Surface treatment agent

Abstract

The present application provides a surface treatment agent containing a silane compound having a fluoro-substituted polyether group, a compound having a fluoro-substituted polyether group, and a solvent, the content of the silane compound having a fluoro-substituted polyether group being 0.02 to 50.0 mass%, the content of the compound having a fluoro-substituted polyether group being 0.1 to 95.0 mass%, and the content of the solvent being 1 to 99.88 mass%, relative to the total amount of the silane compound having a fluoro-substituted polyether group, the compound having a fluoro-substituted polyether group, and the solvent, the silane compound having a fluoro-substituted polyether group being a silane compound having a fluoro-substituted polyether group represented by formula (1) or (2), and the compound having a fluoro-substituted polyether group having a boiling point of 105 to 210°C. F1 α -X A -R Si β (1) R Si γ -X A -R F2 -X A -R Si γ (2)

Description

Technical Field

[0001] The present invention relates to surface treatment agents and articles having a layer formed by the surface treatment agent. Background Technology

[0002] It is known that when certain types of fluorinated silane compounds are used for surface treatment of substrates, they can provide excellent water repellency, oil repellency, and stain resistance. The layer obtained from the surface treatment agent containing the fluorinated silane compound (hereinafter also referred to as the "surface treatment layer") is applied as a so-called functional film to a wide variety of substrates such as glass, plastics, fibers, hygiene products, and building materials (Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-218639 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] The fluorinated silane compounds described in Patent Document 1 can form surface treatment layers with excellent functions, but there is still a need for surface treatment layers with higher wear resistance.

[0008] The purpose of this invention is to provide an article with a surface treatment layer that has higher wear resistance.

[0009] Technical means for solving technical problems

[0010] The present invention includes the following methods.

[0011] [1] A surface treatment agent comprising a fluorinated polyether silane compound, a fluorinated polyether compound, and a solvent.

[0012] Relative to the total amount of the fluorinated polyether-based silane compound, the fluorinated polyether-based compound, and the solvent, the content of the fluorinated polyether-based silane compound is 0.02–50.0% by mass, the content of the fluorinated polyether-based compound is 0.1–95.0% by mass, and the content of the solvent is 1–99.88% by mass.

[0013] The above-mentioned fluorinated polyether-containing silane compounds are fluorinated polyether-containing silane compounds represented by formula (1) or (2).

[0014] R F1 α -X A -R Si β (1)

[0015] R Si γ X A -R F2 -X A -R Si γ (2)

[0016] [In the formula,

[0017] R F1 Each occurrence is independently assigned to Rf. 1 -R F -O q -;

[0018] R F2 -Rf 2 p -R F -O q -;

[0019] Rf 1 Each time it appears, it is independently a C that can be substituted by one or more fluorine atoms. 1-16 alkyl;

[0020] Rf 2 C atoms that can be substituted by one or more fluorine atoms 1-6 Alkylene;

[0021] R F Each time it appears, it is independently a divalent fluorinated polyether group;

[0022] p is 0 or 1;

[0023] q is 0 or 1 independently each time it appears;

[0024] R Si Each time it appears, it is independently represented by a group as shown in formula (S1), (S2), (S3), or (S4).

[0025]

[0026] -SiR a1 k1 R b1 11 R c1 m1 (S2)

[0027] -CR d1 k2 R e1 12 R f1 m2 (S3)

[0028] -NR g1 R h1 (S4)

[0029] (in the formula,

[0030] R 11 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0031] R 12 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0032] n1 in each (SiR) 11 n1 R 12 3-n1 Each unit contains an independent integer from 0 to 3;

[0033] X 11 Each time it appears, it is independently either a single bond or a divalent organic group;

[0034] R 13 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0035] R 14 Each time it appears, it is independently a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 ;

[0036] R 15 Each time it appears, it is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkene group having 1 to 6 carbon atoms;

[0037] Each occurrence of t is an integer greater than 2.

[0038] R a1 Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ;

[0039] Z 1 Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0040] R 21 Each occurrence is independently -Z 1′ -SiR21′ p1′ R 22′ q1′ R 23′ r1′ ;

[0041] R 22 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0042] R 23 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0043] p1 is an integer from 0 to 3 each time it appears;

[0044] Each occurrence of q1 is an independent integer from 0 to 3;

[0045] r1 is an integer from 0 to 3 each time it appears;

[0046] The sum of p1, q1, and r1 in each (SiR) 21 p1 R 22 q1 R 23 r1 The value in unit ) is 3;

[0047] Z 1′ Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0048] R 21′ Each occurrence is independently -Z 1″ -SiR 22″ q1″ R 23″ r1″ ;

[0049] R 22′ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0050] R 23′ Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0051] p1′ is an integer from 0 to 3 each time it appears;

[0052] Each occurrence of q1′ is an independent integer from 0 to 3;

[0053] r1′ is an integer from 0 to 3 each time it appears;

[0054] The sum of p1′, q1′, and r1′ in each (SiR 21′p1′ R 22′ q1′ R 23′ r1′ The value in unit ) is 3;

[0055] Z 1″ Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0056] R 22″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0057] R 23″ Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0058] q1″ is an integer from 0 to 3 each time it appears;

[0059] r1″ is an integer from 0 to 3 each time it appears;

[0060] The sum of q1″ and r1″ in each (SiR 22″ q1″ R 23″ r1″ The value in unit ) is 3;

[0061] R b1 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0062] R c1 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0063] k1 is an integer from 0 to 3 each time it appears;

[0064] l1 is an integer from 0 to 3 each time it appears;

[0065] m1 is an integer from 0 to 3 each time it appears;

[0066] The sum of k1, l1, and m1 in each (SiR) a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3;

[0067] R d1 Each occurrence is independently -Z 2 -CR 31 p2 R 32 q2 R 33r2 ;

[0068] Z 2 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0069] R 31 Each occurrence is independently -Z 2′ -CR 32′ q2′ R 33′ r2′ ;

[0070] R 32 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ;

[0071] R 33 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0072] p2 is an integer from 0 to 3 each time it appears;

[0073] q2 is an integer from 0 to 3 each time it appears;

[0074] r2 is an integer from 0 to 3 each time it appears;

[0075] The sum of p2, q2, and r2 in each (CR 31 p2 R 32 q2 R 33 r2 The value in unit ) is 3;

[0076] Z 2′ Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0077] R 32′ Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ;

[0078] R 33′ Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0079] Each occurrence of q2′ is an independent integer from 0 to 3;

[0080] r2′ is an integer from 0 to 3 each time it appears;

[0081] The sum of q2′ and r2′ in each (CR 32′ q2′ R 33′ r2′ The value in unit ) is 3;

[0082] Z 3 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0083] R 34 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0084] R 35 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0085] n2 is an integer from 0 to 3 each time it appears;

[0086] R e1 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ;

[0087] R f1 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0088] k2 is an integer from 0 to 3 each time it appears;

[0089] l2 is an integer from 0 to 3 each time it appears;

[0090] m2 is an integer from 0 to 3 each time it appears;

[0091] The sum of k2, l2, and m2 in each (CR d1 k2 R e1 l2 R f1 m2 The value in unit ) is 3;

[0092] R g1 and R h1 Each occurrence is independently -Z 4 -SiR 11 n1 R 12 3－n1 -Z 4 -SiR a1k1 R b1 l1 R c1 m1 or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ;

[0093] Z 4 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0094] In formulas (S1), (S2), (S3), and (S4), there exists at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

[0095] X A Each is independently a single bond or a 2- to 10-valent organic group;

[0096] α is an integer from 1 to 9;

[0097] β is an integer from 1 to 9;

[0098] γ can be an independent integer from 1 to 9.

[0099] The boiling points of the above-mentioned fluorinated polyether compounds are 105–210 °C.

[0100] [2] As described in [1] above, the surface treatment agent, wherein Rf 1 Each occurrence is independently assigned the number C. 1－16 Perfluoroalkyl, Rf 2 C 1－6 Perfluoroalkylene groups.

[0101] [3] The surface treatment agent as described in [1] or [2] above, wherein R F Each occurrence is represented independently: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0102] [In the formula, R] Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0103] a, b, c, d, e, and f are each an independent integer from 0 to 200. The sum of a, b, c, d, e, and f is greater than or equal to 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula, but it applies to all R... Fa If the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f must be 1 or more.

[0104] [4] The surface treatment agent as described in [3] above, wherein R Fa It is a fluorine atom.

[0105] [5] The surface treatment agent as described in any one of [1] to [4] above, wherein R F Each time it appears, it is independently represented by a group as shown in formula (f1), (f2), (f3), (f4), or (f5).

[0106] -(OC3F6) d -(OC2F4) e -(f1)

[0107] [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]

[0108] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0109] [In the formula, c and d are independent integers from 0 to 30;]

[0110] e and f are independent integers from 1 to 200;

[0111] The sum of c, d, e and f is an integer between 10 and 200;

[0112] The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0113] -(R) 6 -R 7 ) g -(f3)

[0114] [In the formula, R] 6 It is either OCF2 or OC2F4;

[0115] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12The groups in the group, or a combination of two or three groups selected from these groups;

[0116] g is an integer from 2 to 100.

[0117] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f4)

[0118] [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0119] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f5)

[0120] [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, and the order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary.]

[0121] [6] The surface treatment agent as described in any one of [1] to [5] above, wherein α, β and γ are 1.

[0122] [7] The surface treatment agent as described in any one of [1] to [6] above, wherein the ratio of fluorine atoms to carbon atoms in the fluorinated polyether compound is 3.00 or more.

[0123] [8] The surface treatment agent as described in any one of [1] to [7] above, wherein the fluorinated polyether group compound is the fluorinated polyether group compound shown in formula (3).

[0124] Rf 5 -(OC) h1 H h2 F h3 ) j -Rf 6···(3)

[0125] [In the formula,

[0126] Rf 5 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0127] Rf 6 C atoms that can be substituted by one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms;

[0128] h1 is an integer from 1 to 4 each time it appears;

[0129] h2 is an integer from 0 to 8 each time it appears;

[0130] h3 is an integer from 0 to 8 each time it appears;

[0131] Here, in (OC) h1 H h2 F h3 In unit ), 2×h1=h2+h3;

[0132] j is an integer from 1 to 10.

[0133] [9] The surface treatment agent as described in any one of [1] to [8] above, wherein the fluorinated polyether group compound is the fluorinated polyether group compound shown in formula (3′).

[0134] Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 ···(3′)

[0135] [In the formula,

[0136] Rf 5 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0137] Rf 6 C atoms that can be substituted by one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms;

[0138] a′, b′, c′, and d′ are each an independent integer from 0 to 10, and the sum of a′, b′, c′, and d′ is an integer from 1 to 10.

[0139] The order of repeated units marked with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula.

[0140]

[10] The surface treatment agent as described in any one of [1] to [9] above, wherein the content of the fluorinated polyether compound is 0.1 to 50% by mass.

[0141]

[11] The surface treatment agent as described in any one of [1] to

[10] above, wherein the boiling point of the solvent is below 105°C.

[0142]

[12] The surface treatment agent as described in any one of [1] to

[11] above, wherein it is used as an antifouling coating agent or a waterproof coating agent.

[0143]

[13] The surface treatment agent as described in any one of [1] to

[12] above, wherein the surface treatment agent is used for wet covering purposes.

[0144]

[14] An article comprising a substrate and a layer formed on the substrate by any of the surface treatment agents described in any one of [1] to

[13] .

[0145]

[15] The article as described in

[14] above, wherein the substrate is a glass substrate.

[0146]

[16] The article as described in

[14] above, wherein the article is an optical component.

[0147]

[17] A method for manufacturing an article, the article comprising a substrate and a surface treatment layer formed on the substrate, the method comprising:

[0148] The step of forming a film of the surface treatment agent described in any one of [1] to

[13] on the substrate by means of wet covering; and

[0149] The step of vaporizing the fluorinated polyether compound in the above surface treatment agent from the above membrane.

[0150] Invention Effects

[0151] According to the present invention, it is possible to provide articles comprising a surface treatment layer having better wear resistance. Detailed Implementation

[0152] In this specification, "monovalent organic group" refers to a monovalent group containing carbon. 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 "organic group," it means a monovalent organic group. Furthermore, "divalent to decavalent organic group" refers to a group containing carbon with a 2 to 10 valence. There is no particular limitation on what constitutes a 2 to 10 valence organic group; examples include groups with 2 to 10 valences obtained by further removing 1 to 9 hydrogen atoms from an organic group. For example, there is no particular limitation on what constitutes a divalent organic group; examples include groups with 2 to 10 valences obtained by further removing one hydrogen atom from an organic group.

[0153] In this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, meaning a group that has lost one hydrogen atom from a hydrocarbon. There is no particular limitation on what constitutes this 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 any of the following: straight-chain, branched-chain, or cyclic; and can be any of the following: saturated or unsaturated. In addition, the hydrocarbon group can contain one or more ring structures.

[0154] In the context of this specification, the substituent for "hydrocarbon group" is not particularly limited, and examples include those selected from halogen atoms, those that can be substituted by one or more halogen atoms, and C. 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] In the context of this specification, "hydrolyzable group" refers to a group that can undergo hydrolysis, that is, a group that can be removed from the main skeleton of a compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO, halogen (in these formulas, R h C indicates substitution or non-substitution. 1－4 Alkyl groups, etc.

[0156] The surface treatment agent of the present invention contains a fluorinated polyether silane compound, a fluorinated polyether compound, and a solvent.

[0157] (Silane compounds containing fluorinated polyether groups)

[0158] The fluorinated polyether-based silane compounds mentioned above are fluorinated polyether-based silane compounds represented by formula (1) or (2).

[0159] R F1 α -X A -R Si β (1)

[0160] R Si γ -X A -R F2 -X A -R Si γ (2)

[0161] [In the formula,

[0162] R F1 Each occurrence is independently assigned to Rf. 1 -R F -O q -;

[0163] R F2 -Rf 2 p -R F -O q -;

[0164] Rf 1 Each time it appears, it is independently a C that can be substituted by one or more fluorine atoms. 1-16 alkyl;

[0165] Rf 2 C atoms that can be substituted by one or more fluorine atoms 1-6 Alkylene;

[0166] R F Each time it appears, it is independently a divalent fluorinated polyether group;

[0167] p is 0 or 1;

[0168] q is 0 or 1 independently each time it appears;

[0169] R Si Each time it appears, it is independently represented by a group as shown in formula (S1), (S2), or (S3).

[0170]

[0171] -SiR a1 k1 R b1 11 R c1 m1 (S2)

[0172] -CR d1 k2 R e1 12 R f1 m2 (S3)

[0173] -NR g1 R h1 (S4)

[0174] (in the formula,

[0175] R 11 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0176] R 12 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0177] n1 in each (SiR) 11 n1 R 12 3-n1 Each unit contains an independent integer from 0 to 3;

[0178] X 11 Each time it appears, it is independently either a single bond or a divalent organic group;

[0179] R 13 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0180] R 14 Each time it appears, it is independently a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 ;

[0181] R 15 Each time it appears, it is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkene group having 1 to 6 carbon atoms;

[0182] Each occurrence of t is an integer greater than 2.

[0183] R a1Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ;

[0184] Z 1 Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0185] R 21 Each occurrence is independently -Z 1′ -SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ;

[0186] R 22 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0187] R 23 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0188] p1 is an integer from 0 to 3 each time it appears;

[0189] Each occurrence of q1 is an independent integer from 0 to 3;

[0190] r1 is an integer from 0 to 3 each time it appears;

[0191] Z 1′ Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0192] R 21′ Each occurrence is independently -Z 1″ -SiR 22″ q1″ R 23″ r1″ ;

[0193] R 22′ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0194] R 23′ Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0195] p1′ is an integer from 0 to 3 each time it appears;

[0196] Each occurrence of q1′ is an independent integer from 0 to 3;

[0197] r1′ is an integer from 0 to 3 each time it appears;

[0198] Z 1″ Each time it appears, it is independently either an oxygen atom or a divalent organic group;

[0199] R 22″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0200] R 23″ Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0201] q1″ is an integer from 0 to 3 each time it appears;

[0202] r1″ is an integer from 0 to 3 each time it appears;

[0203] R b1 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0204] R c1 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0205] k1 is an integer from 0 to 3 each time it appears;

[0206] l1 is an integer from 0 to 3 each time it appears;

[0207] m1 is an integer from 0 to 3 each time it appears;

[0208] R d1 Each occurrence is independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 ;

[0209] Z 2 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0210] R 31 Each occurrence is independently -Z 2′ -CR 32′ q2′ R 33′ r2′ ;

[0211] R 32 Each occurrence is independently -Z 3-SiR 34 n2 R 35 3－n2 ;

[0212] R 33 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0213] p2 is an integer from 0 to 3 each time it appears;

[0214] q2 is an integer from 0 to 3 each time it appears;

[0215] r2 is an integer from 0 to 3 each time it appears;

[0216] Z 2′ Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0217] R 32′ Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ;

[0218] R 33′ Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0219] Each occurrence of q2′ is an independent integer from 0 to 3;

[0220] r2′ is an integer from 0 to 3 each time it appears;

[0221] Z 3 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0222] R 34 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0223] R 35 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0224] n2 is an integer from 0 to 3 each time it appears;

[0225] R e1 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ;

[0226] R f1 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group;

[0227] k2 is an integer from 0 to 3 each time it appears;

[0228] l2 is an integer from 0 to 3 each time it appears;

[0229] m2 is an integer from 0 to 3 each time it appears;

[0230] R g1 and R h1 Each occurrence is independently -Z 4 -SiR 11 n1 R 12 3－n1 -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ;

[0231] Z 4 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group;

[0232] In formulas (S1), (S2), (S3), and (S4), there exists at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

[0233] X A Each is independently a single bond or a 2- to 10-valent organic group;

[0234] α is an integer from 1 to 9;

[0235] β is an integer from 1 to 9;

[0236] γ can be an independent integer from 1 to 9.

[0237] In equation (1) above, R F1 Each occurrence is independently assigned to Rf. 1 -R F -O q -.

[0238] In equation (2) above, R F2-Rf 2 p -R F -O q -.

[0239] In the above formula, Rf 1 Each time it appears, it is independently a C that can be substituted by one or more fluorine atoms. 1－16 alkyl.

[0240] The above C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0241] The above Rf 1 Preferably, the C atom can be substituted by one or more fluorine atoms. 1－16 Alkyl groups, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0242] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0243] In the above formula, Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0244] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0245] The above Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C1－3 Perfluoroalkylene groups.

[0246] The above C 1－6 Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkylene groups, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0247] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0248] In the above formula, q is independently 0 or 1 each time it appears. In one case, q is 0. In another case, q is 1.

[0249] In equations (1) and (2) above, R F Each time it appears, it is independently a divalent fluorinated polyether group.

[0250] R F Preferred formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0251] [In the formula,

[0252] R Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0253] a, b, c, d, e, and f are each an independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is greater than 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula. However, in all R... Fa If the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f must be 1 or more.

[0254] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0255] a, b, c, d, e, and f can each be an integer from 0 to 100 independently.

[0256] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, it can be 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0257] These repeating units can be linear or branched. For example, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 - can be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(that is, R in the above formula) Fa The fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- can be any one of -(OCF2CF2)- and -(OCF(CF3))-.

[0258] In one embodiment, the repeating units are in a straight chain shape. By making the repeating units in a straight chain shape, the surface lubricity and wear resistance of the surface treatment layer can be improved.

[0259] 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.

[0260] In one approach, R F Each time it appears, it is independently represented by any of the following formulas (f1) to (f5).

[0261] -(OC3F6) d -(OC2F4) e -(f1)

[0262] [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]

[0263] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0264] In the formula, c and d are independent integers above 0 and below 30, and e and f are independent integers above 1 and below 200.

[0265] The sum of c, d, e, and f is 2 or more.

[0266] The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0267] -(R) 6 -R 7 ) g -(f3)

[0268] [In the formula, R] 6 It is either OCF2 or OC2F4.

[0269] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups independently selected from these groups,

[0270] g is an integer from 2 to 100.

[0271] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f4)

[0272] [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of the repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0273] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f5)

[0274] [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, and the order of the repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0275] In the above formula (f1), d is preferably an integer from 5 to 200, more preferably from 10 to 100, even more preferably from 15 to 50, for example from 25 to 35. OC3F6 in the above formula (f1) is preferably a group represented by (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), more preferably a group represented by (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2).

[0276] In the above formula (f2), e and f are each preferably independent integers from 5 to 200, more preferably from 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - The group shown. In another embodiment, formula (f2) can be -(OC2F4). e -(OCF2) f - The group shown.

[0277] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7Preferably, 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 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 -.

[0278] In the above formula (f4), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0279] In the above formula (f5), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0280] In one approach, the aforementioned R F The group is represented by the formula (f1) above.

[0281] In one approach, the aforementioned R F The group is shown in the above formula (f2).

[0282] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0283] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0284] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0285] In the above R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the slip properties, wear resistance, and chemical resistance (e.g., resistance to artificial sweat) of the surface-treated layer obtained from this compound are further improved. The smaller the e / f ratio, the higher the slip properties and wear resistance of the surface-treated layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the higher the stability of the compound.

[0286] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0287] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or higher, and more preferably 1.0 to 2.0.

[0288] In the above-mentioned fluorinated polyether compounds, R F1 and R F2 The number-average molecular weight of the fraction is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R... F1 and R F2 The number average molecular weight is obtained through 19 The value measured by F-NMR.

[0289] In another way, R F1 and R F2 The number average molecular weight of the fraction is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0290] In another way, R F1 and R F2 The number average molecular weight of the fraction is 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0291] In equations (1) and (2) above, R Si It is a group represented by the following formula (S1), (S2), (S3) or (S4).

[0292]

[0293] -SiR a1 k1 R b1 11 R c1 m1 (S2)

[0294] -CR d1 k2 R e1 12 R f1 m2 (S3)

[0295] -NR g1 R h1 (S4)

[0296] In the above formula, R 11 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0297] R 11 Preferably, each occurrence is an independently hydrolyzable group.

[0298] R 11 Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h -NCO 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.

[0299] In the above formula, R 12 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 group mentioned above.

[0300] In R12 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0301] In the above formula, n1 is in each (SiR 11 n1 R 12 3－n1 Each element contains an independent integer from 0 to 3. In R... Si When the group is as shown in formula (S1), at least one (SiR) group with n1 being 1 to 3 is present in formula (S1). 11 n1 R 12 3－n1 The unit is defined as follows: That is, not all n1 in formula (S1) are simultaneously 0. In other words, at least one Si atom bonded with a hydroxyl or hydrolyzable group exists in formula (S1).

[0302] n1 in each (SiR) 11 n1 R 12 3－n1 The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0303] In the above formula, X 11 Each time it appears, it is independently either a single bond or a divalent organic group. The divalent organic group is preferably -R. 28 -O x -R 29 -(where R) 28 and R 29 Each occurrence is independently a single key or a C. 1－20 Alkylene, x is 0 or 1). The C 1－20 The alkylene group can be straight-chain or branched, preferably straight-chain. The C 1－20 Alkylene is preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0304] In one manner, X 11 Each occurrence is independently -C 1－6 Alkylene-O-C 1－6 alkylene- or -O-C 1－6 Alkylene-.

[0305] In the preferred embodiment, X 11 Each occurrence is independently either a single bond or a linear chain of C. 1－6 Alkylene, preferably single-bonded or straight-chain C1－3 Alkylene, more preferably a single bond or a straight-chain C 1－2 Alkylene, more preferably straight-chain C 1－2 Alkylene.

[0306] In the above formula, R 13 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably composed of a carbon atom (C). 1－20 alkoxy groups, or C 1－20 Alkyl, more preferably C 1－20 Alkyl group. The C 1－20 The alkyl group can be straight-chain or branched, preferably straight-chain. This contains C... 1－20 Examples of alkoxy groups include the following groups.

[0307]

[0308] [In the formula, X is independently a hydroxyl or hydrolyzable group, L is independently methylene, ethylene, propylene, or butylene, l is an integer from 1 to 20, R is methyl, ethyl, propyl, or butyl, d′ is an integer from 0 to 10, and e′ is an integer from 2 to 10.]

[0309] In the preferred embodiment, R 13 Each time it appears, it is independently either a hydrogen atom or a straight-chain C. 1－6 Alkyl groups, preferably hydrogen atoms or straight-chain C atoms. 1－3 Alkyl group, preferably a hydrogen atom or a methyl group.

[0310] In the above formula, t is an integer greater than 2 each time it appears.

[0311] In the preferred embodiment, t is an integer from 2 to 10 each time it appears, preferably an integer from 2 to 6.

[0312] In the above formula, R 14 Each time it appears, it is independently a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 The halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 It is a hydrogen atom.

[0313] In the above formula, R 15 Each time it appears, it is independently a single bond, an oxygen atom, an alkylene group with 1 to 6 carbon atoms, or an alkene group with 1 to 6 carbon atoms.

[0314] In one approach, R 15Each time it appears, it is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkene group having 1 to 6 carbon atoms.

[0315] In the preferred embodiment, R 15 It is a single key.

[0316] In one approach, equation (S1) is the following equation (S1-a).

[0317]

[0318] [In the formula,

[0319] R 11 R 12 R 13 X 11 The meanings of n1 and n1 are the same as those stated in the above formula (S1);

[0320] t1 and t2 are each an integer greater than 1 each time they appear, preferably an integer from 1 to 10, more preferably an integer from 2 to 10, for example an integer from 1 to 5 or an integer from 2 to 5;

[0321] The order of the repeating units labeled t1 and t2 and enclosed in parentheses is arbitrary in the formula.

[0322] In the preferred embodiment, equation (S1) is the following equation (S1-b).

[0323]

[0324] [In the formula, R] 11 R 12 R 13 X 11 The meanings of n1 and t are the same as those stated in the above formula (S1).

[0325] In the above formula, R a1 Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 .

[0326] The above Z 1 Each time it appears, it is independently either an oxygen atom or a divalent organic group. Hereinafter, it is denoted as Z. 1 The right side of the structure and (SiR) 21 p1 R 22 q1 R 23 r1) bond.

[0327] In the preferred method, Z 1 It is a divalent organic group.

[0328] In the preferred method, Z 1 Excluding Z 1 The bonded Si atoms form siloxane bonds. In preferred formula (S2), (Si-Z 1 -Si) does not contain siloxane bonds.

[0329] The above Z 1 C is preferred 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 - (where z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6) or - (CH2) z3 -Phenylidene-(CH2) z4 —(In the formula, z3 is an integer from 0 to 6, for example, an integer from 1 to 6; z4 is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0330] In the preferred method, Z 1 C 1－6 Alkylene or -(CH2) z3 -Phenylidene-(CH2) z4 -, preferably -phenylene-(CH2) z4 - In Z 1 When such a group is present, light tolerance, especially ultraviolet tolerance, is further improved.

[0331] In another preferred embodiment, the aforementioned Z 1 C 1－3 Alkylene. In one manner, Z 1 It can be -CH2CH2CH2-. In another way, Z 1 It can be -CH2CH2-.

[0332] The above R 21 Each occurrence is independently -Z 1′ -SiR 21′ p1′ R 22′ q1′ R 23′r1′ .

[0333] The above Z 1′ Each time it appears, it is independently either an oxygen atom or a divalent organic group. Hereinafter, it is denoted as Z. 1′ The right side of the structure and (SiR) 21′ p1′ R 22′ q1′ R 23′ r1′ ) bond.

[0334] In the preferred method, Z 1′ It is a divalent organic group.

[0335] In the preferred method, Z 1′ Excluding Z 1′ The bonded Si atoms form siloxane bonds. In preferred formula (S2), (Si-Z) 1′ -Si) does not contain siloxane bonds.

[0336] The above Z 1′ C is preferred 1－6 Alkylene, -(CH2) z1′ -O-(CH2) z2′ -(where z1′ is an integer from 0 to 6, for example, an integer from 1 to 6, and z2′ is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z3′ -Phenylidene-(CH2) z4′ —(In the formula, z3′ is an integer from 0 to 6, for example, an integer from 1 to 6, and z4′ is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0337] In the preferred method, Z 1′ C 1－6 Alkylene or -(CH2) z3′ -Phenylidene-(CH2) z4′ -, preferably -phenylene-(CH2) z4′ -,. In Z 1′ When these groups are present, light tolerance, especially ultraviolet tolerance, is further improved.

[0338] In another preferred embodiment, the aforementioned Z 1′ C 1－3 Alkylene. In one manner, Z1′ It can be -CH2CH2CH2-. In another way, Z 1′ It can be -CH2CH2-.

[0339] The above R 21′ Each occurrence is independently -Z 1″ -SiR 22″ q1″ R 23″ r1″ .

[0340] The above Z 1″ Each time it appears, it is independently either an oxygen atom or a divalent organic group. Hereinafter, it is denoted as Z. 1″ The right side of the structure and (SiR) 22″ q1″ R 23″ r1″ ) bond.

[0341] In the preferred method, Z 1″ It is a divalent organic group.

[0342] In the preferred method, Z 1″ Excluding Z 1″ The bonded Si atoms form siloxane bonds. Preferably, in formula (S2) (Si-Z) 1″ -Si) does not contain siloxane bonds.

[0343] The above Z 1″ C is preferred 1－6 Alkylene, -(CH2) z1″ -O-(CH2) z2″ - (where z1″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z2″ is an integer from 0 to 6, for example, an integer from 1 to 6) or - (CH2) z3″ -Phenylidene-(CH2) z4″ —(In the formula, z3″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z4″ is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0344] In the preferred method, Z 1″ C 1－6 Alkylene or -(CH2) z3″ -Phenylidene-(CH2) z4″- Preferably -phenylene-(CH2) z4″ - In Z 1″ When these groups are present, light tolerance, especially ultraviolet tolerance, is further improved.

[0345] In another preferred embodiment, the aforementioned Z 1″ C 1－3 Alkylene. In one manner, Z 1″ It can be -CH2CH2CH2-. In another way, Z 1″ It can be -CH2CH2-.

[0346] The above R 22″ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0347] The above R 22″ Preferably, each occurrence is an independently hydrolyzable group.

[0348] The above R 22″ Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO 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.

[0349] The above R 23″ 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 group mentioned above.

[0350] In the above R 23″ In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0351] Each occurrence of q1″ is an independent integer from 0 to 3, and each occurrence of r1″ is an independent integer from 0 to 3. The sum of q1″ and r1″ is within the range (SiR). 22″q1″ R 23″ r1″ The value in unit ) is 3.

[0352] The above q1″ in each (SiR 22″ q1″ R 23″ r1″ The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0353] The above R 22′ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0354] R 22′ Preferably, each occurrence is an independently hydrolyzable group.

[0355] R 22′ Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO 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.

[0356] The above R 23′ 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 group mentioned above.

[0357] In R 23′ In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0358] Each occurrence of p1′ is an independent integer from 0 to 3, each occurrence of q1′ is an independent integer from 0 to 3, and each occurrence of r1′ is an independent integer from 0 to 3. The sum of p′, q1′, and r1′ is within the range (SiR). 21′ p1′ R 22′q1′ R 23′ r1′ The value in unit ) is 3.

[0359] In one mode, p1′ is 0.

[0360] In one manner, p1′ in each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ The units can be independently integers of 1 to 3, 2 to 3, or 3. In the preferred embodiment, p1′ is 3.

[0361] In one manner, q1′ is in each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0362] In one mode, p1′ is 0, and q1′ is in each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0363] The above R 22 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0364] R 22 Preferably, each occurrence is an independently hydrolyzable group.

[0365] R 22 Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO 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 hExamples 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.

[0366] The above R 23 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 group mentioned above.

[0367] In R 23 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0368] Each occurrence of p1 is an independent integer from 0 to 3, each occurrence of q1 is an independent integer from 0 to 3, and each occurrence of r1 is an independent integer from 0 to 3. The sum of p1, q1, and r1 is within the range (SiR). 21 p1 R 22 q1 R 23 r1 The value in unit ) is 3.

[0369] In one mode, p1 is 0.

[0370] In one manner, p1 in each (SiR) 21 p1 R 22 q1 R 23 r1 The units can be independently integers of 1 to 3, 2 to 3, or 3. In the preferred embodiment, p1 is 3.

[0371] In one approach, q1 is in each (SiR) 21 p1 R 22 q1 R 23 r1 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0372] In one mode, p1 is 0, and q1 is in each (SiR) 21 p1 R 22 q1 R 23 r1Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0373] In the above formula, R b1 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0374] The above R b1 Preferably, each occurrence is an independently hydrolyzable group.

[0375] The above R b1 Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO 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.

[0376] In the above formula, R c1 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 group mentioned above.

[0377] In the above R c1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0378] Each occurrence of k1 is an independent integer from 0 to 3, each occurrence of l1 is an independent integer from 0 to 3, and each occurrence of m1 is an independent integer from 0 to 3. The sum of k1, l1, and m1 is within the range (SiR). a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3.

[0379] In one approach, k1 is in each (SiR) a1 k1 R b1l1 R c1 m1 Each of the units is an independent integer from 1 to 3, preferably 2 or 3, more preferably 3. In the preferred embodiment, k1 is 3.

[0380] In equations (1) and (2) above, in R Si When the group is as shown in formula (S2), it is preferable that at least two Si atoms bonded with hydroxyl or hydrolyzable groups are present at the end portions of formulas (1) and (2).

[0381] In a preferred embodiment, the group represented by formula (S2) has -Z 1 -SiR 22 q1 R 23 r1 (In the formula, q1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer from 0 to 2), -Z 1′ -SiR 22′ q1′ R 23′ r1′ (In the formula, q1′ is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer from 0 to 2) or -Z 1″ -SiR 22″ q1″ R 23″ r1″ (In the formula, q1″ is an integer from 1 to 3, preferably 2 or 3, more preferably 3, and r1″ is an integer from 0 to 2) any one of Z. 1 Z 1′ Z 1″ R 22 R 23 R 22′ R 23′ R 22″ and R 23″ The meaning is the same as above.

[0382] In the preferred embodiment, R exists in equation (S2). 21′ In the case of at least one, preferably all, R 21′ In this context, q1″ is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0383] In the preferred embodiment, R exists in equation (S2). 21 In the case of at least one, preferably all, R 21 In this context, p1′ is 0, and q1′ is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0384] In the preferred embodiment, R exists in equation (S2). a1In the case of at least one, preferably all, R a1 In this context, p1 is 0, and q1 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0385] In the preferred embodiment, in formula (S2), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

[0386] R d1 Each occurrence is independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .

[0387] Z 2 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 2 The right side of the structure and (CR 31 p2 R 32 q2 R 33 r2 ) bond.

[0388] In the preferred method, Z 2 It is a divalent organic group.

[0389] The above Z 2 C is preferred 1－6 Alkylene, -(CH2) z5 -O-(CH2) z6 - (where z5 is an integer from 0 to 6, for example, an integer from 1 to 6, and z6 is an integer from 0 to 6, for example, an integer from 1 to 6) or - (CH2) z7 -Phenylidene-(CH2) z8 —(In the formula, z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0390] In the preferred method, Z 2 C 1－6 Alkylene or -(CH2) z7 -Phenylidene-(CH2) z8 - Preferably -phenylene-(CH2)z8 - In Z 2 When these groups are used, light tolerance, especially ultraviolet tolerance, can be further improved.

[0391] In another preferred embodiment, the aforementioned Z 2 C 1－3 Alkylene. In one manner, Z 2 It can be -CH2CH2CH2-. In another way, Z 2 It can be -CH2CH2-.

[0392] R 31 Each occurrence is independently -Z 2′ -CR 32′ q2′ R 33′ r2′ .

[0393] Z 2′ Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 2′ The right side of the structure and (CR 32′ q2′ R 33′ r2′ ) bond.

[0394] The above Z 2′ C is preferred 1－6 Alkylene, -(CH2) z5′ -O-(CH2) z6′ -(where z5′ is an integer from 0 to 6, for example, an integer from 1 to 6, and z6′ is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z7′ -Phenylidene-(CH2) z8′ —(In the formula, z7′ is an integer from 0 to 6, for example, an integer from 1 to 6, and z8′ is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0395] In the preferred method, Z 2′ C 1－6 Alkylene or -(CH2) z7′ -Phenylidene-(CH2) z8′ -, preferably -phenylene-(CH2) z8′ - In Z 2′When these groups are present, light tolerance, especially ultraviolet tolerance, is further improved.

[0396] In another preferred embodiment, the aforementioned Z 2′ C 1－3 Alkylene. In one manner, Z 2′ It can be -CH2CH2CH2-. In another way, Z 2′ It can be -CH2CH2-.

[0397] The above R 32′ Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 .

[0398] The above Z 3 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 3 The right side of the structure and (SiR) 34 n2 R 35 3－n2 ) bond.

[0399] In one approach, Z 3 It is an oxygen atom.

[0400] In one approach, Z 3 It is a divalent organic group.

[0401] The above Z 3 C is preferred 1－6 Alkylene, -(CH2) z5″ -O-(CH2) z6″ -(where z5″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z6″ is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z7″ -Phenylidene-(CH2) z8″ —(In the formula, z7″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z8″ is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0402] In the preferred method, Z 3 C 1－6 Alkylene or -(CH2)z7″ -Phenylidene-(CH2) z8″ - Preferably -phenylene-(CH2) z8″ - In Z 3 When these groups are used, light tolerance, especially ultraviolet tolerance, can be further improved.

[0403] In another preferred embodiment, the aforementioned Z 3 C 1－3 Alkylene. In one manner, Z 3 It can be -CH2CH2CH2-. In another way, Z 3 It can be -CH2CH2-.

[0404] The above R 34 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0405] R 34 Preferably, each occurrence is an independently hydrolyzable group.

[0406] R 34 Ideally, each occurrence should be independently set to -OR. h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO 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.

[0407] The above R 35 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 group mentioned above.

[0408] In the above R 35 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl group, more preferably methyl group.

[0409] In the above formula, n2 is in each (SiR) 34 n2 R35 3－n2 Each element contains an independent integer from 0 to 3. In R... Si In the case of the group shown in formula (S3), at least one (SiR) group with n2 of 1 to 3 exists at the end portion of formulas (1) and (2). 34 n2 R 35 3－n2 ) unit. That is, in this terminal part, all n2 are not simultaneously 0. In other words, in the terminal part of formulas (1) and (2), there is at least one Si atom bonded with a hydroxyl or hydrolyzable group.

[0410] n2 in each (SiR) 34 n2 R 35 3－n2 The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0411] The above R 33′ Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0412] In the above R 33′ In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, particularly preferably methyl groups.

[0413] In one approach, R 33′ It is a hydroxyl group.

[0414] In another way, R 33′ It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0415] Each occurrence of q2′ is an independent integer from 0 to 3, and each occurrence of r2′ is an independent integer from 0 to 3. The sum of q2′ and r2′ is within (CR... 32′ q2′ R 33′r2′ The value in unit ) is 3.

[0416] q2′ in each (CR 32′ q2′ R 33′ r2′ The units are preferably integers of 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0417] R 32 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 The -Z 3 -SiR 34 n2 R 35 3－n2 The meaning of R above is the same as above. 32′ The records are the same.

[0418] The above R 33 Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0419] In the above R 33 In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, particularly preferably methyl groups.

[0420] In one approach, R 33 It is a hydroxyl group.

[0421] In another way, R 33 It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0422] Each occurrence of p2 is an independent integer from 0 to 3, each occurrence of q2 is an independent integer from 0 to 3, and each occurrence of r2 is an independent integer from 0 to 3. The sum of p2, q2, and r2 is within (CR...31 p2 R 32 q2 R 33 r2 The value in unit ) is 3.

[0423] In one mode, p2 is 0.

[0424] In one approach, p2 in each (CR 31 p2 R 32 q2 R 33 r2 The units can be independently integers of 1 to 3, 2 to 3, or 3. In the preferred embodiment, p2 is 3.

[0425] In one approach, q2 is in each (CR) 31 p2 R 32 q2 R 33 r2 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0426] In one mode, p2 is 0, and q2 is in each (CR) 31 p2 R 32 q2 R 33 r2 Each of the units is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0427] The above R e1 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 The -Z 3 -SiR 34 n2 R 35 3－n2 The meaning of R above is the same as above. 32′ The records are the same.

[0428] The above R f1 Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the hydrolyzable groups mentioned above.

[0429] In the above R f1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl or -(Cs H 2s ) t1 -(O-C s H 2s ) t2 (In the formula, s is an integer from 1 to 6, preferably an integer from 2 to 4; t1 is 1 or 0, preferably 0; t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, particularly preferably methyl groups.

[0430] In one approach, R f1 It is a hydroxyl group.

[0431] In another way, R f1 It is a monovalent organic group, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0432] Each occurrence of k2 is an independent integer from 0 to 3, each occurrence of l2 is an independent integer from 0 to 3, and each occurrence of m2 is an independent integer from 0 to 3. The sum of k2, l2, and m2 is within (CR... d1 k2 R e1 l2 R f1 m2 The value in unit ) is 3.

[0433] In one approach, in R Si When n2 is a group represented by formula (S3), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR). 34 n2 R 35 3－n2 The unit has two or more units in each end part of formula (1) and formula (2), for example, 2 to 27 units, preferably 2 to 9 units, more preferably 2 to 6 units, even more preferably 2 to 3 units, and especially preferably 3 units.

[0434] In the preferred embodiment, R exists in equation (S3). 32′ In the case of at least one, preferably all, R 32′ In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0435] In the preferred embodiment, R exists in equation (S3). 32 In the case of at least one, preferably all, R 32 In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0436] In the preferred embodiment, R exists in equation (S3). e1 In the case of at least one, preferably all, R a1 In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0437] In the preferred embodiment, in formula (S3), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0438] The above R g1 and R h1 Each occurrence is independently -Z 4 -SiR 11 n1 R 12 3－n1 -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 -Z 4 -CR d1 k2 R e1 l2 R f1 m2 Here, R 11 R 12 R a1 R b2 R c1 R d1 R e1 R f1 The meanings of n1, k1, l1, m1, k2, l2, and m2 are the same as above.

[0439] In the preferred embodiment, R g1 and R h1 Each independently is -Z 4 -SiR 11 n1 R 12 3－n1 .

[0440] The above Z 4 Each occurrence is independently a single bond, an oxygen atom, or a divalent organic group. Hereinafter, it is denoted as Z. 4 The right side of the structure and (SiR) 11 n1 R 12 3－n1 ) bond.

[0441] In one approach, Z 4 It is an oxygen atom.

[0442] In one approach, Z 4 It is a divalent organic group.

[0443] The above Z 4 C is preferred 1－6 Alkylene, -(CH2) z5″ -O-(CH2) z6″ -(where z5″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z6″ is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z7″ -Phenylidene-(CH2) z8″ —(In the formula, z7″ is an integer from 0 to 6, for example, an integer from 1 to 6, and z8″ is an integer from 0 to 6, for example, an integer from 1 to 6). This C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. 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, preferably unsubstituted.

[0444] In the preferred method, Z 4 C 1－6 Alkylene or -(CH2) z7″ -Phenylidene-(CH2) z8″ -, preferably -phenylene-(CH2) z8″ - In Z 3 When these groups are used, light tolerance, especially ultraviolet tolerance, can be further improved.

[0445] In another preferred embodiment, the aforementioned Z 4 C 1－3 Alkylene. In one manner, Z 4 It can be -CH2CH2CH2-. In another way, Z 4 It can be -CH2CH2-.

[0446] In one approach, R Si These are groups represented by formulas (S2), (S3), or (S4). These compounds can form surface-treated layers with high surface slip properties.

[0447] In one approach, R Si These compounds can have multiple hydrolyzable groups branching from a Si or C atom at one end, thus enabling the formation of surface treatment layers with higher wear resistance.

[0448] In one approach, R SiIt is the group represented by formula (S1).

[0449] In one approach, R Si The group is represented by formula (S2).

[0450] In one approach, R Si It is the group shown in formula (S3).

[0451] In one approach, R Si It is the group shown in formula (S4).

[0452] In equations (1) and (2) above, X A This can be understood as referring to the fluorinated polyether portion (R) that primarily provides water repellency and surface lubrication. F1 and R F2 ) and the portion that provides bonding capability with the substrate (R Si The connection base is the X. A Any compound shown in formulas (1) and (2) can be stable and can be a single bond or any group.

[0453] In equation (1) above, α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β can vary according to the valence of X. The sum of α and β equals X. A The valence. For example, X A When the organic group is decavalent, the sum of α and β is 10. For example, it can be α = 9 and β = 1, α = 5 and β = 5, or α = 1 and β = 9. Additionally, in X... A When the organic group is divalent, α and β are 1.

[0454] In equation (2) above, γ is an integer from 1 to 9. γ can correspond to X. A The valence changes with X. That is, γ changes from X. A The value after subtracting 1 from the valence.

[0455] X A Each can be a single bond or a 2- to 10-valent organic group.

[0456] The divalent to decavalent organic groups in X above are preferably divalent to octvalent organic groups. In one embodiment, the divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups. In another embodiment, the divalent to decavalent organic groups are preferably trivalent to octvalent organic groups, more preferably trivalent to hexavalent organic groups.

[0457] In one manner, X A It is a single bond or a divalent organic group, with α = 1 and β = 1.

[0458] In one manner, X AIt is a single bond or a divalent organic group, and γ is 1.

[0459] In one manner, X A It consists of 3 to 6 valent organic groups, with α being 1 and β being 2 to 5.

[0460] In one manner, X A It consists of 3- to 6-valent organic groups, with γ ranging from 2 to 5.

[0461] In one manner, X A It is a trivalent organic group, with α = 1 and β = 2.

[0462] In one manner, X A It is a trivalent organic group, and γ is 2.

[0463] When X is a single bond or a divalent organic group, formulas (1) and (2) are represented by the following formulas (1′) and (2′).

[0464] R F1 -X A -R Si (1')

[0465] R Si -X A -R F2 -X A -R Si (2')

[0466] In one manner, X A It is a single key.

[0467] In another way, X A It is a divalent organic group.

[0468] In one way, as X A For example, single keys or the following formulas can be listed: -(R 51 ) p5 -(X 51 ) q5 - The divalent organic group shown.

[0469] [In the formula,

[0470] R 51 Indicates a single bond, -(CH2) s5 - Or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -,

[0471] s5 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.

[0472] X 51 Represents -(X)52 ) l5 -,

[0473] X 52 Each occurrence independently represents a selection from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -C(O)O-, -Si(R) 53 )2-、-(Si(R 53 )2O) m5 -Si(R) 53 )2-、-CONR 54 -、-O-CONR 54 -, -NR 54 - and (CH2) n5 - group,

[0474] R 53 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,

[0475] R 54 Each time it appears, it independently represents a hydrogen atom, a phenyl group, and a carbon atom. 1－6 Alkyl (preferably methyl) or an oxyalkylene group having 1 to 10 carbon atoms,

[0476] Each occurrence of m5 is an independent integer from 1 to 100, preferably an integer from 1 to 20.

[0477] Each time n5 appears, it is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0478] l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0479] p5 is either 0 or 1.

[0480] q5 is either 0 or 1.

[0481] Here, at least one of p5 and q5 is 1, and the order of the repeating units labeled p5 or q5 and enclosed in parentheses is arbitrary.

[0482] Here, X A (typically X) A The hydrogen atom can be replaced by a fluorine atom, C 1－3 Alkyl and C 1－3 One or more substituents in a fluoroalkyl group. In a preferred embodiment, X A It is not replaced by these groups.

[0483] The alkylene groups containing 1 to 10 carbon atoms mentioned above are those containing -O and -C. 1－10 alkylene groups, for example, -R 55 -(-O-C) 1－10 Alkylene) n -R 56 (where R is in the formula) 55 R is a single bond or a divalent organic group. 55 It is a monovalent organic group, preferably C. 1－6 Alkylene, where n is any integer, preferably an integer from 2 to 10. The alkylene can be straight-chain or branched.

[0484] In the preferred embodiment, the above X A Each independently is -(R) 51 ) p5 -(X) 51 ) q5 -R 52 -. R 52 Indicates a single bond, -(CH2) t5 - Or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). t5 - t5 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 52 (typically R) 52 The hydrogen 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. In a preferred embodiment, R 56 It is not replaced by these groups.

[0485] Preferably, the above X A Each independently is:

[0486] single bond,

[0487] C 1－20 Alkylene

[0488] -R 51 -X 53 -R 52 -,or

[0489] -X 54 -R 5 -.

[0490] [In the formula, R] 51 and R 52 The meaning is the same as above.

[0491] X 53 express

[0492] -O-、

[0493] -S-、

[0494] -C(O)O-,

[0495] -CONR 54 -、

[0496] -O-CONR 54 -、

[0497] -Si(R) 53 )2-、

[0498] -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0499] -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0500] -O-(CH2) u5 -Si(R) 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-、

[0501] -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-,

[0502] -CONR 54 -(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、

[0503] -CONR 54 -(CH2) u5 -N(R) 54 )-,or

[0504] -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 53 )2-,

[0505] (where R is in the formula) 53 R 54 The meaning of m5 is the same as above.

[0506] u5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0507] X 54 express

[0508] -S-、

[0509] -C(O)O-,

[0510] -CONR 54 -、

[0511] -O-CONR 54 -、

[0512] -CONR 54 -(CH2) u5 -(Si(R) 54 )2O) m5 -Si(R) 54 )2-、

[0513] -CONR 54 -(CH2) u5 -N(R) 54 )-,or

[0514] -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 54 )2-。 (In the formula, the meanings of each symbol are the same as above.)]

[0515] More preferably, the above-mentioned X A Each independently is:

[0516] single bond,

[0517] C 1－20 Alkylene

[0518] -(CH2) s5 -X 53 -、

[0519] -(CH2) s5 -X 53 -(CH2) t5 -

[0520] -X 54 -,or

[0521] -X 54 -(CH2) t5 -.

[0522] [In the formula, X] 53 X 54 The meanings of s5 and t5 are the same as above.

[0523] More preferably, the above-mentioned X A Each independently is:

[0524] single bond,

[0525] C 1－20 Alkylene

[0526] -(CH2) s5 -X 53 -(CH2) t5 -,or

[0527] -X 54 -(CH2) t5 -.

[0528] [In the formula, the meanings of each symbol are the same as above.]

[0529] In the preferred embodiment, the above X A They can be considered independently as follows:

[0530] single bond,

[0531] C 1－20 Alkylene

[0532] -(CH2) s5 -X 53 -,or

[0533] -(CH2) s5 -X 53 -(CH2) t5 -.

[0534] [In the formula,

[0535] X 53 -O-, -CONR 54 - or - O-CONR 54 -,

[0536] R 54 Each time it appears, it is independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl,

[0537] s5 is an integer from 1 to 20.

[0538] t5 is an integer from 1 to 20.

[0539] In the preferred embodiment, the above X A They can be considered independently as follows:

[0540] -(CH2) s5 -O-(CH2) t5 -

[0541] -CONR54 -(CH2) t5 -.

[0542] [In the formula,

[0543] R 54 Each time it appears, it independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl,

[0544] s5 is an integer from 1 to 20.

[0545] t5 is an integer from 1 to 20.

[0546] In one manner, the aforementioned X A They can be considered independently as follows:

[0547] single bond,

[0548] C 1－20 Alkylene

[0549] -(CH2) s5 -O-(CH2) t5 -、

[0550] -(CH2) s5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -、

[0551] -(CH2) s5 -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -,or

[0552] -(CH2) s5 -O-(CH2) t5 -Si(R) 53 )2-(CH2) u5 -Si(R) 53 )2-(C v H 2v )-.

[0553] [In the formula, R] 53 The meanings of m5, s5, t5, and u5 are the same as above, and v5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0554] In the above formula, -(C v H 2v- can be a straight chain or a branched chain, for example, it can be -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0555] The above X A It can be independently selected from fluorine atoms, C atoms 1－3 Alkyl and C 1－3 Fluoroalkyl (preferably C) 1－3 One or more substituents are substituted in the perfluoroalkyl group. In one manner, X A It is not a substitute.

[0556] Among them, the above X A The various left sides and R F1 or R F2 Bonding, right side with R Si Bonding.

[0557] In one manner, X A They can be independently -O-C 1－6 Groups other than alkylene groups.

[0558] In another way, as X A For example, the following groups can be listed.

[0559]

[0560]

[0561] [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;

[0562] D indicates that it is selected from:

[0563] -CH2O(CH2)2-,

[0564] -CH2O(CH2)3-,

[0565] -CF2O(CH2)3-,

[0566] -(CH2)2-,

[0567] -(CH2)3-,

[0568] -(CH2)4-,

[0569] -CONH-(CH2)3-,

[0570] -CON(CH3)-(CH2)3-,

[0571] -CON(Ph)-(CH2)3-(where Ph means phenyl) and

[0572]

[0573] the groups in

[0574] (where, R 42 independently represents a hydrogen atom, an alkyl group of C 1－6 or an alkoxy group of C 1－6 , preferably represents a methyl group or a methoxy group, more preferably represents a methyl group.)

[0575] E is -(CH2) n -(n is an integer from 2 to 6),

[0576] D is bonded to R F1 or R F2 in the main chain of the molecule, and E is bonded to R Si .)

[0577] As specific examples of the above X A , for example, the following can be listed:

[0578] a single bond,

[0579] -CH2OCH2-,

[0580] -CH2O(CH2)2-,

[0581] -CH2O(CH2)3-,

[0582] -CH2O(CH2)4-,

[0583] -CH2O(CH2)5-,

[0584] -CH2O(CH2)6-,

[0585] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0586] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0587] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,

[0588] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,

[0589] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2 one

[0590] -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2 one

[0591] -CH2OCF2CHFOCF2-

[0592] -CH2OCF2CHFOCF2CF2-

[0593] -CH2OCF2CHFOCF2CF2CF2-

[0594] -CH2OCH2CF2CF2OCF2-

[0595] -CH2OCH2CF2CF2OCF2CF2-

[0596] -CH2OCH2CF2CF2OCF2CF2CF2-

[0597] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-

[0598] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-

[0599] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-

[0600] -CH2OCH2CHFCF2OCF2-

[0601] -CH2OCH2CHFCF2OCF2CF2-

[0602] -CH2OCH2CHFCF2OCF2CF2CF2-

[0603] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-

[0604] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-

[0605] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-

[0606] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-

[0607] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0608] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-,

[0609] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-,

[0610] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0611] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-,

[0612] -(CH2)2-Si(CH3)2-(CH2)2-,

[0613] -CH2-,

[0614] -(CH2)2-,

[0615] -(CH2)3-,

[0616] -(CH2)4-,

[0617] -(CH2)5-,

[0618] -(CH2)6-,

[0619] -CO-,

[0620] -CONH-,

[0621] -CONH-CH2-,

[0622] -CONH-(CH2)2-,

[0623] -CONH-(CH2)3-,

[0624] -CONH-(CH2)4-,

[0625] -CONH-(CH2)5-,

[0626] -CONH-(CH2)6-,

[0627] -CON(CH3)-CH2-,

[0628] -CON(CH3)-(CH2)2-,

[0629] -CON(CH3)-(CH2)3-,

[0630] -CON(CH3)-(CH2)4-,

[0631] -CON(CH3)-(CH2)5-,

[0632] -CON(CH3)-(CH2)6-,

[0633] -CON(Ph)-CH2- (where Ph refers to phenyl),

[0634] -CON(Ph)-(CH2)2- (where Ph refers to phenyl),

[0635] -CON(Ph)-(CH2)3- (where Ph refers to phenyl),

[0636] -CON(Ph)-(CH2)4- (where Ph refers to phenyl),

[0637] -CON(Ph)-(CH2)5- (where Ph refers to phenyl),

[0638] -CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0639] -CONH-(CH2)2NH(CH2)3-,

[0640] -CONH-(CH2)6NH(CH2)3-,

[0641] -CH2O-CONH-(CH2)3-,

[0642] -CH2O-CONH-(CH2)6-,

[0643] -S-(CH2)3-,

[0644] -(CH2)2S(CH2)3-,

[0645] -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0646] -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)-2,

[0647] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)-2,

[0648] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)-2,

[0649] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、

[0650] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、

[0651] -C(O)O-(CH2)3-,

[0652] -C(O)O-(CH2)6-,

[0653] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)-2,

[0654] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,

[0655] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)-3,

[0656] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[0657] -OCH2-,

[0658] -O(CH2)3-,

[0659] -OCFHCF2-,

[0660]

[0661] wait.

[0662] In yet another way, X A Each independently is a formula: -(R) 16 ) x1 -(CFR) 17 ) y1 -(CH2) z1 - The group shown. In the formula, x1, y1 and z1 are independent integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0663] 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. 18 It is an oxygen atom or a divalent polar group.

[0664] As for the aforementioned "divalent polar groups", there are no particular limitations; examples include -C(O)- and -C(=NR). 19 )- and -C(O)NR 19 -(In these formulas, 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.

[0665] 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.

[0666] In yet another way, as X A Examples of such groups can be listed below.

[0667]

[0668] [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;

[0669] In each X A In the base, any number of T are R with respect to the molecular backbone. F1 or R F2 The following groups are bonded:

[0670] -CH2O(CH2)2-,

[0671] -CH2O(CH2)3-,

[0672] -CF2O(CH2)3-,

[0673] -(CH2)2-,

[0674] -(CH2)3-,

[0675] -(CH2)4-,

[0676] -CONH-(CH2)3-,

[0677] -CON(CH3)-(CH2)3-,

[0678] -CON(Ph)-(CH2)3- (where Ph refers to phenyl), or

[0679]

[0680] [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.

[0681] Several other T molecules are related to the R molecules in the molecular backbone. Si In the presence of bonds, the remaining T atoms are independently methyl, phenyl, and C, respectively. 1－6 Alkyl groups, free radical scavenging groups, or ultraviolet-absorbing groups.

[0682] There are no particular limitations on free radical scavenging groups as long as they can capture free radicals generated by light irradiation. Examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate esters, crotonic acid esters, malondiamide esters, organic acrylates, hindered amines, hindered phenols, or triazines.

[0683] 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, oxaloyl aniline, benzoxazinones, and benzoxazoles.

[0684] In preferred embodiments, examples of preferred free radical scavenging groups or ultraviolet absorbing groups include:

[0685]

[0686] In this method, X A They can be 3 to 10 valent organic groups independently.

[0687] In yet another way, as X A Examples can be listed below for the following groups:

[0688]

[0689] [In the formula, R] 25 R 26 and R27 Each is an independent 2- to 6-valent organic group.

[0690] R 25 With at least one R F1 Bonding, R 26 and R 27 With at least one R Si Bonding.

[0691] In one approach, the aforementioned R 25 For single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene, C 5－20 Aromatic, -R 57 -X 58 -R 59 -、-X 58 -R 59 - or -R 57 -X 58 - The above R 57 and R 59 Each independently represents a single bond and a C bond. 1－20 Alkylene, C 3－20 Cycloalkyl or C 5－20 Alpha-aryl. The above X 58 It can be -O-, -S-, -CO-, -O-CO-, or -COO-.

[0692] In one approach, the aforementioned R 26 and R 27 Each of the following is an independent hydrocarbon, or a group having at least one atom selected from N, O, and S in the end or main chain of a hydrocarbon, preferably C. 1－6 Alkyl, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-etc. Here, R 36 Each is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 It is N, O, or S, preferably N or O. R 38 -R 45 -R 46 -R 45 -、-R 46 -R 45 - or -R 45 -R 46 —. Here, R 45 Each is an alkyl group having 1 to 6 carbon atoms. R 46 It can be N, O, or S, with O being the preferred choice.

[0693] In this method, X A They can be 3 to 10 valent organic groups independently.

[0694] The fluorinated polyether compounds shown in formula (1) or formula (2) above can have 5 × 10 2 ~1×10 5 The average molecular weight is not particularly limited. Within this range, from the viewpoint of wear durability, an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, is preferred. Here, "average molecular weight" refers to exponential average molecular weight, which is determined by... 19 Values ​​measured by F-NMR.

[0695] In one embodiment, in the surface treatment agent of the present invention, the fluorinated polyether-based silane compound is a compound represented by formula (1).

[0696] In another embodiment, in the surface treatment agent of the present invention, the fluorinated polyether-based silane compound is the compound shown in formula (2).

[0697] In another embodiment, in the surface treatment agent of the present invention, the fluorinated polyether-based silane compound is the compound shown in formula (1) and the compound shown in formula (2).

[0698] In the surface treatment agent of the present invention, the compound shown in formula (2) is preferably 0.1 mol% to 35 mol% or less relative to the total of the compounds shown in formula (1) and formula (2). The lower limit of the content of the compound shown in formula (2) relative to the total of the compounds shown in formula (1) and formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, further preferably 0.5 mol%, further preferably 1 mol%, particularly preferably 2 mol%, and especially preferably 5 mol%. The upper limit of the content of the compound shown in formula (2) relative to the total of the compounds shown in formula (1) and formula (2) is preferably 35 mol%, more preferably 30 mol%, further preferably 20 mol%, further preferably 15 mol% or 10 mol%. Relative to the total of the compounds shown in formula (1) and formula (2), the compound shown in formula (2) is preferably 0.1 mol% to 30 mol% or less, more preferably 0.1 mol% to 20 mol% or less, even more preferably 0.2 mol% to 10 mol% or less, even more preferably 0.5 mol% to 10 mol% or less, particularly preferably 1 mol% to 10 mol% or less, for example 2 mol% to 10 mol% or 5 mol% to 10 mol% or less. By making the compound shown in formula (2) fall within such a range, wear durability can be further improved.

[0699] The compounds represented by formula (1) or (2) above can be obtained, for example, by the methods described in Patent Document 1 above.

[0700] The above-mentioned fluorinated polyether group compounds are compounds having fluorinated polyether groups, and are compounds other than those shown in formula (1) or (2) above.

[0701] The ratio (mass ratio) of fluorine atoms to carbon atoms in the above-mentioned fluorinated polyether compounds is preferably 3.00 or more, more preferably 3.20 or more, and even more preferably 3.50.

[0702] In a preferred embodiment, the fluorinated polyether compound is the fluorinated polyether compound shown in formula (3).

[0703] Rf 5 -(OC) h1 H h2 F h3 ) j -Rf 6 ···(3)

[0704] [In the formula,

[0705] Rf 5 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0706] Rf 6 C atoms that can be substituted by one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms;

[0707] h1 is an integer from 1 to 4 each time it appears;

[0708] h2 is an integer from 0 to 8 each time it appears;

[0709] h3 is an integer from 0 to 8 each time it appears;

[0710] Among them, in (OC) h1 H h2 F h3 In unit ) 2×h1=h2+h3;

[0711] j is an integer from 1 to 10.

[0712] The above Rf 5 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl.

[0713] The above Rf 6 C atoms that can be substituted by one or more fluorine atoms1－16 Alkyl, fluorine or hydrogen atoms.

[0714] In the above Rf 5 and Rf 6 In the above, C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0715] The above Rf 5 and Rf 6 Each C atom is preferably substituted with one or more fluorine atoms independently. 1－16 Alkyl groups, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0716] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0717] h1 is preferably an integer from 1 to 3 each time it appears.

[0718] h2 is preferably an integer from 0 to 4 each time it appears, more preferably an integer from 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0719] In the above equation (3), in (OC) h1 H h2 F h3 In unit ), 2×h1=h2+h3.

[0720] In a preferred embodiment, the fluorinated polyether compound represented by formula (3) is the fluorinated polyether compound represented by formula (3′).

[0721] Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf6 ···(3′)

[0722] [In the formula,

[0723] Rf 5 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0724] Rf 6 C atoms that can be substituted by one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms;

[0725] a′, b′, c′, and d′ are each an independent integer from 0 to 10, and the sum of a′, b′, c′, and d′ is an integer from 1 to 10.

[0726] The order of repeated units marked with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula.

[0727] In the above formula, a′, b′, c′, and d′ represent the number of the four repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are each an independent integer from 0 to 10. The sum of a′, b′, c′, and d′ is at least an integer from 1 to 10, preferably an integer from 2 to 5. The order of the repeating units marked 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))-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-. -(OC2F4)- can be any one of -(OCF2CF2)- and (OCF(CF3))-.

[0728] Examples of compounds containing fluorinated polyether groups as shown in formula (3) above can be listed as compounds represented by any of the following general formulas (3a), (3b) or (3c) (which may be one or a mixture of two or more).

[0729] Rf 5 -(OCF(CF)3CF2) b″ -(OCF2) c″ -Rf 6···(3a)

[0730] Rf 5 -(OCF2CF2CF2) b″ -Rf 6 ···(3b)

[0731] Rf 5 -(OCF2CF2CF2CF2) a″ -(OCF2CF2CF2) b″ -(OCF2CF2) c″ -(OCF2) d″ -Rf 6 ···(3c)

[0732] In these formulas, Rf 5 and Rf 6 As described above; in equation (3a), b″ is an integer from 1 to 9, and c″ is an integer from 1 to 9; in equation (3b), b″ is an integer from 1 to 10; in equation (3c), a″ and b″ are independently integers from 0 to 8, and c″ and d″ are independently integers from 1 to 9. The order of the repeating units marked with subscripts a″, b″, c″, and d″ and enclosed in parentheses is arbitrary in the equations.

[0733] The boiling points (at atmospheric pressure) of the aforementioned fluorinated polyether compounds are 105–210 °C. Because the boiling points of the fluorinated polyether compounds fall within this range, when the surface treatment agent of the present invention is applied to a substrate, a surface treatment layer with higher wear resistance can be formed. The present invention is not limited to any particular theory, but it can be considered that because the aforementioned fluorinated polyether compounds have boiling points within this range, they do not immediately vaporize when applied to the substrate, but remain on the substrate for a certain period of time, thus allowing the fluorinated polyether silane compounds to react fully with the substrate.

[0734] The boiling point of the above-mentioned fluorinated polyether compounds is preferably 105-180°C, more preferably 110-180°C, and even more preferably 110-150°C.

[0735] The surface treatment agent of this invention contains a solvent.

[0736] The solvents used are not particularly limited, and include, for example, perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); and polyfluoroaliphatic hydrocarbons (e.g., C6F...). 13CH2CH3 (e.g., ASAHIKLIN AC-6000 manufactured by Asahi Glass Co., Ltd., a registered trademark); 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA H manufactured by ZEON Corporation, a registered trademark); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., a registered trademark); perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec 7000 manufactured by Sumitomo 3M Co., Ltd., a registered trademark). 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.

[0737] The boiling point (at atmospheric pressure) of the solvent is preferably below 105°C, more preferably below 90°C, and even more preferably below 80°C. Because the solvent has a boiling point within the above range, when the surface treatment agent of the present invention is applied to a substrate, it can be vaporized more easily without heating, thus reducing the time and energy required for the surface treatment process. The lower limit of this boiling point is not particularly limited; for example, it can be 30°C or higher, preferably 50°C or higher.

[0738] In the surface treatment agent of the present invention, relative to the total amount of the fluorinated polyether-based silane compound, the fluorinated polyether-based compound, and the solvent, the content of the fluorinated polyether-based silane compound is 0.02 to 50.0% by mass, the content of the fluorinated polyether-based compound is 0.1 to 95.0% by mass, and the content of the solvent is 1 to 99.88% by mass. Having the above composition, the surface treatment layer formed by the surface treatment agent of the present invention exhibits excellent water and oil repellency and high wear durability.

[0739] The content of the fluorinated polyether-based silane compound is preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, even more preferably 0.04 to 25.0% by mass, and particularly preferably 0.05 to 20.0% by mass. By keeping the content of the fluorinated polyether-based silane compound within the above range, higher water and oil repellency can be obtained.

[0740] The content of the above-mentioned fluorinated polyether compound is preferably 0.1 to 80.0% by mass, more preferably 0.1 to 50.0% by mass, even more preferably 0.2 to 40.0% by mass, and particularly preferably 0.2 to 20.0% by mass. By keeping the content of the above-mentioned fluorinated polyether compound within the above range, higher wear durability can be obtained.

[0741] The content of the above solvent is preferably 50-99.7% by mass, more preferably 60-99.7% by mass, further preferably 70-99.7% by mass, and particularly preferably 80-99.7% by mass.

[0742] In a preferred embodiment, relative to the total amount of the fluorinated polyether-based silane compound, the fluorinated polyether-based compound, and the solvent, the content of the fluorinated polyether-based silane compound is 5.0 to 25.0% by mass, preferably 10.0 to 20.0% by mass; the content of the fluorinated polyether-based compound is 0.2 to 20.0% by mass, preferably 0.5 to 10.0% by mass; and the content of the solvent is 50 to 90% by mass, preferably 70 to 90% by mass.

[0743] The surface treatment agent of the present invention may further contain (non-reactive) fluorinated polyether compounds that can be understood as fluorinated oils, preferably perfluorinated (poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), (non-reactive) organosilicon compounds that can be understood as silicone oils (hereinafter referred to as "silicone oils"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc. Furthermore, other components are components different from the fluorinated polyether-based silane compounds, fluorinated polyether-based compounds, and solvents described above.

[0744] As a fluorinated oil, there are no particular limitations, for example, the following compounds (perfluoro(poly)ether compounds) can be listed as general formula (4).

[0745] Rf 5 -(OC4F8) a″ -(OC3F6) b″ -(OC2F4) c″ -(OCF2) d″ -Rf 6 ···(4)

[0746] In the formula, Rf 5 This indicates a C atom that can be substituted by one or more fluorine atoms. 1－16 Alkyl (preferably C) 1―16 perfluoroalkyl), Rf 6 This indicates a C atom that can be substituted by one or more fluorine atoms. 1－16 Alkyl (preferably C) 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0747] 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. The sum of a″, b″, c″, and d″ is greater than 30, preferably 40 to 300, and more preferably 50 to 300. The order of the repeating units marked 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.

[0748] As an example of the perfluoro(poly)ether compound represented by the above general formula (4), compounds represented by any of the following general formulas (4a) and (4b) can be listed (which may be a mixture of one or more compounds).

[0749] Rf 5 -(OCF2CF2CF2) b″ -Rf 6 ···(4a)

[0750] Rf 5 -(OCF2CF2CF2CF2) a″ -(OCF2CF2CF2) b″ -(OCF2CF2) c″ -(OCF2) d″ -Rf 6 ···(4b)

[0751] In these formulas, Rf 5 and Rf 6As described above; in equation (4a), b″ is an integer greater than 1 and less than 100; in equation (4b), 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.

[0752] Alternatively, from another perspective, fluorinated oils can be classified using the general formula Rf. 3 -F(where Rf) 3 C 5－16 Compounds shown as perfluoroalkyl groups. Also, they can be trichlorofluoroethylene oligomers.

[0753] The aforementioned fluorinated oil preferably has a number average molecular weight of 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. Furthermore, the aforementioned fluorinated oil preferably has a number average molecular weight of 30000 or less, more preferably 20000 or less, and even more preferably 10000 or less. The molecular weight of the fluorinated oil can be determined using GPC.

[0754] Compared to the surface treatment agent of the present invention, the aforementioned fluorinated oil may contain, for example, 0-50% by mass, preferably 0-30% by mass, and more preferably 0-5% by mass. In one embodiment, the surface treatment agent 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.

[0755] In one approach, the number-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, superior wear durability and surface lubrication can be achieved, particularly when the surface treatment layer is formed using vacuum evaporation.

[0756] In one approach, the number-average molecular weight of the fluorinated oil can be lower than that 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 such a compound and to form a cured product with high wear resistance and high surface lubricity.

[0757] Fluorinated oils help improve the surface lubricity of layers formed by the surface treatment agents of this invention.

[0758] 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 conventional silicone oils and modified silicone oils. Examples of conventional silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrosilicone oil. Examples of modified silicone oils include modified silicone oils obtained by modifying conventional silicone oils with alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil, etc.

[0759] In the surface treatment agent of the present invention, relative to the total of 100 parts by mass of the fluorinated polyether-based silane compounds of the present invention (or the total of two or more, the same below), the silicone oil may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

[0760] Silicone oil helps improve the surface lubrication of surface treatment layers.

[0761] Examples of the aforementioned alcohols include alcohols with 1 to 6 carbon atoms that can be substituted by one or more fluorine atoms, such as methanol, ethanol, isopropanol, tert-butanol, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH. Adding these alcohols to the surface treatment agent can improve the stability of the agent and enhance the compatibility of the fluorinated polyether-based silane compound with the solvent.

[0762] In the surface treatment agent, the content of the alcohol, relative to the aforementioned metal compound, is preferably 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times in molar ratio. By keeping the alcohol content within the above range, the stability of the surface treatment layer can be further improved.

[0763] 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.).

[0764] The catalyst can promote the hydrolysis and dehydration condensation of the fluorinated polyether-based silane compound of the present invention, and can promote the formation of the layer formed by the surface treatment agent of the present invention.

[0765] Other components, besides those mentioned above, may include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

[0766] 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.

[0767] In addition to the above-mentioned components, the surface treatment agent of the present invention may also contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, silane condensates, etc.

[0768] The items of the present invention will now be described.

[0769] The article of the present invention includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate by the surface treatment agent of the present invention.

[0770] The substrates that can be used in this invention can be made of, for example, glass, resin (natural or synthetic resin, such as common plastic materials), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, pottery, stone, building components, hygiene products, or any suitable material.

[0771] For example, if the desired article is an optical component, the material constituting the surface of the substrate can be a material used in optical components, such as glass or transparent plastic. Additionally, if the desired article is an optical component, the surface (outermost layer) of the substrate can have certain layers (or films), such as a hard coating or an anti-reflective layer. The anti-reflective layer can be either a single-layer or multi-layer anti-reflective layer. Examples of inorganic materials that can be used as anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., in the form of a mixture). When fabricating 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 substrate (glass) surface 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 films, hard coatings, polarizing films, retardation films, and liquid crystal display modules, depending on its specific design.

[0772] The shape of the substrate is not particularly limited; for example, it can be a plate, a film, or other forms. Furthermore, 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 design of the article to be manufactured.

[0773] In one approach, the substrate may be composed, at least in its surface portion, of a material that inherently possesses hydroxyl groups. Examples of such materials include glass, and also 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 inherently lacks hydroxyl groups, certain pretreatments can be performed on the substrate to introduce or increase the number of hydroxyl groups on its 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 pre-forming an interfacial adsorbent with carbon-carbon unsaturated bonds in the form of a monolayer on the substrate surface using methods such as the Langmuir-Blodgett method or chemisorption, followed by breaking the unsaturated bonds in an atmosphere containing oxygen, nitrogen, etc.

[0774] In another approach, such a substrate may be at least partially composed of a material containing an organosilicon compound having one or more other reactive groups, such as Si-H groups, or an alkoxysilane.

[0775] In a preferred embodiment, the substrate is glass. Preferred types of glass include sapphire glass, soda-lime glass, alkaline aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass. Particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkaline aluminosilicate glass, and chemically bonded borosilicate glass.

[0776] The article of the present invention can be manufactured by forming a layer of the surface treatment agent of the present invention on the surface of the above-mentioned substrate, and then performing post-treatment on the layer as needed, thereby forming a layer of the surface treatment agent of the present invention.

[0777] Regarding the layer formation of the surface treatment agent of the present invention, it can be implemented by applying the surface treatment agent to the surface of the substrate in a manner that covers the surface. The covering method is not particularly limited. For example, wet covering and dry covering methods can be used, with wet covering being preferred.

[0778] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0779] 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.

[0780] Alternatively, atmospheric pressure plasma method can be used for coverage.

[0781] 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 a 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 before application to the substrate surface. When using the dry coating method, the surface treatment agent of the present invention with added catalyst 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 added catalyst impregnated in a porous metal such as iron or copper.

[0782] The catalyst can be any suitable acid or base. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0783] The surface-treated layer formed using the surface-treated agent of the present invention does not substantially contain the fluorinated polyether compounds contained in the surface-treated agent of the present invention.

[0784] Therefore, the present invention provides an article comprising a substrate and a surface treatment layer formed on the substrate, the surface treatment layer being formed of a fluorinated polyether-based silane compound and substantially free of fluorinated polyether-based compounds.

[0785] The surface treatment layer included in the article of the present invention has high wear resistance. In addition to high wear resistance, the surface treatment layer, depending on the composition of the surface treatment agent used, 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.), surface slippage (or lubrication, such as the ability to wipe away dirt such as fingerprints and excellent tactile feel for fingers), and chemical resistance, making it suitable for use as a functional film.

[0786] Therefore, the present invention also relates to optical materials having the above-described surface treatment layer as the outermost layer.

[0787] In addition to the optical materials related to displays as exemplified later, various 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.

[0788] The articles of this invention can be optical components, but are not particularly limited thereto. Examples of optical components include the following: lenses for eyeglasses, etc.; front protective panels, anti-reflective panels, polarizing panels, and anti-glare panels for displays such as PDPs and LCDs; touch screens for devices such as portable telephones and portable information terminals; disc surfaces for Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers; and the display surfaces of clocks and watches.

[0789] In addition, the articles of the present invention can also be medical devices or medical materials.

[0790] The thickness of the aforementioned layer is not particularly limited. In the case of an optical component, from the viewpoints of optical performance, wear resistance, and anti-fouling properties, a thickness of 1–50 nm, 1–30 nm, or preferably 1–15 nm is preferred.

[0791] The present invention also provides a method for manufacturing an article, the article comprising a substrate and a surface treatment layer formed on the substrate, the method comprising:

[0792] The step of forming a film of the surface treatment agent of the present invention by wetting and covering the above-mentioned substrate; and

[0793] The step of vaporizing the fluorinated polyether compound in the above surface treatment agent from the above membrane.

[0794] In the manufacturing method of the present invention, post-treatment can be performed after the film of the surface treatment agent is formed, such as a process of vaporizing the fluorinated polyether compound, or heating.

[0795] According to the method of the present invention, in the film of the surface treatment agent formed on the substrate, the fluorinated polyether compound does not immediately vaporize, but remains on the substrate for a certain period of time. After a certain period of time, the fluorinated polyether compound vaporizes, and the surface treatment layer formed by the fluorinated polyether silane compound remains on the substrate.

[0796] The article and its manufacturing method of the present invention have been described in detail above. However, the article and its manufacturing method are not limited to the examples described above.

[0797] Example

[0798] The articles of the present invention will now be described in the embodiments, but the present invention is not limited to the following embodiments. In these embodiments, the order of the repeating units constituting the fluorinated polyether is arbitrary, and the chemical formulas shown below represent the average composition.

[0799] The following compounds are used as fluorinated polyether-based silane compounds, fluorinated polyether-based compounds, and solvents.

[0800] • Silane compounds containing fluorinated polyether groups (Compound A)

[0801] CF3O-(CF2O) k -(CF2CF2O) l -(CF2CF2CF2O) m -(CF2CF2CF2CF2) n CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3 (where k = 36, l = 22, m = 0.6, n = 0.2)

[0802] (Compound B)

[0803] CF3O-(CF2O) k -(CF2CF2O) l -(CF2CF2CF2O) m -(CF2CF2CF2CF2) n CF2CON[CH2CH2CH2Si(OCH3)]2 (where k = 36, l = 22, m = 0.6, n = 0.2)

[0804] (Compound C)

[0805] CF3O-(CF2O) k -(CF2CF2O) l -(CF2CF2CF2O) m -(CF2CF2CF2CF2) n CF2-C[CH2CH2CH2Si(OCH3)3]2[OCH2CH2OCH2CH2OCH3] (where k=27, l=29, m=0.6, n=0.2) (Compound D)

[0806] CF3CF2CF2O-(CF2CF2CF2O) o -CF2CF2-CONH-CH2CH2CH2-Si(OCH2CH3)3 (where o = 28)

[0807] · Compounds containing fluorinated polyether groups

[0808]

[0809] (Compound a)

[0810] It has the above structural formula and a boiling point (at atmospheric pressure) of 135℃ (Solvay Galden (registered trademark) HT135).

[0811] (Compound b)

[0812] It has the above structural formula and a boiling point (at atmospheric pressure) of 170℃ (Solvay Galden (registered trademark) HT170).

[0813] (Compound C)

[0814] It has the above structural formula and a boiling point (at atmospheric pressure) of 110℃ (Solvay Galden (registered trademark) HT110).

[0815] (compound d)

[0816] CF3O-C2F4O-C2F4O-C2F4O-C2F4O-CF3

[0817] (C10ETH manufactured by Exfluor, boiling point (at atmospheric pressure) 138℃)

[0818] Solvent

[0819] (Compound 1)

[0820] Perfluorobutyl ethyl ether (C4F9OC2H5)

[0821] (Novec 7200 manufactured by Sumitomo 3M Corporation, boiling point (at atmospheric pressure) 76°C) (Compound 2)

[0822] Perfluorohexyl methyl ether

[0823] (Novec 7300 manufactured by Sumitomo 3M Corporation, boiling point (at atmospheric pressure) 98°C) (Compound 3)

[0824] 2-(trifluoromethyl)-3-ethoxydodecylfluorohexane

[0825] (Novec 7500 manufactured by Sumitomo 3M Corporation, boiling point (at atmospheric pressure) 130°C) (Preparation of surface treatment agent)

[0826] Examples 1-15

[0827] A surface treatment agent was prepared by mixing the fluorinated polyether-based silane compound, the fluorinated polyether-based compound, and the solvent as shown in Table 1. The obtained surface treatment agent was then applied to a tempered glass substrate using a spray coating apparatus. The substrate was then heated at 150°C for 30 minutes and allowed to stand at room temperature for 24 hours to form a surface treatment layer on the substrate.

[0828] [Table 1]

[0829]

[0830] Comparative Examples 1-8

[0831] [Table 2]

[0832]

[0833] <Evaluation>

[0834] The wear durability of the substrates obtained in Examples 1-15 and Comparative Examples 1-8 was measured.

[0835] (Rubber abrasion resistance test)

[0836] Using a friction tester (manufactured by Shin-To Science Co., Ltd.), the water contact angle was measured every 2500 wipings under the following conditions, and the test continued until the water contact angle was less than 100°. The test environment conditions were 25°C and 40% RH.

[0837] Eraser: Raber Eraser (manufactured by Minoan)

[0838] Grounding area:

[0839] Travel distance (one way): 30mm

[0840] Movement speed: 40 round trips per minute

[0841] load:

[0842] (Angle of contact with water)

[0843] Using a DropMaster700 fully automated contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), 2 μL of water was dropped onto a horizontally placed substrate using a microsyringe. A still image was captured 1 second after the water was dropped using a camera microscope, and the static contact angle of the water was determined from this.

[0844] [Table 3]

[0845]

[0846] Industrial availability

[0847] The surface treatment agent of the present invention is suitable for a wide variety of applications.

Claims

1. A surface treatment agent, characterized in that: Silane compounds containing fluorinated polyether groups, compounds containing fluorinated polyether groups, and solvents. Relative to the total amount of the fluorinated polyether-based silane compound, the fluorinated polyether-based compound, and the solvent, the content of the fluorinated polyether-based silane compound is 0.02–50.0% by mass, the content of the fluorinated polyether-based compound is 0.1–95.0% by mass, and the content of the solvent is 1–99.88% by mass. The fluorinated polyether-containing silane compound is a fluorinated polyether-containing silane compound of formula (1) or (2). In equation (1) or equation (2), R F1 Each occurrence is independently assigned to Rf. 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 Each occurrence is independently assigned the number C. 1－16 Alkyl groups or C atoms substituted with one or more fluorine atoms 1－16 alkyl; Rf 2 C 1－6 Alkylene or C atoms substituted with one or more fluorine atoms 1－6 Alkylene; R F Each time it appears, it is independently a divalent fluorinated polyether group; p is 0 or 1; q is 0 or 1 independently each time it appears; R Si Each time it appears, it is independently represented by a group shown in the following formula (S1), (S2), (S3), or (S4). In formulas (S1), (S2), (S3), or (S4), R 11 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 12 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. n1 in each (SiR) 11 n1 R 12 3－n1 Each unit contains an independent integer from 0 to 3. X 11 Each time it appears, it is independently either a single bond or a divalent organic group. R 13 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. R 14 Each time it appears, it is independently a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 , R 15 Each time it appears, it is independently a single bond, an oxygen atom, an alkylene group with 1 to 6 carbon atoms, or an alkene group with 1 to 6 carbon atoms. Each occurrence of t is an independent integer greater than 2. R a1 Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 , Z 1 Each time it appears, it is independently either an oxygen atom or a divalent organic group. R 21 Each occurrence is independently -Z 1′ -SiR 21′ p1′ R 22′ q1′ R 23′ r1′ , R 22 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 23 Each time it appears, it is independently either a hydrogen atom or a monovalent organic 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. The sum of p1, q1, and r1 in each (SiR) 21 p1 R 22 q1 R 23 r1 The value in unit ) is 3. Z 1′ Each time it appears, it is independently either an oxygen atom or a divalent organic group. R 21′ Each occurrence is independently -Z 1′′ -SiR 22′′ q1′′ R 23′′ r1′′ , R 22′ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 23′ Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. p1′ is an integer from 0 to 3 each time it appears. Each occurrence of q1′ is an independent integer from 0 to 3. r1′ is an integer from 0 to 3 each time it appears. The sum of p1′, q1′, and r1′ in each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ The value in unit ) is 3. Z 1′′ Each time it appears, it is independently either an oxygen atom or a divalent organic group. R 22′′ Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 23′′ Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. Each occurrence of q1′′ is an independent integer from 0 to 3. r1′′ is an integer from 0 to 3 each time it appears. The sum of q1′′ and r1′′ in each (SiR 22′′ q1′′ R 23′′ r1′′ The value in unit ) is 3. R b1 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R c1 Each time it appears, it is independently either a hydrogen atom or a monovalent organic 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. The sum of k1, l1, and m1 in each (SiR) a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3. R d1 Each occurrence is independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 , Z 2 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group. R 31 Each occurrence is independently -Z 2′ -CR 32′ q2′ R 33′ r2′ , R 32 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 , R 33 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic 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. The sum of p2, q2, and r2 in each (CR 31 p2 R 32 q2 R 33 r2 The value in unit ) is 3. Z 2′ Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group. R 32′ Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 , R 33′ Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic group. q2′ is an independent integer from 0 to 3 each time it appears. r2′ is an integer from 0 to 3 each time it appears. The sum of q2′ and r2′ in each (CR 32′ q2′ R 33′ r2′ The value in unit ) is 3. Z 3 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group. R 34 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group. R 35 Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. n2 is an integer from 0 to 3 each time it appears. R e1 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 , R f1 Each time it appears, it is independently represented by a hydrogen atom, a hydroxyl group, or a monovalent organic 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 in each (CR) d1 k2 R e1 l2 R f1 m2 The value in unit ) is 3. R g1 and R h1 Each occurrence is independently -Z 4 -SiR 11 n1 R 12 3－n1 -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 , Z 4 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group. In formulas (S1), (S2), (S3) and (S4), there is at least one Si atom bonded with a hydroxyl group or a hydrolyzable group; X A Each is an independent single bond or an organic group with a valence of 2 to 10. α is an integer from 1 to 9; β is an integer from 1 to 9; γ are independent integers from 1 to 9. The fluorinated polyether compound is the fluorinated polyether compound shown in formula (3). Rf 5 -(OC h1 H h2 F h3 ) j -Rf 6 ・・・(3) In equation (3), Rf 5 C 1－16 Alkyl groups or C atoms substituted with one or more fluorine atoms 1－16 alkyl, Rf 6 C 1－16 Alkyl groups, C atoms substituted with one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms h1 is an integer from 1 to 4 each time it appears. h2 is an integer from 0 to 8 each time it appears. h3 is an integer from 0 to 8 each time it appears. Here, in (OC) h1 H h2 F h3 In unit ), 2 × h1 = h2 + h3, j is an integer from 1 to 10. The fluorinated polyether compound has a boiling point of 105–210 °C, and the solvent has a boiling point below 105 °C.

2. The surface treatment agent as described in claim 1, characterized in that: Rf 1 Each occurrence is independently assigned the number C. 1－16 Perfluoroalkyl, Rf 2 C 1－6 Perfluoroalkylene groups.

3. The surface treatment agent as described in claim 1 or 2, characterized in that: R F Each occurrence is independently represented by the formula: -(OC6F 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - The group shown, In the formula, R Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200. The sum of a, b, c, d, e, and f is greater than or equal to 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula, but it applies to all R... Fa In the case of hydrogen or chlorine atoms, at least one of a, b, c, e, and f is 1 or more.

4. The surface treatment agent as described in claim 3, characterized in that: R Fa It is a fluorine atom.

5. The surface treatment agent as described in claim 1 or 2, characterized in that: R F Each time it appears, it is independently represented by a group as shown in the following formula (f1), (f2), (f3), (f4), or (f5). -(OC3F6) d -(OC2F4) e - (f1) In equation (f1), d is an integer from 1 to 200, and e is 0 or 1; -(OC4F8) c -(OC3F6) d -(OC2F4) e - (OCF2) f - (f2) In equation (f2), c and d are independent integers from 0 to 30. e and f are independent integers from 1 to 200. The sum of c, d, e, and f is an integer between 10 and 200. The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula; -(R 6 -R 7 ) g - (f3) In equation (f3), R 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, g is an integer from 2 to 100; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) In equation (f4), e is an integer greater than 1 and less than 200, a, b, c, d and f are each an integer greater than 0 and less than 200, and the order of the repeated units marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the equation; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) In equation (f5), f is an integer greater than 1 and less than 200, a, b, c, d and e are each an integer greater than 0 and less than 200, and the order of the repeated units marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the equation.

6. The surface treatment agent as described in claim 1 or 2, characterized in that: α, β and γ are 1.

7. The surface treatment agent as described in claim 1 or 2, characterized in that: The ratio of fluorine atoms to carbon atoms in the fluorinated polyether compound is 3.00 or more by mass.

8. The surface treatment agent as described in claim 1 or 2, characterized in that: The fluorinated polyether compound is the fluorinated polyether compound shown in formula (3′). Rf 5 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 6 ・・・(3′) In the formula, Rf 5 C 1－16 Alkyl groups or C atoms substituted with one or more fluorine atoms 1－16 alkyl, Rf 6 C 1－16 Alkyl groups, C atoms substituted with one or more fluorine atoms 1－16 Alkyl, fluorine or hydrogen atoms a′, b′, c′, and d′ are each an independent integer from 0 to 10, and the sum of a′, b′, c′, and d′ is an integer from 1 to 10. The order of repeated units marked with subscripts a′, b′, c′ or d′ and enclosed in parentheses is arbitrary in the formula.

9. The surface treatment agent as described in claim 1 or 2, characterized in that: The content of the fluorinated polyether compound is 0.1 to 50% by mass.

10. The surface treatment agent as described in claim 1 or 2, characterized in that: Used as a stain-resistant or waterproof coating.

11. The surface treatment agent as described in claim 1 or 2, characterized in that: The surface treatment agent is used for wet covering purposes.

12. An article characterized by: It includes a substrate and a layer formed on the substrate by any one of claims 1 to 11.

13. The article as claimed in claim 12, characterized in that: The substrate is a glass substrate.

14. The article as claimed in claim 12, characterized in that: The item in question is an optical component.

15. A method of manufacturing an article, said article comprising a substrate and a surface treatment layer formed on the substrate, the method characterized in that it comprises: The step of forming a film of the surface treatment agent according to any one of claims 1 to 11 on the substrate by wet covering; and The step of vaporizing the fluorinated polyether compound in the surface treatment agent from the membrane.

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