Surface treatment agents

Abstract

To provide a surface treatment agent capable of realizing a film having good abrasion resistance.SOLUTION: There is provided a composition which comprises a silane compound (A) having a fluoropolyether group and a compound (B) having a fluoropolyether group and an allyl ether group. The silane compound (A) having a fluoropolyether group may be a compound having a fluoropolyether group and a hydrolyzable silyl group and preferably containing no allyl ether group and the compound (B) having a fluoropolyether group and an allyl ether group is not particularly limited but may have an average molecular weight of 5×102 to 1×105. Among such a range, the compound (B) has an average molecular weight of 2000 to 32000, more preferably 2500 to 12000 from the viewpoint of abrasion resistance.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a surface treatment agent. [Background technology]

[0002] It is known that certain fluoropolyether group-containing silane compounds, when used for surface treatment of substrates, can provide excellent water repellency, oil repellency, antifouling properties, etc. Layers obtained from surface treatment agents containing fluoropolyether group-containing silane compounds (hereinafter also referred to as "surface treatment layers") are applied as so-called functional thin films to a wide variety of substrates, such as glass, plastics, textiles, sanitary products, and building materials (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-218639 Summary of the Invention [Problem to be solved by the invention]

[0004] The fluoropolyether group-containing silane compound described in Patent Document 1 can provide a surface treatment layer with excellent functionality, but there is a demand for a surface treatment layer with higher durability.

[0005] An object of the present disclosure is to provide a surface treatment agent that can realize a film with good abrasion resistance. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. [1] a silane compound (A) having a fluoropolyether group; Fluoropolyether groups and -O-CH=CH-CH 3 (Hereinafter, in this specification, an "allyl ether group" refers to -O-CH=CH-CH 3 (meaning Compound (B) having the formula and, The compound (B) is represented by the following 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 formula: Each A is independently a C atom or a Si atom; R F1 are each independently Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R B1 -R B3 -O-CH=CH-CH3; R B2 are each independently -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3-ε and hydrogen atoms; R B3 are each independently a single bond or C 1-20 is an alkylene group; R B4 are each independently a hydroxyl group or a hydrolyzable group; R B5 are each independently a hydrogen atom or a monovalent organic group; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In formula (5), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer from 1 to 9; Each δ is independently an integer of 1 to 3. Each ε is independently an integer of 1 to 3. A composition comprising at least one compound represented by the formula (provided that compound (A) and compound (B) are different). [2] The silane compound (A) having a fluoropolyether group is represented by the formula (1) or (2): [ka] [In formula: R F1 are each independently Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In each of formula (1) or formula (2), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; In each of formula (1) and formula (2), R Si teeth, -O-CH=CH-CH excluding 3; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer of 1 to 9. The composition according to [1], comprising at least one compound represented by the formula: [3] R contained in the composition Si and R B1 R contained in the composition relative to the total B1The composition according to [1] or [2], wherein the proportion of [4] The silane compound (A) is represented by the formula (1a): R F1 -X A -R Si (1a) [In formula: R F1 are each independently Rf 1 -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; R F are each independently a divalent fluoropolyether group; Each q is independently 0 or 1; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In formula (1), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; In formula (1), R Si teeth, -O-CH=CH-CH excluding 3; X A are each independently a single bond or a divalent to decavalent organic group. In X A is a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 is a single bond, -(CH2) s5 - or an o-, m- or p-phenylene group, preferably -(CH2) s5 - and s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X 51 is -(X 52 ) l5 - represents X 52 are each independently -O-, -S-, o-, m- or p-phenylene group, -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 represents a group selected from the group consisting of - R 53 are each independently a phenyl group, C 1-6 Alkyl group or C 1-6 represents an alkoxy group, preferably a phenyl group or C 1-6 is an alkyl group, more preferably a methyl group; R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group (preferably a methyl group), m5 is independently an integer of 1 to 100, preferably an integer of 1 to 20, n5 is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1; q5 is 0 or 1, Here, at least one of p5 and q5 is 1, and the repeating units enclosed in parentheses with p5 or q5 may be present in any order.] is a group represented by R Si However, the following equation (S3): -SiR a1 k1 R b1 l1 R c1 m1 (S3) [In the formula, R a1 are each independently -Z 1 -SiR 22 q1 R 23 r1 represents; Z 1 each independently represents an oxygen atom or a divalent organic group, and Z 1 The structure written as 22 q1 R 23 r1 ) and bind to it; R 22 each independently represents a hydroxyl group or a hydrolyzable group; R 23 each independently represents a hydrogen atom or a monovalent organic group; q1 is (SiR 22 q1 R 23 r1 ) units are each independently an integer from 1 to 3; R b1 each independently represents a hydroxyl group or a hydrolyzable group; R c1 each independently represents a hydrogen atom or a monovalent organic group; Each k1 is independently an integer of 0 to 3, each l1 is independently an integer of 0 to 3, and each m1 is independently an integer of 0 to 3, and the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, the value is 3. The compound (B) is represented by the formula (3): R F1 α -X A -[AR B1 δ R B2 3-δ ] β (3) [In formula: Each A is independently a C atom or a Si atom; R F1 are each independently Rf 1 -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; R F are each independently a divalent fluoropolyether group; Each q is independently 0 or 1; R B1 -R B3 -O-CH=CH-CH3; R B2 are each independently -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3-ε and hydrogen atoms; R B3 are each independently a single bond or C 1-20 is an alkylene group; R B4 are each independently a hydroxyl group or a hydrolyzable group; R B5 are each independently a hydrogen atom or a monovalent organic group; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer of 1 to 9. The composition according to any one of [1] to [3], which contains a compound represented by the following formula: [5] A surface treatment agent comprising the composition according to any one of [1] to [4]. [6] The surface treatment agent according to [5], further comprising one or more components selected from fluorine-containing oils and silicone oils. [7] The surface treatment agent according to [5] or [6], which is used as an antifouling coating agent or a waterproof coating agent. [8] An article comprising a substrate and a layer formed on the surface of the substrate from the composition according to any one of [1] to [4]. [9] An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent according to any one of [5] to [7]. [Effects of the Invention]

[0007] According to the present invention, a surface treatment agent capable of realizing a film with good abrasion resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] The composition of the present disclosure includes a silane compound (A) having a fluoropolyether group and a compound (B) having a fluoropolyether group and an allyl ether group. Because the composition of the present disclosure includes the compound (A) and the compound (B), it can realize a film with good abrasion resistance. However, the compound (A) and the compound (B) are different.

[0009] The use of silane compound (A) can provide a film with good abrasion resistance, particularly abrasion resistance against steel wool. According to the study by the present inventors, it has been found that by using compound (B) in addition to compound (A), a film can be obtained that not only has good abrasion resistance against steel wool, but also has good abrasion resistance against softer materials, such as resin-based materials such as erasers. Although the present disclosure should not be interpreted as being limited to a particular theory, compound (B) has a vinyl ether group at its terminal, and it is believed that this group can exert the effect of suppressing damage to the film when friction occurs with a soft material.

[0010] (Fluoropolyether group-containing silane compound (A)) The silane compound (A) having a fluoropolyether group may be a compound having a fluoropolyether group and a hydrolyzable silyl group, and preferably does not contain an allyl ether group. In a preferred embodiment, the compound (A) is represented by the following formula (1) or (2): [ka] [In formula: R F1 are each independently Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In each of formula (1) or formula (2), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; In each of formula (1) and formula (2), R Si does not contain an allyl ether group; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer of 1 to 9. It is preferable that the composition contains at least one compound represented by the following formula:

[0011] In the above formula (1), R F1 are each independently Rf 1 -R F -O q -It is.

[0012] In the above formula (2), R F2 is -Rf 2 p -R F -O q -It is.

[0013] In the above formula, Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 It is an alkyl group.

[0014] C optionally substituted with one or more fluorine atoms 1-16 "C" in alkyl group 1-16 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 Alkyl groups, especially straight or branched C 1-3 alkyl group, more preferably a straight-chain C1-6 Alkyl groups, especially straight-chain C 1-3 It is an alkyl group.

[0015] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0016] Above C 1-16 The perfluoroalkyl group may be a straight or branched chain, and is preferably a straight or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically, -CF3, -CF2CF3, or -CF2CF2CF3.

[0017] In the above formula, Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group.

[0018] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0019] Above Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0020] Above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0021] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0022] In the above formula, each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0023] In the above formulas (1) and (2), R F are each independently a divalent fluoropolyether group.

[0024] R F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or greater.] It is a group represented by the formula (hereinafter also referred to as a group represented by "PFPE").

[0025] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or greater.

[0026] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0027] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 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, and may be, for example, 50 or less or 30 or less.

[0028] These repeating units may be linear or branched, and may contain a ring structure. For example, -(OCF 12 )- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10)- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCFCFCF)-, -(OCF(CF)CF)-, and -(OCFCF(CF))-. -(OCF)- may be any of -(OCFCF)- and -(OCF(CF))-.

[0029] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [ka] [In the formula, * indicates the bonding position.]

[0030] The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0031] The repeating unit having a ring structure may preferably be the following unit. [ka] [In the formula, * indicates the bonding position.]

[0032] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the film (surface treatment layer) can be improved.

[0033] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the film (surface treatment layer) can be increased.

[0034] In one embodiment, R F are each independently a group represented by any one of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 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 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, preferably a fluorine atom; c and d are each independently an integer of 0 or more and 30 or less; e and f are each independently an integer of 1 or more and 200 or less; the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.]; -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination 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’ -R6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 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 teeth, [ka] (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 of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f 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 of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0035] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer of 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0036] In the formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the formula (f2) is preferably -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -, more preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f In yet another embodiment, the formula (f2) may be a group represented by -(OC4F8) c -(OCF2CF2(CR Fa)2) d10 -(OCF2CF(CF3)) d11 -(OCF2CF2) e -(OCF2) f d10 and d11 each independently represent an integer of 0 to 200, preferably an integer of 5 to 200, more preferably an integer of 10 to 200. However, the sum of d10 and d11 is 0 to 200, preferably 5 to 200, more preferably 10 to 200.

[0037] In the above formula (f3), R 6 is preferably OC2F4, and in another embodiment, OCF2. In (f3) above, R 7 is preferably a group 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. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g-or-(OC2F4-OC4F8) g -It is.

[0038] In the above formula (f4), R 6 , R 7 and g have the same meanings as those in the formula (f3) above, and have the same embodiments. 6’ , R 7’ and g' are R 6 , R 7 and g have the same meaning and similar aspects. r is preferably [ka] [In the formula, * indicates the bonding position.] and more preferably [ka] [In the formula, * indicates the bonding position.] is.

[0039] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0040] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0041] In one embodiment, the R F is a group represented by the above formula (f1).

[0042] In one embodiment, the R F is a group represented by the above formula (f2).

[0043] In one embodiment, the RF is a group represented by the above formula (f3).

[0044] In one embodiment, the R F is a group represented by the above formula (f4).

[0045] In one embodiment, the R F is a group represented by the above formula (f5).

[0046] Above R F In the formula, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, 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 more improved the slipperiness and abrasion resistance of the film. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The higher the e / f ratio, the more improved the stability of the compound.

[0047] In the above fluoropolyether group-containing silane compound, R F1 and R F2 The number average molecular weight of the R moiety 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. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0048] In another embodiment, R F1 and R F2 The number average molecular weight of the moiety may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example from 3,000 to 6,000.

[0049] In another embodiment, R F1 and R F2 The number average molecular weight of the moiety can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.

[0050] In the above formulas (1) and (2), R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom bonded to a monovalent organic group, and at least one R Si R is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. Si contributes to adhesion to the substrate and may chemically react with the material of the substrate.

[0051] In a preferred embodiment, R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0052] In a preferred embodiment, R Si is expressed by the following formula (S3) or (S4): [ka] It is a group represented by the following formula:

[0053] In the above formula, R a1 are each independently -Z 1 -SiR 22 q1 R 23 r1 is.

[0054] Above Z 1 are each independently an oxygen atom or a divalent organic group. 1 The structure written as 22 q1 R 23 r1 )

[0055] In a preferred embodiment, Z 1 is a divalent organic group.

[0056] In a preferred embodiment, Z 1 is Z 1 Preferably, in formula (S3), (Si-Z) does not include a compound that forms a siloxane bond with the Si atom to which (Si-Z) is bonded. 1 —Si) does not contain a siloxane bond.

[0057] Above Z 1 is preferably C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted with one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0058] In a preferred embodiment, Z 1 is C 1-6 Alkylene group or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -It is. Z 1 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0059] In another preferred embodiment, the Z 1 is C 1-3 In one embodiment, Z is an alkylene group. 1 can be -CH2CH2CH2-. In another embodiment, Z 1can be -CH2CH2-.

[0060] Above R 22 are each independently a hydroxyl group or a hydrolyzable group.

[0061] R 22 are preferably each independently a hydrolyzable group.

[0062] R 22 are preferably each independently -OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j , —NCO, or halogen (wherein R j is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). j Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0063] Above R 23 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0064] R 23 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0065] Each of the above q1's is independently an integer of 0 to 3, and each of the r1's is independently an integer of 0 to 3. The sum of q1 and r1 is (SiR 22 q1 R 23 r1 ) units, it is 3.

[0066] In one embodiment, q1 is (SiR 22 q1 R 23 r1 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0067] In one embodiment, q1 is (SiR 22 q1 R 23 r1 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0068] In the above formula, R b1 are each independently a hydroxyl group or a hydrolyzable group.

[0069] Above R b1 are preferably each independently a hydrolyzable group.

[0070] Above R b1 are preferably each independently -OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j , —NCO, or halogen (wherein R j is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). jExamples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0071] In the above formula, R c1 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0072] Above R c1 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0073] The above k1s are each independently an integer of 0 to 3, the l1s are each independently an integer of 0 to 3, and the m1s are each independently an integer of 0 to 3. The sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, it is 3.

[0074] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0075] In the above formulas (1) and (2), R SiWhen is a group represented by formula (S3), preferably, at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups are present in the terminal portions of formula (1) and formula (2).

[0076] In a preferred embodiment, in formula (S3), R a1 When present, at least one, preferably all, R a1 In the formula, q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0077] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, and q1 is 2 or 3, preferably 3.

[0078] Above R e1 are each independently -Z 3 -SiR 34 n2 R 35 3-n2 is.

[0079] Above Z 3 are each independently a single bond, an oxygen atom, or a divalent organic group. 3 The structure written as 34 n2 R 35 3-n2 )

[0080] In one embodiment, Z 3 is an oxygen atom.

[0081] In one embodiment, Z 3 is a divalent organic group.

[0082] Above Z 3 is preferably C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z7”-phenylene-(CH2) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted with one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0083] In a preferred embodiment, Z 3 is C 1-6 Alkylene group or -(CH2) z7” -phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -It is. Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0084] In another preferred embodiment, the Z 3 is C 1-3 In one embodiment, Z is an alkylene group. 3 can be -CH2CH2CH2-. In another embodiment, Z 3 can be -CH2CH2-.

[0085] Above R 34 are each independently a hydroxyl group or a hydrolyzable group.

[0086] R 34 are preferably each independently a hydrolyzable group.

[0087] R 34 are preferably each independently -OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j , —NCO, or halogen (wherein Rj is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). j Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R j is a methyl group, and in another embodiment, R j is an ethyl group.

[0088] Above R 35 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0089] Above R 35 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0090] In the above formula, n2 is (SiR 34 n2 R 35 3-n2 ) units are each independently an integer of 0 to 3, provided that R Si is a group represented by formula (S4), n2 is 1 to 3 in the terminal portion of formula (1) and formula (2) (SiR 34 n2 R 35 3-n2 ) unit is present. That is, in such a terminal portion, all n2s do not simultaneously become 0. In other words, in the terminal portion of formula (1) and formula (2), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0091] n2 is (SiR 34 n2 R 353-n2 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0092] Above R f1 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0093] Above R f1 In the formula, the monovalent organic group is preferably C 1-20 Alkyl group or -(C s H 2s ) t1 -(OC s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4; t1 is 1 or 0, preferably 0; and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), and more preferably C 1-20 alkyl group, more preferably C 1-6 An alkyl group, particularly preferably a methyl group.

[0094] In one embodiment, R f1 is a hydroxyl group.

[0095] In another embodiment, R f1 is a monovalent organic group, preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.

[0096] In the above formulas (1) and (2), R Si When is a group represented by formula (S4), preferably, at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups are present in the terminal portions of formula (1) and formula (2).

[0097] In one embodiment, R Si is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34n2 R 35 3-n2 ) units are present at each terminal portion of formula (1) and formula (2) by two or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.

[0098] In a preferred embodiment, in formula (S4), R e1 When present, at least one, preferably all, R e1 In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0099] In a preferred embodiment, in formula (S4), l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0100] In one embodiment, R Si is a group represented by formula (S3) or (S4). These compounds can have multiple hydrolyzable groups branched from one Si atom or C atom at one end, and can therefore form a film with even higher abrasion resistance.

[0101] In one embodiment, R Si is a group represented by formula (S3).

[0102] In one embodiment, R Si is a group represented by formula (S4).

[0103] X A may each independently be a single bond or a divalent to decavalent organic group.

[0104] Above X A The divalent to decavalent organic group in the formula (I) is preferably a divalent to octavalent organic group. In one embodiment, the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another embodiment, the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.

[0105] In one embodiment, X A is a single bond or a divalent organic group, α is 1, and β is 1.

[0106] In one embodiment, X A is a single bond or a divalent organic group, and γ is 1.

[0107] In one embodiment, X A is a trivalent to hexavalent organic group, α is 1, and β is 2 to 5.

[0108] In one embodiment, X A is a trivalent to hexavalent organic group, and γ is 2 to 5.

[0109] In one embodiment, X A is a trivalent organic group, α is 1, and β is 2.

[0110] In one embodiment, X A is a trivalent organic group and γ is 2.

[0111] X A When is a single bond or a divalent organic group, formulas (1) and (2) are represented by the following formulas (1a) and (2a). [ka]

[0112] In each of formula (1a) or formula (2a), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. Si does not contain an allyl ether group.

[0113] In one embodiment, X A is a single bond.

[0114] In another embodiment, X A is a divalent organic group.

[0115] In one embodiment, X A Examples of the group include a single bond and the group represented by the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In formula: R 51 is a single bond, -(CH2) s5 - or an o-, m- or p-phenylene group, preferably -(CH2) s5 - and s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X 51 is -(X 52 ) l5 - represents X 52 are each independently -O-, -S-, o-, m- or p-phenylene group, -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 represents a group selected from the group consisting of - R 53 are each independently a phenyl group, C 1-6 Alkyl group or C 1-6 represents an alkoxy group, preferably a phenyl group or C 1-6 is an alkyl group, more preferably a methyl group; R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group (preferably a methyl group), m5 is independently an integer of 1 to 100, preferably an integer of 1 to 20, n5 is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1; q5 is 0 or 1, Here, at least one of p5 and q5 is 1, and the repeating units enclosed in parentheses with p5 or q5 may be present in any order.] Here, X is a divalent organic group represented by the formula: A (Typically X A hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, X A is not substituted with these groups.

[0116] In a preferred embodiment, the X A are each independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -R 52 is a single bond, -(CH2) t5 - or an o-, m- or p-phenylene group, preferably -(CH2) t5 t5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 52 (typically R 52 hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, R 56 is not substituted with these groups.

[0117] Preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -R 51 -X53 -R 52 -or -X 54 -R 52 - [In the formula, R 51 and R 52 has the same meaning as above, X 53 teeth, -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-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 and m5 have the same meaning as above, u5 represents an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 3; X 54 teeth, -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-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as above.) represents.] It could be.

[0118] More preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -(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 meanings as above.] is.

[0119] More preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -or -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It could be.

[0120] In a preferred embodiment, the X A are each independently Single bond C 1-20 an alkylene group, -(CH2) s5 -X 53 -or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 - or -O-CONR 54 - and R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.

[0121] In a preferred embodiment, the X A are each independently -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [In the formula, R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.

[0122] In one embodiment, the X A are each independently single bond, C 1-20 an alkylene group, -(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 are as defined above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.] is.

[0123] In the above formula, -(C v H 2v )- can be straight or branched chain, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0124] Above X A are each independently a fluorine atom, C 1-3 Alkyl groups and C 1-3 Fluoroalkyl groups (preferably C1-3 In one embodiment, X may be substituted with one or more substituents selected from the group consisting of fluoroalkyl groups, perfluoroalkyl groups, and the like. A is non-substituted.

[0125] Furthermore, the above X A The left side of each equation is R F1 or R F2 and the right side is R Si Combine with.

[0126] In one embodiment, X A are each independently -OC 1-6 It may be other than an alkylene group.

[0127] In another embodiment, X A Examples of the group include the following: [ka] [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, or C 1-6 Alkyl group or C 1-6 an alkoxy group, preferably a methyl group; D is -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- (wherein Ph means phenyl), and [ka] (In the formula, R 42 are each independently a hydrogen atom, C 1-6or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. is a group selected from E is -(CH2) n - (n is an integer from 2 to 6), D is the R of the molecular main chain F1 or R F2 E is bonded to R Si Binds to.]

[0128] Above X A Specific examples include: 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)-CH- (wherein Ph means phenyl), -CON(Ph)-(CH)- (wherein Ph means phenyl), -CON(Ph)-(CH2)3- (wherein Ph means phenyl), -CON(Ph)-(CH2)4- (wherein Ph means phenyl), -CON(Ph)-(CH2)5- (wherein Ph means phenyl), -CON(Ph)-(CH2)6- (wherein Ph means 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-, [ka] Examples include:

[0129] In yet another embodiment, X A are each independently a group of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 In the formula, x1, y1, and z1 each independently represent an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.

[0130] In the above formula, R 16 each independently represents an oxygen atom, phenylene, carbazolylene, or -NR 18-(In the formula, R 18 represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, R 18 is an oxygen atom or a divalent polar group.

[0131] The "divalent polar group" is not particularly limited, but examples thereof include -C(O)-, -C(=NR 19 )- and -C(O)NR 19 -(wherein R 19 represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" includes, for example, C 1-6 Alkyl groups, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

[0132] In the above formula, R 17 are each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" can be, for example, C 1-6 , preferably C 1-3 Fluoroalkyl groups, preferably C 1-3 A perfluoroalkyl group is more preferred, a trifluoromethyl group or a pentafluoroethyl group is more preferred, and a trifluoromethyl group is even more preferred.

[0133] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, or C 1-6 Alkyl group or C 1-6 The alkoxy group is preferably a methyl group; each X A In the group, any number of T's may be R's in the molecular main chain. F1 or R F2 The following groups are attached to: -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- (wherein Ph means phenyl), or [ka] [In the formula, R 42 are each independently a hydrogen atom, C 1-6 or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.] and some of the other Ts are Rs in the molecular backbone. Si and if present, the remaining Ts are each independently a methyl group, a phenyl group, or a C 1-6 It is an alkoxy group, a radical scavenger group, or an ultraviolet absorbing group.

[0134] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, and triazines.

[0135] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0136] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include groups represented by the following formulas: [ka]

[0137] In this embodiment, X A may each independently be a trivalent to decavalent organic group.

[0138] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 25 , R 26 and R 27 are each independently a divalent to hexavalent organic group, R 25 is at least one R F1 Binds to R 26 and R 27 Each has at least one R Si Binds to.]

[0139] In one embodiment, the R 25 is a single bond, C 1-20 Alkylene group, C 3-20 Cycloalkylene group, C 5-20 Arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 - or -R 57 -X 58 -. Above, R 57 and R 59 are each independently a single bond, C 1-20 Alkylene group, C 3-20 cycloalkylene group, or C 5-20 The above X is an arylene group. 58 is —O—, —S—, —CO—, —O—CO— or —COO—.

[0140] In one embodiment, the R 26 and R 27are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the main chain of the hydrocarbon, and preferably C 1-6 Alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. Here, R 36 are each independently a single bond or C 1-6 Alkyl groups, preferably C 1-6 is an alkyl group. 37 is N, O or S, preferably N or O. 38 -R 45 -R 46 -R 45 -, -R 46 -R 45 -or-R 45 -R 46 -. Here, R 45 are each independently 1-6 is an alkyl group. 46 is N, O or S, preferably O.

[0141] The compound is not particularly limited, but may be 5×10 2 ~1×10 5 In particular, it is preferable that the average molecular weight is 2,000 to 30,000, and more preferably 2,500 to 12,000, from the viewpoint of UV resistance and abrasion durability. In the present disclosure, "average molecular weight" refers to a number average molecular weight, and "average molecular weight" is 19 The value is measured by F-NMR.

[0142] In one embodiment, compound (A) may be preferably a compound represented by formula (1), more preferably a compound represented by formula (1a), and even more preferably a compound represented by formula (1b); in another embodiment, compound (A) may be preferably a compound represented by formula (2), more preferably a compound represented by formula (2a), and even more preferably a compound represented by formula (2b).

[0143] The fluoropolyether group-containing silane compound represented by the formula (1) or (2) is not particularly limited, but may be 5×10 2 ~1×10 5 Within this range, it is preferable from the viewpoint of abrasion resistance that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000. Note that the "average molecular weight" refers to a number average molecular weight, and the "average molecular weight" is 19 The value is measured by F-NMR.

[0144] The total content of the compounds represented by formula (1) or formula (2) in compound (A) may be 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.

[0145] (Compound (B) Having a Fluoropolyether Group and an Allyl Ether Group) The compound (B) having a fluoropolyether group and an allyl ether group has a fluoropolyether group and an allyl ether group, and in a preferred embodiment, is represented by the following 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 -[ARB1 δ R B2 3-δ ] γ (5) and a compound (B) represented by the formula: [In formula: Each A is independently a C atom or a Si atom; R F1 are each independently Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 each independently represents a C optionally substituted by one or more fluorine atoms; 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluoropolyether group; p is 0 or 1; Each q is independently 0 or 1; R B1 -R B3 -O-CH=CH-CH3; R B2 are each independently -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3-ε and hydrogen atoms; R B3 are each independently a single bond or C 1-20 is an alkylene group; R B4 are each independently a hydroxyl group or a hydrolyzable group; R B5 are each independently a hydrogen atom or a monovalent organic group; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group is bonded; In formula (5), at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X A are each independently a single bond or a divalent to decavalent organic group; α is an integer from 1 to 9; β is an integer from 1 to 9; Each γ is independently an integer from 1 to 9; Each δ is independently an integer of 1 to 3; Each ε is independently an integer of 1 to 3. The compound contains at least one compound represented by the formula:

[0146] By including the above compound, a film with good abrasion resistance can be realized.

[0147] In the above formulas (3), (4) and (5), R F1 , R F2 , R Si , X A , α, β and γ have the same meanings as above.

[0148] Each A is independently a C atom or a Si atom. In one embodiment, A is a C atom. In another embodiment, A is a Si atom. A is preferably a Si atom.

[0149] R B1 are each independently -R B3 -O-CH=CH-CH3.

[0150] R B2 are each independently -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3-εand hydrogen atoms. B2 -R B3 -O-CH2CH2CH2-SiR B4 ε R B5 3-ε In another embodiment, R B2 can be a hydrogen atom.

[0151] Above R B3 are each independently a single bond or C 1-20 In one embodiment, R B3 is preferably a single bond. B3 is preferably C 1-20 Alkylene groups, more preferably C 1-6 It may be an alkylene group.

[0152] R B4 are each independently a hydroxyl group or a hydrolyzable group.

[0153] R B4 are preferably each independently a hydrolyzable group.

[0154] R B4 are preferably each independently -OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j , —NCO, or halogen (wherein R j is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR j (i.e., an alkoxy group). j Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R jis a methyl group, and in another embodiment, R j is an ethyl group.

[0155] Above R B5 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0156] R B5 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0157] In one embodiment, ε is (SiR B4 ε R B5 3-ε ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0158] In one embodiment, δ is (AR B1 δ R B2 3-δ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0159] The compound (B) represented by the above formula (3), formula (4) or formula (5) is not particularly limited, but may be 5×10 2 ~1×10 5 Within this range, it is preferable that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of wear resistance.

[0160] In the above composition, R contained in the above composition Si and R B1 R contained in the composition relative to the total B1The proportion is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, and may be, for example, 0.1 mol% or more, or even 1 mol% or more. When the proportion is within this range, it can be easy to provide a film that has better abrasion resistance, particularly abrasion resistance against soft materials (for example, resin-based materials such as erasers).

[0161] The content of the compound (B) represented by the formula (3), (4), or (5) is preferably 0.1% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, based on 100% by mass of the total of the compounds (A) and (B). When the content is within this range, it can be easy to provide a film having better abrasion resistance, particularly abrasion resistance against soft materials (for example, resin-based materials such as erasers).

[0162] In the composition, the total content of the compound (A) and the compound (B) may be 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.

[0163] (Surface treatment agent) The surface treatment agent of the present disclosure includes the above-described composition. The total content of the compound (A) and the compound (B) in the surface treatment agent (100% by mass) is preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, even more preferably 0.04 to 25.0% by mass, and particularly preferably 0.05 to 20.0% by mass. By setting the content of the fluoropolyether group-containing silane compound within the above range, higher water and oil repellency can be obtained. In the composition of the present disclosure, the non-volatile content may be the portion excluding the solvent from the total amount of the composition.

[0164] (Other ingredients) The surface treatment agent of the present disclosure may further contain a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc. Note that these other components are components different from the above-mentioned compound (A) and compound (B). In a preferred embodiment, the surface treatment agent of the present disclosure further comprises one or more components selected from fluorine-containing oils and silicone oils.

[0165] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (6) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a” -(OC3F6) b” -(OC2F4) c” -(OCF2) d” -Rf 6 ···(6) In the formula, Rf 5 C optionally substituted with one or more fluorine atoms 1-16 Alkyl groups (preferably C 1-16 Rf represents a perfluoroalkyl group 6 C optionally substituted with one or more fluorine atoms 1-16 Alkyl groups (preferably C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 More preferably, each independently represents C 1-3 It is a perfluoroalkyl group. a", b", c", and d" respectively represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and 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 occurrence of each repeating unit enclosed in parentheses with the subscript a", b", c", or d" is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0166] Examples of the perfluoro(poly)ether compound represented by the above general formula (6) include compounds represented by either of the following general formulas (6a) and (6b) (which may be one type or a mixture of two or more types): 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 6is as defined above; in formula (6a), b" is an integer of 1 or more and 100 or less; in formula (6b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0167] From another perspective, fluorine-containing oils are those represented by the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented by the formula: wherein R is a perfluoroalkyl group.) It may also be a chlorotrifluoroethylene oligomer.

[0168] The above-mentioned fluorinated oil may have a number average molecular weight of preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. The above-mentioned fluorinated oil may also have a number average molecular weight of preferably 30000 or less, more preferably 20000 or less, and even more preferably 10000 or less. The molecular weight of the fluorinated oil can be measured using GPC.

[0169] The fluorinated oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent. In one embodiment, the surface treatment agent of the present disclosure is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the surface treatment agent does not contain any fluorinated oil, or may contain a very small amount of fluorinated oil.

[0170] In one embodiment, the number average molecular weight of the fluorine-containing oil may be smaller than the number average molecular weight of the fluorine-containing silane compound. By setting the number average molecular weight in this range, it is possible to form a cured product having high abrasion resistance and high surface slipperiness while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0171] The fluorine-containing oil can contribute to improving the surface slip properties of the layer formed by the surface treatment agent of the present disclosure.

[0172] As the silicone oil, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0173] In the surface treatment agent of the present disclosure, such silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorine-containing silane compounds of the present disclosure (the total of these when two or more types are used, the same applies hereinafter).

[0174] Silicone oil can contribute to improving the surface slip properties of the surface treatment layer.

[0175] Examples of the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with 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 also improves the compatibility of the fluorine-containing silane compound with the solvent.

[0176] The alcohol is contained in the surface treatment agent in an amount, in molar ratio, of preferably 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times the metal compound. By setting the content ratio of the alcohol within the above range, the stability of the surface treatment layer can be further improved.

[0177] Examples of the catalyst include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), and transition metals (for example, Ti, Ni, Sn, etc.).

[0178] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.

[0179] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0180] The surface treatment agent of the present disclosure can be impregnated into a porous substance, such as a porous ceramic material or a metal fiber, such as a flocculated steel wool, to form pellets, which can be used for vacuum deposition, for example.

[0181] In addition to the components described above, the surface treatment agent of the present disclosure may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

[0182] (Goods) The articles of the present disclosure are described below.

[0183] The article of the present disclosure includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the composition and / or surface treatment agent of the present disclosure. In one embodiment, the article of the present disclosure includes a substrate and a layer formed on the surface of the substrate from the composition of the present disclosure. In another embodiment, the article of the present disclosure includes a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present disclosure.

[0184] Substrates that can be used in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0185] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. Furthermore, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the substrate. The antireflection layer may be either a single-layer antireflection layer or a multilayer antireflection layer. Examples of inorganic materials that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, YO3, SnO2, MgF2, and WO3. These inorganic materials may be used alone or in combination (e.g., as a mixture) of two or more of them. When a multilayer antireflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[0186] The shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other form. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the use and specific specifications of the product to be manufactured.

[0187] In one embodiment, at least the surface portion of such a substrate may be made of a material that originally contains hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, and the like, on whose surfaces native oxide or thermal oxide films form. Alternatively, for materials such as resins, which do not have sufficient hydroxyl groups or do not originally contain hydroxyl groups, some pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups on the surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface and can also be used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is first formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption, followed by cleavage of the unsaturated bonds in an atmosphere containing oxygen, nitrogen, or the like.

[0188] In another embodiment, the substrate may have at least a surface portion made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

[0189] In a preferred embodiment, the substrate is glass, such as sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, with chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass being particularly preferred.

[0190] The article of the present disclosure can be produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and then post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.

[0191] The layer formation of the surface treatment agent of the present disclosure can be carried out by applying the surface treatment agent to the surface of a substrate so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0192] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0193] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum 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.

[0194] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0195] When using the wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., CF 13CH2CH3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), Alkyl perfluoroalkyl ethers (the perfluoroalkyl group and alkyl group may be linear or branched) such as perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec™ 7200 manufactured by Sumitomo 3M Limited) and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited), or CF3CH2OCF2CHF2 (e.g., Asahiklin™ AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroethers are preferred, with perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) being particularly preferred.

[0196] When the dry coating method is used, the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

[0197] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent of the present disclosure to which the catalyst has been added may be directly subjected to vapor deposition (usually vacuum deposition), or a pellet-shaped material impregnated with the surface treatment agent of the present disclosure to which the catalyst has been added may be subjected to vapor deposition (usually vacuum deposition) on a porous metal such as iron or copper.

[0198] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts that can be used include ammonia and organic amines.

[0199] The surface treatment layer included in the article of the present disclosure has both high abrasion resistance and water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (for example, preventing water penetration into electronic components), surface slipperiness (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel), chemical resistance, etc., depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0200] Therefore, the present disclosure also relates to an optical material having the above-described surface treatment layer as the outermost layer.

[0201] Preferred examples of the optical material include optical materials related to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0202] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.

[0203] The article of the present disclosure may also be a medical device or medical material.

[0204] The thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm, from the viewpoints of optical performance, abrasion resistance, and antifouling properties.

[0205] The article of the present disclosure has been described in detail above. However, the article and the method for manufacturing the article of the present disclosure are not limited to the examples given above. [Example]

[0206] The present invention will be described in more detail with reference to the following examples, but is not limited thereto. In these examples, the order of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below indicates the average composition.

[0207] (Synthesis Example 1) In a 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer, add 100 mL of water with an average composition of CFO (CFCFO) 26 (CF2O) 2620 g of a perfluoropolyether-modified allyloxy compound represented by CF2CH2OCH2CH=CH2 (note that the mixture also contains trace amounts of compounds containing repeating units of (CF2CF2CF2O) and / or (CF2CF2CF2CF2O), but these are not considered due to their extremely small amounts), 20 g of 1,3-bis(trifluoromethyl)benzene, and 1.36 g of trichlorosilane were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Next, 0.094 mL of a xylene solution containing 2% 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. The reaction mixture was cooled to room temperature, and the volatiles were distilled off under reduced pressure. This mixture was dissolved in 5 g of 1,3-bis(trifluoromethyl)benzene and charged into a short column packed with silica gel, followed by the application of 40 g of 1,3-bis(trifluoromethyl)benzene as an eluent. The eluate was concentrated to obtain 8 g of a perfluoropolyether group-containing allyl compound (B1) having an allyl group at the end, as shown below: Perfluoropolyether group-containing allyl compound (B1): CF3O(CF2CF2O) 26 (CF2O) 26 CF2CH2O CH=CHCH3

[0208] (Synthesis Example 2) In a 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer, add CF3CF2CF2O (CF2CF2CF2O) of average composition 20 20 g of a perfluoropolyether-modified allyloxy compound represented by CFCFCHOCHCH=CH, 20 g of 1,3-bis(trifluoromethyl)benzene, 0.06 g of triacetoxymethylsilane, and 1.36 g of trichlorosilane were charged and stirred at 5°C for 30 minutes under a nitrogen stream. Next, 0.094 ml of a xylene solution containing 2% 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. Volatiles were then removed under reduced pressure to obtain 19 g of a perfluoropolyether group-containing silane compound (A1) with trichlorosilane at the end, as shown below: Perfluoropolyether group-containing silane compound (A1): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2SiCl3

[0209] A 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 19 g of the perfluoropolyether group-containing trichlorosilane compound (A1) having trichlorosilane at its terminal and 20 g of 1,3-bis(trifluoromethyl)benzene, and the mixture was stirred at 5°C for 30 minutes under a nitrogen stream. Subsequently, 26.4 mL of a diethyl ether solution containing 0.7 mol / L allylmagnesium bromide was added, and the mixture was warmed to room temperature and stirred at this temperature for 10 hours. The mixture was then cooled to 5°C, 5 mL of methanol was added, and the mixture was warmed to room temperature and filtered to remove insoluble matter. Subsequently, the volatiles were distilled off under reduced pressure, and the non-volatiles were diluted with perfluorohexane and washed with methanol in a separatory funnel three times (more specifically, the operation of maintaining fluoro-based compounds in the perfluorohexane phase (fluorous phase) and separating and removing non-fluoro-based compounds in the methanol phase (organic phase)). Subsequently, the volatile matter was distilled off under reduced pressure to obtain 20 g of the following perfluoropolyether group-containing allyl compound (A2) having an allyl group at the terminal. Perfluoropolyether group-containing allyl compound (A2): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si(CH2CH=CH2)3

[0210] A 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 15 g of the perfluoropolyether group-containing allyl compound (A2) having an allyl group at the end, 15 g of 1,3-bis(trifluoromethyl)benzene, 0.05 g of triacetoxymethylsilane, and 3.15 g of trichlorosilane, and the mixture was stirred at 5°C for 30 minutes under a nitrogen stream. Subsequently, 0.141 ml of a xylene solution containing 2% 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. Volatiles were then removed under reduced pressure to obtain 16 g of the following perfluoropolyether group-containing trichlorosilane compound (A3) having trichlorosilane at the end. Perfluoropolyether group-containing trichlorosilane compounds (A3): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si(CH2CH2CH2SiCl3)3

[0211] A 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 16 g of the perfluoropolyether group-containing trichlorosilane compound (A3) having trichlorosilane at the terminal and 15 g of 1,3-bis(trifluoromethyl)benzene, and the mixture was stirred at 50°C for 30 minutes under a nitrogen stream. Subsequently, a mixed solution of 0.78 g of methanol and 36 g of trimethyl orthoformate was added, and the mixture was heated to 65°C and stirred at this temperature for 3 hours. The volatiles were then removed under reduced pressure to obtain 17 g of the following perfluoropolyether group-containing silane compound (A4) having trimethylsilyl groups at the terminal. Perfluoropolyether group-containing silane compounds (A4): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3

[0212] (Examples 1 to 6 and Comparative Example 1) A composition was prepared by mixing the compound (B1) obtained in Synthesis Example 1 and the compound (A4) obtained in Synthesis Example 2 so that the proportion of the compound (B1) was the value shown in Table 1. In the composition, the proportion (mol %) of the compound (B1) was R Si and R B1 R for the sum of B1 This corresponds to a percentage of

[0213] The above composition was dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M) so that the concentration (total concentration of compound (B1) and compound (A4)) was 20 mass % to prepare a surface treatment agent.

[0214] The surface treatment agent prepared above was vacuum-deposited onto chemically strengthened glass (Corning "Gorilla" glass, thickness 0.7 mm). The vacuum deposition treatment conditions were a pressure of 3.0 × 10 -3 First, silicon dioxide was deposited on the surface of this chemically strengthened glass by electron beam deposition to a thickness of 7 nm to form a silicon dioxide film. Subsequently, 2 mg of a surface treatment agent (i.e., containing a total of 0.4 mg of compound (B1) and compound (A4)) was deposited per piece of chemically strengthened glass (55 mm × 100 mm). The chemically strengthened glass with the deposited film was then left to stand for 24 hours in an atmosphere at a temperature of 20°C and a humidity of 65%. This caused the deposited film to harden, forming a surface treatment layer.

[0215] The static contact angle of water was measured for the surface treatment layers formed on the substrate surfaces in the above examples and comparative examples using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) with 1 μL of water. First, as an initial evaluation, the static contact angle of water was measured after the surface treatment layer was formed without any contact with the surface (zero number of frictions). Then, as an evaluation of friction durability, a steel wool friction durability evaluation was performed. Specifically, the substrate with the surface treatment layer formed was placed horizontally, and steel wool (count #0000, dimensions 5 mm x 10 mm x 10 mm) was brought into contact with the exposed upper surface of the surface treatment layer, and a load of 1,000 gf was applied thereon. Then, with the load applied, the steel wool was moved back and forth at a speed of 140 mm / s. The static contact angle of water (degrees) was measured every 1,000 reciprocations, and the maximum number of reciprocations at which the measured contact angle remained at 100 degrees was used as an index of abrasion durability. The results are shown in Tables 1 and 2.

[0216] [Table 1]

[0217] [Table 2]

[0218] Examples 1 to 6 are examples of the present disclosure, and it was confirmed that the films obtained from these compositions had good abrasion resistance. Comparative Example 1 is an example that does not contain the compound (B), and although the initial water contact angle was good, the abrasion resistance was not as good as that of Examples 1-6. [Industrial Applicability]

[0219] The article of the present disclosure can be suitably used in a wide variety of applications, for example, as an optical component such as a touch panel.

Claims

1. a silane compound (A) having a fluoropolyether group; Fluoropolyether group and —O—CH═CH—CH ３ Compound (B) having the formula and, The silane compound (A) is represented by the formula (1a): R Ｆ１ -X Ａ -R Ｓｉ (1a) [In the formula: R Ｆ１ is Rf １ -R Ｆ -O ｑ - and; Rf １ is C １－１６ is a perfluoroalkyl group; R Ｆ is -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -; Each R Fa is independently a fluorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula; q is 0 or 1; R Ｓｉ is expressed by the following formula (S3): -SiR a1 k1 R b1 l1 R c1 m1 (S3) [In the formula, Each R a1 independently represents —Z 1 —SiR 22 q1 R 23 r1 ; Z 1 s each independently represent a C 1-6 alkylene group or —(CH 2 ) z3 -phenylene-(CH 2 ) z4 —, and the right side of the structure hereinafter described as Z 1 is bonded to (SiR 22 q1 R 23 r1 ); R 22 each independently represents a hydroxyl group or a hydrolyzable group; R 23 each independently represents a hydrogen atom or a C 1-6 alkyl group; q1 is independently an integer of 1 to 3 for each (SiR 22 q1 R 23 r1 ) unit; R b1 each independently represents a hydroxyl group or a hydrolyzable group; R c1 each independently represents a hydrogen atom or a C 1-6 alkyl group; Each k1 is independently an integer of 1 to 3, each l1 is independently an integer of 0 to 3, and each m1 is independently an integer of 0 to 3, and the sum of k1, l1, and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit. is a group represented by -O-CH=CH-CH ３ Does not include; X Ａ represents a single bond or the following formula: -R 51 -X 53 -R 52 - [In the formula: R ５１ is a single bond, -(CH ２ ) ｓ５ - or an o-, m- or p-phenylene group; s5 is an integer from 1 to 20, X 53 is -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 ) 2 -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-(CH 2 ) u5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-(CH 2 ) u5 -Si(R 53 ) 2 -O-Si(R 53 ) 2 -CH 2 CH 2 -Si(R 53 ) 2 -O-Si(R 53 ) 2 -, -O-(CH 2 ) u5 -Si(OCH 3 ) 2 OSi(OCH 3)2-, -CONR54-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-, -CONR54-(CH2)u5-N(R54)- or -CONR54-(o-, m- or p-phenylene)-Si(R53)2-; R ５３ are each independently a phenyl group, C １－６ Alkyl group or C １－６ represents an alkoxy group, R ５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group, m5 each independently represents an integer of 1 to 100; Each u5 is independently an integer from 1 to 20, R 52 represents a single bond, —(CH 2 ) t5 —, or an o-, m-, or p-phenylene group; t5 is an integer from 1 to 20. is a group represented by the following formula: is expressed as The compound (B) is represented by the following formula (3): RF1 -X Ａ -[AR Ｂ１ δ R Ｂ２ ３－δ ] (3) [In the formula: Each A is independently a C atom or a Si atom; R Ｆ１ are each independently Rf １ -R Ｆ -O ｑ - and; Rf １ are each independently C １－１６ is a perfluoroalkyl group; R Ｆ are each independently a -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - group; Each R Fa is independently a fluorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula; Each q is independently 0 or 1; R Ｂ１ is -R Ｂ３ -O-CH=CH-CH ３ and R Ｂ２ are each independently -R Ｂ３ -O-CH ２ CH ２ CH ２ -SiR Ｂ４ ε R Ｂ５ ３－ε and hydrogen atoms; R Ｂ３ are each independently a single bond or C １－２０ an alkylene group; R Ｂ４ are each independently a hydroxyl group or a hydrolyzable group; R Ｂ５ are each independently a hydrogen atom or a C 1-6 alkyl group; X Ａ represents a single bond or the following formula: -R 51 -X 53 -R 52 - [In the formula: R 51 represents a single bond, —(CH 2 ) s5 —, or an o-, m-, or p-phenylene group; s5 is an integer from 1 to 20, X 53 is -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 ) 2 -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-(CH 2 ) u5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -O-(CH 2 ) u5 -Si(R 53 ) 2 -O-Si(R 53 ) 2 -CH 2 CH 2 -Si(R 53 ) 2 -O-Si(R 53 ) 2 -, -O-(CH 2 ) u5 -Si(OCH 3 ) 2 OSi(OCH 3)2-, -CONR54-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-, -CONR54-(CH2)u5-N(R54)- or -CONR54-(o-, m- or p-phenylene)-Si(R53)2-; R 53 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group; R 54 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; m5 each independently represents an integer of 1 to 100; Each u5 is independently an integer from 1 to 20, R 52 represents a single bond, —(CH 2 ) t5 —, or an o-, m-, or p-phenylene group; t5 is an integer from 1 to 20. is a group represented by Each δ is independently an integer from 1 to 3; Each ε is independently an integer of 1 to 3. (provided that the compound (A) and the compound (B) are different), the content of the compound (B) containing the formula (3) is 0.1 mass% or more and 25 mass% or less, relative to 100 mass% of the total of the compound (A) and the compound (B), R Ｓｉ and R Ｂ１ R for the sum of Ｂ１ is 25 mol % or less, The composition, wherein the total content of the compound (A) and the compound (B) is 80% by mass or more and 100% by mass or less.

2. A surface treatment agent comprising the composition of claim 1.

3. The surface treatment agent according to claim 2 , further comprising one or more components selected from fluorine-containing oils and silicone oils.

4. The surface treatment agent according to claim 2, which is used as an antifouling coating agent or a waterproof coating agent.

5. An article comprising a substrate and a layer formed from the composition of claim 1 on a surface of the substrate.

6. An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent according to any one of claims 2 to 4.

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