JP2016132719A - Surface-treating agent containing perfluoro(poly)ether group-containing silane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treating agent containing a perfluoro(poly)ether group-containing silane compound which has water repellency, oil repellency, antifouling property and water resistance and can form a layer having high friction durability.SOLUTION: There is provided a surface-treating agent which comprises (1) at least one perfluoro(poly)ether group-containing silane compound represented by a specific formula and (2) at least one fluorine-containing compound represented by a specific formula, wherein the mass ratio between (1) the perfluoro(poly)ether group-containing silane compound and (2) the fluorine-containing compound is 1:50 to 50:1.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound and a fluorine-containing compound.

  It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. Yes.

  As such a fluorine-containing compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to an Si atom at the molecular terminal or terminal part is known. (See Patent Documents 1 and 2). When this surface treatment agent containing a perfluoropolyether group-containing silane compound is applied to a substrate, hydrolyzable groups bonded to Si atoms react with the substrate and between the compounds to form a surface treatment layer. Do

JP 2002-348370 A JP 2012-72272 A

  The surface treatment layer is required to have high durability so as to provide a desired function to the base material over a long period of time. Since the layer obtained from the surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit the above-described functions even in a thin film, it is suitable for optical members such as glasses and touch panels that require optical transparency or transparency. In particular, these applications are required to further improve the friction durability.

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

  The present invention relates to a surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound capable of forming a layer having water repellency, oil repellency, antifouling properties, waterproof properties and high friction durability. The purpose is to provide.

  As a result of intensive studies, the present inventors have improved friction durability by adding a fluorine-containing compound having a functional group to a surface treatment agent containing a perfluoro (poly) ether group-containing silane compound. The present inventors have found that a surface treatment layer can be formed and have completed the present invention.

［式中：
ＰＦＰＥは、各出現においてそれぞれ独立して、−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−を表し、ここに、ａおよびｂは、それぞれ独立して、０以上３０以下の整数であり、ｃおよびｄは、それぞれ独立して、１以上２００以下の整数であり、ａ、ｂ、ｃおよびｄの和は、１以上であり、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り；
Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
Ｒ^１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^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎは、（−ＳｉＲ^１ _ｎＲ^２ _３−ｎ）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Ｒ^２が存在し；
Ｘ^４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−ＳｉＲ^７１ _ｐＲ^７２ _ｑＲ^７３ _ｒを表し；
Ｚ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；
ｐは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒは、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、一のＲ^ａにおいて、ｐ、ｑおよびｒの和は３であり、式（Ｃ１）および（Ｃ２）において、少なくとも１つのＲ^７２が存在し；
Ｒ^ｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^ｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋは、各出現においてそれぞれ独立して、１〜３の整数であり；
ｌは、各出現においてそれぞれ独立して、０〜２の整数であり；
ｍ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、γを付して括弧でくくられた単位において、ｋ、ｌおよびｍの和は３である。］
および
（２）下記式（Ｄ１）、（Ｄ２）、（Ｅ１）、（Ｅ２）、（Ｆ１）、（Ｆ２）、（Ｇ１）および（Ｇ２）のいずれかで表される少なくとも１種の含フッ素化合物：

［式中：
Ａは、各出現においてそれぞれ独立して、−ＯＨ、−ＳＨ、−ＣＯＯＲ^５、−ＣＯＳＨ、−ＣＯＮＨ_２、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＮＲ^５ _２、

を表し；
Ｒ^５は、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；
Ｘ^１は、ＯまたはＳを表し；
Ｍ_１およびＭ_２は、それぞれ独立して、水素原子またはアルカリ金属を表し；
Ｙ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；
ＰＦＰＥは、各出現においてそれぞれ独立して、−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−を表し、ここに、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０以上２００以下の整数であり、ａ、ｂ、ｃおよびｄの和は、１以上であり、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り；
Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
Ｒ^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；
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；
Ｘ^８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；
Ｘ^３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；
εは、それぞれ独立して、１〜９の整数であり；
ε’は、それぞれ独立して、１〜９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；
χは、それぞれ独立して、１〜９の整数であり；
χ’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−ＳｉＲ^７４ _ｐ’Ｒ^７５ _ｑ’Ｒ^７６ _ｒ’を表し；
Ｚ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^７４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^７５は、各出現においてそれぞれ独立して、−Ｘ^１０−Ｙ−Ａを表し；
Ｘ^１０は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基を表し；
Ｒ^７６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐ’は、各出現においてそれぞれ独立して、１〜３の整数であり；
ｑ’は、各出現においてそれぞれ独立して、０〜２の整数であり；
ｒ’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^ｄにおいて、ｐ’、ｑ’およびｒ’の和は３であり、式（Ｆ１）および（Ｆ２）において、少なくとも１つのＲ^７５が存在し；
Ｒ^ｅは、各出現においてそれぞれ独立して、−Ｘ^１０−Ｙ−Ａ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；
ｋは、各出現においてそれぞれ独立して、１〜３の整数であり；
ｌは、各出現においてそれぞれ独立して、０〜２の整数であり；
ｍ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、χを付して括弧でくくられた単位において、ｋ、ｌおよびｍの和は３であり；
Ｘ^６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；
θは、それぞれ独立して、１〜９の整数であり；
θ’は、それぞれ独立して、１〜９の整数であり；
Ｒ^９１は、フッ素原子、−ＣＨＦ_２または−ＣＦ_３を表し；
Ｒｆ’は、炭素数１〜２０のパーフルオロアルキレン基を表す。］
を含んでなる、表面処理剤が提供される。 That is, according to the first aspect of the present invention, (1) at least 1 represented by any of the following formulas (A1), (A2), (B1), (B2), (C1) and (C2) Perfluoro (poly) ether group-containing silane compounds:

[Where:
PFPE is independently at each _{occurrence, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - represents, here, a and b is independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, and the sum of a, b, c and d is 1 or more. Yes, the order of presence of each repeating unit in parentheses with the suffix a, b, c or d is arbitrary in the formula;
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 1 n R 2}} 3-n) independently for each unit, an integer from 0 to 3;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one R ² is present;
Each X ⁴ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
X ⁵ each independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer of 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
However, in one R ^a , the sum of p, q and r is 3, and in formulas (C1) and (C2), there is at least one R ⁷² ;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
However, the sum of k, l, and m is 3 in the unit enclosed in parentheses with γ. ]
And (2) at least one fluorine-containing compound represented by any of the following formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and (G2) Compound:

[Where:
A is independently at each _{^{occurrence, -OH, -SH, -COOR 5,}} -COSH, -CONH 2, -P (O) (OH) 2, -OP (O) (OH) 2, -NR ⁵ ₂ ,

Represents;
Each R ⁵ independently represents a hydrogen atom or a lower alkyl group;
X ¹ represents O or S;
M ₁ and M ₂ each independently represents a hydrogen atom or an alkali metal;
Y represents a single bond or a divalent organic group independently at each occurrence;
PFPE is independently at each _{occurrence, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - represents, here, a, b, c, and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, and d is 1 or more, and the subscripts a, b, c, or d are attached to parentheses. The order of presence of each recurring unit enclosed is arbitrary in the formula;
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
Each X ⁸ independently represents a single bond or a divalent to 10-valent organic group;
each δ is independently an integer from 1 to 9;
each δ ′ is independently an integer from 1 to 9;
Each X ³ independently represents a single bond or a divalent to 10-valent organic group;
each ε is independently an integer from 1 to 9;
each ε ′ is independently an integer from 1 to 9;
Each X ⁹ independently represents a single bond or a divalent to 10-valent organic group;
each χ is independently an integer from 1 to 9;
each χ ′ is independently an integer from 1 to 9;
R ^d independently represents at each occurrence —Z—SiR ⁷⁴ _{p ′} R ⁷⁵ _{q ′} R ⁷⁶ _{r ′} ;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷⁴ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is synonymous with R ^d ;
In R ^d , the maximum number of Si linked in a straight chain via the Z group is 5;
R ⁷⁵ is independently at each ^occurrence, represents ^-X 10 -Y-A;
X ¹⁰ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence;
R ⁷⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p ′ is independently an integer from 1 to 3 at each occurrence;
q ′ is independently an integer from 0 to 2 at each occurrence;
r ′ is independently an integer from 0 to 2 at each occurrence;
Provided that in one R ^d , the sum of p ′, q ′ and r ′ is 3, and in formulas (F1) and (F2), there is at least one R ⁷⁵ ;
R ^e is, independently at each ^occurrence, represents ^-X 10 -Y-A;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
Provided that the sum of k, l and m is 3 in the unit enclosed in parentheses with χ;
Each X ⁶ independently represents a single bond or a divalent to 10-valent organic group;
each θ is independently an integer from 1 to 9;
each θ ′ is independently an integer from 1 to 9;
R ⁹¹ represents a fluorine atom, —CHF ₂ or —CF ₃ ;
Rf ′ represents a C 1-20 perfluoroalkylene group. ]
A surface treatment agent comprising: is provided.

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

  According to the present invention, a novel surface treatment agent that is a mixture of a perfluoro (poly) ether group-containing silane compound and a fluorine-containing compound is provided. By using these, it is possible to form a surface treatment layer having water repellency, oil repellency, antifouling property, waterproof property and excellent friction durability.

  Hereinafter, the surface treating agent of the present invention will be described.

  The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, waterproofness and friction durability to the substrate, and is not particularly limited, but the antifouling coating agent Or it can be used suitably as a waterproof coating agent.

  As used herein, “2 to 10 valent organic group” means a 2 to 10 valent group containing carbon. The divalent to 10-valent organic group is not particularly limited, and examples thereof include a 2 to 10-valent group in which 1 to 9 hydrogen atoms are eliminated from a hydrocarbon group. For example, the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.

および
（２）下記式（Ｄ１）、（Ｄ２）、（Ｅ１）、（Ｅ２）、（Ｆ１）、（Ｆ２）、（Ｇ１）および（Ｇ２）のいずれかで表される少なくとも１種の含フッ素化合物：

を含んでなる表面処理剤を提供する（以下、「本発明の表面処理剤」ともいう）。 The present invention provides (1) at least one perfluoro (poly) ether group represented by any of the following formulas (A1), (A2), (B1), (B2), (C1) and (C2) Containing silane compounds:

And (2) at least one fluorine-containing compound represented by any of the following formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and (G2) Compound:

Is provided (hereinafter also referred to as “the surface treatment agent of the present invention”).

The formula (A1), (A2), (B1), (B2), in (C1) and (C2), PFPE _{is, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F ₄ ) _c — (OCF ₂ ) _d — and corresponding to a perfluoro (poly) ether group. Here, a, b, c and d are each independently an integer of 0 or 1 and are not particularly limited as long as the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 to 200, for example, an integer of 1 to 200, more preferably an integer of 0 to 100, for example, 1 An integer of 100 or less. More preferably, the sum of a, b, c and d is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less. Further, the order of presence of each repeating unit with a, b, c or d in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (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 ))-may be used, but preferably _{- (OCF 2 CF 2 CF 2} CF 2) - a. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. Further,-(OC ₂ F ₄ )-may be either-(OCF ₂ CF ₂ )-or-(OCF (CF ₃ ))-, preferably-(OCF ₂ CF ₂ )-. is there.

In one embodiment, PFPE is — (OC ₃ F ₆ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). _{preferably, - (OCF 2 CF 2 CF} 2) b - ( wherein, b is 1 to 200, preferably 5 to 200, more preferably an integer of 10 to 200 or less).

In another embodiment, PFPE _{is, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - ( wherein, a and b are each independently And c and d are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the subscripts a, b, c or the order of the repeating units in parentheses are given the d is optional is in the formula), preferably _{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF _{2) b - (OCF 2 CF} 2) c - (OCF 2) d - a.

In yet another embodiment, PFPE ^{_{is, - (OC 2 F 4 -R}} 8) n "-. A group represented in ^{formula, R} 11 _{is, OC 2 F 4, OC 3} F 6 and _OC 4 F ₈ is a group selected from, or independent of _{.OC 2 F 4, OC 3 F} 6 and _OC 4 _{F 8} is a combination of two or three groups independently selected from these groups Examples of the combination of 2 or 3 groups selected are 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 O _{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 n ″ 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 and OC ₄ F ₈ may be either linear or branched, preferably linear. In this embodiment, PFPE is _{preferably, - (OC 2 F 4 -OC} 3 F 6) n "- or _{- (OC 2 F 4 -OC 4} F 8) n" - is. In these formulas, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ are preferably OCF ₂ CF ₂ , OCF ₂ CF ₂ CF ₂ and OCF ₂ CF ₂ CF ₂ CF ₂ , respectively.

  In the above formulas (A1), (B1) and (C1), Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

  The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is 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.

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

The C 1-16 perfluoroalkyl group may be linear or branched, and is preferably linear or branched, having 1 to 6 carbon atoms, particularly 1 to 1 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ . .

In the above formulas (A1), (A2), (B1) and (B2), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably 1 to 4 carbon atoms. Represents an alkyl group.

In the above formulas (A1), (A2), (B1) and (B2), R ² each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

The “hydrolyzable group” as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (in these formulas, R is substituted or unsubstituted) Represents an alkyl group having 1 to 4 carbon atoms, preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

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

In the above formulas (A1) and (A2), R ¹¹ each independently represents a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom.

In the above formulas (A1) and (A2), R ¹² 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, 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 (A1), (A2), (B1) and (B2), n is an integer of 0 to 3 independently for each (-SiR ¹ _n R ² _3-n ) unit, In formulas (A1), (A2), (B1) and (B2), at least one R ² is present. In other words, not all n in the formula will be zero.

In the above formulas (A1) and (A2), X ² each independently represents a single bond or a divalent organic group. In a preferred embodiment, X ² is a single bond or — (CH ₂ ) _s — (wherein s is 1 or 2).

  In the above formulas (A1) and (A2), t is an integer of 1 to 10 independently at each occurrence. In a preferred embodiment, t is an integer from 1-6.

^X 4 in the formula (A1) and (A2), (B1) and ^X 5 in (B2), ^{X 7} in (C1) and (C2) are each independently a single bond or 2-10 monovalent organic Represents a group. In the above formula, α, β and γ are each independently an integer of 1 to 9, and α ′, β ′ and γ ′ are each independently an integer of 1 to 9. The X ⁴ , X ^5, and X ⁷ are those that can stably exist the compounds represented by the formulas (A1), (A2), (B1), (B2), (C1), and (C2). , Any 2 to 10 valent organic group may be used. Depending on the valency of X ⁴ , X ⁵ and X ⁷ , α, β and γ and α ′, β ′ and γ ′ in the formula may vary. For example, in the formulas (A1), (B1), and (C1), the valences of X ⁴ , X ^5, and X ⁷ are respectively the sum of α and α ′, the sum of β and β ′, and γ and γ ′. Is the same as the sum of For example, when X ⁴ is a 10-valent organic group, the sum of α and α ′ is 10, for example, α is 9 and α ′ is 1, α is 5 and α ′ is 5, or α is 1 and α 'Can be nine. In the formulas (A2), (B2), and (C2), α, β, and γ are values obtained by subtracting 1 from the valences of X ⁴ , X ^5, and X ⁷ , respectively. For example, when X ⁴ is a divalent organic group, α is 1, and when X ⁴ is a 10 valent organic group, α is 9.

In a preferred embodiment, X ⁴ , X ⁵ and X ⁷ are divalent to tetravalent organic groups, α, β and γ are each 1 to 3, α ′, β ′ and γ ′ are 1, and more Preferably, X ⁴ , X ⁵ and X ⁷ are divalent organic groups, α, β and γ are 1, and α ′, β ′ and γ ′ are 1.

Examples of X ⁴ , X ⁵ and X ⁷ are not particularly limited. For example, the following formula:
− (R ³¹ ) _{p ″} − (X ^a ) _{q ″} −
[Where:
R ³¹ represents a single bond, — (CH ₂ ) _{s ′} — (wherein s ′ is an integer of 1 to 20) or an o-, m-, or p-phenylene group;
^Xa represents-( ^Xb ) _l'- (wherein l 'is an integer of 1 to 10);
X ^b is independently at each occurrence, —O—, —S—, o—, m- or p-phenylene group, —C (O) O—, —Si (R ³³ ) ₂ —, — ( Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ — (wherein m ′ is an integer of 1 to 100), —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ —. And represents a group selected from the group consisting of — (CH ₂ ) _{n ′} — (wherein n ′ is an integer of 1 to 20);
R ³³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group at each occurrence;
R ³⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group at each occurrence;
p ″ is 0 or 1;
q ″ is 0 or 1;
Here, at least one of p ″ and q ″ is 1, and the order of presence of each repeating unit in parentheses with p ″ and q ″ is arbitrary in the formula;
R ³¹ and X ^a may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group. ]
The group which is is mentioned.

Preferably, X ⁴ , X ⁵ and X ⁷ are each independently — (R ³¹ ) _{p ″} —X ^{a ′} —R ³² —, wherein R ³² is a single bond, — (CH ₂ ) _{t. '-} or o-, represents m- or p- phenylene group, preferably - _(CH 2) _t' - is .t 'is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably X ^{a ′} is a group obtained by removing a portion corresponding to R ³² from X ^a , wherein R ³² is a fluorine atom, a C _1-3 alkyl group and C _1. Optionally substituted by one or more substituents selected from _-3 fluoroalkyl groups.

Preferably, said X ⁴ , X ⁵ and X ⁷ are each independently
A 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 ⁴ , X ⁵ and X ⁷ are each independently
A C _1-20 alkylene group,
_{- (CH 2) s' -X} c -,
_{- (CH 2) s '-X} c - (CH 2) t' -
-X ^d- , or -X ^d- (CH ₂ ) _{t '} -
[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, and more preferably an integer of 2 to 3. ]. 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 ⁴ , X ⁵ and X ⁷ are each independently
A 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 ⁴ , X ⁵ and X ⁷ are each independently
A C _1-20 alkylene group,
_{- (CH 2) s '-O-} (CH 2) t' -,
_{- (CH 2) s' -} (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
_{- (CH 2) s '-O-} (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - _(CH 2) _{s' -O- (CH 2) t} '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) -
[Wherein, R ³³ , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1-20, preferably an integer of 2-6, more preferably 2-3]. It is an integer. ]
It is.

In the above formula, — (C _v H _2v ) — may be linear or branched. For example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH It may be (CH ₃ ) —, —CH (CH ₃ ) CH ₂ —.

X ⁴ , X ⁵ and X ⁷ are one or more 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 substituted with a substituent.

などが挙げられる。 More specifically, examples of X ⁴ , X ⁵ and X ⁷ are not particularly limited.
_{-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 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 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 -,

Etc.

［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に結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ Other examples of X ⁴ , X ⁵ and X ⁷ include the following groups:

[Wherein, R ⁴¹ each 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

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

In still another embodiment, X ⁴ 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 in which each repeating unit enclosed in parentheses is in the formula Is optional.

In the above formula, R ¹⁶ is each independently an oxygen atom, 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.

The “divalent polar group” is not particularly limited, but —C (O) —, —C (═NR ²⁷ ) —, and —C (O) NR ²⁷ — (in these formulas, R ²⁷ is Represents 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, n-propyl, and these may be substituted with one or more fluorine atoms.

In the above formula, R ¹⁷ is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence. 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, 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 and brackets The order in which each repeating unit is included is arbitrary in the formula).

As the group represented by the above formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z —, for example, — (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; 'Is 0 or 1.) The left end of these groups is bonded to the PFPE side.

Another example of X ⁴ is —O—CFR ¹³ — (CF ₂ ) _e —. In the formula, R ¹³ represents a fluorine atom or a lower fluoroalkyl group, and e is 0 or 1. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. 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と反対の基（即ち、式（Ａ１）および（Ａ２）においては炭素原子、また、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、フェニル基またはＣ_１−６アルコキシ基である。］ Further examples of other X ⁴ , X ⁵ and X ⁷ include the following groups:

[Where:
Each of R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ¹ group, any some of T are attached to the PFPE of the molecular backbone:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
- _{(CH 2)} 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 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 is a group opposite to PFPE of the molecular main chain (ie, a carbon atom in the formulas (A1) and (A2), and the formulas (B1), (B2), (C1) and (C2) are bonded to Si atoms) in _{- (CH 2) n "-} (n" is an integer of 2-6), if present, the remainder are each independently a methyl group, a phenyl group Or a C _1-6 alkoxy group. ]

In this embodiment, X ⁴ , X ⁵ and X ⁷ can each independently be a trivalent to 10 valent organic group.

In the formulas (C1) and (C2), R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence.

  Z in each occurrence independently represents an oxygen atom or a divalent organic group.

  Said Z preferably does not contain what forms a siloxane bond with the Si atom of the terminal of the molecular principal chain in Formula (C1) or Formula (C2).

Z is preferably a C _1-6 alkylene group, — (CH ₂ ) _{s ′} —O— (CH ₂ ) _{t ′} — (wherein s ′ is an integer of 1 to 6, and t ′ is 1-6 of an integer), or, - phenylene _{- (CH 2) u '-} ( wherein, u' is an a) integer from 0 to 6, more preferably _{C 1-3} alkylene group is there. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

R ⁷¹ represents R ^{a ′} independently at each occurrence.

R ^{a ′} has the same meaning as R ^a .

During R ^a, Si is connected to the linear through the Z group is a five at the maximum. That is, in the above R ^a , when at least one R ⁷¹ is present, there are two or more Si atoms linearly linked via a Z group in R ^a , The maximum number of Si atoms connected in a chain is five. The "number of Si atoms linearly linked via a Z group in R ^a" is equal to -Z-Si- repeating number of which is connected to a linear during R ^a.

For example, an example in which Si atoms are linked through a Z group in R ^a is shown below.

In the above formula, * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition. The number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *. That is, the chain in which the ZSi repeat is completed in Si ² has “the number of Si atoms linearly linked through the Z group in R ^a ”, and similarly, Si ³ , Si ⁴ and The chain in which the ZSi repetition is completed in Si ⁵ has “number of Si atoms connected in a straight chain via the Z group in ^Ra ” being 3, 4 and 5, respectively. As is apparent from the above equation, is in the R ^a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.

In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z group in R ^a ” is one (left formula) or two (right formula) in all chains. Formula).

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

R ⁷² represents a hydroxyl group or a hydrolyzable group independently at each occurrence. Examples of the hydrolyzable group include those described for R ² above. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

R ⁷³ represents a hydrogen atom or a lower alkyl group independently 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.

Where p is independently an integer from 0 to 3 at each occurrence; q is independently an integer from 0 to 3 at each occurrence; and r is independently at each occurrence. And an integer of 0 to 3. However, in one R ^a , the sum of p, q and r is 3, and in formulas (C1) and (C2), there is at least one R ⁷² .

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q is preferably 2 or more, for example 2 or 3, more preferably 3. When q takes such a value, the adhesive force with the base material is improved and the durability is improved.

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

R ^b is preferably a hydroxyl group, —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (in these formulas, R is substituted or unsubstituted) Represents an alkyl group having 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 a group produced by hydrolysis of a hydrolyzable group. More preferably, R ^b is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

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

  Wherein k is independently an integer from 1 to 3 at each occurrence; l is independently an integer from 0 to 2 at each occurrence; m is independently at each occurrence. And an integer of 0-2. However, the sum of k, l, and m is 3 in the unit enclosed in parentheses with γ.

  The compound represented by the formulas (A1), (A2), (B1), (B2), (C1) and (C2) can be appropriately produced by those skilled in the art using techniques known in the art. it can.

  For example, the compounds represented by the formulas (A1) and (A2) can be synthesized by the method described in WO 97/07155.

  For example, the compounds represented by the formulas (B1) and (B2) can be synthesized by the method described in JP-T-2008-534696.

  For example, the compounds represented by formulas (C1) and (C2) can be synthesized by the method described in JP-A No. 2014-218639.

In the above formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and (G2), PFPE is independently at each occurrence, — (OC _{4 F 8) a - (OC 3} F 6) b - (OC 2 F 4) c - (OCF 2) d - represents, here, a, b, c and d are each independently, 200 0 or more The sum of a, b, c and d is 1 or more, and the order of presence of each repeating unit in parentheses with the suffix a, b, c or d is as follows: Is optional;
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is an integer of 1 to 10 independently at each occurrence. These are equivalent to those described for the above formulas (A1), (A2), (B1), (B2), (C1) and (C2).

を表す。好ましくは、−ＳＨ、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２−ＮＲ^５ _２、または

である。 In the above formula, A is independently at each occurrence —OH, —SH, —COOR ⁵ , —COSH, —CONH ₂ , —P (O) (OH) ₂ , —OP (O) (OH). ₂ , -NR ⁵ ₂ ,

Represents. _{Preferably, -SH, -P (O) (} OH) 2, -OP (O) (OH) 2 -NR 5 2 _or,

It is.

In the above formula, each R ⁵ 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 still more preferably an alkyl group having 1 to 3 carbon atoms.
Said X < ¹ > represents O or S each independently.
M ₁ and M ₂ each independently represents a hydrogen atom or an alkali metal. The alkali metal is preferably Li, Na or K, for example.

Y represents a single bond or a divalent organic group independently at each occurrence. Preferably, Y may be a single bond or a hydrocarbon group (preferably an optionally substituted C _1-6 alkyl group).

X ³ , X ⁶ , X ⁸ and X ⁹ each independently represent a single bond or a 2 to 10 valent organic group, preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably 2 Valent organic group. These have the same meanings as X ⁴ , X ⁵ and X ⁷ in the above formulas (A1), (A2), (B1), (B2), (C1) and (C2), particularly X ⁸ , X ³ and X ⁹ corresponds to X ⁴ , X ⁵ and X ⁷ , respectively.

In the above formula, δ, ε, χ and θ are each independently an integer of 1 to 9, and δ ′, ε ′, χ ′ and θ ′ are each independently an integer of 1 to 9. is there. These δ, ε, χ, θ, δ ′, ε ′, χ ′ and θ ′ are determined according to the valences of X ³ , X ⁶ , X ⁸ and X ⁹ . For example, the sum of the formula (D1), [delta] and [delta] 'is the same as the valence of X ^8. For example, when X ⁸ 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 nine. Further, when X ⁸ is a divalent organic group, δ and δ ′ are 1. In formula (D2), [delta] is a value obtained by subtracting 1 from the valence of the value of X ^8. The same applies to ε, χ, θ, ε ′, χ ′, θ ′.

In the above formulas (F1) and (F2), R ^d independently represents —Z—SiR ⁷⁴ _{p ′} R ⁷⁵ _{q ′} R ⁷⁶ _{r ′} at each occurrence.

  Z in each occurrence independently represents an oxygen atom or a divalent organic group. Z has the same meaning as Z in the above formulas (C1) and (C2).

R ⁷⁴ represents R ^{d ′} independently at each occurrence.

R ^{d ′} has the same meaning as R ^d .

In R ^d , the maximum number of Si linked in a straight chain via the Z group is 5. The "number of Si atoms linearly linked via a Z group in R ^d" is equal to -Z-Si- repeating number of which is connected to a linear during R ^d.

In one embodiment, the number of Si atoms connected in a straight chain via a Z group in R ^d is 1 or 2, preferably 1.

R ⁷⁵ is independently at each ^occurrence, represents an ^-X 10 -Y-A.

X ¹⁰ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence.

X ¹⁰ is preferably a C _1-6 alkylene group or a phenylene group, and more preferably a C _1-3 alkylene group. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

  Y and A are as defined above.

R ⁷⁶ represents a hydrogen atom or a lower alkyl group independently 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.

Where p ′ is independently an integer from 0 to 3 at each occurrence; q ′ is independently an integer from 0 to 3 at each occurrence; r ′ is at each occurrence. Each independently represents an integer of 0 to 3. However, in one R ^d , the sum of p ′, q ′ and r ′ is 3, and at least one R ⁷⁵ is present in the formulas (F1) and (F2).

In the above formula, R ^e independently represents —X ¹⁰ —YA at each occurrence. X ¹⁰ , Y and A are as defined above.

In the above formula, R ⁹¹ represents a fluorine atom, —CHF ₂ or —CF ₃ , preferably a fluorine atom or —CF ₃ .

Rf ′ represents a C 1-20 perfluoroalkylene group. Rf ′ preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 3 to 6 carbon atoms. Specific examples of _{Rf ', -CF 2 -, -} CF 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, _{-CF 2 CF (CF 3) -} , - C (CF 3) -, - (CF 2) 4 CF 2 -, - (CF 2) 2 CF (CF 3) -, - CF 2 C (CF 3) - _{, -CF (CF 3) CF 2} CF 2 CF 2 -, - (CF 2) 5 CF 2 -, - (CF 2) 3 CF (CF 3) 2, - (CF 2) 4 CF (CF 3) 2 , -C ₈ F ₁₇ , and among them, linear perfluoroalkylene having 3 to 6 carbon atoms, for example, —CF ₂ CF ₂ CF ₂ CF ₂ —, —CF ₂ CF ₂ CF ₂ — and the like are preferable.

  Compounds of the above formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and (G2) are known to those skilled in the art. It can be suitably manufactured using technology.

For example, the compound represented by the formula (D1) is obtained by introducing iodine to the terminal using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and then —CH ₂ CR ¹² (X ² -YA). )-Can be obtained by reacting a vinyl monomer corresponding to-.

  For example, the compound represented by the formula (E1) is obtained by using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing a hydroxyl group at the terminal, and then a group corresponding to the -YA moiety, such as a terminal It can be obtained by subjecting a compound having an alkyl halide to a Williamson reaction.

For example, the compound represented by the formula (F1) introduces -SiHal ₃ group (Hal is halogen) into the perfluoropolyether derivative corresponding to the Rf-PFPE- moiety using hydrosilylation, etc. , -YA, can be obtained by reacting with a Grignard reagent corresponding to the moiety, for example, Hal-Mg-YA.

For example, the compound represented by the formula (G1) includes, for example, a fluoroalkyl derivative corresponding to the R ⁹¹ —Rf′- moiety as a raw material, a hydroxyl group introduced into the terminal, and a group corresponding to the —YA moiety, For example, it can be obtained by subjecting a compound having an alkyl halide at the terminal to a Williamson reaction.

  Further, these compounds can be produced by synthesizing a compound in which the YA moiety is a precursor group, and converting the precursor group into a YA group by a method known in the art. it can.

  In a preferred embodiment, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by any one of formula (A1) and formula (A2). More preferably, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by the formula (A1).

  In a preferred embodiment, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by any one of formulas (B1) and (B2). More preferably, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by the formula (B1).

  In a preferred embodiment, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by any one of formula (C1) and formula (C2). More preferably, the perfluoro (poly) ether group-containing silane compound is one or more compounds represented by the formula (C1).

  In a preferred embodiment, the fluorine-containing compound is one or more compounds represented by any one of formula (D1) and formula (D2). More preferably, the fluorine-containing compound is one or more compounds represented by the formula (D1).

  In another preferred embodiment, the fluorine-containing compound is one or more compounds represented by any one of formula (E1) and formula (E2). More preferably, the fluorine-containing compound is one or more compounds represented by the formula (E1).

  In another preferred embodiment, the fluorine-containing compound is one or more compounds represented by any one of formula (F1) and formula (F2). More preferably, the fluorine-containing compound is one or more compounds represented by the formula (F1).

  In another preferred embodiment, the fluorine-containing compound is one or more compounds represented by any one of formula (G1) and formula (G2). More preferably, the fluorine-containing compound is one or more compounds represented by the formula (G1).

  In one embodiment, in the surface treatment agent of the present invention, (1) perfluoro represented by any one of formulas (A1), (A2), (B1), (B2), (C1) and (C2) A poly) ether group-containing silane compound (hereinafter also referred to as “perfluoro (poly) ether group-containing silane compound (1)”), and (2) formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and mass ratio (hereinafter also referred to as “fluorinated compound (2)”) represented by any one of (G2) In some cases, the sum thereof (and so on) is preferably 1:50 to 50: 1, more preferably 1:10 to 10: 1, and even more preferably 1: 4 to 4: 1. . By setting it as this range, the friction durability of a surface treating agent can be improved more.

The surface treating agent of the present invention may be diluted with a solvent. Such a solvent is not particularly limited. For example, perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 1,1,1, 2,2,3,3,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name Etc.), C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₆ F ₁₃ CH═CH ₂ , xylene hexafluoride, perfluorobenzene, methyl pentadeca fluoro heptyl ketone, trifluoroethanol, pentafluoropropanol, _{hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH} , Mechirutorifuru B methanesulfonate, trifluoroacetic acid and _{CF 3 O (CF 2 CF 2} O) m (CF 2 O) n CF 2 CF 3 [ wherein, m and n are each independently zero or greater than 1,000 integer, The order of presence of each repeating unit with m or n enclosed in parentheses is arbitrary in the formula, provided that the sum of m and n is 1 or more.], 1,1-dichloro-2,3, 3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4 , 4-hexafluoro-2-butene And a solvent selected from the group, which can be used alone or as a mixture of two or more.

  Furthermore, the surface treating agent of the present invention may contain other components. Such other components are not particularly limited. For example, (non-reactive) fluoropolyether compounds, preferably perfluoro (poly) ether compounds (hereinafter referred to as “containing”) that can be understood as fluorine-containing oils. (Referred to as “fluorine oil”), (non-reactive) silicone compounds that can be understood as silicone oil (hereinafter referred to as “silicone oil”), catalysts, and the like.

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

As an example of the perfluoro (poly) ether compound represented by the general formula (3), a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds) may be used. May be included).
Rf ^1- (OCF ₂ CF ₂ CF ₂ ) _{b ″} -Rf ² (3a)
_{^{Rf 1 - (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 2 · .. (3b)
In these formulas, Rf ¹ and Rf ² are as described above; in formula (3a), b ″ is an integer of 1 to 100; in formula (3b), a ″ and b ″ are Each independently represents an integer of 1 to 30, and c ″ and d ″ are each independently an integer of 1 to 300. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.

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

  In the surface treatment agent, the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound (1) and the fluorine-containing compound (2). , The same applies to the following), for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.

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

  In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (3b). In such an embodiment, the mass ratio of the sum of the perfluoro (poly) ether group-containing silane compound (1) and the fluorine-containing compound (2) in the surface treatment agent to the compound represented by the formula (3b) is 4 : It is preferable that it is 1-1: 4.

  In a preferred embodiment, when the antifouling coating layer is formed by vacuum deposition, the perfluoro (poly) ether group-containing silane compound is more preferable than the perfluoro (poly) ether group-containing silane compound (1). The average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of (1) and the fluorine-containing compound (2). By setting such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf ³ -F and the chlorotrifluoroethylene oligomer are preferred in that high affinity is obtained with the compound represented by the above-mentioned fluorine-containing compound whose terminal is a C _1-16 perfluoroalkyl group.

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

  In the surface treatment agent of the present invention, the silicone oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound (1) and the fluorine-containing compound (2). , The same applies hereinafter), for example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass.

  Silicone oil contributes to improving 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 contained in the surface treatment agent promotes hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound of the present invention, and promotes formation of the surface treatment layer.

  Other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

  The surface treatment agent of the present invention may be in the form of one solution (or suspension or dispersion), or may contain a solution of a separate perfluoro (poly) ether group-containing silane compound (1) and The form which mixes with the solution of a fluorine compound (2) just before use may be sufficient.

  The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form. The pellet can be used for, for example, vacuum deposition.

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

  The article of the present invention comprises a substrate and a surface treatment agent comprising the perfluoro (poly) ether group-containing silane compound and fluorine-containing compound of the present invention on the surface of the substrate (hereinafter referred to simply as “ A layer (so-called surface treatment layer) formed from the surface treatment agent of the present invention). This article can be manufactured, for example, as follows.

  First, a base material is prepared. Substrates that can be used in the present invention include, for example, glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, a film, and other forms), a metal, or a metal oxide (It may be a simple metal such as aluminum, copper, iron, or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. Can be composed of any suitable material.

  In a preferred embodiment, the substrate is glass or sapphire. When the substrate is glass, examples thereof include glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass.

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. Further, when the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO ₂ and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is 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 or the like.

  The shape of the substrate is not particularly limited. In addition, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.

  As such a base material, at least a surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors. Alternatively, if it does not suffice if it has hydroxyl groups, such as resin, or if it does not have hydroxyl groups originally, it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the surface of the substrate by the LB method (Langmuir-Blodgett method) or chemical adsorption method. And then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.

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

  Next, a film of the above-described surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.

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

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

  Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, chemical vapor deposition (CVD) and similar methods. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, electron beam, high frequency heating, 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 the wet coating method is used, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C _5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C ₆ F ₁₃ CH ₂ CH ₃ (eg Asahi Glass) ASAHIKLIN (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365 fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo Novec (trade name) 7000) manufactured by 3M Corporation, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C _{4 F 9 OC 2 H 5)} ( e.g., Sumitomo 3M Limited of Novec (TM) 7200), perfluorohexyl methyl ether _{(C 2 F 5 CF (OCH} 3) C 3 F 7) ( e.g., Sumitomo Novec (trade name) 73 manufactured by Co., Ltd. 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Vertrel (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents can be used alone or in combination as a mixture of two or more thereof, for example, to adjust the solubility of the perfluoro (poly) ether group-containing silane compound. Can also be mixed.

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

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

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

Although the usage method of the surface treatment composition of this invention is not limited, It is preferable to perform the film formation of a surface treatment composition by a vapor deposition method. The vapor deposition method of the present invention includes using the surface treatment composition as a vapor deposition material to form a vapor deposition film on the surface of the substrate. This deposition method is usually vacuum deposition performed in a vacuum (that is, a pressure lower than atmospheric pressure). The pressure at the time of vapor deposition is, for example, 2 × 10 ⁻³ Pa to 1 × 10 ⁻⁵ Pa, preferably 1 × 10 ⁻³ Pa to 1 × 10 ⁻⁴ Pa, and the temperature at the time of vapor deposition is, for example, 20 ° C. to 1000 ° C. The temperature may be raised stepwise or gradually within such a range, but is not limited thereto.

  The layer formed by the surface treatment agent of the present invention may be composed of a single layer or two or more layers. When the surface treatment layer is composed of a single layer, the perfluoro (poly) ether group-containing silane compound (1) and the fluorine-containing compound (2) may be present substantially uniformly in the layer. The concentration of one compound (preferably perfluoro (poly) ether group-containing silane compound (1)) is high on the material side, and the concentration of the other compound (preferably fluorine-containing compound (2)) is high on the exposed surface side. It may be. When a surface treatment layer consists of two or more layers, the lower layer which contact | connects a base material and the upper layer (which comprises an exposed surface) located in the surface of a surface treatment layer are included. Preferably, the lower layer contains one compound and the upper layer contains the other compound. More preferably, the lower layer contains a large amount of perfluoro (poly) ether group-containing silane compound (1), and the upper layer contains a large amount of fluorine-containing compound (2). In other words, the content ratio of the upper fluorine compound (2) is higher than the content ratio of the lower fluorine compound (2). In addition, as long as the content rate of the fluorine-containing compound in the surface treatment layer is significantly different between the lower layer and the upper layer, the boundary between the lower layer and the upper layer may not necessarily be clear, or 1 between the lower layer and the upper layer. There may be more than one intermediate layer.

  In a preferred embodiment, the layer formed from the surface treatment agent includes a lower layer in contact with the substrate and an upper layer located on the surface of the layer formed from the surface treatment agent, and contains the lower fluorine-containing compound (2). The content ratio of the upper fluorine compound (2) is higher than the ratio.

  Next, the film is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.

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

  When moisture is supplied to the precursor film, water acts on the hydrolyzable group bonded to Si of the perfluoro (poly) ether group-containing silane compound in the surface treatment agent of the present invention, and the compound is rapidly removed. It is thought that it can be hydrolyzed.

  The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

  Next, the precursor film is heated on the surface of the base material in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure. Although the time at this time is not specifically limited, For example, 30 minutes-5 hours, Preferably, 1-3 hours may be sufficient.

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

  Superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point, and exceeds 100 ° C. under normal pressure, generally 500 ° C. or lower, for example, 300 ° C. or lower, and has a boiling point. It is a gas that has become an unsaturated water vapor pressure by heating to a temperature exceeding. When the substrate on which the precursor film is formed is exposed to superheated water vapor, first, dew condensation occurs on the surface of the precursor film due to the temperature difference between the superheated water vapor and the relatively low temperature precursor film. Moisture is supplied to the membrane. Eventually, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film is vaporized in a dry atmosphere by the superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the amount of moisture on the surface of the precursor film is reduced, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam, thereby the temperature of the superheated steam ( It will be heated to a temperature exceeding 100 ° C. under normal pressure. Therefore, if superheated steam is used, moisture supply and drying heating can be carried out continuously only by exposing the substrate on which the precursor film is formed to superheated steam.

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

  As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer obtained by this has both high surface slipperiness and high friction durability. In addition to high friction durability, this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the surface treatment agent used. As a functional thin film, it can be waterproof (to prevent water from entering electronic parts, etc.), surface slippery (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch to fingers). It can be suitably used.

  The article having a surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of the optical member include the following optical members: For example, a cathode ray tube (CRT: eg, TV, personal computer monitor), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection type Display, display such as fluorescent display tube (VFD), field emission display (FED), or front protective plate, antireflection plate, polarizing plate, antiglare plate, or antireflection film treatment on the surface of these displays A lens such as glasses; a touch panel sheet of a device such as a mobile phone or a personal digital assistant; a disc surface of an optical disc such as a Blu-ray (registered trademark) disc, a DVD disc, a CD-R, or an MO; Optical fa Bar; the display surface of the watch, such as.

  Other articles having a surface treatment layer obtained by the present invention may include ceramic products, coated surfaces, fabric products, leather products, medical products, plasters and the like.

  The article having the 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 preferably in the range of 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability, and antifouling properties.

  Hereinabove, the articles obtained using the surface treatment agent of the present invention have been described in detail. In addition, the use of the surface treating agent of the present invention, the method of use or the method of manufacturing the article are not limited to those exemplified above.

The perfluoro (poly) ether group-containing silane compound, the production method thereof, and the surface treatment agent including the perfluoro (poly) ether group according to the present invention will be described more specifically through the following examples, but the present invention is limited to these examples. It is not a thing. In this example, four types of repeating units (CF ₂ O), (CF ₂ CF ₂ O), (CF ₂ CF ₂ CF ₂ O) and (CF ₂ CF ₂ CF ₂ ) constituting the perfluoropolyether are used. The order of presence of CF ₂ O) is arbitrary. Moreover, the formula showing a compound shows an average composition.

Example 1
Perfluoropolyether group-containing silane compound (A) and perfluoropolyether compound (D) having the following average composition in a mass ratio of 2: 1 (concentration 20 wt% (compound (A) and compound (D)) The surface treatment agent was prepared by dissolving in hydrofluoroether (manufactured by 3M, Novec HFE7200). The prepared surface treatment agent was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm). The processing conditions for vacuum deposition were set at a pressure of 3.0 × 10 ⁻³ Pa. First, silicon dioxide was deposited on the surface of the chemically tempered glass by an electron beam deposition method, and then one piece of chemically tempered glass (55 mm × 100 mm). ) 2 mg (that is, containing 0.4 mg of a mixture of the compound (A) and the compound (D)) was deposited. Thereafter, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%.
・ Perfluoropolyether group-containing silane compound (A)
CF ₃ O (CF ₂ CF ₂ O) ₂₀ (CF ₂ O) ₁₆ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃
(Note that the average composition, but contained repeating units 0.18 units of _{(CF 2 CF 2 CF 2 CF} 2 O repeating units 0.17 units and (CF ₂ CF ₂ CF ₂ O) of) , Omitted because of the trace amount.)
・ Perfluoropolyether group-containing alcohol compound (D)
CF ₃ O (CF ₂ CF ₂ O) ₁₉ (CF ₂ O) ₁₆ CF ₂ CH ₂ OH

Example 2
A surface treatment agent was prepared in the same manner as in Example 1 except that a perfluoropolyether group-containing silane compound (B) having the following average composition was used instead of the compound (A), and a surface treatment layer Formed.
・ Perfluoropolyether group-containing silane compound (B)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃

（式中、ｍは１〜６の整数である。） Example 3
A surface treatment agent was prepared in the same manner as in Example 1 except that a perfluoropolyether group-containing silane compound (C) having the following average composition was used instead of the compound (A), and a surface treatment layer Formed.
・ Perfluoropolyether group-containing silane compound (C)

(In the formula, m is an integer of 1 to 6.)

Example 4
A surface treatment agent was prepared in the same manner as in Example 1 except that a perfluoropolyether group-containing silane compound (E) having the following average composition was used instead of the compound (D), and a surface treatment layer Formed.
・ Perfluoropolyether group-containing alcohol compound (E)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ OH

Example 5
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 4 except that the compound (B) was used instead of the compound (A).

Example 6
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 4 except that the compound (C) was used instead of the compound (A).

Example 7
A surface treatment agent was prepared in the same manner as in Example 1 except that a perfluoropolyether group-containing silane compound (F) having the following average composition was used instead of the compound (D). Formed.
・ Perfluoropolyether group-containing alcohol compound (F)
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₀ CF ₂ CF ₂ CH ₂ OH

Example 8
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 7 except that the compound (B) was used instead of the compound (A).

Example 9
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 7 except that the compound (C) was used instead of the compound (A).

Comparative Example 1
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (G) having the following average composition was used instead of the compound (D).
・ Perfluoropolyether compounds (G)
CF ₃ O (CF ₂ CF ₂ O) ₂₀ (CF ₂ O) ₁₉ CF ₃
(Note that the average composition contained a small amount of repeating units of (CF ₂ CF ₂ CF ₂ CF ₂ O) and (CF ₂ CF ₂ CF ₂ O), but was omitted.)

Comparative Example 2
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1 except that the compound (B) was used instead of the compound (A).

Comparative Example 3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1 except that the compound (C) was used instead of the compound (A).

Comparative Example 4
The surface treatment layer was prepared in the same manner as in Example 1 except that the surface treatment agent was prepared by dissolving the compound (A) in hydrofluoroether (manufactured by 3M, Novec HFE7200) to a concentration of 20 wt%. The surface treatment agent prepared above was vacuum-deposited on chemically strengthened glass (manufactured by Corning, “Gorilla” glass, thickness 0.7 mm). ⁻³ Pa, first, silicon dioxide was vapor-deposited on the surface of the chemically strengthened glass by an electron beam evaporation method, and then 2 mg of surface treatment agent (that is, compound (A) per chemically strengthened glass (55 mm × 100 mm)). Then, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere at a temperature of 20 ° C. and a humidity of 65%.

Comparative Example 5
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 4 except that the compound (B) was used in place of the compound (A).

Comparative Example 6
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 4 except that the compound (C) was used instead of the compound (A).

-Friction durability evaluation About the surface treatment layer formed in the base-material surface in the said Example and comparative example, the static contact angle of water was measured. The static contact angle of water was measured with 1 μL of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).

  First, as an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured with nothing touching the surface yet (the number of frictions was zero).

  Then, steel wool friction durability evaluation was implemented as friction durability evaluation. Specifically, the base material on which the surface treatment layer is formed is horizontally arranged, and steel wool (count # 0000, dimensions 5 mm × 10 mm × 10 mm) is brought into contact with the exposed upper surface of the surface treatment layer, and 1,000 gf of the steel wool is placed thereon. A load was applied, and then the steel wool was reciprocated at a speed of 140 mm / sec with the load applied. The static contact angle (degree) of water was measured at every fixed number of reciprocations. The evaluation was stopped when the measured value of the contact angle became less than 100 degrees or when the number of frictions exceeded 20000. The results are shown in Table 1 and Table 2 below.

  As can be understood from Table 1 and Table 2 above, Examples 1 to 9 in which the perfluoropolyether group-containing silane compound of the present invention is mixed with the perfluoropolyether group-containing alcohol compound, It was confirmed that the friction durability was remarkably improved as compared with Comparative Examples 1 to 3 in which a fluoropolyether compound was mixed or Comparative Examples 4 to 6 containing only a perfluoropolyether group-containing silane compound. Although the present invention is not bound by any theory, this is because the functional groups such as alcohols interact with oxygen atoms of the perfluoropolyether chain forming the layer and hydrogen bonds and the like, and the carrying force on the layer is large. It is considered that the wear resistance was improved.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for forming a surface treatment layer on a variety of substrates, particularly on the surface of optical members that require transparency.

Claims (30)

(1) At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formulas (A1), (A2), (B1), (B2), (C1) and (C2):

[Where:
PFPE is independently at each _{occurrence, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - represents, here, a, b, c, and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, and d is 1 or more, and the subscripts a, b, c, or d are attached to parentheses. The order of presence of each recurring unit enclosed is arbitrary in the formula;
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 1 n R 2}} 3-n) independently for each unit, an integer from 0 to 3;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one R ² is present;
Each X ⁴ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
X ⁵ each independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer of 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
However, in one R ^a , the sum of p, q and r is 3, and in formulas (C1) and (C2), there is at least one R ⁷² ;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
However, the sum of k, l, and m is 3 in the unit enclosed in parentheses with γ. ]
And (2) at least one fluorine-containing compound represented by any of the following formulas (D1), (D2), (E1), (E2), (F1), (F2), (G1) and (G2) Compound:

[Where:
A is independently at each _{^{occurrence, -OH, -SH, -COOR 5,}} -COSH, -CONH 2, -P (O) (OH) 2, -OP (O) (OH) 2, -NR ⁵ ₂ ,

Represents;
Each R ⁵ independently represents a hydrogen atom or a lower alkyl group;
X ¹ represents O or S;
M ₁ and M ₂ each independently represents a hydrogen atom or an alkali metal;
Y represents a single bond or a divalent organic group independently at each occurrence;
PFPE is independently at each _{occurrence, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - represents, here, a, b, c, and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, and d is 1 or more, and the subscripts a, b, c, or d are attached to parentheses. The order of presence of each recurring unit enclosed is arbitrary in the formula;
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
Each X ⁸ independently represents a single bond or a divalent to 10-valent organic group;
each δ is independently an integer from 1 to 9;
each δ ′ is independently an integer from 1 to 9;
Each X ³ independently represents a single bond or a divalent to 10-valent organic group;
each ε is independently an integer from 1 to 9;
each ε ′ is independently an integer from 1 to 9;
Each X ⁹ independently represents a single bond or a divalent to 10-valent organic group;
each χ is independently an integer from 1 to 9;
each χ ′ is independently an integer from 1 to 9;
R ^d independently represents at each occurrence —Z—SiR ⁷⁴ _{p ′} R ⁷⁵ _{q ′} R ⁷⁶ _{r ′} ;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷⁴ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is synonymous with R ^d ;
In R ^d , the maximum number of Si linked in a straight chain via the Z group is 5;
R ⁷⁵ is independently at each ^occurrence, represents ^-X 10 -Y-A;
X ¹⁰ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence;
R ⁷⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p ′ is independently an integer from 0 to 3 at each occurrence;
q ′ is independently an integer from 0 to 3 at each occurrence;
r ′ is independently an integer from 0 to 3 at each occurrence;
Provided that in one R ^d , the sum of p ′, q ′ and r ′ is 3, and in formulas (F1) and (F2), there is at least one R ⁷⁵ ;
R ^e is, independently at each ^occurrence, represents ^-X 10 -Y-A;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
Provided that the sum of k, l and m is 3 in the unit enclosed in parentheses with χ;
Each X ⁶ independently represents a single bond or a divalent to 10-valent organic group;
each θ is independently an integer from 1 to 9;
each θ ′ is independently an integer from 1 to 9;
R ⁹¹ represents a fluorine atom, —CHF ₂ or —CF ₃ ;
Rf ′ represents a C 1-20 perfluoroalkylene group. ]
A surface treatment agent comprising:   The surface treating agent according to claim 1, wherein Rf is a C 1-16 perfluoroalkyl group. In the perfluoro (poly) ether group-containing silane compound, PFPE has the following formula (a), (b) or (c):
(A):-(OC ₃ F ₆ ) _b-
[In formula (a), b is an integer of 1 or more and 200 or less];
_{(B) :-( OC 4 F 8} ) a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d -
[In Formula (b), a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, and a, b, c and the sum of d is 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix a, b, c or d is arbitrary in the formula];
_{(C) :-( OC 2 F 4} -R 8) n "-
[In formula (c), R ⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ ;
n ″ is an integer of 2 to 100.]
The surface treating agent according to claim 1 or 2, which is a group represented by the formula: In PFPE in a perfluoro (poly) ether group-containing silane compound:
OC ₄ F ₈ is OCF ₂ CF ₂ CF ₂ CF ₂ ,
OC ₃ F ₆ is OCF ₂ CF ₂ CF ₂ ,
OC ₂ F ₄ is OCF ₂ CF ₂ ,
The surface treating agent according to any one of claims 1 to 3. X ⁴ , X ⁵ and X ⁷ are each independently a divalent to tetravalent organic group, α, β and γ are each independently 1 to 3, α ′, β ′ and γ The surface treating agent according to any one of claims 1 to 4, wherein 'is 1. X ⁴ , X ⁵ and X ⁷ are divalent organic groups, α, β and γ are 1, and α ′, β ′ and γ ′ are 1. Surface treatment agent. X ⁴ , X ⁵ and X ⁷ are each independently-(R ³¹ ) _{p "} -(X ^a ) _q" -
[Where:
R ³¹ represents a single bond, — (CH ₂ ) _{s ′} — (wherein s ′ is an integer of 1 to 20) or an o-, m-, or p-phenylene group;
^Xa represents-( ^Xb ) _l'- (wherein l 'is an integer of 1 to 10);
X ^b is independently at each occurrence, —O—, —S—, o—, m- or p-phenylene group, —C (O) O—, —Si (R ³³ ) ₂ —, — ( Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ — (wherein m ′ is an integer of 1 to 100), —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ —. And represents a group selected from the group consisting of — (CH ₂ ) _{n ′} — (wherein n ′ is an integer of 1 to 20);
R ³³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group at each occurrence;
R ³⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group at each occurrence;
p ″ is 0 or 1;
q ″ is 0 or 1;
Here, at least one of p ″ and q ″ is 1, and the order of presence of each repeating unit in parentheses with p ″ and q ″ is arbitrary in the formula;
R ³¹ and X ^a may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group. ]
The surface treating agent according to any one of claims 1 to 6, which is a group represented by: X ⁴ , X ⁵ and X ⁷ are each independently:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF ₂ -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -
_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 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 -,

The surface treating agent according to any one of claims 1 to 7, which is selected from the group consisting of: X ⁴ is —O—CFR ¹³ — (CF ₂ ) _e —,
R ¹³ represents a fluorine atom or a lower fluoroalkyl group,
e is 0 or 1;
The surface treating agent according to claim 1. X ² is — (CH ₂ ) _s —,
s is an integer from 0 to 2,
The perfluoro (poly) ether group containing silane compound in any one of Claims 1-9. The perfluoro (poly) ether group-containing silane compound according to any one of claims 1 to 10, wherein in formulas (C1) and (C2), k is 3, and q is 3 in ^Ra . 12. The perfluoro (poly) ether group-containing silane compound according to claim 1, wherein X ⁴ , X ^5, and X ⁷ are each independently a trivalent to trivalent organic group. X ⁴ , X ⁵ and X ⁷ are each independently:

[Wherein, in each group, at least one of T is the following group bonded to PFPE in the formulas (A1), (A2), (B1), (B2), (C1) and (C2):
_{-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 is bonded to a carbon atom or a Si atom in formulas (A1), (A2), (B1), (B2), (C1) and (C2) — (CH ₂ ) _n — (N is an integer of 2 to 6), and the rest are each independently a methyl group, a phenyl group or an alkoxy group,
R ⁴¹ is 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,
R ⁴² represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group. ]
The surface treating agent according to any one of claims 1 to 12, which is selected from the group consisting of: A is —OH, —SH, —P (O) (OH) ₂ , —OP (O) (OH) ₂ , —NR ⁵ ₂ , or

The surface treating agent according to any one of claims 1 to 13, which is   The surface treatment according to any one of claims 1 to 14, wherein a mass ratio of (1) perfluoro (poly) ether group-containing silane compound and (2) fluorine-containing compound is 1:50 to 50: 1. Agent.   The surface treatment according to any one of claims 1 to 15, wherein a mass ratio of (1) perfluoro (poly) ether group-containing silane compound and (2) fluorine-containing compound is 1:10 to 10: 1. Agent.   The surface treatment according to any one of claims 1 to 16, wherein a mass ratio of (1) perfluoro (poly) ether group-containing silane compound and (2) fluorine-containing compound is 1: 4 to 4: 1. Agent.   The surface treating agent according to any one of claims 1 to 17, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. The fluorine-containing oil has the formula (3):
^{_{R 21 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -R 22
... (3)
[Where:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom, which may be substituted with one or more fluorine atoms;
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1 and the order of presence of each repeating unit in parentheses with the subscript a ′, b ′, c ′ or d ′ is given by the formula Is optional. ]
The surface treating agent according to claim 1, which is one or more compounds represented by the formula: The fluorine-containing oil has the formula (3a) or (3b):
^{_{R 21 - (OCF 2 CF 2}} CF 2) b '' -R 22 ··· (3a)
^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) a '' - (OCF 2 CF 2 CF 2) b '' - (OCF 2 CF 2) c '' - (OCF 2) d '' -R 22 · .. (3b)
[Where:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom, which may be substituted with one or more fluorine atoms;
In formula (3a), b ″ is an integer of 1 to 100;
In formula (3b), a ″ and b ″ are each independently an integer of 0 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less;
The order of presence of each repeating unit in parentheses with the suffix a ″, b ″, c ″ or d ″ is arbitrary in the formula. ]
The surface treating agent according to any one of claims 1 to 19, which is one or more compounds represented by:   Furthermore, the surface treating agent in any one of Claims 1-20 containing a solvent.   The surface treating agent according to any one of claims 1 to 21, which is used as an antifouling coating agent or a waterproof coating agent.   The surface treating agent according to any one of claims 1 to 22, which is used for vacuum deposition.   The pellet containing the surface treating agent in any one of Claims 1-23.   An article comprising a substrate and a layer formed from the surface treatment agent according to any one of claims 1 to 23 on the surface of the substrate.   The layer formed from the surface treatment agent includes a lower layer in contact with the base material and an upper layer located on the surface of the layer formed from the surface treatment agent. 26. The article of claim 25, wherein the compound content is higher.   27. The article of claim 25 or 26, wherein the substrate is glass or sapphire glass.   28. The article of claim 27, wherein the glass is a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.   The article according to any one of claims 25 to 28, wherein the article is an optical member.   30. The article according to any of claims 25 to 29, wherein the article is a display.