JP2019077879A - Surface treatment agent comprising silane compound containing perfluoro(poly)ether group, and pellets and article using the same - Google Patents

Abstract

To provide a surface treatment agent suitable for obtaining a surface treatment layer with improved durability.SOLUTION: The present invention provides a surface treatment agent comprising a silane compound which contains a perfluoro(poly)ether group, OPC, and a compound which includes an atom with an unshared electron pair in the molecular structure. The perfluoro (poly) ether group independently represents, every time it appears, a group represented by -(OCF)-(OCF)-(OCF)-(OCF)-(OCF)-(OCF)- (a, b, c, d, e and f independently represent an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f is at least 1; in the formula, parenthesized repeating units with symbols of a, b, c, d, e and f are arranged in any order).SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing silane compound, and a pellet and an article using the same.

  It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, stain resistance and the like when used for surface treatment of a substrate. As such fluorine-containing silane compounds, perfluoropolyether group-containing silane compounds having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal end are known. It is done. For example, Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal end.

  The layer obtained from the surface treatment agent containing the fluorine-containing silane compound as described above (hereinafter also referred to as "surface treatment layer") is applied to glass or the like as a so-called functional thin film. In particular, since the surface treatment layer can exhibit the above-described function even with a thin film, it is applied to optical members such as glasses, touch panels, and operation screens of portable terminals that are required to have light transparency or transparency.

JP, 2013-117012, A

  The surface treatment layer as described above is required to have good durability in order to impart the desired function to the surface of the substrate over a long period of time. However, it was found by the study of the present inventors that the surface treatment layer as described above may not have sufficient durability.

  An object of the present invention is to provide a surface treatment agent suitable for obtaining a surface treatment layer with improved durability.

［式中：
ＰＦＰＥは、各出現においてそれぞれ独立して、式：
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−
（ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
Ｒ^１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^１４は、各出現においてそれぞれ独立して、水素原子または炭素数１〜２２のアルキル基を表し；
Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎは、（−ＳｉＲ^１３ _ｎＲ^１４ _３−ｎ）単位毎に独立して、０〜３の整数であり；
ただし、式（Ａ１）および（Ａ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
Ｘ^１は、各出現においてそれぞれ独立して、単結合または２〜１０価の有機基を表し；
Ｘ^２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
ｔは、各出現においてそれぞれ独立して、１〜１０の整数であり；
αは、各出現においてそれぞれ独立して、１〜９の整数であり；
α’は、それぞれ独立して、１〜９の整数であり；
Ｘ^３は、各出現においてそれぞれ独立して、単結合または２〜１０価の有機基を表し；
βは、各出現においてそれぞれ独立して、１〜９の整数であり；
β’は、それぞれ独立して、１〜９の整数であり；
Ｒ^ａは、各出現においてそれぞれ独立して、−Ｚ^１−ＳｉＲ^１ _ｐＲ^２ _ｑＲ^３ _ｒを表し；
Ｚ^１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
Ｒ^１は、各出現においてそれぞれ独立して、Ｒ^ａ’を表し；
Ｒ^ａ’は、Ｒ^ａと同意義であり；
Ｒ^ａ中、Ｚ^１基を介して直鎖状に連結されるＳｉは最大で５個であり；
Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒは、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、−Ｚ^１−ＳｉＲ^１ _ｐＲ^２ _ｑＲ^３ _ｒ毎において、ｐ、ｑおよびｒの和は３であり、式（Ｂ１）および（Ｂ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
Ｒ^ｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^ｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ１は、各出現においてそれぞれ独立して、０〜２の整数であり；
ｍ１は、各出現においてそれぞれ独立して、０〜２の整数であり；
ただし、−ＳｉＲ^ａ _ｋ１Ｒ^ｂ _ｌ１Ｒ^ｃ _ｍ１毎において、ｋ１、ｌ１およびｍ１の和は３であり、
Ｘ^４は、各出現においてそれぞれ独立して、単結合または２〜１０価の有機基を表し；
γは、各出現においてそれぞれ独立して、１〜９の整数であり；
γ’は、それぞれ独立して、１〜９の整数であり；
Ｒ^ｄは、各出現においてそれぞれ独立して、−Ｚ^２−ＣＲ^８１ _ｐ２Ｒ^８２ _ｑ２Ｒ^８３ _ｒ２を表し；
Ｚ^２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
Ｒ^８１は、各出現においてそれぞれ独立して、Ｒ^ｄ’を表し；
Ｒ^ｄ’は、Ｒ^ｄと同意義であり；
Ｒ^ｄ中、Ｚ^２基を介して直鎖状に連結されるＣは最大で５個であり；
Ｒ^８２は、各出現においてそれぞれ独立して、−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２を表し；
Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
Ｒ^８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎ２は、（−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２）単位毎に独立して、０〜３の整数を表し；
Ｒ^８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、−Ｚ^２−ＣＲ^８１ _ｐ２Ｒ^８２ _ｑ２Ｒ^８３ _ｒ２毎において、ｐ２、ｑ２およびｒ２の和は３であり；
Ｒ^ｅは、各出現においてそれぞれ独立して、−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２を表し；
Ｒ^ｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、、（ＣＲ^ｄ _ｋ２Ｒ^ｅ _ｌ２Ｒ^ｆ _ｍ２）毎において、ｋ２、ｌ２およびｍ２の和は３であり、式（Ｃ１）および（Ｃ２）において、−Ｙ−ＳｉＲ^８５で表される基が２以上存在する。］
のいずれかで表されるパーフルオロ（ポリ）エーテル基含有シラン化合物、および分子構造内に非共有電子対を有する原子を含む化合物を含有する表面処理剤が提供される。 According to a first aspect of the present invention, there are provided: Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1) or Formula (C2):

[In the formula:
The PFPEs each independently at each occurrence have the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹³ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ¹⁴ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n is an integer of 0 to 3 independently for each (-SiR ¹³ _n R ¹⁴ _3-n ) unit;
However, in the formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present;
X ¹ represents independently at each occurrence a single bond or a di- to 10-valent organic group;
X ² represents independently at each occurrence a single bond or a divalent organic group;
t is an integer of 1 to 10 independently at each occurrence;
α is an integer of 1 to 9 independently at each occurrence;
α 'is each independently an integer of 1 to 9;
X ³ represents independently at each occurrence a single bond or a di- to 10-valent organic group;
β is each independently an integer of 1 to 9 at each occurrence;
β 'is each independently an integer of 1 to 9;
R ^a independently represents -Z ¹ -SiR ¹ _p R ² _q R ³ _r at each occurrence;
Z ¹ independently represents an oxygen atom or a divalent organic group at each occurrence;
R ¹ represents R ^{a ′} independently at each occurrence;
R ^{a '} is as defined the R ^a ;
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ² each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p is each independently an integer of 0 to 3 at each occurrence;
q is each independently an integer of 0 to 3 at each occurrence;
r is each independently an integer of 0 to 3 at each occurrence;
Provided that, for each -Z ¹ -SiR ¹ _p R ² _q R ³ _r , the sum of p, q and r is 3, and in formulas (B1) and (B2), they are bonded to a hydroxyl group or a hydrolysable group At least two Si are present;
R ^b independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ^c independently at each occurrence represents a hydrogen atom or a lower alkyl group;
k1 each independently at each occurrence is an integer of 0 to 3;
l 1 is each independently an integer of 0 to 2 at each occurrence;
m1 is each independently an integer of 0 to 2 at each occurrence;
Provided that ^the sum of _{-SiR a} ^k1 _R b ^l1 in each _{R c m1,} k1, l1 and m1 is 3,
X ⁴ independently at each occurrence represents a single bond or a di- to 10-valent organic group;
γ is an integer of 1 to 9 independently at each occurrence;
γ 'is each independently an integer of 1 to 9;
R ^d independently at each occurrence represents -Z ² -CR ⁸¹ _{p 2} R ⁸² _{q 2} R ⁸³ _{r 2} ;
Z ² each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is the same as R ^d ;
In ^Rd, at most 5 Cs linked in a linear fashion via a Z ² group;
R ⁸² independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence;
Y represents, independently at each occurrence, a divalent organic group;
R ⁸⁵ each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n2 represents an integer of 0 to 3 independently for each (-Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ) unit;
R ⁸³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p2 is each independently an integer of 0 to 3 at each occurrence;
q2 is each independently an integer of 0 to 3 at each occurrence;
r2 each independently at each occurrence is an integer from 0 to 3;
With the proviso that for every -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r 2 the sum of p2, q2 and r2 is 3;
R ^e each independently at each occurrence represents —Y—SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ;
R ^f independently at each occurrence independently represents a hydrogen atom or a lower alkyl group;
k2 each independently at each occurrence is an integer from 0 to 3;
l2 is each independently an integer of 0 to 3 at each occurrence;
m2 is each independently an integer of 0 to 3 at each occurrence;
However, in every (CR ^d _{k 2} R ^{e 1} ₂ R ^f _{m 2} ), the sum of k 2, 12 and m 2 is 3, and in the formulas (C 1) and (C 2), the group represented by —Y—SiR ⁸⁵ is There are two or more. ]
There is provided a surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound represented by any of the following, and a compound containing an atom having an unshared electron pair in the molecular structure.

  According to a second aspect of the present invention, there is provided a pellet containing the surface treatment agent of the present invention.

  According to a third aspect of the present invention, there is provided an article comprising a substrate and a layer formed of the surface treatment agent of the present invention on the surface of the substrate.

  According to the present invention, there is provided a novel surface treatment agent comprising a perfluoro (poly) ether group (hereinafter sometimes referred to as "PFPE")-containing silane compound. The surface treatment agent of the present invention is suitable for forming a surface treatment layer with improved durability, in particular, a surface treatment layer that exhibits good durability even in the presence of an acid or an alkali. Further, according to the present invention, a pellet containing the surface treatment agent of the present invention is provided. According to the present invention, there is provided an article comprising a substrate and a layer formed of the surface treatment agent of the present invention on the surface of the substrate.

  As used herein, "hydrocarbon group" refers to a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group, Aromatic hydrocarbon groups and the like can be mentioned. 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. Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.

As used herein, the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C _1-6 alkyl which may be substituted by one or more halogen atoms Group, _C2-6 alkenyl group, _C2-6 alkynyl group, _C3-10 cycloalkyl group, _C3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from C _6-10 aryl group and 5- to 10-membered heteroaryl group.

In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified. The substituent of such groups include, but are not limited to, for example, a halogen atom, C _1-6 alkyl group in which one or more groups selected from C _2-6 alkenyl and C _2-6 alkynyl group It can be mentioned.

  As used herein, "di- to 10-valent organic group" means a carbon-containing di- to 10-valent group. Although it does not specifically limit as this 2-10-valent organic group, The 2-10-valent group which eliminated 1-9 hydrogen atoms further from the hydrocarbon group is mentioned.

[Surface treatment agent]
Hereinafter, the surface treatment agent of the present invention will be described.

  The surface treatment agent of the present invention contains a PFPE-containing silane compound and a compound containing an atom having a noncovalent electron pair in the molecular structure.

(PFPE-containing silane compounds)
The PFPE-containing silane compound is a compound represented by any of Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1) or Formula (C2).

  The PFPE-containing silane compound is preferably contained in an amount of 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the surface treatment agent.

The PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . Among these ranges, it is preferable from the viewpoint of friction durability to have a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000. In the present invention, the number average molecular weight is a value measured by ¹⁹ F-NMR.

  In one aspect, the PFPE-containing silane compound of the present invention is 1,000 to 40,000, preferably 1,000 to 32,000, more preferably 1,000 to 20,000, still more preferably 1,000. It may have a number average molecular weight of ̃12,000.

  Hereinafter, PFPE containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1) and (C2) will be described.

Formulas (A1) and (A2):

  In the above formulae, R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.

  The "C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by one or more fluorine atoms is a branched chain even if it is linear or It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

The above Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, and more preferably a CF ₂ H—C _1-15 perfluoroalkylene group or C _{1 — It is a 16} perfluoroalkyl group, more preferably a C _1-16 perfluoroalkyl group.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms, in a linear or branched chain. a 3 perfluoroalkyl group, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, straight-chain, specifically is _-CF 3, _-CF 2 CF ₃ or _-CF 2 _CF 2 CF _3, .

In the above formula, PFPE is independently at each occurrence:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
Is a group represented by In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.

These repeating units may be linear or branched, but are preferably linear. For _{example, - (OC 6 F 12)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2 CF 2) -, - (OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- _{, - (OCF 2 CF 2 CF} 2 CF 2 CF (CF 3)) - may be, etc., but preferably _{- (OCF 2 CF 2 CF 2} CF 2 CF 2 CF 2) - a. - _{(OC 5 F} 10) - _{is, - (OCF 2 CF 2 CF} 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ))-or the like, but is preferably-( _{OCF 2 CF 2 CF 2 CF 2} CF 2) - a. - _{(OC 4} F 8) - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) - _{, - (OCF 2 CF 2 CF} (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF ₃ )),-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-, but is preferably-(OCF ₂ CF _2). CF ₂ CF ₂₎ - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. _{Also, - (OC 2 F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but it may be any of, preferably - _{(OCF 2} CF 2) - in is there.

In one embodiment, the PFPE may - is (wherein, d is 1 to 200, preferably 5 to 200, more preferably 10 to 200 _{integer) - (OC 3 F 6)} d . Preferably, PFPE is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d 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 (CF ₃ ) CF ₂ ) _d — (wherein d 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, PFPE is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d 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) .

In another embodiment, the PFPE is — (OC ₄ F ₈ ) _c — (OC ₃ F ₆ ) _d — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f —, wherein c and d are each independently And e and f are each independently 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 c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula). Preferably, PFPE _{is, - (OCF 2 CF 2 CF} 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a. In one aspect, PFPE is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).

In one aspect, PFPE is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).

  In the above formula, in PFPE, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5.0 or less, and more preferably It is 0.2 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less. By setting the e / f ratio in the above range, the water repellency, oil repellency and chemical resistance of the cured product obtained from this compound (for example, durability against aqueous solution of salt, acid or basic solution, acetone, oleic acid or hexane) ) Can be further improved. The smaller the e / f ratio, the better the water repellency, oil repellency and chemical resistance of the cured product. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.

In still another aspect, PFPE is a group represented by-(R ⁶ -R ⁷ ) _j- . In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or selected independently from these groups A combination of two or three groups. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ It is a selected group, or a combination of 2 or 3 groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. For example, -OC ₂ F ₄ OC ₃ F _6- , -OC ₂ F ₄ OC ₄ F ₈ −, −OC ₃ F ₆ OC ₂ F ₄ −, −OC ₃ F ₆ OC ₃ F ₆ −, −OC ₃ F ₆ OC ₄ F ₈ −, −OC ₄ F ₈ OC ₄ F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC ₄ F ₈ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ −, −OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ −, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 _{F 4 OC 3 F 6 -,} - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _{-OC 4 F 8 OC 2 F 4} OC 2 F 4 - , and the like. The j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear . In this embodiment, PFPE is _{preferably, - (OC 2 F 4 -OC} 3 F 6) j - or _{- (OC 2 F 4 -OC 4} F 8) j - is.

In one aspect, wherein PFPE is independently at each occurrence:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
And at least one branched structure in PFPE. That is, in the present embodiment, the PFPE has at least one CF ₃ terminal (specifically, -CF ₃ , -C ₂ F ₅ or the like, more specifically -CF ₃ ). The UV durability, water repellency, oil repellency, stain resistance (for example, dirt such as fingerprints) of a layer (for example, surface treated layer) formed using the surface treating agent of the present invention by having PFPE of such a structure (3), chemical resistance, hydrolysis resistance, anti-slip effect, high friction durability, heat resistance, moisture resistance and the like may be further improved.

  In the above embodiment, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.

  In the above embodiment, the PFPE preferably has at least 5 branched structures, more preferably 10, and particularly preferably 20.

  In the above embodiment, the number of repeating units having a branched structure is 40 or more in the PFPE structure with respect to the total number of repeating units (for example, the sum of the above a, b, c, d, e and f) 100. Is preferably 60 or more, more preferably 80 or more. In the PFPE structure, the number of repeating units having a branched structure may be 100 or less, for example, 90 or less, with respect to the total number 100 of the number of repeating units.

  In the above embodiment, the number of repeating units having a branched structure is preferably in the range of 40 to 100, more preferably in the range of 60 to 100, with respect to the total number 100 of repeating units in the PFPE structure. Preferably, it is particularly preferably in the range of 80 to 100.

In the above aspect, as the branched chain in the branched structure, for example, CF ₃ can be mentioned.

In the above embodiment, as the repeating unit having a branched structure, for _{example, - (OC 6 F 12)} - _{As, - (OCF (CF 3)} CF 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF ( _{CF 3) CF 2 CF 2 CF} 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF 2 CF (CF 3) CF 2) -, - ( _{OCF 2 CF 2 CF 2 CF 2} CF (CF 3)) - , and the like. - _{(OC 5 F 10)} - _{As, - (OCF (CF 3)} CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF _{(CF 3) CF 2) -} , - (OCF 2 CF 2 CF 2 CF (CF 3)) - , and the like. - _(OC 4 _{F 8)} - _{The, - (OCF (CF 3)} CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) -, - (OCF 2 CF 2 CF (CF 3) _{) -, - (OC (CF} 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF (CF 3)) -, - (OCF (C 2 F ₅₎ CF ₂₎ - and _{- (OCF 2 CF (C 2} F 5)) - can be exemplified. - _(OC 3 _{F 6)} - _{The, - (OCF (CF 3)} CF 2) - and _{- (OCF 2 CF (CF 3} )) - can be exemplified. - _(OC 2 _{F 4)} - _{The, - (OCF (CF 3)} ) - can be exemplified.

In the above embodiment, the PFPE may include a linear repeating unit together with the repeating unit having a branched structure. The repeating unit of _{linear, - (OCF 2 CF 2 CF} 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF 2 CF 2 CF _{2) -, - (OCF 2} CF 2 CF 2) -, - (OCF 2 CF 2) - can be exemplified.

In the above embodiments, preferably, in the above PFPE, repeating unit _{- (OC 6 F 12) -} , - (OC 5 F 10) -, - (OC 4 F 8) -, and - _(OC 3 _{F 6)} - is It has a branched structure.

In the above embodiment, more preferably, the PFPE consists of repeating units OC ₆ F ₁₂ , OC ₅ F ₁₀ , OC ₄ F ₈ , and OC ₃ F _{6 of} branched structure.

In one aspect, the PFPE is — (OC ₃ F ₆ ) _d — (wherein d 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) , At least one branch structure in the PFPE.

In the above embodiments, PFPE further linear repeating unit _{- (OCF 2 CF 2 CF 2} ) - may contain.

In the above aspect, the PFPE preferably comprises a repeating unit OC ₃ F ₆ having a branched structure. The PFPE has the formula _{:-( OCF 2 CF (CF 3)} ) It is more preferably represented _d. In In the above formula, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less.

In another embodiment, the PFPE is — (OC ₄ F ₈ ) _c — (OC ₃ F ₆ ) _d — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f —, wherein c and d are each independently And e and f are each independently 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 c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order of existence of the respective repeating units enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula), It has at least one branched structure in PFPE.

In yet another embodiment, PFPE is a group represented by-(R ⁶ -R ⁷ ) _j- and has at least one branched structure in PFPE. In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or selected independently from these groups A combination of two or three groups. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ It is a selected group, or a combination of 2 or 3 groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. For example, -OC ₂ F ₄ OC ₃ F _6- , -OC ₂ F ₄ OC ₄ F ₈ −, −OC ₃ F ₆ OC ₂ F ₄ −, −OC ₃ F ₆ OC ₃ F ₆ −, −OC ₃ F ₆ OC ₄ F ₈ −, −OC ₄ F ₈ OC ₄ F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC ₄ F ₈ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ −, −OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ −, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 _{F 4 OC 3 F 6 -,} - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _{-OC 4 F 8 OC 2 F 4} OC 2 F 4 - , and the like. The j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ preferably have a branched structure.

More preferably, in the above aspect, the PFPE consists of repeating units OC ₆ F ₁₂ , OC ₅ F ₁₀ , OC ₄ F ₈ , and OC ₃ F _{6 of} branched structure.

  The average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.

  In another embodiment, the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.

  In another aspect, the number average molecular weight of the Rf-PFPE-moiety or -PFPE-moiety may be from 4,000 to 30,000, preferably 5,000 to 10,000.

In the above formulae, R ¹³ independently at each occurrence represents a hydroxyl group or a hydrolysable group.

The above "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving a main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N = CR ₂ , —NR ₂ , —NHR, and a halogen atom (in these formulas, R represents a substituted or unsubstituted C 1 -C 1 carbon atom) And the like), and preferably -OR (i.e., an alkoxy group). 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 them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The above “hydroxy group” is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group.

In the above formulae, R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms at each occurrence.

In the above formulas, each occurrence of R ¹¹ independently represents a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.

In the above formulas, each occurrence of R ¹² independently represents 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 examples thereof include a methyl group, an ethyl group and a propyl group.

In the above formulae, n is independently an integer of 0 to 3, preferably 1 to 3, and more preferably 3 for each (-SiR ¹³ _n R ¹⁴ _3-n ) unit. However, in the formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group exist. That is, in the formulas (A1) and (A2), at least two structures of SiR ¹³ exist.

In the above formulae, each X ¹ independently represents a single bond or a di- to 10-valent organic group. The said X ¹ is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (A1) and (A2) And a silane moiety that provides the ability to bind to a substrate (ie, a group that is bracketed with a). Accordingly, X ¹ may be any organic group as long as the compounds represented by formulas (A1) and (A2) can stably exist.

In another aspect, X ¹ represents X ^e . X ^e represents a single bond or a 2-10 monovalent organic group, preferably a single bond or _-C 6 _{H 4} -, (i.e. - - phenylene. Hereinafter, a phenylene group.) - CO- (carbonyl group 2) a divalent to 10-valent organic group having at least one selected from the group consisting of -NR ⁴ -and -SO _2- ; Each R ⁴ independently represents a hydrogen atom, a phenyl group, or a C _1-6 alkyl group (preferably a methyl group), and is preferably a hydrogen atom or a methyl group. Additional _{-C 6 H 4 -, - CO} -, - NR 4 - or -SO ₂ - is preferably contained in the molecular backbone of the PFPE-containing silane compound. Here, the molecular main chain refers to a relatively long linked PFPE in the molecule of the PFPE-containing silane compound.

X ^e is more preferably a single bond or _{^{-C 6 H 4 -, - CONR}} 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR _{^{4 -, - SO 2 NR 4}} -C 6 H 4 -, - SO 2 -, and _-SO 2 _-C 6 _{H 4} - represents a 2-10 monovalent organic group having at least one selected from the group consisting of . Additional _{^{-C 6 H 4 -, - CONR}} 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - _{C 6 H 4 -, - SO} 2 -, or _-SO 2 _-C 6 _{H 4} - is preferably contained in the molecular backbone of the PFPE-containing silane compound.

In said formula, (alpha) is an integer of 1-9, and (alpha) 'is an integer of 1-9. These α and α ′ can vary depending on the valence of X ¹ . In formula (A1), the sum of α and α ′ is the same as the valence of X ¹ . For example, when X ¹ is a 10-valent organic group, the sum of α and α ′ is 10, eg, α is 9 and α ′ is 1, α is 5 and α ′ is 5 or 'Can be nine. When X ¹ is a divalent organic group, α and α ′ are 1. In formula (A2), α is a value obtained by subtracting 1 from the valence of X ¹ .

The above X ¹ is preferably 2 to 7 valences, more preferably 2 to 4 valences, and still more preferably a divalent organic group.

In one aspect, X ¹ is a divalent to tetravalent organic group, α is 1 to 3 and α ′ is 1.

In another embodiment, X ¹ is a divalent organic group, α is 1 and α ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).

Although it does not specifically limit as an example of said X ¹ , For example, following formula:
_{^{- (R 31) p '-}} (X a) q' -
[In the formula:
R ³¹ represents a single bond, - _(CH 2) _{s '-} or o-, represents m- or p- phenylene, preferably - _(CH 2) _s' - a and,
s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2.
X ^a represents-(X ^b ) _{l '} -
X ^b is each independently -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 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - _(CH 2) _n' - is selected from the group consisting of Represents a group
R ³³ each independently represents, in each occurrence, a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group And
R ³⁴ independently at each occurrence represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group),
m 'is independently at each occurrence an integer of 1 to 100, preferably an integer of 1 to 20,
n 'in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 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 or 1 and
q 'is 0 or 1 and
Here, at least one of p 'and q' is 1, and the existence order of each repeating unit enclosed in parentheses with p 'or q' is arbitrary.]
The bivalent group represented by these is mentioned. Here, R ³¹ and X ^a (typically, ^a hydrogen atom of R ³¹ and X ^a ) are one or more selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group It may be substituted by the substituent of

Preferably, the above X ¹ _is- (R ³¹ ) _{p '} -(X ^a ) _q' -R ^32- . R ³² represents a single bond,-(CH ₂ ) _{t '} -or o-, m- or p-phenylene group, preferably-(CH ₂ ) _t'- . t 'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R ³² (typically, a hydrogen atom of R ³² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group It may be

Preferably, said X ¹ is
C _1-20 alkylene group,
-R ³¹ -X ^c -R ³² - or ^-X d ^{-R 32,} -
[Wherein, R ³¹ and R ³² are as defined above. ]
It can be. In addition, an alkylene group is a group which has _a- (C ( _delta ) H2 ( _delta ))-structure, may be substituted or unsubstituted, and may be linear or branched form.

More preferably, X ¹ is
C _1-20 alkylene group,
_{- (CH 2) s' -X} c -,
-(CH ₂ ) _{s '} -X ^c- (CH ₂ ) _t'- ,
-X ^d- or-X ^d- (CH ₂ ) _{t '} -
[Wherein, s ′ and t ′ are as defined above. ]
It is.

In the above formula, X ^c is
-O-,
-S-,
-C (O) O-,
-CONR ³⁴ -,
-O-CONR ³⁴ -,
-Si (R ³³ ) _2- ,
_{^{- (Si (R 33) 2}} O) m '-Si (R 33) 2 -,
_{-O- (CH 2) u '-} (Si (R 33) 2 O) m' -Si (R 33) 2 -,
^{_{-O- (CH 2) u '-Si}} (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -,
_{-O- (CH 2) u '-Si} (OCH 3) 2 OSi (OCH 3) 2 -,
_{^{-CONR 34 - (CH 2) u}} '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
_{^{-CONR 34 - (CH 2) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[Wherein, R ³³ , R ³⁴ and m ′ are as defined above,
u 'is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Represents]. X ^c is preferably -O-.

In the above formula, X ^d is
-S-,
-C (O) O-,
-CONR ³⁴ -,
_{^{-CONR 34 - (CH 2) u}} '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
_{^{-CONR 34 - (CH 2) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[Wherein each symbol is as defined above. ]
Represents

More preferably, X ¹ is
C _1-20 alkylene group,
_{- (CH 2) s' -X} c - (CH 2) t '-, or _{^{-X d - (CH 2) t}} ' -
[Wherein each symbol is as defined above. ]
It can be.

Even more preferably, X ¹ is
C _1-20 alkylene group,
_{- (CH 2) s '-O-} (CH 2) t' -,
_{- (CH 2) s' -} (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
_{- (CH 2) s '-O-} (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - _(CH 2) _{s' -O- (CH 2) t} '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) -
[Wherein, R ³³ , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3] It is an integer. ]
It is.

In the above formulae,-(C _v H _2v ) _{-may be} linear or branched, and for example, -CH _2- , -CH ₂ CH _2- , -CH ₂ CH ₂ CH _{2 -, - CH (CH 3} ) -, - CH (CH 3) CH 2 - may be.

The X ¹ group is substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group (preferably, a C _1-3 perfluoroalkyl group) It may be done.

In one aspect, the X ¹ group may be other than an —O—C _1-6 alkylene group.

［式中、Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基、好ましくはメチル基であり；
Ｄは、
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）₄−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、および

（式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
Ｅは、−（ＣＨ_２）_ｎｅ−（ｎｅは２〜６の整数）であり、
Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, the X ¹ group includes, for example, the following groups:

[Wherein, each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl), and

(Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group).
Is a group selected from
E is _- a (ne is an integer of from 2 to _6), - _{(CH 2)} ne
D is attached to the PFPE of the molecular backbone and E is attached to the opposite group to the PFPE. ]

などが挙げられる。 Specific examples of the above X ¹ include, for example:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{- (CH 2) 2 -Si (} CH 3) 2 - (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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 OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
- _{(CH 2)} 6 -,
-CO-,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-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 NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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- ,

Etc.

In another preferred embodiment, X ¹ represents X ^{e ′} . X ^{e ′} is a single bond, an alkylene group having 1 to 6 carbon atoms, -R ⁵¹ -C ₆ H ₄ -R ^52- , -R ⁵¹ -CONR ⁴ -R ^52- , -R ⁵¹ -CONR ⁴ -C ₆ H ₄ -R ^52- , -R ⁵¹ -CO-R ^52- , -R ⁵¹ -CO-C ₆ H ₄ -R ^52- , -R ⁵¹ -SO ₂ NR ⁴ -R ^52- , -R ⁵¹ -SO ₂ NR ⁴ -C ₆ H ₄ -R ^52- , -R ⁵¹ -SO ₂ -R ^52- , or -R ⁵¹ -SO ₂ -C ₆ H ₄ -R ^52- . R ⁵¹ and R ⁵² each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R ⁴ is as defined above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. As a substituent of the said alkylene group, a halogen atom, Preferably a fluorine atom can be mentioned, for example. The alkylene group is linear or branched, and is preferably linear.

In a further preferred embodiment X ^{e ′} is
Single bond,
An alkylene group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-C ₆ H ₄ -R ^{52 '} -,
-CONR ^{4 '-R 52'} -,
_{^{-CONR 4 '-C 6 H 4 -R}} 52' -,
-CO-R ^{52 '} -,
^{_{-CO-C 6 H 4 -R 52}} '-,
_{^{-SO 2 NR 4 '-R 52'}} -,
_{^{-SO 2 NR 4 '-C 6 H}} 4 -R 52' -,
-SO ₂ -R ^{52 '} -,
-SO ₂ -C ₆ H ₄ -R ^{52 '} -,
_{^{-R 51 '-C 6 H 4 -}} ,
-R ^{51 '-CONR 4'} -,
_{^{-R 51 '-CONR 4' -C 6}} H 4 -,
-R ^{51 '} -CO-,
_{^{-R 51 '-CO-C 6 H}} 4 -,
_{^{-R 51 '-SO 2 NR 4'}} -,
_{^{-R 51 '-SO 2 NR 4'}} -C 6 H 4 -,
-R ^{51 '} -SO _2- ,
_{^{-R 51 '-SO 2 -C 6 H}} 4 -,
-C ₆ H ₄ -,
-CONR ^{4 '} -,
_{^{-CONR 4 '-C 6 H 4 -}} ,
-CO-,
_{-CO-C 6 H} 4 -,
-SO ₂ NR ^{4 '} -,
_{^{-SO 2 NR 4 '-C 6 H}} 4 -,
-SO ₂ -, or _-SO 2 _-C 6 _{H 4} -
(Wherein, R ^{51 ′} and R ^{52 ′} each independently represent a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
R ^{4 ′} is a hydrogen atom or a methyl group. )
It can be.

In the present embodiment, specific examples of X ^{e ′} include, for example,
Single bond,
An alkylene group having 1 to 6 carbon atoms,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON _(CH 3) -,
_{-CON (CH 3) -CH 2 -} ,
_{-CON (CH 3) - (CH} 2) 2 -,
_{-CON (CH 3) - (CH} 2) 3 -,
-CH ₂ -CONH-,
-CH _{2 -CONH-CH 2} -,
_{-CH 2 -CONH- (CH 2) 2} -,
_{-CH 2 -CONH- (CH 2) 3} -,
_{-CONH-C 6 H} 4 -,
_{-CON (CH 3) -C 6 H} 4 -,
_{-CH 2 -CON (CH 3) -CH} 2 -,
-CH ₂ -CON (CH ₃ )-(CH ₂ ) _2- ,
_{-CH 2 -CON (CH 3) -} (CH 2) 3 -,
_{-CON (CH 3) -C 6 H} 4 -,
-CO-,
_{-CO-C 6 H} 4 -,
-C ₆ H ₄ -,
-SO ₂ NH-,
-SO _{2 NH-CH 2} -,
_{-SO 2 NH- (CH 2) 2} -,
_{-SO 2 NH- (CH 2) 3} -,
_{-SO 2 NH-C 6 H 4} -,
_{-SO 2 N (CH 3) -} ,
_{-SO 2 N (CH 3) -CH} 2 -,
_{-SO 2 N (CH 3) -} (CH 2) 2 -,
_{-SO 2 N (CH 3) -} (CH 2) 3 -,
_{-SO 2 N (CH 3) -C} 6 H 4 -,
-SO _2- ,
-SO ₂ -CH _2- ,
-SO _2- (CH ₂ ) _2- ,
_{-SO 2 - (CH 2) 3} -, or _-SO 2 _-C 6 _{H 4} -
Etc.

In one embodiment, X ^{e ′} is a single bond. In this embodiment, the group having the binding ability between PFPE and the base layer (that is, the group enclosed in parentheses with α in (A1) and (A2)) is directly bonded.

In still another embodiment, X ¹ is a group represented by the formula:-(R ¹⁶ ) _x- (CFR ¹⁷ ) _y- (CH ₂ ) _z- . In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each repeating unit enclosed in parentheses is Is optional.

In the above ^{formula, R 16} are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, ^{-NR 18} - ^{(wherein, R 18} represents a hydrogen atom or an organic group) or a divalent organic group is there. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

The “divalent polar group” is not particularly limited, but —C (O) —, —C (= NR ¹⁹ ) —, and —C (O) NR ¹⁹ — (in these formulas, R ¹⁹ is , A hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group or an n-propyl group, which may be substituted by one or more fluorine atoms Good.

In the above formulae, R ¹⁷ in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, It is a pentafluoroethyl group, more preferably a trifluoromethyl group.

In this embodiment, X ¹ is preferably of the formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z —, wherein x, y and z are as defined above; The order of existence of each repeating unit enclosed is arbitrary group in the formula).

The formula _{:-( O) x - (CF 2} ) y - the group represented by, for _{example, - - (CH 2) z} (O) x '- (CH 2) z "-O - [(CH _{2) z '''-O-]} z "", and _{- (O) x' - (} CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- _Z ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.

In another preferred ^{embodiment, X} 1 _{^{is, -O-CFR 20 - (CF}} 2) e '- a.

The above R ²⁰ each independently represents a fluorine atom or a lower fluoroalkyl group. Here, the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably trifluoro. It is a methyl group.

  The above e's are each independently 0 or 1.

In one embodiment, R ²⁰ is a fluorine atom and e ′ is 1.

［式中、
Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基、好ましくはメチル基であり；
各Ｘ^１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−ＣＨ_２−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）₄−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、または

［式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基に結合する−（ＣＨ_２）_ｎ”−（ｎ”は２〜６の整数）であり、存在する場合、残りのＴは、それぞれ独立して、メチル基、フェニル基、Ｃ_１−６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X ¹ groups include:

[In the formula,
Each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ¹ group, any part of T is attached to PFPE of the molecular backbone:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl), or

[Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T's are — (CH ₂ ) _{n ′ ′} (where n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular backbone T may be each independently a methyl group, a phenyl group, a C _1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group.

  The radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.

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

が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups are

Can be mentioned.

In this embodiment, X ¹ , X ³ and X ⁴ may be a trivalent to ten-valent organic group.

In the above formulae, X ² each independently represents a single bond or a divalent organic group at each occurrence. X ² is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably-(CH ₂ ) _u- (wherein u is an integer of 0 to 2).

  In the above formulae, t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer of 1 to 6. In another preferred embodiment, t is an integer of 2 to 10, preferably an integer of 2 to 6.

  In one embodiment, the compounds represented by formulas (A1) and (A2) have α of 2 or more.

  In one embodiment, the compounds represented by formulas (A1) and (A2) have t of 2 or more.

  In one embodiment, the compounds represented by formulas (A1) and (A2) have α of 1, α ′ of 1, and t of 2 or more.

［式中：
ＰＦＰＥは、それぞれ独立して、式：
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
Ｒ^１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^１４は、各出現においてそれぞれ独立して、水素原子または炭素数１〜２２のアルキル基を表し；
Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎは、１〜３の整数であり、好ましくは３であり；
ただし、式（Ａ１’）および（Ａ２’）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
Ｘ^１は、各出現においてそれぞれ独立して、−Ｏ−ＣＦＲ^２０−（ＣＦ_２）_ｅ’−であり；
Ｒ^２０は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり；
ｅ’は、各出現においてそれぞれ独立して、０または１であり；
Ｘ^２は、−（ＣＨ_２）_ｕ−であり；
ｕは、各出現においてそれぞれ独立して、０〜２の整数であり；
ｔは、各出現においてそれぞれ独立して、１〜１０の整数である。］
で表される化合物である。 Preferred compounds represented by the formulas (A1) and (A2) have the following formulas (A1 ′) and (A2 ′):

[In the formula:
Each PFPE is independently of the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1). The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹³ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ¹⁴ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n is an integer of 1 to 3, preferably 3;
However, in the formulas (A1 ′) and (A2 ′), at least two Si bonded to a hydroxyl group or a hydrolyzable group exist;
X ¹ is independently at each _{^{occurrence, -O-CFR 20 - (CF}} 2) e '- a and;
R ²⁰ each independently at each occurrence is a fluorine atom or a lower fluoroalkyl group;
e 'is independently at each occurrence either 0 or 1;
X ² is-(CH ₂ ) _u- ;
u is an integer of 0 to 2 independently at each occurrence;
t is an integer of 1 to 10 independently at each occurrence. ]
It is a compound represented by

The formula (A1) and a compound represented by (A2), for example, a perfluoropolyether derivative corresponding to Rf-PFPE-section as the starting material, after introduction of iodine at the _end, -CH ^{2 CR} 12 (X It can be obtained by reacting a vinyl monomer corresponding to ^2- SiR ¹³ _n R ¹⁴ _3-n )-.

Formulas (B1) and (B2):

  In the above formulas (B1) and (B2), Rf and PFPE are as defined in the above formulas (A1) and (A2).

In the above formulae, X ³ each independently represents a single bond or a di- to 10-valent organic group at each occurrence. The said X ³ is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (B1) and (B2) And a silane moiety that provides the ability to bind to a substrate (ie, a group that is bracketed with .beta.). Accordingly, X ³ may be any organic group as long as the compounds represented by formulas (B1) and (B2) can stably exist.

In another aspect, X ³ represents X ^e . X ^e is as defined above.

In the above formula, β is an integer of 1 to 9, and β ′ is an integer of 1 to 9. These β and β ′ can vary depending on the valence of X ³ . In formula (B1), the sum of β and β ′ is the same as the valence of X3. For example, when X 3 is a 10-valent organic group, the sum of β and β ′ is 10, for example, β is 9 and β ′ is 1, β is 5 and β ′ is 5, or β is 1 and β ′. Can be 9. When X ³ is a divalent organic group, β and β ′ are 1. In Formula (B2), β is a value obtained by subtracting 1 from the valence of X ³ .

The above X ³ is preferably 2 to 7 valences, more preferably 2 to 4 valences, and still more preferably a divalent organic group.

In one embodiment, X ³ is a divalent to tetravalent organic group, β is 1 to 3 and β ′ is 1.

In another embodiment, X ³ is a divalent organic group, β is 1 and β ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).

Examples of the X ^3, is not particularly limited, examples thereof include the same as described for X ^1.

などが挙げられる。 Among them, preferred specific X ³ is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{- (CH 2) 2 -Si (} CH 3) 2 - (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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 OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
- _{(CH 2)} 6 -,
-CO-,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-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 NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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- ,

Etc.

In another preferred embodiment, X ³ represents X ^{e ′} . X ^{e ′} is as defined above.

In one embodiment, X ^{e ′} is a single bond. In this embodiment, the group having the binding ability between PFPE and the substrate layer (that is, the group enclosed in parentheses and attached with β in (B1) and (B2)) is directly bonded.

In the above formulas (B1) and (B2), R ^a independently represents -Z ¹ -SiR ¹ _p R ² _q R ³ _r at each occurrence.

In the formula, each Z ¹ independently represents an oxygen atom or a divalent organic group.

The above Z ¹ is preferably a divalent organic group, and forms a siloxane bond with the Si atom at the end of the molecular main chain in the formula (B1) or the formula (B2) (Si atom to which ^Ra is bonded) Do not include what you do.

The above Z ¹ is preferably an alkylene group, — (CH ₂ ) _g —O— (CH ₂ ) _h — (wherein, g is an integer of 1 to 6 and h is an integer of 1 to 6) Or -phenylene- (CH ₂ ) _i- (wherein i is an integer of 0 to 6). These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. . From the viewpoint of particularly good UV resistance (ultraviolet light durability), the above Z ¹ is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group. . The number of carbon atoms constituting the above-mentioned alkylene group of Z ¹ is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3. The alkylene group is as described above.

In the formula, R ¹ independently represents ^{Ra '} at each occurrence. R ^{a ′} is as defined in R ^a .

The maximum number of Sis linked in a straight line via a Z ¹ group in ^Ra is five. That is, the in R ^a, when R ¹ is present at least one, but Si atom connected to R ^a linear through the Z ¹ group in the there are two or more, via such Z ¹ group Thus, the number of Si atoms linked in a linear manner is at most five. The phrase "through the Z ¹ group in R ^a number of Si atoms linearly linked" is equal to the repetition number of -Z ¹ -Si- being linearly linked in a R ^a Become.

For example, an example in which Si atoms are linked via a Z ¹ group in ^Ra will be shown below.

In the above formulae, * means a site to be bonded to Si in the main chain, ... indicates that a predetermined group other than Z ¹ Si is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of the repetition of Z ¹ Si. Moreover, the number on the right of Si means the appearance number of Si linearly linked via Z ¹ group counted from *. That is, the chain in which the Z ¹ Si repeat is completed in Si ² is “the number of Si atoms linearly linked via the Z ¹ group in R ^a ” is 2, similarly, Si ³ , Si ⁴ and Si ^{5 in} which the Z ¹ Si repeat ends are “number of Si atoms linearly linked via Z ¹ group in R ^a ” of 3, 4 and 5, respectively Is one. As is apparent from the above formula, ^a plurality of Z ¹ Si chains are present in R ^a , but they do not have to have the same length, and may have any length.

In a preferred embodiment, as shown below, “the number of Si atoms linearly linked via the Z ¹ group in R ^a ” is 1 (left equation) or 2 (all the chains) in all chains. Right).

In one embodiment, the number of Si atoms linearly linked via the Z ¹ group in R ^a is one or two, preferably one.

In the formula, each R ² independently at each occurrence represents a hydroxyl group or a hydrolysable group.

  Examples of the above-mentioned "hydrolyzable group" include those similar to formulas (A1) and (A2).

Preferably, R ² is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group.

In the formulae, R ³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. 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 still more preferably a methyl group.

In the formula, p is independently an integer of 0 to 3 at each occurrence; q is an integer of 0 to 3 independently at each occurrence; r is independently at each occurrence Is an integer of 0 to 3. However, the sum of p, q and r is 3 every -Z ¹ -SiR ¹ _p R ² _q R ³ _r .

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, ^{R a} is a distal end, at least _{^{one, -Si (-Z 1 -SiR 2 q}} R 3 r) 2 or _{^{-Si (-Z 1 -SiR 2 q R}} 3 r) 3, preferably may have _{^{-Si (-Z 1 -SiR 2 q R}} 3 r) 3. _{^{Wherein, (- Z 1 -SiR 2 q}} R 3 r) units are preferably ^(-Z 1 -SiR ² _3). In a further preferred embodiment, the distal end of the ^{R a,} all _{^{-Si (-Z 1 -SiR 2 q R}} 3 r) 3, preferably may be _{^{-Si (-Z 1 -SiR 2 3)}} 3.

In the above formulas (B1) and (B2), at least two Si bonded to a hydroxyl group or a hydrolyzable group exist. That is, at least two groups represented by SiR ² and / or SiR ^b are present. By having such a configuration, the PFPE-containing silane compound of the present invention can form a surface treatment layer that can be well bonded to the substrate surface and the like.

In the above formulas, each R ^b independently represents a hydroxyl group or a hydrolysable group.

The above R ^b is preferably a hydroxyl group, —OR, —OCOR, —O—N = C (R) ₂ , —N (R) ₂ , —NHR, halogen, wherein R is a substituted or unsubstituted group. (Indicating an alkyl group having 1 to 4 carbon atoms), and more preferably -OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group. More preferably, R ^b is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group.

In the above formulae, R ^c independently at each occurrence represents 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 still more preferably a methyl group.

In the formula, k1 is independently an integer of 0 to 3 at each occurrence; 11 is an integer of 0 to 3 independently at each occurrence; m1 is independently at each occurrence Is an integer of 0 to 3. Provided that ^the sum of _{-SiR a} ^k1 _R b ^l1 in each _{R c m1,} k1, l1 and m1 is 3. k1 is preferably 1 to 3, and more preferably 3.

  The compounds represented by the above formulas (B1) and (B2) have, for example, an unsaturated bond at the end after introducing a hydroxyl group at the end using the perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material A group is introduced, a group having this unsaturated bond is reacted with a silyl derivative having a halogen atom, and further a hydroxyl group is introduced at the end of this silyl group, and the introduced group having an unsaturated bond and a silyl derivative are reacted It can be obtained by For example, it can be synthesized as described in WO 2014/069592.

Formulas (C1) and (C2):

  In the above formulas (C1) and (C2), Rf and PFPE are as defined for the above formulas (A1) and (A2).

In the above formulas, each X ⁴ independently represents a single bond or a di- to 10-valent organic group. The said X ⁴ is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (C1) and (C2) And a portion that provides the ability to bind to a substrate (ie, a group that is attached by γ and enclosed in parentheses). Accordingly, X ⁴ may be any organic group as long as the compounds represented by formulas (C1) and (C2) can stably exist.

In another aspect, X ⁴ represents X ^e . X ^e is as defined above.

In said formula, (gamma) is an integer of 1-9, and (gamma) 'is an integer of 1-9. These γ and γ ′ can change according to the valence of X ⁴ . In formula (C1), the sum of γ and γ ′ is the same as the valence of X ⁴ . For example, when X ⁴ is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5 or γ is 1 and γ 'Can be nine. When X ⁴ is a divalent organic group, γ and γ ′ are 1. In Formula (C2), γ is a value obtained by subtracting 1 from the valence of X ⁴ .

The above-mentioned X ⁴ is preferably a 2- to 7-valent, more preferably a 2- to 4-valent, more preferably a divalent organic group.

In one embodiment, X ⁴ is a divalent to tetravalent organic group, γ is 1 to 3 and γ ′ is 1.

In another embodiment, X ⁴ is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).

Examples of X ⁴ include, but are not particularly limited to, the same ones as described for X ¹ .

などが挙げられる。 Among them, preferred specific X ⁴ is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{- (CH 2) 2 -Si (} CH 3) 2 - (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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 OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
- _{(CH 2)} 6 -,
-CO-,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-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 NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 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- ,

Etc.

In another preferred embodiment, X ³ represents X ^{e ′} . X ^{e ′} is as defined above.

In one embodiment, X ^{e ′} is a single bond. In this embodiment, a group capable of binding PFPE to the substrate layer (that is, a group enclosed by parentheses in γ in (C1) and (C2)) is directly bonded. By having such a structure, it is considered that the bonding strength between PFPE and a group which is attached with γ and in parentheses becomes stronger. In addition, carbon atoms directly bonded to PFPE (that is, carbon atoms bonded to R ^d _, R ^e and R ^{f in} the parenthesized group attached with γ) have less charge bias, and as a result, the above carbon Nucleophilic reactions and the like are unlikely to occur in atoms, and are considered to be stably bonded to the substrate layer. Such a structure is advantageous from the viewpoint of further improving the friction durability of the surface treatment layer to be formed.

In the above formulae, R ^d independently represents -Z ² -CR ⁸¹ _{p 2} R ⁸² _{q 2} R ⁸³ _r ² at each occurrence.

In the formula, Z ² independently represents an oxygen atom or a divalent organic group at each occurrence.

The above Z ² is preferably a C _1-6 alkylene group,-(CH ₂ ) _g -O- (CH ₂ ) _h- (wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6) H is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene- (CH ₂ ) _i- (wherein, i is an integer of 0 to 6), and Preferably, it is a C _1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In the formula, R ⁸¹ independently represents R ^{d ′} at each occurrence. R ^{d ′} is as defined the R ^d .

In ^Rd , Cs linked in a linear fashion via a Z ² group are at most five. That is, in the above ^Rd , when at least one R ⁸¹ is present, two or more C atoms linearly linked via the Z ² group are present in R ^d , but via such Z ² group The maximum number of C atoms linked in a straight chain is five. The phrase "through the Z ² group in R ^d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 ^-C- being linearly linked in a R ^d Become.

In a preferred embodiment, as shown below, “the number of C atoms linearly linked via the Z ² group in R ^d ” is 1 (left equation) or 2 (all the chains) in all chains. Right).

In one embodiment, the number of C atoms to be linked via Z ² groups R ^d linearized is one or two, preferably one.

In the formulae, R ⁸² each independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence.

  Y's each independently represent a divalent organic group at each occurrence.

In a preferred embodiment, _{Y, C 1-6} alkylene _{group, - (CH 2) g '} -O- (CH 2) h' - ( wherein, g 'is from 0 to 6 integer, for example from 1 to 6 H is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH ₂ ) _{i '} -(wherein i' is an integer of 0 to 6) ). These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In one embodiment, Y _{is, C 1-6} alkylene group or - phenylene - _(CH 2) _{i '-} may be. When Y is the above radical, the light resistance, in particular the UV resistance, may be higher.

R ⁸⁵ each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

  Examples of the above-mentioned "hydrolyzable group" include those similar to formulas (A1) and (A2).

Preferably, R ⁸⁵ is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.

R ⁸⁶ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. 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 still more preferably a methyl group.

n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3 for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) unit It is.

The above R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. 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 still more preferably a methyl group.

In the formula, p2 is independently an integer of 0 to 3 at each occurrence; q2 is an integer of 0 to 3 independently at each occurrence; r2 is independently at each occurrence Is an integer of 0 to 3. ^{However, -} in _{^{(Z 2 -CR 81 p2 R 82}} q2 R 83 r2) each, the sum of p2, q2 and r2 is 3.

In a preferred embodiment, ^{'(if R d'} is absent, ^{R d)} end of ^{R d} in ^{R d} in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, at least one of the end portions of the ^{R d _{is, -C (-Y-SiR 85 n2}} R 86 3-n2) 2 or _{^{-C (-Y-SiR 85 n2 R}} 86 3-n2) 3, preferably may be the _{^{-C (-Y-SiR 85 n2 R}} 86 3-n2) 3. _{^{Wherein, (- Y-SiR 85 n2}} R 86 3-n2) units is preferably ^{(-Y-SiR 85} _3). In a further preferred embodiment, the distal end of the ^{R d} are all _{^{-C (-Y-SiR 85 n2 R}} 86 3-n2) 3, may be preferably _{^{-C (-Y-SiR 85 3)}} 3.

In the above formulae, R ^e independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence. Here, Y, R ⁸⁵ , R ⁸⁶ and n 2 are as defined in R ⁸² above.

In the above formulae, R ^f independently at each occurrence represents 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 still more preferably a methyl group.

In the formula, k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k 2, l 2 and m 2 is 3 for each (CR ^d _{k 2} R ^{e 1} ₂ R ^f _{m 2} ).

  In one embodiment, at least one k2 is 2 or 3, preferably 3.

  In one embodiment, k2 is 2 or 3, preferably 3.

  In one embodiment, l2 is 2 or 3, preferably 3.

In formulas (C1) and (C2), two or more groups represented by -Y-SiR ⁸⁵ are present. Preferably, in formulas (C1) and (C2), one or more carbon atoms bonded to two or more groups represented by -Y-SiR ⁸⁵ are present. That is, it is preferable that one or more groups represented by -C- (Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) ₂ exist (in the formula, n2 is an integer of 1 to 3).

Preferably, in the above formulas (C1) and (C2), n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one 12 is 2 or 3. . That is, there are at least two -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups in the formula.

［式中：
ＲｆおよびＰＦＰＥは、それぞれ上記と同意義であり；
Ｘ^４’は、Ｘ^４と同意義であり、好ましくはＸ^ｅを表し；
Ｘ^ｅは、上記と同意義であり；
γおよびγ’は、それぞれ上記と同意義であり；
Ｒ^ｄ’は、各出現においてそれぞれ独立して、−Ｚ^２’−ＣＲ^８１ _ｐ２’Ｒ^８２’ _ｑ２’Ｒ^８３ _ｒ２’を表し；
Ｒ^８１およびＲ^８３は、それぞれ上記と同意義であり；
Ｚ^２’は、各出現においてそれぞれ独立して、−Ｒ^ｇ−Ｚ’−を表し；
Ｒ^ｇは、各出現においてそれぞれ独立して、低級アルキレン基を表し；
Ｚ’は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基を表し；
Ｒ^８２’は、各出現においてそれぞれ独立して、−Ｒ^ｈ−Ｙ’−ＳｉＲ^８５ _ｎ２’Ｒ^８６ _{３−ｎ２’}を表し；
Ｒ^ｈは、各出現においてそれぞれ独立して、低級アルキレン基を表し；
Ｙ’は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基を表し；
ｎ２’は、（−Ｒ^ｈ−Ｙ’−ＳｉＲ^８５ _ｎ２’Ｒ^８６ _{３−ｎ２’}）単位毎に独立して、１〜３の整数を表し、好ましくは２または３、より好ましくは３であり；
Ｒ^８５およびＲ^８６は、それぞれ上記と同意義であり；
ｐ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
（−Ｚ^２’−ＣＲ^８１ _ｐ２’Ｒ^８２’ _ｑ２’Ｒ^８３ _ｒ２’）単位毎において、ｐ２’、ｑ２’およびｒ２’の和は３であり；
Ｒ^ｅ’は、各出現においてそれぞれ独立して、−Ｒ^ｈ−Ｙ’−ＳｉＲ^８５ _ｎ２’Ｒ^８６ _{３−ｎ２’}を表し；
Ｒ^ｆは、上記と同意義であり；
ｋ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、（ＣＲ^ｄ’ _ｋ２’Ｒ^ｅ’ _ｌ２’Ｒ^ｆ _ｍ２’）毎において、ｋ２’、ｌ２’およびｍ２’の和は３であり、式中、少なくとも１つのｑ２’は３であるか、あるいは、少なくとも１つのｌ２’は３である。］ In one aspect, Formulas (C1) and (C2) are represented by the following Formulas (C1 ′ ′) and (C2 ′ ′).

[In the formula:
Rf and PFPE are as defined above;
X ^{4 ′} is as defined for X ⁴ and preferably represents X ^e ;
X ^e is as defined above;
γ and γ ′ are respectively as defined above;
R ^{d '} independently at each occurrence independently represents -Z ^2' -CR ⁸¹ _{p2 '} R ^82' _{q2 '} R ⁸³ _r2' ;
R ⁸¹ and R ⁸³ are as defined above;
Z ^{2 '} each independently at each occurrence represents -R ^g -Z'-;
R ^g is independently at each occurrence a lower alkylene group;
Z 'represents independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ^{82 ′} represents independently at each occurrence -R ^h -Y'-SiR ⁸⁵ _{n2 '} R ⁸⁶ _3-n2' ;
R ^h independently at each occurrence represents a lower alkylene group;
Y 'represents independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
n2 'independently represents an integer of 1 to 3 and preferably 2 or 3, more preferably 3 for each (-R ^h -Y'-SiR ⁸⁵ _n2' R ⁸⁶ _{3-n2 '} ) unit; ;
R ⁸⁵ and R ⁸⁶ are as defined above;
p2 'is each independently an integer of 0 to 3 at each occurrence;
q2 'is each independently an integer of 0 to 3 at each occurrence;
r2 'is, independently at each occurrence, an integer from 0 to 3;
In each (-Z ^{2 '} -CR ⁸¹ _p2' R ^{82 '} _q2' R ⁸³ _{r2 '} ) unit, the sum of p2', q2 'and r2' is 3;
R ^{e ′} each independently represents -R ^h -Y'-SiR ⁸⁵ _{n2 '} R ⁸⁶ _3-n2' at each occurrence;
R ^f is as defined above;
k2 'is each independently an integer of 0 to 3 at each occurrence;
12 'is each independently an integer of 0 to 3 at each occurrence;
m2 'is each independently an integer of 0 to 3 at each occurrence;
With the proviso that, for each (CR ^{d '} _k2' R ^{e '12} _' R ^f _{m2 '} ), the sum of k2', 12 'and m2' is 3, and wherein at least one q2 'is 3 or Alternatively, at least one 12 'is 3. ]

The above R ^g independently represents a lower alkylene group at each occurrence. The lower alkylene group is preferably a C _1-20 alkylene group, more preferably a C _1-6 alkylene group, still more preferably a C _1-3 alkylene group, and particularly preferably methylene.

The above Z ′ is preferably an oxygen atom or a divalent organic group, more preferably a divalent organic group, and still more preferably a C _1-6 alkylene group,-(CH ₂ ) _{j 1} -O- ( CH ₂ ) _h 1-(wherein, j 1 is an integer of 0 to 6, for example, an integer of 1 to 6, and h 1 is an integer of 0 to 6, for example, an integer of 1 to 6); -(CH ₂ ) _{i 1-} (wherein, i 1 is an integer of 0 to 6), particularly preferably a C _1-6 alkylene group or -phenylene- (CH ₂ ) _{i 1-} , more preferably It is a _C1-6 alkylene group (preferably, a _C1-3 alkylene group). These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. . In a preferred embodiment, Z 'is unsubstituted.

The above Z ^{2 ′} may be preferably a C _1-3 alkylene group, specifically, —CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —.

The above R ^h independently represents a lower alkylene group at each occurrence. The lower alkylene group is preferably a C _1-20 alkylene group, more preferably a C _1-6 alkylene group, still more preferably a C _1-3 alkylene group, and particularly preferably methylene.

The above Y ′ is, in a preferred embodiment, an oxygen bond or a divalent organic group. Y ′ is more preferably a divalent organic group, and particularly preferably a C _1-6 alkylene group, — (CH ₂ ) _{g1 ′} —O— (CH ₂ ) _h1′— (wherein g1 ′ is 0-6 integer, for example an integer from 1 to 6, h1 'is an integer of 0 to 6, such as an integer from 1 to 6), or - phenylene _{- (CH 2) i1' -} ( wherein, i1 'is an integer of 0 to 6), more preferably _{C 1-6} alkylene group or - phenylene - _{(CH 2) i1'} -, and particularly preferably _{C 1-6} alkylene group (preferably , C _1-3 alkylene group). These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In one embodiment, Y _{'is, C 1-6} alkylene _{group, -O- (CH 2) h1'} - or - phenylene - _{(CH 2) i1 '-} may be. If Y 'is a group as described above, the light resistance, in particular the UV resistance, may be higher.

In a preferred embodiment, the ^-R h -Y'- _{is, -CH} 2 _{C 1-3} alkylene group, specifically _{-, - CH 2 CH 2 -} , or _-CH 2 _CH 2 CH ₂ - may be.

  In one embodiment, at least one k2 'is 2 or 3, preferably 3.

  In one embodiment, k2 'is 2 or 3, preferably 3.

  In one embodiment, 12 'is 2 or 3, preferably 3.

  In a preferred embodiment, l2 'is 3, and n2' is 3.

In the above formulas (C1 ′ ′) and (C2 ′ ′), at least one q2 ′ is 3 or at least 1 12 ′ is 3. That is, wherein at least one ^{-X 4 '-C (-R h -Y'} -SiR 85 n2' R 86 3-n2 ') 3 group or -Z ^2' -C ^(-R h -Y'- SiR ⁸⁵ _{n2 ′} R ⁸⁶ _{3-n2 ′} ) ₃ groups are present. By having such a structure, the PFPE-containing silane compound of the present embodiment has chemical durability (for example, in an acid and / or alkaline environment, more specifically, also in an environment where sweat can be attached). It can contribute to the formation of a surface treatment layer that is resistant to deterioration. In addition, the PFPE-containing silane compound of the present embodiment can contribute to the formation of a surface treatment layer having good friction durability by having the structure as described above, and in particular, an environment susceptible to exposure to an acid and / or alkaline environment. Also in the above, it can contribute to the formation of a surface treatment layer having improved friction resistance.

In the above formula (C1 ′ ′) or (C2 ′ ′), more preferably, γ is 1, γ ′ is 1, and X ^{4 ′} represents X ^{e ′} . X ^{e ′} is as defined above.

The PFPE-containing silane compound represented by formula (C1) or formula (C2) can be produced by combining known methods. For example, the compound represented by the formula (C1 ′) in which X ⁴ is divalent can be produced as follows, but not limited thereto.

A group containing a double bond to a polyhydric alcohol represented by HO-X ⁴ -C (YOH) ₃ (wherein, X ⁴ and Y each independently represent a divalent organic group). (Preferably allyl) and halogen (preferably bromo) are introduced into Hal-X ⁴ -C (Y-O-R-CH = CH ₂ ) ₃ , wherein Hal is a halogen such as Br, R is a divalent organic group such as an alkylene group)) to obtain a double bond-containing halide represented by Then, the terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R ^PFPE -OH (wherein R ^PFPE is a perfluoropolyether group-containing group) to obtain R ^PFPE- O—X ⁴ —C (Y—O—R—CH = CH ₂ ) ₃ is obtained. Then, by reacting the terminal -CH = CH ₂ with HSiCl ₃ and alcohol or HSiR ⁸⁵ ₃ , R ^PFPE -O-X ⁴ -C (Y-O-R-CH ₂ -CH ₂ -SiR ⁸⁵ ₃ ) You can get _three .

In another embodiment, a PFPE-containing compound represented by the formula (C1 ′ ′) or the formula (C2 ^{′ ′} ) and having —R ⁵¹ —CONH—R ⁵² — as X ^{4 ′} is selected from, but not limited to: It can be manufactured in the same way.

Reacting a compound having a double bond-containing group (preferably allyl) and an amino group (for example, H ₂ NR ⁵² C (CH ₂ —CH = CH ₂ ) ₃ with R ^PFPE —R ⁵¹ —COOCH ₃ Synthesizes R ^PFPE -R ⁵¹ -CONH-R ⁵² C (-CH ₂ -CH = CH ₂ ) _{3. The} compound obtained is reacted with HSiCl ₃ and alcohol or HC (OCH ₃ ) ₃ , PFPE-containing compound R ^PFPE -R ⁵¹ -CONH-R ⁵² C (CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) _{3. In the} above, R ^PFPE is a PFPE-containing group, R ⁵¹ and R ⁵² is as defined above.

(Compound containing an atom having a noncovalent electron pair in its molecular structure)
The surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having improved friction resistance. Furthermore, the surface treatment agent of the present invention is a surface treatment layer with improved durability, in particular, chemically stable, for example, to form a surface treatment layer which is deteriorated even in the presence of acid and / or alkali. It can contribute. It is considered that this is because the compound containing an atom having a noncovalent electron pair in the molecular structure exerts a catalytic effect to make the bond between the substrate and the Si atom stronger.

  The compound containing an atom having a noncovalent electron pair in the above molecular structure preferably contains at least one atom selected from the group consisting of nitrogen atom, oxygen atom, phosphorus atom and sulfur atom, and contains sulfur atom or nitrogen atom Is more preferred.

  The compound containing an atom having a noncovalent electron pair in the above molecular structure is at least selected from the group consisting of an amino group, an amido group, a sulfinyl group, a P = O group, an S = O group and a sulfonyl group in the molecular structure. It is preferable to include one functional group, and more preferably to include at least one functional group selected from the group consisting of P = O group and S お よ び O group.

  In a preferred embodiment, the compound containing an atom having an unshared electron pair in the molecular structure contains an SSO group among the above functional groups.

In the above aspect, the compound containing an atom having an unshared electron pair in the molecular structure is preferably a compound represented by the formula: R ⁹¹ -S (= O) -R ⁹² .

In the above ^{formula, R 91} is a hydrocarbon group having 1 to 12 carbon ^{atoms, R 92} is a hydrocarbon group having 1 to 12 carbon atoms. Preferably, R ⁹¹ is a hydrocarbon group having 1 to 6 carbon atoms, and R ⁹² is a hydrocarbon group having 1 to 6 carbon atoms.

  As said hydrocarbon group, a saturated hydrocarbon group, the unsaturated hydrocarbon group which has a carbon-carbon unsaturated bond of at least 1, or an aromatic hydrocarbon group can be mentioned. Preferably, as the above-mentioned hydrocarbon group, an alkyl group or a phenyl group can be mentioned.

In a preferred embodiment, R ⁹¹ and R ⁹² are each independently an alkyl group of 1 to 6 carbon atoms (specifically a methyl group) at each occurrence.

In the above formulae, R ⁹¹ and R ⁹² may be combined with each other, and together with the S atom bonded to R ⁹¹ and R ⁹² , may form a ring structure. The ring structure preferably consists of at least one S atom (preferably one S atom) and 3 to 12 carbon atoms, and at least one S atom (preferably one S atom) and four to six carbon atoms. It is more preferable that

  As the ring structure, for example, a saturated four-membered ring structure consisting of 1 S atom and 3 carbon atoms, a saturated 5-membered ring structure consisting of 1 S atom and 4 carbon atoms, 1 S atom and 5 Saturated six-membered ring structure consisting of carbon atoms, unsaturated five-membered ring structure consisting of one S atom and four carbon atoms, unsaturated six-membered ring structure consisting of one S atom and five carbon atoms, etc. Specifically, examples thereof include a saturated five-membered ring structure consisting of one S atom and four carbon atoms, and an unsaturated five-membered ring structure consisting of one S atom and four carbon atoms, and the like. be able to. In the carbon atom constituting the ring structure, at least one hydrogen atom bonded to the carbon atom may be substituted by a substituent such as an alkyl group (for example, 1 to 6 carbon atoms), a phenyl group, etc. It does not have to have a substituent.

  The compound containing an atom having a noncovalent electron pair in the above molecular structure is at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds and sulfoxide compounds. At least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds, more preferably sulfoxide compounds, aliphatic amine compounds and Particularly preferred is at least one compound selected from the group consisting of aromatic amine compounds, and more preferred is a sulfoxide compound.

  Examples of the aliphatic amine compound include diethylamine and triethylamine. Examples of the aromatic amine compound include aniline and pyridine. As said phosphoric acid amide compound, hexamethyl phosphoramide etc. can be mentioned, for example. Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. it can. Tetramethyl urea etc. can be mentioned as said urea compound. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.

  The compound containing an atom having an unshared electron pair in the above molecular structure may have a molecular weight, for example, in the range of 50 to 500, and particularly in the range of 50 to 200.

  The compound containing the atom which has a non-covalent electron pair in molecular structure may be contained, for example with 0.0002 mass% or more with respect to the whole surface treatment agent. It is preferable that 0.02 mass% or more is contained with respect to the whole surface treatment agent, and, as for the said compound, it is more preferable that 0.04 mass% or more is contained. The above-mentioned compound may be contained, for example, at 10% by mass or less, particularly at 1% by mass or less, based on the whole surface treatment agent. The surface treatment agent of the present invention can contribute to the formation of a more durable surface treatment layer by containing the above-mentioned compound in the concentration as described above.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is contained in the surface treatment agent in an amount of 0.01 mol or more per 1 mol of Si atom bonded to the hydroxyl group or hydrolyzable group of the PFPE-containing silane compound Is preferably contained, more preferably 0.03 mol or more, still more preferably 0.15 mol or more, and particularly preferably 0.33 mol or more. The surface treatment agent of the present invention can particularly contribute to the formation of a highly durable surface treatment layer by containing the compound containing the atom having the non-covalent electron pair in the molecular structure in the concentration as described above.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 10 moles or less per mole of Si atom bonded to a hydroxyl group or a hydrolyzable group of the PFPE containing silane compound. It is more preferably contained in an amount of 6 mol or less, particularly preferably 2 mol or less. By including a compound containing an atom having a noncovalent electron pair in the molecular structure in the concentration as described above, the handleability of the surface treatment agent of the present invention can be improved, and in particular, the clouding of the surface treatment agent can be prevented. it can.

  In one embodiment, the compound containing an atom having a noncovalent electron pair in the molecular structure is 3 mol or less per 1 mol of Si atom bonded to the hydroxyl group or hydrolyzable group of the PFPE-containing silane compound in the surface treatment agent It may be included.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is contained in the surface treatment agent in an amount of 0.01 to 10 moles relative to 1 mole of Si atom bonded to the hydroxyl group or hydrolyzable group of the PFPE-containing silane compound Is preferably contained, more preferably 0.01 to 3 moles, and particularly preferably 0.33 to 2 moles.

  In one embodiment, the compound containing an atom having a non-covalent electron pair in the molecular structure is 0.03 per 1 mol of Si atom bonded to the hydroxyl group or hydrolyzable group of the PFPE-containing silane compound in the surface treatment agent. It is preferably contained in 3 to 3 mol, and more preferably 0.3 to 3 mol.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 0.01 mol or more, preferably 0.1 mol or more, per mol of the PFPE-containing silane compound. Is more preferably contained, more preferably 0.15 mol or more, still more preferably 0.2 mol or more, and particularly preferably 0.3 mol or more. The surface treatment agent of the present invention can particularly contribute to the formation of a highly durable surface treatment layer by containing the compound containing the atom having the non-covalent electron pair in the molecular structure in the concentration as described above.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained 15 mol or less, more preferably 10 mol or less, per mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferable to contain 7 moles or less.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 6 mol or less, more preferably 3 mol or less, per mol of the PFPE-containing silane compound. It is particularly preferable to contain 1 mole or less. By including a compound containing an atom having a noncovalent electron pair in the molecular structure in the concentration as described above, the handleability of the surface treatment agent of the present invention can be improved, and in particular, the clouding of the surface treatment agent can be prevented. it can.

  In one embodiment, the compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 0.01 to 15 moles, relative to 1 mole of the PFPE-containing silane compound, More preferably, it is contained in an amount of 10 to 10 mol, further preferably 0.1 to 10 mol, particularly preferably 0.3 to 7 mol, and even more preferably 0.5 to 7 mol.

  The compound containing an atom having a noncovalent electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 0.01 to 6 moles, preferably 0.1 to 3 moles, per mole of the PFPE-containing silane compound. It is more preferably contained in an amount of 0.3 to 2 moles.

  The concentration of the compound containing an atom having a noncovalent electron pair in the molecular structure, which is contained in the surface treatment agent, can be measured, for example, using glass chromatography, 1 H-NMR or the like.

  The surface treatment agent of the present invention can impart water repellency, oil repellency, stain resistance, friction durability, UV resistance to a substrate, and is not particularly limited, but the stain resistant coating It can be suitably used as an agent.

The surface treatment agent of the present invention may be diluted with a solvent. Such solvent is not particularly limited, but, for example:
Perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHF CHFC ₂ F ₅ , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane (such as Zeorora H (trade name)), C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₆ F ₁₃ CH = CH ₂ , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF ₂ CF ₂ CH ₂ OH, methyl trifluoromethanesulfonate, trifluoroacetate and _CF 3 O (C During _{2 CF 2 O) m1 (CF} 2 O) n1 CF 2 CF 3 [ wherein m1 and n1, are each independently zero or greater than 1,000 integer bracketed bear the m1 or n1 The order of existence of each repeating unit is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1 , 2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3,3 Trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene Solvents containing fluorine atoms selected from Be

As the solvent, C ₆ F ₁₃ OCH ₃ may be used.

  It is preferable that the water content contained in the said solvent is 20 ppm or less in mass conversion. The water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the surface treatment agent can be improved.

  The surface treatment agent of the present invention may further contain other components. Such other components include, but are not limited to, for example, other surface treatment compounds, fluoropolyether compounds (non-reactive) that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. A compound (hereinafter referred to as "fluorine-containing oil"), a (non-reactive) silicone compound (hereinafter referred to as "silicone oil") that can be understood as a silicone oil, a catalyst and the like can be mentioned.

Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by following General formula (1) is mentioned.
^{_{Rf 5 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -Rf 6 ··· (1)
In the formula, R f ⁵ represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and R f ⁶ represents Rf ⁵ and Rf ^{6 each} represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; And more preferably each independently a C _1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less; The sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300. The order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula. Among these repeating _{units, - (OC 4 F 8)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ) —, — (OCF (C ₂ F ₅ ) CF ₂ ) — and — (OCF ₂ CF (C ₂ F ₅ )) —, which may be any of _{- (OCF 2 CF 2 CF 2} CF 2) - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.

Examples of the perfluoro (poly) ether compound represented by the above general formula (1) include a compound represented by any one of the following general formulas (1a) and (1b) (one or a mixture of two or more) May be mentioned.
^{_{Rf 5 - (OCF 2 CF 2}} CF 2) b '' -Rf 6 ··· (1a)
Rf ^5- (OCF ₂ CF ₂ CF ₂ CF ₂ ) _{a ''} -(OCF ₂ CF ₂ CF ₂ ) _{b ''} -(OCF ₂ CF ₂ ) _{c ''} -(OCF ₂ ) _{d ''} -Rf ^6. (1b)
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (1a), b ′ ′ is an integer of 1 or more and 100 or less; in formula (1b), a ′ ′ and b ′ ′ are Each is independently an integer of 1 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 in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′ and d ′ ′ is given is arbitrary in the formula.

  The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.

  In the surface treatment agent of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the above-mentioned perfluoro (poly) ether group-containing silane compound and the above-mentioned carboxylic acid ester compound (in the case of 2 or more And the like, for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.

  The compound represented by the general formula (1a) and the compound represented by the general formula (1b) may be used alone or in combination. It is more preferable to use the compound represented by the general formula (1b) than the compound represented by the general formula (1a) because higher surface slipperiness can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (1a) to the compound represented by the general formula (1b) is preferably 1: 1 to 1:30, and 1: 1 to 1:30. 10 is more preferable. According to this mass ratio, it is possible to obtain a surface treatment layer excellent in the balance between surface slipperiness and friction durability.

  In one aspect, the fluorine-containing oil comprises one or more compounds represented by General Formula (1b). In such an embodiment, the mass ratio of the perfluoro (poly) ether group-containing silane compound in the surface treatment agent to the compound represented by the formula (1b) is preferably 10: 1 to 1:10. It is more preferable that it is 4: 1 to 1: 4.

  In one aspect, the average molecular weight of the compound represented by formula (1a) is preferably 2,000 to 8,000.

  In one aspect, the average molecular weight of the compound represented by Formula (1b) is preferably 8,000 to 30,000.

  In another aspect, the average molecular weight of the compound represented by formula (1b) is preferably 3,000 to 8,000.

  In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the number average molecular weight of the fluorine-containing oil may be larger than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound. For example, the number average molecular weight of the fluorine-containing oil is increased by 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound It is also good. By setting it as such a number average molecular weight, more superior friction durability and surface slipperiness can be obtained.

From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C _5-16 perfluoroalkyl group). Moreover, a chloro trifluoro ethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are characterized in that they can obtain high affinity with the above perfluoro (poly) ether group-containing silane compound in which Rf ¹ is a C _1-16 perfluoroalkyl group. preferable.

  The fluorine-containing oil contributes to the improvement of the surface slipperiness of the surface treatment layer.

  As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. The cyclic silicone oil may, for example, be a cyclic dimethylsiloxane oil.

  In the surface treatment agent of the present invention, such silicone oil is, for example, 0 to 300 parts by mass, preferably 100 parts by mass of the above-mentioned PFPE-containing silane compound (in the case of two or more, the total of them, the same applies hereinafter). It may be contained in an amount of 0 to 200 parts by mass.

  The silicone oil contributes to the improvement of the surface slipperiness of the surface treatment layer.

  Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid etc.), bases (eg, ammonia, triethylamine, diethylamine etc.), transition metals (eg, Ti, Ni, Sn etc.) and the like.

  The catalyst promotes the hydrolysis and dehydration condensation of the above-mentioned perfluoro (poly) ether group-containing silane compound and promotes the formation of a surface treatment layer.

  As other components, other than the above, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like can also be mentioned.

  As another component, a C1-C6 alcohol compound is mentioned other than the above, for example.

[pellet]
The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material, metal fiber such as steel wool into a cotton-like form. The said pellet can be used for vacuum evaporation, for example.

  The surface treatment agent of the present invention is suitably used as a surface treatment agent because it can impart water repellency, oil repellency, stain resistance, waterproofness, high friction durability and UV resistance to a substrate. Ru. Specifically, the surface treatment agent of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.

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

  The article of the present invention comprises a substrate and a layer (surface treated layer) formed on the surface of the substrate from the surface treatment agent of the present invention. This article can be manufactured, for example, as follows.

  First, a base material is prepared. Substrates that can be used in the present invention are, for example, glass, resin (natural or synthetic resin such as general plastic material, may be plate-like, film, other form), metal (aluminum, copper) May be a simple substance of metal such as iron or a complex such as alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven fabric, etc.), fur, leather, wood, ceramic, stone etc., construction members, etc. , May be composed of any suitable material.

The glass is preferably sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, non-alkali glass, crystal glass, quartz glass, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, And chemically bonded borosilicate glass are particularly preferred.
As the resin, acrylic resin and polycarbonate are preferable.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. When the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflective layer may be formed on the surface (the outermost layer) of the substrate. For the antireflective layer, either a single layer antireflective layer or a multilayer antireflective layer may be used. Examples of inorganic substances that can be used for the antireflective layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ and MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). If the multilayer antireflection layer, it is preferable to use SiO ₂ and / or SiO in its outermost layer. When the article to be manufactured is an optical glass part for a touch panel, it has a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide on a part of the surface of a substrate (glass) It may be In addition, the base material may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, according to the specific specifications and the like. And a liquid crystal display module.

  The shape of the substrate is not particularly limited. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the application and specific specifications of the article to be manufactured.

  As such a substrate, at least the surface portion may be made of a material originally having a hydroxyl group. Examples of such a material include glass, and further, metals (in particular, base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermal oxide film is formed on the surface. Alternatively, as in the case of resin or the like, when having hydroxyl groups is not sufficient or when the hydroxyl groups are not originally contained, the substrate is subjected to some pretreatment to introduce hydroxyl groups on the surface of the substrate. Can be increased or decreased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign substances and the like). In addition, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously coated on the surface of the substrate by the LB method (Langmuir-Blodgett method), chemical adsorption method or the like. It may be formed in a form and then the unsaturated bond may be cleaved under an atmosphere containing oxygen, nitrogen and the like.

  Alternatively, as such a substrate, at least the surface portion thereof may be made of a material containing a silicone compound having one or more other reactive groups such as Si-H group, or an alkoxysilane.

  Next, a film of the above-mentioned surface treatment agent of the present invention is formed on the surface of such a substrate, and this film is post-treated if necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention Do.

  Film formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent of the present invention to the surface of a substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating can be used.

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

  Examples of dry coating methods include vapor deposition (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the deposition method (usually, vacuum deposition method) include resistance heating, high frequency heating using an electron beam, microwave and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.

  Furthermore, coating by the atmospheric pressure plasma method is also possible.

When using a wet coating method, the surface treatment agent of the present invention can be diluted with a solvent and then applied to the substrate surface. 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: C _5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and the like) Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg, C ₆ F ₁₃ CH ₂ CH ₃ (eg, Asahi Glass) ASAHIKLIN (registered trademark) AC-6000), 1, 1, 2, 2, 3, 3,4-heptafluorocyclopentane (eg, Zeoror (registered trademark) H, manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbons (HFCs) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365) fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo Novec (trade name) 7000 manufactured by 3M Co., Ltd., perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (eg, Novec (trade name) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C) ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Ltd.), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Sumitomo ₃ M Novec (brand name) 73 manufactured by Corporation 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrel (registered trademark) Scion manufactured by DuPont Fluorochemicals, Inc.) and the like. These solvents can be used alone or as a mixture of two or more, and further, for example, adjusting the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether modified compound, etc. Can also be mixed with another solvent.

  When the dry coating method is used, the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

  Film formation is preferably carried out such 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 wet coating, after diluting the surface treatment agent of the present invention with a solvent, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention just before application to the substrate surface. In the case of the dry coating method, the catalyst-added surface treatment agent of the present invention is directly subjected to vapor deposition (usually, vacuum deposition), or the catalyst-added surface treatment agent of the present invention is applied to metal porous bodies such as iron and copper. The material may be subjected to vapor deposition (usually vacuum evaporation) using a pellet-like substance impregnated with

  Any suitable acid or base can be used for the catalyst. As an acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines etc. can be used, for example.

  The membrane is then post-treated if necessary. This post-treatment is not particularly limited, but may be, for example, sequentially performing water supply and dry heating, and more specifically, may be performed as follows.

  After the surface treatment agent of the present invention is formed into a film on the substrate surface as described above, water is supplied to this film (hereinafter also referred to as "precursor film"). The method of supplying water is not particularly limited, and, for example, a method such as condensation due to a temperature difference between the precursor film (and the substrate) and the ambient atmosphere, spraying of steam (steam), or the like may be used.

  The supply of water may be carried out, for example, in an atmosphere of 0 to 250 ° C., preferably 60 ° C. or more, more preferably 100 ° C. or more, preferably 180 ° C. or less, more preferably 150 ° C. or less. By supplying water in such a temperature range, it is possible to allow the hydrolysis to proceed. The pressure at this time is not particularly limited, but may be simply normal pressure.

  Next, the precursor film is heated on the surface of the substrate under a dry atmosphere over 60 ° C. The method of drying and heating is not particularly limited, and the precursor film and the base material are temperatures higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower, and not It may be disposed under an atmosphere of saturated water vapor pressure. The pressure at this time is not particularly limited, but may be simply normal pressure.

  Under such an atmosphere, groups bonded to Si after hydrolysis are rapidly dehydrated and condensed among the perfluoro (poly) ether group-containing silane compounds of the present invention. In addition, between such a compound and the substrate, the compound which is bonded to Si after hydrolysis of the compound rapidly reacts with the reactive group present on the surface of the substrate and is present on the surface of the substrate When the reactive group is a hydroxyl group, dehydration condensation occurs. As a result, a bond is formed between the perfluoro (poly) ether group-containing silane compound and the substrate.

  The water supply and the drying and heating described above may be carried out continuously by using superheated steam.

  Post-processing can be performed as described above. It should be noted that such post-treatments may be carried out to further improve the friction durability, but are not essential for producing the articles of the present invention. For example, after applying the surface treatment agent of the present invention to the substrate surface, it may be left standing as it is.

  As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate to produce the article of the present invention. The surface treatment layer obtained thereby has good UV resistance. In addition to good UV resistance, this surface treatment layer is water-repellent, oil-repellent, antifouling (for example, prevents adhesion of stains such as fingerprints), although it depends on the composition of the composition used. It may have surface slipperiness (or lubricity, for example, the ability to wipe off dirt such as fingerprints, excellent touch to a finger), high friction durability, and the like, and may be suitably used as a functional thin film.

  That is, the present invention further relates to an optical material having the cured product in the outermost layer.

  As the optical material, in addition to optical materials related to displays as exemplified later, a wide variety of optical materials are preferably mentioned: For example, a cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs) or protective plates of those displays, or reflections on those surfaces Those with a protective film treatment.

  An article having a surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; front protective plates for displays such as PDPs and LCDs; anti-reflection plates; polarizing plates; anti-glare plates; devices such as mobile phones and personal digital assistants Touch panel sheet; disc surface of optical disc such as Blu-ray (registered trademark) disc, DVD disc, CD-R, MO, etc .; optical fiber etc.

  In addition, the article having a surface treatment layer obtained by the present invention may be a medical device or a medical material.

  The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, particularly preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability and antifouling It is preferable from the point of sex.

  As another form, after forming a layer separately on the surface of a substrate, you may form the film of the surface treatment layer obtained by this invention on the surface of the layer.

  Hereinabove, the article obtained using the surface treatment agent of the present invention has been described in detail. In addition, the use of the surface treatment agent of this invention, the usage method, and the manufacturing method of articles | goods etc. are not limited to what was illustrated above.

  The surface treatment agent of the present invention will be more specifically described through the following examples, but the present invention is not limited to these examples.

(Examples 1 to 4 and Comparative Example 1)
The surface treatment agent was prepared by dissolving each of the mixtures or compounds shown in Table 1 below in a hydrofluoroether (Novec HFE 7200 manufactured by 3M) so that the total concentration would be 20 wt%.

The compounds A used in Examples and Comparative Examples are as follows.
・ Perfluoropolyether group-containing silane compound (A)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃

The surface treatment agent prepared above was vacuum deposited on chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning). The processing conditions for vacuum deposition were a pressure of 3.0 × 10 ⁻³ Pa. First, a silicon dioxide film with a thickness of 5 nm is formed on the surface of a chemically strengthened glass, and subsequently, 4 mg of a surface treatment agent (that is, compound A and in Examples 1 to 4) per 1 sheet of chemically strengthened glass (55 mm × 100 mm) 0.8 mg of a mixture of DMSO (0.8 mg of compound A in Comparative Example 1) was deposited. Next, the obtained chemically strengthened glass with a deposited film was allowed to stand in an atmosphere at a temperature of 150 ° C. for 30 minutes, and then allowed to cool to room temperature to form a surface treatment layer.

<Evaluation of friction durability>
The friction durability test shown below was implemented about evaluation of actual use durability about the surface treatment layer formed in said Examples 1-4 and the comparative example 1. FIG.

  As an initial evaluation, after the formation of the surface treatment layer, the static contact angle of water was measured with nothing touching the surface (friction number: zero). The measurement of the static contact angle of water was performed in 1 μL of water using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd.).

Thereafter, the sample article on which the surface treatment layer is formed is placed horizontally, the following friction elements are brought into contact with the surface of the surface treatment layer (the contact surface is a circle 1 cm in diameter), a load of 5 N is applied thereon, and then Under load, the friction element was reciprocated at a speed of 40 mm / sec. The friction element was reciprocated up to 4000 times, and the static contact angle (degree) of water was measured every reciprocation number (friction number) 1000 times. The test was discontinued when the measured static contact angle of water was less than 60 degrees. The results are shown in Table 2 (in the table, the symbol "-" is not measured).
-Friction child As a friction child, what covered the surface (diameter 1 cm) of the silicone rubber processed goods shown below using the cotton which soaked the artificial sweat of the composition shown below was used.
-Composition of artificial sweat Anhydrous disodium hydrogen phosphate: 2 g
Sodium chloride: 20 g
85% lactic acid: 2 g
Histidine hydrochloride: 5 g
Distilled water: 1 kg
-Processed silicone rubber product Made of Tigers Polymer, silicone rubber plug SR-51 processed into a cylindrical shape having a diameter of 1 cm and a thickness of 1 cm.

  From the results of Table 2, it was confirmed that the surface treatment layers of Examples 1 to 4 exhibited a reduction in the contact angle and exhibited excellent durability. It is considered that the catalytic effect of DMSO improved both the chemical resistance and the abrasion resistance of the formed surface treatment layer, and the PFPE-containing silane compound and the substrate (tempered glass) were more firmly bonded. Be

  The present invention can be suitably used to form a surface treatment layer on the surface of a wide variety of substrates, in particular optical members for which transparency is required.

Claims (16)

Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1) or Formula (C2):

[In the formula:
The PFPEs each independently at each occurrence have the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹³ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ¹⁴ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n is an integer of 0 to 3 independently for each (-SiR ¹³ _n R ¹⁴ _3-n ) unit;
However, in the formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present;
X ¹ represents independently at each occurrence a single bond or a di- to 10-valent organic group;
X ² represents independently at each occurrence a single bond or a divalent organic group;
t is an integer of 1 to 10 independently at each occurrence;
α is an integer of 1 to 9 independently at each occurrence;
α 'is each independently an integer of 1 to 9;
X ³ represents independently at each occurrence a single bond or a di- to 10-valent organic group;
β is each independently an integer of 1 to 9 at each occurrence;
β 'is each independently an integer of 1 to 9;
R ^a independently represents -Z ¹ -SiR ¹ _p R ² _q R ³ _r at each occurrence;
Z ¹ independently represents an oxygen atom or a divalent organic group at each occurrence;
R ¹ represents R ^{a ′} independently at each occurrence;
R ^{a '} is as defined the R ^a ;
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ² each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p is each independently an integer of 0 to 3 at each occurrence;
q is each independently an integer of 0 to 3 at each occurrence;
r is each independently an integer of 0 to 3 at each occurrence;
Provided that, for each -Z ¹ -SiR ¹ _p R ² _q R ³ _r , the sum of p, q and r is 3, and in formulas (B1) and (B2), they are bonded to a hydroxyl group or a hydrolysable group At least two Si are present;
R ^b independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ^c independently at each occurrence represents a hydrogen atom or a lower alkyl group;
k1 each independently at each occurrence is an integer of 0 to 3;
l 1 is each independently an integer of 0 to 3 at each occurrence;
m1 is each independently an integer of 0 to 3 at each occurrence;
Provided that ^the sum of _{-SiR a} ^k1 _R b ^l1 in each _{R c m1,} k1, l1 and m1 is 3,
X ⁴ independently at each occurrence represents a single bond or a di- to 10-valent organic group;
γ is an integer of 1 to 9 independently at each occurrence;
γ 'is each independently an integer of 1 to 9;
R ^d independently at each occurrence represents -Z ² -CR ⁸¹ _{p 2} R ⁸² _{q 2} R ⁸³ _{r 2} ;
Z ² each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is the same as R ^d ;
In ^Rd, at most 5 Cs linked in a linear fashion via a Z ² group;
R ⁸² independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence;
Y represents, independently at each occurrence, a divalent organic group;
R ⁸⁵ each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n2 represents an integer of 0 to 3 independently for each (-Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ) unit;
R ⁸³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p2 is each independently an integer of 0 to 3 at each occurrence;
q2 is each independently an integer of 0 to 3 at each occurrence;
r2 each independently at each occurrence is an integer from 0 to 3;
With the proviso that for every -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r 2 the sum of p2, q2 and r2 is 3;
R ^e each independently at each occurrence represents —Y—SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ;
R ^f independently at each occurrence independently represents a hydrogen atom or a lower alkyl group;
k2 each independently at each occurrence is an integer from 0 to 3;
l2 is each independently an integer of 0 to 3 at each occurrence;
m2 is each independently an integer of 0 to 3 at each occurrence;
However, in every (CR ^d _{k 2} R ^{e 1} ₂ R ^f _{m 2} ), the sum of k 2, 12 and m 2 is 3, and in the formulas (C 1) and (C 2), the group represented by —Y—SiR ⁸⁵ is There are two or more. ]
A surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound represented by any one of the above, and a compound containing an atom having a noncovalent electron pair in a molecular structure.   The surface treatment agent according to claim 1, wherein the compound containing an atom having a noncovalent electron pair in its molecular structure contains at least one atom selected from the group consisting of nitrogen atom, oxygen atom, phosphorus atom, and sulfur atom. .   The compound containing an atom having a noncovalent electron pair in the molecular structure is at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds, and sulfoxide compounds. The surface treatment agent according to claim 1 or 2, which is   The compound according to any one of claims 1 to 3, wherein the compound containing an atom having a noncovalent electron pair in the molecular structure is at least one compound selected from the group consisting of a sulfoxide compound, an aliphatic amine compound and an aromatic amine compound. The surface treatment agent as described in a term.   The compound containing 0.01 to 10 moles of a compound containing an atom having a noncovalent electron pair in the molecular structure is contained with respect to 1 mole of Si atom bonded to a hydroxyl group or a hydrolyzable group of the PFPE-containing silane compound. The surface treating agent according to any one of the above.   The surface treatment agent according to any one of claims 1 to 5, wherein Rf is independently a C 1-16 perfluoroalkyl group at each occurrence. PFPE independently at each occurrence is either of the following formulas (a), (b) or (c):
− (OC ₃ F ₆ ) _d − (a)
[Wherein, d is an integer of 1 to 200. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d each independently represent 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 an integer of 10 or more and 200 or less;
The order in which each repeating unit enclosed in parentheses with a subscript c, d, e or f is given is arbitrary in the formula. ]
-(R ^6- R ⁷ ) _j- (c)
[Wherein, R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or two or three selected from these groups A combination of groups;
j is an integer of 2 to 100. ]
The surface treatment agent according to any one of claims 1 to 6, which is   The surface treatment agent according to any one of claims 1 to 7, wherein the number average molecular weight of the Rf-PFPE portion is independently 500 to 30,000. The surface treatment agent according to any one of claims 1 to 8, wherein X ¹ , X ³ and X ⁴ are each independently a divalent organic group at each occurrence.   The surface treatment agent according to any one of claims 1 to 9, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts.   The surface treatment agent according to any one of claims 1 to 10, further comprising a solvent.   The surface treatment agent according to any one of claims 1 to 11, which is used as an antifouling coating agent or a waterproof coating agent.   The surface treatment agent according to any one of claims 1 to 12, which is for vacuum deposition.   The pellet containing the surface treating agent of any one of Claims 1-13.   An article comprising a substrate and a layer formed of the surface treatment agent according to any one of claims 1 to 13 on the surface of the substrate.   The article of claim 15, wherein the article is an optical member.