JP6707101B2 - Surface treatment agent containing perfluoro(poly)ether group-containing silane compound, pellets and articles using the same - Google Patents

Description

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

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

A layer obtained from a surface treatment agent containing the above-mentioned fluorine-containing silane compound (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-mentioned functions even in a thin film, it is applied to an optical member such as glasses, a touch panel, an operation screen of a mobile terminal, which is required to have light transmissivity or transparency.

Japanese Patent Laid-Open No. 2013-117012

The surface-treated layer as described above is required to have good durability in order to impart a desired function to the surface of the substrate for a long period of time. However, studies by the present inventors have revealed 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 having 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 the first aspect of the present invention, formula (A1), formula (A2), formula (B1), formula (B2), formula (C1) or formula (C2):

[In the formula:
PFPE has 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, and a, b , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
Is a group represented by
Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹³ independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^14's each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms in each occurrence;
R ¹¹ each independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 13 n R 14}} 3-n) independently for each unit, an integer from 0 to 3;
However, in formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present;
X ¹ independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
X ² independently represents a single bond or a divalent organic group at each occurrence;
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 independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
β is an integer from 1 to 9 independently at each occurrence;
β′ are 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 each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ¹ independently represents R ^a′ at each occurrence;
^Ra' has the same meaning as ^Ra ;
In R ^a , the number of Si linearly linked via the Z ¹ group is at most 5;
R ² independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p is an integer of 0 to 3 independently at each occurrence;
q is, independently at each occurrence, an integer from 0 to 3;
r is, independently at each occurrence, an integer from 0 to 3;
However, 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), it is bonded to a hydroxyl group or a hydrolyzable group. There is at least two Si;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k1 is, independently at each occurrence, an integer from 0 to 3;
l1 is, independently at each occurrence, an integer from 0 to 2;
m1 is an integer of 0 to 2 independently at each occurrence;
However, for each —SiR ^a _k1 R ^b _l1 R ^c _m1 , the sum of k1, l1 and m1 is 3,
X ⁴ independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
γ is, independently at each occurrence, an integer from 1 to 9;
γ′ is each independently an integer of 1 to 9;
R ^d independently represents -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 at each occurrence;
Z ² independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^d′ at each occurrence;
R ^d′ has the same meaning as R ^d ;
In R ^d , the maximum number of Cs linearly linked via the Z ² group is 5;
R ⁸² each independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence;
Y independently represents a divalent organic group at each occurrence;
R ⁸⁵ independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 ^{_{is, (- Y-SiR 85 n2}} R 86 3-n2) independently for each unit, an integer of 0 to 3;
R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is an integer from 0 to 3 independently at each occurrence;
q2 is an integer of 0 to 3 independently at each occurrence;
r2 is, independently at each occurrence, an integer from 0 to 3;
^However, in each ^{_{-Z 2 -CR 81 p2 R 82 q2}} R 83 r2, the sum of p2, q2 and r2 is 3;
R ^e is, independently at each ^occurrence, represents ^{_{-Y-SiR 85 n2 R 86 3}} -n2;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is an integer of 0 to 3 independently at each occurrence;
l2 is, independently at each occurrence, an integer from 0 to 3;
m2 is an integer of 0 to 3 independently at each occurrence;
However ^,, in each ^{_{(CR d k2 R e l2 R}} f m2), the sum of k2, l2 and m2 is 3, in the formula (C1) and (C2), a group represented by ^{-Y-SiR 85} There are two or more. ]
There is provided a perfluoro(poly)ether group-containing silane compound represented by any of the above, and a surface treating agent containing 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 including a base material and a layer formed on the surface of the base material by the surface treatment agent of the present invention.

According to the present invention, a novel surface treatment agent containing a perfluoro(poly)ether group (hereinafter sometimes referred to as “PFPE”)-containing silane compound is provided. The surface treatment agent of the present invention is suitable for forming a surface treatment layer having improved durability, particularly a surface treatment layer exhibiting good durability even in the presence of an acid or an alkali. Moreover, according to this invention, the pellet containing the surface treatment agent of this invention is provided. According to the present invention, there is provided an article including a substrate and a layer formed from the surface treatment agent of the present invention on the surface of the substrate.

As used herein, the term “hydrocarbon group” means a group containing carbon and hydrogen, in which one hydrogen atom has been removed from the hydrocarbon. The hydrocarbon group is not particularly limited, but is a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with one or more substituents, for example, an aliphatic hydrocarbon group, Examples thereof include aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. In addition, such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or in the molecular chain.

As used in the present specification, the substituent of the “hydrocarbon group” is not particularly limited, but is, for example, a halogen atom; C _1-6 alkyl optionally substituted by one or more halogen atoms. Group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from groups, C _6-10 aryl groups and 5-10 membered heteroaryl groups.

In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted unless otherwise specified. The substituent for such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group and a C _2-6 alkynyl group. Can be mentioned.

As used herein, the “2- to 10-valent organic group” means a 2- to 10-valent group containing carbon. The 2- to 10-valent organic group is not particularly limited, and examples thereof include a 2- to 10-valent group obtained by removing 1 to 9 hydrogen atoms from a hydrocarbon group.

[Surface treatment]
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 an unshared electron pair in its molecular structure.

(PFPE-containing silane compound)
The PFPE-containing silane compound is a compound represented by any one of formula (A1), formula (A2), formula (B1), formula (B2), formula (C1) and 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, based on 100 parts by mass of the surface treatment agent.

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

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

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

Formulas (A1) and (A2):

In the above formula, Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence.

The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain. It may also be a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a straight-chain alkyl group having 1 to 3 carbon atoms.

The Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted with one or more fluorine atoms, 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 is preferably linear or branched and has 1 to 6 carbon atoms, particularly 1 to 1 carbon atoms. 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, and more specifically 10 or more and 100 or less. In addition, the order of existence of each repeating unit in parentheses with a, b, c, d, e or f attached 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) 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, but preferably -( OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. - _{(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 ))-, but 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 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 1 to 200, preferably 5 to 200, more preferably an integer of 10 to 200) or - ( _{OCF (CF 3) CF 2)} d - ( wherein, d is 1 to 200, preferably 5 to 200, more preferably an integer of 10 to 200). More preferably, PFPE _is - is (wherein, d is 1 to 200, preferably 5 to 200, more preferably 10 to 200 _{integer) - (OCF 2 CF 2 CF} 2) d .

In another embodiment, 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 Is an integer of 0 or more and 30 or less, 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 each repeating unit enclosed in parentheses with subscript c, d, e or f 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 embodiment, PFPE _{is, - (OC 2 F 4)} e - (OCF 2) f - ( wherein, e and f are 1 to 200 independently, preferably 5 to 200, more preferably Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a subscript e or f is arbitrary in the formula).

In one embodiment, PFPE _{is, - (OC 2 F 4)} e - (OCF 2) f - ( wherein, e and f are 1 to 200 independently, preferably 5 to 200, more preferably Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a subscript e or f is 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, and 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 salt water, acid or basic aqueous solution, acetone, oleic acid or hexane) ) Can be improved. The smaller the e/f ratio, the more improved the water repellency, oil repellency and chemical resistance of the cured product. On the other hand, when the e/f ratio is 0.1 or more, the stability of the compound can be further enhanced. The higher the e/f ratio, the more stable the compound.

In yet another embodiment, PFPE _{^{is, - (R 6 -R 7)}} j - is a group represented by. 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 is independently selected from these groups. It is 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 is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F _12. It is a group selected or a combination of 2 or 3 groups independently selected from these groups. Examples of the combination of _{OC 2 F 4, OC 3 F} 6 and _OC 4 2 or 3 groups independently selected from _{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 above j is 2 or more, preferably 3 or more, more preferably 5 or more, and is an integer of 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, and are 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, 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 -
And has at least one branched structure in PFPE. That is, in this aspect, the PFPE has at least one CF ₃ terminal (specifically, —CF ₃ , —C ₂ F _5, etc., more specifically —CF ₃ ). By having PFPE having such a structure, the layer (eg, surface-treated layer) formed by using the surface-treating agent of the present invention has UV durability, water repellency, oil repellency, and stain resistance (for example, stains such as fingerprints). Can be improved), chemical resistance, hydrolysis resistance, effect of suppressing slipperiness, high friction durability, heat resistance, moisture resistance, etc. can be improved.

In the above aspect, 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, and more specifically 10 or more and 100 or less. In addition, the order of existence of each repeating unit in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula.

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

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

In the above aspect, 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 of repeating units of 100 in the PFPE structure. It is particularly preferably in the range of 80 to 100.

In the above aspect, examples of the branched chain in the branched structure include CF ₃ .

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 aspect, the PFPE may include a linear repeating unit together with a 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, PFPE is a repeating unit of the branched structure _{OC 6 F 12, OC 5 F} 10, OC 4 F 8, and consisting of _OC 3 _{F 6.}

In one embodiment, the PFPE _{is, - (OC 3 F 6)} d - ( wherein, d is 1 to 200, preferably 5 to 200, more preferably an integer of 10 to 200) be , PFPE has at least one branched structure.

In the above aspect, the PFPE may further include a linear repeating unit —(OCF ₂ CF ₂ CF ₂ )—.

In the above aspect, it is preferable that the PFPE is composed of 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 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, 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 Is an integer of 0 or more and 30 or less, 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 repeating units enclosed in parentheses with subscripts 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, - (R 6 -R 7)}} j - in a group represented, having at least one branched structure 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 is independently selected from these groups. It is 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 is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F _12. It is a group selected or a combination of 2 or 3 groups independently selected from these groups. Examples of the combination of _{OC 2 F 4, OC 3 F} 6 and _OC 4 2 or 3 groups independently selected from _{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 above j is 2 or more, preferably 3 or more, more preferably 5 or more, and is an integer of 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 is composed of repeating units OC ₆ F ₁₂ , OC ₅ F ₁₀ , OC ₄ F ₈ and OC ₃ F ₆ having a 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, and more preferably 2,000 to 10,000.

In another embodiment, the Rf-PFPE moiety has a number average molecular weight of 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 the -PFPE-moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.

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

The term “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable _{groups, -OR, -OCOR, -O-N} = CR 2, -NR 2, -NHR, halogen atom (in these formulas, R is a substituted or unsubstituted carbon atoms 1 4 is an alkyl group) and is preferably —OR (that is, an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as 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 above-mentioned "hydroxyl group" is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group.

In the above formula, R ¹⁴ 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 in each occurrence.

In the above formula, R ¹¹ at each occurrence, 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 formula, R ¹² at each occurrence 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 formula, n is an integer of 0 to 3, independently of each (-SiR ¹³ _n R ¹⁴ _3-n ) unit, preferably 1 to 3, and more preferably 3. However, in formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in the formulas (A1) and (A2), there are at least two SiR ¹³ structures.

In the above formula, X ^1's each independently represent a single bond or a divalent to 10-valent organic group. The X ¹ is a perfluoropolyether moiety (that is, an Rf-PFPE moiety or a -PFPE- moiety) that mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2). And a silane moiety that provides the ability to bind to the substrate (ie, the group parenthesized with α). Therefore, the X ¹ may be any organic group as long as the compounds represented by the formulas (A1) and (A2) can exist stably.

In another aspect, X ¹ represents X ^e . X ^e represents a single bond or a divalent to 10-valent organic group, preferably a single bond or -C ₆ H ₄ -(that is, -phenylene-; hereinafter, a phenylene group) and -CO-(carbonyl group. ), —NR ⁴ —, and —SO ₂ — represent a divalent to 10-valent organic group having at least one selected from the group consisting of —SO ₂ —. R ^{4 s} each independently represent a hydrogen atom, a phenyl group, or a C _1-6 alkyl group (preferably a methyl group), and 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 represents a binding chain containing PFPE which is relatively longest 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 the above formula, α is an integer of 1 to 9 and α′ is an integer of 1 to 9. These α and α′ can change 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, for example, α is 9 and α′ is 1, α is 5 and α′ is 5, or α is 1 and α. 'Can be 9. Further, when X ¹ is a divalent organic group, α and α′ are 1. In the formula (A2), α is a value obtained by subtracting 1 from the valence of X ¹ .

The above X ¹ is preferably a divalent to 7-valent, more preferably a divalent to tetravalent, and even more preferably a divalent organic group.

In one embodiment, 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′).

The example of X ¹ is not particularly limited, but for example, the 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 _{is, - (X b) l '}} - it represents,
X ^b is independently -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R ³³ ) ₂ -, -( at each occurrence. _{^{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 Group,
R ³³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group in each occurrence, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group. And
R ³⁴ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) in each occurrence,
m′ is, at each occurrence, independently an integer of 1 to 100, preferably an integer of 1 to 20,
n′ is, at each occurrence, each independently an integer of 1 to 20, preferably an integer of 1 to 6, and 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,
q′ is 0 or 1,
Here, at least one of p′ and q′ is 1, and the order of existence of each repeating unit with parentheses attached to p′ or q′ is arbitrary]
And a divalent group represented by Here, R ³¹ and X ^a (typically hydrogen atoms 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-, represents m- or p- phenylene, preferably - _(CH 2) _t' - a. 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 the 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. May be.

Preferably, X ¹ is
A C _1-20 alkylene group,
-R ³¹ -X ^c -R ³² - or ^-X d ^{-R 32,} -
[Wherein, R ³¹ and R ³² have the same meanings as described above. ]
Can be The alkylene group is a group having a -(C _δ H 2 _δ ) _-structure , which may be substituted or unsubstituted, and may be linear or branched.

More preferably, X ¹ is
A 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}} '-
[In the formula, s′ and t′ have the same meanings as described above. ]
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′ have the same meanings as described above,
u'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. ] Is represented. 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 -
[In the formula, each symbol has the same meaning as described above. ]
Represents.

More preferably, X ¹ is
A C _1-20 alkylene group,
_{- (CH 2) s' -X} c - (CH 2) t '-, or _{^{-X d - (CH 2) t}} ' -
[In the formula, each symbol has the same meaning as described above. ]
Can be

Even more preferably, X ¹ is
A 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) -
[In the formula, R ³³ , m′, s′, t′, and u′ have the same meanings as described above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. It is an integer. ]
Is.

In the above _{formula, - (C v H 2v)} - can be linear, may be branched, for _{example, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH _{2 -, - CH (CH 3} ) -, - CH (CH 3) CH 2 - it may be.

The above X ¹ group 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 (preferably a C _1-3 perfluoroalkyl group). It may have been done.

In one aspect, the X ¹ group can 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 aspect, X ¹ groups include, for example:

[Wherein, R ⁴¹ is independently 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

(In the formula, R ^42's each independently represent a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, and 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 PFPE of the molecular main chain, and E is attached to a group opposite to PFPE. ]

などが挙げられる。 Specific examples of 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 -,

And so on.

In another preferred embodiment, X ¹ represents X ^e′ . X ^{e 'represents} 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 - is. R ⁵¹ and R ⁵² each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, and preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R ⁴ has the same meaning as above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, and preferably a fluorine atom. The alkylene group is linear or branched, and preferably linear.

In a further preferred embodiment, X ^e′ is
Single bond,
An alkylene group having 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} -
(In the formula, R ^{51 ′} and R ^{52 ′} are each independently 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. )
Can be

In the present aspect, 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} -
And so on.

In one aspect, ^Xe' is a single bond. In the present embodiment, the group capable of binding PFPE to the base material layer (that is, in (A1) and (A2), a group enclosed by parentheses with α) is directly bonded.

In yet another embodiment, ^{X 1} is the formula _{^{:-( R 16) x - (CFR}} 17) y - (CH 2) z - is a group represented by. 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 in parentheses is Is optional in.

In the above formula, R ¹⁶ is independently an oxygen atom, phenylene, carbazolylene, —NR ¹⁸ — (wherein R ¹⁸ represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. 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 — (wherein 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, for example, a methyl group, an ethyl group, an n-propyl group, which may be substituted with one or more fluorine atoms. Good.

In the above formula, R ¹⁷ is, independently at each occurrence, a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, and 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 aspect, X ¹ is preferably of the formula: —(O) _x —(CF ₂ ) _y —(CH ₂ ) _z — (where x, y and z are as defined above, The order of existence of each repeating unit surrounded by is arbitrary 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"" (In the formula, x'is 0 or 1, y", z" and z'" are each independently an integer of 1 to 10, and z"" is 0 or 1 And 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's each independently represent 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, a pentafluoroethyl group, further preferably a trifluoromethyl group. It is a methyl group.

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

In one embodiment, R ²⁰ is a fluorine atom, 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 aspect, examples of X ¹ groups include the following groups:

[In the formula,
R ⁴¹ is independently 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 of T is any of the following groups attached to PFPE in 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

[In the formula, each R ⁴² 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, and more preferably a methyl group. ]
, And the some alternative T, then binds to the PFPE opposite groups of molecular backbone _{- (CH 2) n "-} (n" is an integer of from 2 to 6) and, if present, remaining Each T may independently be 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 trap a radical generated by light irradiation, and examples thereof include benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, and organoacrylates. , Residues of hindered amines, hindered phenols, or triazines.

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

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

Is mentioned.

In this aspect, X ¹ , X ³ and X ⁴ can be tri- to monovalent organic groups.

In the above formula, X ² 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 formula, t is independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer of 2-10, preferably 2-6.

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

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

In one embodiment, in the compounds represented by formulas (A1) and (A2), α is 1, α′ is 1, and t is 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) are represented by the following formulas (A1′) and (A2′):

[In the formula:
PFPEs each independently 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 -
(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. The order of existence of each repeating unit in parentheses with a, b, c, d, e or f attached is arbitrary in the formula.)
Is a group represented by
Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹³ independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^14's each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms in each occurrence;
R ¹¹ each independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
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 are present;
X ¹ is independently at each _{^{occurrence, -O-CFR 20 - (CF}} 2) e '- a and;
R ²⁰ is, independently at each occurrence, a fluorine atom or a lower fluoroalkyl group;
e'is independently 0 or 1 at each occurrence;
X ² is, - _{(CH 2) u} - a and;
u is an integer of 0 to 2 independently at each occurrence;
t is an integer of 1 to 10 independently at each occurrence. ]
Is a compound represented by.

The compounds represented by the above formulas (A1) and (A2) are, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and after introducing iodine at the end thereof, -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 formulas (B1) and (B2), Rf and PFPE have the same meanings as described in the formulas (A1) and (A2).

In the above formula, X ³ independently represents a single bond or a divalent to 10-valent organic group at each occurrence. The X ³ is a perfluoropolyether moiety (that is, an Rf-PFPE moiety or a -PFPE- moiety) that mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (B1) and (B2). And a silane moiety that provides the ability to bind to the substrate (ie, the group bracketed with β) is understood as a linker. Therefore, X ³ may be any organic group as long as the compounds represented by the formulas (B1) and (B2) can exist stably.

In another aspect, X ³ represents X ^e . X ^e has the same meaning as 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 change depending on the valence of X ³ . In the formula (B1), the sum of β and β′ is the same as the valence of X3. For example, when X3 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. Further, when X ³ is a divalent organic group, β and β′ are 1. In the formula (B2), β is a value obtained by subtracting 1 from the valence of X ³ .

X ³ is preferably a divalent to 7-valent, more preferably a divalent to a tetravalent, and even more preferably a divalent organic group.

In one aspect, 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 X ³ are not particularly limited, but include, for example, the same ones as those described for X ¹ .

などが挙げられる。 Among them, preferable 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 -,

And so on.

In another preferred embodiment, ^{X 3} represents a X ^{e '.} X ^{e ′} has the same meaning as above.

In one aspect, ^Xe' is a single bond. In this embodiment, a group having a binding ability between PFPE and the base material layer (that is, in (B1) and (B2), a group parenthesized with β) is directly bonded.

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

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

Said ^{Z 1} is preferably an alkylene _{group, - (CH 2) g -O-} (CH 2) h - ( wherein, g is an integer from 1 to 6, h is an integer of from 1 to 6 there) or, - phenylene - _{(CH 2) i} - (wherein, i is an integer of 0 to 6) there. These groups may be substituted with, for example, 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 (UV durability), Z ¹ is more preferably a linear or branched alkylene group, and further preferably a linear alkylene group. .. The number of carbon atoms constituting the alkylene group for Z ¹ is preferably in the range of 1 to 6, more preferably 1 to 3. The alkylene group is as described above.

In the formula, R ¹ independently represents R ^{a ′} at each occurrence. ^Ra' has the same meaning as ^Ra .

In R ^a , the maximum number of Si linked linearly via the Z ¹ group is 5. 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 The maximum number of linearly linked Si atoms is 5. 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, the following shows an example in which a Si atom in R ^a is linked via a Z ¹ group.

In the above formula, * means a site bonded to Si in the main chain, and... means that a predetermined group other than Z ¹ Si is bonded, that is, all three bonds of Si atom are... In the case of, it means the end point of the repetition of Z ¹ Si. The number on the right side of Si means the number of appearances of Si linearly linked through the Z ¹ group counted from *. That is, a chain in which Z ¹ Si repetition is completed in Si ² has “the number of Si atoms linearly linked through the Z ¹ group in R ^a ”and similarly Si ³ , Si ⁴ and Si ⁵ have Z ¹ Si repeating ends terminated with “number of Si atoms linearly linked through the Z ¹ group in R ^a ”respectively 3, 4, and 5 It is an individual. As is clear from the above formula, ^a plurality of Z ¹ Si chains are present in R ^a , but it is not necessary that they all have the same length, and each may have an arbitrary 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 formula) or 2 (in left chain) in all chains. Right formula).

In one embodiment, the number of Si atoms linearly linked via the Z ¹ group in R ^a is 1 or 2, preferably 1.

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

Examples of the above-mentioned "hydrolyzable group" include the same as those in formulas (A1) and (A2).

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

In the formula, R ^3's each independently represent 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 further preferably a methyl group.

In the formula, p is an integer of 0 to 3 independently at each occurrence; q is an integer of 0 to 3 independently at each occurrence; r is independently at each occurrence. And is an integer of 0 to 3. However, the sum of p, q, and r is 3 for each —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 are present. That is, there are at least two groups represented by SiR ² and/or SiR ^b . Due to having such a constitution, the PFPE-containing silane compound of the present invention can form a surface-treated layer capable of being favorably bonded to the surface of a substrate or the like.

In the above formula, R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

^Rb is preferably a hydroxyl group, -OR, -OCOR, -ON=C(R) ₂ , -N(R) ₂ , -NHR, halogen (wherein, R is substituted or unsubstituted). Represents an alkyl group having 1 to 4 carbon atoms), 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 a hydroxyl group generated 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 formula, R ^c 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 further preferably a methyl group.

In the formula, k1 is independently an integer of 0 to 3 at each occurrence; l1 is an integer of 0 to 3 independently at each occurrence; m1 is independently at each occurrence. And is an integer of 0 to 3. However, the sum of k1, l1 and m1 is 3 for each —SiR ^a _k1 R ^b _l1 R ^c _m1 . k1 is preferably 1 to 3, and more preferably 3.

The compounds represented by the formulas (B1) and (B2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and after introducing a hydroxyl group at the terminal, have an unsaturated bond at the terminal. Introduce a group, react the group having an unsaturated bond with a silyl derivative having a halogen atom, further introduce a hydroxyl group at the terminal to the silyl group, and react the group having an introduced unsaturated bond with the silyl derivative Can be obtained. For example, it can be synthesized as described in WO2014/069592.

Formulas (C1) and (C2):

In the formulas (C1) and (C2), Rf and PFPE have the same meanings as described in the formulas (A1) and (A2).

In the above formula, X ^4's each independently represent a single bond or a divalent to 10-valent organic group. The X ⁴ is a perfluoropolyether moiety (that is, Rf-PFPE moiety or -PFPE- moiety) that mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (C1) and (C2). And a moiety that provides the ability to bind to a base material (ie, a group enclosed by brackets with γ). Therefore, X ⁴ may be any organic group as long as the compounds represented by the formulas (C1) and (C2) can exist stably.

In another aspect X ⁴ represents X ^e . X ^e has the same meaning as above.

In the above formula, γ is an integer of 1 to 9 and γ'is an integer of 1 to 9. These γ and γ′ can change depending on 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, and for example, γ is 9 and γ′ is 1, γ is 5 and γ′ is 5, or γ is 1 and γ. 'Can be 9. When X ⁴ is a divalent organic group, γ and γ′ are 1. In the formula (C2), γ is a value obtained by subtracting 1 from the valence of X ⁴ .

X ⁴ is preferably an organic group having a valence of 2 to 7, more preferably a valence of 2 to 4, and further preferably a valence of 2.

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

In another aspect, 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′).

The example of X ⁴ is not particularly limited, and examples thereof include the same as those described for X ¹ .

などが挙げられる。 Among them, preferable 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 -,

And so on.

In another preferred embodiment, ^{X 3} represents a X ^{e '.} X ^{e ′} has the same meaning as above.

In one aspect, ^Xe' is a single bond. In this embodiment, a group having a binding ability between PFPE and the base material layer (that is, in (C1) and (C2), a group parenthesized with γ) is directly bonded. By having such a structure, it is considered that the binding force between PFPE and a group attached with γ and enclosed in parentheses becomes stronger. In addition, the carbon atom directly bonded to PFPE (that is, the carbon atom bonded to R ^d _, R ^e and R ^{f in} the parenthesized group with γ) has less bias in charge, and as a result, It is considered that a nucleophilic reaction or the like is unlikely to occur in the atom and that the atom is stably bonded to the base material layer. Such a structure is advantageous in that the friction durability of the formed surface treatment layer is further improved.

In the above formula, R ^d independently represents —Z ² —CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 at each occurrence.

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

Said ^{Z 2} is _{preferably, C 1-6} alkylene _{group, - (CH 2) g -O-} (CH 2) h - ( wherein, g is an integer of 0 to 6, for example 1 to 6 integer There, h is an integer of 0 to 6, such as an integer from 1 to 6) or - phenylene - _{(CH 2) i} - (wherein, i is a an a) an integer of 0 to 6, and more Preferably, it is a C _1-3 alkylene group. These groups may be substituted with, for example, 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′ has the same meaning as R ^d .

In R ^d, at most 5 Cs are linearly linked via the Z ² group. That is, the in R ^d, when R ⁸¹ is present at least one, but C atoms linked in R ^d in Z ² group via a linear there are two or more, via such Z ² group The maximum number of linearly linked C atoms is 5. 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 " means 1 (left formula) or 2 (in the left chain) in all chains. Right formula).

In one aspect, the number of C atoms linearly linked via the Z ² group of R ^d is 1 or 2, preferably 1.

In the formula, R ⁸² independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence.

Y independently represents 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 is an integer, h 'is an integer of 0 to 6, for example 1 to 6 which is an integer), or - phenylene _{- (CH 2) i' -} ( wherein, i 'is an integer from 0 to 6 ). These groups may be substituted with, for example, 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. If Y is a radical as described above, it may be more light-resistant, in particular UV-resistant.

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

Examples of the above-mentioned "hydrolyzable group" include the same as those in formulas (A1) and (A2).

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

The R ^{86 s} each independently represent a hydrogen atom or a lower alkyl group in 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 further preferably a methyl group.

n2 _{^{is, (- Y-SiR 85 n2}} R 86 3-n2) independently for each unit, an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, particularly preferably 3 Is.

The R ^{83 s} each independently represent a hydrogen atom or a lower alkyl group in 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 further 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. And 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 It 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 formula, R ^e independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence. Here, Y, R ⁸⁵ , R ⁸⁶ and n2 have the same meanings as described in R ⁸² .

In the above formula, R ^f 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 further preferably a methyl group.

In the formula, k2 is, independently at each occurrence, an integer of 0 to 3; l2 is independently at each occurrence, an integer of 0 to 3; m2 is independently at each occurrence. And is an integer of 0 to 3. ^However, in each _{^{(CR d k2 R e l2 R}} f m2), the sum of k2, l2 and m2 is 3.

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

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

In one aspect, 12 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, _-C- group represented by _{^{(Y-SiR 85 n2 R 86}} 3-n2) 2 is preferably present one or more (wherein, n2 is an integer of 1-3.).

Preferably, in the 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 l2 is 2 or 3. .. That is, in the formula, at least two —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups are present.

［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 embodiment, the 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′ has the same meaning as X ⁴ and preferably represents X ^e ;
X ^e has the same meaning as above;
γ and γ′ are as defined above;
R ^{d 'are} each, independently at each occurrence, -Z ^2' represents _{^{-CR 81 p2 'R 82' q2}} 'R 83 r2';
R ⁸¹ and R ⁸³ are each as defined above;
Z ^2′ each independently represents —R ^g —Z′— at each occurrence;
R ^g independently represents a lower alkylene group at each occurrence;
Z'in each occurrence independently represents a single bond, an oxygen atom or a divalent organic group;
R ^82′ each independently represents —R ^h —Y′—SiR ⁸⁵ _n2′ R ⁸⁶ _3-n2′ at each occurrence;
R ^h each independently represents a lower alkylene group at each occurrence;
Y'in each occurrence independently represents a single bond, an oxygen atom or a divalent organic group;
n2 ^{'is, (- R h -Y'-SiR} 85 n2' R 86 3-n2 ') independently for each unit represents an integer of 1 to 3, preferably 2 or 3, more preferably 3 ;
R ⁸⁵ and R ⁸⁶ are each as defined above;
p2′ is an integer of 0 to 3 independently at each occurrence;
q2′ is an integer of 0 to 3 independently at each occurrence;
r2′ is, independently at each occurrence, an integer from 0 to 3;
_'In each ^{unit, p2 (-Z 2' -CR 81} p2 'R 82' q2 'R 83 r2)', the sum of q2 'and r2'3;
R ^{e 'is} independently at each _{^{occurrence, -R h -Y'-SiR 85 n2}} ' represents R ⁸⁶ _{3-n2 ';}
R ^f has the same meaning as above;
k2' is, independently at each occurrence, an integer from 0 to 3;
l2′ is each independently an integer of 0 to 3 at each occurrence;
m2′ is an integer of 0 to 3 independently at each occurrence;
However, in each (CR ^d′ _k2′ R ^e′ _l2′ R ^f _m2′ ), the sum of k2′, l2′ and m2′ is 3, and in the formula, at least one q2′ is 3, or Alternatively, at least one 12' is 3. ]

The above R ^g's each independently represent a lower alkylene group in 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, particularly preferably methylene.

Z′ is preferably an oxygen atom or a divalent organic group, more preferably a divalent organic group, and further preferably a C _1-6 alkylene group, —(CH ₂ ) _j1 —O—( (in the formula, j1 is an integer of 0 to 6, 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, - - CH _{2) h1} phenylene - _{(CH 2) i1} - (wherein, i1 is an integer of 0-6), and particularly preferably _{C 1-6} alkylene group or - phenylene - _{(CH 2) i1} - is, more preferably It is a C _1-6 alkylene group (preferably a C _1-3 alkylene group). These groups may be substituted with, for example, 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 Z ^2′ may preferably be a C _1-3 alkylene group, specifically —CH ₂ —, —CH ₂ CH ₂ —, or —CH ₂ CH ₂ CH ₂ —.

The above R ^h's each independently represent a lower alkylene group in 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, particularly preferably methylene.

In a preferred embodiment, Y'is an oxygen bond or a divalent organic group. Y 'is more preferably a divalent organic group, 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 a C _1-6 alkylene group or —phenylene-(CH ₂ ) _i1′- , and particularly preferably a C _1-6 alkylene group (preferably , C _1-3 alkylene group). These groups may be substituted with, for example, 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 radical 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 aspect, at least one k2' is 2 or 3, preferably 3.

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

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

In a preferred embodiment, 12' is 3 and n2' is 3.

In the above formulas (C1″) and (C2″), at least one q2′ is 3 or at least one 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'- There are SiR ⁸⁵ _n2′ R ⁸⁶ _3-n2′ ) ₃ groups. By having such a structure, the PFPE-containing silane compound of the present embodiment has chemical durability (for example, even in an acid and/or alkaline environment, more specifically, in an environment where sweat can adhere) It can contribute to the formation of a surface treatment layer (which is less likely to deteriorate). Further, the PFPE-containing silane compound of the present embodiment can contribute to the formation of the surface-treated layer having good friction durability by having the structure as described above, and particularly in an environment easily exposed to an acid and/or alkaline environment. Also in the case, it can contribute to the formation of the surface-treated layer having improved abrasion resistance.

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

The PFPE-containing silane compound represented by the formula (C1) or the 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 is not limited thereto.

_{^{HO-X 4 -C (YOH)}} 3 ( wherein, ^{X 4} and Y are each independently a divalent organic group.) A polyhydric alcohol represented by, containing a double-bonded group (preferably allyl), and halogen (preferably bromo) by ^introducing, in Hal-X 4 -C (Y- O-R-CH = CH 2) 3 ( wherein, Hal is halogen, e.g. Br, R is a divalent organic group, for example, an alkylene group) to obtain a double bond-containing halide. Next, the halogen at the terminal is reacted with a perfluoropolyether group-containing alcohol represented by R ^PFPE —OH (wherein R ^PFPE is a perfluoropolyether group-containing group), and R ^PFPE — obtaining ^{O-X 4 -C (Y-} O-R-CH = CH 2) 3. Then, a -CH = _CH 2 end, ^is reacted with HSiCl ₃ and an alcohol or ^{_{HSiR 85 3, R PFPE -O-}} X 4 -C (Y-O-R-CH 2 -CH 2 -SiR 85 3) ₃ can be obtained.

In another embodiment, PFPE-containing compounds of formula (C1″) or formula (C2″) having —R ⁵¹ —CONH—R ⁵² — as X ^4′ include, but are not limited to: It can be manufactured in this manner.

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 R ^PFPE -R ⁵¹ -CONH-R ⁵² C(-CH ₂ -CH=CH ₂ ) ₃ is synthesized by reacting the obtained compound with HSiCl ₃ and an 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 is obtained, wherein R ^PFPE is a PFPE-containing group, and R ⁵¹ and R ⁵² has the same meaning as above.

(Compound containing an atom having an unshared electron pair in the molecular structure)
The surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having improved abrasion resistance. Further, the surface treatment agent of the present invention is a surface treatment layer having improved durability, particularly chemically stable, and for example, for forming a surface treatment layer which is resistant to deterioration in the presence of an acid and/or an alkali. Can contribute. This is considered to be because the compound containing an atom having an unshared electron pair in the molecular structure exerts a catalytic effect, so that the bond between the base material and the Si atom becomes stronger.

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

The compound containing an atom having an unshared electron pair in the molecular structure is at least selected from the group consisting of an amino group, an amide group, a sulfinyl group, a P=O group, an S=O group and a sulfonyl group in the molecular structure. It preferably contains one functional group, and more preferably contains at least one functional group selected from the group consisting of P═O group and S═O group.

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

In the above embodiments, a compound containing an atom having an unshared electron pair in the molecule structure of the formula: R ^{91 -S} (= O) is preferably a compound represented by -R ^92.

In the above formula, R ⁹¹ is a hydrocarbon group having 1 to 12 carbon atoms, and 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.

Examples of the hydrocarbon group include a saturated hydrocarbon group, an unsaturated hydrocarbon group having at least one carbon-carbon unsaturated bond, or an aromatic hydrocarbon group. Preferably, the hydrocarbon group may be an alkyl group or a phenyl group.

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

In the above formula, R ⁹¹ and R ⁹² may be bonded to each other and form a ring structure together with the S atom bonded to R ⁹¹ and R ⁹² . The above ring structure preferably comprises 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 4 to 6 carbon atoms. It is more preferable that

Examples of the ring structure include a saturated four-membered ring structure composed of 1 S atom and 3 carbon atoms, a saturated 5-membered ring structure composed of 1 S atom and 4 carbon atoms, 1 S atom and 5 Saturated 6-membered ring structure consisting of carbon atoms of 1, unsaturated 5-membered ring structure consisting of 1 S atom and 4 carbon atoms, unsaturated 6-membered ring structure consisting of 1 S atom and 5 carbon atoms, etc. Specific examples include a saturated five-membered ring structure composed of 1 S atom and 4 carbon atoms, and an unsaturated five-membered ring structure composed of 1 S atom and 4 carbon atoms. be able to. In the carbon atom constituting the above ring structure, at least one hydrogen atom bonded to the carbon atom may be substituted with a substituent such as an alkyl group (for example, having 1 to 6 carbon atoms) or a phenyl group. It may not have a substituent.

The compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound and a sulfoxide compound. Is preferred, and at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds is more preferred, and 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. Examples of the phosphoramide compound include hexamethylphosphoramide. 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. Examples of the urea compound include tetramethylurea. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide and the like. Among these compounds, it is preferable to use dimethyl sulfoxide or tetramethylene sulfoxide.

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

The compound containing an atom having an unshared electron pair in the molecular structure can be contained in an amount of, for example, 0.0002% by mass or more based on the entire surface treatment agent. The above compound is preferably contained in an amount of 0.02% by mass or more, more preferably 0.04% by mass or more, based on the entire surface treatment agent. The above compound may be contained in an amount of, for example, 10% by mass or less, particularly 1% by mass or less, based on the entire surface treatment agent. The surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having better durability by containing the above-mentioned compound in the above concentration.

The compound containing an atom having an unshared electron pair in the molecular structure is contained in the surface treatment agent in an amount of 0.01 mol or more based on 1 mol of the Si atom bonded to the hydroxyl group or the hydrolyzable group of the PFPE-containing silane compound. Is preferred, more preferably 0.03 mol or more is contained, still more preferably 0.15 mol or more is contained, and particularly preferably 0.33 mol or more is contained. By containing the compound containing an atom having an unshared electron pair in the molecular structure in the above concentration, the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.

The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 10 mol or less based on 1 mol of the Si atom bonded to the hydroxyl group or the hydrolysis group of the PFPE-containing silane compound. , 6 mol or less is more preferable, and 2 mol or less is particularly preferable. By containing the compound containing an atom having an unshared electron pair in the molecular structure in the above concentration, the surface treatment agent of the present invention can have good handleability, and in particular, can prevent clouding of the surface treatment agent. it can.

In one embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is 3 mol or less with respect to 1 mol of the Si atom bonded to the hydroxyl group or the hydrolysis group of the PFPE-containing silane compound in the surface treatment agent. May be included.

The compound containing an atom having an unshared electron pair in the molecular structure is contained in the surface treatment agent in an amount of 0.01 to 10 mol based on 1 mol of the Si atom bonded to the hydroxyl group or the hydrolysis group of the PFPE-containing silane compound. It is preferable that 0.01 to 3 mol is contained, and it is particularly preferable that 0.33 to 2 mol is contained.

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

The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 0.01 mol or more, and preferably 0.1 mol or more, based on 1 mol of the PFPE-containing silane compound. Is more preferable, 0.15 mol or more is more preferable, 0.2 mol or more is more preferable, 0.3 mol or more is particularly preferable. By containing the compound containing an atom having an unshared electron pair in the molecular structure in the above concentration, the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.

The compound containing an atom having an unshared electron pair in its molecular structure is contained in the surface treatment agent in an amount of preferably 15 mol or less, more preferably 10 mol or less, based on 1 mol of the PFPE-containing silane compound. It is particularly preferable that the content is 7 mol or less.

The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in 6 mol or less, more preferably 3 mol or less, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferable that the content is 1 mol or less. By containing the compound containing an atom having an unshared electron pair in the molecular structure in the above concentration, the surface treatment agent of the present invention can have good handleability, and in particular, can prevent clouding of the surface treatment agent. it can.

In one embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in the surface treatment agent in an amount of 0.01 to 15 mol, based on 1 mol of the PFPE-containing silane compound. It is more preferably contained in an amount of 01 to 10 moles, still more preferably 0.1 to 10 moles, particularly preferably 0.3 to 7 moles, and more preferably 0.5 to 7 moles.

The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 to 6 mol, and preferably 0.1 to 3 mol, per 1 mol of the PFPE-containing silane compound in the surface treatment agent. Is more preferable, and it is particularly preferable that it is contained in an amount of 0.3 to 2 mol.

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

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

The surface treatment agent of the present invention may be diluted with a solvent. Such a 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 CHFCHFCFC ₂ F ₅ , 1,1,1,2,2,3,3,4,5,5,6 , 6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorora H (trade name), etc.), 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, methyltrifluoromethanesulfonate, trifluoroacetic acid and CF ₃ O(CF ₂ CF ₂ O) _m1 (CF ₂ O) _n1 CF ₂ CF ₃ [wherein m 1 and n 1 are each independently It is an integer of 0 or more and 1000 or less, and the order of existence of each repeating unit in parentheses with m1 or n1 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-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, Examples thereof include a fluorine atom-containing solvent selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene.

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

The water content contained in the solvent is preferably 20 ppm or less in terms of mass. The water content can be measured using the Karl Fischer method. With 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 are not particularly limited, but include, for example, other surface treatment compounds, (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oil, preferably perfluoro(poly)ether. Examples thereof include 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.

The fluorinated oil is not particularly limited, but examples thereof include compounds represented by the following general formula (1) (perfluoro(poly)ether compounds).
^{_{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, Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms (preferably a C _1-16 perfluoroalkyl group), and Rf ⁶ represents Represents an alkyl group having 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group) which may be substituted with one or more fluorine atoms, a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ are , And more preferably each independently a C _1-3 perfluoroalkyl group.
a', b', c'and d'represent the number of four kinds of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, each independently an integer of 0 or more and 300 or less , A', b', c'and d'is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of the repeating units enclosed in parentheses with the subscripts a′, b′, c′ or d′ 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 It may be any of (CF ₃ )CF(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 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 general formula (1) include compounds represented by any of the following general formulas (1a) and (1b) (one kind or a mixture of two or more kinds. May be included).
^{_{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 the formula (1a), b″ is an integer of 1 or more and 100 or less; in the 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 of existence of each repeating unit in parentheses with subscripts a″, b″, c″, d″ is arbitrary in the formula.

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

In the surface-treating agent of the present invention, the fluorine-containing oil is 100 parts by mass in total of the perfluoro(poly)ether group-containing silane compound and the carboxylic acid ester compound (in the case of two or more kinds, respectively, the total of these, The same can be said), 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 preferable to use the compound represented by the general formula (1b) rather than the compound represented by the general formula (1a) since higher surface slipperiness can be obtained. When these are used in combination, the mass ratio of the compound represented by General Formula (1a) and the compound represented by General Formula (1b) is preferably 1:1 to 1:30, and 1:1 to 1:1. :10 is more preferable. With such a mass ratio, a surface-treated layer having an excellent balance of surface slipperiness and friction durability can be obtained.

In one embodiment, the fluorinated oil contains one or more compounds represented by general formula (1b). In this 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 preferably 4:1 to 1:4.

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

In one embodiment, the compound represented by formula (1b) preferably has an average molecular weight of 8,000 to 30,000.

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

In a preferred embodiment, when the surface treatment layer is formed by the vacuum vapor 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 made 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more larger than the number average molecular weight of the perfluoro(poly)ether group-containing silane compound. Good. With such a number average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

From another viewpoint, the fluorinated oil may be a compound represented by the general formula Rf′-F (wherein Rf′ is a C _5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer have high affinity with the above-mentioned perfluoro(poly)ether group-containing silane compound in which Rf ¹ is a C _1-16 perfluoroalkyl group. preferable.

The fluorinated oil contributes to improve 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. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil. Examples of the modified silicone oil include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethyl siloxane 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 with respect to 100 parts by mass of the PFPE-containing silane compound (in the case of two or more kinds, the sum of these, the same applies below). It may be included in an amount of 0 to 200 parts by mass.

Silicone oil contributes to improve the surface slipperiness of the surface treatment layer.

Examples of the catalyst include acids (such as acetic acid and trifluoroacetic acid), bases (such as ammonia, triethylamine, diethylamine and the like), transition metals (such as Ti, Ni and Sn) 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 the surface treatment layer.

In addition to the above, examples of the other component include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

In addition to the above, examples of the other component include alcohol compounds having 1 to 6 carbon atoms.

[pellet]
The surface treating agent of the present invention can be impregnated into a pellet by impregnating a porous material such as a porous ceramic material, a metal fiber such as steel wool hardened into a cotton shape. The pellet can be used for vacuum deposition, for example.

The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, waterproof property, high friction durability and UV resistance to a substrate, and thus is preferably used as a surface treatment agent. It 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.

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

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

First, a base material is prepared. Substrates that can be used in the present invention include, for example, glass, resin (natural or synthetic resin, which may be a common plastic material, and may be plate-shaped, film, or other form), metal (aluminum, copper). , May be a simple metal such as iron or a composite such as an alloy), ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabric, non-woven fabric, etc.), fur, leather, wood, porcelain, stone materials, building materials, etc. , May be composed of any suitable material.

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

For example, when the article to be manufactured is an optical member, the material constituting the surface of the base material 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 antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection 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 thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO ₂ and/or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, it has a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide on a part of the surface of the substrate (glass). 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 atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, depending on its specific specifications. And a liquid crystal display module or the like.

The shape of the base material is not particularly limited. Further, the surface region of the base material on which the surface-treated layer is to be formed may be at least a part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.

At least the surface portion of the base material may be made of a material that originally has a hydroxyl group. Examples of such a material include glass, and also include metals (particularly base metals) on the surface of which a natural oxide film or a thermal oxide film is formed, ceramics, semiconductors, and the like. Alternatively, if the resin does not have enough hydroxyl groups, such as a resin, or if it does not originally have hydroxyl groups, the substrate is subjected to some pretreatment to introduce hydroxyl groups to the surface of the substrate. You can increase or decrease. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase hydroxyl groups on the surface of the base material, and can also be suitably used for cleaning the surface of the base material (removing foreign matters). Further, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on the surface of the substrate by a LB method (Langmuir-Blodgett method) or a chemical adsorption method. There is a method in which the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, etc.

Alternatively, such a base material may be one in which at least the surface portion thereof is made of a material containing a silicone compound having another reactive group, for example, one or more Si—H groups, 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 as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.

The surface treatment agent of the present invention can be formed into a film 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 methods and dry coating methods 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 evaporation (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the vapor deposition method (usually a vacuum vapor deposition method) include resistance heating, high frequency heating using electron beam, microwave, etc., ion beam and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD and similar methods.

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

When using the wet coating method, the surface treatment agent of the present invention can be diluted with a solvent and then applied to the 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 (for example, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (eg, C ₆ F ₁₃ CH ₂ CH ₃ (eg, Asahi Glass) Asahi Clean (registered trademark) AC-6000), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc)); Hydrochlorofluorocarbon (for example, HCFC-225 (Asahiclin (registered trademark) AK225)); Hydrofluoro ether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo 3M Limited of Novec (TM) 7000), perfluorobutyl methyl ether _{(C 4} F 9 _OCH 3) (For example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutylethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited), per Alkyl perfluoroalkyl ether (perfluoroalkyl group and alkyl group) such as fluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Limited) May be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahi Klin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), 1,2-dichloro-1, 3,3,3-Tetrafluoro-1-propene (for example, Bertrel (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents may be used alone or as a mixture of two or more kinds. Further, for example, to adjust the solubility of the perfluoro(poly)ether group-containing silane compound and the perfluoropolyether modified compound, another solvent is used. It can also be mixed with.

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 diluted with the above-mentioned solvent and then subjected to the dry coating method.

The film formation is preferably carried out so that the surface treatment agent of the present invention is present in the film together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of the wet coating method, after diluting the surface treatment agent of the present invention with a solvent, a catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately before application to the substrate surface. In the case of the dry coating method, the surface-treating agent of the present invention to which the catalyst is added is directly subjected to vapor deposition (usually vacuum vapor deposition), or the surface-treating agent of the present invention to which a catalyst is added to a metal porous body such as iron or copper. Vapor deposition (usually vacuum vapor deposition) may be performed using a pellet-shaped substance impregnated with.

Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid or the like can be used. As the base catalyst, for example, ammonia, organic amines or the like can be used.

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

After the surface treatment agent of the present invention is formed into a film on the surface of the substrate 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 dew condensation due to a temperature difference between the precursor film (and the base material) and the ambient atmosphere or spraying of steam (steam) may be used.

The water can be supplied, for example, in an atmosphere of 0 to 250° C., preferably 60° C. or higher, more preferably 100° C. or higher, preferably 180° C. or lower, more preferably 150° C. or lower. Hydrolysis can be promoted by supplying water in such a temperature range. The pressure at this time is not particularly limited, but may be conveniently atmospheric pressure.

Next, the precursor film is heated on the surface of the base material in a dry atmosphere exceeding 60°C. The drying and heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60° C., preferably higher than 100° C., for example, 250° C. or lower, preferably 180° C. or lower, and non-heated. It may be arranged under an atmosphere of saturated steam pressure. The pressure at this time is not particularly limited, but may be conveniently atmospheric pressure.

In such an atmosphere, between the perfluoro(poly)ether group-containing silane compounds of the present invention, the groups bonded to Si after hydrolysis are rapidly dehydrated and condensed. Further, between the compound and the base material, the group bonded to Si after the hydrolysis of the compound and the reactive group present on the surface of the base material react rapidly to exist on the surface of the base material. When the reactive group is a hydroxyl group, dehydration condensation is performed. As a result, a bond is formed between the perfluoro(poly)ether group-containing silane compound and the substrate.

The above-described water supply and dry heating may be continuously performed by using superheated steam.

Post-processing can be performed as described above. It should be noted that such post-treatment may be carried out to further improve rub durability, but is not essential to making the articles of the present invention. For example, the surface treatment agent of the present invention may be applied to the surface of the base material and then allowed to stand as it is.

As described above, the surface-treated layer derived from the film of the surface-treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface-treated layer thus obtained has good UV resistance. In addition to good UV resistance, this surface-treated layer also has water repellency, oil repellency, and antifouling properties (for example, to prevent adhesion of dirt such as fingerprints), depending on the composition of the composition used. It can have surface slipperiness (or lubricity, for example, wipeability of stains such as fingerprints and excellent touch to fingers) and high friction durability, and can 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 the optical materials related to displays as exemplified below, a wide variety of optical materials are preferably cited: for example, cathode ray tube (CRT; eg TV, personal computer monitor), liquid crystal display, plasma display, A display such as an organic EL display, an inorganic thin film EL dot matrix display, a rear projection display, a fluorescent display tube (VFD), a field emission display (FED; Field Emission Display) or a protective plate for those displays, or reflection on their surface. Those that have been subjected to a preventive film treatment.

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

The article having the surface-treated 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-treated layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm, as the optical performance, surface slipperiness, friction durability and antifouling property. It is preferable in terms of sex.

As another form, a layer may be separately formed on the surface of the substrate, and then the film of the surface treatment layer obtained by the present invention may be formed on the surface of the layer.

The articles obtained by using the surface treatment agent of the present invention have been described in detail above. Note that the use, use method, and manufacturing method of articles of the surface treatment agent of the present invention are not limited to those exemplified above.

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

(Examples 1 to 4 and Comparative Example 1)
Each of the mixtures or compounds shown in Table 1 below was dissolved in hydrofluoroether (Novec HFE7200 manufactured by 3M Co., Ltd.) so that the total concentration was 20 wt %, to prepare a surface treatment agent.

The compound A used in the examples and comparative examples is 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 treating agent prepared above was vacuum-deposited on chemically strengthened glass ("Gorilla" glass manufactured by Corning, thickness 0.7 mm). The processing conditions for vacuum vapor deposition were a pressure of 3.0×10 ⁻³ Pa. First, a silicon dioxide film having a thickness of 5 nm is formed on the surface of the chemically strengthened glass, and then 4 mg of the surface treatment agent (that is, compound A and 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 vapor deposition film was allowed to stand for 30 minutes in an atmosphere at a temperature of 150° C., and then allowed to cool to room temperature to form a surface treatment layer.

<Evaluation of friction durability>
For the surface-treated layers formed in Examples 1 to 4 and Comparative Example 1 described above, the following friction durability test was carried out as an evaluation of actual use durability.

As an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured (the number of times of friction was zero) without touching anything on the surface. The static contact angle of water was measured with a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) with 1 μL of water.

Then, the sample article on which the surface treatment layer was formed was placed horizontally, the following friction element was brought into contact with the surface of the surface treatment layer (the contact surface was a circle having a diameter of 1 cm), and a load of 5 N was applied thereon, and thereafter, The friction element was reciprocated at a speed of 40 mm/sec while a load was applied. The friction element was reciprocated up to 4000 times, and the static contact angle (degree) of water was measured every 1000 times of reciprocation (rubbing frequency). The test was stopped 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).
-Frictional element As the frictional element, a silicone rubber processed product having the surface (diameter 1 cm) shown below covered with cotton soaked with artificial sweat having the composition shown below was used.
・Artificial sweat composition anhydrous disodium hydrogen phosphate: 2 g
Sodium chloride: 20g
85% lactic acid: 2g
Histidine hydrochloride: 5 g
Distilled water: 1Kg
-Silicone rubber processed product Silicone rubber stopper SR-51 made of Tigers Polymer is processed into a cylindrical shape having a diameter of 1 cm and a thickness of 1 cm.

From the results shown in Table 2, it was confirmed that the surface-treated layers of Examples 1 to 4 exhibited excellent durability while suppressing a decrease in contact angle. This is probably because 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 base material (tempered glass) were more firmly bonded. Be done.

INDUSTRIAL APPLICABILITY The present invention can be suitably used for forming a surface treatment layer on a wide variety of substrates, especially on the surface of an optical member that is required to have transparency.

Claims (14)

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

[In the formula:
PFPE has 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, and a, b , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
Is a group represented by
Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹³ independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^14's each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms in each occurrence;
R ¹¹ each independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 13 n R 14}} 3-n) independently for each unit, an integer from 0 to 3;
However, in formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present;
X ¹ independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
X ² independently represents a single bond or a divalent organic group at each occurrence;
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 independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
β is an integer from 1 to 9 independently at each occurrence;
β′ are 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 each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ¹ independently represents R ^a′ at each occurrence;
^Ra' has the same meaning as ^Ra ;
In R ^a , the number of Si linearly linked via the Z ¹ group is at most 5;
R ² independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p is an integer of 0 to 3 independently at each occurrence;
q is, independently at each occurrence, an integer from 0 to 3;
r is, independently at each occurrence, an integer from 0 to 3;
However, 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), it is bonded to a hydroxyl group or a hydrolyzable group. There is at least two Si;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k1 is, independently at each occurrence, an integer from 0 to 3;
l1 is, independently at each occurrence, an integer from 0 to 3;
m1 is, independently at each occurrence, an integer from 0 to 3;
However, for each —SiR ^a _k1 R ^b _l1 R ^c _m1 , the sum of k1, l1 and m1 is 3,
X ⁴ independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
γ is, independently at each occurrence, an integer from 1 to 9;
γ′ is each independently an integer of 1 to 9;
R ^d independently represents -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 at each occurrence;
Z ² independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^d′ at each occurrence;
R ^d′ has the same meaning as R ^d ;
In R ^d , the maximum number of Cs linearly linked via the Z ² group is 5;
R ⁸² each independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence;
Y independently represents a divalent organic group at each occurrence;
R ⁸⁵ independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 ^{_{is, (- Y-SiR 85 n2}} R 86 3-n2) independently for each unit, an integer of 0 to 3;
R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is an integer from 0 to 3 independently at each occurrence;
q2 is an integer of 0 to 3 independently at each occurrence;
r2 is, independently at each occurrence, an integer from 0 to 3;
^However, in each ^{_{-Z 2 -CR 81 p2 R 82 q2}} R 83 r2, the sum of p2, q2 and r2 is 3;
R ^e is, independently at each ^occurrence, represents ^{_{-Y-SiR 85 n2 R 86 3}} -n2;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is an integer of 0 to 3 independently at each occurrence;
l2 is, independently at each occurrence, an integer from 0 to 3;
m2 is an integer of 0 to 3 independently at each occurrence;
However, in each (CR ^d _k2 R ^e _l2 R ^f _m2 ), the sum of k2, l2 and m2 is 3, and in formulas (C1) and (C2), n2 is at least two integers of 1 to 3 ^{_{-Y-SiR 85 n2 R 86 3}} -n2 group is present. ]
Which is a surface treatment agent containing a perfluoro(poly)ether group-containing silane compound represented by any of the above, and a compound containing an atom having an unshared electron pair in the molecular structure,
The compound containing an atom having an unshared electron pair in the molecular structure is aniline, pyridine, hexamethylphosphoramide, N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N. -Dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide, and at least one compound selected from the group consisting of tetramethylenesulfoxide,
The compound containing an atom having an unshared electron pair in the molecular structure is contained in an amount of 0.0002 mass% or more and 1 mass % or less with respect to the entire surface treatment agent ,
Compounds containing atoms having an unshared electron pair in the molecule structure, perfluoro (poly) relative to an ether group-containing silane compound to 1 mol, surface treatment agent that is part of 0.15 mol or more. A compound containing an atom having an unshared electron pair in its molecular structure is contained in an amount of 0.01 to 10 mol with respect to 1 mol of Si atom bonded to a hydroxyl group or a hydrolyzable group of a perfluoro(poly)ether group-containing silane compound. The surface treatment agent according to claim 1. A compound containing an atom having an unshared electron pair in its molecular structure is contained in an amount of 0.3 to 10 mol per 1 mol of Si atom bonded to a hydroxyl group or a hydrolyzable group of a perfluoro(poly)ether group-containing silane compound. The surface treatment agent according to claim 1. The surface treating agent according to claim 1, wherein Rf is independently a perfluoroalkyl group having 1 to 16 carbon atoms in each occurrence. PFPE is, at each occurrence, independently of the following formula (a), (b) or (c):
_{- (OC 3 F 6) d} - (a)
[In formula, d is an integer of 1-200. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less;
e and f are each independently an integer of 1 or more and 200 or less;
The sum of c, d, e and f is an integer of 10 or more and 200 or less;
The order of existence of each repeating unit in parentheses with subscript c, d, e or f 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 2 or 3 selected from these groups. A combination of groups;
j is an integer of 2 to 100. ]
In it, a surface treatment agent according to any one of claims 1-4. The number average molecular weight of Rf-PFPE unit are each independently a 500 to 30,000, a surface treatment agent according to any one of claims 1-5. X ^1, X ³ and X ⁴ are each independently in each occurrence a divalent organic radical, a surface treatment agent according to any one of claims 1-6. Fluorinated oils, silicone oils, and further contain one or more other components selected from catalysts, surface treatment agent according to any one of claims 1-7. Further comprising a solvent, a surface treatment agent according to any one of claims 1-8. Proof is used as fouling resistant coatings or waterproofing coating, surface treatment agent according to any one of claims 1-9. A vacuum vapor deposition, surface treatment agent according to any one of claims 1-10. Pellet containing the surface treatment agent according to any one of claims 1 to 11. An article comprising a substrate and a surface of the substrate, and a layer formed from the surface treatment agent according to any one of claims 1 to 11. The article according to claim 13 , wherein the article is an optical member.