Perfluoro(poly)ether group-containing silane compounds

Abstract

To provide a novel perfluoro(poly)ether group-containing silane compound having water repellency, oil repellency and antifouling property and capable of forming a layer having high friction durability.SOLUTION: There is provided a perfluoro(poly)ether group-containing silane compound represented by the formula (1a) or the formula (1b), where each symbol has the same meaning as described in the specifications of this application.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a perfluoro(poly)ether group-containing silane compound. [Background technology]

[0002] It is known that certain fluorine-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 fluorine-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, fibers, and building materials.

[0003] Known examples of such fluorine-containing compounds include perfluoropolyether group-containing silane compounds that have a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular end or terminal portion (see Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2008-534696 [Patent Document 2] International Publication No. 97 / 07155 Summary of the Invention [Problem to be solved by the invention]

[0005] The surface treatment layer is required to have high durability so as to provide the desired functions to the substrate for a long period of time. The layer obtained from the surface treatment agent containing the perfluoropolyether group-containing silane compound can exhibit the above-mentioned functions even in a thin film, and therefore is suitably used for optical components such as glasses and touch panels that require light transmittance or transparency. In particular, in these applications, further improvement in friction durability is required.

[0006] However, the layer obtained from the conventional surface treatment agent containing the perfluoropolyether group-containing silane compound as described above is no longer necessarily sufficient to meet the increasingly increasing demand for improved friction durability.

[0007] An object of the present invention is to provide a novel perfluoro(poly)ether group-containing silane compound that can form a layer that has water repellency, oil repellency, antifouling properties, and high abrasion resistance. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the friction durability of the surface treatment layer can be improved by using a perfluoropolyether group-containing silane compound having multiple Si atoms with hydrolyzable groups, and have thus completed the present invention.

[0009] That is, according to the first aspect of the present invention, there is provided a compound represented by formula (1a) or formula (1b): [ka] [In formula: Rf, in each occurrence, independently represents an alkyl group having 1 to 16 carbon atoms optionally substituted with one or more fluorine atoms; PFPE independently at each occurrence has the formula: -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d - (In the formula, a, b, c, and d each independently represent an integer of 0 to 200, the sum of a, b, c, and d is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a, b, c, or d is arbitrary in the formula.) is a group represented by the formula: X's each independently represent a single bond or a divalent to decavalent organic group; Each a is independently an integer from 1 to 9; β is an integer from 1 to 9; R a are each independently in each occurrence -Z-CR 1 p R 2 q R 3 r represents; Z, in each occurrence, independently represents an oxygen atom or a divalent organic group; R 1 independently in each occurrence, R a’ represents; R a’ is R a is equivalent to; R a wherein the number of C's linearly linked via Z groups is at most 5; R 2 independently in each occurrence -Y-SiR 5 n R 6 3-n represents; Y, independently in each occurrence, represents a divalent organic group; R 5 represents, independently in each occurrence, a hydroxyl group or a hydrolyzable group; R 6 represents, independently in each occurrence, a hydrogen atom or a lower alkyl group; n is (-Y-SiR 5 n R 6 3-n ) each unit independently represents an integer of 1 to 3; R 3 represents, independently in each occurrence, a hydrogen atom or a lower alkyl group; p, in each occurrence, is independently an integer from 0 to 3; q is independently in each occurrence an integer from 0 to 3; r, in each occurrence, is independently an integer from 0 to 3; R b independently in each occurrence -Y-SiR 5n R 6 3-n represents; R c represents, independently in each occurrence, a hydrogen atom or a lower alkyl group; k, independently in each occurrence, is an integer from 0 to 3; l, in each occurrence, is independently an integer from 0 to 3; m, in each occurrence, is independently an integer from 0 to 3; provided that, in the formula, at least one q is 2 or 3, or at least one l is 2 or 3. The perfluoro(poly)ether group-containing silane compound is represented by the following formula:

[0010] According to a second aspect of the present invention, there is provided a surface treatment agent containing the above-mentioned perfluoro(poly)ether group-containing silane compound.

[0011] According to a third aspect of the present invention, there is provided a pellet containing the above-mentioned surface treatment agent.

[0012] According to a fourth aspect of the present invention, there is provided an article comprising a substrate and a layer formed on the surface of the substrate from the perfluoropolyether group-containing silane compound or the surface treatment agent. [Effects of the Invention]

[0013] According to the present invention, a novel perfluoro(poly)ether group-containing silane compound is provided. Furthermore, a surface treatment agent obtained using the perfluoro(poly)ether group-containing silane compound of the present invention is also provided. By using these, a surface treatment layer having water repellency, oil repellency, antifouling properties, and excellent light resistance can be formed. DETAILED DESCRIPTION OF THE INVENTION

[0014] The compounds of the present invention will be described below.

[0015] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, resulting from the elimination of one hydrogen atom from a hydrocarbon. Examples of such hydrocarbon groups include, but are not limited to, hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at its terminal or in the molecular chain.

[0016] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom; a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0017] As used herein, the term "organic group" refers to a group containing carbon. The organic group is not particularly limited, but may be a hydrocarbon group. Furthermore, the term "divalent to decavalent organic group" refers to a divalent to decavalent group containing carbon. Examples of such divalent to decavalent organic groups include, but are not particularly limited to, divalent to decavalent groups in which one to nine hydrogen atoms have been eliminated from a hydrocarbon group. For example, examples of divalent organic groups include, but are not particularly limited to, divalent groups in which one hydrogen atom has been eliminated from a hydrocarbon group.

[0018] The present invention provides a perfluoro(poly)ether group (hereinafter also referred to as "PFPE")-containing silane compound represented by formula (1a) or formula (1b) (hereinafter also referred to as "the PFPE-containing silane compound of the present invention"). [ka]

[0019] In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

[0020] The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

[0021] The above Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably CF2H-C 1-15 It is a fluoroalkylene group, and more preferably a perfluoroalkyl group having 1 to 16 carbon atoms.

[0022] The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and is preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0023] In the above formula, PFPE is -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d-, which corresponds to a perfluoro(poly)ether group. Here, a, b, c, and d are each independently an integer of 0 or 1 or greater, and the sum of a, b, c, and d is at least 1. Preferably, a, b, c, and d are each independently an integer of 0 or greater and 200 or less, for example, an integer from 1 to 200, and more preferably, are each independently an integer of 0 or greater and 100 or less, for example, an integer from 1 to 200. Preferably, the sum of a, b, c, and d is 5 or greater, more preferably 10 or greater, for example, 10 or greater and 200 or less. Furthermore, the order of occurrence of each repeating unit enclosed in parentheses with a, b, c, or d is arbitrary in the formula. Among 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)-. Furthermore, -(OC2F4)- may be either -(OCF2CF2)- or -(OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0024] In one embodiment, the PFPE is -(OC3F6) b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less), and preferably -(OCFCFCF) b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or -(OCF(CF3)CF2) b- (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less), more preferably -(OCFCFCF) b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less).

[0025] In another embodiment, the PFPE is -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d - (wherein a and b each independently represent an integer of 0 to 30, c and d each independently represent an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a, b, c, or d in the formula is arbitrary), preferably -(OCFCFCFCFCF) a -(OCF2CF2CF2) b -(OCF2CF2) c -(OCF2) d In one embodiment, the PFPE is -(OC2F4). c -(OCF2) d -(wherein c and d each independently represent an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript c or d in the formula is arbitrary).

[0026] In one embodiment, the -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) dIn -, the lower limit of the ratio of c to d (hereinafter referred to as "c / d ratio") can be 0.2, preferably 0.3, and the upper limit of the c / d ratio can be 1.5, preferably 1.3, more preferably 1.1, and even more preferably 0.9. By setting the c / d ratio to 1.5 or less, the slipperiness and friction durability of the surface treatment layer obtained from this compound can be further improved. The smaller the c / d ratio, the more improved the slipperiness and friction durability of the surface treatment layer. On the other hand, by setting the c / d ratio to 0.2 or more, the stability of the compound can be further improved. The larger the c / d ratio, the more improved the stability of the compound.

[0027] In yet another embodiment, the PFPE is -(OC2F4-R 8 ) n” In the formula, R 8 is a group selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups. Examples of combinations of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 include, but are not limited to, -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. The above n" is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC2F4, OC3F6, and OC4F8 may be either a linear or branched chain, and are preferably linear. In this embodiment, the PFPE is preferably -(OC2F4-OC3F6) n” -or-(OC2F4-OC4F8) n” -It is.

[0028] In the above formula, X each independently represents a single bond or a divalent to decavalent organic group. In the compounds represented by formulas (1a) and (1b), X is understood to be a linker that connects the perfluoropolyether portion (i.e., the Rf-PFPE portion or -PFPE- portion) that primarily provides water repellency and surface slipperiness, etc., to the portion that provides the ability to bond to the substrate (i.e., the group enclosed in parentheses with α). Therefore, X may be any organic group as long as it allows the compounds represented by formulas (1a) and (1b) to exist stably.

[0029] In the above formula, α is an integer of 1 to 9, and β is an integer of 1 to 9. These α and β can change depending on the valence of X. In formula (1a), the sum of α and β is the same as the valence of X. For example, when X is a decavalent organic group, the sum of α and β is 10, and it can be, for example, α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9. Furthermore, when X is a divalent organic group, α and β are 1. In formula (1b), α is the value obtained by subtracting 1 from the valence of X.

[0030] The above X is preferably a divalent to heptavalent organic group, more preferably a divalent to tetravalent organic group, and even more preferably a divalent organic group.

[0031] In one embodiment, X is a divalent to tetravalent organic group, α is 1 to 3, and β is 1.

[0032] In another embodiment, X is a divalent organic group, α is 1, and β is 1. In this case, formulas (1a) and (1b) are represented by the following formulas (1a') and (1b'). [ka]

[0033] Examples of the above X include, but are not limited to, the following formula: -(R 31 ) p’ -(X a ) q’ - [In formula: R 31 are each independently a single bond, -(CH2) s’ - or an o-, m- or p-phenylene group, preferably -(CH2) s’ - and s' 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 a is -(X b ) l’ - represents X b each occurrence independently represents an -O-, -S-, o-, m-, or p-phenylene group, -C(O)O-, -Si(R 33 )2-, -(Si(R 33 )2O) m’ -Si(R 33 )2-, -CONR 34 -, -O-CONR 34 -, -NR 34 - and -(CH2) n’ represents a group selected from the group consisting of - R 33 independently in each occurrence 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 34 are each independently in each occurrence a hydrogen atom, a phenyl group or C 1-6 represents an alkyl group (preferably a methyl group), m' in each occurrence is independently an integer from 1 to 100, preferably an integer from 1 to 20; n', in each occurrence, is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3; l' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p' is 0, 1 or 2; q' is 0 or 1, wherein at least one of p' and q' is at least 1, and the repeating units enclosed in parentheses with p' or q' may be present in any order. Here, R 31 and X a (Typically R 31 and X a hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 It may be substituted with one or more substituents selected from fluoroalkyl groups.

[0034] Preferably, X is C 1-20 an alkylene group, -R 31 -X c -R 31 -,or -X d -R 31 - [In the formula, R 31 has the same meaning as above.] It could be.

[0035] More preferably, X is C 1-20 an alkylene group, -(CH2) s’ -X c -, -(CH2) s’ -X c -(CH2) t’ - -X d -,or -X d -(CH2) t’ - [In the formula, s' and t' are defined as above.] is.

[0036] In the above formula, X c teeth, -O-, -S-, -C(O)O-, -CONR 34 -, -O-CONR 34 -, -Si(R 33 )2-, -(Si(R 33 )2O) m’ -Si(R 33 )2-, -O-(CH2) u’ -(Si(R 33 )2O) m’ -Si(R 33 )2-, -O-(CH2) u’ -Si(R 33 )2-O-Si(R 33 )2-CH2CH2-Si(R 33 )2-O-Si(R 33 )2-, -O-(CH2) u’ -Si(OCH3)2OSi(OCH3)2-, -CONR 34 -(CH2) u’ -(Si(R 33 )2O) m’ -Si(R 33 )2-, -CONR 34 -(CH2) u’ -N(R 34 )-,or -CONR 34 -(o-, m- or p-phenylene)-Si(R 33 )2- [In the formula, R 33 , R 34 and m' are as defined above; and u' is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. X c is preferably —O—.

[0037] In the above formula, X d teeth, -S-, -C(O)O-, -CONR 34 -, -CONR 34 -(CH2) u’ -(Si(R33 )2O) m’ -Si(R 33 )2-, -CONR 34 -(CH2) u’ -N(R 34 )-,or -CONR 34 -(o-, m- or p-phenylene)-Si(R 33 )2- [In the formula, each symbol has the same meaning as above.] Represents.

[0038] More preferably, X is C 1-20 an alkylene group, -(CH2) s’ -X c -(CH2) t’ -,or -X d -(CH2) t’ - [In the formula, each symbol has the same meaning as above.] It could be.

[0039] Even more preferably, said X is C 1-20 an alkylene group, -(CH2) s’ -O-(CH2) t’ -, -(CH2) s’ -(Si(R 33 )2O) m’ -Si(R 33 )2-(CH2) t’ -, -(CH2) s’ -O-(CH2) u’ -(Si(R 33 )2O) m’ -Si(R 33 )2-(CH2) t’ -,or -(CH2) s’ -O-(CH2) t’ -Si(R 33 )2-(CH2) u’ -Si(R 33 )2-(Cv H 2v )- [In the formula, R 33 , m', s', t', and u' are defined as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.] is.

[0040] In the above formula, -(C v H 2v )- can be straight or branched chain, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0041] The X group is a fluorine atom, C 1-3 Alkyl groups and C 1-3 Fluoroalkyl groups (preferably C 1-3 perfluoroalkyl groups).

[0042] In another embodiment, X groups include, for example, the following groups: [ka] [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, 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 1-6 alkyl group or 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 bonded to the PFPE in the molecular main chain, and E is bonded to the group opposite the PFPE.

[0043] Specific examples of X above include: -CH2O(CH2)2-, -CH2O(CH2)3-, -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- -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-, -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), -CONH-(CH2)6-, -CON(CH3)-(CH2)6-, -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)-、 [[ID=三十二]]-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-、 <x

Chem.

[0044] In another embodiment, each X can independently be a trivalent to decavalent organic group.

[0045] In this embodiment, examples of X groups include the following: [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 The alkoxy group is preferably a methyl group; In each X group, any of the T's may be the following groups attached to the PFPE of the molecular backbone of formulas (1a) and (1b): -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 alkyl group or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.] Some of the other Ts are groups opposite to the PFPE in the molecular backbone (i.e., -CR in formulas (1a) and (1b)). a k R b l R c m ) bonded to -(CH2) n” -(n" is an integer from 2 to 6), and if present, the remainder are each independently a methyl group, a phenyl group, or a C1-6 It is an alkoxy group.

[0046] In the above formula, R a are each independently in each occurrence -Z-CR 1 p R 2 q R 3 r Represents.

[0047] In the formula, Z independently in each occurrence represents an oxygen atom or a divalent organic group.

[0048] The Z is preferably C 1-6 Alkylene group, -(CH2) g -O-(CH2) h - (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6, and h is an integer of 0 to 6, for example, an integer of 1 to 6), or -phenylene-(CH2) i - (wherein i is an integer of 0 to 6), and more preferably C 1-3 These groups are, 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.

[0049] In the formula, R 1 independently in each occurrence, R a’ Represents R a’ is R a It has the same meaning as:

[0050] R a Among them, the number of Cs connected in a linear chain via Z groups is at most 5. That is, a In R 1 If there is at least one a There are two or more C atoms connected in a linear chain via Z groups in the "R" group, but the number of C atoms connected in a linear chain via such Z groups is up to five. aThe number of C atoms linearly linked via Z groups in R a The number of repeats of -ZC- linked in a linear chain is equal to the number of repeats of -ZC- in the

[0051] For example, in the following a An example in which the C atom is linked via a Z group is shown. [ka]

[0052] In the above formula, * means the site of bonding to C in the main chain, and ... means that a specific group other than ZC is bonded, that is, when all three bonds of the C atom are ..., it means the end point of the ZC repetition. Also, the number on the right side of C means the number of occurrences of C linked in a linear chain via the Z group, counted from *. That is, C 2 The chain where the ZC repeat ends is "R a The number of C atoms connected in a linear chain through Z groups in the 3 , C 4 and C 5 The chains where the ZC repeat ends are called "R a The number of C atoms linearly linked through the Z group in R is 3, 4, and 5. a There are multiple ZC chains in the molecule, but they do not all need to be the same length, and each may be any length.

[0053] In a preferred embodiment, as shown below, a The number of C atoms linearly linked via Z groups in the formula is 1 (left formula) or 2 (right formula) in all chains. [ka]

[0054] In one embodiment, R a The number of C atoms linearly linked via Z groups in the aryl group is 1 or 2, preferably 1.

[0055] In the formula, R 2 -Y-SiR 5 n R 6 3-n Represents.

[0056] Y, in each occurrence, independently represents a divalent organic group.

[0057] In a preferred embodiment, Y is C 1-6 Alkylene group, -(CH2) g’ -O-(CH2) h’ - (wherein g' is an integer of 0 to 6, for example, an integer of 1 to 6, and h' is an integer of 0 to 6, for example, an integer of 1 to 6), or -phenylene-(CH2) i’ - (wherein i' is an integer of 0 to 6). These groups include, for example, a fluorine atom, 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.

[0058] In one embodiment, Y is C 1-6 Alkylene group, -O-(CH2) h’ -or-phenylene-(CH2) i’ When Y is the above group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0059] Above R 5 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group.

[0060] As used herein, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, -ON=C(R), -N(R), -NHR, and halogens (wherein R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), with -OR (alkoxy group) being preferred. 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, with methyl or ethyl groups being more preferred. The hydroxyl group is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group.

[0061] Preferably, R 5 is -OR (wherein R is a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, especially a methyl group).

[0062] Above R 6 are each independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0063] n is (-Y-SiR 5 n R 6 3-n ) units independently represent an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0064] Above R 3 are each independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0065] In the formula, p, at each occurrence, is independently an integer from 0 to 3; q, at each occurrence, is independently an integer from 0 to 3; and r, at each occurrence, is independently an integer from 0 to 3, with the proviso that the sum of p, q, and r is 3.

[0066] In a preferred embodiment, R a R at the end of the middle a '(R a If ' does not exist, R a In the above formula (I), q is preferably 2 or more, for example, 2 or 3, and more preferably 3.

[0067] In the above formula, R b independently in each occurrence -Y-SiR 5 n R 6 3-n where Y and R 5 , R 6 and n is the above R 2 This has the same meaning as the description in

[0068] In the above formula, R c are each independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0069] In the formula, k, at each occurrence, is independently an integer from 0 to 3; l, at each occurrence, is independently an integer from 0 to 3; and m, at each occurrence, is independently an integer from 0 to 3, provided that the sum of k, l, and m is 3.

[0070] In one embodiment, at least one k is 2 or 3, preferably 3.

[0071] In one embodiment, k is 2 or 3, preferably 3.

[0072] In one embodiment, 1 is 2 or 3, preferably 3.

[0073] In the above formulas (1a) and (1b), at least one q is 2 or 3, or at least one l is 2 or 3. That is, in the formulas, at least two -Y-SiR 5 n R 6 3-n There is a group.

[0074] In the perfluoro(poly)ether group-containing silane compound represented by the above formula (1a) or formula (1b), the average molecular weight of the Rf-PFPE portion is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000.

[0075] The perfluoro(poly)ether group-containing silane compound of the present invention represented by the above formula (1a) or (1b) is not particularly limited, but may be 5×10 2 ~1×10 5 Within this range, it is preferable from the viewpoint of friction durability that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000. In the present invention, 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.

[0076] The perfluoro(poly)ether group-containing silane compound represented by formula (1a) or formula (1b) can be produced by combining known methods. For example, the compound represented by formula (1a') in which X is divalent can be produced as follows, but is not limited thereto.

[0077] A double bond-containing group (preferably allyl) and a halogen (preferably bromo) are introduced into a polyhydric alcohol represented by HO-XC(YOH)3 (wherein X and Y are each independently a divalent organic group) to obtain a double bond-containing halide represented by Hal-XC(YOR-CH=CH2)3 (wherein Hal is a halogen, such as Br, and R is a divalent organic group, such as an alkylene group). Next, the terminal halogen and R PFPE -OH(in the formula, R PFPE is a perfluoropolyether group-containing group. PFPE -OXC(YOR-CH=CH2)3 is obtained. Then, the terminal -CH=CH2 is reacted with HSiCl3 and alcohol or HSiR 5 3 and react with R PFPE -OXC(YOR-CH2-CH2-SiR 5 3) You can get 3.

[0078] Those skilled in the art can adjust the reaction conditions for producing the perfluoro(poly)ether group-containing silane compound of the present invention to within suitable preferred ranges.

[0079] Next, the surface treatment agent of the present invention will be described.

[0080] The surface treatment agent of the present invention contains at least one perfluoro(poly)ether group-containing silane compound represented by formula (1a) or formula (1b).

[0081] The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling properties, surface slip properties, and friction durability to a substrate, and can be suitably used as, but not limited to, an antifouling coating agent or a waterproof coating agent.

[0082] In one embodiment, the compound represented by formula (1a) or formula (1b) contained in the surface treatment agent of the present invention is a compound in which X is a divalent organic group, and α and β are 1.

[0083] In one embodiment, in the compound represented by formula (1a) or formula (1b) contained in the surface treatment agent of the present invention, l is 3 and n is 3.

[0084] In one embodiment, the perfluoropolyether group-containing silane compound contained in the surface treatment agent of the present invention is represented by formula (1a).

[0085] The surface treatment agent may contain other components in addition to the compound represented by formula (1a) or formula (1b). Such other components are not particularly limited, but include, for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter 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"), a catalyst, etc.

[0086] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds). R 21 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -R 22 ···(3) In the formula, R 21 C optionally substituted with one or more fluorine atoms 1-16 alkyl groups (preferably C 1-16 (perfluoroalkyl group), and R 22 C optionally substituted with one or more fluorine atoms 1-16 alkyl groups (preferably C 1-16 a perfluoroalkyl group), a fluorine atom or a hydrogen atom, and R 21 and R 22 More preferably, each independently represents C 1-3 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 at least 1, preferably 1 to 300, and more preferably 20 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. Among 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)-.

[0087] Examples of the perfluoro(poly)ether compound represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one type or a mixture of two or more types): R 21 -(OCF2CF2CF2) b’’ -R 22 (3a) R 21 -(OCF2CF2CF2CF2) a’’ -(OCF2CF2CF2) b’’ -(OCF2CF2) c’’ -(OCF2) d’’ -R 22 (3b) In these formulas, R 21 and R 22is as defined above; in formula (3a), b'' is an integer of 1 or more and 100 or less; in formula (3b), 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 within the formula.

[0088] The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000, which allows high surface slippage to be achieved.

[0089] In the surface treatment agent of the present invention, the fluorinated oil may be contained in an amount of, for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 25 to 400 parts by mass relative to a total of 100 parts by mass of the PFPE-containing silane compounds of the present invention (when two or more types are used, the total of these compounds; the same applies hereinafter).

[0090] The compound represented by general formula (3a) and the compound represented by general formula (3b) may be used alone or in combination. The compound represented by general formula (3b) is preferred over the compound represented by general formula (3a) because it provides higher surface slipperiness. When these compounds are used in combination, the mass ratio of the compound represented by general formula (3a) to the compound represented by general formula (3b) is preferably 1:1 to 1:30, more preferably 1:1 to 1:10. This mass ratio allows for the formation of a surface treatment layer with an excellent balance between surface slipperiness and friction durability.

[0091] In one embodiment, the fluorinated oil contains one or more compounds represented by general formula (3b). In such an embodiment, the mass ratio of the compound represented by formula (1a) or formula (1b) to the compound represented by formula (3b) in the surface treatment agent is preferably 4:1 to 1:4.

[0092] In one preferred embodiment, the surface treatment agent of the present invention is such that PFPE is -(OCF2CF2CF2) b- (b is an integer of 1 to 200), and a compound represented by formula (3b). By using such a surface treatment agent to form a surface treatment layer by a wet coating method or a vacuum deposition method, preferably a vacuum deposition method, it is possible to obtain excellent surface slip properties and friction durability.

[0093] In one more preferred embodiment, the surface treatment agent of the present invention is such that PFPE is -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d - (wherein a and b each independently represent an integer of 0 or more and 30 or less, preferably 0 or more and 10 or less; c and d each independently represent an integer of 1 or more and 200 or less; and the sum of a, b, c and d is an integer of 10 or more and 200 or less. The order of the repeating units enclosed in parentheses with the subscript a, b, c or d can be any order in the formula), and compounds represented by formula (3b). By forming a surface treatment layer using such a surface treatment agent by a wet coating method or a vacuum deposition method, preferably by vacuum deposition, it is possible to obtain better surface smoothness and friction durability.

[0094] In these embodiments, the number average molecular weight of the compound represented by formula (3a) is preferably 2,000 to 8,000.

[0095] In these embodiments, the number average molecular weight of the compound represented by formula (3b) is preferably 2,000 to 30,000. When the surface treatment layer is formed by a dry coating method, such as a vacuum deposition method, the number average molecular weight of the compound represented by formula (3b) is preferably 8,000 to 30,000, and when the surface treatment layer is formed by a wet coating method, such as a spray treatment, the number average molecular weight is preferably 2,000 to 10,000, and particularly preferably 3,000 to 5,000.

[0096] In a preferred embodiment, when the surface treatment layer is formed by vacuum deposition, the average molecular weight of the fluorinated oil may be larger than the average molecular weight of the compound represented by formula (1a) or formula (1b). By setting the average molecular weights of the compound represented by formula (1a) or formula (1b) and the fluorinated oil to such values, better surface smoothness and friction durability can be obtained.

[0097] From another perspective, the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf' is C 5-16 The compound represented by Rf'-F may be a compound represented by the formula: 1-16 This is preferred in that it provides high affinity with the compound represented by the above formula (1a) or (1b), which is a perfluoroalkyl group.

[0098] The fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.

[0099] The silicone oil may be, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds. 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.

[0100] In the surface treatment agent of the present invention, 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 PFPE-containing silane compounds of the present invention (the total of these when two or more types are used; the same applies hereinafter).

[0101] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0102] 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.).

[0103] The catalyst promotes the hydrolysis and dehydration condensation of the PFPE-containing silane compound of the present invention, and promotes the formation of a surface treatment layer.

[0104] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0105] The surface treatment agent of the present invention can be impregnated into a porous substance, such as a porous ceramic material or a metal fiber, such as a cotton-like mass of steel wool, to form pellets, which can be used, for example, for vacuum deposition.

[0106] Next, the article of the present invention will be described.

[0107] The article of the present invention includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the PFPE-containing silane compound or surface treatment agent of the present invention (hereinafter, these will be collectively referred to simply as the "surface treatment agent of the present invention"). This article can be produced, for example, as follows.

[0108] First, a substrate is prepared. Substrates that can be used in the present invention may be made of any suitable material, such as glass, resin (natural or synthetic resin, for example, a common plastic material, which may be in the form of a plate, film, or other form), metal (a simple metal such as aluminum, copper, or iron, or a composite such as an alloy), ceramics, semiconductors (silicon, germanium, etc.), fiber (woven fabric, nonwoven fabric, etc.), fur, leather, wood, ceramics, stone, etc., or building materials.

[0109] 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 in the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, 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 made of 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.

[0110] The shape of the substrate is not particularly limited. 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 application and specific specifications of the article to be manufactured.

[0111] Such substrates may be made of materials that inherently contain hydroxyl groups, at least on their surface. Examples of such materials include glass, metals (especially base metals), ceramics, and semiconductors, which form natural or thermal oxide films on their surfaces. Alternatively, for materials such as resins, which do not inherently contain hydroxyl groups, or materials that do not have sufficient hydroxyl groups, pretreatment can be performed to introduce or increase the number of hydroxyl groups on the substrate 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.

[0112] Alternatively, at least the surface portion of such a substrate may be made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

[0113] Next, a film of the surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention.

[0114] The film formation of the surface treatment agent of the present invention can be carried out by applying the above-mentioned 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.

[0115] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

[0116] 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.

[0117] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0118] When using the wet coating method, the surface treatment agent of the present invention can be diluted with a solvent and then applied to the surface of a substrate. From the viewpoint of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., 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), and 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 these, hydrofluoroethers are preferred, with perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) being particularly preferred.

[0119] When the dry coating method is used, the surface treatment agent of the present invention 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.

[0120] Film formation is preferably carried out so that the surface treatment agent of the present invention is present in the film 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 invention 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 invention immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent of the present invention 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 invention to which the catalyst has been added may be used to perform vapor deposition (usually vacuum deposition) on a porous metal such as iron or copper.

[0121] 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.

[0122] Next, if necessary, the membrane is subjected to post-treatment. This post-treatment is not particularly limited, but may be, for example, a treatment in which moisture supply and dry heating are carried out sequentially. More specifically, the post-treatment may be carried out as follows.

[0123] After forming a film of the surface treatment agent of the present invention on the surface of the substrate as described above, moisture is supplied to this film (hereinafter also referred to as "precursor film"). The method of supplying moisture is not particularly limited, and may be, for example, condensation due to the temperature difference between the precursor film (and substrate) and the surrounding atmosphere, or spraying water vapor (steam).

[0124] It is believed that when moisture is supplied to the precursor film, the water acts on the hydrolyzable groups bonded to Si in the perfluoro(poly)ether group-containing silane compound in the surface treatment agent of the present invention, thereby rapidly hydrolyzing the compound.

[0125] The supply of water can be carried out in an atmosphere of, for example, 0 to 250°C, preferably 60°C or higher, more preferably 100°C or higher, and preferably 180°C or lower, more preferably 150°C or lower. By supplying water in such a temperature range, it is possible to promote hydrolysis. The pressure at this time is not particularly limited, but can be set to normal pressure for convenience.

[0126] Next, the precursor film is heated on the surface of the substrate in a dry atmosphere at a temperature exceeding 60° C. The dry heating method is not particularly limited, and the precursor film may be placed together with the substrate in an atmosphere of unsaturated water vapor pressure at a temperature exceeding 60° C., preferably exceeding 100° C., for example, at a temperature of 250° C. or less, preferably 180° C. or less. The pressure at this time is not particularly limited, but may conveniently be normal pressure.

[0127] In such an atmosphere, between the PFPE-containing silane compounds of the present invention, the group bonded to Si after hydrolysis (R 1 are all hydroxyl groups, the hydroxyl groups are the hydroxyl groups. The same applies below) rapidly undergo dehydration condensation with each other. Furthermore, between such compounds and a substrate, the group bonded to Si after hydrolysis of the compound rapidly reacts with the reactive group present on the substrate surface, and when the reactive group present on the substrate surface is a hydroxyl group, dehydration condensation occurs. As a result, bonds are formed between the PFPE-containing silane compounds of the present invention, and also bonds are formed between the compounds and the substrate.

[0128] The above-mentioned moisture supply and dry heating may be carried out continuously by using superheated steam.

[0129] Superheated steam is a gas obtained by heating saturated steam to a temperature higher than its boiling point. Under normal pressure, the temperature exceeds 100°C, generally below 250°C, for example below 180°C, and the gas becomes unsaturated by heating to a temperature above the boiling point. When a substrate on which a precursor film has been formed is exposed to superheated steam, condensation first occurs on the precursor film surface due to the temperature difference between the superheated steam and the relatively low-temperature precursor film, thereby supplying moisture to the precursor film. As the temperature difference between the superheated steam and the precursor film gradually decreases, the moisture on the precursor film surface evaporates in the dry atmosphere created by the superheated steam, and the moisture content on the precursor film surface gradually decreases. While the moisture content on the precursor film surface is decreasing, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam and is heated to the temperature of this superheated steam (a temperature above 100°C under normal pressure). Therefore, when superheated steam is used, the supply of moisture and the drying and heating can be carried out continuously by simply exposing the substrate on which the precursor film has been formed to the superheated steam.

[0130] Post-treatment can be carried out as described above. While such post-treatment can be carried out to further improve friction durability, it should be noted that it is not essential for producing the article of the present invention. For example, the surface treatment agent of the present invention may be applied to the surface of a substrate and then simply left to stand.

[0131] As described above, a surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer obtained thereby has both high surface slippage and high friction durability. Furthermore, in addition to high friction durability, depending on the composition of the surface treatment agent used, this surface treatment layer may have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water penetration into electronic components, etc.), surface slippage (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel to the fingers), etc., and can be suitably used as a functional thin film.

[0132] That is, the present invention also relates to an optical material having the above-mentioned cured product as an outermost layer.

[0133] 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.

[0134] The article having a surface treatment layer obtained by the present invention is not particularly limited, and may be an optical member. Examples of optical members include lenses for eyeglasses, 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 display surfaces of watches.

[0135] Furthermore, the article having a surface treatment layer obtained by the present invention may be a medical device or a medical material.

[0136] The thickness of the surface treatment layer is not particularly limited. In the case of optical members, the thickness of the surface treatment 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, surface smoothness, friction durability, and antifouling properties.

[0137] The above describes in detail the articles obtained using the surface treatment agent of the present invention. However, the uses, methods of use, and methods of manufacturing articles of the surface treatment agent of the present invention are not limited to those exemplified above. [Example]

[0138] The surface treatment agent of the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples. In these examples, the four repeating units constituting the perfluoropolyether, (CF2O), (CF2CF2O), (CF(CF3)CF2O), (CF2CF2CF2O), and (CF2CF2CF2CF2O), may be present in any order.

[0139] Synthesis Example 1 A 100 mL four-neck flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 4.62 g of NaH and 0.41 g of tetrabutylammonium bromide, and then 23 g of 1,3-bis(trifluoromethyl)benzene, 42 g of 1,4-dibromobutane, and 10 g of pentaerythritol triallyl ether were added and stirred at 65°C. The mixture was then separated and purified to obtain 5.23 g of the following pentaerythritol triallyl ether bromo adduct (A). Pentaerythritol triallyl ether bromo adduct (A): BrCH2CH2CH2CH2OCH2C(CH2OCH2CH=CH2)3

[0140] Synthesis Example 2 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) 20 (CF2O) 16 8.96 g of a perfluoropolyether denatured alcohol represented by CF2CH2OH (note that the mixture also contains trace amounts of compounds containing repeating units of (CF2CF2CF2CF2O) and / or (CF2CF2CF2O), but these are not taken into consideration due to their extremely small amounts), 51 g of 1,3-bis(trifluoromethyl)benzene, and 0.39 g of KOH were charged and stirred at 70°C. Subsequently, 3.60 g of the pentaerythritol triallyl ether bromo adduct (A) obtained in Synthesis Example 1 and 0.14 g of tetrabutylammonium bromide were added and stirred at 70°C, followed by separation and purification to obtain 4.86 g of the following perfluoropolyether group-containing allyloxy compound (B) having an allyl group at the terminal. Perfluoropolyether group-containing allyloxy compound (B): CF3O(CF2CF2O) 20 (CF2O) 16 CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH=CH2)3

[0141] Synthesis Example 3 A 50 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 3.33 g of the perfluoropolyether group-containing allyloxy compound (B) synthesized in Synthesis Example 2, 7.24 g of 1,3-bis(trifluoromethyl)benzene, and 0.01 g of triacetoxymethylsilane, and stirred for 30 minutes. Subsequently, 1.16 g of trichlorosilane and 0.03 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, and the mixture was stirred at 60°C for 3 hours. The volatiles were then removed under reduced pressure, and a mixed solution of 0.13 g of methanol and 5.25 g of trimethyl orthoformate was added. The mixture was stirred at 50°C, and then purified to obtain 3.12 g of the following perfluoropolyether group-containing silane compound (C) with terminal trimethoxysilyl groups. Perfluoropolyether group-containing silane compound (C): CF3O(CF2CF2O) 20 (CF2O) 16 CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH2CH2Si(OMe)3)3

[0142] Synthesis Example 4 In a 100 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer, add CF3CF2CF2O (CF2CF2CF2O) of average composition 208.5 g of a perfluoropolyether modified alcohol represented by CF2CF2CH2OH, 45 g of 1,3-bis(trifluoromethyl)benzene, and 0.33 g of KOH were charged and stirred at 70° C. Subsequently, 3.10 g of the pentaerythritol triallyl ether bromo adduct (A) obtained in Synthesis Example 1 and 0.12 g of tetrabutylammonium bromide were added, and the mixture was stirred at 70° C., followed by separation and purification to obtain 4.81 g of the following perfluoropolyether group-containing allyloxy compound (D) having an allyl group at the terminal. Perfluoropolyether group-containing allyloxy compound (D): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH=CH2)3

[0143] Synthesis Example 5 A 50 mL four-neck flask equipped with a reflux condenser, thermometer, and stirrer was charged with 4.5 g of the perfluoropolyether group-containing allyloxy compound (D) synthesized in Synthesis Example 4, 8.87 g of 1,3-bis(trifluoromethyl)benzene, and 0.01 g of triacetoxymethylsilane and stirred for 30 minutes. Subsequently, 1.42 g of trichlorosilane and 0.04 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by stirring at 60°C for 3 hours. The volatiles were then removed under reduced pressure, and a mixture of 0.16 g of methanol and 6.44 g of trimethyl orthoformate was added. The mixture was stirred at 50°C, followed by separation and purification, yielding 4.36 g of the following perfluoropolyether group-containing silane compound (E) with terminal trimethoxysilyl groups. Perfluoropolyether group-containing silane compound (E): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH2CH2Si(OMe)3)3

[0144] Synthesis Example 6 In a 50 mL four-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, a perfluoropolyether group-containing allyloxy compound CFO (CFCFO) 20 (CF2O) 16 5.0 g of CF2C(OCH2CH=CH2)(CH2CH=CH2)2) (Note: The mixture also contains trace amounts of compounds containing repeating units of (CF2CF2CF2CF2O) and / or (CF2CF2CF2O), but these amounts are so small that they are not taken into account), 9.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.01 g of triacetoxymethylsilane were charged and stirred for 30 minutes. Next, 1.50 g of trichlorosilane and 0.05 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, and the mixture was stirred at 60°C for 3 hours. Thereafter, the volatile matter was distilled off under reduced pressure, and a mixed solution of 0.20 g of methanol and 7.0 g of trimethyl orthoformate was added, followed by stirring at 50°C, followed by separation and purification to obtain 5.32 g of the following perfluoropolyether group-containing silane compound (F) having a trimethoxysilyl group at the end. Perfluoropolyether group-containing silane compound (F): CF3O(CF2CF2O) 20 (CF2O) 16 CF2C[OCH2CH2CH2Si(OMe)3][CH2CH2CH2Si(OMe)3]2

[0145] Synthesis Example 7 In a 50 mL four-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, a perfluoropolyether group-containing allyloxy compound CF3CF2CF2O (CF2CF2CF2O) 204.0 g of CF2CF2C(OCH2CH=CH2)(CH2CH=CH2)2), 7.2 g of 1,3-bis(trifluoromethyl)benzene, and 0.01 g of triacetoxymethylsilane were added and stirred for 30 minutes. Next, 1.20 g of trichlorosilane and 0.04 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, and the mixture was stirred at 60°C for 3 hours. The volatiles were then removed under reduced pressure, and a mixed solution of 0.16 g of methanol and 5.6 g of trimethyl orthoformate was added. The mixture was stirred at 50°C, and then separated and purified to obtain 4.4 g of the following perfluoropolyether group-containing silane compound (G) with a terminal trimethoxysilyl group. Perfluoropolyether group-containing silane compound (G): CF3CF2CF2O(CF2CF2CF2O) 20 CF2CF2C[OCH2CH2CH2Si(OMe)3][CH2CH2CH2Si(OMe)3]2

[0146] Example 1 Surface treatment agent 1 was prepared by dissolving the compound (C) obtained in Synthesis Example 3 above in hydrofluoroether (Novec HFE7200, manufactured by 3M) to a concentration of 20 wt %.

[0147] The surface treatment agent 1 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 A 7 nm silicon dioxide film was formed on the surface of the chemically strengthened glass, and then 2 mg of the surface treatment agent (i.e., 0.4 mg of compound (C)) was vapor-deposited per piece of chemically strengthened glass (55 mm × 100 mm). The chemically strengthened glass with the vapor-deposited film was then left to stand for 24 hours in an atmosphere at a temperature of 20°C and a humidity of 65%.

[0148] Example 2 A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that compound (E) obtained in Synthesis Example 5 above was used instead of compound (C).

[0149] Example 3 A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that compound (F) obtained in Synthesis Example 6 above was used instead of compound (C).

[0150] Example 4 A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that compound (G) obtained in Synthesis Example 7 above was used instead of compound (C).

[0151] Example 5 A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the perfluoropolyether group-containing silane compound (H) shown below was used instead of the compound (C). Perfluoropolyether group-containing silane compound (H): CF3O(CF2CF2O) 20 (CF2O) 16 CF2C[OC(O)NHCH2CH2CH2Si(OMe)3][CH2CH2CH2Si(OMe)3]2

[0152] Comparative Examples 1 to 3 Surface treatment agents were prepared and surface treatment layers were formed in the same manner as in Example 1, except that the following control compounds 1 to 3 were used instead of compound (C). Control compound 1 CF3O(CF2CF2O) 20 (CF2O) 16 CF2CH2OCH2CH2CH2Si(OCH3)3 Control compound 2 [ka] (wherein g is an integer of 1 to 6) Control Compound 3 [ka] (wherein g is an integer of 1 to 6)

[0153] Friction durability evaluation 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.

[0154] 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 friction count). Then, as an evaluation of friction durability, a steel wool friction durability evaluation was performed. Specifically, the substrate with the surface treatment layer was placed horizontally, and steel wool (count #0000, dimensions 5 mm x 10 mm x 10 mm) was placed in contact with the exposed upper surface of the surface treatment layer. A load of 1,000 gf was applied, and then the steel wool was moved back and forth at a speed of 140 mm / s while the load was applied. The static contact angle of water (degrees) was measured every 2,500 reciprocations, and the evaluation was stopped when the measured contact angle fell below 100 degrees. The results are shown in Table 1 (in the table, the symbol "-" indicates no measurement).

[0155] [Table 1]

[0156] As can be seen from the above results, it was confirmed that Examples 1 to 5, which used the perfluoropolyether group-containing silane compound of the present invention having multiple Si(OMe)3 groups branched from the carbon atoms of the main chain, had improved friction durability compared to Comparative Examples 1 to 3, which used compounds without such a structure.

[0157] The present invention can be suitably used to form a surface treatment layer on the surface of a wide variety of substrates, particularly optical members that are required to have transparency.

Claims

1. Formula (1a) or Formula (1b): 【Chemical 1】 [In the formula: In formula (1a), Rf, in each occurrence, independently represents a perfluoroalkyl group having 1 to 16 carbon atoms; PFPE independently at each occurrence has the formula: -(OC ４ F ８ ) ａ -(OC ３ F ６ ) ｂ -(OC ２ F ４ ) ｃ -(OCF ２ ) ｄ - (In the formula, a, b, c, and d each independently represent an integer of 0 to 200, the sum of a, b, c, and d is at least 1, and the order of the repeating units enclosed in parentheses with the subscript a, b, c, or d is arbitrary in the formula.) is a group represented by The number average molecular weight of the Rf-PFPE portion is 500 to 30,000; In formula (1b), PFPE has the formula: -(OC 4 F 8 ) a - (OC 3 F 6 ) b - (OC 2 F 4 ) c - (OCF 2 ) d - (In the formula, a, b, c, and d each independently represent an integer of 0 to 200, the sum of a, b, c, and d is 4 or more, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a, b, c, or d is arbitrary in the formula.) is a group represented by Each X is independently -(R ３１ ) ｐ’ -(X ａ ) ｑ’ - is a group represented by R ３１ are each independently a single bond, -(CH ２ ) ｓ’ - (wherein s' is an integer from 1 to 20) or an o-, m-, or p-phenylene group; X ａ is -(X ｂ ) ｌ’ - (wherein l' is an integer from 1 to 10); X ｂ each occurrence independently represents an —O—, —S—, o-, m-, or p-phenylene group, —C(O)O—, —Si(R ３３ ) ２ -, -(Si(R ３３ ) ２ O) ｍ’ -Si(R ３３ ) ２ -(wherein m' is an integer of 1 to 100), -CONR ３４ --, --O-CONR ３４ -, -NR ３４ - and -(CH ２ ) ｎ’ - (wherein n' is an integer from 1 to 20); R ３３ is independently in each occurrence a phenyl group, C １－６ Alkyl group or C １－６ represents an alkoxy group; R ３４ is independently in each occurrence a hydrogen atom, a phenyl group or C １－６ represents an alkyl group; p' is 0, 1 or 2; q' is 0 or 1; wherein at least one of p' and q' is 1 or more, and the repeating units enclosed in parentheses with p' or q' may be present in any order in the formula; R ３１ and X ａ is a fluorine atom, C １－３ Alkyl group and C １－３ may be substituted with one or more substituents selected from fluoroalkyl groups; α is 1; β is 1; R ａ is independently at each occurrence -Z-CR １ ｐ R ２ ｑ R ３ ｒ represents; Z, in each occurrence, independently represents an oxygen atom or a divalent organic group; R １ represents, independently at each occurrence, R ａ’ represents; R ａ’ is R ａ is equivalent to; R ａ wherein the number of C's linearly linked via Z groups is at most 5; R ２ is independently at each occurrence -Y-SiR ５ ｎ R ６ ３－ｎ represents; Y, independently in each occurrence, is C １－６ Alkylene group, -(CH ２ ) ｇ’ -O-(CH ２ ) ｈ’ - (wherein g' is an integer of 0 to 6, and h' is an integer of 0 to 6), or -phenylene-(CH ２ ) ｉ’ - (wherein i' is an integer from 0 to 6); R ５ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R ６ represents, independently in each occurrence, a hydrogen atom or a group having 1 to 20 carbon atoms; n is (-Y-SiR ５ ｎ R ６ ３－ｎ ) units independently represent an integer of 1 to 3; R ３ each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; p is independently in each occurrence an integer from 0 to 3; q is independently in each occurrence an integer from 0 to 3; r, in each occurrence, is independently an integer from 0 to 3; R ｂ is independently at each occurrence -Y-SiR ５ ｎ R ６ ３－ｎ represents; R ｃ each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; k is 0; l is 2; m is 1; The hydrolyzable group is -OR, -OCOR, -ON=C(R) 2 , -N(R) 2 , -NHR, or halogen (wherein R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms). A perfluoro(poly)ether group-containing silane compound represented by the formula:

2. 2. The perfluoro(poly)ether group-containing silane compound according to claim 1, wherein Rf is a perfluoroalkyl group having 1 to 16 carbon atoms.

3. The PFPE is represented by any one of the following formulas (i) to (iv): -(OCF ２ CF ２ CF ２ ) ｂ - (i) [In the formula, b is an integer of 1 to 200.] -(OCF(CF ３ )CF ２ ) ｂ - (ii) [In the formula, b is an integer of 1 to 200.] -(OCF ２ CF ２ CF ２ CF ２ ) ａ -(OCF ２ CF ２ CF ２ ) ｂ -(OCF ２ CF ２ ) ｃ -(OCF ２ ) ｄ - (iii) [In the formula, a and b each independently represent an integer of 0 to 30, c and d each independently represent an integer of 1 to 200, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a, b, c, or d is arbitrary in the formula.] or -(OC ２ F ４ -R ８ ) ｎ” - (iv) [In the formula, R ８ is O.C. ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ or a combination of two or three groups independently selected from these groups; and n" is an integer from 2 to 100. The perfluoro(poly)ether group-containing silane compound according to claim 1 or 2, wherein the silane compound is a group represented by the formula:

4. X is independently: -CH ２ O(CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ -、 -CH ２ O(CH ２ ) ６ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ OCF ２ CHFOCF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ - -CH ２ OCH ２ (CH) ２ ) ７ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ３ -、 -(CH ２ ) ２ -、 -(CH ２ ) ３ -、 -(CH ２ ) ４ -、 -(CH ２ ) ５ -、 -(CH ２ ) ６ -、 -CONH-(CH ２ ) ３ -、 -CON(CH ３ )-(CH ２ ) ３ -、 -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), -CONH-(CH ２ ) ６ -、 -CON(CH ３ )-(CH ２ ) ６ -、 -CON(Ph)-(CH ２ ) ６ - (wherein Ph means phenyl), -CONH-(CH ２ ) ２ H ２ ) ３ -、 -CONH-(CH ２ ) ６ H ２ ) ３ -、 -CH ２ P.S. ２ ) ３ -、 -CH ２ P.S. ２ ) ６ -、 -S-(CH ２ ) ３ -、 -(CH ２ ) ２ S(CH ２ ) ３ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) 2 H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０ H ３ ) ２ (CH ２ ) ２ - -C(O)O-(CH ２ ) ３ -、 -C(O)O-(CH ２ ) ６ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ２ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ )-、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ３ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ )-CH ２ -、 -OCH ２ -、 -O(CH ２ ) ３ -、 -OCFHCF ２ -、 【Chemistry 2】 The perfluoro(poly)ether group-containing silane compound according to claim 1 or 2, selected from the group consisting of:

5. X is a single bond; R ｂ is -Y-SiR ５ ３ and Y, in each occurrence, is independently —O—(CH ２ ) ｈ’ - and h' is an integer from 1 to 6, R ５ is independently at each occurrence -OR; R is an alkyl group having 1 to 4 carbon atoms, R ｃ is a hydrogen atom, The perfluoro(poly)ether group-containing silane compound according to any one of claims 1 to 3.

6. The perfluoro(poly)ether group-containing silane compound according to any one of claims 1 to 5, which has a number average molecular weight of 2,000 to 32,000.

7. A surface treatment agent comprising at least one perfluoro(poly)ether group-containing silane compound represented by formula (1a) and / or formula (1b) according to any one of claims 1 to 6.

8. 8. The surface treatment agent according to claim 7, further comprising one or more other components selected from the group consisting of fluorine-containing oils, silicone oils, and catalysts.

9. The fluorine-containing oil is represented by the formula (3): R ２１ -(OC ４ F ８ ) ａ’ -(OC ３ F ６ ) ｂ’ -(OC ２ F ４ ) ｃ’ -(OCF ２ ) ｄ’ -R ２２ ・・・（３） [In the formula: R ２１ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; R ２２ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, a fluorine atom, or a hydrogen atom; 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, the sum of a', b', c', and d' is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula.] The surface treatment agent according to claim 8, which is one or more compounds represented by the following formula:

10. The fluorinated oil is represented by the formula (3a) or (3b): R ２１ -(OCF ２ CF ２ CF ２ ) ｂ’’ -R ２２ ・・・(3a) R ２１ -(OCF ２ CF ２ CF ２ CF ２ ) ａ’’ -(OCF ２ CF ２ CF ２ ) ｂ’’ -(OCF ２ CF ２ ) ｃ’’ -(OCF ２ ) ｄ’’ -R ２２ ・・・(3b) [In the formula: R ２１ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; R ２２ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, a fluorine atom, or a hydrogen atom; In formula (3a), b″ is an integer of 1 or more and 100 or less; In formula (3b), a″ and b″ each independently represent an integer of 0 or more and 30 or less, and c″ and d″ each independently represent an integer of 1 or more and 300 or less; The order of occurrence of each repeating unit enclosed in parentheses with the subscript a'', b'', c'', or d'' is arbitrary in the formula.] The surface treatment agent according to claim 8 or 9, which is one or more compounds represented by the following formula:

11. The surface treatment agent according to claim 10, comprising at least one compound represented by formula (3b):

12. The surface treatment agent according to claim 10 or 11, wherein the mass ratio of the at least one perfluoro(poly)ether group-containing silane compound represented by formula (1a) or formula (1b) according to any one of claims 1 to 6 to the compound represented by formula (3b) is 4:1 to 1:

4.

13. The surface treatment agent according to any one of claims 10 to 12, wherein the compound represented by formula (3a) has a number average molecular weight of 2,000 to 8,000.

14. The surface treatment agent according to any one of claims 10 to 13, wherein the compound represented by formula (3b) has a number average molecular weight of 2,000 to 30,000.

15. The surface treatment agent according to any one of claims 10 to 14, wherein the compound represented by formula (3b) has a number average molecular weight of 8,000 to 30,000.

16. The surface treatment agent according to any one of claims 7 to 15, further comprising a solvent.

17. The surface treatment agent according to any one of claims 7 to 16, which is used as an antifouling coating agent or a waterproof coating agent.

18. The surface treatment agent according to any one of claims 7 to 17, which is for vacuum deposition.

19. A pellet containing the surface treatment agent according to any one of claims 7 to 18.

20. An article comprising a substrate and a layer formed on the surface of the substrate from the compound according to any one of claims 1 to 6 or the surface treatment agent according to any one of claims 7 to 18.

21. 21. The article of claim 20, wherein the article is an optical element.

22. 21. The article of claim 20, wherein the article is a display.

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