Surface treatment agent

Abstract

The purpose of the present invention is to provide a surface treatment agent with which a film having good wear resistance can be achieved. The composition of the present invention contains a silane compound (A) having a fluoropolyether group and a compound (B) having a fluoropolyether group and an allyl ether group, the compound (B) includes at least one compound represented by formula (3), (4) or (5): RF1 [alpha]-XA-[ARB1 [delta] RB 23-[delta]] [beta] (3) [RB1 [delta] RB 23-[delta] A] [gamma]-XA-RF2-XA-[ARB1 [delta] RB 23-[delta]] [gamma] (4) RSi [gamma]-XA-RF2-XA-[ARB1 [delta] RB 23-[delta]] [gamma] (5) [wherein A each independently represents a C atom or a Si atom; the RF1 is respectively and independently Rf1-RF-Oq-; rF2 is-Rf < 2 > -RF-Oq <->; rf1 each independently may be substituted by a C1-16 alkyl group of one or more fluorine atoms; rf2 represents a C1-6 alkylene group which may be substituted by one or more fluorine atoms; each RF independently represents a divalent fluoropolyether group; p is 0 or 1; q are each independently 0 or 1; rB1 is-RB < 3 >-O-CH = CH-CH3, and RB < 2 > is-RB Each RB2 independently represents one or more elements selected from the group consisting of-RB3-O-CH2CH2CH2-SiRB4 [epsilon] RB53-[epsilon] and a hydrogen atom; rB3 are each independently a single bond or a C1-20 alkylene group; each RB4 independently represents a hydroxyl group or a hydrolyzable group; each RB5 independently represents a hydrogen atom or a monovalent organic group; each RSi independently represents a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group is bonded; in formula (5), at least one RSi represents a monovalent group including an Si atom to which a hydroxyl group or a hydrolyzable group is bonded; each XA independently represents a single bond or an organic group having a valence of 2 to 10; alpha is an integer from 1 to 9; beta is an integer from 1 to 9; each gamma independently represents an integer of 1 to 9; and each delta independently represents an integer of 1-3. And each epsilon independently represents an integer of 1-3. ] (wherein compound (A) is different from compound (B)).

Description

Technical Field

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

[0002] It is known that certain fluorinated polyether-based silane compounds can provide excellent water repellency, oil repellency, and stain resistance when used for surface treatment of substrates. The layer obtained by the surface treatment agent containing the fluorinated polyether-based silane compound (hereinafter also referred to as the "surface treatment layer") has been 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 Patent documents Patent Document 1: Japanese Patent Application Publication No. 2014-218639 Summary of the Invention

[0004] The problem that the invention aims to solve The fluorinated polyether-based silane compound described in Patent Document 1 can improve the surface treatment layer with excellent functions, but requires a surface treatment layer with higher durability.

[0005] The purpose of this invention is to provide a surface treatment agent that can achieve a film with good wear resistance.

[0006] Technical solutions for solving the problem The present invention includes the following methods.

[0007] [1] A composition comprising: Silane compounds (A) having fluorinated polyether groups, and Compound (B) having fluorinated polyether groups and allyl ether groups. The above-mentioned compound (B) includes at least one compound represented by formula (3), (4) or (5): R F1 α -X A - [AR] B1 δ R B2 3－δ ] β (3) [R] B1 δ R B2 3－δ A] γ -X A -R F2 -X A - [AR] B1δ R B2 3－δ ] γ (4) R Si γ -X A -R F2 -X A - [AR] B1 δ R B2 3－δ ] γ (5) [In the formula:] A can be either a C atom or a Si atom, respectively. R F1 Rf, independently 1 -R F -O q -; R F2 -Rf 2 p -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R B1 -R B3 -O-CH=CH-CH3; R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the following: hydrogen atoms; R B3 Each independently is a single bond or C 1－20 Alkylene; R B4 Each can be an independent hydroxyl group or a hydrolyzable group; R B5 Each can be an organic group that is independently a hydrogen atom or a monovalent organic group; RSi Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In equation (5), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; 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; δ can be an integer from 1 to 3, respectively. ε can be an independent integer from 1 to 3. (Among them, compound (A) is different from compound (B).)

[0008] [2] The composition as described in [1], wherein, The above-mentioned silane compound (A) having a fluorinated polyether group includes at least one compound represented by formula (1) or (2): [In the formula:] R F1 Rf, independently 1 -R F -O q -; R F2 -Rf 2 p -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In each of equations (1) or (2), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; In either equation (1) or equation (2), R Si It does not contain allyl ether groups; 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 can be an independent integer from 1 to 9. [3] The composition as described in [1] or [2], wherein, relative to the R contained in the above composition Si and R B1 In total, the R contained in the above composition B1 The proportion is less than 25 mol%.

[0009] [4] The composition as described in any one of [1] to [3], wherein, The above-mentioned silane compound (A) includes the compound shown in formula (1a): R F1 -X A -R Si (1a) [In the formula:] R F1 Rf, independently 1 -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; R F Each is independently a divalent fluorinated polyether group; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In equation (1), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; In equation (1), R Si It does not contain allyl ether groups; X A Each of these can be an independent single bond or an organic group with a valence of 2 to 10. In equation (1a), X A For a single bond or the following formula - (R 51 ) p5 - (X) 51 )q5 - The group shown, - (R) 51 ) p5 - (X) 51 ) q5 - [In the formula:] R 51 Indicates a single bond, -(CH2). s5 - or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -, 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. X 51 Represents - (X) 52 ) l5 -, X 52 Each of the following can be independently represented by a combination of -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, R 53 Represent phenyl and C independently, respectively. 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl, R 54 Each can be independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably methyl), m5 can be an integer from 1 to 100, preferably an integer from 1 to 20. n5 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3. l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3. p5 is either 0 or 1. q5 is either 0 or 1. Where at least one of p5 and q5 is 1, and the order of the repeating units with p5 or q5 enclosed in parentheses is arbitrary. R Si The group is represented by the following formula (S3). -SiR a1 k1 R b1 l1 R c1 m1 (S3) [In the formula,] R a1 Represent -Z independently. 1 -SiR 22 q1 R 23 r1 ; Z 1 Each of these can be used independently to represent an oxygen atom or a divalent organic group, hereinafter referred to as Z. 1 The right side of the recorded structure and (SiR) 22 q1 R 23 r1 ) combination; R 22 Each can be used independently to represent a hydroxyl group or a hydrolyzable group; R 23 Each can independently represent a hydrogen atom or a monovalent organic group; q1 in each (SiR) 22 q1 R 23 r1 Each unit is an independent integer from 1 to 3; R b1 Each can be used independently to represent a hydroxyl group or a hydrolyzable group; R c1 Each can independently represent a hydrogen atom or a monovalent organic group; k1 is an independent integer from 0 to 3, l1 is an independent integer from 0 to 3, m1 is an independent integer from 0 to 3, and the sum of k1, l1, and m1 is within (SiR). a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3. The above compound (B) includes the compound shown in formula (3): R F1 α -X A - [AR] B1 δ R B2 3－δ ] β (3) [In the formula:] A can be either a C atom or a Si atom, respectively. R F1 Rf, independently 1 -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; R F Each is independently a divalent fluorinated polyether group; q can be 0 or 1 independently; R B1 And -R B3 -O-CH=CH-CH3; R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the following: hydrogen atoms; R B3 Each independently is a single bond or C 1－20 Alkylene; R B4 Each can be an independent hydroxyl group or a hydrolyzable group; R B5 Each can be an organic group that is independently a hydrogen atom or a monovalent organic group; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic 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. [5] A surface treatment agent comprising any one of the compositions described in [1] to [4].

[0010] [6] The surface treatment agent as described in [5] further contains one or more components selected from fluorinated oils and silicone oils.

[0011] [7] The surface treatment agent described in [5] or [6] is used as an antifouling coating or a waterproof coating.

[0012] [8] An article comprising a substrate and a layer formed on the surface of the substrate by any one of the compositions described in [1] to [4].

[0013] [9] An article comprising a substrate and a layer formed on the surface of the substrate by any one of the surface treatment agents described in [5] to [7].

[0014] Invention Effects According to the present invention, it is possible to improve the surface treatment agent that can achieve a film with good wear resistance. Detailed Implementation

[0015] The compositions of the present invention comprise a silane compound (A) having a fluorinated polyether group and a compound (B) having both a fluorinated polyether group and an allyl ether group. The compositions of the present invention, by comprising the aforementioned compound (A) and compound (B), can achieve a film with good abrasion resistance. Compound (A) is different from compound (B).

[0016] By using silane compound (A), a film with good abrasion resistance, particularly against steel wool, can be provided. According to the inventors' research, by using compound (B) in addition to compound (A), a film with good abrasion resistance not only against steel wool but also against softer materials, such as resin-based materials like erasers, can be obtained. This invention should not be limited to a specific theoretical interpretation, but it can be considered that compound (B) has an vinyl ether group at the end, which can inhibit film damage when rubbed against soft materials.

[0017] (Silane compound with fluorinated polyether group (A)) The aforementioned silane compound (A) having a fluorinated polyether group can be a compound having a fluorinated polyether group and a hydrolyzable silane group, preferably free of an allyl ether group. In a preferred embodiment, the aforementioned compound (A) preferably includes at least one compound represented by formula (1) or (2) below: [In the formula:] R F1 Rf, independently 1 -R F -O q -; R F2 -Rf 2 p -R F -O q -; Rf 1Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In each of equations (1) or (2), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; In either equation (1) or equation (2), R Si It does not contain allyl ether groups; 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 can be an independent integer from 1 to 9. In the above equation (1), R F1 Rf, independently 1 -R F -O q -.

[0018] In equation (2) above, R F2 -Rf 2 p -R F -O q -.

[0019] In the above formula, Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl.

[0020] The above C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 Alkyl groups can be straight-chain or branched, preferably straight-chain or branched C-type. 1－6 Alkyl groups, especially straight-chain or branched C4 groups 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially straight-chain C4 groups 1－3 alkyl.

[0021] 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.

[0022] The above C 1－16 Perfluoroalkyl groups can be linear or branched, preferably linear or branched C-type. 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.

[0023] In the above formula, Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0024] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 The "alkylene group" can be linear or branched, preferably linear or branched C. 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0025] The above Rf 2 Preferably, the C atom can be substituted by one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0026] The above C 1－6 Perfluoroalkylene groups can be linear or branched, preferably linear or branched C-type. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0027] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0028] In the above formula, q is either 0 or 1 independently. In one case, q is 0. In another case, q is 1.

[0029] In equations (1) and (2) above, R FEach is independently a divalent fluorinated polyether group.

[0030] R F Preferably, the group is represented by the following formula (hereinafter also referred to as the group represented by "PFPE"): - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - [In the formula:] R Fa Each can be independently composed of 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, and the sum of a, b, c, d, e, and f is greater than 1. The order of repeated units with a, b, c, d, e, or f enclosed in parentheses is arbitrary in the formula. Wherein, in all R... Fa When the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f must be 1 or higher. R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Wherein, in all R... Fa When the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.

[0031] a, b, c, d, e, and f can each be an integer from 0 to 100 independently.

[0032] 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.

[0033] These repeating units can be linear, branched, or contain ring structures. 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 the following: -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of the following: -(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, in the above formula, R 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))-.

[0034] The above-mentioned ring structure can be a ternary ring, a quaternary ring, a quinary ring, or a hexaternary ring. [In the formula, * indicates the bonding location.] The aforementioned ring structure can preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0035] The repeating unit with a ring structure is preferably the unit described below. [In the formula, * indicates the bonding location.] In one embodiment, the repeating units are in a linear chain shape. By making the repeating units linear, the surface lubrication and wear resistance of the film (surface treatment layer) can be improved.

[0036] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of kinetic friction of the film (surface treatment layer) can be increased.

[0037] In one approach, R F Each of the following formulas (f1) to (f6) represents a group independently.

[0038] - (OC3F6) d - (OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - (f2) [In the formula, R] Fa Each atom is independently a hydrogen atom, a fluorine atom, or a chlorine atom, preferably a fluorine atom; c and d are independently integers greater than or equal to 0 and less than 30; e and f are independently integers greater than or equal to 1 and less than 200. The sum of c, d, e, and f is 2 or more. 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 the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the text, or combinations of two or three groups independently selected from these groups, g is an integer from 2 to 100. - (R) 6 -R 7 ) g -R r - (R) 7’ -R 6’ ) g’ - (f4) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups, R 6’ It is either OCF2 or OC2F4. R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100. g' is an integer from 2 to 100. R r for (In the formula, * indicates the bonding position.) - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f5) [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 repeating units with a, b, c, d, e, or f enclosed in parentheses is arbitrary in the formula.] - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f6) [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 repeating units with a, b, c, d, e, or f enclosed in parentheses is arbitrary in the formula.] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer from 25 to 35. In the above formula (f1), OC3F6 is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). In the above formula (f1), (OC2F4) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0039] 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 -(OC4F8). c - (OC3F6) d - (OC2F4) e - (OCF2) f The group shown is more 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. In other alternatives, the above formula (f2) can be -(OC4F8). c - (OCF2CF2(CR) Fa )2) d10 - (OCF2CF(CF3)) d11 - (OCF2CF2) e - (OCF2) f - d10 and d11 are each an independent integer from 0 to 200, preferably from 5 to 200, and more preferably from 10 to 200. The sum of d10 and d11 is 0 to 200, preferably from 5 to 200, and more preferably from 10 to 200.

[0040] In the above equation (f3), R 6 Preferably OC2F4, in another embodiment, OCF2. 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-, -OC2F 4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4-、and-OC4F8OC2F4OC2F4-, etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or - (OC2F4 - OC4F8) g -.

[0041] In the above equation (f4), R 6 R 7 The meaning of 'g' is the same as that of the above formula (f3), and they have the same manner. R 6’ R 7’ and g' are respectively related to R recorded in the above formula (f3) 6 R 7 It has the same meaning as g and follows the same pattern. R r Preferred [In the formula, * indicates the bonding position.], more preferably... [In the formula, * indicates the bonding position.]

[0042] In the above formula (f5), 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.

[0043] In the above formula (f6), 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.

[0044] In one approach, the aforementioned R F The group is represented by the formula (f1) above.

[0045] In one approach, the aforementioned R F The group is represented by the formula (f2) above.

[0046] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0047] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0048] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0049] 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, even more 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 lubricity, abrasion resistance, and chemical resistance of the film (surface treatment layer) obtained from this compound are further improved. The smaller the e / f ratio, the better the lubricity and abrasion resistance of the film. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound is further improved. The larger the e / f ratio, the better the stability of the compound.

[0050] In the above-mentioned fluorinated polyether-containing silane 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 Values ​​measured by F-NMR.

[0051] In another way, R F1 and R F2The number average molecular weight of the fraction can be 500-30000, preferably 1000-20000, more preferably 2000-15000, and even more preferably 2000-10000, for example 3000-6000.

[0052] In another way, R F1 and R F2 The number average molecular weight of the fraction can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0053] In equations (1) and (2) above, R Si Each of the following is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group, and at least one R Si R is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups. Si It improves adhesion to the substrate and can chemically react with the material of the substrate.

[0054] In the preferred embodiment, R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups.

[0055] In the preferred embodiment, R Si The group is represented by the following formula (S3) or (S4): .

[0056] In the above formula, R a1 Each independently is -Z 1 -SiR 22 q1 R 23 r1 .

[0057] The above Z 1 Each can be an oxygen atom or a divalent organic group. Additionally, the following are designated as Z. 1 The right side of the recorded structure and (SiR) 22 q1 R 23 r1 ( ) combined.

[0058] In the preferred method, Z 1 It is a divalent organic group.

[0059] In the preferred method, Z 1 Excluding Z 1 The bonded Si atoms form siloxane bonds. Preferably, in formula (S3) (Si-Z) 1 -Si) does not contain siloxane bonds.

[0060] 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). Such a 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, but preferably unsubstituted.

[0061] In the preferred method, Z 1 C 1－6 Alkylene or -(CH2) z3 -Phenylidene-(CH2) z4 - Preferably -phenylene-(CH2) z4 -. Z 1 When such a group is present, light tolerance, especially ultraviolet tolerance, can be increased.

[0062] In another preferred embodiment, the above Z 1 C 1－3 Alkylene. In one manner, Z 1 It can be -CH2CH2CH2-. In another way, Z 1 It can be -CH2CH2-.

[0063] The above R 22 Each can be an independent hydroxyl group or a hydrolyzable group.

[0064] R 22 Preferably, each group is a hydrolyzable group.

[0065] R 22 Preferably, each is independently -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO, or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl), more preferably -ORj (i.e., alkoxy group). As R j 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 more preferably methyl or ethyl. In one embodiment, R j For methyl, in another manner, R j It is an ethyl group.

[0066] The above R 23 Each of these can be an organic group that is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is any monovalent organic group other than the hydrolyzable groups mentioned above.

[0067] In R 23 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0068] The above q1 and r1 are independent integers from 0 to 3. Furthermore, the sum of q1 and r1 is within (SiR). 22 q1 R 23 r1 The value in unit ) is 3.

[0069] In one approach, q1 is in each (SiR) 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.

[0070] In one approach, q1 is in each (SiR) 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.

[0071] In the above formula, R b1 Each can be an independent hydroxyl group or a hydrolyzable group.

[0072] The above R b1 Preferably, each group is a hydrolyzable group.

[0073] The above R b1 Preferably, each is independently -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j, -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl), more preferably -OR j (i.e., alkoxy group). As R j 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 more preferably methyl or ethyl. In one embodiment, R j For methyl, in another manner, R j It is an ethyl group.

[0074] In the above formula, R c1 Each of these can be an organic group that is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is any monovalent organic group other than the hydrolyzable groups mentioned above.

[0075] In the above R c1 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0076] In the above examples, k1, l1, and m1 are all independent integers from 0 to 3. Furthermore, 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.

[0077] In one approach, k1 is in each (SiR) a1 k1 R b1 l1 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.

[0078] In equations (1) and (2) above, R Si When the group is as shown in formula (S3), 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).

[0079] In the preferred embodiment, R exists in equation (S3). a1 At that time, in at least one, preferably all, R a1 In this context, q1 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0080] In the preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, and q1 is 2 or 3, preferably 3.

[0081] The above R e1 Each independently is -Z 3 -SiR 34 n2 R 35 3－n2 .

[0082] The above Z 3 These are organic groups that are independently single bonds, oxygen atoms, or divalent groups. Additionally, the following are designated as Z. 3 The right side of the recorded structure and (SiR) 34 n2 R 35 3－n2 ( ) combined.

[0083] In one approach, Z 3 It is an oxygen atom.

[0084] In one approach, Z 3 It is a divalent organic group.

[0085] 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; z8” is an integer from 0 to 6, for example, an integer from 1 to 6). Such a 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.

[0086] In the preferred method, Z 3 C 1－6 Alkylene or -(CH2) z7” -Phenylidene-(CH2) z8” - Preferably -phenylene-(CH2) z8” -. Z 3 When such a group is present, light tolerance, especially ultraviolet tolerance, can be increased.

[0087] In another preferred embodiment, the above Z 3 C 1－3 Alkylene. In one manner, Z 3 It can be -CH2CH2CH2-. In another way, Z 3 It can be -CH2CH2-.

[0088] The above R 34 Each can be an independent hydroxyl group or a hydrolyzable group.

[0089] R 34 Preferably, each group is a hydrolyzable group.

[0090] R 34 Preferably, each is independently -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl), more preferably -OR j (i.e., alkoxy group). As R j 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 more preferably methyl or ethyl. In one embodiment, R j For methyl, in another manner, R j It is an ethyl group.

[0091] The above R 35 Each of these can be an organic group that is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is any monovalent organic group other than the hydrolyzable groups mentioned above.

[0092] In the above R 35 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0093] In the above formula, n2 is in each (SiR) 34 n2 R 35 3－n2 Each element in the unit contains an independent integer from 0 to 3. Specifically, in R... Si When the group is as shown in formula (S4), at least one (SiR) group with n2 of 1 to 3 is present at the end portion of formulas (1) and (2). 34 n2 R 353－n2 ) unit. That is, in such a terminal part, not all n2 are 0 at the same time. In other words, in the terminal parts of formula (1) and formula (2), there is at least one Si atom bonded with a hydroxyl group or a hydrolyzable group.

[0094] n2 in each (SiR) 34 n2 R 35 3－n2 Each of the units is preferably an integer from 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0095] The above R f1 Each of these can be an organic group that is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is any monovalent organic group other than the hydrolyzable groups mentioned above.

[0096] In the above R f1 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.

[0097] In one approach, R f1 It is a hydroxyl group.

[0098] In another way, R f1 The organic group is monovalent, preferably C. 1－20 Alkyl, more preferably C 1－6 alkyl.

[0099] In equations (1) and (2) above, in R Si When the group is as shown in formula (S4), it is preferable that at least two Si atoms bonded with hydroxyl or hydrolyzable groups are present in the terminal portions of formulas (1) and (2).

[0100] In one approach, in R Si When n2 is a group as shown in formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR). 34 n2 R 35 3－n2The number of units in each end portion of formulas (1) and (2) is more than two, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, further preferably 2 to 3, and especially preferably 3.

[0101] In the preferred embodiment, in equation (S4), when R exists... e1 At that time, at least one, preferably all, of R e1 In this context, n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0102] In the preferred embodiment, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3, in formula (S4).

[0103] 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 films with higher wear resistance.

[0104] In one approach, R Si The group is represented by formula (S3).

[0105] In one approach, R Si The group is represented by formula (S4).

[0106] X A Each is an organic group that is independently a single bond or has a 2 to 10 valence.

[0107] The above X A The 2- to 10-valent organic groups are preferably 2- to 8-valent organic groups. In one embodiment, such 2- to 10-valent organic groups are preferably 2- to 4-valent organic groups, more preferably 2-valent organic groups. In another embodiment, such 2- to 10-valent organic groups are preferably 3- to 8-valent organic groups, more preferably 3- to 6-valent organic groups.

[0108] In one manner, X A It is a single bond or a divalent organic group, with α = 1 and β = 1.

[0109] In one manner, X A It is a single bond or a divalent organic group, and γ is 1.

[0110] In one manner, X A It is an organic group with a valence of 3 to 6, where α is 1 and β is 2 to 5.

[0111] In one manner, X A It is an organic group with a valence of 3 to 6, and γ is 2 to 5.

[0112] In one manner, X A It is a trivalent organic group, with α = 1 and β = 2.

[0113] In one manner, X A It is a trivalent organic group, and γ is 2.

[0114] X A When the organic group is a single bond or divalent, formulas (1) and (2) are represented by the following formulas (1a) and (2a). In each of equations (1a) or (2a), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups. Additionally, in each formula (1a) or formula (2a), R... Si Allyl ether group is excluded.

[0115] In one manner, X A It is a single key.

[0116] In another way, X A It is a divalent organic group.

[0117] In one way, as X A For example, examples include single bonds or divalent organic groups represented by the following formulas: - (R) 51 ) p5 - (X) 51 ) q5 - [In the formula:] R 51 Indicates a single bond, -(CH2). s5 - or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -, 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. X 51 Represents - (X) 52 ) l5 -, X 52 Each of the following can be independently represented by a combination of -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 -, -NR54 - and - (CH2) n5 - group in R 53 Represent phenyl and C independently, respectively. 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl, R 54 Each can be independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably methyl), m5 can be an integer from 1 to 100, preferably an integer from 1 to 20. n5 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3. l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3. p5 is either 0 or 1. q5 is either 0 or 1. Where at least one of p5 and q5 is 1, and the order of the repeating units with p5 or q5 enclosed in parentheses is arbitrary. Among them, X A (Typical X) A The hydrogen atom can be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, X A It is not replaced by these groups.

[0118] 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. Wherein, R 52 (typically R) 52 The hydrogen atom can be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, R 56 It is not replaced by these groups.

[0119] The above X is preferredA Each independently is: single bond, C 1－20 Alkylene -R 51 -X 53 -R 52 -,or -X 54 -R 52 - [In the formula, R] 51 and R 52 Same meaning as above, X 53 express: -O-、 -S-、 -C(O)O-, -CONR 54 -、 -O-CONR 54 -、 -Si(R) 53 )2-、 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、 -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、 -O-(CH2) u5 -Si(R) 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-、 -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 - (CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-、 -CONR 54 - (CH2) u5 -N(R) 54 )-,or -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 53)2- (where R) 53 R 54 m5 has the same meaning as mentioned above. u5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. X 54 express: -S-、 -C(O)O-, -CONR 54 -、 -O-CONR 54 -、 -CONR 54 - (CH2) u5 -(Si(R) 54 )2O) m5 -Si(R) 54 )2-、 -CONR 54 - (CH2) u5 -N(R) 54 )-,or -CONR 54 -(o-phenylene, m-phenylene, or p-phenylene)-Si(R) 54 )2- (In the formula, each symbol has the same meaning as described above.)

[0120] More preferably, the above-mentioned X A Each independently is: single bond, C 1－20 Alkylene - (CH2) s5 -X 53 -、 - (CH2) s5 -X 53 - (CH2) t5 - -X 54 -,or -X 54 - (CH2) t5 - [In the formula, X] 53 X 54 s5 and t5 have the same meaning as described above.

[0121] More preferably, the above-mentioned X A Each independently is: single bond, C 1－20 Alkylene - (CH2)s5 -X 53 - (CH2) t5 -,or -X 54 - (CH2) t5 - [In the formula, each symbol has the same meaning as described above.]

[0122] In the preferred embodiment, the above X A Each independently is: single bond, C 1－20 Alkylene - (CH2) s5 -X 53 -,or - (CH2) s5 -X 53 - (CH2) t5 - [In the formula,] X 53 -O-, -CONR 54 - or -O-CONR 54 -, R 54 Each can be independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl, s5 is an integer from 1 to 20. t5 is an integer from 1 to 20.

[0123] In the preferred embodiment, the above X A Each independently is: - (CH2) s5 -O-(CH2) t5 -、 -CONR 54 - (CH2) t5 - [In the formula,] R 54 Each can be independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 alkyl, s5 is an integer from 1 to 20. t5 is an integer from 1 to 20.

[0124] In one manner, the aforementioned X A Each independently is: single bond, C 1－20 Alkylene - (CH2) s5 -O-(CH2) t5 -、 - (CH2) s5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -、 - (CH2) s5 -O-(CH2) u5 -(Si(R) 53 )2O) m5 -Si(R) 53 )2-(CH2) t5 -,or - (CH2) s5 -O-(CH2) t5 -Si(R) 53 )2-(CH2) u5 -Si(R) 53 )2-(C v5 H 2v5 ) [In the formula, R] 53 m5, s5, t5, and u5 have the same meaning as described 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.

[0125] In the above formula, -(C v H 2v - can be linear or branched, for example -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0126] The above X A Each atom can be selected independently from fluorine atoms, C atoms, etc. 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.

[0127] In addition, the above X A On the left side of each style and R F1 or R F2 Bonding, right side with R Si Bonding.

[0128] In one manner, X A Each independently is -O-C 1－6 Groups other than alkylene groups.

[0129] In another way, as X A For example, the following groups can be listed: [In the formula, R] 41 Each is independently a hydrogen atom, a phenyl group, and a C atom. 1－6 Alkyl or C 1－6 Alkoxy, preferably methyl; D is selected from the following groups: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (where Ph refers to phenyl), and (where R) 42 Each independently represents a hydrogen atom and a carbon atom. 1－6 alkyl or C 1－6 The alkoxy group is preferably represented by methyl or methoxy, more preferably by methyl. E is -(CH2) n - (n is an integer from 2 to 6). D and R of the molecular backbone F1 or R F2 Combining E and R Si Combine. As for the above X A Specific examples can be listed, for instance: single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, - CH2O(CH2) 3Si(CH3) 2O(Si(CH3) 2O) 2Si(CH3) 2(CH2) 2- - CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2- - CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2- - CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2- -CH2OCF2CHFOCF2-、 -CH2OCF2CHFOCF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 - CH2OCH2(CH2) 7CH2Si(OCH3) 2OSi(OCH3) 2(CH2) 2Si(OCH3) 2OSi(OCH3) 2(CH2) 2- -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-, -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-, -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-, -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-, -(CH2)2-Si(CH3)2-(CH2)2-, -CH2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -CO-, -CONH-、 -CONH-CH2-, -CONH-(CH2)2-, -CONH-(CH2)3-, -CONH-(CH2)4-, -CONH-(CH2)5-, -CONH-(CH2)6-, -CON(CH3)-CH2-, -CON(CH3)-(CH2)2-, -CON(CH3)-(CH2)3-, -CON(CH3)-(CH2)4-, -CON(CH3)-(CH2)5-, -CON(CH3)-(CH2)6-, -CON(Ph)-CH2- (where Ph refers to phenyl), -CON(Ph)-(CH2)2- (where Ph refers to phenyl), -CON(Ph)-(CH2)3- (where Ph refers to phenyl), -CON(Ph)-(CH2)4- (where Ph refers to phenyl), -CON(Ph)-(CH2)5- (where Ph refers to phenyl), -CON(Ph)-(CH2)6-(where Ph refers to phenyl), -CONH-(CH2)2NH(CH2)3-, -CONH-(CH2)6NH(CH2)3-, -CH2O-CONH-(CH2)3-, -CH2O-CONH-(CH2)6-, -S-(CH2)3-, -(CH2)2S(CH2)3-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -C(O)O-(CH2)3-, -C(O)O-(CH2)6-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-, -OCH2-, -O(CH2)3-, -OCFHCF2-, etc.

[0130] In other alternative ways, 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.

[0131] In the above formula, R 16 Each is independently composed of an oxygen atom, a phenylene group, an imidazolyl group, and a -NR group. 18 - (where R is the formula) 18 (Represents a hydrogen atom or an organic group) or a divalent organic group. Preferably R. 18 It is an oxygen atom or a divalent polar group.

[0132] 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). This "lower alkyl group" is, for example, C10. 1－6 Alkyl groups, such as methyl, ethyl, and n-propyl, can be substituted with one or more fluorine atoms.

[0133] In the above formula, R 17 Each of the atoms is independently a hydrogen atom, a fluorine atom, or a lower fluorinated alkyl group, preferably a fluorine atom. The "lower fluorinated alkyl group" is, for example, C10. 1－6 C is preferred. 1－3 Fluoroalkyl, preferably C 1－3 Perfluoroalkyl, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0134] In other alternative ways, as X A Examples can be listed below for the following groups: [In the formula,] R 41 Each is independently a hydrogen atom, a phenyl group, and a C atom. 1－6 Alkyl or C 1－6 Alkoxy, preferably methyl; 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 combined: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (where Ph refers to phenyl), or [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 is preferably represented by methyl or methoxy, more preferably by methyl. In several of the other Ts, the Rs of the molecular backbone Si In combination, when present, the remaining T are independently methyl, phenyl, and C, respectively. 1－6 Alkyl groups, or free radical scavenging groups, or ultraviolet absorbing groups.

[0135] The free radical scavenging group can be any group that can capture free radicals generated by light irradiation, without any particular limitation. 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.

[0136] Ultraviolet absorbing groups are any groups that can absorb ultraviolet light, without any particular limitation. Examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxymyristic esters, oxalamides, oxaloylaniline, benzoxazinones, and benzoxazoles.

[0137] In a preferred embodiment, the groups represented by the following formulas can be listed as preferred free radical scavenging groups or ultraviolet absorbing groups. In this method, X A Each of these groups is an organic group with a valence of 3 to 10, and each group is an organic group with a valence of 3 to 10.

[0138] In other alternative ways, as X A Examples can be listed below for the following groups: [In the formula, R] 25R 26 and R 27 Each is an organic group with an independent valence of 2 to 6. R 25 With at least one R F1 R 26 and R 27 With at least one R Si Bonding. In one approach, the aforementioned R 25 For single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene, C 5－20 Alpha-aryl, -R 57 -X 58 -R 59 -、-X 58 -R 59 - or -R 57 -X 58 - The above R 57 and R 59 Each is independently a single bond, C 1－20 Alkylene, C 3－20 Cycloalkylene or C 5－20 Alpha-aryl. The above X 58 It can be -O-, -S-, -CO-, -O-CO-, or -COO-.

[0139] In one approach, the aforementioned R 26 and R 27 Each of the following groups is independently a hydrocarbon, or has at least one atom selected from N, O, and S at the end or in the main chain of a hydrocarbon, preferably C. 1－6 Alkyl, -R 36 -R 37 -R 36 -、-R 36 -CHR 38 2-etc. Among them, R 36 Each independently is a single bond or C 1－6 Alkyl, preferably C 1－6 Alkyl group. 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 —. Among them, R 45 C independently 1－6 Alkyl group. R 46 It can be N, O, or S, with O being the preferred choice.

[0140] The above compounds are not particularly limited and may have a concentration of 5 × 10⁻⁶. 2 ~1×10 5 The average molecular weight. From the viewpoint of UV resistance and abrasion durability, an average molecular weight of 2000-30000 is preferred, and more preferably 2500-12000. Furthermore, in this invention, "average molecular weight" is exponential average molecular weight, and "average molecular weight" is determined by... 19 Values ​​measured by F-NMR.

[0141] In one embodiment, compound (A) is preferably the compound shown in formula (1), more preferably the compound shown in formula (1a), and even more preferably the compound shown in formula (1b). In another embodiment, compound (A) is preferably the compound shown in formula (2), more preferably the compound shown in formula (2a), and even more preferably the compound shown in formula (2b).

[0142] The fluorinated polyether-based silane compounds shown in formula (1) or formula (2) above are not particularly limited and can have a concentration of 5 × 10⁻⁶. 2 ~1×10 5 The average molecular weight. Within this range, from the viewpoint of wear resistance, an average molecular weight of 2000 to 32000 is preferred, and more preferably 2500 to 12000 is preferred. Furthermore, in this invention, "average molecular weight" is exponential average molecular weight, and "average molecular weight" is determined by... 19 Values ​​measured by F-NMR.

[0143] The total content of the compounds represented by formula (1) or formula (2) in compound (A) is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

[0144] (Compounds having fluorinated polyether groups and allyl ether groups (B)) The above-mentioned compound (B) having fluorinated polyether and allyl ether groups has fluorinated polyether and allyl ether groups, and in a preferred embodiment, comprises at least one compound represented by formula (3), (4) or (5): R F1 α -X A - [AR] B1 δ R B2 3－δ ] β (3) [R] B1 δ R B2 3－δA] γ -X A -R F2 -X A - [AR] B1 δ R B2 3－δ ] γ (4) R Si γ -X A -R F2 -X A - [AR] B1 δ R B2 3－δ ] γ (5) [In the formula:] A can be either a C atom or a Si atom, respectively. R F1 Rf, independently 1 -R F -O q -; R F2 -Rf 2 p -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R B1 -R B3 -O-CH=CH-CH3; R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the following: hydrogen atoms; R B3 Each independently is a single bond or C 1－20 Alkylene; RB4 Each can be an independent hydroxyl group or a hydrolyzable group; R B5 Each can be an organic group that is independently a hydrogen atom or a monovalent organic group; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In equation (5), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; 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; δ can be an integer from 1 to 3, respectively. ε can be an independent integer from 1 to 3. By including the above compounds, it is possible to achieve a film with good wear resistance.

[0145] In equations (3), (4), and (5) above, R F1 R F2 R Si X A α, β, and γ have the same meaning as described above.

[0146] A can be either a C atom or a Si atom, independently. In one embodiment, A is a C atom. In another embodiment, A is a Si atom. Preferably, A is a Si atom.

[0147] R B1 Each independently is -R B3 -O-CH=CH-CH3.

[0148] R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the hydrogen atoms. In one manner, R B2 It can be -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε In another way, R B2 It can be a hydrogen atom.

[0149] The above RB3 Each independently is a single bond or C 1－20 Alkylene. In one manner, R B3 A single bond is preferred. In another embodiment, R B3 C is preferred 1－20 Alkylene, more preferably C 1－6 Alkylene.

[0150] R B4 Each can be an independent hydroxyl group or a hydrolyzable group.

[0151] R B4 Preferably, each group is a hydrolyzable group.

[0152] R B4 Preferably, each is independently -OR j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j , -NCO or halogen (in these formulas, R j C indicates substitution or non-substitution. 1－4 Alkyl), more preferably -OR j (i.e., alkoxy group). As R j 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 more preferably methyl or ethyl. In one embodiment, R... j For methyl, in another manner, R j It is an ethyl group.

[0153] The above R B5 Each of these can be an organic group that is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is any monovalent organic group other than the hydrolyzable groups mentioned above.

[0154] In R B5 In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl groups, more preferably methyl groups.

[0155] In one manner, ε is in each (SiR) B4 ε R B5 3－ε The unit is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0156] In one approach, δ in each (AR) B1 δ R B23－δ The unit is an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

[0157] The compound (B) shown in formula (3), formula (4) or formula (5) above is not particularly limited and may have a content of 5 × 10 2 ~1×10 5 The average molecular weight. Within this range, from the viewpoint of wear resistance, an average molecular weight of 2000 to 32000 is preferred, and more preferably 2500 to 12000 is preferred.

[0158] In the above composition, relative to the R contained in the above composition Si and R B1 In total, the R contained in the above composition B1 The proportion is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. For example, it can be 0.1 mol% or more, and it can also be 1 mol% or more. By keeping the above proportions within such a range, it is easy to provide a film with better abrasion resistance, especially for soft materials (such as resin-based materials like erasers).

[0159] The content of compound (B) shown in formula (3), formula (4) or formula (5) above is preferably 0.1% to 25% by mass, more preferably 1% to 20% by mass, in a total of 100% by mass of the above-mentioned compounds (A) and (B). By keeping the above-mentioned content within such a range, it is easy to provide a film with better abrasion resistance, especially for soft materials (such as resin-based materials like erasers).

[0160] In the above composition, the total content of the above compound (A) and the above compound (B) is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

[0161] (Surface treatment agent) The surface treatment agent of the present invention comprises the above-described composition. The total content of the above-described compound (A) and compound (B) is preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, further preferably 0.04 to 25.0% by mass, and particularly preferably 0.05 to 20.0% by mass in 100% by mass of the surface treatment agent. By placing the content of the above-described fluorinated polyether-based silane compound within the above-described range, higher water and oil repellency can be obtained.

[0162] In the compositions of the present invention, the non-volatile component may be defined as the portion of the total composition minus the solvent.

[0163] (Other ingredients) The surface treatment agent of the present invention may further comprise (non-reactive) fluorinated polyether compounds, preferably perfluorinated (poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), (non-reactive) organosilicon compounds (hereinafter collectively referred to as "silicone oils"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc. Furthermore, other components are components different from those described above as compounds (A) and (B).

[0164] In a preferred embodiment, the surface treatment agent of the present invention further comprises one or more components selected from fluorinated oils and silicone oils.

[0165] As a fluorinated oil, there are no particular limitations, for example, the following compounds (perfluoro(poly)ether compounds) can be listed as general formula (6).

[0166] Rf 5 - (OC4F8) a” - (OC3F6) b” - (OC2F4) c” - (OCF2) d” -Rf 6 …(6) 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, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0167] a”, b”, c”, and d” represent the number of repeating units of the four types of perfluoro(poly)ethers that constitute the main skeleton of the polymer. They are independent of each other and are integers between 0 and 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 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))-, preferably -(OCF2CF2)-.

[0168] As an example of the perfluoro(poly)ether compound represented by the above general formula (6), the compounds represented by any one of the following general formulas (6a) and (6b) can be listed (which may be a mixture of one or more compounds).

[0169] Rf 5 - (OCF2CF2CF2) b” -Rf 6 …(6a) Rf 5 - (OCF2CF2CF2CF2) a” - (OCF2CF2CF2) b” - (OCF2CF2) c” - (OCF2) d” -Rf 6 …(6b) In these formulas, Rf 5 and Rf 6 As described above; in equation (6a), b” is an integer greater than 1 and less than 100; in equation (6b), 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 with subscripts a”, b”, c”, and d” and enclosed in parentheses is arbitrary in the equation.

[0170] Furthermore, from other perspectives, fluorinated oils can be classified using the general formula Rf. 3 -F (where Rf) 3 Question C 5－16 Perfluoroalkyl. The compound shown is also indicated. Alternatively, it can be a trichlorofluoroethylene oligomer.

[0171] 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.

[0172] The fluorinated oil mentioned above can be, for example, 0-50% by mass, preferably 0-30% by mass, and more preferably 0-5% by mass relative to the surface treatment agent. 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.

[0173] In one approach, the number-average molecular weight of the fluorinated oil can be lower than that of the fluorinated silane compound. By setting such an average molecular weight, it is possible to suppress the reduction in transparency of the surface-treated layer obtained from such a compound and to form a hardened material with high wear resistance and high surface lubricity.

[0174] Fluorinated oils help improve the surface slip properties of the layer formed by the surface treatment agent of the present invention.

[0175] As the aforementioned silicone oil, for example, linear or cyclic silicone oils with siloxane bonds of 2000 or less can be used. Linear silicone oils can be so-called ordinary silicone oils and modified silicone oils. Examples of ordinary silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogenated silicone oil. Examples of modified silicone oils include silicone oils obtained by modifying ordinary silicone oils with alkyl, aryl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Cyclic silicone oils include, for example, cyclic dimethylsiloxane oil.

[0176] In the surface treatment agent of the present invention, the silicone oil comprises, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorinated silane compounds of the present invention (or the total of these when there are two or more, and so on below).

[0177] Silicone oil helps improve the surface lubrication of surface treatment layers.

[0178] 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 improves the stability of the surface treatment agent and enhances the compatibility of the fluorinated silane compound with the solvent.

[0179] In the surface treatment agent, the alcohol is preferably contained in a molar ratio of 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times that of the aforementioned metal compound. By keeping the proportion of alcohol within the above range, the stability of the surface treatment layer can be further improved.

[0180] 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.).

[0181] The catalyst promotes the hydrolysis and dehydration condensation of the fluorinated silane compounds of the present invention, and promotes the formation of the layer formed by the surface treatment agent of the present invention.

[0182] Other components, besides those mentioned above, may include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, methylacetoxysilane, etc.

[0183] The surface treatment agent of the present invention can be impregnated in porous materials, such as porous ceramic materials, or in materials in which metal fibers, such as steel wool, are solidified into cotton-like blocks to form granules. These granules are used, for example, in vacuum evaporation.

[0184] In addition to the components mentioned above, the surface treatment agent of the present invention may contain, for example, trace amounts of Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, silane condensates, etc.

[0185] (thing) The items of the present invention will now be described.

[0186] The articles of the present invention comprise a substrate and a layer (surface treatment layer) formed on the surface of the substrate by the composition of the present invention and / or a surface treatment agent. In one embodiment, the articles of the present invention comprise a substrate and a layer formed on the surface of the substrate by the composition of the present invention. In another embodiment, the articles of the present invention comprise a substrate and a layer formed on the surface of the substrate by a surface treatment agent of the present invention.

[0187] The substrates that can be used in this invention can be made of, for example, glass, resin (natural or synthetic resin, such as general plastic materials), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building materials, hygiene products, or any suitable material.

[0188] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Furthermore, if the article to be manufactured is an optical component, a layer (or film), such as a hard coating or an anti-reflective layer, can be formed on the surface of the substrate (outermost layer). The anti-reflective layer can be either a single-layer anti-reflective layer or a multi-layer anti-reflective layer. Examples of inorganic materials that can be used for anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, 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., forming a mixture). In the case of forming a multi-layer anti-reflective layer, it is preferable to use SiO2 and / or SiO in its outermost layer. When the item to be manufactured is an optical glass component for a touch panel, a transparent electrode can be formed on a portion of the substrate (glass) surface, for example, using a thin film such as indium tin oxide (ITO) or indium zinc oxide. Furthermore, depending on its specific specifications, the substrate may also include insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, retardation films, and liquid crystal display modules.

[0189] 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 specifications of the article to be manufactured.

[0190] In one approach, the substrate can be a material whose surface portion is formed from a material that inherently possesses hydroxyl groups. Examples of such materials include glass, as well as metals (especially base metals), ceramics, semiconductors, etc., on which a natural or thermal oxide film is formed. Alternatively, in cases where the substrate, such as resin, possesses hydroxyl groups but not sufficiently, or does not inherently possess hydroxyl groups, hydroxyl groups can be introduced or added to the substrate surface through a pretreatment. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can also be appropriately utilized to introduce or add hydroxyl groups to the substrate surface and to clean the substrate surface (removing foreign matter, etc.). Other examples of such pretreatments include methods such as forming a surface adsorbent with carbon-carbon unsaturated bond groups in the form of a monolayer on the substrate surface using the LB method (Langmuir-Blodgett method) and chemisorption, followed by breaking the unsaturated bonds in an atmosphere containing oxygen and nitrogen.

[0191] In another approach, such a substrate may also be a substrate whose surface portion is formed of an organosilicon compound containing one or more other reactive groups, such as Si-H groups, or a material containing alkoxysilanes.

[0192] In a preferred embodiment, the substrate is glass. Preferred types of glass include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass. Particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

[0193] By forming a layer of the compound or surface treatment agent of the present invention on the surface of the above-mentioned substrate, and performing post-treatment on the layer as needed, a layer is formed by the surface treatment agent of the present invention, thereby enabling the manufacture of articles of the present invention.

[0194] The formation of the surface treatment agent layer of the present invention can be achieved by applying the surface treatment agent to the surface of the substrate in a manner that covers the substrate surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[0195] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0196] 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.

[0197] Alternatively, atmospheric pressure plasma can also be used for coverage.

[0198] When using the wet coating method, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the composition of the present invention and the volatility of the solvent, the following solvents are preferred: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F...). 13 CH2CH3 (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. Hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0199] When using the dry coating method, the surface treatment agent of the present invention can be supplied directly to the dry coating method, or it can be supplied to the dry coating method after being diluted with the solvent described above.

[0200] The formation of the surface treatment agent layer is preferably carried out in such a manner that the surface treatment agent of the present invention coexists with a catalyst for hydrolysis and dehydration condensation in the layer. In short, 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 diluting it with a solvent, just before it is applied to the substrate surface. When using the dry coating method, the surface treatment agent of the present invention with the catalyst added can be directly subjected to vapor deposition (usually vacuum vapor deposition), or the surface treatment agent of the present invention with the catalyst added can be impregnated in a porous metal such as iron or copper to obtain granular material, and the obtained granular material can be subjected to vapor deposition (usually vacuum vapor deposition).

[0201] 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.

[0202] The surface treatment layer contained in the article of the present invention has both high abrasion durability and high wear resistance. In addition to high wear resistance, the surface treatment layer can also have water-repellent, oil-repellent, stain-resistant (e.g., preventing the adhesion of fingerprints and other stains), water-resistant (preventing water from penetrating electronic components, etc.), surface smoothness (or lubricity, such as the ability to wipe away fingerprints and other stains, and excellent finger feel), chemical resistance, etc., depending on the composition of the surface treatment agent used, and can be suitable for use as a functional film.

[0203] Therefore, the present invention also relates to optical materials having the above-described surface treatment layer on the outermost layer.

[0204] In addition to optical materials such as displays exemplified below, a variety of other optical materials can be preferred as optical materials, such as cathode ray tubes (CRTs; for example, computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), and protective plates for these displays, or materials obtained by treating the surfaces of these displays with anti-reflective coatings.

[0205] The items of this invention are not particularly limited and can be optical components. Examples of optical components include: lenses for eyeglasses, etc.; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; disc surfaces for Blu-ray (Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.); optical fibers; and the display surface of clocks, etc.

[0206] In addition, the articles of the present invention can also be medical devices or medical materials.

[0207] The thickness of the aforementioned layer is not particularly limited. In the case of an optical component, considering optical performance, surface smoothness, wear resistance, and stain resistance, the thickness of the aforementioned layer is preferably in the range of 1–50 nm, 1–30 nm, and more preferably 1–15 nm.

[0208] The articles of the present invention have been described in detail above. However, the articles and methods of manufacturing the articles of the present invention are not limited to the examples exemplified above.

[0209] Example The invention is illustrated in more detail by way of the following embodiments, but the invention is not limited to these 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.

[0210] (Synthesis example 1) In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, add CF3O (CF2CF2O) with an average composition. 26 (CF2O) 26 The mixture, consisting of 20 g of a perfluoropolyether-modified allyl oxide, 20 g of 1,3-bis(trifluoromethyl)benzene, and 1.36 g of trichlorosilane (wherein trace amounts of repeating units of (CF2CF2CF2O) and / or (CF2CF2CF2CF2O) are also present, but are disregarded due to their extremely small amounts), was stirred at 5°C for 30 minutes under a nitrogen atmosphere. Next, 0.094 mL of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated to 60°C and stirred at this temperature for 5 hours. After cooling the reaction mixture to room temperature, volatile components were removed by distillation under reduced pressure. The mixture was then dissolved in 5 g of 1,3-bis(trifluoromethyl)benzene, and 40 g of 1,3-bis(trifluoromethyl)benzene was flowed as the eluent after loading onto a short column packed with silica gel. The eluent was concentrated to obtain 8 g of an allyl body (B1) containing a perfluoropolyether group of the following formula with allyl groups at the ends.

[0211] • Allyl groups containing perfluoropolyether groups (B1): CF3O (CF2CF2O) 26 (CF2O) 26 CF2CH2O CH=CHCH3 (Synthesis example 2) In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, add the mixture with the average composition CF3CF2CF2O(CF2CF2CF2O). 20 20 g of a perfluoropolyether-modified allyl oxide (CF2CF2CH2OCH2CH=CH2), 20 g of 1,3-bis(trifluoromethyl)benzene, 0.06 g of triacetoxymethylsilane, and 1.36 g of trichlorosilane were stirred at 5°C for 30 minutes under a nitrogen atmosphere. Next, 0.094 mL of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated to 60°C and stirred at that temperature for 5 hours. Subsequently, volatile components were removed by distillation under reduced pressure, thereby yielding 19 g of a perfluoropolyether-containing silane compound (A1) with a trichlorosilane terminal.

[0212] • Silane compounds containing perfluoropolyether groups (A1): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2SiCl3 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 19 g of the above-mentioned trichlorosilane compound (A1) containing perfluoropolyether groups with trichlorosilane at the ends and 20 g of 1,3-bis(trifluoromethyl)benzene were added. The mixture was stirred at 5 °C for 30 minutes under a nitrogen atmosphere. Next, 26.4 mL of a diethyl ether solution containing 0.7 mol / L allyl magnesium bromide was added, and the mixture was heated to room temperature and stirred at that temperature for 10 hours. Afterward, the mixture was cooled to 5 °C, 5 mL of methanol was added, and the mixture was heated to room temperature. The insoluble residue was filtered off. Then, the volatile components were removed by distillation under reduced pressure, and the non-volatile components were diluted with perfluorohexane. The mixture was then washed three times with methanol using a separatory funnel (more specifically, the operation of maintaining the fluorinated compounds in the perfluorohexane phase (fluorine phase) and separating and removing the non-fluorinated compounds in the methanol phase (organic phase)). Next, by removing volatile components by distillation under reduced pressure, 20g of the following allyl body (A2) containing perfluoropolyether groups with allyl groups at the ends was obtained.

[0213] • Allyl groups containing perfluoropolyether groups (A2): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si(CH2CH=CH2)3 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 15 g of the allyl compound (A2) with terminal allyl groups containing perfluoropolyether groups, 15 g of 1,3-bis(trifluoromethyl)benzene, 0.05 g of triacetoxymethylsilane, and 3.15 g of trichlorosilane were added. The mixture was stirred at 5 °C for 30 minutes under a nitrogen atmosphere. Next, 0.141 mL of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated to 60 °C and stirred at this temperature for 5 hours. Subsequently, volatile components were removed by distillation under reduced pressure, thereby yielding 16 g of the following trichlorosilane compound (A3) with terminal trichlorosilane groups containing perfluoropolyether groups.

[0214] • Trichlorosilane compounds containing perfluoropolyether groups (A3): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si(CH2CH2CH2SiCl3)3 In a 100 mL four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 16 g of the above-mentioned trichlorosilane compound (A3) containing a perfluoropolyether group with a trichlorosilane terminal and 15 g of 1,3-bis(trifluoromethyl)benzene were added, and the mixture was stirred at 50 °C for 30 minutes under a nitrogen atmosphere. Next, a mixed solution of 0.78 g of methanol and 36 g of trimethyl orthoformate was added, and the temperature was raised to 65 °C and stirred at this temperature for 3 hours. Subsequently, volatile components were removed by distillation under reduced pressure to obtain 17 g of the following perfluoropolyether silane compound (A4) containing a trimethylsilyl terminal.

[0215] • Silane compounds containing perfluoropolyether groups (A4): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (Examples 1-6 and Comparative Example 1) A composition was prepared by mixing compound (B1) obtained in Synthesis Example 1 and compound (A4) obtained in Synthesis Example 2 in such a manner that the proportion of compound (B1) was as shown in Table 1. In this composition, the proportion (mol%) of compound (B1) corresponds to R. B1 Relative to R Si and R B1 The total percentage.

[0216] The above composition was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE7200) to make its concentration (the total concentration of compounds (B1) and (A4)) 20% by mass, to prepare a surface treatment agent.

[0217] The surface treatment agent prepared above was vacuum-deposited onto chemically strengthened glass (Corning, "Gorilla" glass, 0.7 mm thick). The vacuum deposition conditions were set to a pressure of 3.0 × 10⁻⁶. －3 First, silicon dioxide is deposited onto the surface of the chemically strengthened glass at a thickness of 7 nm using electron beam evaporation to form a silicon dioxide film. Next, 2 mg of a surface treatment agent (i.e., a total of 0.4 mg containing compounds (B1 and A4)) is deposited onto each piece of chemically strengthened glass (55 mm × 100 mm). Afterward, the chemically strengthened glass with the deposited film is left to stand for 24 hours at 20°C and 65% humidity. This allows the deposited film to solidify, forming a surface treatment layer.

[0218] For the surface treatment layer formed on the substrate surface in the above embodiments and comparative examples, the static contact angle of water was measured. The static contact angle of water was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) and 1 μL of water.

[0219] First, as an initial evaluation, the static contact angle of water (0 friction cycles) was measured after the surface treatment layer was formed, without any contact with its surface. Next, as an evaluation of abrasion durability, a steel wool abrasion durability evaluation was conducted. Specifically, the substrate with the surface treatment layer was horizontally positioned, and steel wool (particle size #0000, dimensions 5mm × 10mm × 10mm) was placed in contact with the exposed upper surface of the surface treatment layer, and a load of 1000gf was applied. Then, under the applied load, the steel wool was moved back and forth at a speed of 140mm / s. The static contact angle of water (in degrees) was measured every 1000 reciprocations, and the maximum number of reciprocations at which the contact angle was maintained at 100 degrees was used as the indicator of abrasion durability.

[0220] The results are shown in Tables 1 and 2.

[0221] [Table 1] [Table 2] Examples 1 to 6 are embodiments of the present invention, confirming that the films obtained from these compositions have good abrasion resistance.

[0222] Comparative Example 1 is an example without compound (B). It has a good initial water contact angle, but its abrasion resistance is not as good as Examples 1-6.

[0223] Industrial availability The article of the present invention can be suitably used in a variety of applications, such as as an optical component of a touch panel.

Claims

1. A composition, characterized in that, Include: Silane compounds (A) having fluorinated polyether groups, and Compound (B) having fluorinated polyether groups and allyl ether groups. The compound (B) includes at least one compound represented by formula (3), (4) or (5): R F1 α -X A -[AR B1 δ R B2 3－δ ] β (3) [R B1 δ R B2 3－δ A] γ -X A -R F2 -X A -[AR B1 δ R B2 3－δ ] γ (4) R Si γ -X A -R F2 -X A -[AR B1 δ R B2 3－δ ] γ (5) In the formula: A can be either a C atom or a Si atom, respectively. R F1 Rf, independently 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R B1 -R B3 -O-CH=CH-CH3; R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the following: hydrogen atoms; R B3 Each independently is a single bond or C 1－20 Alkylene; R B4 Each can be an independent hydroxyl group or a hydrolyzable group; R B5 Each can be an organic group that is independently a hydrogen atom or a monovalent organic group; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In equation (5), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; 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; δ can be an integer from 1 to 3, respectively. ε can be an independent integer from 1 to 3. Among them, silane compound (A) is different from compound (B).

2. The composition according to claim 1, characterized in that: The silane compound (A) having a fluorinated polyether group includes at least one compound represented by formula (1) or (2): In the formula: R F1 Rf, independently 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In either equation (1) or equation (2), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; In either equation (1) or equation (2), R Si It does not contain allyl ether groups; 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 can be an integer from 1 to 9, each independently.

3. The composition according to claim 1 or 2, characterized in that: Relative to the R contained in the composition Si and R B1 The total amount of R contained in the composition B1 The proportion is less than 25 mol%.

4. The composition according to any one of claims 1 to 3, characterized in that: The silane compound (A) includes the compound shown in formula (1a): R F1 -X A -R Si (1a) In formula (1a): R F1 Rf, independently 1 -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; R F Each is independently a divalent fluorinated polyether group; q can be 0 or 1 independently; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; In equation (1), at least one R Si It is a monovalent group containing Si atoms bonded with hydroxyl or hydrolyzable groups; In equation (1), R Si It does not contain allyl ether groups; X A Each is an independent single bond or an organic group with a valence of 2 to 10. In equation (1a), X A For a single bond or the following formula - (R 51 ) p5 - (X) 51 ) q5 - The group shown, Formula - (R) 51 ) p5 - (X) 51 ) q5 -middle: R 51 Indicates a single bond, -(CH2). s5 - or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -, 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. X 51 Represents - (X) 52 ) l5 -, X 52 Each of the following can be independently represented by a combination of -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, R 53 Represent phenyl and C independently, respectively. 1－6 Alkyl or C 1－6 Alkoxy, preferably phenyl or C 1－6 Alkyl, more preferably methyl, R 54 Each can be independently represented by a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably methyl), m5 can be an integer from 1 to 100, preferably an integer from 1 to 20. n5 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3. l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3. p5 is either 0 or 1. q5 is either 0 or 1. In this case, at least one of p5 and q5 is 1, and the order of the repeating units with p5 or q5 enclosed in parentheses is arbitrary. R Si The group is represented by the following formula (S3). -Sir a1 k1 R b1 l1 R c1 m1 (S3) In formula (S3), R a1 Represent -Z independently. 1 -SiR 22 q1 R 23 r1 ; Z 1 Each of these can be used independently to represent an oxygen atom or a divalent organic group, hereinafter referred to as Z. 1 The right side of the recorded structure and (SiR) 22 q1 R 23 r1 ) bonding; R 22 Each can be used independently to represent a hydroxyl group or a hydrolyzable group; R 23 Each can independently represent a hydrogen atom or a monovalent organic group; q1 in each (SiR) 22 q1 R 23 r1 Each unit is an independent integer from 1 to 3; R b1 Each can be used independently to represent a hydroxyl group or a hydrolyzable group; R c1 Each can independently represent a hydrogen atom or a monovalent organic group; k1 is an independent integer from 0 to 3, l1 is an independent integer from 0 to 3, m1 is an independent integer from 0 to 3, and the sum of k1, l1, and m1 is within (SiR). a1 k1 R b1 l1 R c1 m1 The value in unit ) is 3. The compound (B) includes the compound shown in formula (3): R F1 α -X A -[AR B1 δ R B2 3－δ ] β (3) In the formula: A can be either a C atom or a Si atom, respectively. R F1 Rf, independently 1 -R F -O q -; Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl; R F Each is independently a divalent fluorinated polyether group; q can be 0 or 1 independently; R B1 -R B3 -O-CH=CH-CH3; R B2 Each independently selected from -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3－ε And one or more of the following: hydrogen atoms; R B3 Each independently is a single bond or C 1－20 Alkylene; R B4 Each can be an independent hydroxyl group or a hydrolyzable group; R B5 Each can be an organic group that is independently a hydrogen atom or a monovalent organic group; R Si Each of these is a monovalent group, independently comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic 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.

5. A surface treatment agent, characterized in that: The composition comprising any one of claims 1 to 4.

6. The surface treatment agent as described in claim 5, characterized in that: It also contains one or more ingredients selected from fluorinated oils and silicone oils.

7. The surface treatment agent as described in claim 5 or 6, characterized in that: Used as a stain-resistant or waterproof coating.

8. An article characterized by: It includes a substrate and a layer formed on the surface of the substrate by the composition of any one of claims 1 to 4.

9. An article characterized by: It includes a substrate and a layer formed on the surface of the substrate by any one of claims 5 to 7.

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