Curable composition

Abstract

The present invention provides a silane compound containing a fluorinated polyether group represented by the formula (I) [the meanings of the symbols are described in the specification].

Description

Technical Field

[0001] This invention relates to surface treatment agents. Background Technology

[0002] Certain types of fluorinated silane compounds are known to provide excellent water-repellent, oil-repellent, and stain-resistant properties when used for surface treatment of substrates. Layers obtained from surface treatment agents containing fluorinated silane compounds (hereinafter also referred to as "surface treatment layers") are applied as so-called functional films to a wide variety of substrates such as glass, plastics, fibers, and building materials.

[0003] As such fluorinated compounds, silane compounds containing perfluoropolyether groups are known to have a main molecular chain with perfluoropolyether groups and hydrolyzable groups bonded to Si atoms at the molecular ends or end portions (Patent Documents 1 and 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-218639

[0007] Patent Document 2: Japanese Patent Application Publication No. 2017-082194 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] Layers obtained from surface treatment agents containing silane compounds with perfluoropolyether groups exhibit water-repellent, oil-repellent, and stain-resistant properties, even in the case of thin films, making them suitable for optical components such as eyeglasses or touchscreens that require light transmission and transparency. Particularly in these applications, friction durability is required to maintain functionality even under repeated friction.

[0010] The purpose of this invention is to provide a fluorinated polyether-based silane compound capable of forming a layer with high frictional durability.

[0011] Technical solutions for solving technical problems

[0012] The present invention includes the following methods.

[0013] [1] A fluorinated polyether-based silane compound represented by formula (I).

[0014]

[0015] [In the formula,

[0016] R 3 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group.

[0017] R 4 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0018] p is an integer from 0 to 3 each time it appears;

[0019] Among them, (SiR) 3 p R 4 3-p ) j In, at least one SiR 3 p R 4 3-p In this context, p is an integer between 0 and 2.

[0020] Each occurrence of q is an independent integer from 0 to 3;

[0021] Among them, (SiR) 3 q R 4 3-q ) j In, at least one SiR 3 q R 4 3-q In this context, q is an integer between 0 and 2.

[0022] R 5 Each time it appears, it is an organic group with an independent valence of j+1.

[0023] R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -,

[0024] R 15 Each time it appears, it is independently a group containing a cycloalkylene group.

[0025] R 16 Each time it appears, it is independently either a single bond or a divalent organic group.

[0026] R 17 Each time it appears, it is independently either a single bond or a divalent organic group.

[0027] R 7 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1-20 alkyl,

[0028] PFPE 1 Each occurrence is independently assigned to -R. F -R FE-,

[0029] R F For -(C f F 2f )-,

[0030] f is an integer from 1 to 10.

[0031] R FE The formula is: -(OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F 12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown,

[0032] (in the formula,

[0033] a1, a2, a3, a4, a5, a6, a7, and a8 are each independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7, and a8 is at least 5.

[0034] The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula.

[0035] X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When the atom is a hydrogen atom or a chlorine atom, at least one of a1, a2, a4, a5, a6, a7, and a8 must be an integer greater than or equal to 1.

[0036] j is an integer from 1 to 9 each time it appears.

[0037] k is an integer greater than or equal to 1.

[0038] [2] The fluorinated polyether-containing silane compound as described in [1] above, wherein R 15 Each time it appears, it is independently a monocyclic, bicyclic, or tricyclic cycloalkyl group containing 5 to 12 carbon atoms.

[0039] R 16 Each occurrence is independently a single key or a C. 1-6 Alkylene

[0040] R 17 Each occurrence is independently a single key or a C. 1-6 Alkylene.

[0041] [3] The fluorinated polyether-containing silane compound as described in [1] or [2] above, wherein R 6 A group selected from the following groups is a group in which the hydrogen atoms on the ring can be replaced.

[0042]

[0043] [In the formula,

[0044] R 16 Each occurrence is independently a single key or a C. 1-6 Alkylene

[0045] R 17 Each occurrence is independently a single key or a C. 1-6 Alkylene

[0046] R 18 Each occurrence is independently assigned the number C. 1-6 Alkylene.

[0047] [4] A fluorinated polyether-containing silane compound as described in any one of [1] to [3] above, wherein X 10 It is a fluorine atom.

[0048] [5] A fluorinated polyether-containing silane compound as described in any one of [1] to [4] above, wherein R FE Each time it appears, it is independently represented by the group shown in the following formula (f1), (f2), (f3), (f4) or (f5).

[0049] -(OC3F6) a3 -(OC2F4) a2 - (f1)

[0050] [In the formula, a3 is an integer from 5 to 200, and a2 is 0 or 1.]

[0051] -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f2)

[0052] [In the formula, a3 and a4 are independent integers from 0 to 30;]

[0053] a1 and a2 are independent integers from 1 to 200;

[0054] The sum of a1, a2, a3, and a4 is an integer between 10 and 200;

[0055] The order of repeated units marked with subscripts a1, a2, a3, or a4 and enclosed in parentheses is arbitrary in the formula.

[0056] -(R) 16 -R 17 ) g - (f3)

[0057] [In the formula, R] 16 OCF2 is OC2F4;

[0058] R 17 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups, or a combination of two or three groups selected from these groups;

[0059] g is an integer from 2 to 100.

[0060] -(OC6F 12 ) a6 -(OC5F) 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f4)

[0061] [In the formula, a2 is an integer from 1 to 200, a1, a3, a4, a5, and a6 are each an independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, and a6 is at least 5. Furthermore, the order of repeated units labeled a1, a2, a3, a4, a5, or a6 and enclosed in parentheses is arbitrary in the formula.]

[0062] -(OC6F 12 ) a6 -(OC5F) 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f5)

[0063] [In the formula, a1 is an integer from 1 to 200, a2, a3, a4, a5, and a6 are each an independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, and a6 is at least 5. Furthermore, the order of repeated units labeled a1, a2, a3, a4, a5, or a6 and enclosed in parentheses is arbitrary in the formula.]

[0064] [6] A fluorinated polyether-containing silane compound as described in any one of [1] to [5] above, wherein R 7 It is a hydrogen atom.

[0065] [7] A fluorinated polyether-containing silane compound as described in any one of [1] to [6] above, wherein R 5 It is a divalent organic group, and j is 1.

[0066] [8] A fluorinated polyether-containing silane compound as described in any one of [1] to [7] above, wherein R 5 C 1－6 Alkylene, j = 1.

[0067] [9] The fluorinated polyether-based silane compound described in any one of [1] to [8] above is represented by formula (A), (B), (C) or (D).

[0068]

[0069] [In the formula,

[0070] R 11 and R 11″ Each time it appears, it is independently either a hydrogen atom or a halogen atom.

[0071] R 12 and R 12″ Each time it appears, it is independently a hydrogen atom or a lower alkyl group.

[0072] R 13 and R 13″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0073] R 14 and R 14″ Each time it appears, it is independently either a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

[0074] X 2 Each time it appears, it is independently either a single bond or a divalent organic group.

[0075] n1 in each (-SiR) 13 n1 R 14 3－n1) unit or each (-SiR) 13″ n1 R 14″ 3－n1 Each unit contains independent integers from 0 to 3.

[0076] X 1 Each is independently a single bond or a divalent to decavalent organic group connected to an amide bond.

[0077] t are independent integers from 1 to 10.

[0078] α1 is an integer from 1 to 9.

[0079] X 3 Each is an independent organic group ranging from 2 to 10 valents.

[0080] β1 is an integer from 1 to 9.

[0081] X 5 Each is an independent organic group ranging from 2 to 10 valents.

[0082] γ1 is an integer from 1 to 9.

[0083] R a Each occurrence is independently -Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ,

[0084] Z 3 Each time it appears, it is independently either an oxygen atom or a divalent organic group.

[0085] R 71 Each occurrence is independently assigned the value R. a′ ,

[0086] R a′ The meaning of R a same,

[0087] R a via Z 3 The maximum number of Si atoms connected in a straight-chain manner is 5.

[0088] R 72 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0089] R 73 Each time it appears, it is independently a hydrogen atom or a lower alkyl group.

[0090] p1 is an independent integer from 0 to 3 each time it appears.

[0091] q1 is an independent integer from 0 to 3 each time it appears.

[0092] r1 is an independent integer from 0 to 3 each time it appears.

[0093] Among them, in each (-Z) 3 -SiR 71 p1 R 72 q1 R 73 r1 In the given equation, the sum of p1, q1, and r1 is 3.

[0094] R a″ Each occurrence is independently -Z 3 -SiR 71 p1 R 72″ q1 R 73 r1 ,

[0095] Z 3 R 71 R 73 The meanings of p1, q1, and r1 are the same as above.

[0096] R 72″ The meaning of R 72 same,

[0097] R b and R b″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0098] R c and R c″ Each time it appears, it is independently a hydrogen atom or a lower alkyl group.

[0099] k1 is an independent integer from 0 to 3 each time it appears.

[0100] l1 is an integer from 0 to 3 each time it appears.

[0101] Each occurrence of m1 is an independent integer from 0 to 3.

[0102] Among them, in each (SiR) a k1 R b l1 R c m1 ) or each (SiR a″ k1 R b″l1 R c″ m1 In the given information, the sum of k1, l1, and m1 is 3.

[0103] X 7 Each is an independent organic group ranging from 2 to 10 valents.

[0104] δ1 is an integer from 1 to 9.

[0105] R d Each occurrence is independently -Z 4 -CR 81 p2 R 82 q2 R 83 r2 ,

[0106] Z 4 Each time it appears, it is independently either an oxygen atom or a divalent organic group.

[0107] R 81 Each occurrence is independently assigned the value R. d′ ,

[0108] R d′ The meaning of R d same,

[0109] R 82 Each occurrence is independently -Y-SiR 85 n2 R 86 3－n2 ,

[0110] Y is an independent divalent organic group each time it appears.

[0111] R 85 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0112] R 86 Each time it appears, it is independently a hydrogen atom or a lower alkyl group.

[0113] n2 in each (-Y-SiR) 85 n2 R 86 3－n2 ) unit or each (-Y-SiR) 85″ n2 R 86″ 3－n2 Each unit contains independent integers from 0 to 3.

[0114] R 83Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a lower alkyl group.

[0115] p2 is an integer from 0 to 3 each time it appears.

[0116] q2 is an integer from 0 to 3 each time it appears.

[0117] r2 is an integer from 0 to 3 each time it appears.

[0118] Among them, in each (-Z) 4 -CR 81 p2 R 82 q2 R 83 r2 ) or each (-Z 4 -CR 81 p2 R 82″ q2 R 83 r2 In the equation, the sum of p2, q2, and r2 is 3.

[0119] R d″ Each occurrence is independently -Z 4 -CR 81 p2 R 82″ q2 R 83 r2 ,

[0120] R 82″ Each occurrence is independently -Y-SiR 85″ n2 R 86″ 3－n2 ,

[0121] R 85″ and R 86″ The meanings of R are respectively related to 85 and R 86 same,

[0122] R e Each occurrence is independently -Y-SiR 85 n2 R 86 3－n2 ,

[0123] R e″ Each occurrence is independently -Y-SiR 85″ n2 R 86″ 3－n2 ,

[0124] R f and R f″ Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a lower alkyl group.

[0125] k2 is an independent integer from 0 to 3 each time it appears.

[0126] l2 is an integer from 0 to 3 each time it appears.

[0127] Each occurrence of m2 is an independent integer from 0 to 3.

[0128] The sum of k2, l2, and m2 is 3.

[0129] R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -,

[0130] R 15 Each time it appears, it is independently a group containing a cycloalkylene group.

[0131] R 16 Each time it appears, it is independently either a single bond or a divalent organic group.

[0132] R 17 Each time it appears, it is independently either a single bond or a divalent organic group.

[0133] R 7 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－20 alkyl,

[0134] PFPE 1 Each occurrence is independently assigned to -R. F -R FE -,

[0135] R F For -(C f F 2f )-,

[0136] f is an integer from 1 to 10.

[0137] R FE The formula is: -(OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown,

[0138] (in the formula,

[0139] a1, a2, a3, a4, a5, a6, a7, and a8 are each independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7, and a8 is at least 5.

[0140] The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula.

[0141] X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When a hydrogen atom or a chlorine atom is present, at least one of a1, a2, a4, a5, a6, a7, and a8 must be an integer greater than or equal to 1.

[0142] r is an integer greater than or equal to 1.

[0143]

[10] A surface treatment agent containing a silane compound containing a fluorinated polyether group as described in any one of [1] to [9] above.

[0144]

[11] The surface treatment agent as described in

[10] above, wherein it further contains one or more other components selected from fluorinated oil, silicone oil and catalyst.

[0145]

[12] The surface treatment agent as described in

[10] or

[11] above, wherein it further contains a solvent.

[0146]

[13] The surface treatment agent as described in any one of

[10] to

[12] above is used as an antifouling coating agent or a waterproof coating agent.

[0147]

[14] An article comprising: a substrate, and a layer formed on the surface of the substrate by any one of the fluorinated polyether-based silane compounds described in any one of [1] to [9] or any one of the surface treatment agents described in any one of

[10] to

[13] .

[0148]

[15] The item described above in

[14] is an optical component.

[0149] Invention Effects

[0150] According to the present invention, fluorinated polyether-based silane compounds with excellent friction durability can be provided. Detailed Implementation

[0151] The fluorinated polyether-based silane compounds of the present invention will now be described.

[0152] When used in this specification, "monovalent organic group" refers to a carbon-containing monovalent group. There is no particular limitation on what constitutes a monovalent organic group; it can be a hydrocarbon group or its derivative. A hydrocarbon derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, or carbonyloxy groups at the end of the hydrocarbon group or in the molecular chain. When simply referred to as an "organic group," it means a monovalent organic group. Additionally, "j+1 valent organic group" refers to a carbon-containing j+1 valent group. There is no particular limitation on what constitutes a j+1 valent organic group; examples of j+1 valent groups that have further separated j hydrogen atoms from the organic group can be listed. For example, there is no particular limitation on what constitutes a divalent organic group; examples of divalent groups that have further separated one hydrogen atom from the organic group can be listed.

[0153] When used in this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group that has lost one hydrogen atom from a hydrocarbon. There is no particular limitation on what constitutes such a hydrocarbon group; examples include C groups that can be substituted by one or more substituents. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon groups" can be straight-chain, branched, or cyclic, and can be saturated or unsaturated. In addition, hydrocarbon groups can contain one or more ring structures.

[0154] When used in this specification, the term "hydrocarbon group" is not particularly limited, and for example, it can be selected from halogen atoms; C atoms that can be substituted by one or more halogen atoms are also acceptable. 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 One or more groups selected from aryl and 5- to 10-membered heteroaryl groups.

[0155] The fluorinated polyether-based silane compounds of the present invention are represented by the following formula (I).

[0156]

[0157] [In the formula,

[0158] R 3 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group.

[0159] R4 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0160] p is an integer from 0 to 3 each time it appears;

[0161] Among them, (SiR) 3 p R 4 3－p ) j In, at least one SiR 3 p R 4 3－p In this context, p is an integer between 0 and 2.

[0162] Each occurrence of q is an independent integer from 0 to 3;

[0163] Among them, (SiR) 3 q R 4 3－q ) j In, at least one SiR 3 q R 4 3－q In this context, q is an integer between 0 and 2.

[0164] R 5 Each time it appears, it is an organic group with an independent valence of j+1.

[0165] R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -,

[0166] R 15 Each time it appears, it is independently a group containing a cycloalkylene group.

[0167] R 16 Each time it appears, it is independently either a single bond or a divalent organic group.

[0168] R 17 Each time it appears, it is independently either a single bond or a divalent organic group.

[0169] R 7 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－20 alkyl,

[0170] PFPE 1 Each occurrence is independently assigned to -R. F -R FE -,

[0171] R F For -(C f F 2f )-,

[0172] f is an integer from 1 to 10.

[0173] R FE The formula is: -(OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F 12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown,

[0174] (in the formula,

[0175] a1, a2, a3, a4, a5, a6, a7, and a8 are each independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7, and a8 is at least 5.

[0176] The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula.

[0177] X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When the atom is a hydrogen atom or a chlorine atom, at least one of a1, a2, a4, a5, a6, a7, and a8 must be an integer greater than or equal to 1.

[0178] j is an integer from 1 to 9 each time it appears.

[0179] k is an integer greater than or equal to 1.

[0180] PFPE 1 It is the so-called fluorinated polyether group, which is independently -R each time it appears. F -R FE -.

[0181] The above R F For -(C f F 2f )-, where f is an integer from 1 to 10.

[0182] The above f is preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 3.

[0183] The above R FE For example, (OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F 12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown.

[0184] The above X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When a is a hydrogen atom or a chlorine atom, at least one of a1, a2, a4, a5, a6, a7, and a8 is an integer greater than or equal to 1.

[0185] In the preferred embodiment, X 10 It is a fluorine atom.

[0186] The above-mentioned a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, preferably an integer from 0 to 100, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is 5 or more, preferably 10 or more, more preferably 15 or more or 20 or more, preferably 200 or less, more preferably 100 or less, for example, it can be 50 or less or 30 or less.

[0187] The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula.

[0188] These repeating units can be either linear or branched. For example, -(OC8F 16)- can be -(OCF2CF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2CF2CF2)-, -(OCF2CF2CF2CF( CF3)CF2CF2CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF2CF2CF(CF3))-, etc., preferably -(OCF2CF2CF2CF2CF2CF2CF2CF2)-. -(OC7F 14 The following can be used: -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2CF2CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF2CF(CF3))-, etc., preferably -(OCF2CF2CF2CF2CF2CF2CF2CF2)-. -(OC6F 12 The value can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc., preferably -(OCF2CF2CF2CF2CF2CF2CF2)-. -(OC5F 10The value can be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc., with -(OCF2CF2CF2CF2CF2)- being preferred. -(OC4F8)- can 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))-, preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- (that is, X in the above formula) 10 The fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. Additionally, -(OC2F4)- can be any one of -(OCF2CF2)- and -(OCF(CF3))-, preferably -(OCF2CF2)-.

[0189] PFPE in the fluorinated polyether-based silane compound of the present invention 1 Any group that can be used to prepare fluorinated polyether groups is acceptable. In addition to these repeating units, repeating units consisting of oxygen atoms and perfluoroalkyl groups with 9 or more carbon atoms are also acceptable.

[0190] In one embodiment, the repeating units are linear. By making the repeating units linear, the surface lubrication and friction durability of the surface treatment layer can be improved. Furthermore, in this embodiment, the molecular mobility of the fluorinated polyether-based silane compound does not easily decrease at low temperatures. Because it has linear repeating units, the physical properties of the fluorinated polyether-based silane compound (e.g., the elastic modulus at low temperatures) do not easily decrease compared to its value at room temperature, thus enabling its application over a wide temperature range. In this specification, "elastic modulus" refers to the dynamic elastic modulus, and more specifically, the storage modulus.

[0191] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0192] In one approach, R FE Each time it appears, it is independently represented by the group shown in the following formulas (f1) to (f5).

[0193] -(OC3F6) a3 -(OC2F4) a2 (f1)

[0194] [In the formula, a3 is an integer from 5 to 200, and a2 is 0 or 1.]

[0195] -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f2)

[0196] [In the formula, a4 and a3 are independent integers from 0 to 30, and a2 and a1 are independent integers from 1 to 200.]

[0197] The sum of a4, a3, a2, and a1 is 5 or more.

[0198] The order of repeated units marked with subscripts a4, a3, a2, or a1 and enclosed in parentheses is arbitrary in the formula.

[0199] -(R) 6 -R 7 ) g - (f3)

[0200] [In the formula, R] 6 It is either OCF2 or OC2F4.

[0201] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups, or combinations of two or three groups selected independently from these groups,

[0202] g is an integer from 2 to 100.

[0203] -(OC6F 12 ) a6 -(OC5F) 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f4)

[0204] [In the formula, a2 is an integer from 1 to 200, a6, a5, a4, a3, and a1 are each an independent integer from 0 to 200, the sum of a6, a5, a4, a3, a2, and a1 is at least 5, and the order of the repeating units labeled a6, a5, a4, a3, a2, or a1 and enclosed in parentheses is arbitrary in the formula.]

[0205] -(OC6F 12 ) a6 -(OC5F) 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f5)

[0206] [In the formula, a1 is an integer from 1 to 200, a6, a5, a4, a3, and a2 are each an independent integer from 0 to 200, the sum of a6, a5, a4, a3, a2, and a1 is at least 5, and the order of the repeating units labeled a6, a5, a4, a3, a2, or a1 and enclosed in parentheses is arbitrary in the formula.]

[0207] In the above formula (f1), a3 is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, and for example, an integer from 25 to 35. In one embodiment, a2 is 1. In another embodiment, a2 is 0. In the above formula (f1), -(OC3F6) d - Preferably - (OCF2CF2CF2) a3 - or - (OCF(CF3)CF2) a3 The group shown is more preferably -(OCF2CF2CF2). a3 - The group shown.

[0208] In the above formula (f2), a2 and a1 are each preferably integers of 5 to 200, more preferably 10 to 200. Furthermore, the sum of a4, a3, a2, and a1 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) a4 -(OCF2CF2CF2) a3 -(OCF2CF2) a2 -(OCF2) a1 - The group shown. In another embodiment, formula (f2) can be -(OC2F4). a2 -(OCF2) a1 - The group shown.

[0209] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7 Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, 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; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4- etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 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 can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or - (OC2F4 - OC4F8) g -.

[0210] In the above formula (f4), a2 is preferably an integer from 1 to 100, more preferably an integer from 5 to 100. The sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0211] In the above formula (f5), a1 is preferably an integer from 1 to 100, more preferably an integer of 5 or more but less than 100. The sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more but less than 100.

[0212] In one approach, the aforementioned R FE The group is represented by the formula (f1) above.

[0213] In one approach, the aforementioned R FEThe group is shown in the above formula (f2).

[0214] In one approach, the aforementioned R FE The group is represented by the formula (f3) above.

[0215] In one approach, the aforementioned R FE The group is represented by the formula (f4) above.

[0216] In one approach, the aforementioned R FE The group is represented by the formula (f5) above.

[0217] In the above R FE In this compound, the ratio of a2 to a1 (hereinafter referred to as "a2 / a1 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 even more preferably 0.2 to 0.85. When the a2 / a1 ratio is 10 or less, the sliding properties, friction durability, and chemical resistance (e.g., durability against artificial sweat) of the surface-treated layer obtained from this compound are further improved. The smaller the a2 / a1 ratio, the higher the sliding properties and friction durability of the surface-treated layer. On the other hand, when the a2 / a1 ratio is 0.1 or more, the stability of the compound can be further improved. The larger the a2 / a1 ratio, the higher the stability of the compound.

[0218] In one embodiment, the a2 / a1 ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0219] In one embodiment, from the viewpoint of heat resistance, the a2 / a1 ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.

[0220] Among the above-mentioned fluorinated polyether-containing silane compounds, PFPE 1 The number-average molecular weight is not particularly limited, but is, for example, 500 to 100,000, preferably 1,500 to 50,000, and more preferably 2,000 to 10,000. In this specification, PFPE... 1 The number-average molecular weight is obtained through 19 The value measured by F-NMR.

[0221] In another way, PFPE 1 The number average molecular weight of the fraction can be 500 to 100,000, preferably 1,000 to 30,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0222] In another way, PFPE 1The number average molecular weight of the fraction can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0223] In the above-mentioned fluorinated polyether-based silane compound, k in formula (I) represents the following formula in formula (I) - PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O) – The number of repeating units in the structure shown. The value of k is 1 or more. Therefore, the above-mentioned fluorinated polyether-based silane compounds contain at least 2 –PFPE groups. 1 - has -C(=O)NR at both ends 7 The unit of the structure shown, namely, the fluorinated polyether silane compound described above, has at least four -C(=O)NR groups. 7 The structure shown is as described. Regarding the value of k, there is no particular limitation as long as it falls within the range capable of preparing the aforementioned fluorinated polyether-based silane compounds, and it is preferably an integer from 1 to 5. Therefore, it is possible to provide multiple portions within a single molecule that are considered to contribute to the deep curing properties of the curable composition containing the fluorinated polyether-based silane compound.

[0224] In this invention, -C(=O)NR 7 - The oxygen atom of the carbonyl group and R in the structure shown 7 When hydrogen atoms are present, they participate in the formation of hydrogen bonds with water molecules, but this is not limited to a specific theory. This is achieved through the -C(=O)NR in a molecule. 7 The increased number of amide bonds in the structure, as shown, results in a greater number of hydrogen-bonding moieties and enhanced nucleophilicity with water participating in the curing of the curable composition. This facilitates the curing reaction, allowing it to proceed deeper into the curing zone, and is therefore considered preferable. Thus, by having k = 1 or more in the above formula (I), the number of amide bonds per molecule of the fluorinated polyether-based silane compound increases. This structure can be considered to contribute to increased affinity for water molecules through hydrogen bonding, thereby improving the deep curing properties of the curable composition.

[0225] The above -C(=O)NR 7 - R in the structure shown 7 Each time it appears, it independently represents a hydrogen atom or a carbon atom. 1－20 Alkyl group. The above list has the following carbon atom count (C). 1－20 Alkyl groups are preferably C 1－6 Alkyl, more preferably methyl or ethyl, and even more preferably methyl.

[0226] In one approach, R 7At least one, preferably at least three, of the atoms are hydrogen atoms. That is, the fluorinated polyether-based silane compound preferably has a structure showing multiple -C(=O)NH- groups, and the curable composition containing the fluorinated polyether-based silane compound can cure well to a deep depth. In R 7 When one part is a hydrogen atom, at which position is the R in the above-mentioned fluorinated polyether-based silane compound? 7 There are no particular restrictions on the presence of hydrogen atoms. In preparing the aforementioned fluorinated polyether-based silane compounds, the introduction position of the structure shown by -C(=O)NH- can be controlled by selecting the starting materials. From the viewpoint of hydrogen bond formation, all R atoms present in the fluorinated polyether-based silane compounds... 7 A higher proportion of hydrogen atoms further enhances deep curing properties, making it preferable. In a particularly preferred embodiment, all R atoms in the aforementioned fluorinated polyether-based silane compounds... 7 It is a hydrogen atom.

[0227] In the above-mentioned fluorinated polyether-containing silane compounds, the -C(=O)NR... 7 The structure shown is formed by the interaction of its nitrogen atom with R. 5 Or R 6 The organic groups shown are bonded.

[0228] R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -.

[0229] R 15 Each time it appears, it is independently a group containing a cycloalkylene group, R. 16 Each time it appears, it is independently a single bond or a divalent organic group, R. 17 Each time it appears, it is independently a single bond or a divalent organic group.

[0230] The fluorinated polyether-based silane compounds of the present invention contain cycloalkyl subunits between the amide bonds. Surface-treated layers obtained from such fluorinated polyether-based silane compounds of the present invention exhibit high durability. Because the fluorinated polyether-based silane compounds of the present invention contain cycloalkyl subunits between the amide bonds, the surface-treated layers formed when surface-treated with these compounds exhibit increased crystallinity, which can be considered as improving film durability; however, the present invention is not limited to any particular theory.

[0231] Furthermore, the surface treatment layer obtained from the fluorinated polyether-based silane compound of the present invention can impart water-repellent properties to the substrate and maintain ink adhesion through printing and the like. In other words, the surface treatment layer obtained from the fluorinated polyether-based silane compound of the present invention has high ink retention.

[0232] The aforementioned cycloalkylene compounds refer to divalent saturated monocyclic or polycyclic aliphatic hydrocarbons. The hydrogen atoms on the ring of this cycloalkylene compound can be replaced by one or more substituents.

[0233] Substituents for the aforementioned cycloalkylene groups are not particularly limited, and can be, for example, selected from halogen atoms; C atoms that can be substituted by one or more halogen atoms. 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 One or more substituents selected from aryl and 5- to 10-membered heteroaryl groups. In a preferred embodiment, the substituent is C. 1－6 Alkyl, preferably methyl or ethyl, more preferably methyl.

[0234] The aforementioned cycloalkyl-containing groups may include multiple cycloalkyl groups, preferably 1 to 3, more preferably 1 or 2 cycloalkyl groups.

[0235] In one embodiment, the aforementioned cycloalkyl-containing group comprises one cycloalkyl group.

[0236] In another embodiment, the aforementioned cycloalkyl-containing group comprises two cycloalkyl groups.

[0237] In the preferred embodiment, R 15 Each time it appears, it is independently a monocyclic, bicyclic, or tricyclic cycloalkyl group containing 5 to 12 carbon atoms.

[0238] The aforementioned polycyclic cycloalkyl groups can be of any type: fused ring, spiro ring, or bridged ring.

[0239] In one embodiment, the aforementioned cycloalkylene group is a monocyclic compound.

[0240] In another embodiment, the aforementioned cycloalkylene group is bicyclic.

[0241] In another embodiment, the aforementioned cycloalkylene group is tricyclic.

[0242] In the preferred embodiment, R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene, R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene.

[0243] The above R 16 and R 17 With R 15 Direct bonding of cycloalkyl groups.

[0244] In the preferred embodiment, R 15 Each time it appears, it is independently a monocyclic, bicyclic, or tricyclic cycloalkyl group containing 5 to 12 carbon atoms.

[0245] R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene

[0246] R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene.

[0247] In the preferred embodiment, R 15 For a substituted cyclohexanediol, the above R 16 and R 17 Each independently is a single bond or C 1－6 Alkyl groups bonded to each other at the meta or para positions. In one manner, the substituted cyclohexanediyl group is unsubstituted. In another manner, the substituted cyclohexanediyl group is C-shaped. 1－6 The alkyl group is preferably substituted with methyl or ethyl, more preferably with methyl. The number of substituents is preferably 1 to 5, more preferably 1 to 3.

[0248] In the preferred embodiment, R 15 Contains a substituted alkylene bis(cyclohexyl), preferably containing a methylene bis(cyclohexyl), wherein the above R 16 and R 17 Each independently is a single bond or C 1－6 The alkylene groups are bonded to each other at the 4,4′ positions. In one embodiment, the substituted alkylene bis(cyclohexyl) is unsubstituted. In another embodiment, the substituted alkylene bis(cyclohexyl) can be C-substituted. 1－6 The alkyl group is preferably substituted with methyl or ethyl, more preferably with methyl. The substituent is preferably 2 to 5, more preferably 2 to 4.

[0249] In the preferred embodiment, R 6 A group selected from the following groups is a group in which the hydrogen atoms on the ring can be replaced.

[0250]

[0251] [In the formula,

[0252] R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene

[0253] R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene

[0254] R 18 Each occurrence is independently assigned the number C. 1－6 Alkylene, preferably CH2CH2 or CH2.

[0255] In a more preferred manner, R 6 A group selected from the following groups is a group in which the hydrogen atoms on the ring can be replaced.

[0256]

[0257] [In the formula,

[0258] R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene

[0259] R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene

[0260] R 18 Each occurrence is independently assigned the number C. 1－6 Alkylene, preferably CH2CH2 or CH2.

[0261] As R 6 Specific examples, such as the following groups, can be listed.

[0262]

[0263] [In the formula, * represents a valence bond.]

[0264] R 5 It is a linking group that connects the terminal silicon atom to the amide bond. R 5 Each occurrence independently represents a j+1 valence organic group. Here, the value of j represents the number of silicon-containing groups at the end of the aforementioned fluorinated polyether-based silane compounds, and its value ranges from 1 to 9. Therefore, R 5 Each time it appears, it independently represents a divalent to a decavalent organic group. Therefore, this R... 5 Any divalent to decavalent organic group that can stably exist in the aforementioned fluorinated polyether silane compounds can be any group. 5 Preferably, it contains an organic group with a valence of 2 to 7, more preferably 2 to 4, and even more preferably 2. Therefore, the value of j is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. As R 5 Specific examples can be listed in equations (A) to (D) described later as corresponding to R. 5 The groups recorded in part.

[0265] R 5 Preferably, the molecular chain in which silicon atoms are directly linked to amide bonds does not have heteroatoms or aromatic structures; more preferably, it does not have aromatic structures. As R 5 Preferably, it may have an aliphatic hydrocarbon group with heteroatoms, more preferably a non-substituted aliphatic hydrocarbon, more preferably a divalent alkylene group, and even more preferably a C14 group. 1－20 Alkylene, more preferably C 1－6 Alkylenes, specifically methylene, ethylene, propylene, methyl ethylene, butylene, hexamethylene, etc. The two Rs present in the above-mentioned fluorinated polyether silane compounds... 5 They can be the same or different; from the viewpoint of ease of compound preparation, the same is preferred. Additionally, R... 5 Given j+1 valence bonds, which valence bond should be used with -C (=O)NR? 7 - Partial bonding is acceptable.

[0266] In the above formula, R 3 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0267] The above R 3 Preferably, each occurrence is an independently hydrolyzable group.

[0268] The above R 3 Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h Or halogen (in these formulas, R) h C indicates substitution or non-substitution. 1－4 Alkyl group, more preferably -OR h (i.e., alkoxy group). As R h Examples of substituted alkyl groups include non-substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and methyl or ethyl groups are more preferred. In one embodiment, R... h For methyl, in another way R h It is an ethyl group.

[0269] In the above formula, R 3 Each time it appears, it is either a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0270] The above R 3 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6Alkyl groups, more preferably methyl groups.

[0271] In equation (I) above, p in each (SiR) 3 p R 4 3－p In (SiR), the integers are independently from 0 to 3. 3 p R 4 3－p ) j In, at least one SiR 3 p R 4 3－p In this context, p is an integer from 0 to 2. That is, the molecule of formula (I) has at least one Si bonded to a hydrolyzable group at its terminal.

[0272] In one embodiment, all p are integers from 0 to 2, preferably integers from 0 to 1, and more preferably 0.

[0273] In equation (I) above, q is in each (SiR) 3 q R 4 3－q In (SiR), the integers are independently from 0 to 3. 3 q R 4 3－q ) j In, at least one SiR 3 q R 4 3－q In this context, q is an integer from 0 to 2. That is, the molecule of formula (I) has at least one Si bonded to a hydrolyzable group at its terminal.

[0274] In one embodiment, all q are integers from 0 to 2, preferably integers from 0 to 1, and more preferably 0.

[0275] In the preferred embodiment, all p are integers from 0 to 2, preferably integers from 0 to 1, and more preferably 0; all q are integers from 0 to 2, preferably integers from 0 to 1, and more preferably 0.

[0276] In a particularly preferred embodiment, the fluorinated polyether-based silane compound is R. 7 All are hydrogen atoms, R 5 Compounds with a divalent alkylene group, j = 1, and p and q = 0. Fluorinated polyether silane compounds can be used alone or in mixtures of two or more.

[0277] Depending on the preparation method of fluorinated polyether-containing silane compounds, PFPE modified bodies or those derived from R may be generated. 6 Compounds with PFPE-modified bodies whose terminal portions on one or both sides are not incorporating silane groups, and, depending on the case, whose linker groups are not incorporating, are considered to be compounds. Hereinafter, such compounds derived from PFPE... 1 Compounds whose molecular chains do not contain silane groups at at least one end are denoted as "non-terminated PFPE modifiers". It is preferable that the compound represented by formula (I) has high purity, i.e., it is preferable that the proportion of such non-terminated PFPE modifiers is small. However, the fluorinated polyether-based silane compound used to prepare the curable composition may contain non-terminated PFPE modifiers to a extent that does not impair its function as a curable composition. For example, in the case of formula (I) above, it may contain {-PFPE}. 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-} r -PFPE 1 Compounds with structures such as carboxylic acid groups, ester groups, hydroxyl groups, or alkylene-OH groups bonded to them.

[0278] When preparing surface treatment agents containing the fluorinated polyether silane compounds of the present invention, the purity of the fluorinated polyether silane compound used can be determined by the extent to which the silane alkyl group is introduced into the terminator, or by using the silane termination rate as a metric. The termination rate is measured by PFPE. 1 In some parts, relative to not being R 6 The total amount of the sandwiched components is determined by the proportion of the silyl group introduced into that portion. The terminalization rate is preferably 90 mol% or more, more preferably 93 mol% or more, and even more preferably 95 mol% or more. By setting it within such a range, a sufficient amount of a compound with silyl groups at both ends of the molecule can be contained, thus fully realizing its function as a curable composition. The terminalization rate can be determined, for example, by NMR measurement. In the case of the compound of formula (I), using... 19 F-NMR analysis revealed the presence of PFPE 1 The degree of silylation introduced at the molecule's end can be determined by measuring the CF2 group adjacent to the amide group bonded to the linker. In compounds having structures different from those of compound (I), the terminalization rate can be calculated by NMR measurements of the difference between the terminally silanized compound and the non-terminally silanized compound, a method known to those skilled in the art.

[0279] The specific structure of the fluorinated polyether-based silane compound described above will be described in detail below. The fluorinated polyether-based silane compound is preferably a compound of at least one of formulas (A), (B), (C), or (D). The groups and subscripts appearing in the following formulas correspond to the groups and subscripts appearing in the above general formulas, and those skilled in the art can determine their respective correspondences.

[0280]

[0281] (where, PFPE 1 R 6 R 7 The meaning is the same as above.

[0282] The fluorinated polyether-based silane compounds shown in formulas (A), (B), (C), and (D) above will be described below.

[0283] Formula (A):

[0284]

[0285] In the above formula, PFPE 1 R 6 and R 7 The meaning is the same as above.

[0286] In the above formula, r is an integer greater than or equal to 1, preferably an integer from 1 to 5.

[0287] In the above formula, R 13 Each time it appears, it independently represents either a hydroxyl group or a hydrolyzable group. The meaning of the hydrolyzable group is the same as above. That is, R 13 R corresponding to the above formula 4 .

[0288] In the above formula, R 14 Each time it appears, it independently represents either a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. That is, R 14 R corresponding to the above general formula 3 .

[0289] In the above formula, R 11 Each time it appears, it represents either a hydrogen atom or a halogen atom independently. The halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom.

[0290] In the above formula, R 12 Each time it appears, it independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, etc.

[0291] In the above formula, R 11″ R 12″ R 13″ and R 14″ The meanings of R are respectively related to 11 R 12 R 13 and R 14 same.

[0292] In formula (A) above, the Si atom bonded to at least one group selected from hydroxyl and hydrolyzable groups represents an integer n1 of 1 to 3, and (-SiR) 13 n1 R 14 3－n1 ) or (-SiR 13″ n1 R 14″ 3－n1 The Si atoms contained in it.

[0293] In the above formula, n1 is in each (-SiR 13 n1 R 14 3－n1 ) unit or each (-SiR) 13″ n1 R 14″ 3－n1 The units are independently integers from 0 to 3, preferably from 1 to 3, and more preferably 3. In the formula, at least two n1 are integers from 1 to 3, that is, not all n1 are simultaneously 0. That is, in the formula, at least two exist in relation to R. 13 Or R 13″ Bonded Si atoms. In other words, in equation (A), there are at least two -SiR atoms selected from n1 being 1 or higher. 13 n1 R 14 3－n1 Structure (i.e., -SiR) 13 (partial) and n1 is 1 or more -SiR 13″ n1 R 14″ 3－n1 Structure (i.e., -SiR) 13″ The structure in the part. That is, n1 corresponds to the value of 3-p or 3-q in the above general formula.

[0294] Preferably, in formula (A), the Si atoms bonded to at least one group selected from hydroxyl and hydrolyzable groups are located at both ends of the molecular backbone. That is, in formula (A), there is at least one -SiR atom with n1 greater than or equal to 1. 13 n1 R 14 3－n1 Structure (i.e., -SiR) 13(partial), and at least one n1 is 1 or higher -SiR 13″ n1 R 14″ 3－n1 Structure (i.e., -SiR) 13″ part).

[0295] In the above formula, X 1 Each of these independently represents a single bond or a divalent to decavalent organic group linked to an amide bond. This X 1 This can be understood as the perfluoro(poly)ether portion (i.e., -PFPE) in the compound shown in formula (A) primarily providing water repellency and surface lubrication. 1 A portion of the silane portion (a) and a linker group connected to provide bonding ability with the substrate. Therefore, as long as the compound shown in formula (A) can exist stably, the X... 1 It can be a single bond or any organic group. That is, it can be understood as X. 1 And X, which will be discussed later 2 Together with the hydrocarbon group attached thereto, they correspond to R in the above general formula. 5 Part of it. Specifically, in this specification, regarding the designation X... 1 The group, recorded on the left side, is related to PFPE. 1 The amide bonds adjacent to the shown group are bonded, and the right side is bonded to the group enclosed in parentheses. Additionally, regarding the designation X... 1 The group can be used to prepare a stable compound, including groups that are reverse-bonded, such as those in -CO-C6H4-, as well as those denoted as -C6H4-CO-, phenylene, and PFPE. 1 The group shown is adjacent to an amide bonded group.

[0296] In another way, X 1 It can be X e X e It represents a single bond or a 2- to 10-valent organic group, preferably a single bond, or having a group selected from -C6H4- (i.e., -phenylene-, hereinafter referred to as phenylene), -O- (ether group), -CO- (carbonyl group), -NR 40 At least one of the following: - and -SO2-, a divalent to decavalent organic group. The above R 40 Each of these can be independently represented by a hydrogen atom, a phenyl group, or a C1-6 alkyl group (preferably methyl), with hydrogen atom or methyl group being more preferred. The aforementioned -C6H4-, -CO-, and -NR... 40 - or - SO2 - is preferably contained in the molecular backbone of a silane compound (A) containing a perfluoropolyether group.

[0297] X e More preferably, it represents a single bond, or has a bond selected from -C6H4-, -CONR 40 -CONR40 -C6H4-, -CO-, -CO-C6H4-, -O-CO-NR 40 -, -SO2NR 40 -, -SO2NR 40 At least one of -C6H4-, -SO2-, and -SO2-C6H4- contains a divalent to decavalent organic group. The aforementioned -C6H4- and -CONR... 40 -CONR 40 -C6H4-, -CO-, -CO-C6H4-, -SO2NR 40 -, -SO2NR 40 -C6H4-, -SO2-, or -SO2-C6H4- are preferably contained in the molecular backbone of the fluorinated polyether-based silane compound (A).

[0298] In the above formula, α1 is an integer from 1 to 9, which can correspond to X. 1 The valence changes accordingly. In equation (A), α1 is the valence of X. 1 The value of the valence minus 1. In X 1 When the organic group is a single bond or a divalent organic group, α1 is 1. That is, α1 corresponds to the value of j in the above general formula.

[0299] The above X 1 Preferably, the organic group is 2 to 7 valent, more preferably 2 to 4 valent, and even more preferably 2 valent.

[0300] In one manner, X 1 It consists of 2 to 4 valent organic groups, with α1 being 1 to 3.

[0301] In another way, X 1 It is a divalent organic group, and α1 is 1. In this case, formula (A) is represented by the following formula (A′).

[0302]

[0303] As for the above X 1 For example, as long as it can be used with PFPE 1 There are no particular limitations on the formation and stable preparation of compounds by bonding the amide group to the amide group; for example, divalent groups as shown in the following formula can be listed.

[0304] -(R) 31 ) p′ -(X) a ) q′ -

[0305] [In the formula,

[0306] R 31 Indicates a single bond, -(CH2) s′- Or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s′ -,

[0307] s′ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

[0308] Xa represents -(X b ) l′ -,

[0309] Xb, each time it appears, independently represents a selection from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -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′ - group,

[0310] R 33 Each time it appears, it independently represents phenyl and C. 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl,

[0311] R 34 Each time it appears, it independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably methyl), preferably hydrogen atom,

[0312] Each time m′ appears, it is an integer from 1 to 100, preferably an integer from 1 to 20.

[0313] Each time n′ appears, it is independently an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0314] l′ is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0315] p′ is 0 or 1.

[0316] q′ is 0 or 1,

[0317] Where at least one of p′ and q′ is 1, and the order of the repeating units labeled p′ or q′ and enclosed in parentheses is arbitrary.

[0318] Here, R 31 and Xa (typically R) 31 and X a The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. However, in R... 31 When X is a single bond or p′ is 0, a Not for - CONR 34 - or - NR 34 -.

[0319] In one approach, l′ in the above formula is 1.

[0320] The above X is preferred 1 -(R) 31 ) p′ -(X) a ) q′ -R 32 -. R 32 Indicates a single bond, -(CH2) t′ - Or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). t′ - t′ is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Here, R 32 (typically R) 32 The hydrogen atom in the carbon atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents in the fluoroalkyl group are substituted.

[0321] The above X is preferred 1 For single bond, C 1－20 Alkylene, -R 31 -X c -R 32 - or -X d -R 32 - [where R] 31 and R 32 [The meaning is the same as above]. Here, alkylene refers to a compound having -(C... δ H 2δ () - group, can be substituted or unsubstituted, and can be straight-chain or branched.

[0322] More preferably, the above-mentioned X 1 For single bond, C 1－20 Alkylene, -(CH2) s′ -X c -、-(CH2) s′ -X c -(CH2) t′ -、-X d - or -Xd -(CH2) t′ —[In the formula, s′ and t′ have the same meaning as above].

[0323] Further optimization of the above X 1 -X f -、-X f -C 1－20 Alkylene, -X f -(CH2) s′ -X c -、-X f -(CH2) s′ -X c -(CH2) t′ -、-X f -X d - or -X f -X d -(CH2) t′ — In the formula, s′ and t′ have the same meaning as above. In the above formula, X f It is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms, for example, a methylene group. X f The hydrogen atoms in the atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents in the fluoroalkyl group are substituted, preferably substituted. X f It can be linear or branched, preferably linear.

[0324] In the above formula, X c express:

[0325] -O-、

[0326] -S-、

[0327] -C(O)O-,

[0328] -CONR 34 -、

[0329] -O-CONR 34 -、

[0330] -Si(R) 33 )2-、

[0331] -(Si(R) 33 )2O) m′ -Si(R) 33 )2-、

[0332] -O-(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R)33 )2-、

[0333] -O-(CH2) u′ -Si(R) 33 )2-O-Si(R 33 )2-CH2CH2-Si

[0334] (R 33 )2-O-Si(R 33 )2-、

[0335] -O-(CH2) u′ -Si(OCH3)2OSi(OCH3)2-,

[0336] -(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-、

[0337] -(CH2) u′ -N(R) 34 )-、

[0338] -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 33 )2-、

[0339] -CONR 34 -(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-、

[0340] -CONR 34 -(CH2) u′ -N(R) 34 )-,or

[0341] -CONR 34 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 33 )2-

[0342] [In the formula, R] 33 R 34 The meanings of m and m′ are the same as above.

[0343] u′ is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. [However, in R...] 31 In the case of a single key, X c Not the end has -CONR 34 -A group. Preferably -O-.

[0344] In the above formula, X d express:

[0345] -S-、

[0346] -C(O)O-,

[0347] -(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-、

[0348] -(CH2) u′ -N(R) 34 )-、

[0349] -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 33 )2-、

[0350] -CONR 34 -、

[0351] -CONR 34 -(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-、

[0352] -CONR 34 -(CH2) u′ -N(R) 34 )-,or

[0353] -CONR 34 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 33 )2-.

[0354] [In the formula, the meanings of each symbol are the same as above.]

[0355] The above-mentioned X is particularly preferred. 1 for:

[0356] -X f -、

[0357] -X f -C 1－20 Alkylene

[0358] -X f -(CH2) s′ -X c -、

[0359] -X f -(CH2) s′ -X c-(CH2) t′ -

[0360] -X f -X d -,or

[0361] -X f -X d -(CH2) t′ - The group shown.

[0362] [In the formula, X] f The meanings of s′ and t′ are the same as above.

[0363] X c Indicates -O- or -CONR 34 -,

[0364] X d Indicates - CONR 34 -,

[0365] R 34 Each time it appears, it independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl group (preferably methyl).

[0366] In one manner, the aforementioned X 1 for:

[0367] -X f -(CH2) s′ -X c -、

[0368] -X f -(CH2) s′ -X c -(CH2) t′ -

[0369] -X f -X d -,or

[0370] -X f -X d -(CH2) t′ - The group shown.

[0371] [In the formula, X] f The meanings of s′ and t′ are the same as above.

[0372] X c Indicates - CONR 34 -,

[0373] X d Indicates - CONR 34 -,

[0374] R34 Each time it appears, it independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl group (preferably methyl).

[0375] In one manner, the aforementioned X 1 It can be:

[0376] single bond,

[0377] C 1－20 Alkylene

[0378] -(CH2) s′ -X c -(CH2) t′ -,or

[0379] -X d -(CH2) t′ -.

[0380] [In the formula, the meanings of each symbol are the same as above.]

[0381] But at this time X d Not for - CONR 34 -.

[0382] The above X is preferred 1 for:

[0383] single bond,

[0384] C 1－20 Alkylene

[0385] -(CH2) s′ -O-(CH2) t′ -、

[0386] -(CH2) s′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-(CH2) t′ -、

[0387] -(CH2) s′ -O-(CH2) u′ -(Si(R) 33 )2O) m′ -Si(R) 33 )2-(CH2) t′ -,or

[0388] -(CH2) s′ -O-(CH2) t′ -Si(R) 33 )2-(CH2) u′ -Si(R)33 )2-(C v H 2v )-.

[0389] [In the formula, R] 33 The meanings of m′, s′, t′, and u′ are the same as above, and v is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0390] In the above formula, -(C v H 2v - can be a straight chain or a branched chain, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0391] The X1 group mentioned above can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 Fluoroalkyl (preferably C) 1－3 One or more substituents in a perfluoroalkyl group are used for substitution.

[0392] In one manner, X 1 The base can be -O-C 1－6 Groups other than alkylene groups.

[0393] In another way, as X 1 radicals, for example, include the following groups:

[0394]

[0395]

[0396] [In the formula, R] 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C14 group. 1－6 Alkoxy, preferably methyl;

[0397] D is selected from:

[0398] -CH2O(CH2)2-,

[0399] -CH2O(CH2)3-,

[0400] -CF2O(CH2)3-,

[0401] -(CH2)2-,

[0402] -(CH2)3-,

[0403] -(CH2)4- and

[0404] -(1,3-phenylene)-Si(R) 42The group )2-(CH2)2-

[0405] (where R is in the formula) 42 Each independently represents a hydrogen atom and a carbon atom. 1－6 alkyl or C 1－6 The alkoxy group is preferably represented by methyl or methoxy, more preferably by methyl.

[0406] E is -(CH2) ne - (ne is an integer from 2 to 6),

[0407] D-bonded to the molecular backbone with PFPE 1 On one side of the base, E is bonded to the presence of PFPE. 1 The opposite group on one side.

[0408] As for the above X 1 Specific examples can be listed as follows:

[0409] single bond,

[0410] -CH2OCH2-,

[0411] -CH2O(CH2)2-,

[0412] -CH2O(CH2)3-,

[0413] -CH2O(CH2)6-,

[0414] -CF2-CH2-O-CH2-,

[0415] -CF2-CH2-O-(CH2)2-,

[0416] -CF2-CH2-O-(CH2)3-,

[0417] -CF2-CH2-O-(CH2)6-,

[0418] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0419] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0420] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0421] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[0422] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-

[0423] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-

[0424] -CH2OCF2CHFOCF2-、

[0425] -CH2OCF2CHFOCF2CF2-、

[0426] -CH2OCF2CHFOCF2CF2CF2-、

[0427] -CH2OCH2CF2CF2OCF2-、

[0428] -CH2OCH2CF2CF2OCF2CF2-、

[0429] -CH2OCH2CF2CF2OCF2CF2CF2-、

[0430] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[0431] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[0432] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[0433] -CH2OCH2CHFCF2OCF2-、

[0434] -CH2OCH2CHFCF2OCF2CF2-、

[0435] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0436] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0437] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0438] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0439] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0440] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[0441] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、

[0442] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、

[0443] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[0444] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、

[0445] -(CH2)2-Si(CH3)2-(CH2)2-、

[0446] -CH2-、

[0447] -(CH2)2-、

[0448] -(CH2)3-、

[0449] -(CH2)4-、

[0450] -(CH2)5-、

[0451] -(CH2)6-、

[0452] -CF2-、

[0453] -(CF2)2-、

[0454] -CF2-CH2-、

[0455] -CF2-(CH2)2-、

[0456] -CF2-(CH2)3-、

[0457] -CF2-(CH2)4-、

[0458] -CF2-(CH2)5-、

[0459] -CF2-(CH2)6-、

[0460] -WHAT-,

[0461] -CF2CONH-、

[0462] -CF2CONHCH2-,

[0463] -CF2CONH(CH2)2-,

[0464] -CF2CONH(CH2)3-,

[0465] -CF2CONH(CH2)6-,

[0466] -CF2-CON(CH3)-(CH2)3-,

[0467] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0468] -CF2-CON(CH3)-(CH2)6-,

[0469] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0470] -(CH2)2NH(CH2)3-,

[0471] -(CH2)6NH(CH2)3-,

[0472] -CH2O-CONH-(CH2)3-,

[0473] -CH2O-CONH-(CH2)6-,

[0474] -S-(CH2)3-,

[0475] -(CH2)2S(CH2)3-,

[0476] -(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0477] -(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0478] -(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0479] -(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[0480] -(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,

[0481] -(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-,

[0482] -C(O)O-(CH2)3-,

[0483] -C(O)O-(CH2)6-,

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

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

[0486] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-,

[0487] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[0488] -OCH2-,

[0489] -O(CH2)3-,

[0490] -OCFHCF2-,

[0491] 1,3-Phenylidene

[0492] -(1,3-phenylene)-Si(CH3)2-(CH2)2- etc.

[0493] In the above, X 1 Preferred options are:

[0494] single bond,

[0495] -CH2OCH2-,

[0496] -CH2O(CH2)2-,

[0497] -CH2O(CH2)3-,

[0498] -CH2O(CH2)6-,

[0499] -CF2-CH2-O-CH2-,

[0500] -CF2-CH2-O-(CH2)2-,

[0501] -CF2-CH2-O-(CH2)3-,

[0502] -CF2-CH2-O-(CH2)6-、

[0503] -CH2OCF2CHFOCF2-、

[0504] -CH2OCF2CHFOCF2CF2-、

[0505] -CH2OCF2CHFOCF2CF2CF2-、

[0506] -CH2OCH2CF2CF2OCF2-、

[0507] -CH2OCH2CF2CF2OCF2CF2-、

[0508] -CH2OCH2CF2CF2OCF2CF2CF2-、

[0509] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[0510] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[0511] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[0512] -CH2OCH2CHFCF2OCF2-、

[0513] -CH2OCH2CHFCF2OCF2CF2-、

[0514] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0515] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0516] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0517] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0518] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0519] -CH2-、

[0520] -(CH2)2-、

[0521] -(CH2)3-、

[0522] -(CH2)4-,

[0523] -(CH2)5-,

[0524] -(CH2)6-,

[0525] -CF2-,

[0526] -(CF2)2-,

[0527] -CF2-CH2-,

[0528] -CF2-(CH2)2-,

[0529] -CF2-(CH2)3-,

[0530] -CF2-(CH2)4-,

[0531] -CF2-(CH2)5-,

[0532] -CF2-(CH2)6-,

[0533] -CF2CONH-,

[0534] -CF2CONHCH2-,

[0535] -CF2CONH(CH2)2-,

[0536] -CF2CONH(CH2)3-,

[0537] -CF2CONH(CH2)6-,

[0538] -CF2-CON(CH3)-(CH2)3-,

[0539] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0540] -CF2-CON(CH3)-(CH2)6-,

[0541] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0542] -(CH2)2NH(CH2)3-、

[0543] -(CH2)6NH(CH2)3-,

[0544] -CH2O-CONH-(CH2)3-,

[0545] -CH2O-CONH-(CH2)6-,

[0546] -OCH2-,

[0547] -O(CH2)3-, or

[0548] -OCFHCF2-.

[0549] In the above, X 1 More preferably:

[0550] single bond,

[0551] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[0552] -CH2-,

[0553] -(CH2)2-,

[0554] -(CH2)3-,

[0555] -(CH2)6-,

[0556] -CF2CONH-,

[0557] -CF2CONHCH2-,

[0558] -CF2CONH(CH2)2-,

[0559] -CF2CONH(CH2)3-,

[0560] -CF2CONH(CH2)6-,

[0561] -CF2-CON(CH3)-(CH2)3-,

[0562] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0563] -CF2-CON(CH3)-(CH2)6-,

[0564] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0565] -(CH2)2NH(CH2)3-,

[0566] -(CH2)6NH(CH2)3-.

[0567] In one manner, X 1 X represents e′ X e′ It is a single bond, an alkylene group with 1 to 6 carbon atoms, and -R 51 -C6H4-R 52 -、-R 51-CONR 40 -R 52 -、-R 51 -CONR 40 -C6H4-R 52 -、-R 51 -CO-R 52 -、-R 51 -CO-C6H4-R 52 -、-R 51 -SO2NR 40 -R 52 -、-R 51 -SO2NR 40 -C6H4-R 52 -、-R 51 -SO2-R 52 - or -R 51 -SO2-C6H4-R 52 -. R 51 and R 52 Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms (but in R... 51 With -CONR 40 - In the case of connection, R 51 (Not a single bond), preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R 40 The meaning is the same as above. The aforementioned alkylene groups can be substituted or unsubstituted, preferably unsubstituted. Substituents for the aforementioned alkylene groups may include, for example, halogen atoms, preferably fluorine atoms. The aforementioned alkylene groups are linear or branched, preferably linear.

[0568] In the preferred embodiment, X e′ It can be:

[0569] single bond,

[0570] -X f -、

[0571] Alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

[0572] -X f -C 1－6 Alkylene, preferably -X f -C 1－3 Alkylene, more preferably -X f -C 1－2 Alkylene

[0573] -C6H4-R 52 ′-、

[0574] -R 52 ′-、

[0575] -C6H4-R 52 ′-、

[0576] -X f -CONR 4′ -R 52 ′-、

[0577] -X f -CONR 4′ -C6H4-R 52 ′-、

[0578] -CO-R 52 ′-、

[0579] -CO-C6H4-R 52 ′-、

[0580] -SO2NR 4′ -R 52 ′-、

[0581] -SO2NR 4′ -C6H4-R 52 ′-、

[0582] -SO2-R 52 ′-、

[0583] -SO2-C6H4-R 52 ′-、

[0584] -R 51 ′-C6H4-、

[0585] -R 51 ′-CONR 4′ -、

[0586] -R 51 ′-CONR 4′ -C6H4-、

[0587] -R 51 ′-CO-、

[0588] -R 51 ′-CO-C6H4-、

[0589] -R 51 ′-SO2NR 4′ -、

[0590] -R 51 ′-SO2NR 4′ -C6H4-、

[0591] -R 51 ′-SO2-、

[0592] -R51 ′-SO2-C6H4-、

[0593] -C6H4-,

[0594] -X f -CONR 4′ -、

[0595] -X f -CONR 4′ -C6H4-,

[0596] -CO-,

[0597] -CO-C6H4-,

[0598] -SO2NR 4′ -、

[0599] -SO2NR 4′ -C6H4-,

[0600] -SO2-, or

[0601] -SO2-C6H4-.

[0602] (where R is in the formula) 51 ′ and R 52 Each of the above-mentioned alkylene groups is independently a straight-chain alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As described above, the alkylene group may be substituted or unsubstituted, and examples of substituents for the alkylene group include halogen atoms, preferably fluorine atoms. 4′ (This can be a hydrogen atom or a methyl group.)

[0603] In the above, X e′ Preferred options are:

[0604] -X f -、

[0605] Alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

[0606] -X f -C 1－6 Alkylene, preferably -X f -C 1－3 Alkylene, more preferably -X f -C 1－2 Alkylene

[0607] -R 52 ′-、

[0608] -C6H4-R 52 ′-、

[0609] -X f -CONR4′ -R 52 ′-、

[0610] -X f -CONR 4′ -C6H4-R 52 ′-、

[0611] -R 51 ′-CONR 4′ -、

[0612] -R 51 ′-CONR 4′ -C6H4-,

[0613] -X f -CONR 4′ -、

[0614] -X f -CONR 4′ -C6H4-,

[0615] -R 51 ′-CONR 4′ -,or

[0616] -R 51 ′-CONR 4′ -C6H4-.

[0617] In the formula, X f R 51 ′ and R 52 The meanings of ′ are the same as above.

[0618] In the above, X e′ More preferably:

[0619] single bond,

[0620] -R 52 ′-、

[0621] -C6H4-R 52 ′-、

[0622] -X f -CONR 4′ -R 52 ′-、

[0623] -X f -CONR 4′ -C6H4-R 52 ′-、

[0624] -R 51 ′-CONR 4′ -、

[0625] -R51 ′-CONR 4′ -C6H4-,

[0626] -C6H4-,

[0627] -X f -CONR 4′ -,or

[0628] -X f -CONR 4′ -C6H4-.

[0629] In this method, as X e′ Specific examples can be listed as follows:

[0630] single bond,

[0631] Alkyl groups having 1 to 6 carbon atoms

[0632] Perfluoroalkylene groups having 1 to 6 carbon atoms (e.g., -CF2-, -(CF2)2-, etc.)

[0633] -CF2-C 1－6 Alkylene

[0634] -CH2-,

[0635] -(CH2)2-,

[0636] -(CH2)3-,

[0637] -CF2-CONH-,

[0638] -CF2CONHCH2-,

[0639] -CF2CONH(CH2)2-,

[0640] -CF2CONH(CH2)3-,

[0641] -CF2-CON(CH3)-,

[0642] -CF2-CON(CH3)CH2-,

[0643] -CF2-CON(CH3)-(CH2)2-,

[0644] -CF2-CON(CH3)-(CH2)3-,

[0645] -CH2-CONH-,

[0646] -CH2-CONH-CH2-,

[0647] -CH2-CONH-(CH2)2-,

[0648] -CH2-CONH-(CH2)3-、

[0649] -CF2-CH2-CONH-、

[0650] -CF2-CH2-CONH-CH2-、

[0651] -CF2-CH2-CONH-(CH2)2-、

[0652] -CF2-CH2-CONH-(CH2)3-、

[0653] -C6H4-、

[0654] -CH2-CON(CH3)-CH2-、

[0655] -CH2-WITH(CH3)-(CH2)2-、

[0656] -CH2-WITH(CH3)-(CH2)3-、

[0657] -CF2-CONH-C6H4-、

[0658] -CF2-CON(CH3)-C6H4-、

[0659] -CF2-CH2-CON(CH3)-CH2-、

[0660] -CF2-CH2-CON(CH3)-(CH2)2-、

[0661] -CF2-CH2-CON(CH3)-(CH2)3-、

[0662] -CF2-CON(CH3)-C6H4-、

[0663] -CO-,

[0664] -CO-C6H4-、

[0665] -C6H4-、

[0666] -SO2NH-、

[0667] -SO2NH-CH2-、

[0668] -SO2NH-(CH2)2-、

[0669] -SO2NH-(CH2)3-、

[0670] -SO2NH-C6H4-、

[0671] -SO2N(CH3)-,

[0672] -SO2N(CH3)-CH2-,

[0673] -SO2N(CH3)-(CH2)2-、

[0674] -SO2N(CH3)-(CH2)3-、

[0675] -SO2N(CH3)-C6H4-,

[0676] -SO2-,

[0677] -SO2-CH2-,

[0678] -SO2-(CH2)2-,

[0679] -SO2-(CH2)3-, or

[0680] -SO2-C6H4- etc.

[0681] In the above examples, X is the preferred one. e′ Examples include:

[0682] single bond,

[0683] Alkyl groups having 1 to 6 carbon atoms

[0684] Perfluoroalkylene groups having 1 to 6 carbon atoms (e.g., -CF2-, -(CF2)2-, etc.)

[0685] -CF2-C 1－6 Alkylene

[0686] -CH2-,

[0687] -(CH2)2-,

[0688] -(CH2)3-,

[0689] -CF2CONH-,

[0690] -CF2CONHCH2-,

[0691] -CF2CONH(CH2)2-,

[0692] -CF2CONH(CH2)3-,

[0693] -CF2-CON(CH3)-,

[0694] -CF2-CON(CH3)CH2-,

[0695] -CF2-CON(CH3)-(CH2)2-,

[0696] -CF2-CON(CH3)-(CH2)3-,

[0697] -CH2-CONH-,

[0698] -CH2-CONH-CH2-,

[0699] -CH2-CONH-(CH2)2-,

[0700] -CH2-CONH-(CH2)3-,

[0701] -CF2-CH2-CONH-,

[0702] -CF2-CH2-CONH-CH2-,

[0703] -CF2-CH2-CONH-(CH2)2-,

[0704] -CF2-CH2-CONH-(CH2)3-,

[0705] -C6H4-,

[0706] -CH2-CON(CH3)-CH2-,

[0707] -CH2-CON(CH3)-(CH2)2-,

[0708] -CH2-CON(CH3)-(CH2)3-,

[0709] -CF2-CONH-C6H4-,

[0710] -CF2-CON(CH3)-C6H4-,

[0711] -CF2-CH2-CON(CH3)-CH2-,

[0712] -CF2-CH2-CON(CH3)-(CH2)2-,

[0713] -CF2-CH2-CON(CH3)-(CH2)3-,

[0714] -CF2-CON(CH3)-C6H4- etc.

[0715] In the above examples, X is a more preferred option. e′ Examples include:

[0716] single bond,

[0717] -CH2-,

[0718] -(CH2)2-,

[0719] -(CH2)3-,

[0720] -CF2CONH-

[0721] -CF2CONHCH2-,

[0722] -CF2CONH(CH2)2-、

[0723] -CF2CONH(CH2)3-、

[0724] -CF2-CON(CH3)-、

[0725] -CF2-CON(CH3)CH2-、

[0726] -CF2-CON(CH3)-(CH2)2-、

[0727] -CF2-CON(CH3)-(CH2)3-、

[0728] -CH2-CONH-,

[0729] -CH2-CONH-CH2-,

[0730] -CH2-CONH-(CH2)2-、

[0731] -CH2-CONH-(CH2)3-、

[0732] -CF2-CH2-CONH-、

[0733] -CF2-CH2-CONH-CH2-、

[0734] -CF2-CH2-CONH-(CH2)2-、

[0735] -CF2-CH2-CONH-(CH2)3-、

[0736] -C6H4-

[0737] -CH2-CON(CH3)-CH2-,

[0738] -CH2-CON(CH3)-(CH2)2-、

[0739] -CH2-CON(CH3)-(CH2)3-、

[0740] -CF2-CONH-C6H4-、

[0741] -CF2-CON(CH3)-C6H4-,

[0742] -CF2-CH2-CON(CH3)-CH2-,

[0743] -CF2-CH2-CON(CH3)-(CH2)2-,

[0744] -CF2-CH2-CON(CH3)-(CH2)3-, or

[0745] -CF2-CON(CH3)-C6H4- etc.

[0746] In one manner, X e′ It is a single key.

[0747] In yet another way, X 1 For example: -(R) 16 ) x -(CFR) 17 ) y -(CH2) z - The group shown. In the formula, x, y, and z are independent integers from 0 to 10, the sum of x, y, and z is 1 or more, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0748] In the above formula, R 16 Each time it appears, it is independently represented by an oxygen atom, a phenylene group, an imidazolyl group, or a -NR group. 18 -(where R) 18 (Represents a hydrogen atom or an organic group) or a divalent organic group. R is preferred. 16 It is an oxygen atom or a divalent polar group.

[0749] As for the aforementioned "divalent polar groups", there are no particular limitations; examples include -C(O)- and -C(=NR). 19 )-(where R 19 (Indicates a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

[0750] In the above formula, R 17 Each time it appears, it is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0751] In this method, X 1 The preferred formula is: -(O)x -(CF2) y -(CH2) z - (where x, y, and z have the same meaning as above, and the order of the repeating units enclosed in parentheses is arbitrary in the formula) group shown.

[0752] As in the above expression: -(O) x -(CF2) y -(CH2) z The group indicated by - can be exemplified by, for example: -(O) x′ -(CH2) z″ -O-[(CH2) z″′ -O-] z″″ and -(O) x′ -(CF2) y″ -(CH2) z″ -O-[(CH2) z″′ -O-] z″″ The group shown.

[0753] (In the formula, x′ is 0 or 1, y″, z″ and z″′ are independent integers from 1 to 10, and z″″ is 0 or 1.) Furthermore, the left end of these groups is bonded to the PFPE side.

[0754] In another preferred embodiment, X 1 -O-CFR 20 -(CF2) e′ -.

[0755] The above R 20 Each fluorine atom or lower fluoroalkyl group is represented independently. Here, the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0756] The above e′ are independently 0 or 1.

[0757] In a specific example, R 20 is a fluorine atom, and e′ is 1.

[0758] In yet another way, as X 1 Examples of radicals can be listed below:

[0759]

[0760] [In the formula,

[0761] R 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C14 group. 1－6 Alkoxy, preferably methyl;

[0762] In each X 1 In the base, one of T is PFPE in the molecular backbone. 1 The following groups are bonded to the amide bond:

[0763] -CH2O(CH2)2-,

[0764] -CH2O(CH2)3-,

[0765] -CF2O(CH2)3-,

[0766] -CH2-,

[0767] -(CH2)2-,

[0768] -(CH2)3-,

[0769] -(CH2)4-, or

[0770] -(1,3-phenylene)-Si(R) 42 )2-(CH2)2-,

[0771] [In the formula, R] 42 Each independently represents a hydrogen atom and a carbon atom. 1－6 alkyl or C 1－6 The alkoxy group preferably represents methyl or methoxy, more preferably methyl.

[0772] Several of the other T groups are -(CH2) groups bonded to groups opposite to PFPE in the molecular backbone. n″ -(n″ is an integer from 2 to 6), where, if present, the remaining T are independently methyl, phenyl, C. 1－6 Alkyl groups, or free radical scavenging groups, or ultraviolet-absorbing groups. Wherein, in the above-mentioned manner, denoted as X... 1 In the group, the left side is related to PFPE 1 The amide bonds attached to the groups shown are on the right side with PFPE. 1 The groups shown are bonded to opposite sides.

[0773] There are no particular limitations on the free radical scavenging group as long as it can capture free radicals generated by irradiation. Examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate esters, crotonic acid esters, malonyl esters, organic acrylates, hindered amines, hindered phenols, or triazines.

[0774] There are no particular limitations on ultraviolet absorbing groups as long as they can absorb ultraviolet light. Examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxalyl diphenylamines, benzoxazinones, and benzoxazoles.

[0775] In preferred embodiments, examples of preferred free radical scavenging groups or ultraviolet absorbing groups include:

[0776]

[0777] In the above formula (A), X 2 Each instance of X represents a single bond or a divalent organic group independently. 2 Preferably, it is an alkylene group having 1 to 20 carbon atoms, more preferably -(CH2). u —(where u is an integer from 0 to 2).

[0778] In the above formulas, t is an integer from 1 to 10, each independently. In a preferred embodiment, t is an integer from 1 to 6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.

[0779] The preferred compound represented by formula (A) is the compound represented by formula (A′) below.

[0780]

[0781] [In the formula,

[0782] PFPE 1 R 6 and R 7 Each is independently defined as described above;

[0783] R 13 Each time it appears, it independently represents a hydroxyl group or a hydrolyzable group;

[0784] R 14 Each time it appears, it independently represents either a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

[0785] R 11 Each time it appears, it independently represents a hydrogen atom or a halogen atom;

[0786] R 12 Each time it appears, it independently represents a hydrogen atom or a lower alkyl group;

[0787] R 11″ R 12″ R 13″ and R 14″ The meanings of R are respectively related to 11R 12 R 13 and R 14 same;

[0788] n 1 It is an integer from 1 to 3, preferably 3;

[0789] X 1 Each occurrence is independently -O-CFR 20 -(CF2) e′ -;

[0790] R 20 Each time it appears, it is independently a fluorine atom or a lower fluorinated alkyl group;

[0791] e′ is 0 or 1 independently each time it appears;

[0792] X 2 For -(CH2) u -;

[0793] u is an integer from 0 to 2 each time it appears;

[0794] Each occurrence of t is an independent integer from 2 to 10;

[0795] r is an integer greater than or equal to 1.

[0796] The compound shown in formula (A) above can, for example, be synthesized by reacting with -PFPE 1 - Using some of the corresponding perfluoro(poly)ether derivatives as raw materials, after introducing iodine at the end, it reacts with the corresponding -CH2CR... 12 (X 2 -SiR 13 n1 R 14 3－n1 It is obtained by reacting vinyl monomers with )-.

[0797] Formula (B):

[0798]

[0799] In equation (B) above, PFPE 1 R 6 R 7 ,r,R 13 R 13″ R 14 R 14″ The meanings of n1 and n1 are the same as those recorded in the above formula (A).

[0800] In formula (B) above, the Si atom bonded to at least one group selected from hydroxyl and hydrolyzable groups represents an integer n1 of 1 to 3 and (SiR) 13 n1 R 14 3－n1 ) or (-SiR 13″ n1 R 14″ 3－n1 The Si atoms contained in ).

[0801] In the above formula, n1 is in each (-SiR 13 n1 R 14 3－n1 ) unit or each (-SiR) 13″ n1 R 14″ 3－n1 The units are independently integers from 0 to 3, preferably from 1 to 3, and more preferably 3. In the formula, at least two n1 are integers from 1 to 3, that is, not all n1 are simultaneously 0. That is, in the formula, there exist at least two R... 13 Or R 13″ That is, in equation (B), there exist at least two -SiRs selected from n1 being 1 or more. 13 n1 R 14 3－n1 Structure (i.e., -SiR) 13 (partial) and n1 is 1 or more -SiR 13″ n1 R 14″ 3－n 1 structure (i.e., -SiR) 13″ The structure in (partial).

[0802] More preferably, in formula (B), at least one Si bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular backbone of the fluorinated polyether-based silane compound. That is, at least one -SiR is present. 13 Partial, and at least one -SiR exists 13″ part.

[0803] In the above formula, X 3 Each of these can independently represent a divalent to a decavalent organic group. That is, X 3 R corresponding to the above general formula 5 The X 3 This can be understood as the compound shown in formula (B) consisting of a perfluoro(poly)ether portion (i.e., the -PFPE1- portion) that provides water repellency and surface lubrication, and a silane portion (specifically, the -SiR portion) that provides adhesion to the substrate. 13 n1 R 143－n1 or -SiR 13″ n1 R 14″ 3－n1 The connection base is the X. 3 Any organic group can exist stably, provided that the compound represented by formula (B) exists. In this specification, it is denoted as X. 3 The left side of the structure with PFPE 1 The amide bonds to which the shown groups are attached are bonded to groups marked β1 and enclosed in parentheses on the right.

[0804] In another way, X 3 X represents e X e The meaning is the same as above.

[0805] In the above formula, β1 is an integer from 1 to 9, which can correspond to X. 3 The valence changes accordingly. In equation (B), β1 is the valence of X. 3 The value obtained by subtracting 1 from the value of X. 3 When it is a single bond, β1 is 1.

[0806] The above X 3 Preferably, the organic group is 2 to 7 valent, more preferably 2 to 4 valent, and even more preferably 2 valent.

[0807] In one manner, X 3 It consists of 2 to 4 valent organic groups, and β1 is 1 to 3.

[0808] In another way, X 3 It is a divalent organic group, and β1 is 1. In this case, formula (B) is represented by the following formula (B′).

[0809]

[0810] As for the above X 3 Examples, as long as it can be used with PFPE 1 There are no particular limitations on the groups to which the amide group is bonded and which can stably prepare the compound. For example, groups related to X can be listed. 1 The groups recorded are the same, and are groups other than single bonds.

[0811] Among them, the preferred specific X 3 Examples can be listed:

[0812] -CH2OCH2-,

[0813] -CH2O(CH2)2-,

[0814] -CH2O(CH2)3-,

[0815] CH2O(CH2)6

[0816] CF2-CH2-O-CH2-、

[0817] -CF2-CH2-O-(CH2)2-、

[0818] -CF2-CH2-O-(CH2)3-、

[0819] -CF2-CH2-O-(CH2)6-、

[0820] CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2

[0821] CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、

[0822] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、

[0823] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、

[0824] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-

[0825] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-

[0826] -CH2OCF2CHFOCF2-、

[0827] -CH2OCF2CHFOCF2CF2-、

[0828] -CH2OCF2CHFOCF2CF2CF2-、

[0829] -CH2OCH2CF2CF2OCF2-、

[0830] -CH2OCH2CF2CF2OCF2CF2-、

[0831] -CH2OCH2CF2CF2OCF2CF2CF2-、

[0832] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[0833] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[0834] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[0835] -CH2OCH2CHFCF2OCF2-、

[0836] -CH2OCH2CHFCF2OCF2CF2-、

[0837] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0838] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0839] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0840] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0841] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0842] CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2

[0843] CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3

[0844] CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、

[0845] CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2

[0846] CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、

[0847] -(CH2)2-Si(CH3)2-(CH2)2-、

[0848] -CH2-、

[0849] -(CH2)2-、

[0850] -(CH2)3-,

[0851] -(CH2)4-,

[0852] -(CH2)5-,

[0853] -(CH2)6-,

[0854] -CF2-,

[0855] -(CF2)2-,

[0856] -CF2-CH2-,

[0857] -CF2-(CH2)2-,

[0858] -CF2-(CH2)3-,

[0859] -CF2-(CH2)4-,

[0860] -CF2-(CH2)5-,

[0861] -CF2-(CH2)6-,

[0862] -CO-,

[0863] -CF2CONH-,

[0864] -CF2CONHCH2-,

[0865] -CF2CONH(CH2)2-,

[0866] -CF2CONH(CH2)3-,

[0867] -CF2CONH(CH2)6-,

[0868] -CF2-CON(CH3)-(CH2)3-,

[0869] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0870] -CF2-CON(CH3)-(CH2)6-,

[0871] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0872] -(CH2)2NH(CH2)3-,

[0873] -(CH2)6NH(CH2)3-,

[0874] CH2O CONH (CH2)3

[0875] CH2O CONH (CH2)6

[0876] -S-(CH2)3-、

[0877] -(CH2)2S(CH2)3-

[0878] -(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-

[0879] -(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-

[0880] -(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-

[0881] -(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-

[0882] (CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-

[0883] (CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-

[0884] -C(O)O-(CH2)3-、

[0885] -C(O)O-(CH2)6-、

[0886] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、

[0887] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、

[0888] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、

[0889] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、

[0890] -OCH2-、

[0891] -O(CH2)3-,

[0892] -OCFHCF2-,

[0893] 1,3-Phenylidene

[0894] -(1,3-phenylene)-Si(CH3)2-(CH2)2- etc.

[0895] In the above, X 3 Preferred options are:

[0896] -CH2OCH2-,

[0897] -CH2O(CH2)2-,

[0898] -CH2O(CH2)3-,

[0899] -CH2O(CH2)6-,

[0900] -CF2-CH2-O-CH2-,

[0901] -CF2-CH2-O-(CH2)2-,

[0902] -CF2-CH2-O-(CH2)3-,

[0903] -CF2-CH2-O-(CH2)6-,

[0904] -CH2OCF2CHFOCF2-,

[0905] -CH2OCF2CHFOCF2CF2-,

[0906] -CH2OCF2CHFOCF2CF2CF2-,

[0907] -CH2OCH2CF2CF2OCF2-,

[0908] -CH2OCH2CF2CF2OCF2CF2-,

[0909] -CH2OCH2CF2CF2OCF2CF2CF2-,

[0910] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-,

[0911] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-,

[0912] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-,

[0913] -CH2OCH2CHFCF2OCF2-、

[0914] -CH2OCH2CHFCF2OCF2CF2-、

[0915] -CH2OCH2CHFCF2OCF2CF2CF2-、

[0916] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[0917] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[0918] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[0919] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0920] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[0921] -CH2-、

[0922] -(CH2)2-、

[0923] -(CH2)3-、

[0924] -(CH2)4-、

[0925] -(CH2)5-、

[0926] -(CH2)6-、

[0927] -CF2-、

[0928] -(CF2)2-、

[0929] -CF2-CH2-、

[0930] -CF2-(CH2)2-、

[0931] -CF2-(CH2)3-、

[0932] -CF2-(CH2)4-、

[0933] -CF2-(CH2)5-、

[0934] -CF2-(CH2)6-、

[0935] -CF2CONH-、

[0936] -CF2CONHCH2-,

[0937] -CF2CONH(CH2)2-,

[0938] -CF2CONH(CH2)3-,

[0939] -CF2CONH(CH2)6-,

[0940] -CF2-CON(CH3)-(CH2)3-,

[0941] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0942] -CF2-CON(CH3)-(CH2)6-,

[0943] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0944] -(CH2)2NH(CH2)3-,

[0945] -(CH2)6NH(CH2)3-,

[0946] -CH2O-CONH-(CH2)3-,

[0947] -CH2O-CONH-(CH2)6-,

[0948] -OCH2-,

[0949] -O(CH2)3-,

[0950] -OCFHCF2-.

[0951] In the above, X 3 More preferably:

[0952] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[0953] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[0954] -CH2-,

[0955] -(CH2)2-,

[0956] -(CH2)3-,

[0957] -(CH2)6-,

[0958] -CF2CONH-,

[0959] -CF2CONHCH2-,

[0960] -CF2CONH(CH2)2-,

[0961] -CF2CONH(CH2)3-,

[0962] -CF2CONH(CH2)6-,

[0963] -CF2-CON(CH3)-(CH2)3-,

[0964] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0965] -CF2-CON(CH3)-(CH2)6-,

[0966] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0967] -(CH2)2NH(CH2)3-,

[0968] -(CH2)6NH(CH2)3-.

[0969] In another preferred embodiment, X 3 X represents e′ X e′ Except for not being a single key, the meaning is the same as above.

[0970] In one embodiment, formula (B) contains at least two Si groups bonded to hydroxyl or hydrolyzable groups. That is, formula (B) contains at least two -SiR groups. 13 part.

[0971] The preferred compound represented by formula (B) is the compound represented by formula (B′) below.

[0972]

[0973] [In the formula,

[0974] PFPE 1 R 6 R 7 The definitions of r are as described above;

[0975] R 13 Each time it appears, it independently represents a hydroxyl group or a hydrolyzable group;

[0976] R 14 Each time it appears, it independently represents either a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

[0977] R 13″ and R 14″ The meanings of R are respectively related to 13 and R 14 same;

[0978] n1 is an integer from 1 to 3, preferably 3;

[0979] X 3 It is an alkylene group having 1 to 20 carbon atoms, or -CH2O(CH2)2−, -CH2O(CH2)3−, or -CH2O(CH2)6−.

[0980] The compound shown in formula (B) above can be manufactured by known methods, such as the method described in Japanese Patent Application Publication No. 2013-117012 or a modified method thereof.

[0981] Formula (C):

[0982]

[0983] In the above formula (C), PFPE 1 R 6 R 7 The meanings of r and r are the same as those recorded in equation (A) above.

[0984] In the above formula, X 5 Each of these can independently represent a divalent to a decavalent organic group. That is, X 5 R corresponding to the above general formula 5 The X 5 This can be understood as the compound shown in formula (C) primarily providing the perfluoro(poly)ether portion (i.e., -PFPE) with properties such as water repellency and surface lubrication. 1 - Part) and a silane part (specifically -SiR) that provides bonding capability with the substrate. a k1 R b l1 R c m1 Matrix or -SiR a″ k1 R b″ l1 R c″ m1 The connection base is the base of the connection. Therefore, the X 5 Any organic group can exist stably, provided that the compound represented by formula (C) exists. In this specification, it is denoted as X. 5 The left side of the structure with PFPE 1 The shown group bond is bonded to the group marked γ1 and enclosed in parentheses on the right.

[0985] In another way, X 5X represents e X e The meaning is the same as above.

[0986] In another way, equation (C) is represented by the following equation (C′).

[0987]

[0988] As for the above X 5 Examples, as long as it can be used with PFPE 1 There are no particular limitations on the groups to which the amide group is bonded and which can stably prepare the compound. For example, groups related to X can be listed. 1 The groups recorded are the same, and are groups other than single bonds.

[0989] Among them, the preferred specific X 5 Examples can be listed:

[0990] -CH2OCH2-,

[0991] -CH2O(CH2)2-,

[0992] -CH2O(CH2)3-,

[0993] -CH2O(CH2)6-,

[0994] -CF2-CH2-O-CH2-,

[0995] -CF2-CH2-O-(CH2)2-,

[0996] -CF2-CH2-O-(CH2)3-,

[0997] -CF2-CH2-O-(CH2)6-,

[0998] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0999] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[1000] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[1001] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[1002] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10 Si(CH3)2(CH2)2-

[1003] CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-

[1004] -CH2OCF2CHFOCF2-、

[1005] -CH2OCF2CHFOCF2CF2-、

[1006] -CH2OCF2CHFOCF2CF2CF2-、

[1007] -CH2OCH2CF2CF2OCF2-、

[1008] -CH2OCH2CF2CF2OCF2CF2-、

[1009] -CH2OCH2CF2CF2OCF2CF2CF2-、

[1010] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[1011] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[1012] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[1013] -CH2OCH2CHFCF2OCF2-、

[1014] -CH2OCH2CHFCF2OCF2CF2-、

[1015] -CH2OCH2CHFCF2OCF2CF2CF2-、

[1016] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[1017] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[1018] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[1019] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1020] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[1021] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、

[1022] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、

[1023] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[1024] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、

[1025] -(CH2)2-Si(CH3)2-(CH2)2-、

[1026] -CH2-、

[1027] -(CH2)2-、

[1028] -(CH2)3-、

[1029] -(CH2)4-、

[1030] -(CH2)5-、

[1031] -(CH2)6-、

[1032] -CF2-、

[1033] -(CF2)2-、

[1034] -CF2-CH2-、

[1035] -CF2-(CH2)2-、

[1036] -CF2-(CH2)3-、

[1037] -CF2-(CH2)4-、

[1038] -CF2-(CH2)5-、

[1039] -CF2-(CH2)6-、

[1040] -WHAT-,

[1041] -CF2CONH-、

[1042] -CF2CONHCH2-,

[1043] -CF2CONH(CH2)2-,

[1044] -CF2CONH(CH2)3-,

[1045] -CF2CONH(CH2)6-,

[1046] -CF2-CON(CH3)-(CH2)3-,

[1047] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[1048] -CF2-CON(CH3)-(CH2)6-,

[1049] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[1050] -(CH2)2NH(CH2)3-,

[1051] -(CH2)6NH(CH2)3-,

[1052] -CH2O-CONH-(CH2)3-,

[1053] -CH2O-CONH-(CH2)6-,

[1054] -S-(CH2)3-,

[1055] -(CH2)2S(CH2)3-,

[1056] -(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[1057] -(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[1058] -(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[1059] -(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[1060] -(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,

[1061] -(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-,

[1062] -C(O)O-(CH2)3-,

[1063] -C(O)O-(CH2)6-,

[1064] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-,

[1065] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,

[1066] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-,

[1067] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[1068] -OCH2-,

[1069] -O(CH2)3-,

[1070] -OCFHCF2-,

[1071] 1,3-Phenylidene

[1072] -(1,3-phenylene)Si(CH3)2-(CH2)2- etc.

[1073] In the above, X 5 Preferred options are:

[1074] -CH2OCH2-,

[1075] -CH2O(CH2)2-,

[1076] -CH2O(CH2)3-,

[1077] -CH2O(CH2)6-,

[1078] -CF2-CH2-O-CH2-,

[1079] -CF2-CH2-O-(CH2)2-,

[1080] -CF2-CH2-O-(CH2)3-,

[1081] -CF2-CH2-O-(CH2)6-,

[1082] -CH2OCF2CHFOCF2-、

[1083] -CH2OCF2CHFOCF2CF2-、

[1084] -CH2OCF2CHFOCF2CF2CF2-、

[1085] -CH2OCH2CF2CF2OCF2-、

[1086] -CH2OCH2CF2CF2OCF2CF2-、

[1087] -CH2OCH2CF2CF2OCF2CF2CF2-、

[1088] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[1089] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[1090] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[1091] -CH2OCH2CHFCF2OCF2-、

[1092] -CH2OCH2CHFCF2OCF2CF2-、

[1093] -CH2OCH2CHFCF2OCF2CF2CF2-、

[1094] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[1095] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[1096] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[1097] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1098] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1099] -CH2-、

[1100] -(CH2)2-、

[1101] -(CH2)3-,

[1102] -(CH2)4-,

[1103] -(CH2)5-,

[1104] -(CH2)6-,

[1105] -CF2-,

[1106] -(CF2)2-,

[1107] -CF2-CH2-,

[1108] -CF2-(CH2)2-,

[1109] -CF2-(CH2)3-,

[1110] -CF2-(CH2)4-,

[1111] -CF2-(CH2)5-,

[1112] -CF2-(CH2)6-,

[1113] -CF2CONH-,

[1114] -CF2CONHCH2-,

[1115] -CF2CONH(CH2)2-,

[1116] -CF2CONH(CH2)3-,

[1117] -CF2CONH(CH2)6-,

[1118] -CF2-CON(CH3)-(CH2)3-,

[1119] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[1120] -CF2-CON(CH3)-(CH2)6-,

[1121] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[1122] -(CH2)2NH(CH2)3-,

[1123] -(CH2)6NH(CH2)3-,

[1124] -CH2O-CONH-(CH2)3-,

[1125] -CH2O-CONH-(CH2)6-,

[1126] -OCH2-,

[1127] -O(CH2)3-,

[1128] -OCFHCF2-.

[1129] In the above, X 5 More preferably:

[1130] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[1131] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[1132] -CH2-, -(CH2)2-,

[1133] -(CH2)3-,

[1134] -(CH2)6-,

[1135] -CF2CONH-,

[1136] -CF2CONHCH2-,

[1137] -CF2CONH(CH2)2-,

[1138] -CF2CONH(CH2)3-,

[1139] -CF2CONH(CH2)6-,

[1140] -CF2-CON(CH3)-(CH2)3-,

[1141] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[1142] -CF2-CON(CH3)-(CH2)6-,

[1143] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[1144] -(CH2)2NH(CH2)3-,

[1145] -(CH2)6NH(CH2)3-.

[1146] In another preferred embodiment, X 5 X represents e′ X e′The meaning is the same as above, except that it is not a single key.

[1147] In the above formula, R a Each occurrence is represented independently as -Z 3 -SiR 71 p1 R 72 q1 R 73 r1 .

[1148] In the formula, Z 3 Each time it appears, it independently represents an oxygen atom or a divalent organic group.

[1149] The above Z 3 Preferably, it is a divalent organic group, excluding groups that form siloxane bonds with the Si atoms (Si atoms bonded to Ra) at the end of the molecular backbone of formula (C).

[1150] The above Z 3 C is preferred 1－6 Alkylene, -(CH2) g -O-(CH2) h - (where g is an integer from 1 to 6, and h is an integer from 1 to 6) or -phenylene-(CH2) i —(where i is an integer from 0 to 6), more preferably C 1－3 Alkylene groups. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted. From the viewpoint of particularly good UV durability, the above Z... 3 More preferably, it is a linear or branched alkylene group, and even more preferably a linear alkylene group. The above Z constitutes... 3 The number of carbon atoms in the alkylene group is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3. The alkylene group is as described above.

[1151] In the formula, R 71 R is represented independently each time it appears. a′ R a′ The meaning of R a same.

[1152] R a China via Z 3 The maximum number of Si atoms connected in a straight-chain manner is five. That is, in the above R... a There exists at least one R 71 In the case of R a China via Z 3There are more than two Si atoms connected in a straight chain, but through this Z 3 The maximum number of Si atoms connected in a straight chain is 5. Among them, "R a Through Z 3 The number of Si atoms connected in a straight chain is equal to R. a -Z connected in a straight chain 3 The number of repetitions of -Si-.

[1153] For example, R is shown below. a Si atoms pass through Z 3 An example of a base connection.

[1154]

[1155] In the above formula, * indicates the site bonded to Si in the main chain, and … indicates the site bonded to Z. 3 The specified groups other than Si, that is, when all three bonds of the Si atom are ..., represent Z. 3 The end of the repetition of Si. Furthermore, the number in the upper right corner of Si indicates the number counting from * through Z. 3 The number of times Z represents the Si atoms connected in a linear chain. 3 The repetition of Si in Si 2 The chain ending at a certain point is represented by "R". a Through Z 3 The number of Si atoms connected in a straight chain is 2. Similarly, Z 3 The repetition of Si in Si 3 Si 4 and Si 5 The chains ending at each point represent "R" respectively. a Through Z 3 The number of Si atoms linked in a straight chain is 3, 4, and 5. It should be noted that, as shown in the above formula, in R... a There are multiple Z in 3 Si chains do not need to be all the same length; each can be of any length.

[1156] In the preferred embodiment, as shown above, "R" a Through Z 3 The number of Si atoms connected in a straight chain is either 1 (left-hand side) or 2 (right-hand side) in all chains.

[1157]

[1158] In one approach, R a Through Z 3 The number of Si atoms connected in a straight chain is 1 or 2, preferably 1.

[1159] In the formula, R 72 Each time it appears, it independently represents either a hydroxyl group or a hydrolyzable group. The meaning of "hydrolyzable group" is the same as above.

[1160] R 72 Preferably, it is -OR (where R is a substituted or unsubstituted C). 1－3 Alkyl, more preferably methyl).

[1161] In the formula, R 73 Each instance of the hydrogen atom or a lower alkyl group is represented independently. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[1162] In the formula, p1 is an independent integer from 0 to 3 each time it appears; q1 is an independent integer from 0 to 3 each time it appears; r1 is an independent integer from 0 to 3 each time it appears. Wherein, in each (-Z)... 3 -SiR 71 p1 R 72 q1 R 73 r1 The sum of p1, q1 and r1 in () is 3.

[1163] In the preferred embodiment, R a R at the end of the middle a′ (R does not exist) a′ When it is R a In the above, q1 is preferably 2 or more, for example 2 or 3, and more preferably 3.

[1164] In a preferred embodiment, at least one of the ends of Ra can be -Si(-Z). 3 -SiR 72 q1 R 73 r1 )2R b l1 R c m1 (where either l1 or m1 is 1 and the other is 0) or -Si(-Z) 3 -SiR 72 q1 R 73 r1 )3, preferably -Si(-Z) 3 -SiR 72 q1 R 73 r1 )3 (where the sum of q1 and r1 is 3). In the formula, (-Z 3 -SiR72 q1 R 73 r1 The preferred unit is (−Z). 3 -SiR 72 3). In a more preferred manner, R a The terminal part can be entirely -Si (-Z) 3 -SiR 72 q1 R 73 r1 3. Preferably -Si(-Z) 3 -SiR 72 3)3.

[1165] In the above formula, R a″ Each occurrence is represented independently as -Z 3 -SiR 71 p1 R 72″ q1 R 73 r1 Z 3 R 71 R 73 The meanings of p1, q1, and r1 are the same as above. R 72″ The meaning of R 72 same.

[1166] In the preferred embodiment, R a″ At least one of the terminal portions is -Si(-Z) 3 -SiR 72″ q1 R 73 r1 )2R b″ l1 R c″ m1 (where either l1 or m1 is 1 and the other is 0) or -Si(-Z) 3 -SiR 72″ q1 R 73 r1 )3, preferably -Si(-Z) 3 -SiR 72″ q1 R 73 r1 )3 (where q1 and r1 together equal 3. In the formula, (-Z 3 -SiR 72″ q1 R 73 r1 The preferred unit is (−Z). 3 -SiR 72″3). In a more preferred manner, R a The terminal part can be entirely -Si (-Z) 3 -SiR 72″ q1 R 73 r1 3. Preferably -Si(-Z) 3 -SiR 72″ 3)3.

[1167] In formula (C), there are at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups. That is, there are at least two Si atoms selected from SiR. 72 (specifically -SiR) 71 p1 R 72 q1 R 73 r1 The shown groups (where q1 is an integer from 1 to 3), SiR 72″ (specifically -SiR) 71 p1 R 72″ q1 R 73 r1 The shown groups (where q1 is an integer from 1 to 3), SiR b (specifically -SiR) a k1 R b l1 R c m1 The shown groups (where l1 is an integer from 1 to 3) and SiR b″ (specifically -SiR) a″ k1 R b″ l1 R c″ m1 The structure of the group shown (where l1 is an integer from 1 to 3). R b and R b″ To be discussed later.

[1168] More preferably, in formula (C), at least one Si atom bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular backbone of the fluorinated polyether-based silane compound (A). That is, at least one SiR atom is present. 72 and / or SiR b The structure contains at least one SiR 72″ and / or SiR b″ The structure.

[1169] In the above formula, R b Each time it appears, it independently represents either a hydroxyl group or a hydrolyzable group.

[1170] The above R b Preferably, the compounds are hydroxyl groups, -OR, -OCOR, -O-N=C(R)2, -N(R)2, -NHR, or halogens (in these formulas, R represents a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms), more preferably -OR. R includes unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl, and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially unsubstituted alkyl groups, more preferably methyl or ethyl. The hydroxyl group is not particularly limited and can be generated by hydrolysis of a hydrolyzable group. More preferably, R... b -OR (where R represents substituted or unsubstituted C) 1－3 Alkyl, more preferably methyl).

[1171] In the above formula, R b″ The meaning of R b same.

[1172] In the above formula, R c Each instance of the hydrogen atom or a lower alkyl group is represented independently. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[1173] In the above formula, R c″ The meaning of R c same.

[1174] In the formula, k1 is an independent integer from 0 to 3 each time it appears; l1 is an independent integer from 0 to 3 each time it appears; m1 is an independent integer from 0 to 3 each time it appears. Wherein, in each (SiR) a k1 R b l1 R c m1 ) or each (SiR a″ k1 R b″ l1 R c″ m1 In ), the sum of k1, l1 and m1 is 3.

[1175] In one embodiment, k1 is preferably 1 to 3, more preferably 3.

[1176] The compound represented by formula (C) above can be synthesized, for example, as described in International Publication No. 2014 / 069592.

[1177] Formula (D):

[1178]

[1179] In the above formula (D), PFPE 1 R 6 R 7 The meanings of r and r are the same as those in the above formula (A).

[1180] In the above formula, X 7 Each can independently represent a single bond or a divalent to decavalent organic group. This X 7 This can be understood as the perfluoro(poly)ether portion (i.e., -PFPE) in the compound shown in formula (D) primarily providing water repellency and surface lubrication. 1 A connecting group (i.e., the group marked δ1 and enclosed in parentheses) that provides bonding ability with the substrate. Therefore, the X 7 As long as the compound represented by formula (D) can exist stably, it can be a single bond or any organic group. In this specification, it is denoted as X. 7 The left side of the structure with PFPE 1 The amide bonds adjacent to the shown group are bonded to the group marked δ1 and enclosed in parentheses on the right.

[1181] In another way, X 7 X represents e X e The meaning is the same as above.

[1182] In the above formula, δ1 is an integer from 1 to 9, and δ1 corresponds to X. 7 The valence changes accordingly. In equation (D), δ1 is the valence of X. 7 The value obtained by subtracting 1 from the valence. In X 7 When it is a single bond, δ1 is 1.

[1183] The above X 7 Preferably, the organic group is 2 to 7 valent, more preferably 2 to 4 valent, and even more preferably 2 valent.

[1184] In one manner, X 7 It consists of 2- to 4-valent organic groups, with δ1 ranging from 1 to 3.

[1185] In another way, X 7 It is a divalent organic group, and δ1 is 1. In this case, formula (D) is represented by the following formula (D′).

[1186]

[1187] As for the above X 7 Examples, as long as it can be used with PFPE 1 There are no particular limitations on the groups to which the amide group is bonded and which can stably prepare the compound. For example, groups related to X can be listed. 1The same group as the one recorded.

[1188] Among them, the preferred specific X 7 Examples can be listed:

[1189] single bond,

[1190] -CH2OCH2-,

[1191] -CH2O(CH2)2-,

[1192] -CH2O(CH2)3-,

[1193] -CH2O(CH2)6-,

[1194] -CF2-CH2-O-CH2-,

[1195] -CF2-CH2-O-(CH2)2-,

[1196] -CF2-CH2-O-(CH2)3-,

[1197] -CF2-CH2-O-(CH2)6-,

[1198] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[1199] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[1200] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[1201] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[1202] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,

[1203] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-,

[1204] -CH2OCF2CHFOCF2-,

[1205] -CH2OCF2CHFOCF2CF2-,

[1206] -CH2OCF2CHFOCF2CF2CF2-,

[1207] -CH2OCH2CF2CF2OCF2-、

[1208] -CH2OCH2CF2CF2OCF2CF2-、

[1209] -CH2OCH2CF2CF2OCF2CF2CF2-、

[1210] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[1211] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[1212] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[1213] -CH2OCH2CHFCF2OCF2-、

[1214] -CH2OCH2CHFCF2OCF2CF2-、

[1215] -CH2OCH2CHFCF2OCF2CF2CF2-、

[1216] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[1217] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[1218] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[1219] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1220] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、

[1221] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、

[1222] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、

[1223] CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2

[1224] CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、

[1225] -(CH2)2-Si(CH3)2-(CH2)2-、

[1226] -CH2-、

[1227] -(CH2)2-、

[1228] -(CH2)3-、

[1229] -(CH2)4-、

[1230] -(CH2)5-、

[1231] -(CH2)6-、

[1232] -CF2-、

[1233] -(CF2)2-、

[1234] -CF2-CH2-、

[1235] -CF2-(CH2)2-、

[1236] -CF2-(CH2)3-、

[1237] -CF2-(CH2)4-、

[1238] -CF2-(CH2)5-、

[1239] -CF2-(CH2)6-、

[1240] -CO-、

[1241] -CF2CONH-、

[1242] -CF2CONHCH2-、

[1243] -CF2CONH(CH2)2-、

[1244] -CF2CONH(CH2)3-、

[1245] -CF2CONH(CH2)6-、

[1246] -CF2-CON(CH3)-(CH2)3-、

[1247] -CF2-CON(Ph)-(CH2)3- (where Ph means phenyl),

[1248] -CF2-CON(CH3)-(CH2)6-,

[1249] -CF2-CON(Ph)-(CH2)6- (where Ph means phenyl),

[1250] -CONH-(CH2)2NH(CH2)3-,

[1251] -CONH-(CH2)6NH(CH2)3-,

[1252] -CH2O-CONH-(CH2)3-,

[1253] -CH2O-CONH-(CH2)6-,

[1254] -S-(CH2)3-,

[1255] -(CH2)2S(CH2)3-,

[1256] -(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[1257] -(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[1258] -(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[1259] -(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[1260] -(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,

[1261] -(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-,

[1262] -C(O)O-(CH2)3-,

[1263] -C(O)O-(CH2)6-,

[1264] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-,

[1265] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,

[1266] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-,

[1267] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[1268] -OCH2-,

[1269] -O(CH2)3-,

[1270] -OCFHCF2-,

[1271] 1,3-Phenylidene

[1272] -(1,3-phenylene)-Si(CH3)2-(CH2)2- etc.

[1273] Of the above, the more preferred specific X 7 Preferred options are:

[1274] -CH2OCH2-,

[1275] -CH2O(CH2)2-,

[1276] -CH2O(CH2)3-,

[1277] -CH2O(CH2)6-,

[1278] -CF2-CH2-O-CH2-,

[1279] -CF2-CH2-O-(CH2)2-,

[1280] -CF2-CH2-O-(CH2)3-,

[1281] -CF2-CH2-O-(CH2)6-,

[1282] -CH2OCF2CHFOCF2-,

[1283] -CH2OCF2CHFOCF2CF2-,

[1284] -CH2OCF2CHFOCF2CF2CF2-,

[1285] -CH2OCH2CF2CF2OCF2-,

[1286] -CH2OCH2CF2CF2OCF2CF2-、

[1287] -CH2OCH2CF2CF2OCF2CF2CF2-、

[1288] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、

[1289] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、

[1290] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、

[1291] -CH2OCH2CHFCF2OCF2-、

[1292] -CH2OCH2CHFCF2OCF2CF2-、

[1293] -CH2OCH2CHFCF2OCF2CF2CF2-、

[1294] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、

[1295] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、

[1296] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、

[1297] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1298] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、

[1299] -CH2-、

[1300] -(CH2)2-、

[1301] -(CH2)3-、

[1302] -(CH2)4-、

[1303] -(CH2)5-、

[1304] -(CH2)6-、

[1305] -CF2-、

[1306] -(CF2)2-、

[1307] -CF2-CH2-,

[1308] -CF2-(CH2)2-,

[1309] -CF2-(CH2)3-,

[1310] -CF2-(CH2)4-,

[1311] -CF2-(CH2)5-,

[1312] -CF2-(CH2)6-,

[1313] -CF2CONH-,

[1314] -CF2CONHCH2-,

[1315] -CF2CONH(CH2)2-,

[1316] -CF2CONH(CH2)3-,

[1317] -CF2CONH(CH2)6-,

[1318] -CF2-CON(CH3)-(CH2)3-,

[1319] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[1320] -CF2-CON(CH3)-(CH2)6-,

[1321] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[1322] -(CH2)2NH(CH2)3-,

[1323] -(CH2)6NH(CH2)3-,

[1324] -CH2O-CONH-(CH2)3-,

[1325] -CH2O-CONH-(CH2)6-,

[1326] -OCH2-,

[1327] -O(CH2)3-,

[1328] -OCFHCF2-.

[1329] In the above, X 7 More preferably:

[1330] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[1331] -CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[1332] -CH2-,

[1333] -(CH2)2-,

[1334] -(CH2)3-,

[1335] -(CH2)6-,

[1336] -CF2CONH-,

[1337] -CF2CONHCH2-,

[1338] -CF2CONH(CH2)2-,

[1339] -CF2CONH(CH2)3-,

[1340] -CF2CONH(CH2)6-,

[1341] -CF2-CON(CH3)-(CH2)3-,

[1342] -CF2-CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[1343] -CF2-CON(CH3)-(CH2)6-,

[1344] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[1345] -(CH2)2NH(CH2)3-,

[1346] -(CH2)6NH(CH2)3-.

[1347] In a more preferred manner, X 7 X represents e′ X e′ The meaning is the same as above. In one method, X e′ It is a single key.

[1348] In the above formula, R d Each occurrence is represented independently as -Z 4 -CR 81 p2 R 82 q2 R 83 r2.

[1349] In the formula, Z 4 Each time it appears, it independently represents an oxygen atom or a divalent organic group.

[1350] The above Z 4 C is preferred 1－6 Alkylene, -(CH2) g -O-(CH2) h -(where g is an integer from 0 to 6, for example, an integer from 1 to 6, and h is an integer from 0 to 6, for example, an integer from 1 to 6) or -phenylene-(CH2) i —(where i is an integer from 0 to 6), more preferably C 1－3 Alkylene groups. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted.

[1351] In the formula, R 81 R is represented independently each time it appears. d′ R d′ The meaning of R d same.

[1352] R d China via Z 4 The number of C atoms connected in a linear chain is at most 5. That is, in the above R... d There exists at least one R 81 In the case of R d China via Z 4 There are more than two C atoms connected in a straight chain, but they are linked by Z. 4 The maximum number of C atoms linked in a straight chain is 5. Among them, "R" d Through Z 4 The number of C atoms linked in a straight chain is equal to R. d -Z connected in a straight chain 4 The number of repetitions of -C-.

[1353] In a preferred embodiment, as shown below, “R” d Through Z 4 The number of C atoms connected in a straight chain is either 1 (left-hand side) or 2 (right-hand side) in all chains.

[1354]

[1355] In one approach, R d via Z 4 The number of C atoms connected in a straight chain is 1 or 2, preferably 1.

[1356] In the formula, R 82 Each occurrence is independently represented as -Y-SiR. 85 n2 R 86 3－n2 .

[1357] Y represents a divalent organic group each time it appears.

[1358] In the preferred embodiment, Y is C. 1－6 Alkylene, -(CH2) g′ -O-(CH2) h′ -(where g′ is an integer from 0 to 6, for example, an integer from 1 to 6, and h′ is an integer from 0 to 6, for example, an integer from 1 to 6) or -phenylene-(CH2) i′ —(where i′ is an integer from 0 to 6). These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted.

[1359] In one approach, Y can be C 1－6 Alkylene or -phenylene-(CH2) i′ When Y is one of the above-mentioned groups, light resistance, especially UV resistance, is further improved.

[1360] The above R 85 Each time it appears, it independently represents either a hydroxyl group or a hydrolyzable group.

[1361] The “hydrolyzable groups” mentioned above can be the same groups as those in formula (C).

[1362] R 85 Preferably, it is -OR (where R represents substituted or unsubstituted C). 1－3 Alkyl, more preferably ethyl or methyl, especially methyl).

[1363] The above R 86 Each instance of the hydrogen atom or a lower alkyl group is represented independently. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[1364] n2 in each (-Y-SiR) 85 n2 R 86 3－n2 ) unit or each (-Y-SiR) 85″ n2 R 86″ 3－n2The unit independently represents an integer from 0 to 3, preferably an integer from 1 to 3, more preferably 2 or 3, and particularly preferably 3. 85″ and R 86″ To be discussed later.

[1365] The above R 83 Each instance of the hydrogen atom, hydroxyl group, or lower alkyl group is represented independently, preferably by a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl.

[1366] In the formula, p2 is an integer from 0 to 3 each time it appears; q2 is an integer from 0 to 3 each time it appears; and r2 is an integer from 0 to 3 each time it appears. Wherein, in each (-Z)... 4 -CR 81 p2 R 82 q2 R 83 r2 ) or each (-Z 4 -CR 81 p2 R 82″ q2 R 83 r2 In equation (R), the sum of p2, q2, and r2 is 3. 82″ To be discussed later.

[1367] In the preferred method, in R d R at the end of the middle d′ (R does not exist) d′ When it is R d In the above, q2 is preferably 2 or more, for example 2 or 3, and more preferably 3.

[1368] In the preferred embodiment, R d At least one of the terminal portions can be -C(-Y-SiR) 85 n2 R 86 3－n2 )2(specifically -C(-Y-SiR) 85 n2 R 86 3－n2 )2R 83 ) or -C(-Y-SiR 85 n2 R 86 3－n2 3. Preferably, it is -C(-Y-SiR) 85 n2 R 86 3－n23. Where n2 is an integer from 1 to 3. In the formula, (-YSiR 85 n2 R 86 3－n2 The preferred unit is (-Y-SiR). 85 3). In a more preferred manner, R d The terminal portion can be entirely -C(-Y-SiR) 85 n2 R 86 3－n2 3. Preferably, it is -C(-Y-SiR) 85 3)3.

[1369] In a more preferred manner, (CR d k2 R e l2 R f m2 The terminal of the group shown is C(-Y-SiR) 85 n2 R 86 3－n2 )2R f ) or C(-Y-SiR 85 n2 R 86 3－n2 3. Preferably, it is C(-Y-SiR) 85 n2 R 86 3－n2 3. Where n2 is an integer from 1 to 3. In the formula, (-Y-SiR 85 n2 R 86 3－n2 The preferred unit is (-Y-SiR). 85 3). In a more preferred embodiment, the terminal portion of the above-mentioned base may be entirely -C(-Y-SiR). 85 n2 R 86 3－n2 3. Preferably, it is -C(-Y-SiR) 85 3)3.

[1370] In the above formula, R d″ Each occurrence is represented independently as -Z 4 -CR 81 p2 R 82″ q2 R 83 r2 Z 4 R 81 R 83The meanings of p2, q2, and r2 are the same as above. R 82″ Each occurrence is independently represented as -Y-SiR. 85″ n2 R 86″ 3－n2 In this context, Y and n2 have the same meanings as above. R 85″ and R 86″ The meanings of R are respectively related to 85 and R 86 same.

[1371] In the preferred method, in R d″ R at the end of the middle d ′(in the absence of R) d When ′ is R d″ In the above, q2 is preferably 2 or more, for example 2 or 3, and more preferably 3.

[1372] In the preferred embodiment, R d″ At least one of the terminal portions can be -C(-Y-SiR) 85″ n2 R 86″ 3－n2 )2(specifically -C(-Y-SiR) 85″ n2 R 86″ 3－n2 )2R 83 ) or -C(-Y-SiR 85″ n2 R 86″ 3－n2 3. Preferably, it is -C(-Y-SiR) 85″ n2 R 86″ 3－n2 3. Where n2 is an integer from 1 to 3. In the formula, (-Y-SiR 85″ n2 R 86″ 3－n2 The preferred unit is (-Y-SiR). 85″ 3). In a more preferred manner, R d The terminal portion can be entirely -C(-Y-SiR) 85″ n2 R 86″ 3－n2 3. Preferably, it is -C(-Y-SiR) 85″ 3)3.

[1373] In a more preferred manner, (CR d″ k2 R e″ l2 R f″m2 The terminal of the group shown is C(-Y-SiR) 85″ n2 R 86 ″ 3－n2 )2R f″ ) or C(-Y-SiR 85″ n2 R 86″ 3－n2 3. Preferably, it is C(-Y-SiR) 85″ n2 R 86″ 3－n2 3. Where n2 is an integer from 1 to 3. In the formula, (-Y-SiR 85″ n2 R 86″ 3－n2 The preferred unit is (-Y-SiR). 85″ 3). In a more preferred embodiment, the terminal portion of the above-mentioned groups may all be -C(-Y-SiR). 85″ n2 R 86″ 3－n2 3. Preferably, it is -C(-Y-SiR) 85″ 3)3.

[1374] In the above formula, R e Each occurrence is independently represented as -Y-SiR. 85 n2 R 86 3－n2 Among them, Y and R 85 R 86 The meanings of n2 and n2 are the same as those of R above. 82 The records are the same.

[1375] In the above formula, R e″ Each occurrence is independently represented as -Y-SiR. 85″ n2 R 86″ 3－n2 Among them, R 85″ R 86″ The meanings of Y and n2 are the same as above.

[1376] In the above formula, R f Each occurrence independently represents a hydrogen atom, hydroxyl group, or lower alkyl group. R is preferred. f Each instance of the hydrogen atom or a lower alkyl group is represented independently. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[1377] In the above formula, Rf″ The meaning of R f same.

[1378] In the formula, k2 is an independent integer from 0 to 3 each time it appears; l2 is an independent integer from 0 to 3 each time it appears; and m2 is an independent integer from 0 to 3 each time it appears. The sum of k2, l2, and m2 is 3.

[1379] In one manner, at least one k2 is 2 or 3, preferably 3.

[1380] In one embodiment, k2 is 2 or 3, preferably 3.

[1381] In one embodiment, l2 is 2 or 3, preferably 3.

[1382] In the above equation (D), there are more than two selections from -Y-SiR. 85 The groups shown and -Y-SiR 85″ The groups shown are radicals. In the above formula (D), it is preferable to have one or more -Y-SiR radicals. 85 The indicated group, and the presence of more than one -Y-SiR 85″ The indicated group. More preferably, one or more of the following groups are present: -Y-SiR. 85 n2 R 86 3－n2 The carbon atoms bonded to the shown groups, and the presence of one or more -Y-SiR groups, are present. 85″ n2 R 86″ 3－n2 The carbon atoms bonded to the shown groups. In the formula, n2 is an integer from 1 to 3. That is, preferably, there is one or more carbon atoms selected from -C-Rd. k2 (Y-SiR) 85 n2 R 86 3－n2 ) l2 Rf m2 The shown groups (where l2 is 2 or 3, and the total of k2, l2 and m2 is 3) and -CR 81 p2 (Y-SiR) 85 n2 R 86 3－n2 ) q2 R 83 r2 The indicated groups (where q2 is 2 or 3, and the total of p2, q2, and r2 is 3) contain one or more groups selected from -C-Rd. k2 (Y-SiR) 85″n2 R 86″ 3－n2 ) l2 Rf m2 The shown groups (where l2 is 2 or 3, and the total of k2, l2 and m2 is 3) and -C-R 81 p2 (Y-SiR) 85″ n2 R 86″ 3－n2 ) q2 R 83 r2 The group shown (where q2 is 2 or 3, and the total of p2, q2 and r2 is 3) is the group shown (where n2 is an integer from 1 to 3).

[1383] In one embodiment, in equation (D) above, preferably there is one or more -C-(Y-SiR) atoms. 85 n2 R 86 3－n2 The group shown in )2, and the presence of more than one -C-(Y-SiR) 85″ n2 R 86″ 3－n2 The group shown in )2 (where n2 is an integer from 1 to 3).

[1384] In one embodiment, in equation (D) above, preferably there is one or more -C-(Y-SiR) atoms. 85 n2 R 86 3－n2 The group shown in )3, and the presence of more than one -C-(Y-SiR) 85″ n2 R 86″ 3－n2 The group shown in )3 (where n2 is an integer from 1 to 3).

[1385] In the above formula (D), n2 is an integer from 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3.

[1386] In the above formula (D), preferably there are at least 2 -Y-SiR atoms. 85 n2 R 86 3－n2 Y-SiR 85″ n2 R 86″ 3－n2 In the above formula (D), it is more preferable that there is one or more -YSiR. 85 n2 R 863－n2 The base, and the presence of more than one -Y-SiR 85″ n2 R 86″ 3－n2 Base. That is, preferably containing -SiR. 85 Groups and -SiR 85″ The groups are present at both ends of the molecular backbone of the fluorinated polyether silane compound (A).

[1387] The compound shown in formula (D) above can be manufactured by combining known methods.

[1388] In a preferred embodiment, the fluorinated polyether-based silane compound is represented by formula (B) or (C).

[1389] In one manner, the fluorinated polyether-based silane compound is represented by formula (A), (C), or (D).

[1390] In one embodiment, the fluorinated polyether-based silane compound has two or more, preferably three or more, Si atoms with hydroxyl or hydrolyzable groups at at least one end.

[1391] The aforementioned fluorinated polyether-based silane compounds are not particularly limited; in one embodiment, they may have a content of 5 × 10⁻⁶. 2 ~1×10 5 The number average molecular weight. Within this range, a number average molecular weight of 2,000 to 50,000 is preferred, more preferably 2,500 to 30,000, and even more preferably 3,000 to 10,000 is preferred. In this invention, the number average molecular weight is determined by... 19 Values ​​measured by F-NMR.

[1392] The present invention provides compositions containing the fluorinated polyether silane compounds of the present invention described above, and typically provides surface treatment agents.

[1393] The fluorinated polyether-based silane compound of the invention contained in the above composition may be contained alone or in multiple forms. For example, it may contain compounds in which k or r is any integer from 1 to 5. Furthermore, the composition of the present invention may contain compounds in which k or r is 0. Preferably, the average value of k or r in the composition is 1.

[1394] The surface treatment agent of the present invention may contain solvents, (non-reactive) fluorinated polyether compounds which can be understood as fluorinated oils, preferably perfluorinated (poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), (non-reactive) compounds which can be understood as silicone oils (hereinafter referred to as "silicone oils"), catalysts, surfactants, polymerization inhibitors, sensitizers, etc.

[1395] Examples of solvents mentioned above include: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, acetic acid cellosol, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl 2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; and ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve butyrate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether, and other glycol ethers; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, tert-pentanol, etc.; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; N,N-dimethyl... Amides such as formamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; fluorinated solvents such as 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), ZEORORA H, HFE7100, HFE7200, and HFE7300, etc. Alternatively, you can list two or more of these mixed solvents.

[1396] As a fluorinated oil, there are no particular limitations, for example, the following compounds (perfluoro(poly)ether compounds) can be listed as general formula (3).

[1397] Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 ···(3)

[1398] In the formula, Rf 5 This refers to an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1―16 perfluoroalkyl), Rf 6This indicates an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[1399] a′, b′, c′, and d′ represent the number of four repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are independent integers ranging from 0 to 300. Furthermore, 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 the repeating units labeled with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula. Among these repeating units, -(OC4F8)- can 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))-, preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. -(OC2F4)- can be either -(OCF2CF2)- or (OCF(CF3))-, with -(OCF2CF2)- being preferred.

[1400] As an example of the perfluoro(poly)ether compound represented by the above general formula (3), any of the compounds represented by the following general formulas (3a) and (3b) can be listed (which may be a mixture of one or more compounds).

[1401] Rf 5 -(OCF2CF2CF2) b″ -Rf 6 ···(3a)

[1402] Rf 5 -(OCF2CF2CF2CF2) a″ -(OCF2CF2CF2) b″ -(OCF2CF2) c″ -(OCF2) d″ -Rf 6 ···(3b)

[1403] In these formulas, Rf 5 and Rf 6 As described above; in equation (3a), b″ is an integer greater than 1 and less than 100; in equation (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 the repeated units marked with subscripts a″, b″, c″, and d″ and enclosed in parentheses is arbitrary in the equation.

[1404] Alternatively, from another perspective, fluorinated oils can be of the general formula Rf 3 -F(where Rf) 3 C 5－16 The compound is shown as a perfluoroalkyl group. Alternatively, it can be a trichlorofluoroethylene oligomer.

[1405] The aforementioned fluorinated oils can have an average molecular weight of 500–10,000. The molecular weight of fluorinated oils can be determined using GPC.

[1406] The fluorinated oil may contain, for example, 0-50% by mass, preferably 0-30% by mass, and more preferably 0-5% by mass relative to the composition of the present invention. In one embodiment, the composition of the present invention is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means completely free of fluorinated oil, or may contain trace amounts of fluorinated oil.

[1407] In one approach, the average molecular weight of the fluorinated oil can be greater than that of the fluorinated polyether-based silane compound. By setting such an average molecular weight, especially when the surface treatment layer is formed by vacuum evaporation, superior friction durability and surface lubrication can be obtained.

[1408] In one approach, the average molecular weight of the fluorinated oil can be lower than the average molecular weight of the fluorinated polyether-based silane compound. By setting such an average molecular weight, it is possible to suppress the decrease in transparency of the surface treatment layer obtained from the compound and to form a cured product with high friction durability and high surface lubricity.

[1409] Fluorinated oils help improve the surface slip properties of layers formed from the compositions of the present invention.

[1410] As the aforementioned silicone oil, linear or cyclic silicone oils with siloxane bonds of 2,000 or less can be used. Linear silicone oils can be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrosilicone oil. Examples of modified silicone oils include silicone oils obtained by modifying straight silicone oils with alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, etc. Cyclic silicone oils include, for example, cyclic dimethylsiloxane silicone oil.

[1411] In the composition of the present invention (e.g., a surface treatment agent), the silicone oil may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorinated polyether-based silane compounds of the present invention (or their total when there are two or more, the same below).

[1412] Silicone oil helps improve the surface lubrication of surface treatment layers.

[1413] Examples of catalysts mentioned above include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), and transition metals (such as Ti, Ni, Sn, etc.).

[1414] The catalyst can promote the hydrolysis and dehydration condensation of the fluorinated polyether-based silane compounds of the present invention, and can promote the formation of layers formed by the compositions of the present invention (e.g., surface treatment agents).

[1415] Other components, besides those mentioned above, include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

[1416] The compositions of the present invention can be used as surface treatment agents for surface treatment of substrates.

[1417] The surface treatment agent of the present invention can be impregnated into porous materials, such as porous ceramic materials, metal fibers, or products such as steel wool fixed into a cotton-like state, to form granules. These granules can be used, for example, for vacuum evaporation.

[1418] The items of the present invention will now be described.

[1419] The articles of the present invention include: a substrate, and a layer (surface treatment layer) formed on the surface of the substrate by a surface treatment agent of the present invention containing a fluorinated polyether group of a silane compound.

[1420] The substrate that can be used in this invention can be made of any suitable material, such as glass, resin (natural or synthetic resin, which can be, for example, a general plastic material, which can be in the form of a plate, film, or other form), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building components, etc.

[1421] For example, when the desired product is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Additionally, when the desired product is an optical component, certain layers (or films), such as hard coatings or anti-reflective layers, can be formed on the surface (outermost layer) of the substrate. The anti-reflective layer can be either a single-layer or multi-layer anti-reflective layer. Examples of inorganic materials that can be used for anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials can be used alone or in combination of two or more (e.g., as a mixture). In the case of a multi-layer anti-reflective layer, it is preferable to use SiO2 and / or SiO for the outermost layer. When the desired product is an optical glass component for a touchscreen, a portion of the surface of the substrate (glass) can have transparent electrodes, such as thin films using indium tin oxide (ITO) or indium zinc oxide. Additionally, the substrate can have insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, retardation films, and liquid crystal display modules, depending on its specific design.

[1422] There are no particular limitations on the shape of the substrate. In addition, the surface area of ​​the substrate to which the surface treatment layer is to be formed only needs to be at least a portion of the substrate surface, and can be appropriately determined according to the intended use and specific style of the article to be manufactured.

[1423] The substrate can be at least partially composed of a material that inherently possesses hydroxyl groups. Examples of such materials include glass, and metals (especially base metals), ceramics, semiconductors, etc., with a natural or thermal oxide film formed on their surface. Alternatively, in cases where the substrate possesses hydroxyl groups but not sufficiently, or where it originally lacks hydroxyl groups, such as resins, certain pretreatments can be applied to introduce or increase hydroxyl groups on the substrate surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) or ion beam irradiation. Plasma treatment is also suitable for introducing or increasing hydroxyl groups on the substrate surface and for cleaning the substrate surface (removing foreign matter, etc.). Another example of such pretreatment is the method of forming an interfacial adsorbent film with carbon-carbon unsaturated bonds in the form of a monolayer on the substrate surface using the LB method (Langmuir-Blodgett method) or chemisorption, followed by breaking the unsaturated bonds in an atmosphere containing oxygen or nitrogen.

[1424] Alternatively, the substrate may be composed at least of a material containing an organosilicon compound having one or more other reactive groups, such as Si-H groups, or an alkoxysilane.

[1425] Next, a layer of the surface treatment agent of the present invention is formed on the surface of the substrate, and the layer is post-treated as needed, thereby forming a layer from the surface treatment agent of the present invention.

[1426] The layer formation of the surface treatment agent of the present invention can be achieved by applying the above composition to the surface of a substrate in a manner that covers the surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[1427] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[1428] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) 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.

[1429] Furthermore, it can also be covered using atmospheric pressure plasma method.

[1430] When using a wet coating method, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the composition of the present invention and the volatility of the solvent, the following solvents are preferred: perfluoroaliphatic hydrocarbons with 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 AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA H manufactured by ZEON Corporation of Japan); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd.) Alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl groups can be straight-chain or branched) such as 7100), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Corporation), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Corporation), or CF3CH2OCF2CHF2 (e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or in mixtures of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[1431] When using the dry coating method, the surface treatment agent of the present invention can be used directly in the dry coating method, or diluted with the above-mentioned solvent and then used in the dry coating method.

[1432] The formation of the surface treatment agent layer is preferably carried out in a manner in which the surface treatment agent of the present invention coexists with the catalyst for hydrolysis and dehydration condensation in the layer. For simplicity, when using the wet coating method, the catalyst can be added to the diluted solution of the surface treatment agent of the present invention after dilution with a solvent and just before application to the substrate surface. When using the dry coating method, the surface treatment agent of the present invention with the catalyst added can be directly vapor-deposited (usually vacuum vapor-deposited), or vapor-deposited (usually vacuum vapor-deposited) using granular material of the surface treatment agent of the present invention with the catalyst added impregnated in a porous metal such as iron or copper.

[1433] The catalyst can be any suitable acid or base. As an acid catalyst, acetic acid, formic acid, trifluoroacetic acid, etc., can be used. As a base catalyst, ammonia, organic amines, etc., can be used.

[1434] As described above, a layer of the surface treatment agent of the present invention is formed on the surface of a substrate to manufacture the article of the present invention. The resulting layer has both high surface slip properties and high friction durability. In addition to high friction durability, depending on the composition of the surface treatment agent used, the layer can also have properties such as water repellency, oil repellency, stain resistance (e.g., preventing the adhesion of dirt such as fingerprints), water resistance (preventing water from penetrating electronic components, etc.), and surface slip properties (or lubrication, such as the ability to wipe away dirt such as fingerprints, and excellent tactile feel for fingers), making it suitable for use as a functional film.

[1435] That is, the present invention also relates to optical materials having the above-mentioned surface treatment agent layer as the outermost layer.

[1436] In addition to the optical materials related to displays exemplified later, a variety of other optical materials are preferably listed, such as: displays of cathode ray tubes (CRTs, such as computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), etc., or protective plates for these displays, or materials on which anti-reflective coatings have been applied.

[1437] Articles having the layer obtained by the present invention can be optical components, but are not particularly limited thereto. Examples of optical components include the following: lenses for eyeglasses, etc.; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch screens for devices such as portable telephones and portable information terminals; disc surfaces for optical discs such as Blu-ray discs, DVD discs, CD-Rs, and MO discs; optical fibers; and the display surface of clocks, etc.

[1438] In addition, articles having the layer obtained by the present invention can also be medical devices or medical materials.

[1439] The thickness of the aforementioned layer is not particularly limited. In the case of an optical component, from the viewpoints of optical performance, surface lubricity, friction durability, and anti-fouling properties, the thickness of the aforementioned layer is preferably in the range of 1–50 nm, 1–30 nm, and more preferably 1–15 nm.

[1440] The above provides a detailed description of articles obtained by using the fluorinated polyether-based silane compound of the present invention typically as a surface treatment agent. However, the uses, methods of use, and methods of manufacturing articles of the fluorinated polyether-based silane compound or compositions containing the fluorinated polyether-based silane compound of the present invention are not limited to the examples described above.

[1441] Example

[1442] The surface treatment agent of the present invention will be specifically described through the following embodiments, but the present invention is not limited to these embodiments. In these embodiments, the chemical formulas shown below represent average compositions, and the order of the repeating units constituting the perfluoropolyether is arbitrary.

[1443] Example 1

[1444] Add CH3OCO-CF2-(OCF2) to a 50 mL four-necked flask equipped with a reflux cooler, thermometer, and stirrer, with an even composition. 29 -(OCF2CF2) 17 20 g of PFPE-modified ester (represented by -OCF2-COOCH3) and 10 g of 1,3-bis(trifluoromethyl)benzene were added under a nitrogen stream using a dropping funnel with 0.53 mL of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane added, and the mixture was stirred at 25°C for 1 hour. Next, 1.0 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatile components were then removed by distillation under reduced pressure, yielding the PFPE-containing silane compound (A) shown in the following formula.

[1445] PFPE-containing silane compound (A):

[1446] (CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3

[1447] In the formula, R is a group represented by the following formula.

[1448]

[1449] Of these, 4.8% contained compounds with CF3O- at one end. Additionally, trace amounts of (CH3O)3Si-CH2CH2CH2-NHCO-{CF2-(OCF2) were identified as byproducts. 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO} n -CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3 (n is 0 or 2).

[1450] Example 2

[1451] Add CH3OCO-CF2-(OCF2) to a 50 mL four-necked flask equipped with a reflux cooler, thermometer, and stirrer, with an even composition. 29 -(OCF2CF2) 17 -OCF2-COOCH3 represents 20 g of PFPE-modified ester and 10 g of 1,3-bis(trifluoromethyl)benzene. Under a nitrogen stream, 0.61 g of 4,4′-methylenebis(cyclohexylamine) was added using a dropping funnel, and the mixture was stirred at 25°C for 1 hour. Then, 1.0 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatile components were then removed by distillation under reduced pressure, yielding the PFPE-containing silane compound (B) shown in the following formula.

[1452] PFPE-containing silane compounds (B):

[1453] (CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3

[1454] In the formula, R is a group represented by the following formula.

[1455]

[1456] Of these, 4.8% contained compounds with CF3O- at one end. Additionally, trace amounts of (CH3O)3Si-CH2CH2CH2-NHCO-{CF2-(OCF2) were identified as byproducts. 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO} n -CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3 (n is 0 or 2).

[1457] Example 3

[1458] Add CH3OCO-CF2-(OCF2) to a 50 mL four-necked flask equipped with a reflux cooler, thermometer, and stirrer, with an even composition. 29 -(OCF2CF2) 1720 g of PFPE-modified ester (represented by -OCF2-COOCH3) and 10 g of 1,3-bis(trifluoromethyl)benzene were added under a nitrogen stream using a dropping funnel, followed by stirring at 25°C for 1 hour. Then, 1.0 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatile components were then removed by distillation under reduced pressure, yielding the PFPE-containing silane compound (C) shown in the following formula.

[1459] PFPE-containing silane compounds (C):

[1460] (CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3

[1461] In the formula, R is a group represented by the following formula.

[1462]

[1463] Of these, 4.8% contained compounds with CF3O- at one end. Additionally, trace amounts of (CH3O)3Si-CH2CH2CH2-NHCO-{CF2-(OCF2) were identified as byproducts. 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO} n -CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3 (n is 0 or 2).

[1464] Comparative Example 1

[1465] Add CH3OCO-CF2-(OCF2) to a 50 mL four-necked flask equipped with a reflux cooler, thermometer, and stirrer, with an even composition. 29 -(OCF2CF2) 1720 g of PFPE-modified ester represented by -OCF2-COOCH3 and 10 g of 1,3-bis(trifluoromethyl)benzene were added under a nitrogen stream using a dropping funnel, followed by stirring at 25°C for 1 hour. Then, 1.0 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. Volatile components were then removed by distillation under reduced pressure, yielding the PFPE-containing silane compound (D) shown in the following formula.

[1466] PFPE-containing silane compounds (D):

[1467] (CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3

[1468] In the formula, R is a group represented by the following formula.

[1469]

[1470] Of these, 4.8% contained compounds with CF3O- at one end. Additionally, trace amounts of (CH3O)3Si-CH2CH2CH2-NHCO-{CF2-(OCF2) were identified as byproducts. 29 -(OCF2CF2) 17 -OCF2-CONH-R-NHCO} n -CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3 (n is 0 or 2).

[1471] Comparative Example 2

[1472] Add CH3OCO-CF2-(OCF2) to a 50 mL four-necked flask equipped with a reflux cooler, thermometer, and stirrer, with an even composition. 29 -(OCF2CF2) 1720 g of PFPE-modified ester (represented by -OCF2-COOCH3) and 10 g of 1,3-bis(trifluoromethyl)benzene were added under a nitrogen atmosphere using a dropping funnel, followed by stirring at 70°C for 16 hours. The reaction solution was then cooled to 25°C, and 1.0 mL of 3-aminopropyltrimethoxysilane was added, followed by stirring at 25°C for 1 hour. Volatile components were then removed by distillation under reduced pressure, yielding the PFPE-containing silane compound (E) shown in the following formula.

[1473] PFPE-containing silane compounds (E):

[1474] (CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-R-CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3

[1475] In the formula, R is a group represented by the following formula.

[1476]

[1477] Of these, 4.8% contained compounds with CF3O- at one end. Additionally, trace amounts of (CH3O)3Si-CH2CH2CH2-NHCO-{CF2-(OCF2) were identified as byproducts. 29 -(OCF2CF2) 17 -OCF2-R} n -CF2-(OCF2) 29 -(OCF2CF2) 17 -OCF2-CONH-CH2CH2CH2-Si(OCH3)3 (n is 0 or 2).

[1478] Evaluation (Preparation of surface treatment agents)

[1479] Surface treatment agents 1-5 were prepared by dissolving the perfluoropolyether-containing silane compounds obtained in Examples 1-3 and Comparative Examples 1-2 in Novec 7200 (manufactured by 3M) to a concentration of 20 wt%.

[1480] (Formation of the surface treatment layer)

[1481] The surface treatment agents 1 to 6 prepared above were vacuum-deposited onto chemically strengthened glass (Gorilla glass, Corning, 0.7 mm thick) using a resistance heating evaporation machine (SHINCRON, Ltd.), with specific chamber dimensions. Vacuum degree 5.0E-05, current 240A, voltage 10V, substrate temperature 40℃. Next, the chemically strengthened glass after vapor deposition is left to stand in an atmosphere at 150℃ for 30 minutes, and then cooled to room temperature to form a surface treatment layer on the glass substrate.

[1482] <Resistant to Rubber Abrasion Test After Constant Temperature and Humidity Exposure>

[1483] The glass, after undergoing the above surface treatment, was exposed to an environment of 40°C / 80%RH for 300 hours. Specifically, using an ISUZU SEISAKUSHO TPAV-210-20 low-temperature and humidity test chamber, the surface-treated glass was placed horizontally in a tank set at 40°C / 80%RH and left to stand for 300 hours. Afterwards, using a friction tester (manufactured by Shinto Science Co., Ltd.), the water resistance contact angle was measured every 250 rubs under the following conditions, and the test was continued until it fell below 100°. The test environment conditions were 40°C and 90%RH. The results are shown in Table 1 below.

[1484] Eraser: Raber Eraser (Made by Minoan)

[1485] Grounding area:

[1486] Movement distance (single lane): 30mm

[1487] Movement speed: 3,600 mm / min

[1488] Load: 1kg /

[1489] <Universal Pen Rejection Experiment>

[1490] The repellency of the multi-purpose pen was confirmed on the glass surface prepared as described above. Specifically, a straight line of 1 cm in diameter and 10 cm in length was drawn on the surface-treated glass using the multi-purpose pen. Then, the surface was dry-rubbed 10 times with 1 kg of wiping paper, and the surface was observed. After wiping, if the ink was removed, it was rated as ×; if some ink remained, it was rated as △; and if the ink remained completely, it was rated as ○. The evaluation results are shown in Table 1. The multi-purpose pen used was an ultra-fine oil-based marker manufactured by Zebra.

[1491] [Table 1]

[1492] Eraser durability (times) Universal pen rejection Example 1 1750 〇 Example 2 2000 〇 Example 3 2000 〇 Comparative Example 1 750 △ Comparative Example 2 1000 △

[1493] Industrial availability

[1494] The fluorinated polyether-based silane compounds of the present invention are suitable for forming surface treatment layers on a wide variety of substrates.

Claims

1. A fluorinated polyether-containing silane compound represented by formula (I) below, In the formula, R 3 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. R 4 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. p is an integer from 0 to 3 each time it appears; in, (SiR 3 p R 4 3－p ) j In, at least one SiR 3 p R 4 3－p In this context, p is an integer between 0 and 2. Each occurrence of q is an independent integer from 0 to 3; Among them, (SiR) 3 q R 4 3- q ) j In, at least one SiR 3 q R 4 3- q In this context, q is an integer between 0 and 2. R 5 Each time it appears, it is an organic group with an independent valence of j+1. R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -, R 15 Each time it appears, it is independently a group containing a cycloalkylene group. R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene R 7 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－20 alkyl, PFPE 1 Each occurrence is independently assigned to -R. F -R FE -, R F For -(C f F 2f )-, f is an integer from 1 to 10. R FE The formula is: -(OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F 12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown, In the formula, a1, a2, a3, a4, a5, a6, a7, and a8 are each an independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7, and a8 is at least 5. The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula. X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When the atom is a hydrogen atom or a chlorine atom, at least one of a1, a2, a4, a5, a6, a7, and a8 is an integer greater than or equal to 1. j is an integer from 1 to 9 each time it appears. k is an integer greater than or equal to 1.

2. The fluorinated polyether-containing silane compound as described in claim 1, characterized in that, R 15 Each time it appears, it is independently a monocyclic, bicyclic, or tricyclic cycloalkyl group containing 5 to 12 carbon atoms. R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene.

3. The fluorinated polyether-containing silane compound as described in claim 1 or 2, characterized in that, R 6 A group selected from the following groups in which the hydrogen atoms on the ring can be replaced. In the formula, R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene R 18 Each occurrence is independently assigned the number C. 1－6 Alkylene.

4. The fluorinated polyether-containing silane compound as described in claim 1 or 2, characterized in that, X 10 It is a fluorine atom.

5. The fluorinated polyether-based silane compound as described in claim 1 or 2, characterized in that, R FE Each time it appears, it is independently represented by a group as shown in formula (f1), (f2), (f3), (f4), or (f5). -(OC3F6) a3 -(OC2F4) a2 - (f1) In equation (f1), a3 is an integer from 5 to 200, and a2 is 0 or 1. -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f2) In equation (f2), a3 and a4 are independent integers from 0 to 30; a1 and a2 are independent integers from 1 to 200; The sum of a1, a2, a3, and a4 is an integer between 10 and 200; The order of repeated units marked with subscripts a1, a2, a3, or a4 and enclosed in parentheses is arbitrary in the formula. -(R 16 -R 17 ) g - (f3) In equation (f3), R 16 It is either OCF2 or OC2F4; R 17 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups, or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. -(OC6F 12 ) a6 -(OC5F 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f4) In equation (f4), a2 is an integer from 1 to 200, a1, a3, a4, a5, and a6 are each an independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, and a6 is at least 5. Furthermore, the order of repeated units labeled a1, a2, a3, a4, a5, or a6 and enclosed in parentheses is arbitrary in the equation. -(OC6F 12 ) a6 -(OC5F 10 ) a5 -(OC4F8) a4 -(OC3F6) a3 -(OC2F4) a2 -(OCF2) a1 - (f5) In equation (f5), a1 is an integer from 1 to 200, a2, a3, a4, a5 and a6 are each an independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5 and a6 is at least 5. In addition, the order of the repeated units marked a1, a2, a3, a4, a5 or a6 and enclosed in parentheses is arbitrary in the equation.

6. The fluorinated polyether-containing silane compound as described in claim 1 or 2, characterized in that, R 7 It is a hydrogen atom.

7. The fluorinated polyether-based silane compound as described in claim 1 or 2, characterized in that, R 5 It is a divalent organic group, and j is 1.

8. The fluorinated polyether-containing silane compound as described in claim 1 or 2, characterized in that, R 5 C 1－6 Alkylene, j = 1.

9. The fluorinated polyether-based silane compound as described in claim 1 or 2, characterized in that, Represented by equations (A), (B), (C), or (D), In the formula, R 11 and R 11″ Each time it appears, it is independently either a hydrogen atom or a halogen atom. R 12 and R 12″ Each time it appears, it is independently a hydrogen atom or a lower alkyl group. R 13 and R 13″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 14 and R 14″ Each time it appears, it is independently either a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. X 2 Each time it appears, it is independently either a single bond or a divalent organic group. n1 in each (-SiR) 13 n1 R 14 3－n1 ) unit or each (-SiR) 13″ n1 R 14″ 3－n1 Each unit contains independent integers from 0 to 3. X 1 Each is independently a single bond or a divalent to decavalent organic group connected to an amide bond. t are independent integers from 1 to 10. α1 is an integer from 1 to 9. X 3 Each is an independent organic group ranging from 2 to 10 valents. β1 is an integer from 1 to 9. X 5 Each is an independent organic group ranging from 2 to 10 valents. γ1 is an integer from 1 to 9. R a Each occurrence is independently -Z 3 -SiR 71 p1 R 72 q1 R 73 r1 , Z 3 Each time it appears, it is independently either an oxygen atom or a divalent organic group. R 71 Each occurrence is independently assigned the value R. a′ , R a′ The meaning of R a same, R a via Z 3 The maximum number of Si atoms connected in a straight chain is five. R 72 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 73 Each time it appears, it is independently a hydrogen atom or a lower alkyl group. p1 is an independent integer from 0 to 3 each time it appears. q1 is an independent integer from 0 to 3 each time it appears. r1 is an independent integer from 0 to 3 each time it appears. Among them, in each (-Z) 3 -SiR 71 p1 R 72 q1 R 73 r1 In the given equation, the sum of p1, q1, and r1 is 3. R a″ Each occurrence is independently -Z 3 -SiR 71 p1 R 72″ q1 R 73 r1 , Z 3 R 71 R 73 The meanings of p1, q1, and r1 are the same as above. R 72″ The meaning of R 72 same, R b and R b″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R c and R c″ Each time it appears, it is independently a hydrogen atom or a lower alkyl group. k1 is an independent integer from 0 to 3 each time it appears. l1 is an integer from 0 to 3 each time it appears. Each occurrence of m1 is an independent integer from 0 to 3. Among them, in each (SiR) a k1 R b l1 R c m1 ) or each (SiR a″ k1 R b″ l1 R c″ m1 In the given information, the sum of k1, l1, and m1 is 3. X 7 Each is an independent organic group ranging from 2 to 10 valents. δ1 is an integer from 1 to 9. R d Each occurrence is independently -Z 4 -CR 81 p2 R 82 q2 R 83 r2 , Z 4 Each time it appears, it is independently either an oxygen atom or a divalent organic group. R 81 Each occurrence is independently assigned the value R. d′ , R d′ The meaning of R d same, R 82 Each occurrence is independently -Y-SiR 85 n2 R 86 3－n2 , Y is an independent divalent organic group each time it appears. R 85 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 86 Each time it appears, it is independently a hydrogen atom or a lower alkyl group. n2 in each (-Y-SiR) 85 n2 R 86 3－n2 ) unit or each (-Y-SiR) 85″ n2 R 86″ 3- n2 Each unit contains independent integers from 0 to 3. R 83 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a lower alkyl group. p2 is an integer from 0 to 3 each time it appears. q2 is an integer from 0 to 3 each time it appears. r2 is an integer from 0 to 3 each time it appears. Among them, in each (-Z) 4 -CR 81 p2 R 82 q2 R 83 r2 ) or each (-Z 4 -CR 81 p2 R 82″ q2 R 83 r2 In the equation, the sum of p2, q2, and r2 is 3. R d″ Each occurrence is independently -Z 4 -CR 81 p2 R 82″ q2 R 83 r2 , R 82″ Each occurrence is independently -Y-SiR 85″ n2 R 86″ 3－n2 , R 85″ and R 86 The meanings of "" are respectively related to R 85 and R 86 same, R e Each occurrence is independently -Y-SiR 85 n2 R 86 3－n2 , R e″ Each occurrence is independently -Y-SiR 85″ n2 R 86″ 3－n2 , R f and R f″ Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a lower alkyl group. k2 is an independent integer from 0 to 3 each time it appears. l2 is an integer from 0 to 3 each time it appears. Each occurrence of m2 is an independent integer from 0 to 3. The sum of k2, l2, and m2 is 3. R 6 Each occurrence is independently assigned to -R. 16 -R 15 -R 17 -, R 15 Each time it appears, it is independently a group containing a cycloalkylene group. R 16 Each occurrence is independently a single key or a C. 1－6 Alkylene R 17 Each occurrence is independently a single key or a C. 1－6 Alkylene R 7 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－20 alkyl, PFPE 1 Each occurrence is independently assigned to -R. F -R FE -, R F For -(C f F 2f )-, f is an integer from 1 to 10. R FE The formula is: -(OCF2) a1 -(OC2F4) a2 -(OC3X) 10 6) a3 -(OC4F8) a4 -(OC5F) 10 ) a5 -(OC6F 12 ) a6 -(OC7F) 14 ) a7 -(OC8F 16 ) a8 - The divalent fluorinated polyether group shown, In the formula, a1, a2, a3, a4, a5, a6, a7, and a8 are each independent integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7, and a8 is at least 5. The order of repeated units marked with subscripts a1, a2, a3, a4, a5, a6, a7, or a8 and enclosed in parentheses is arbitrary in the formula. X 10 Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom, where, in all X... 10 When the atom is a hydrogen atom or a chlorine atom, at least one of a1, a2, a4, a5, a6, a7, and a8 is an integer greater than or equal to 1. r is an integer greater than or equal to 1.

10. A surface treatment agent, characterized in that, A silane compound containing a fluorinated polyether group as described in any one of claims 1 to 9.

11. The surface treatment agent as described in claim 10, characterized in that, It also contains one or more other components selected from fluorinated oils, silicone oils and catalysts.

12. The surface treatment agent as described in claim 10 or 11, characterized in that, It also contains solvents.

13. The surface treatment agent as described in claim 10 or 11, characterized in that, Used as a stain-resistant or waterproof coating.

14. An article characterized in that, include: Substrate, and A layer formed on the surface of the substrate by any one of the fluorinated polyether-based silane compounds according to claims 1 to 9, or any one of the surface treatment agents according to claims 10 to 13.

15. The article as claimed in claim 14, characterized in that, The item in question is an optical component.

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