JPWO2018047695A1 - Composition comprising a perfluoro (poly) ether group-containing silane compound - Google Patents

Abstract

The present invention relates to the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): At least one perfluoro (poly) ether group-containing silane compound represented by any one of the same as the above description, and the following formula (E1): [wherein each symbol is the same as the description in the specification] A composition comprising at least one compound of the formula

Description

  The present invention relates to a composition comprising a perfluoro (poly) ether group-containing silane compound, specifically a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative About.

  It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, stain resistance and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter, also referred to as "surface treatment layer") is applied as a so-called functional thin film to various substrates such as glass, plastics, fibers, building materials ing.

  As such fluorine-containing silane compounds, perfluoropolyether group-containing silane compounds having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal end are known. It is done. For example, Patent Literatures 1 and 2 describe a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal end.

WO 97/07155 Japanese Patent Publication No. 2008-534696

  A layer obtained from a surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit functions such as water repellency, oil repellency, and antifouling properties even in a thin film, and thus glasses for which light transparency and transparency are required And optical members such as touch panels. In particular, in these applications, friction durability is required so that such function can be maintained even under repeated friction.

  The present invention is a composition comprising a perfluoro (poly) ether group-containing silane compound capable of forming a layer having water repellency, oil repellency, soil resistance, waterproofness, and high friction durability. It aims to provide goods.

  As a result of intensive investigations, the present inventors achieved high friction durability by using a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative. It has been found that it is possible to form a surface treatment layer having the present invention, and the present invention has been completed.

［式中：
ＰＦＰＥ^１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−
（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^１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^１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^２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；
ｎ１は、（−ＳｉＲ^１ _ｎ１Ｒ^２ _３−ｎ１）単位毎に独立して、０〜３の整数であり；
ただし、式（Ａ１）、（Ａ２）、（Ｂ１）および（Ｂ２）において、少なくとも１つのｎ１が、１〜３の整数であり；
Ｘ^１は、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、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^５は、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、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；
Ｘ^７は、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、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^ａは、各出現においてそれぞれ独立して、−Ｚ^１−ＳｉＲ^７１ _ｐ１Ｒ^７２ _ｑ１Ｒ^７３ _ｒ１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^７１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^７２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^７３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；
ｐ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ１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、式（Ｃ１）および（Ｃ２）において、少なくとも１つのｑ１が１〜３の整数であり；
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、１〜３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；
Ｘ^９は、それぞれ独立して、単結合または２〜１０価の有機基を表し；
δは、それぞれ独立して、１〜９の整数であり；
δ’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、１〜３の整数を表し；
ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｎ２は１〜３の整数であり；
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；
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、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。］
のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、および
下記式（Ｅ１）：

［式中：
ＰＦＰＥ^２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−
（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^２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；
Ｚ^２は、単結合または２価の有機基を表し；
ｘは１または２であり；
ｘが１である場合、Ａは、−ＣＯＯＲ^３、−ＰＯ（ＯＲ^３）_２、−ＳＯ_２（ＯＲ^３）、または−ＳＯ（ＯＲ^３）であり；
ｘが２である場合、Ａは、−ＰＯ（ＯＲ^３）−であり；
Ｒ^３は、水素原子または炭化水素基である。］
で表される少なくとも１種の化合物
を含む組成物が提供される。That is, according to the first aspect of the present invention, the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D2) and (D2):

[In the formula:
PFPE ¹ independently at each occurrence, the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n1 _{^{is, (- SiR 1 n1 R 2}} 3-n1) independently for each unit, an integer from 0 to 3;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one n1 is an integer of 1 to 3;
Each X ¹ independently represents a single bond or a di- to 10-valent organic group;
X ² represents independently at each occurrence a single bond or a divalent organic group;
t is an integer of 1 to 10 independently at each occurrence;
α is each independently an integer of 1 to 9;
α 'is each independently an integer of 1 to 9;
Each X ⁵ independently represents a single bond or a di- to 10-valent organic group;
β is each independently an integer of 1 to 9;
β 'is each independently an integer of 1 to 9;
Each X ⁷ independently represents a single bond or a di- to 10-valent organic group;
γ is each independently an integer of 1 to 9;
γ 'is each independently an integer of 1 to 9;
R ^a each independently represents -Z ¹ -SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 at each occurrence;
Z ¹ independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁷¹ independently at each occurrence represents R ^{a ′} ;
R ^{a '} is as defined the R ^a ;
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ⁷² independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ⁷³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p1 is each independently an integer of 0 to 3 at each occurrence;
q1 is each independently an integer of 0 to 3 at each occurrence;
r 1 each independently at each occurrence is an integer from 0 to 3;
However, in formulas (C1) and (C2), at least one q1 is an integer of 1 to 3;
R ^b independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ^c independently at each occurrence represents a hydrogen atom or a lower alkyl group;
k1 is an integer of 1 to 3 independently at each occurrence;
l 1 is each independently an integer of 0 to 2 at each occurrence;
m1 is each independently an integer of 0 to 2 at each occurrence;
Each X ⁹ independently represents a single bond or a di- to 10-valent organic group;
δ is each independently an integer of 1 to 9;
each δ 'is independently an integer of 1 to 9;
R ^d independently at each occurrence represents -Z ² -CR ⁸¹ _{p 2} R ⁸² _{q 2} R ⁸³ _{r 2} ;
Z ² each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is the same as R ^d ;
In ^Rd, at most 5 Cs linked in a linear fashion via a Z ² group;
R ⁸² independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence;
Y represents, independently at each occurrence, a divalent organic group;
R ⁸⁵ each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n2 represents an integer of 1 to 3 independently for each (-Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ) unit;
Provided that in formulas (D1) and (D2), at least one n2 is an integer of 1 to 3;
R ⁸³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p2 is each independently an integer of 0 to 3 at each occurrence;
q2 is each independently an integer of 0 to 3 at each occurrence;
r2 each independently at each occurrence is an integer from 0 to 3;
R ^e each independently at each occurrence represents —Y—SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ;
R ^f independently at each occurrence independently represents a hydrogen atom or a lower alkyl group;
k2 each independently at each occurrence is an integer from 0 to 3;
l2 is each independently an integer of 0 to 3 at each occurrence;
m2 is each independently an integer of 0 to 3 at each occurrence;
However, in the formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one 12 is 2 or 3. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formulas (E1):

[In the formula:
PFPE ² independently at each occurrence, the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
Rf ² each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Z ² represents a single bond or a divalent organic group;
x is 1 or 2;
When x is ^{1, A} is, -COOR ^3, be _{-PO (OR 3) 2, -SO} 2 (OR 3), or -SO (OR ^3);
When x is 2, A is, -PO (OR ³⁾ - a and;
R ³ is a hydrogen atom or a hydrocarbon group. ]
There is provided a composition comprising at least one compound represented by

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

［式中：
Ｒｆ^２は、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；
ＰＦＰＥ^２は、それぞれ独立して、−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−を表し、ここに、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り；
Ｚ^２は、単結合または２価の有機基を表し；
ｘは１または２であり；
ｘが１である場合、Ａは、−ＣＯＯＲ^３、−ＰＯ（ＯＲ^３）_２、−ＳＯ_２（ＯＲ^３）、または−ＳＯ（ＯＲ_３）であり；
ｘが２である場合、Ａは、−ＰＯ（ＯＲ^３）−であり；
Ｒ^３は、水素原子または炭化水素基である。］
で表される少なくとも１種の化合物を含む、パーフルオロ（ポリ）エーテル基含有シラン化合物の縮合促進剤が提供される。According to a third aspect of the present invention, there is provided a compound of formula (E1):

[In the formula:
Each Rf ² independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Each of PFPE ² independently represents — (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} - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f The sum of at least one, and the order of the presence of each repeating unit bracketed by a, b, c, d, e or f is arbitrary in the formula;
Z ² represents a single bond or a divalent organic group;
x is 1 or 2;
When x is ^{1, A} is, -COOR ^3, be _{-PO (OR 3) 2, -SO} 2 (OR 3), or -SO (OR _3);
When x is 2, A is, -PO (OR ³⁾ - a and;
R ³ is a hydrogen atom or a hydrocarbon group. ]
There is provided a condensation promoter for a perfluoro (poly) ether group-containing silane compound, which comprises at least one compound represented by

  Forming a surface treatment layer having high friction durability by using a composition containing the perfluoro (poly) ether group-containing silane compound of the present invention and a perfluoro (poly) ether group-containing acid or acid derivative Can.

  Hereinafter, the composition of the present invention will be described.

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

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

  As used herein, "di- to 10-valent organic group" means a carbon-containing di- to 10-valent group. Although it does not specifically limit as this 2-10-valent organic group, The 2-10-valent group which eliminated 1-9 hydrogen atoms further from the hydrocarbon group is mentioned. For example, the divalent organic group is not particularly limited, and examples thereof include divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.

のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、および
下記式（Ｅ１）：

で表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有酸または酸誘導体（以下、「パーフルオロ（ポリ）エーテル変性化合物」ともいう）
を含んでなる組成物を提供する（以下、「本発明の組成物」ともいう）。The present invention relates to the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formulas (E1):

Or at least one perfluoro (poly) ether group-containing acid or acid derivative (hereinafter, also referred to as “perfluoro (poly) ether modified compound”)
(Hereinafter, also referred to as “the composition of the present invention”).

  Hereinafter, the perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) explain.

Formulas (A1) and (A2):

In the above formula, each PFPE ¹ is independently
_{- (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, for example 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.

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

In one aspect, the PFPE ¹ is — (OC ₃ F ₆ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). is there. Preferably, PFPE ¹ is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or — (OCF (CF ₃ ) CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, PFPE ¹ is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) is there.

In another embodiment, PFPE ¹ 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, it is 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, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, subscripts c, d, The order of existence of each repeating unit with parentheses attached with e or f is arbitrary in the formula). Preferably, PFPE ¹ 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 —. In one aspect, PFPE ¹ is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein, e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably It is preferably an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed by parentheses with the subscript e or f is attached is arbitrary in the formula).

In still another embodiment, PFPE ¹ is a group represented by-(R ⁶ -R ⁷ ) _q- . In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or selected independently from these groups A combination of two or three groups. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups independently selected from these groups is there. The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. For example, -OC ₂ F ₄ OC ₃ F _6- , -OC ₂ F ₄ OC ₄ F ₈ −, −OC ₃ F ₆ OC ₂ F ₄ −, −OC ₃ F ₆ OC ₃ F ₆ −, −OC ₃ F ₆ OC ₄ F ₈ −, −OC ₄ F ₈ OC ₄ F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC ₄ F ₈ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ −, −OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ −, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 _{F 4 OC 3 F 6 -,} - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _{-OC 4 F 8 OC 2 F 4} OC 2 F 4 - , and the like. The above q is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear . In this embodiment, PFPE ¹ is _{preferably, - (OC 2 F 4 -OC} 3 F 6) q - or _{- (OC 2 F 4 -OC 4} F 8) q - is.

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

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

The above Rf ¹ is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted by one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoro alkylene group, and further, Preferably it is a C1-C16 perfluoroalkyl group.

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

In the above formulas, R ¹ each independently represents a hydroxyl group or a hydrolysable group at each occurrence.

The above "hydrolyzable group" as used herein means a group that can be removed from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N = CR ₂ , —NR ₂ , —NHR, halogen (in these formulas, R represents a substituted or unsubstituted C 1 to 4 carbon atom) And the like), and preferably -OR (i.e., an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.

In the above formulae, R ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms at each occurrence.

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

In the above formulas, each occurrence of R ¹² independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.

In the above formulas, n1 ^{_{is, (- SiR 1 n1 R 2}} 3-n1) independently for each unit, an integer of 0 to 3, preferably 1 to 3, more preferably 3. However, in the formula, all n1 can not be 0 simultaneously. In other words, at least one R ¹ is present in the formula.

In the above formulae, each X ¹ independently represents a single bond or a di- to 10-valent organic group. In the compounds represented by the formulas (A1) and (A2), the X ¹ is a perfluoropolyether moiety that mainly provides water repellency and surface slip properties (ie, ¹ part of Rf ¹ -PFPE or -PFPE ¹ And -parts) are understood to be linkers which link the silane part (i.e. the group which is enclosed in brackets and attached with .alpha.) Which provides the ability to bind to the substrate. Accordingly, X ¹ may be any organic group as long as the compounds represented by formulas (A1) and (A2) can stably exist.

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

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

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

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

Although it does not specifically limit as an example of said X ¹ , For example, following formula:
_{^{- (R 31) p '-}} (X a) q' -
[In the formula:
R ³¹ are each independently a single bond, - _(CH 2) _{s '-} or o-, represents m- or p- phenylene, preferably - _(CH 2) _s' - a and,
s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2.
X ^a represents-(X ^b ) _{l '} -
X ^b is each independently -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ³³ ) ₂ -,-(-) _{^{Si (R 33) 2 O)}} m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - _(CH 2) _n' - is selected from the group consisting of Represents a group
R ³³ each independently represents, in each occurrence, a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group And
R ³⁴ independently at each occurrence represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group),
m 'is independently at each occurrence an integer of 1 to 100, preferably an integer of 1 to 20,
n 'in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,
l 'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p 'is 0, 1 or 2 and
q 'is 0 or 1 and
Here, at least one of p 'and q' is 1, and the order of existence of each repeating unit enclosed in parentheses with p 'or q' is arbitrary. ]
The bivalent group represented by these is mentioned. Here, R ³¹ and X ^a (typically, ^a hydrogen atom of R ³¹ and X ^a ) are one or more selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group It may be substituted by the substituent of

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

Preferably, said X ¹ is
Single bond,
C _1-20 alkylene group,
-R ³¹ -X ^c -R ³² - or ^-X d ^{-R 32,} -
[Wherein, R ³¹ and R ³² are as defined above. ]
It can be.

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

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

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

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

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

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

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

［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）_ｎ−（ｎは２〜６の整数）であり、
Ｄは、分子主鎖のＰＦＰＥ^１に結合し、Ｅは、ＰＦＰＥ^１と反対の基に結合する。］In another embodiment, the X ¹ group includes, for example, the following groups:

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

(Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group).
Is a group selected from
E is-(CH ₂ ) _n- (n is an integer of 2 to 6),
D is attached to PFPE ¹ of the molecular backbone and E is attached to the opposite group to PFPE ¹ . ]

などが挙げられる。Specific examples of the above X ¹ include, for example:
Single bond,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-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 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 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- ,
-(CH ₂ ) ₂ -Si (CH ₃ ) _2- (CH ₂ ) _2-
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
_{-CON (CH 3) - (CH} 2) 6 -,
-CON (Ph)-(CH ₂ ) _6- (wherein Ph means phenyl),
-CONH- (CH ₂ ) ₂ NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) _{2-
-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,
-OCH _2- ,
-O _{(CH 2)} 3 -,
-OCFHCF _2- ,

Etc.

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

In the above ^{formula, R 16} are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, ^{-NR 26} - ^{(wherein, R 26} represents a hydrogen atom or an organic group) or a divalent organic group is there. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

As the "divalent polar group" is not particularly limited, -C (O) -, - C (= NR 27) -, and -C (O) ^{NR 27} - (in these ^{formulas, R 27} is , A hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl and n-propyl, which may be substituted by one or more fluorine atoms.

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

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

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

In another preferred ^{embodiment, X} 1 _{^{is, -O-CFR 13 - (CF}} 2) g - is.

The above R ¹³ each independently represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably a trifluoromethyl group It is.

  The above g is each independently 0 or 1.

In one embodiment, R ¹³ is a fluorine atom and e is 1.

In still another embodiment, X ¹ is a group represented by -X ^c -CO-NR ¹⁴ -X ^d -or -X ^c -CO-N (-X ^d- ) ₂ . -X ^c -CO-NR ¹⁴ -X ^d -is a divalent group, and -X ^c -CO-N (-X ^d- ) ₂ is a trivalent group.

R ¹⁴ represents a hydrogen atom, a lower alkyl group or a phenyl group. Lower alkyl group, preferably a C _1-6 alkyl group, more preferably an alkyl group of C _1-3, more preferably a methyl group.

The above X ^c represents a single bond or a divalent organic group.

The divalent organic group in the above X ^c is preferably
_{^{- (CR 8 2) k1 -}} (O) k2 - (NR 9) k3 -
[In the formula:
Each R ⁸ independently represents a hydrogen atom or a fluorine atom;
Each R ⁹ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k1 is an integer of 1 to 20;
k2 is an integer of 0 to 10;
k3 is an integer of 0 to 10;
Here, the order in which each repeating unit enclosed in parentheses with k1, k2 or k3 attached is arbitrary in the formula. ]
And may be a group represented by

The above X ^d represents a divalent organic group.

The divalent organic group in the above X ^d is preferably
_{^{- (CR 20 2) k4 -}} (O) k5 - (NR 21) k6 -,
[In the formula:
Each R ²⁰ independently represents a hydrogen atom or a fluorine atom;
Each R ²¹ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k4 is an integer of 1 to 20;
k5 is an integer of 0 to 10;
k6 is an integer of 0 to 10;
Here, the order in which each repeating unit enclosed in parentheses with k4, k5 or k6 attached is arbitrary in the formula. ]
And may be a group represented by

In one aspect, X ^c is — (CF ₂ ) _k1′— or — (CF ₂ ) _{k1 ′} — (O) _k2′—
[In the formula:
k1 'is an integer of 1 to 6;
k2 'is an integer of 1 to 3;
Here, the existence order of the respective repeating units enclosed in parentheses with k1 'or k2' is arbitrary in the formula. ]
And
X ^d is — (CH ₂ ) _{k 4 ′} — or — (CH ₂ ) _{k 4 ′} —O _{k 5 ′} —
[In the formula:
k4 'is an integer of 1 to 6;
k5 'is an integer of 1 to 3;
Here, the order in which each repeating unit with parentheses attached with k4 'or k5' is arbitrary in the formula. ]
It is.

［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^１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）_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^１と反対の基（即ち、式（Ａ１）、
（Ａ２）、（Ｄ１）および（Ｄ２）においては炭素原子、また、下記する式（Ｂ１）、（Ｂ２）、（Ｃ１）および（Ｃ２）においてはＳｉ原子）に結合する−（ＣＨ_２）_ｎ”−（ｎ”は２〜６の整数）であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基、Ｃ_１−６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。In yet another embodiment, examples of X ¹ groups include:

[In the formula,
Each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ¹ group, any part of T is attached to PFPE ^{1 of the} molecular backbone:
_{-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), or

[Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T's are groups opposite to PFPE ^{1 of the} molecular backbone (ie, Formula (A1),
-(CH ₂ ) _n bound to a carbon atom in (A2), (D1) and (D2), or to a formula (B1), (B2), (C1) and (C2) described below _“ -(N” is an integer of 2 to 6), and when present, the rest may each independently be a methyl group, a phenyl group, a C _1-6 alkoxy group or a radical trapping group or an ultraviolet absorbing group .

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

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

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

Can be mentioned.

In this embodiment, each X ¹ may independently be a trivalent to ten valent organic group.

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

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

［式中：
ＰＦＰＥ^１は、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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^１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^１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^２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；
ｎ１は、１〜３の整数であり、好ましくは３であり；
Ｘ^１は、−Ｏ−ＣＦＲ^１３−（ＣＦ_２）_ｅ−であり；
Ｒ^１３は、フッ素原子または低級フルオロアルキル基であり；
ｅは、０または１であり；
Ｘ^２は、−（ＣＨ_２）_ｕ−であり；
ｕは、０〜２の整数であり（ｕが０の場合Ｘ^２は単結合である）；
ｔは、１〜１０の整数である。］
で表される化合物である。Preferred compounds represented by the formulas (A1) and (A2) have the following formulas (A1 ′) and (A2 ′):

[In the formula:
Each PFPE ¹ independently has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1; subscripts a, b, c or d The order of existence of each repeating unit enclosed in parentheses and attached is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n1 is an integer of 1 to 3, preferably 3;
X ^{1 _{is, -O-CFR 13 - (CF}} 2) e - a is;
R ¹³ is a fluorine atom or a lower fluoroalkyl group;
e is 0 or 1;
X ² is-(CH ₂ ) _u- ;
u is an integer of 0 to 2 (when u is 0, X ² is a single bond);
t is an integer of 1 to 10. ]
It is a compound represented by

The compounds represented by the above formulas (A1) and (A2) are, for example, -CH ₂ CR ¹² after iodine is introduced at the terminal using a perfluoropolyether derivative corresponding to the Rf ¹ -PFPE ¹ -moiety as a raw material. It can be obtained by reacting a vinyl monomer corresponding to (X ² -SiR ¹ _n1 R ² _3-n1 )-.

Formulas (B1) and (B2):

In the above formulas (B1) and (B2), Rf ¹ , PFPE ¹ , R ¹ , R ² and n 1 are as defined for the above formulas (A1) and (A2).

In the above formulas, X ⁵ each independently represent a single bond or a 2-10 monovalent organic group. In the compounds represented by the formulas (B1) and (B2), the X ⁵ is a perfluoropolyether moiety (Rf ¹ -PFPE ¹ part or -PFPE ¹ -part) which mainly provides water repellency and surface slip property and the like. ) and, in the silane portion to provide a binding capability to a substrate ^{(specifically,} it is understood as a linker connecting the 1 _{ⁿ¹ R 2 ^3-n1)} and _-SiR. Accordingly, X ⁵ may be any organic group as long as the compounds represented by formulas (B1) and (B2) can stably exist.

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 ′ are determined according to the valence of X ³ , and in the formula (B1), the sum of β and β ′ is the same as the valence of X ⁵ . For example, when X ⁵ 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 nine. Also, when X ⁵ is a divalent organic group, β and β ′ are 1. In formula (B2), β is a value obtained by subtracting 1 from the value of the valence of X ⁵ .

The above X ⁵ is preferably a di- to heptavalent, more preferably a to-bivalent, more preferably a divalent organic group.

In one embodiment, X ⁵ is a divalent to tetravalent organic group, β is 1 to 3 and β ′ is 1.

In another embodiment, X ⁵ 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 ⁵ include, but are not particularly limited to, the same ones as described for X ¹ .

In one preferred embodiment, X ⁵ may be a group represented by -X ^c -CO-NR ¹⁴ -X ^d -or -X ^c -CO-N (-X ^d- ) ₂ . X ^c , X ^d and R ¹⁴ are the same as described for X ¹ above.

などが挙げられる。Preferred specific X ⁵ is
Single bond,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-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 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 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- ,
-(CH ₂ ) ₂ -Si (CH ₃ ) _2- (CH ₂ ) _2-
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
_{-CON (CH 3) - (CH} 2) 6 -,
-CON (Ph)-(CH ₂ ) _6- (wherein Ph means phenyl),
-CONH- (CH ₂ ) ₂ NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) _{2-
-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,
-OCH _2- ,
-O _{(CH 2)} 3 -,
-OCFHCF _2- ,

Etc.

［式中：
ＰＦＰＥ^１は、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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^１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^１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^２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；
ｎ１は、１〜３の整数であり、好ましくは３であり；
Ｘ^５は、−ＣＨ_２Ｏ（ＣＨ_２）_２−、−ＣＨ_２Ｏ（ＣＨ_２）_３−または−ＣＨ_２Ｏ（ＣＨ_２）_６−である］
で表される化合物である。Preferred compounds represented by the formulas (B1) and (B2) have the following formulas (B1 ′) and (B2 ′):

[In the formula:
Each PFPE ¹ independently has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1; subscripts a, b, c or d The order of existence of each repeating unit enclosed in parentheses and attached is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
n1 is an integer of 1 to 3, preferably 3;
X ⁵ is —CH ₂ O (CH ₂ ) ₂ —, —CH ₂ O (CH ₂ ) ₃ — or —CH ₂ O (CH ₂ ) ₆ —]
It is a compound represented by

［式中：
ＰＦＰＥ^１は、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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^１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；
Ｘ^５’は、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、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^９２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＭ_３（式中、Ｍは、それぞれ独立して、ハロゲン原子、Ｒ^１またはＲ^２であり、Ｒ^１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であり、Ｒ^２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のアルキル基である）と反応させて、必要に応じて、上記ハロゲン原子を、Ｒ^１またはＲ^２に変換して、式（Ｂ１”）または（Ｂ２”）：

［式中、ＰＦＰＥ^１、Ｒｆ^１、Ｘ^５’、β、β’およびＲ^９２は、上記と同意義であり；
ｎ１は、０〜３の整数である。］
で表される化合物として得ることができる。The compounds represented by the above formulas (B1) and (B2) can be produced by known methods, for example, the method described in Patent Document 1 or a modified method thereof. For example, the compounds represented by the formulas (B1) and (B2) have the following formulas (B1-4) or (B2-4):

[In the formula:
Each PFPE ¹ independently has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1; subscripts a, b, c or d The order of existence of each repeating unit enclosed in parentheses and attached is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
X5 ^' each independently represents a single bond or a di- to 10-valent organic group;
β is each independently an integer of 1 to 9;
β 'is each independently an integer of 1 to 9;
R ⁹² is a single bond or a divalent organic group. ]
The compound represented by, HSIM ₃ (wherein, M is each independently a halogen atom, ^{R 1} or ^{R 2, R 1} are each independently, can be a hydroxyl group or hydrolyzable at each occurrence And R ² independently at each occurrence is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and the above halogen atom is optionally reacted with R ¹ or R ² Convert to the formula (B1 ′ ′) or (B2 ′ ′):

[Wherein, PFPE ¹ , Rf ¹ , X ^{5 '} , β, β' and R ⁹² are as defined above;
n1 is an integer of 0 to 3; ]
Can be obtained as a compound represented by

In formula (B1 ^{′ ′} ) or (B2 ^{′ ′} ), the moiety from X ^{5 ′} to R ⁹² —CH ₂ CH ₂ — corresponds to X ⁵ in formula (B1) or (B2).

Formulas (C1) and (C2):

In the above formulas (C1) and (C2), Rf ¹ and PFPE ¹ are as defined for the above formulas (A1) and (A2).

In the above formulae, each X ⁷ independently represents a single bond or a di- to 10-valent organic group. In the compounds represented by the formulas (C1) and (C2), the X ⁷ is a perfluoropolyether moiety (Rf ¹ -PFPE ¹ part or -PFPE ¹ -part) which mainly provides water repellency and surface slip property and the like. ) and, in the silane portion to provide a binding capability to a substrate ^{(specifically,} it is understood _{^{-SiR a k1 R b l1 R c}} m1 group) and a linker connecting. Accordingly, the X ⁷ may be any organic group as long as the compounds represented by the formulas (C1) and (C2) can stably exist.

Γ in the above formula is an integer of 1 to 9, and γ ′ is an integer of 1 to 9. These γ and γ ′ are determined according to the valence of X ⁷ , and in the formula (C1), the sum of γ and γ ′ is the same as the valence of X ⁷ . For example, when X ⁷ is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5 or γ is 1 and γ 'Can be nine. Further, when X ⁷ is a divalent organic group, γ and γ ′ are 1. In the formula (C1), γ is a value obtained by subtracting 1 from the value of the valence of X ⁷ .

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

In one embodiment, X ⁷ is a divalent to tetravalent organic group, γ is 1 to 3 and γ ′ is 1.

In another embodiment, X ⁷ is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).

Examples of X ⁷ include, but are not particularly limited to, the same ones as those described for X ¹ .

In one preferred embodiment, X ⁵ may be a group represented by -X ^c -CO-NR ¹⁴ -X ^d -or -X ^c -CO-N (-X ^d- ) ₂ . X ^c and X ^d are the same as described above for X ¹ .

などが挙げられる。Preferred specific X ⁷ is
Single bond,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-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 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 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- ,
-(CH ₂ ) ₂ -Si (CH ₃ ) _2- (CH ₂ ) _2-
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
_{-CON (CH 3) - (CH} 2) 6 -,
-CON (Ph)-(CH ₂ ) _6- (wherein Ph means phenyl),
-CONH- (CH ₂ ) ₂ NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) _{2-
-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,
-OCH _2- ,
-O _{(CH 2)} 3 -,
-OCFHCF _2- ,

Etc.

In the above formulae, R ^a independently represents -Z ¹ -SiR ⁷¹ _p ¹ R ⁷² _{q 1} R ⁷³ _r ¹ at each occurrence.

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

The above Z ¹ is preferably a divalent organic group, and forms a siloxane bond with the Si atom at the end of the molecular main chain in the formula (C1) or the formula (C2) (Si atom to which R ^a is bonded) Do not include what you do.

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

In the formula, R ⁷¹ independently represents ^{Ra '} at each occurrence. R ^{a ′} is as defined in R ^a .

The maximum number of Sis linked in a straight line via a Z ¹ group in ^Ra is five. That is, in the above R ^a , when at least one R ⁷¹ is present, two or more Si atoms linearly linked in R ^a via the Z ¹ group are present, but via such a Z group The number of Si atoms linearly linked is at most five. The "number of Si atoms linearly linked via a Z group in R ^a" is equal to -Z ¹ -Si- repetition rate of which is connected to a linear during R ^a .

For example, an example in which Si atoms are linked via a Z ¹ group (hereinafter simply referred to as “Z”) in R ^a will be shown below.

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

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

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

In the formula, each R ⁷² independently at each occurrence represents a hydroxyl group or a hydrolysable group.

The above "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolysable groups include —OR, —OCOR, —O—N = C (R) ₂ , —N (R) ₂ , —NHR, halogen, wherein R is a substituted or unsubstituted group. (Indicating an alkyl group of 1 to 4 carbon atoms) and the like, and the like, and preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.

Preferably, R ⁷² is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group.

In the formulae, R ⁷³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  In the formula, p1 is independently an integer of 0 to 3 at each occurrence; q1 is an integer of 0 to 3 independently at each occurrence; r1 is independently at each occurrence Is an integer of 0 to 3. However, the sum of p1, q1 and r1 is 3.

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, at least one of the terminal parts of R ^a is -Si (-Z ¹ -SiR ⁷² _q R ⁷³ _r ) ₂ or -Si (-Z ¹ -SiR ⁷² _q R ⁷³ _r ) ₃ , preferably- It may be Si (-Z ¹ -SiR ⁷² _q R ⁷³ _r ) ₃ . ^Wherein, - the unit of _{^{(Z 1 -SiR 72 q R 73}} r) is preferably ^(-Z 1 -SiR ⁷² _3). In a further preferred embodiment, the distal end of the ^{R a,} all _{^{-Si (-Z 1 -SiR 72 q R}} 73 r) 3, preferably may be _{^{-Si (-Z 1 -SiR 72 3)}} 3.

In the above formulas (C1) and (C2), at least one R ⁷² is present.

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

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

In the above formulae, R ^c independently at each occurrence represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  In the formula, k1 is independently an integer of 0 to 3 at each occurrence; 11 is an integer of 0 to 3 independently at each occurrence; m1 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k1, l1 and m1 is 3.

The compounds represented by the above formulas (C1) and (C2) are, for example, unsaturated bonds at the end after introducing a hydroxyl group at the end using a perfluoropolyether derivative corresponding to the Rf ¹ -PFPE ¹ -moiety as a raw material A group having an unsaturated bond, the silyl derivative having a halogen atom is reacted with the group having an unsaturated bond, and a hydroxyl group is introduced at the end of the silyl group, and the introduced group having an unsaturated bond and the silyl derivative Can be obtained by reacting For example, it can be obtained as follows.

［式中：
ＰＦＰＥ^１は、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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^１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；
Ｘ^７は、−ＣＨ_２Ｏ（ＣＨ_２）_２−、−ＣＨ_２Ｏ（ＣＨ_２）_３−または−ＣＨ_２Ｏ（ＣＨ_２）_６−を表し；
Ｒ^ａは、各出現においてそれぞれ独立して、−Ｚ^１−ＳｉＲ^７１ _ｐ１Ｒ^７２ _ｑ１Ｒ^７３ _ｒ１を表し；
Ｚ^１は、Ｃ_１−６アルキレン基を表し；
Ｒ^７１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^７２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^７３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；
ｐ１は、各出現においてそれぞれ独立して、０〜２の整数であり；
ｑ１は、各出現においてそれぞれ独立して、１〜３の整数、好ましくは３であり；
ｒ１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、一のＲ^ａにおいて、ｐ１、ｑ１およびｒ１の和は３である。］
で表される化合物である。Preferred compounds represented by the formulas (C1) and (C2) have the following formulas (C1 ′ ′) and (C2 ′ ′):

[In the formula:
Each PFPE ¹ independently has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1; subscripts a, b, c or d The order of existence of each repeating unit enclosed in parentheses and attached is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
X ⁷ represents -CH ₂ O (CH ₂ ) _2- , -CH ₂ O (CH ₂ ) ₃ -or -CH ₂ O (CH ₂ ) _6- ;
R ^a each independently represents -Z ¹ -SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 at each occurrence;
Z ¹ represents a C _1-6 alkylene group;
R ⁷¹ independently at each occurrence represents R ^{a ′} ;
R ^{a '} is as defined the R ^a ;
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ⁷² independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ⁷³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p1 is each independently an integer of 0 to 2 at each occurrence;
q1 is each independently an integer of 1 to 3, preferably 3 at each occurrence;
r 1 each independently at each occurrence is an integer from 0 to 2;
However, in one ^Ra , the sum of p1, q1 and r1 is 3. ]
It is a compound represented by

［式中：
ＰＦＰＥ^１は、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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^１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；
Ｘ^７’は、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、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^９２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＲ^９３ _ｋ１Ｒ^ｂ _ｌ１Ｒ^ｃ _ｍ１（式中、Ｒ^９３はハロゲン原子、例えばフッ素原子、塩素原子、臭素原子またはヨウ素原子、好ましくは塩素原子であり、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１〜３の整数であり、ｌ１およびｍ１は、それぞれ独立して、０〜２の整数であり、ｋ１、ｌ１およびｍ１の和は３である。）で表される化合物と反応させて、式（Ｃ１−５）または（Ｃ２−５）：

［式中、Ｒｆ^１、ＰＦＰＥ^１、Ｒ^９２、Ｒ^９３、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。The compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows. The following formula (C1-4) or (C2-4):

[In the formula:
Each PFPE ¹ independently has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1; subscripts a, b, c or d The order of existence of each repeating unit enclosed in parentheses and attached is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Each X ^{7 ′} independently represents a single bond or a di- to 10-valent organic group;
γ is each independently an integer of 1 to 9;
γ 'is each independently an integer of 1 to 9;
R ⁹² is a single bond or a divalent organic group. ]
Wherein R ⁹³ is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, and R ^b is a compound represented by the formula HSiR ⁹³ _k1 R ^b _{1 1} R ^c _m1 In each occurrence, each independently represents a hydroxyl group or a hydrolysable group, R ^c independently represents each independently a hydrogen atom or a lower alkyl group in each occurrence, k 1 is an integer of 1 to 3, and 11 And m1 are each independently an integer of 0 to 2, and the sum of k1, l1 and m1 is 3.) to form a compound of the formula (C1-5) or (C2- 5):

[Wherein, Rf ¹ , PFPE ¹ , R ⁹² , R ⁹³ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k 1, l 1 and m 1 are as defined above. ]
To obtain a compound represented by

［式中、Ｒｆ^１、ＰＦＰＥ^１、Ｒ^９２、Ｒ^９４、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。The obtained compound represented by the formula (C1-5) or (C2-5) can be prepared as Hal-JR ⁸⁴ -CH = CH ₂ (wherein Hal is a halogen atom (eg, I, Br, Cl, And the like, wherein J represents Mg, Cu, Pd or Zn, R ⁹⁴ represents a single bond or a divalent organic group), and is reacted with a compound represented by formula (C1-6) Or (C2-6):

[Wherein, Rf ¹ , PFPE ¹ , R ⁹² , R ⁹⁴ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k 1, l 1 and m 1 are as defined above. ]
To obtain a compound represented by

［式中、Ｒｆ^１、ＰＦＰＥ^１、Ｒ^７２、Ｒ^７３、Ｒ^９２、Ｒ^９４、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ１、ｌ１およびｍ１は、上記と同意義であり；
ｑ１は、各出現においてそれぞれ独立して、１〜３の整数であり；
ｒ１は、各出現においてそれぞれ独立して、０〜２の整数である。］
で表される化合物を得ることができる。The obtained compound represented by the formula (C1-6) or (C2-6) can be HSiM ₃ (wherein, M is each independently a halogen atom, R ⁷² or R ⁷³ and R ⁷² is And each occurrence of R ⁷³ independently represents a hydroxyl group or a hydrolysable group, and each occurrence of R ⁷³ independently in each occurrence represents a hydrogen atom or a lower alkyl group. , The above halogen atom is converted to R ⁷² or R ⁷³ to give a compound of the formula (C1 ′ ′ ′) or (C2 ′ ′ ′):

[Wherein, Rf ¹ , PFPE ¹ , R ⁷² , R ⁷³ , R ⁹² , R ⁹⁴ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k 1, l 1 and m 1 are as defined above] ;
q1 is each independently an integer of 1 to 3 at each occurrence;
r1 is an integer of 0 to 2 independently at each occurrence. ]
The compound represented by these can be obtained.

In the formula (C1 ′ ′ ′) or (C2 ′ ′ ′), the moiety from X ^{7 ′} to R ⁹² —CH ₂ CH ₂ — corresponds to X ⁷ in the formula (C1) or (C2), and —R ⁹⁴ -CH ₂ CH _2- corresponds to Z in formula (C1) or (C2).

Formulas (D1) and (D2):

In the above formulas (D1) and (D2), Rf ¹ and PFPE ¹ are as defined for the above formulas (A1) and (A2).

In the above formulae, each X ⁹ independently represents a single bond or a di- to 10-valent organic group. The X has the formula (D1) and in the compounds represented by (D2), perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc. ^(i.e., Rf ¹ -PFPE 1 part or -PFPE ¹ - Part) and a part providing bondability with a substrate (ie, a group which is attached with .delta. And enclosed in parentheses). Accordingly, X may be any organic group as long as the compounds represented by the formulas (D1) and (D2) can stably exist.

In the above formula, δ is an integer of 1 to 9, and δ ′ is an integer of 1 to 9. These δ and δ ′ can change according to the valence of X. In formula (D1), the sum of δ and δ ′ is the same as the valence of X. For example, when X is a 10-valent organic group, the sum of δ and δ ′ is 10, for example, δ is 9 and δ ′ is 1, δ is 5 and δ ′ is 5 or δ is 1 and δ ′. Can be 9. Further, when X ⁹ is a divalent organic group, δ and δ ′ are 1. In formula (D2), δ is a value obtained by subtracting 1 from the valence of X ⁹ .

The above-mentioned X ⁹ is preferably a 2 to 7-valent, more preferably a 2 to 4-valent, more preferably a divalent organic group.

In one embodiment, X ⁹ is a divalent to tetravalent organic group, δ is 1 to 3 and δ ′ is 1.

In another embodiment, X ⁹ is a divalent organic group, δ is 1 and δ ′ is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).

Examples of X ⁹ include, but are not particularly limited to, the same ones as described for X ¹ .

In one preferred embodiment, X ⁵ may be a group represented by -X ^c -CO-NR ¹⁴ -X ^d -or -X ^c -CO-N (-X ^d- ) ₂ . X ^c and X ^d are the same as described above for X ¹ .

などが挙げられる。Preferred specific X ⁹ is
Single bond,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-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 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 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- ,
-(CH ₂ ) ₂ -Si (CH ₃ ) _2- (CH ₂ ) _2-
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
_{-CON (CH 3) - (CH} 2) 6 -,
-CON (Ph)-(CH ₂ ) _6- (wherein Ph means phenyl),
-CONH- (CH ₂ ) ₂ NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) _{2-
-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,
-OCH _2- ,
-O _{(CH 2)} 3 -,
-OCFHCF _2- ,

Etc.

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

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

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

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

In ^Rd , Cs linked in a linear fashion via a Z ² group are at most five. That is, in the above ^Rd , when at least one R ⁸¹ is present, two or more C atoms linearly linked via the Z ² group are present in R ^d , but via such Z ² group The maximum number of C atoms linked in a straight chain is five. The phrase "through the Z ² group in R ^d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 ^-C- being linearly linked in a R ^d Become. This is as described for ^{R a} in formula (C1) and (C2).

In a preferred embodiment, the "number of C atoms linearly linked via a Z ² group in R ^d" are in all chains, and one (the left formula) or two (right type).

In one embodiment, the number of C atoms linked in a linear fashion via the Z ² group in R ^d is one or two, preferably one.

^{Wherein, R 82 represents _{-Y-SiR 85 n2 R 86 3-2n}} .

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

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

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

The above R ⁵ each independently represents a hydroxyl group or a hydrolysable group at each occurrence.

The above "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolysable groups include —OR, —OCOR, —O—N = C (R) ₂ , —N (R) ₂ , —NHR, halogen, wherein R is a substituted or unsubstituted group. (Indicating an alkyl group of 1 to 4 carbon atoms) and the like, and the like, and preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.

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

R ⁸⁶ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

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

The above R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  In the formula, p2 is independently an integer of 0 to 3 at each occurrence; q2 is an integer of 0 to 3 independently at each occurrence; r2 is independently at each occurrence Is an integer of 0 to 3. However, 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 q2}} R 86 r2) 2 or _{^{-C (-Y-SiR 85 q2 R}} 86 r2) 3, preferably -C ( -Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ may be used. _{^{Wherein, (- Y-SiR 85 q2}} R 86 r2) 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 q2 R}} 86 r2) 3, may be preferably _{^{-C (-Y-SiR 85 3)}} 3.

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

In the above formulae, R ^f independently at each occurrence represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  In the formula, k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.

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

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

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

In the above formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l is 2 or 3. That is, there are at least two -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups in the formula.

  The perfluoro (poly) ether group-containing silane compound represented by formula (D1) or formula (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1 ′) in which X is divalent can be produced as follows, but not limited thereto.

HO-X-C (YOH) ₃ (In the formula, X and Y each independently represent a divalent organic group.) A group containing a double bond in a polyhydric alcohol (preferably Is allyl), and a halogen (preferably bromo) to give Hal-X-C (Y-O-R-CH = CH ₂ ) ₃ (wherein Hal is a halogen such as Br and R is A double bond-containing halide represented by the organic group having a valence of, for example, an alkylene group is obtained. Then, the terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R ^PFPE -OH (wherein R ^PFPE is a perfluoropolyether group-containing group) to obtain R ^PFPE- O-X-C (Y- O-R-CH = CH 2) to obtain a _3. Then, by reacting the terminal -CH = CH ₂ with HSiCl ₃ and alcohol or HSiR ⁸⁵ ₃ , R ^PFPE -O-X-C (Y-O-R-CH ₂ -CH ₂ -SiR ⁸⁵ ₃ ) ₃ You can get

The perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) are particularly preferred. It may have, but is not limited to, a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . The number average molecular weight may be preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.

In the present invention, “number average molecular weight” is measured by ¹⁹ F-NMR.

  Next, the perfluoro (poly) ether modified compound represented by the above formula (E1) will be described.

In the above formula, PFPE ² is a perfluoro (poly) ether group similar to PFPE ¹ described above, and each of them is independently of the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
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, for example 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.

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

In one aspect, the above-mentioned PFPE ² is — (OC ₃ F ₆ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). is there. Preferably, PFPE ² is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) (OCF (CF ₃ ) CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, PFPE ² is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.

In another embodiment, PFPE ² 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, it is 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, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, subscripts c, d, The order of existence of each repeating unit with parentheses attached with e or f is arbitrary in the formula). Preferably, PFPE ² 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 —. In one embodiment, PFPE ² is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably It is preferably an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed by parentheses with the subscript e or f is attached is arbitrary in the formula).

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

In the above formulae, R f ² represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.

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

The above Rf ² is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, and further, Preferably it is a C1-C16 perfluoroalkyl group.

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

In the above formula, Z ² represents a single bond or a divalent organic group.

The divalent organic group in the above Z ² is preferably
-(CR _< ¹⁸ _{> 2} ) _k7- (O) _k8- (NR _< ¹⁹ _> ) _k9- ,
[In the formula:
Each R ¹⁸ independently represents a hydrogen atom or a fluorine atom;
Each R ¹⁹ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k7 is an integer of 1 to 20;
k8 is an integer of 0 to 10;
k9 is an integer of 0 to 10;
Here, the order in which each repeating unit enclosed in parentheses with k7, k8 or k9 is present is arbitrary in the formula. ]
It is.

Preferred Z ² is
- _{(CF 2) k7 '-} or _{- (CF 2) k7' -} (O) k8 '-
[In the formula:
k7 'is an integer of 1 to 6;
k8 'is an integer of 1 to 3;
Here, the order in which each repeating unit enclosed in parentheses with k7 'or k8' is present is arbitrary in the formula. ]
It is.

In the above formulae, when x is 1 or 2 and x is 1, A is —COOR ³ , —PO (OR ³ ) ₂ , —SO ₂ (OR ³ ), or —SO (OR ³ ) There, when x is 2, a is, -PO (OR ³⁾ - a. Note that when x is 2, the two ^Rf 2 -PFPE ² can be different even for the same.

In the above formulae, R ³ is a hydrogen atom or a hydrocarbon group.

  The above-mentioned hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

In a preferred embodiment, x is 1, A is -COOR ^3.

  In one preferred embodiment, x is 1 and A is -COOH.

In another preferred embodiment, x is 1, A is -COOCH _3.

  The perfluoro (poly) ether modified compound represented by the above formula (E1) may be an unreacted material of the raw material compound when synthesizing the above perfluoro (poly) ether group-containing silane compound, or may be added separately It may be a compound. The compound added separately may be the same compound as the compound used for the synthesis, or may be a different compound.

The perfluoro (poly) ether modified compound represented by the above formula (E1) is not particularly limited, but may have a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . The number average molecular weight may be preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.

  In a preferred embodiment, the perfluoro (poly) ether group-containing silane represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The difference between the number average molecular weight of the compound and the number average molecular weight of the perfluoro (poly) ether modified compound represented by the formula (E1) is within 2,000, preferably 1,500, more preferably 1,000. More preferably, it is 500 or less.

  The ratio of the content of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether modified compound in the composition of the present invention is 99.99: 0.01 to 70:30, preferably 99. .5: 0.5-80: 20, more preferably 99: 1-90: 10. Within this range, the perfluoro (poly) ether modified compound can efficiently catalyze the reaction of the perfluoro (poly) ether group-containing silane compound with the substrate.

  In one embodiment, the ratio of the content of the above perfluoro (poly) ether group-containing silane compound to the above perfluoro (poly) ether modified compound in the composition of the present invention is 99.99: 0.01 to 97: 3, preferably 99.9: 0.1 to 98: 2. In another embodiment, the ratio of the content of the above perfluoro (poly) ether group-containing silane compound to the above perfluoro (poly) ether modified compound in the composition of the present invention is 95: 5 to 70:30, preferably It may be 92: 8-80: 20.

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

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

Examples of the perfluoro (poly) ether compound represented by the above general formula (3) include a compound represented by any one of the following general formulas (3a) and (3b) (one or a mixture of two or more) May be mentioned.
^{_{Rf 5 - (OCF 2 CF 2}} CF 2) b '' -Rf 6 ··· (3a)
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. (3b)
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (3a), b ′ ′ is an integer of 1 or more and 100 or less; in formula (3b), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and d ′ ′ are each independently an integer of 1 or more and 300 or less. The order in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′ and d ′ ′ is given is arbitrary in the formula.

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

  In the composition of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the above-mentioned perfluoro (poly) ether group-containing silane compound and the above-mentioned perfluoro (poly) ether modified compound (each in the case of two or more For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass may be contained with respect to the total of the following.

  The compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is more preferable to use the compound represented by the general formula (3b) than the compound represented by the general formula (3a) because higher surface slipperiness can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (3a) to the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and 1: 1 to 1:30. 10 is more preferable. According to this mass ratio, it is possible to obtain a surface treatment layer excellent in the balance between surface slipperiness and friction durability.

  In one aspect, the fluorine-containing oil comprises one or more compounds represented by the general formula (3b). In this aspect, the mass ratio of the total of the above perfluoro (poly) ether group-containing silane compound and the above perfluoro (poly) ether modified compound in the surface treatment agent to the compound represented by the formula (3b) is It is preferable that it is 4: 1 to 1: 4.

  In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, a fluorine-containing oil may be formed more than the average molecular weight of the above perfluoro (poly) ether group-containing silane compound and the above perfluoro (poly) ether modified compound. The average molecular weight may be increased. By setting it as such an average molecular weight, more excellent friction durability and surface slip property can be obtained.

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

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

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

  In the composition of the present invention, such silicone oil is a total of 100 parts by mass of the above-mentioned perfluoro (poly) ether group-containing silane compound and the above-mentioned perfluoro (poly) ether modified compound The same applies to the following, for example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass.

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

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

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

  The composition of the present invention may be in the form of one solution (or suspension or dispersion), or separately the above-mentioned perfluoro (poly) ether group-containing silane compound and the above-mentioned perfluoro (poly) ether It may be in the form of mixing with the solution of the modifying compound immediately before use.

  The composition of the present invention can be impregnated into a porous material, such as a porous ceramic material, metal fibers, such as steel wool, and made into a pellet. The said pellet can be used for vacuum evaporation, for example.

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

  Next, the article of the present invention will be described.

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

  First, a base material is prepared. Substrates that can be used in the present invention are, for example, glass, sapphire glass, resins (natural or synthetic resins, such as common plastic materials, may be plate-like, films, other forms), metals (metals) It may be a simple substance of metal such as aluminum, copper, iron or a complex such as alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven cloth, etc.), fur, leather, wood, ceramic, stone, etc. It may be constructed of any suitable material, such as a building component.

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

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

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

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

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

  Next, a film of the composition of the present invention is formed on the surface of the substrate, and the film is optionally post-treated to form a surface treatment layer from the composition of the present invention.

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

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

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

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

When using a wet coating method, the composition 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 composition 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 Perfluorocarbon) Fluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbon (eg, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbon (eg, C ₆ F ₁₃ CH ₂ CH ₃ (eg, Asahi Glass Co., Ltd.) Asahiklin (registered trademark) AC-6000) manufactured by the company, 1,1,2,2,3,3,4 heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydro Fluorocarbons (HFCs) (eg, 1,1,1,3,3-pentafluorobutane (HFC-365 mf) )); Hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo Novec (trade name) 7000), Perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (eg, Novec (trade name) 7100, manufactured by Sumitomo 3M Ltd.), Perfluorobutyl Ethyl Ether (C ₄₎ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Ltd.), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Sumitomo 3M stock Company-made NovecTM 7300 Alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. (registered trademark A) AE-3000)), 1,2-Dichloro-1,3,3,3-tetrafluoro-1-propene (e.g., Bertrel (R) Scion, manufactured by DuPont Fluorochemicals, Inc., etc.) These solvents. These can be used alone or as a mixture of two or more, and further, for example, for adjusting the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether modified compound, etc. Can be mixed with another solvent.

  When the dry coating method is used, the composition of the present invention may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

  Film formation is preferably carried out in such a way that the composition of the invention is present in a film together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of wet coating, after diluting the composition of the invention with a solvent, the catalyst may be added to the dilution of the composition of the invention just prior to application to the substrate surface. In the case of the dry coating method, the catalyst-added composition of the present invention is directly subjected to vapor deposition (usually, vacuum deposition), or impregnated with the catalyst-added composition of the present invention into metal porous bodies such as iron and copper. The deposited pellet-like material may be used for deposition (usually, vacuum deposition) treatment.

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

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

  After the film of the composition of the present invention is formed 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 condensation due to a temperature difference between the precursor film (and the substrate) and the ambient atmosphere, spraying of steam (steam), or the like may be used.

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

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

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

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

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

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

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

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

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

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

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

  Hereinabove, the articles obtained using the composition of the present invention have been described in detail. The application of the composition of the present invention, the method of use, the method of producing an article and the like are not limited to those exemplified above.

The composition of the present invention will be more specifically described through the following examples, but the present invention is not limited to these examples. In the present example, all chemical formulas shown below show average compositions, and the order of existence of repeating units (CF ₂ CF ₂ CF ₂ O) constituting a perfluoropolyether is arbitrary.

・ Composition example 1
-Synthesis of perfluoropolyether modified methyl ester compound 240 g of methanol and 19.6 g of triethylamine were charged in a reactor, and the average composition CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) at 5 ° C. under nitrogen stream. 500 g of a perfluoropolyether modified acid fluoro compound represented by ₃₂ CF ₂ CF ₂ COF was added dropwise, and then the temperature was raised to room temperature and stirred. Subsequently, 300 g of perfluorohexane was added and stirred, and then transferred to a separating funnel and allowed to stand. Then, a perfluorohexane layer was separated. Subsequently, a washing operation with 3 N hydrochloric acid aqueous solution was performed. Next, 30 g of anhydrous magnesium sulfate was added to the perfluorohexane layer, and after stirring, insolubles were separated by filtration. Subsequently, the volatile component was distilled off under reduced pressure to obtain 476 g of the following perfluoropolyether modified methyl ester compound (A) having a methyl ester group at the end.
Perfluoropolyether modified methyl ester compound (A):
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CO ₂ CH ₃

・ Composition example 2
Synthesis of Perfluoropolyether Modified Carboxylic Acid Compound 100 g of pure water and 20.4 g of triethylamine were charged in a reactor, and under nitrogen stream at 5 ° C., average composition CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O ) 500 g of a perfluoropolyether modified acid fluoro compound represented by ₃₂ CF ₂ CF ₂ COF was added dropwise, and then the temperature was raised to room temperature and stirred. Subsequently, 400 g of perfluorohexane was added and stirred, transferred to a separatory funnel and allowed to stand, and then the perfluorohexane layer was separated. Subsequently, a washing operation with 3 N hydrochloric acid aqueous solution was performed. Next, 30 g of anhydrous magnesium sulfate was added to the perfluorohexane layer, and after stirring, insolubles were separated by filtration. Subsequently, the volatile component was distilled off under reduced pressure to obtain 476 g of the following perfluoropolyether modified carboxylic acid compound (B) having a carboxylic acid group at the end.
Perfluoropolyether modified carboxylic acid compound (B):
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CO ₂ H

・ Synthesis example 3
Synthesis of perfluoropolyether-modified phosphoric acid ester compound Into a reactor, 200 g of 1,3-bis (trifluoromethyl) benzene and 54.5 g of phosphoryl chloride were charged, and the average composition CF ₃ CF ₂ at 5 ° C. under nitrogen stream. 200 g of a perfluoropolyether modified alcohol compound represented by CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CH ₂ OH was added dropwise, and then the temperature was raised to room temperature and stirred. Subsequently, 400 g of perfluorohexane was added and stirred, and then 100 g of pure water was dropped and stirred. Thereafter, it was transferred to a separating funnel and allowed to stand, and then the perfluorohexane layer was separated. Subsequently, a washing operation with 3 N hydrochloric acid aqueous solution was performed. Next, 10 g of anhydrous magnesium sulfate was added to the perfluorohexane layer, and after stirring, insolubles were separated by filtration. Subsequently, the volatile component was distilled off under reduced pressure to obtain 202 g of the following perfluoropolyether-modified phosphoric acid ester compound (C) having a phosphoric acid group at the end.
Perfluoropolyether group-containing phosphoric acid ester compound (C):
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CH ₂ OP (= O) (OH) ₂

Example 1
The perfluoropolyether modified methyl ester compound (A) obtained in the above Synthesis Example 1 and the perfluoropolyether modified silane compound (X) shown below are mixed at a molar ratio of 2:98, Novec 7200 (manufactured by 3M Co.) The surface treatment agent 1 was prepared to have a concentration of 20 wt%.
・ Perfluoropolyether modified silane compound (X)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

The surface treatment agent 1 prepared above was vacuum deposited on chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning). The processing conditions for vacuum deposition are a pressure of 3.0 × 10 ⁻³ Pa, and first, silicon dioxide is deposited on the surface of this chemically strengthened glass to a thickness of 7 nm by electron beam deposition to form a silicon dioxide film. Subsequently, 2 mg of the surface treatment agent was vapor deposited per one sheet of chemically strengthened glass (55 mm × 100 mm). Thereafter, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours under an atmosphere of a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened | cured and the surface treatment layer was formed.

(Examples 2 to 9)
A surface treatment agent was prepared by mixing the perfluoropolyether modified compounds (A) to (C) and the perfluoropolyether modified silane compounds (X) to (Z) in a combination of the following table at a molar ratio of 2:98. A surface treatment agent was prepared in the same manner as in Example 1 except for forming a surface treatment layer.
・ Perfluoropolyether modified silane compound (Y)
_{CF 3 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CON (CH 3) CH 2 CH 2 CH 2 Si (OCH 3) 3
・ Perfluoropolyether modified silane compound (Z)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃

Comparative Examples 1 to 3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the above perfluoropolyether-modified silane compounds (X) to (Z) were used alone.

Comparative example 4
A surface treatment agent is prepared and surface treatment is carried out in the same manner as in Example 1 except that acetic acid and the above perfluoropolyether-modified silane compound (X) are mixed at a molar ratio of 2:98 to prepare a surface treatment agent. A layer was formed.

  About the surface treatment layer formed in the base-material surface in said Examples 1-9 and Comparative Examples 1-4, the friction durability was evaluated by the eraser friction durability test. Specifically, the sample article on which the surface treatment layer has been formed is placed horizontally, and an eraser (Kokuyo KESHI-70, planar dimension 1 cm × 1.6 cm) is brought into contact with the surface of the surface treatment layer, A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. The static contact angle (degree) of water was measured every 500 reciprocations. Evaluation was stopped when the measured value of the contact angle was less than 100 degrees. Finally, the number of reciprocations when the contact angle exceeds 100 degrees is shown in Table 3.

  From the above results, in Examples 1 to 9 in which the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether modified compound were used in combination, the comparison was made using the perfluoro (poly) ether group-containing silane compound alone. It was confirmed to have higher eraser resistance than Examples 1 to 3. Although the present invention is not restricted by any theory, the perfluoropolyether modified compounds (A) to (C) act as an acidic catalyst at the time of formation of the surface treatment layer, and the perfluoro (poly) ether group-containing silane compounds ( It is thought that the reactivity of the X) to (Z) with the substrate surface was improved, and as a result, excellent eraser durability was obtained. Further, it was confirmed that Example 4 using the perfluoropolyether-modified carboxylic acid compound (B) had higher eraser resistance than Comparative Example 4 in which acetic acid which could simply function as a catalyst was used. Although the present invention is not restricted by any theory, it is considered that the acid itself can contribute to the function of the surface treatment layer by having a perfluoropolyether group.

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

Claims (35)

The following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

[In the formula:
PFPE ¹ independently at each occurrence, the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
Rf ¹ each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ¹ independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ¹¹ independently represents at each occurrence a hydrogen atom or a halogen atom;
R ¹² independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n1 _{^{is, (- SiR 1 n1 R 2}} 3-n1) independently for each unit, an integer from 0 to 3;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one n1 is an integer of 1 to 3;
Each X ¹ independently represents a single bond or a di- to 10-valent organic group;
X ² represents independently at each occurrence a single bond or a divalent organic group;
t is an integer of 1 to 10 independently at each occurrence;
α is each independently an integer of 1 to 9;
α 'is each independently an integer of 1 to 9;
Each X ⁵ independently represents a single bond or a di- to 10-valent organic group;
β is each independently an integer of 1 to 9;
β 'is each independently an integer of 1 to 9;
Each X ⁷ independently represents a single bond or a di- to 10-valent organic group;
γ is each independently an integer of 1 to 9;
γ 'is each independently an integer of 1 to 9;
R ^a each independently represents -Z ¹ -SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 at each occurrence;
Z ¹ independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁷¹ independently at each occurrence represents R ^{a ′} ;
R ^{a '} is as defined the R ^a ;
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ⁷² independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ⁷³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p1 is each independently an integer of 0 to 3 at each occurrence;
q1 is each independently an integer of 0 to 3 at each occurrence;
r 1 each independently at each occurrence is an integer from 0 to 3;
However, in formulas (C1) and (C2), at least one q1 is an integer of 1 to 3;
R ^b independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ^c independently at each occurrence represents a hydrogen atom or a lower alkyl group;
k1 is an integer of 1 to 3 independently at each occurrence;
l 1 is each independently an integer of 0 to 2 at each occurrence;
m1 is each independently an integer of 0 to 2 at each occurrence;
Each X ⁹ independently represents a single bond or a di- to 10-valent organic group;
δ is each independently an integer of 1 to 9;
each δ 'is independently an integer of 1 to 9;
R ^d independently at each occurrence represents -Z ² -CR ⁸¹ _{p 2} R ⁸² _{q 2} R ⁸³ _{r 2} ;
Z ² each independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is the same as R ^d ;
In ^Rd, at most 5 Cs linked in a linear fashion via a Z ² group;
R ⁸² independently represents -Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ at each occurrence;
Y represents, independently at each occurrence, a divalent organic group;
R ⁸⁵ each independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n2 represents an integer of 1 to 3 independently for each (-Y-SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ) unit;
Provided that in formulas (D1) and (D2), at least one n2 is an integer of 1 to 3;
R ⁸³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group;
p2 is each independently an integer of 0 to 3 at each occurrence;
q2 is each independently an integer of 0 to 3 at each occurrence;
r2 each independently at each occurrence is an integer from 0 to 3;
R ^e each independently at each occurrence represents —Y—SiR ⁸⁵ n ₂ R ⁸⁶ _3- n ₂ ;
R ^f independently at each occurrence independently represents a hydrogen atom or a lower alkyl group;
k2 each independently at each occurrence is an integer from 0 to 3;
l2 is each independently an integer of 0 to 3 at each occurrence;
m2 is each independently an integer of 0 to 3 at each occurrence;
However, in the formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one 12 is 2 or 3. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formulas (E1):

[In the formula:
PFPE ² independently at each occurrence, the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
Rf ² each independently represents at each occurrence an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Z ² represents a single bond or a divalent organic group;
x is 1 or 2;
When x is ^{1, A} is, -COOR ^3, be _{-PO (OR 3) 2, -SO} 2 (OR 3), or -SO (OR ^3);
When x is 2, A is, -PO (OR ³⁾ - a and;
R ³ is a hydrogen atom or a hydrocarbon group. ]
A composition comprising at least one compound represented by The composition according to claim 1, wherein R f ¹ is a C 1-16 perfluoroalkyl group. PFPE ¹ has the following formula (a), (b) or (c):
− (OC ₃ F ₆ ) _d − (a)
[Wherein, d is an integer of 1 or more and 200 or less. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d each independently represent an integer of 0 or more and 30 or less;
e and f are each independently an integer of 1 or more and 200 or less;
The sum of c, d, e and f is an integer of 10 or more and 200 or less;
The order in which each repeating unit enclosed in parentheses with a subscript c, d, e or f is given is arbitrary in the formula. ]
-(R ^6- R ⁷ ) _q- (c)
[Wherein, R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or a combination of 2 or 3 groups selected from these groups ;
q is an integer of 2 to 100; ]
The composition according to claim 1 or 2, which is The X ¹ , X ⁵ , X ⁷ and X ⁹ are divalent organic groups, α, β, γ and δ are 1 and α ′, β ′, γ ′ and δ ′ are 1 The composition of any one of 1 to 3. X ¹ , X ⁵ , X ⁷ and X ⁹ are each independently-(R ³¹ ) _{p '} -(X ^a ) _q'-
[In the formula:
Each R ³¹ independently represents a single bond,-(CH ₂ ) _s'- (wherein s' is an integer of 1 to 20) or an o-, m- or p-phenylene group;
X ^a represents-(X ^b ) _l'- (wherein l 'is an integer of 1 to 10);
X ^b is each independently -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ³³ ) ₂ -,-(-) _{^{Si (R 33) 2 O)}} m '-Si (R 33) 2 - ( wherein, m' is an integer of ^{1~100), - CONR 34 -,} - O-CONR 34 -, - NR 34 - And-(CH ₂ ) _{n '} -(wherein n' is an integer of 1 to 20) represents a group selected from the group consisting of
R ³³ independently at each occurrence represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group;
R ³⁴ each independently at each occurrence represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
p 'is 0, 1 or 2;
q 'is 0 or 1;
Here, at least one of p 'and q' is 1, and the order of existence of each repeating unit enclosed in parentheses with p 'or q' is arbitrary in the formula;
R ³¹ and X ^a may be substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. ]
The composition according to any one of claims 1 to 4, which is a group represented by X ¹ , X ⁵ , X ⁷ and X ⁹ each independently:
Single bond,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-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 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 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- ,
-(CH ₂ ) ₂ -Si (CH ₃ ) _2- (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- ,

The composition according to any one of claims 1 to 5, which is selected from the group consisting of k1 is 3, in ^{R a,} q1 is 3, A composition according to any one of claims 1 to 6.   The composition according to any one of claims 1 to 7, wherein l2 is 3 and n2 is 3. Y is a C _1-6 alkylene group, — (CH ₂ ) _{g ′} —O— (CH ₂ ) _{h ′} — (wherein, g ′ is an integer of 0 to 6 and h ′ is an integer of 0 to 6) in a), or - phenylene _{- (CH 2) i '-} ( wherein, i' is an is an integer from 0 to 6) the composition according to any one of claims 1-8. The composition according to any one of claims 1 to 3, wherein each of X ¹ , X ⁵ , X ⁷ and X ⁹ independently represents a trivalent to ten-valent organic group. X ¹ , X ⁵ , X ⁷ and X ⁹ each independently:

[Wherein, in each group, at least one of T is PFPE in the formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) ^The following groups attached to ¹ :
_{-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

And
At least one of the other T's is a carbon atom or a Si atom in formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) -(CH ₂ ) _n- (n is an integer of 2 to 6) to be bound, and the rest are each independently a methyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, or a radical trapping group or an ultraviolet absorption And
Each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms,
Each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group. ]
11. The composition of claim 10, wherein said composition is selected from the group consisting of   Number average molecular weight of the perfluoro (poly) ether group-containing silane compound represented by the formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The composition according to any one of claims 1 to 11, wherein L is 1,000 to 30,000.   The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any of formulas (A1) and (A2). .   The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any one of formulas (B1) and (B2). .   The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any of formulas (C1) and (C2). .   The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any of formulas (D1) and (D2). . The composition according to any one of claims 1 to 16, wherein Rf ² is a C 1-16 perfluoroalkyl group. The PFPE ² has the following formula (a), (b) or (c):
− (OC ₃ F ₆ ) _d − (a)
[Wherein, d is an integer of 1 or more and 200 or less. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d each independently represent an integer of 0 or more and 30 or less;
e and f are each independently an integer of 1 or more and 200 or less;
The sum of c, d, e and f is an integer of 10 or more and 200 or less;
The order in which each repeating unit enclosed in parentheses with a subscript c, d, e or f is given is arbitrary in the formula. ]
-(R ^6- R ⁷ ) _q- (c)
[Wherein, R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or two or three groups independently selected from these groups A combination;
q is an integer of 2 to 100; ]
The composition according to any one of claims 1 to 17, which is The divalent organic group in Z ² is
-(CR _< ¹⁸ _{> 2} ) _k7- (O) _k8- (NR _< ¹⁹ _> ) _k9- ,
[In the formula:
Each R ¹⁸ independently represents a hydrogen atom or a fluorine atom;
Each R ¹⁹ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k7 is an integer of 1 to 20;
k8 is an integer of 0 to 10;
k9 is an integer of 0 to 10;
Here, the order in which each repeating unit enclosed in parentheses with k7, k8 or k9 is present is arbitrary in the formula. ]
The composition according to any one of the preceding claims, which is Z ² _{is, - (CF 2) k7 '} - or _{- (CF 2) k7' -} (O) k8 '-
[In the formula:
k7 'is an integer of 1 to 6;
k8 'is an integer of 1 to 3;
Here, the order in which each repeating unit enclosed in parentheses with k7 'or k8' is present is arbitrary in the formula. ]
The composition according to any one of the preceding claims, which is A is -COOR ^3, A composition according to any one of claims 1 to 20.   The composition according to any one of claims 1 to 21, wherein the number average molecular weight of the compound represented by formula (E1) is 1,000 to 30,000.   Number average molecular weight of the perfluoro (poly) ether group-containing silane compound represented by the formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The composition according to any one of claims 1 to 21, wherein the difference in the number average molecular weight of the compound represented by the formula (E1) is within 2,000.   The composition according to any one of claims 1 to 23, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. The fluorine-containing oil has the formula (3):
Rf ^3- (OC ₄ F ₈ ) a _1- (OC ₃ F ₆ ) _{b 1-} (OC ₂ F ₄ ) _c 1-(OCF ₂ ) _{d 1-} Rf ⁴ (3)
[In the formula:
R f ³ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R f ⁴ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;
Each of a1, b1, c1 and d1 represents the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and is independently an integer of 0 or more and 300 or less and a1 or b1 The sum of c1 and d1 is at least 1, and the order in which each repeating unit enclosed in parentheses with the subscripts a1, b1, c1 or d1 is present is arbitrary in the formula. ]
25. The composition of claim 24, which is one or more compounds represented by   26. The composition of any one of the preceding claims, further comprising a solvent.   The composition according to any one of claims 1 to 26, which is a surface treatment agent.   28. The composition according to any one of the preceding claims, wherein it is used as a stain resistant coating or a waterproof coating.   A pellet containing the composition according to any one of the preceding claims.   An article comprising a substrate, and a layer formed of the composition according to any one of claims 1 to 28 on the surface of the substrate.   31. The article of claim 30, wherein the substrate is glass.   The article of claim 30, wherein the substrate is a glass selected from the group consisting of sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.   The article according to any one of claims 30 to 32, which is an optical member.   34. An article according to any one of claims 30 to 33, which is a display. Following formula (E1):

[In the formula:
Each Rf ² independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Each of PFPE ² independently represents — (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} - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f The sum of at least one, and the order of the presence of each repeating unit bracketed by a, b, c, d, e or f is arbitrary in the formula;
Z ² represents a single bond or a divalent organic group;
x is 1 or 2;
When x is ^{1, A} is, -COOR ^3, be _{-PO (OR 3) 2, -SO} 2 (OR 3), or -SO (OR _3);
When x is 2, A is, -PO (OR ³⁾ - a and;
R ³ is a hydrogen atom or a hydrocarbon group. ]
A condensation promoter for a perfluoro (poly) ether group-containing silane compound, which comprises at least one compound represented by