) In formula (1) or (2), R F1 is Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; R 1 C 1-16 Alkyl or C substituted with one or more fluorine atoms 1-16 alkyl; R 2 C 1-6 Alkylene or C substituted with one or more fluorine atoms 1-6 Alkylene; R F Each occurrence is independently of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - the groups shown; a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary; R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom; p is independently 0 or 1 at each occurrence; q is independently 0 or 1 at each occurrence; X A are independently represented by the following formulas, R n -X on each occurrence 1 -R Si The groups shown, hydrogen atoms, phenyl groups or C 1-6 alkyl; X 1 Each occurrence is independently a single bond or a divalent organic group selected from fluorine atoms, C 1-3 Alkyl and C 1-3 One or more substituents in the fluoroalkyl group are substituted or unsubstituted; α, β and γ are 1; R Si Each occurrence is independently any one of the following groups represented by formula (S1) to (S2), -SiR a1 k1 R b1 11 R c1 m1 (S1) -CR d1 k2 R e1 12 R f1 m2 (S2) R a1 -Z independently at each occurrence 1 -SiR 41 r1 R 42 r2 R 43 r3 ; Z 1 Each occurrence is independently an oxygen atom or a divalent organic group; R 41 -Z independently at each occurrence 1′ -SiR 41′ r1′ R 42′ r2′ R 43′ r3′ ; Z 1′ Each occurrence is independently an oxygen atom or a divalent organic group; R 41′ -Z independently at each occurrence 1″ -SiR 41″ r1″ R 42″ r2″ ; Z 1″ Each occurrence is independently an oxygen atom or a divalent organic group; R 41″ Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 42″ Each occurrence is independently a hydrogen atom or a monovalent organic group; r1″ is independently an integer from 0 to 3 at each occurrence; r2″ is independently an integer from 0 to 3 at each occurrence; R 42′ Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 43′ Each occurrence is independently a hydrogen atom or a monovalent organic group; r1′ is independently an integer from 0 to 3 at each occurrence; r2′ is independently an integer from 0 to 3 at each occurrence; r3′ is independently an integer from 0 to 3 at each occurrence; R 42 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 43 Each occurrence is independently a hydrogen atom or a monovalent organic group; r1 is independently an integer from 0 to 3 at each occurrence; r2 is independently an integer from 0 to 3 at each occurrence; r3 is independently an integer from 0 to 3 at each occurrence; R b1 Each occurrence is independently a hydroxyl group or a hydrolyzable group; R c1 Each occurrence is independently a hydrogen atom or a monovalent organic group; k1 is independently an integer from 0 to 3 at each occurrence; l1 is independently an integer from 0 to 3 each time it appears; m1 is independently an integer from 0 to 3 at each occurrence; Wherein, in formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group; R d1 Each time it occurs, it is independently -Z 2 -CR 51 s1 R 52 s2 R 53 s3 ; Z 2 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group; R 51 Each time it occurs, it is independently -Z 2′ -CR 51′ s1′ R 52′ s2′ ; Z 2′ Each occurrence is independently a single bond, an oxygen atom or a divalent organic group; R 51′ Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ; Z 3 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group; R 51″ Each occurrence is independently a hydroxyl group or a hydrolyzable group; R 52″ Each occurrence is independently a hydrogen atom or a monovalent organic group; m1″ is independently an integer from 0 to 3 at each occurrence; R 52′ Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group; s1′ is independently an integer from 0 to 3 at each occurrence; s2′ is independently an integer from 0 to 3 at each occurrence; R 52 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ; R 53 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group; s1 is independently an integer from 0 to 3 each time it appears; s2 is independently an integer from 0 to 3 at each occurrence; s3 is independently an integer from 0 to 3 at each occurrence; R e1 Each time it occurs, it is independently -Z 3 -SiR 51″ m1″ R 52″ 3－m1″ ; R f1 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group; k2 is independently an integer from 0 to 3 at each occurrence; l2 is independently an integer from 0 to 3 at each occurrence; m2 is independently an integer from 0 to 3 at each occurrence; In formula (S2), there is at least one -SiR 51″ m1″ R 52″ 3-m1″ ; The hydrolyzable group is independently -OR at each occurrence. h1 、-OCOR h1 、-ON=CR h1 2. -NR h1 2. -NHR h1 , -NCO or halogen, in which R h1 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, Rf 3 -X 31 -SiR 31 n3 R 32 3-n3 (B1) In formula (B1), R 3 C is substituted with one or more fluorine atoms 1-6 alkyl; X 31 By -(X 311 ) z11 -(Z 31 ) z12 -express, X 311 C 1-6 Alkylene or C substituted with one or more fluorine atoms 1-6 Alkylene, z11 is an integer from 1 to 3, Z 31 are independently an oxygen atom or a sulfur atom, z12 is an integer from 0 to 2, The order of existence of the repeating units enclosed in brackets is X 31 The middle is arbitrary; R 31 are independently a hydroxyl group or a hydrolyzable group; R 32 are each independently a hydrogen atom or a monovalent organic group; n3 is an integer from 1 to 3; The hydrolyzable group is independently -OR at each occurrence. h1 、-OCOR h1 、-ON=CR h1 2. -NR h1 2. -NHR h1 , -NCO or halogen, in which R h1 It represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

2. The surface treatment liquid composition according to claim 1, characterized in that The 60% cumulative distribution particle size in the particle size distribution based on the scattering intensity obtained by the dynamic light scattering method is 1 to 700 nm. The measurement conditions of the particle size distribution are the same as the measurement conditions of the average hydrodynamic particle size.

3. The surface treatment liquid composition according to claim 1 or 2, characterized in that: The solvent is at least one selected from the group consisting of perfluorobutyl methyl ether, perfluorobutyl ethyl ether and perfluorohexyl methyl ether.

4. The surface treatment liquid composition according to claim 1 or 2, characterized in that: The ratio of the number of moles of the silane compound containing a fluorinated alkyl group to the number of moles of the silane compound containing a fluorinated polyether group is 0.001 to 1.

5.

5. The surface treatment liquid composition according to claim 1 or 2, characterized in that: R 3 C 1－6 Perfluoroalkyl.

6. The surface treatment liquid composition according to claim 1 or 2, characterized in that: Also contains fluorinated oil.

7. The surface treatment liquid composition according to claim 1 or 2, characterized in that: The fluorinated polyether group-containing silane compound includes a fluorinated polyether group-containing silane compound represented by formula (1) and a fluorinated polyether group-containing silane compound represented by formula (2). The liquid composition further contains fluorine-containing oil.

8. The surface treatment liquid composition according to claim 6, wherein The fluorine-containing oil is represented by the formula: Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 express, R 5 and Rf 6 are each independently an alkyl group having 1 to 16 carbon atoms or an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, a′ and b′ are each independently an integer from 0 to 30, c′ and d′ are each independently an integer from 1 to 200, the sum of a′, b′, c′ and d′ is at least 5, and the order of existence of the repeating units marked with subscripts a′, b′, c′ or d′ and enclosed in brackets in the formula is arbitrary.

9. The surface treatment liquid composition according to claim 6, wherein: The fluorinated oil is contained in an amount of 0.001 to 50 mol % based on the total amount of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound.

10. The surface treatment liquid composition according to claim 1 or 2, characterized in that: The present invention does not contain oligomers of compounds selected from the silane compounds containing a fluorinated alkyl group.

11. The surface treatment liquid composition according to claim 1 or 2, characterized in that: The average hydrodynamic particle size of the fluorinated polyether group-containing silane compound and the fluorinated alkyl group-containing silane compound in the liquid composition obtained by a dynamic light scattering method is 25 to 1500 nm.

12. The surface treatment liquid composition according to claim 10, wherein The liquid composition is used for wet coating.

13. An article comprising a substrate and a layer formed on the surface of the substrate from the surface-treating liquid composition according to any one of claims 1 to 12.

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