JP6631717B2 - Composition containing perfluoro (poly) ether-modified amidosilane compound - Google Patents

Description

  The present invention relates to a surface treatment agent comprising a perfluoro (poly) ether-modified amide silane compound and a carboxylic acid ester compound.

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

  As such a fluorinated silane compound, a hydrolyzable group having a perfluoro (poly) ether group in the molecular main chain and a terminal or a terminal portion of the fluorinated silane compound via an organic group containing an amide bond is provided. A perfluoro (poly) ether-modified amidosilane compound bonded to a Si atom having the compound is known (see Patent Documents 1 to 3). When a surface treatment agent containing this perfluoro (poly) ether-modified amide silane compound is applied to a substrate, the hydrolyzable group bonded to the Si atom is bonded by reacting with the substrate and between the compounds, A surface treatment layer may be formed.

JP-A-11-29585 JP-A-2000-14399 JP 2000-327772 A

  A layer obtained from a surface treatment agent containing a perfluoro (poly) ether-modified amide silane compound can exhibit functions such as water repellency, oil repellency, and antifouling property even in a thin film, and thus is required to have light transmittance and transparency. It is suitably used for optical members such as glasses and touch panels. In particular, in these applications, friction durability is required so that such a function can be maintained even when repeatedly subjected to friction.

  The present invention relates to a composition comprising a perfluoro (poly) ether-modified amidosilane compound capable of forming a layer having water repellency, oil repellency, antifouling property, waterproof property and high friction durability. The purpose is to provide.

  As a result of intensive studies, the present inventors have found that a surface treatment layer having high friction durability can be formed by using a composition containing a perfluoro (poly) ether-modified amide silane compound and a carboxylic acid ester compound. Thus, the present invention has been completed.

［式中：
Ｒｆ^１は、それぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
ＰＦＰＥ^１は、それぞれ独立して、−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−を表し、ここに、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり；
Ｘ^１は、単結合または２価の有機基を表し；
Ｒ^１は、−Ｘ^２−ＳｉＲ^ａ１ _ｌ１Ｒ^ｂ１ _ｍ１Ｒ^ｃ１ _ｎ１を表し；
Ｘ^２は、２価の有機基を表し；
Ｒ^ａ１は、各出現においてそれぞれ独立して、−Ｚ^１−ＳｉＲ^ａ２ _ｌ２Ｒ^ｂ２ _ｍ２Ｒ^ｃ２ _ｎ２を表し；
Ｚ^１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
Ｒ^ａ２は、各出現においてそれぞれ独立して、Ｒ^ａ１’を表し；
Ｒ^ａ１’は、Ｒ^ａ１と同意義であり；
Ｒ^ａ１中、Ｚ^１基を介して直鎖状に連結されるＳｉは最大で５個であり；
Ｒ^ｂ２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^ｃ２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；
ｌ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｎ２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^ｂ１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^ｃ１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；
ｌ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｎ１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^２は、水素原子、低級アルキル基またはフェニル基を表し；
ｐは、１または２である、
ただし、式中、少なくとも１つのＲ^ｂ１またはＲ^ｂ２が存在する。］
および
少なくとも１種の下記式（２）で表されるカルボン酸エステル化合物：

［式中：
Ｒ^３は、炭化水素基を表し；
Ｒ^４は、有機基を表す。］
を含み、式（１）で表されるパーフルオロ（ポリ）エーテル変性アミドシラン化合物と式（２）で表されるカルボン酸エステル化合物の総含有量に対する、式（２）で表されるカルボン酸エステル化合物の含有量が、４．１ｍｏｌ％以上３５ｍｏｌ％以下である、表面処理剤が提供される。That is, according to a first aspect of the present invention, at least one kind of perfluoro (poly) ether-modified amidosilane compound represented by the following formula (1):

[In the formula:
Rf ¹ each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
PFPE ¹ is independently-(OC ₆ F ₁₂ ) _a- (OC ₅ F ₁₀ ) _b- (OC ₄ F ₈ ) _c- (OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e − _{(OCF 2) f} - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula;
X ¹ represents a single bond or a divalent organic group;
R ¹ represents —X ² —SiR ^a11 _lR ^b1 _m1 R ^c1 _n1 ;
X ² represents a divalent organic group;
R ^a1 is independently at each ^occurrence, represents _{^{-Z 1 -SiR a2 l2 R b2 m2}} R c2 n2;
Z ¹ at each occurrence independently represents an oxygen atom or a divalent organic group;
R ^a2 independently at each occurrence represents R ^{a1 ′} ;
R ^{a1 ′} is as defined for R ^a1 ;
In R ^a1 , the number of ^Sis connected linearly via the Z ¹ group is at most 5;
R ^b2 independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ^c2 independently at each occurrence represents a hydrogen atom or a lower alkyl group;
12 is independently at each occurrence an integer from 0 to 3;
m2 is, independently at each occurrence, an integer from 0 to 3;
n2 is independently at each occurrence an integer from 0 to 3;
R ^b1 independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ^c1 at each occurrence independently represents a hydrogen atom or a lower alkyl group;
l1 is, independently at each occurrence, an integer from 0 to 3;
m1 is, independently at each occurrence, an integer from 0 to 3;
n1 is, independently at each occurrence, an integer from 0 to 3;
R ² represents a hydrogen atom, a lower alkyl group or a phenyl group;
p is 1 or 2;
However, in the formula, at least one R ^b1 or R ^b2 is present. ]
And at least one carboxylate compound represented by the following formula (2):

[In the formula:
R ³ represents a hydrocarbon group;
R ⁴ represents an organic group. ]
And a carboxylate represented by the formula (2) with respect to the total content of the perfluoro (poly) ether-modified amidesilane compound represented by the formula (1) and the carboxylate compound represented by the formula (2) A surface treatment agent having a compound content of 4.1 mol% or more and 35 mol% or less is provided.

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

  By using the composition containing the perfluoro (poly) ether-modified amide silane compound of the present invention and a carboxylic acid ester compound, a surface treatment layer having high friction durability can be formed.

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

  As used herein, “monovalent organic group” or “divalent organic group” means a monovalent or divalent group containing carbon, respectively. Such a monovalent organic group is not particularly limited, but includes a hydrocarbon group. The divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.

  As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, and is a group obtained by removing one hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be substituted by one or more substituents, a hydrocarbon group having 1 to 20 carbon atoms, for example, an aliphatic hydrocarbon group, And an aromatic hydrocarbon group. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. Also, the hydrocarbon group may contain one or more ring structures. In addition, such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain.

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

In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted unless otherwise specified. Examples of the substituent of the group include, but are not particularly limited to, one or more groups selected from a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. No.

および
下記式（２）で表される少なくとも１種のアミン化合物：

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 at least one perfluoro (poly) ether-modified amidosilane compound represented by the following formula (1):
Amidosilane compounds:

And at least one amine compound represented by the following formula (2):

(Hereinafter, also referred to as “surface treatment agent of the present invention”).

Hereinafter, the compound represented by the formula (1) will be described.

In the formula (1), Rf ¹ represents a C _1-16 alkyl group which may be substituted with one or more fluorine atoms.

"Alkyl group of C _1-16" in one or more of the alkyl group optionally C _1-16 optionally substituted by a fluorine atom described above may be straight chain, be branched-chain , preferably, linear or branched alkyl group of _{C 1-6,} and in particular a _{C 1-3} alkyl group, more preferably an alkyl group of _{C 1-3} straight chain.

Rf ¹ is preferably a C _1-16 alkyl group substituted by one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, and still more preferably Is a C _1-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be linear or branched, and preferably is a linear or branched C _1-6 perfluoroalkyl group, particularly _1-3 is a perfluoroalkyl group, more preferably a perfluoroalkyl group of _{C 1-3} straight-chain, specifically _{-CF 3, -CF} 2 CF 3 or _-CF 2 _CF 2 _{CF 3,} is there.

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

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

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

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

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

In PFPE ¹ , the ratio of e to f (hereinafter, referred to as “e / f ratio” or “EM ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, more preferably It is 0.2 or more and 2 or less, more preferably 0.2 or more and 1.5 or less, and even more preferably 0.2 or more and 0.85 or less. By setting the e / f ratio to 10 or less, the surface-treated layer obtained from this compound is further improved in slipperiness, friction durability and chemical resistance (for example, durability against artificial sweat). As the e / f ratio is smaller, the slipperiness and friction durability of the surface treatment layer are more improved. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further increased. The greater the e / f ratio, the better the stability of the compound.

In the above formula (1), X ¹ represents a single bond or a divalent organic group.

Examples of the divalent organic group for X ¹ include, but are not particularly limited to,
_{^{- (CR 8 2) k1 -}} (O) k2 - (NR 9) k3 -,
[In the formula:
R ⁸ is each independently a hydrogen atom or a fluorine atom;
R ⁹ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k1 is an integer from 1 to 20;
k2 is an integer from 0 to 10;
k3 is an integer from 0 to 10;
Here, the order of the respective recurring units enclosed in parentheses with k1, k2 or k3 added is arbitrary in the formula. ]
And the group represented by

In a preferred embodiment, X ¹ is
- _{(CF 2) k1 '-} or _{- (CF 2) k1' -} (O) k2 '-
[In the formula:
k1 ′ is an integer from 1 to 6;
k2 ′ is an integer of 1 to 3;
Here, the order of the respective repeating units enclosed in parentheses with k1 'or k2' is arbitrary in the formula. ]
It is.

In the above formula (1), R ¹ each independently represents —X ² —SiR ^a11 ₁₁ R ^b1 _m1 R ^c1 _n1 .

The ^{X 2} represents a divalent organic group.

Examples of the divalent organic group represented by X ² include, but are not particularly limited to,
_{^{- (CR 10 2) k4 -}} (O) k5 - (NR 11) k6 -,
[In the formula:
R ¹⁰ is each independently a hydrogen atom or a fluorine atom;
R ¹¹ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k4 is an integer from 1 to 20;
k5 is an integer from 0 to 10;
k6 is an integer from 0 to 10;
Here, the order of the respective recurring units enclosed in parentheses by adding k4, k5 or k6 is arbitrary in the formula. ]
And the group represented by

In a preferred embodiment, X ² is
— (CH ₂ ) _{k4 ′} — or — (CH ₂ ) _{k4 ′} —O _{k5 ′} —
[In the formula:
k4 ′ is an integer from 1 to 6;
k5 ′ is an integer of 1 to 3;
Here, the order in which each of the repeating units enclosed in parentheses with k4 'or k5' is arbitrary in the formula. ]
It is.

In one aspect, X ¹ is
- _{(CF 2) k1 '-} or _{- (CF 2) k1' -} (O) k2 '-
[In the formula:
k1 ′ is an integer from 1 to 6;
k2 ′ is an integer of 1 to 3;
Here, the order of the respective repeating units enclosed in parentheses with k1 'or k2' is arbitrary in the formula. ]
And
X ² is,
— (CH ₂ ) _{k4 ′} — or — (CH ₂ ) _{k4 ′} —O _{k5 ′} —
[In the formula:
k4 ′ is an integer from 1 to 6;
k5 ′ is an integer of 1 to 3;
Here, the order in which each of the repeating units enclosed in parentheses with k4 'or k5' is arbitrary in the formula. ]
It is.

The ^{R a1} is independently at each occurrence ^{represents _{-Z 1 -SiR a2 l2 R b2 m2}} R c2 n2.

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

Z ¹ is preferably a divalent organic group. In one embodiment, those not forming a siloxane bond with the Si atom to which R ^a1 is bonded in Formula (1) are not included.

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

In the formula, R ^a2 independently represents R ^{a1 ′} at each occurrence. R ^{a1 ′} has the same meaning as R ^a1 .

Among R ^a1, Si is connected to the linear via Z ¹ group is five at the maximum. That is, in the ^{R a1,} when ^{R a2} are present at least ^one, but Si atom to be linked via ^{Z 1} group in ^{R a1} linearized there are two or more, via such ^{Z 1} group The maximum number of Si atoms connected in a straight line is five. The "number of Si atoms linearly linked via a ^{Z 1} group in ^{R a1" is} equal to the repetition number of ^-Z 1 -Si- being linearly linked in a ^{R a1} Become.

For example, an example in which the Si atoms are linked via Z ¹ group in a R ^a1 below (simply by the following indicated as "Z").

In the above formula, * means a site bonded to Si in the main chain, ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of a Si atom are ... In this case, it means the end point of the repetition of ZSi. The number on the right shoulder of Si means the number of occurrences of Si linked linearly via the Z group counted from *. That is, in the chain in which ZSi repetition is completed in Si ² , the “number of Si atoms linked linearly via the Z ¹ group in R ^a1 ” is two, and similarly, Si ³ , Si ^{3 The} chains whose ZSi repetition ends at ⁴ and Si ⁵ have “the number of Si atoms connected linearly via the Z ¹ group in R ^a1 ” of 3, 4 and 5, respectively. Note that, as is clear from the above formula, ^a plurality of ZSi chains exist in Ra, but they do not all need to have the same length, and each may have an arbitrary length.

In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z ¹ group in R ^a1 ” is 1 (left formula) or 2 ( (Right formula).

In one embodiment, the number of Si atoms linked linearly via the Z ¹ group in R ^a1 is 1 or 2, preferably 1.

R ^b2 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.

The term “hydrolyzable group” as used herein means a group that can undergo a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (wherein R is substituted or unsubstituted) Represents an alkyl group having 1 to 4 carbon atoms), and is preferably -OR (alkoxy group). Examples of R include 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 formed by hydrolysis of a hydrolyzable group.

Preferably, R ^b2 is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, still more preferably a methyl group.

In the formula, R ^c2 at each occurrence independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group.

  Wherein l2 is independently at each occurrence an integer from 0 to 3; m2 is independently at each occurrence an integer from 0 to 3; n2 is independently at each occurrence And an integer of 0 to 3. However, the sum of l2, m2 and n2 is 3.

In a preferred ^{embodiment, '(if} there is no ^{R a1', R a1)} end in ^{R a1 R a1} in said m2 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred ^embodiment, at least one of the end portions of the ^{R a1 _{is, -Si (-Z 1 -SiR b2 m2}} R c2 n2) 2 or _{^{-Si (-Z 1 -SiR b2 m2 R}} c2 n2) 3, preferably - Si may be _{^{(-Z 1 -SiR b2 m2 R c2}} n2) 3. _{^{Wherein, (- Z 1 -SiR b2 m2}} R c2 n2) units are preferably ^(-Z 1 -SiR ^b2 _3). In a further preferred embodiment, the distal end of the ^{R a,} all _{^{-Si (-Z 1 -SiR b2 m2 R}} c2 n2) 3, preferably may be _{^{-Si (-Z 1 -SiR b2 3)}} 3.

In one embodiment, in Formula (1) above, at least one R ^b2 is present.

In the above formula, R ^b1 at each occurrence independently represents a hydroxyl group or a hydrolyzable group.

^Rb1 is preferably a hydroxyl group, -OR, -OCOR, -ON = 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), and is 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 formed by hydrolysis of a hydrolyzable group. More preferably, R ^b1 is —OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, still more preferably a methyl group.

In the above formula, R ^c1 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, further preferably a methyl group.

  Wherein l1 is independently at each occurrence an integer from 0 to 3; m1 is independently at each occurrence an integer from 0 to 3; n1 is independently at each occurrence And an integer of 0 to 3. However, the sum of l1, m1, and n1 is 3.

  In one aspect, 11 is 0. In another embodiment, 11 is 3.

In the above formula (1), R ² represents a hydrogen atom, a lower alkyl group or a phenyl group. A lower alkyl group preferably represents a C _1-6 alkyl group. R ² is preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group.

In one aspect, R ² is a hydrogen atom.

In another aspect, R ² is a lower alkyl group or a phenyl group. In a preferred embodiment, R ² can be a C _1-6 alkyl or phenyl group, preferably a C _1-3 alkyl or phenyl group, more preferably an ethyl or methyl group, even more preferably a methyl group.

  In the above formula (1), p is 1 or 2. In one aspect, p is 1.

In the above formula (1), at least one R ^b1 or R ^b2 exists.

In the perfluoro (poly) ether-modified amide silane compound represented by the above formula, the average molecular weight of ^one part of Rf ¹ -PFPE is not particularly limited, but is 500 to 30,000, preferably 1,000 to 20. 2,000, more preferably 2,000 to 15,000.

The perfluoro (poly) ether-modified amide silane compound represented by the above formula is not particularly limited, but may have an average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . Within this range, it is preferable to have an average molecular weight of 500 to 30,000, preferably 1,500 to 20,000, more preferably 2,500 to 15,000, from the viewpoint of friction durability. In the present invention, “average molecular weight” refers to a number average molecular weight, and “average molecular weight” is a value measured by ¹⁹ F-NMR.

  The perfluoro (poly) ether-modified amidosilane compound represented by the above formula (1) can be produced by a condensation reaction between a perfluorocarboxylic acid derivative and an aminosilane having a hydrolyzable group (see Patent Documents 1 and 2). ).

Hereinafter, the compound represented by the formula (2) will be described.

In the above formula (2), R ³ represents a hydrocarbon group.

R ³ is preferably a lower alkyl group or a phenyl group. The lower alkyl group is preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group, still more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

In the above formula (2), R ⁴ represents a monovalent organic group.

R ⁴ is ^preferably, Rf ² -PFPE 2 -X ³ - can be.

In the above formula (2), Rf ² represents a C _1-16 alkyl group which may be substituted by one or more fluorine atoms.

"Alkyl group of C _1-16" in one or more of the alkyl group optionally C _1-16 optionally substituted by a fluorine atom described above may be straight chain, be branched-chain , preferably, linear or branched alkyl group of _{C 1-6,} and in particular a _{C 1-3} alkyl group, more preferably an alkyl group of _{C 1-3} straight chain.

Rf ² is preferably a C _1-16 alkyl group substituted by one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, and still more preferably Is a C _1-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be linear or branched, and preferably is a linear or branched C _1-6 perfluoroalkyl group, particularly _1-3 is a perfluoroalkyl group, more preferably a perfluoroalkyl group of _{C 1-3} straight-chain, specifically _{-CF 3, -CF} 2 CF 3 or _-CF 2 _CF 2 _{CF 3,} is there.

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

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

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

In another embodiment, PFPE ² _{is, - (OC 4 F 8)} c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - ( wherein, c and d, respectively E and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts c, d, and The order in which each of the repeating units enclosed in parentheses with e or f is arbitrary in the formula). Preferably, PFPE ² _{is, - (OCF 2 CF 2 CF} 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a. In one embodiment, PFPE ² _{is, - (OC 2 F 4)} e - (OCF 2) f - ( wherein, e and f are 1 to 200 independently, 200 or less preferably 5 or more, more It is preferably an integer of 10 or more and 200 or less, and the order of each repeating unit enclosed in parentheses with a subscript e or f may be arbitrary in the formula).

In yet another embodiment, PFPE ^{2 _{is, - (R 6 -R 7)}} q - is a group represented by. Wherein R ⁶ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or is independently selected from these groups. Is a combination of two or three groups. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of two or three groups independently selected from these groups. is there. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but is, for example, —OC ₂ F ₄ OC ₃ F ₆ —, —OC _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, —OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ —, —OC ₃ F ₆ OC _{2 F 4 OC 3 F 6 -,} - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _{-OC 4 F 8 OC 2 F 4} OC 2 F 4 - , and the like. The above q is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be any of a straight chain or a branched chain, and is preferably a straight chain. . In this embodiment, PFPE ² is _{preferably, - (OC 2 F 4 -OC} 3 F 6) q - or _{- (OC 2 F 4 -OC 4} F 8) q - is.

In the above formula (2), X ³ represents a single bond or a divalent organic group.

Examples of the divalent organic group for X ³ include, but are not particularly limited to,
_{^{- (CR 8 2) k1 -}} (O) k2 - (NR 9) k3 -,
[In the formula:
R ⁸ is each independently a hydrogen atom or a fluorine atom;
R ⁹ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k1 is an integer from 1 to 20;
k2 is an integer from 0 to 10;
k3 is an integer from 0 to 10;
Here, the order of the respective recurring units enclosed in parentheses with k1, k2 or k3 added is arbitrary in the formula. ]
And the group represented by

In a preferred embodiment, X ³ is
- _{(CF 2) k1 '-} or _{- (CF 2) k1' -} (O) k2 '-
[In the formula:
k1 ′ is an integer from 1 to 6;
k2 ′ is an integer of 1 to 3;
Here, the order of the respective repeating units enclosed in parentheses with k1 'or k2' is arbitrary in the formula. ]
It is.

Is, ^{Rf 1} -PFPE 1 -X 1 in the formula (1) - - as ^{Rf 2} -PFPE 2 -X ³ of ^{R 4} described above may be the same as or may be different.

In one ^embodiment, Rf ² -PFPE 2 -X ³ - and ^{Rf 1} -PFPE 1 -X 1 - is the same. In another ^embodiment, Rf ² -PFPE 2 -X ³ - and ^{Rf 1} -PFPE 1 -X 1 - is different.

In the carboxylic acid ester compound represented by the above formula (2), the average molecular weight of the Rf ² -PFPE ² moiety is not particularly limited, but is 500 to 30,000, preferably 1,000 to 20,000. And more preferably 2,000 to 15,000.

The carboxylic acid ester compound represented by the formula (2) is not particularly limited, but may have an average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . Within this range, it is preferable to have an average molecular weight of 500 to 30,000, preferably 1,500 to 20,000, more preferably 2,500 to 15,000, from the viewpoint of friction durability.

  The carboxylic acid ester compound of the above formula (2) may be a compound derived from a raw material compound when synthesizing at least one kind of perfluoro (poly) ether-modified amide silane compound represented by the above formula (1). And a carboxylic acid ester compound added separately. The separately added carboxylic acid ester compound may be the same compound as the carboxylic acid ester compound used in the synthesis, or may be a different compound.

  In one embodiment, in the surface treating agent of the present invention, the content of the carboxylic acid ester compound represented by the formula (2) is the same as the content of the perfluoro (poly) ether-modified amide silane compound represented by the formula (1) and the formula ( 4.1 mol% or more and 35 mol% or less, preferably 4.5 to 35 mol%, more preferably 4.5 to 30 mol%, still more preferably 5 to 35 mol% with respect to the total content of the carboxylic acid ester compound represented by 2). 0.0 mol% to 25 mol%, for example, 6.0 mol% or more, 8.0 mol% or more, or 10.0 mol% or more, and may be 20 mol% or less, 18 mol% or less, or 15 mol%. When the content is in such a range, the surface treatment agent of the present invention has high stability, and the friction durability of the surface treatment layer obtained from the surface treatment agent of the present invention is improved.

The surface treatment agent of the present invention may be diluted with a solvent. Such solvents include, but are not limited to, for example:
Perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-Tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeola H (trade name) or the like), 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, perfluoro benzene, methyl pentadecafluorooctyl heptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF ₂ CF ₂ CH ₂ OH, methyl trifluoromethanesulfonate, trifluoroacetate and _CF 3 O (C _{2 CF 2 O) m (CF} 2 O) n CF 2 CF 3 [ wherein, m and n are each independently 0 to 1000 integer bracketed denoted by the m or n The order in which each repeating unit is present 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 fluorine atom-containing solvent selected from the following.

  The surface treating agent of the present invention may contain other components in addition to the perfluoro (poly) ether-modified amide silane compound (1) and the carboxylic acid ester compound (2). Such other components are not particularly limited, but include, for example, other surface treatment compounds, (non-reactive) fluoropolyether compounds which can be understood as fluorinated oils, preferably perfluoro (poly) ether Examples thereof include a compound (hereinafter, referred to as “fluorinated oil”), a silicone compound (hereinafter, referred to as “silicone oil”) that can be understood as a silicone oil (hereinafter, referred to as “silicone oil”), and a catalyst.

［式中：
ＰＦＰＥ^３は、各出現においてそれぞれ独立して、式：
−（ＯＣ_６Ｆ_１２）_ａ１−（ＯＣ_５Ｆ_１０）_ｂ１−（ＯＣ_４Ｆ_８）_ｃ１−（ＯＣ_３Ｆ_６）_ｄ１−（ＯＣ_２Ｆ_４）_ｅ１−（ＯＣＦ_２）_ｆ１−
（式中、ａ１、ｂ１、ｃ１、ｄ１、ｅ１およびｆ１は、それぞれ独立して０以上２００以下の整数であって、ａ１、ｂ１、ｃ１、ｄ１、ｅ１およびｆ１の和は少なくとも１であり、ａ１、ｂ１、ｃ１、ｄ１、ｅ１またはｆ１を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
Ｒｆ^３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^２３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^２４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^２１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^２２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；
ｎ３は、（−ＳｉＲ^２３ _ｎ３Ｒ^２４ _３−ｎ３）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ｎ３が、１〜３の整数であり；
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^５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；
α１は、それぞれ独立して、１〜９の整数であり；
α１’は、それぞれ独立して、１〜９の整数であり；
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；
β１は、それぞれ独立して、１〜９の整数であり；
β１’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；
γ１は、それぞれ独立して、１〜９の整数であり；
γ１’は、それぞれ独立して、１〜９の整数であり；
Ｒ^ａ３は、各出現においてそれぞれ独立して、−Ｚ^３−ＳｉＲ^７１ _ｐ１Ｒ^７２ _ｑ１Ｒ^７３ _ｒ１を表し；
Ｚ^３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^ａ３’を表し；
Ｒ^ａ３’は、Ｒ^ａ３と同意義であり；
Ｒ^ａ３中、Ｚ^３基を介して直鎖状に連結されるＳｉは最大で５個であり；
Ｒ^７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、式（Ｃ１）および（Ｃ２）において、少なくとも１つのｑ１が１〜３の整数であり；
Ｒ^ｂ３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^ｃ３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋ１は、各出現においてそれぞれ独立して、１〜３の整数であり；
ｌ１は、各出現においてそれぞれ独立して、０〜２の整数であり；
ｍ１は、各出現においてそれぞれ独立して、０〜２の整数であり；
Ｘ^９は、それぞれ独立して、単結合または２〜１０価の有機基を表し；
δ１は、それぞれ独立して、１〜９の整数であり；
δ１’は、それぞれ独立して、１〜９の整数であり；
Ｒ^ｄ３は、各出現においてそれぞれ独立して、−Ｚ^４−ＣＲ^８１ _ｐ２Ｒ^８２ _ｑ２Ｒ^８３ _ｒ２を表し；
Ｚ^４は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
Ｒ^８１は、各出現においてそれぞれ独立して、Ｒ^ｄ３’を表し；
Ｒ^ｄ３’は、Ｒ^ｄ３と同意義であり；
Ｒ^ｄ３中、Ｚ^４基を介して直鎖状に連結されるＣは最大で５個であり；
Ｒ^８２は、各出現においてそれぞれ独立して、−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２を表し；
Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
Ｒ^８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎ２は、（−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２）単位毎に独立して、１〜３の整数を表し；
ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｎ２は１〜３の整数であり；
Ｒ^８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｒ^ｅ３は、各出現においてそれぞれ独立して、−Ｙ−ＳｉＲ^８５ _ｎ２Ｒ^８６ _３−ｎ２を表し；
Ｒ^ｆ３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。］
のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物が挙げられる。The other surface treatment compounds are not particularly limited, and include, for example, the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

[In the formula:
PFPE ³ is, independently at each occurrence, independently of the formula:
_{- (OC 6 F 12) a1} - (OC 5 F 10) b1 - (OC 4 F 8) c1 - (OC 3 F 6) d1 - (OC 2 F 4) e1 - (OCF 2) f1 -
(Wherein, a1, b1, c1, d1, e1, and f1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is at least 1, a1, b1, c1, d1, e1, or f1, and the order of the respective recurring units enclosed in parentheses is arbitrary in the formula.)
A group represented by:
Rf ³ independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R ²³ , at each occurrence, independently represents a hydroxyl group or a hydrolysable group;
R ²⁴ independently at each occurrence represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
R ²¹ represents, independently at each occurrence, a hydrogen atom or a halogen atom;
R ²² at each occurrence independently represents a hydrogen atom or a lower alkyl group;
n3 _{^{is, (- SiR 23 n3 R 24}} 3-n3) independently for each unit, an integer from 0 to 3;
However, in the formulas (A1), (A2), (B1) and (B2), at least one n3 is an integer of 1 to 3;
X ⁴ each independently represents a single bond or a divalent to divalent organic group;
X ⁵ independently at each occurrence represents a single bond or a divalent organic group;
t is, independently at each occurrence, an integer from 1 to 10;
α1 is each independently an integer from 1 to 9;
α1 ′ is each independently an integer from 1 to 9;
X ⁶ each independently represents a single bond or a divalent to divalent organic group;
β1 is each independently an integer from 1 to 9;
β1 ′ is each independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to divalent organic group;
γ1 is each independently an integer from 1 to 9;
γ1 ′ is each independently an integer from 1 to 9;
R ^a3 are each independently at each ^occurrence, represents _{^{-Z 3 -SiR 71 p1 R 72 q1}} R 73 r1;
Z ³ , at each occurrence, independently represents an oxygen atom or a divalent organic group;
R ⁷¹ independently at each occurrence represents R ^{a3 ′} ;
R ^{a3 ′} is as defined for R ^a3 ;
Among R ^a3, Si is connected to the linear through the Z ³ group is five at the maximum;
R ⁷² at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ⁷³ at each occurrence independently represents a hydrogen atom or a lower alkyl group;
p1 is, independently at each occurrence, an integer from 0 to 3;
q1 is, independently at each occurrence, an integer from 0 to 3;
r1 is, independently at each occurrence, an integer from 0 to 3;
Provided that, in the formulas (C1) and (C2), at least one q1 is an integer of 1 to 3;
R ^b3 represents, independently at each occurrence, a hydroxyl group or a hydrolysable group;
R ^c3 at each occurrence independently represents a hydrogen atom or a lower alkyl group;
k1 is, independently at each occurrence, an integer from 1 to 3;
11 is independently at each occurrence an integer from 0 to 2;
m1 is, independently at each occurrence, an integer from 0 to 2;
X ⁹ each independently represents a single bond or a divalent to divalent organic group;
δ1 is each independently an integer from 1 to 9;
δ1 ′ is each independently an integer from 1 to 9;
R ^d3 represents independently for each occurrence —Z ⁴ —CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 ;
Z ⁴ in each occurrence independently represents an oxygen atom or a divalent organic group;
R ⁸¹ at each occurrence independently represents R ^{d3 ′} ;
R ^{d3 ′} is as defined for R ^d3 ;
In R ^d3 , the number of C linked linearly via Z ⁴ group is at most 5;
R ⁸² at each occurrence independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
Y at each occurrence independently represents a divalent organic group;
R ⁸⁵ at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R ⁸⁶ at each occurrence independently represents a hydrogen atom or a lower alkyl group;
n2 _{^{is, (- Y-SiR 85 n2}} R 86 3-n2) independently for each unit represents an integer of 1 to 3;
Provided that in formulas (D1) and (D2), at least one n2 is an integer of 1 to 3;
R ⁸³ at each occurrence independently represents a hydrogen atom or a lower alkyl group;
p2 is, independently at each occurrence, an integer from 0 to 3;
q2 is, independently at each occurrence, an integer from 0 to 3;
r2 is, independently at each occurrence, an integer from 0 to 3;
R ^e3 independently at each occurrence represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
R ^f3 represents, independently at each occurrence, a hydrogen atom or a lower alkyl group;
k2 at each occurrence is, independently at each occurrence, an integer from 0 to 3;
12 is independently at each occurrence an integer from 0 to 3;
m2 is, independently at each occurrence, an integer from 0 to 3;
However, in the formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any one of the above.

The fluorinated oil is not particularly limited, and examples thereof include a compound represented by the following general formula (3) (perfluoro (poly) ether compound).
^{_{Rf 5 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -Rf 6 ··· (3)
In the formula, Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and Rf ⁶ is Represents an alkyl group having 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ 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 each independently represents 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 in which each of the repeating units enclosed in parentheses with the subscripts a ', b', c ', or d' is arbitrary in the formula. Among these repeating _{units, - (OC 4 F 8)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF _{(CF 3) CF (CF 3} )) -, - (OCF (C 2 F 5) CF 2) - and _{- (OCF 2 CF (C 2} F 5)) - but it may be any of, preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —. — (OC ₃ F ₆ ) — is 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 one of the following general formulas (3a) and (3b) (one or a mixture of two or more) May be included).
Rf ^5- (OCF ₂ CF ₂ CF ₂ ) _{b ″} -Rf ⁶ (3a)
_{^{Rf 5 - (OCF 2 CF 2}} CF 2 CF 2) a '' - (OCF 2 CF 2 CF 2) b '' - (OCF 2 CF 2) c '' - (OCF 2) d '' -Rf 6 · .. (3b)
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (3a), b ″ is an integer of 1 to 100; in formula (3b), a ″ and b ″ are Each is independently an integer of 1 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less. The order in which each of the repeating units enclosed in parentheses with the subscripts a ″, b ″, c ″, and d ″ is arbitrary in the formula.

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

  In the surface treatment agent of the present invention, the fluorinated oil is used in an amount of 100 parts by mass in total of the perfluoro (poly) ether-modified amide silane compound and the carboxylic acid ester compound (in the case of two or more types, respectively, the total thereof, and also The same), 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) to the compound represented by the general formula (3b) is preferably from 1: 1 to 1:30, and more preferably from 1: 1 to 1: 1. : 10 is more preferred. According to such a mass ratio, it is possible to obtain a surface treatment layer having an excellent balance between surface slipperiness and friction durability.

  In one embodiment, the fluorinated oil contains one or more compounds represented by the general formula (3b). In such an embodiment, the mass ratio of the total of the perfluoro (poly) ether-modified amide silane compound and the carboxylic acid ester compound in the surface treatment agent to the compound represented by the formula (3b) is from 4: 1 to 1: It is preferably 4.

  In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the average molecular weight of the fluorinated oil is set to be larger than the average molecular weights of the perfluoro (poly) ether-modified amide silane compound and the carboxylic acid ester compound. Is also good. With such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

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

  The fluorinated oil contributes to improving the surface slippage of the surface treatment layer.

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

  In the surface treatment agent of the present invention, the silicone oil is used in an amount of 100 parts by mass in total of the perfluoro (poly) ether-modified amide silane compound and the carboxylic acid ester compound (in the case of two or more kinds, the sum of these, and the same 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.).

  The catalyst promotes hydrolysis and dehydration condensation of the perfluoro (poly) ether-modified amide silane compound, and promotes formation of a surface treatment layer.

  The surface treating agent of the present invention may be in the form of one solution (or suspension or dispersion), or alternatively, a solution of the above-mentioned perfluoro (poly) ether-modified amidosilane compound and the above-mentioned carboxylic acid ester A form in which the compound and the solution of the compound are mixed immediately before use may be used.

  The surface treating agent of the present invention can be formed into pellets by impregnating a porous substance, for example, a porous ceramic material, a metal fiber, for example, a cotton wool solidified with a wool. The pellet can be used, for example, for vacuum deposition.

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

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

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

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

As the above glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass are preferable, soda lime glass chemically strengthened, alkali aluminosilicate glass chemically strengthened, and chemical bonding. Borosilicate glass is particularly preferred.
As the resin, acrylic resin and polycarbonate are preferable.

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

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

  As such a substrate, at least the surface portion may be made of a material having a hydroxyl group originally. Examples of such a material include glass, and a metal (especially a base metal) on which a natural oxide film or a thermal oxide film is formed on the surface, a ceramic, a semiconductor, and the like. Alternatively, when it is not sufficient to have a hydroxyl group, such as a resin, or when it does not originally have a hydroxyl group, a hydroxyl group is introduced to the surface of the substrate by performing some pretreatment on the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase the number of hydroxyl groups on the surface of the base material and can be suitably used for cleaning the surface of the base material (removing foreign substances and the like). As another example of such a pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on a substrate surface by a LB method (Langmuir-Blodgett method) or a chemical adsorption method. Then, the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, or the like.

  Alternatively, such a base material may have at least a surface portion made of a material containing another reactive group, for example, a silicone compound having one or more Si—H groups, or an alkoxysilane.

  Next, on the surface of the base material, a film of the surface treatment agent of the present invention is formed, and the film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. I do.

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

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

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

  Further, coating by a normal pressure plasma method is also possible.

When the wet coating method is used, the surface treating agent of the present invention may be diluted with a solvent and then applied to the surface of the substrate. From the viewpoint of the stability of the surface treating agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C _5-12 perfluoroaliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbon (for example, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbon (for example, C ₆ F ₁₃ CH ₂ CH ₃ (for example, Asahi Glass) ASAHIKLIN (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeola (registered trademark) H manufactured by Zeon Corporation); 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 Co., Ltd., 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 Du Pont-Mitsui Fluorochemicals) and the like. Can be used alone or as a mixture of two or more kinds, and further, for example, to adjust the solubility of a perfluoro (poly) ether group-containing silane compound and a perfluoropolyether-modified compound. Can be mixed with another solvent.

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

  The film formation is preferably carried out such that the surface treating agent of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film. Conveniently, in the case of the wet coating method, after diluting the surface treating agent of the present invention with a solvent, a catalyst may be added to a diluting solution of the surface treating agent of the present invention immediately before application to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present invention to which the catalyst has been added may be directly subjected to vapor deposition (usually vacuum deposition), or the catalyst may be added to a porous metal such as iron or copper. (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. In addition, as the base catalyst, for example, ammonia, organic amines and the like can be used.

  Next, the film is post-treated, if necessary. The post-treatment is not particularly limited, but may be, for example, one in which water supply and drying and heating are sequentially performed, and more specifically, may be performed as follows.

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

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

  Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C. The drying and heating method is not particularly limited, and the temperature of the precursor film together with the substrate 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 steam pressure. The pressure at this time is not particularly limited, but may be simply normal pressure.

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

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

  Post-processing can be performed as described above. It should be noted that such post-treatments may be performed to further improve the friction durability, but are not essential for producing the articles of the present invention. For example, after applying the surface treatment agent of the present invention to the surface of a substrate, it may be simply left 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 thus obtained has high friction durability. In addition to the high friction durability, the surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, prevents the attachment of stains such as fingerprints) depending on the composition of the composition used. It can have slipperiness (or lubricity, for example, wiping off stains such as fingerprints, and excellent touch to fingers), and can be suitably used as a functional thin film.

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

  As the optical material, a variety of optical materials are preferable, in addition to the optical materials related to displays and the like exemplified below: for example, a cathode ray tube (CRT; eg, TV, personal computer monitor), a liquid crystal display, a plasma display, Displays such as organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), and field emission displays (FED), or protective plates for those displays, or reflections on their surfaces Those that have been subjected to a protective film treatment.

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

  Further, 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, more preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling properties.

  The article obtained by using the surface treatment agent of the present invention has been described above in detail. In addition, the use, the method of use, the method of manufacturing an article, and the like of the surface treatment agent of the present invention are not limited to those exemplified above.

The surface treatment agent of the present invention will be described more specifically through the following examples, but the present invention is not limited to these examples. In this embodiment, the order of the repeating units (CF ₂ CF ₂ CF ₂ O) constituting the perfluoropolyether is arbitrary.

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

Synthesis Example 2
・ Synthesis of perfluoro (poly) ether-modified amidosilane compound In a reactor, 450 g of a perfluoropolyether group-containing methyl ester compound (A) having a methyl ester at the end synthesized in Synthesis Example 1 was charged, and placed under a nitrogen stream at room temperature. Then, 15.38 g of aminopropyltrimethoxysilane (NH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) was added dropwise, and the mixture was heated to 65 ° C. and stirred. Subsequently, volatiles were distilled off under reduced pressure to obtain 470 g of the following perfluoro (poly) ether-modified amidosilane compound B having a trimethylsilyl group at the terminal.
-Perfluoro (poly) ether-modified amidosilane compound (B):
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃₂ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Example 1
The perfluoro (poly) ether-modified amidosilane compound (B) obtained in Synthesis Example 2 and the perfluoropolyether group-containing methyl ester compound (A) obtained in Synthesis Example 1 were mixed at a molar ratio of 95.5: 4.5. And dissolved in Novec 7200 (manufactured by 3M) to prepare Surface Treatment Agent 1 so as to have a concentration of 20 wt%.

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

(Examples 2 to 4)
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the mixing ratio (molar ratio) of the compound (B) and the compound (A) was changed as shown in the following table.

Comparative Examples 1-3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the mixing ratio (molar ratio) of the compound (B) and the compound (A) was changed as shown in the following table.

Comparative Example 4
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the perfluoro (poly) ether-modified amidosilane compound (B) obtained in Synthesis Example 2 was used alone.

  With respect to the surface-treated layers formed on the substrate surface in Examples 1 to 4 and Comparative Examples 1 to 4, the friction durability was evaluated by an eraser friction durability test. Specifically, the sample article on which the surface treatment layer was formed was placed horizontally, and an eraser (KESHI-70, manufactured by KOKUYO Co., Ltd., plane size: 1 cm × 1.6 cm) was brought into contact with the surface of the surface treatment layer. A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. The static contact angle (degree) of water was measured every 500 reciprocations. The evaluation was stopped when the measured value of the contact angle was less than 100 degrees. Finally, Table 3 shows the number of reciprocations when the contact angle exceeds 100 degrees.

  From the above results, in Examples 1 to 4, the perfluoro (poly) ether-modified amide silane compound (B) has higher eraser durability than Comparative Example 4 using only the perfluoropolyether group-containing methyl ester. The effect of improving the friction durability by adding the compound (A) was confirmed. In Comparative Examples 1 to 3, although the perfluoropolyether group-containing methyl ester compound (A) was added, the effect was not obtained when the content was small, and the eraser durability was excessive when the content was excessive. Deterioration was confirmed.

  Although the present invention is not bound by any theory, it is suggested that the perfluoropolyether group-containing methyl ester compound (A) is hydrolyzed with water to be converted to carboxylic acid when a surface treatment layer is formed, and an acidic catalyst is formed. It is considered that the compound has improved the reactivity between the perfluoro (poly) ether-modified amide silane compound and the substrate surface, and as a result, excellent eraser durability was obtained. Further, when the perfluoropolyether group-containing methyl ester compound (A) is excessive, the reaction between the perfluoro (poly) ether-modified amide silane compound and the substrate surface is inhibited, so that the eraser durability is considered to deteriorate.

  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 an optical member requiring transparency.

Claims (22)

At least one perfluoro (poly) ether-modified amidosilane compound represented by the following formula (1):

[In the formula:
Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
PFPE ¹ is independently-(OC ₆ F ₁₂ ) _a- (OC ₅ F ₁₀ ) _b- (OC ₄ F ₈ ) _c- (OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e − _{(OCF 2) f} - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula;
X ¹ is a single bond or _{^{- (CR 8 2) k1 -}} (O) k2 - (NR 9) k3 -,
(Where:
R ⁸ is each independently a hydrogen atom or a fluorine atom;
R ⁹ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k1 is an integer from 1 to 20;
k2 is an integer from 0 to 10;
k3 is an integer from 0 to 10;
Here, the order of the respective recurring units enclosed in parentheses with k1, k2 or k3 added is arbitrary in the formula. )
Represents a group represented by;
R ¹ each ^{independently} represent a _{^{-X 2 -SiR a1 l1 R b1 m1}} R c1 n1;
X ^{2 _{is, - (CR 10 2) k4}} - (O) k5 - (NR 11) k6 -,
(Where:
R ¹⁰ is each independently a hydrogen atom or a fluorine atom;
R ¹¹ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k4 is an integer from 1 to 20;
k5 is an integer from 0 to 10;
k6 is an integer from 0 to 10;
Here, the order of the respective recurring units enclosed in parentheses by adding k4, k5 or k6 is arbitrary in the formula. )
Represents a group represented by;
R ^a1 is independently at each ^occurrence, represents _{^{-Z 1 -SiR a2 l2 R b2 m2}} R c2 n2;
Z ¹ is, independently at each occurrence, an oxygen atom or a C _1-6 alkylene group, — (CH ₂ ) _g —O— (CH ₂ ) _h — (where g is an integer of 1 to 6, There, h is 1 to 6 which is an integer), or - phenylene - _{(CH 2) i} - (wherein, i is, represents an a) integer from 0 to 6;
R ^a2 independently at each occurrence represents R ^{a1 ′} ;
R ^{a1 ′} is as defined for R ^a1 ;
In R ^a1 , the number of ^Sis connected linearly via the Z ¹ group is at most 5;
R ^b2 independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ^c2 independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms at each occurrence;
12 is independently at each occurrence an integer from 0 to 3;
m2 is, independently at each occurrence, an integer from 0 to 3;
n2 is independently at each occurrence an integer from 0 to 3;
R ^b1 independently at each occurrence represents a hydroxyl group or a hydrolysable group;
R ^c1 independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms at each occurrence;
l1 is, independently at each occurrence, an integer from 0 to 3;
m1 is, independently at each occurrence, an integer from 0 to 3;
n1 is, independently at each occurrence, an integer from 0 to 3;
R ² each independently represents a hydrogen atom, a C _1-6 alkyl group or a phenyl group;
p is 1 or 2;
However, in the formula, at least one R ^b1 or R ^b2 is present. ]
And at least one carboxylate compound represented by the following formula (2):

[In the formula:
R ³ represents a hydrocarbon group;
R ⁴ is, ^{Rf 2} -PFPE 2 -X ³ - was table;
Rf ² independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
PFPE ² are each _{independently, - (OC 6 F 12)} a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - _{(OCF 2) f} - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula;
X ³ represents a single bond or _{^{- (CR 15 2) k7 -}} (O) k8 - (NR 16) k9 -,
(Where:
R ¹⁵ is each independently a hydrogen atom or a fluorine atom;
R ¹⁶ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
k7 is an integer from 1 to 20;
k8 is an integer from 0 to 10;
k9 is an integer from 0 to 10;
Here, k7, k8 or k9 is added, and the order of the respective recurring units enclosed in parentheses is arbitrary in the formula. )
In to display the group represented. ]
And a carboxylate represented by the formula (2) with respect to the total content of the perfluoro (poly) ether-modified amidesilane compound represented by the formula (1) and the carboxylate compound represented by the formula (2) A surface treatment agent having a compound content of 4.1 mol% or more and 35 mol% or less. Rf ¹ is a perfluoroalkyl group having 1 to 16 carbon atoms, a surface treatment agent according to claim 1. PFPE ¹ has the following formula (a), (b) or (c):
− (OC ₃ F ₆ ) _d− (a)
[In the formula, d is an integer of 1 or more and 200 or less. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of the respective recurring units enclosed in parentheses with subscripts c, d, e or f is arbitrary in the formula. ]
_{^{- (R 6 -R 7) q}} - (c)
Wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or a combination of two or three groups selected from these groups. ;
q is an integer of 2 to 100. ]
The surface treatment agent according to claim 1 or 2, wherein X ¹ _{is, - (CF 2) k1 '} - or _{- (CF 2) k1' -} (O) k2 '-
[In the formula:
k1 ′ is an integer from 1 to 6;
k2 ′ is an integer of 1 to 3;
Here, the order of the respective repeating units enclosed in parentheses with k1 'or k2' is arbitrary in the formula. ]
And
X ² _{is, - (CH 2) k4 '} - or _{- (CH 2) k4' -O} k5 '-
[In the formula:
k4 ′ is an integer from 1 to 6;
k5 ′ is an integer of 1 to 3;
Here, the order in which each of the repeating units enclosed in parentheses with k4 'or k5' is arbitrary in the formula. ]
The surface treatment agent according to any one of claims 1 to 3 , wherein The surface treating agent according to any one of claims 1 to 4 , wherein R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group. The surface treatment agent according to any one of claims 1 to 5 , wherein R ^b1 and R ^b2 are OCH ₃ or OC ₂ H ₅ . The surface treatment agent according to any one of claims 1 to 6 , wherein p is 1. Rf ² is a perfluoroalkyl group having 1 to 16 carbon atoms, a surface treatment agent according to any one of claims 1 to 7. PFPE ² has the following formula (a), (b) or (c):
− (OC ₃ F ₆ ) _d− (a)
[In the formula, d is an integer of 1 or more and 200 or less. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of the recurring units in parentheses with subscripts c, d, e or f is arbitrary in the formula. ]
_{^{- (R 6 -R 7) q}} - (c)
Wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or two or three groups independently selected from these groups. A combination;
q is an integer of 2 to 100. ]
The surface treatment agent according to any one of claims 1 to 8, wherein X ³ _{is, - (CF 2) k7 '} - or _{- (CF 2) k7' -} (O) k8 '-
[In the formula:
k7 ′ is an integer from 1 to 6;
k8 ′ is an integer of 1 to 3;
Here, the order of the recurring units enclosed in parentheses with k7 'or k8' is arbitrary in the formula. ]
The surface treatment agent according to any one of claims 1 to 9 , wherein The surface treatment agent according to any one of claims 1 to 10 , wherein R ³ is an alkyl group having 1 to 3 carbon atoms. The content of the carboxylate compound represented by the formula (2) with respect to the total content of the perfluoro (poly) ether-modified amide silane compound represented by the formula (1) and the carboxylate compound represented by the formula (2) The surface treatment agent according to any one of claims 1 to 11 , wherein the amount is 4.5 mol% or more and 35 mol% or less. The surface treatment agent according to any one of claims 1 to 12 , further comprising one or more other components selected from a fluorinated oil, a silicone oil, and a catalyst. When the fluorinated oil has the formula (3):
_{^{Rf 5 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -Rf 6 ··· (3)
[In the formula:
Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
Rf ⁶ represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom which may be substituted by 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 each independently represents an integer of 0 to 300, , A ′, b ′, c ′, and d ′ are at least one, and the order of each repeating unit in parentheses with the subscripts a ′, b ′, c ′, or d ′ is represented by the formula: It is arbitrary in. ]
The surface treating agent according to claim 13 , which is one or more compounds represented by the following formula: The surface treatment agent according to any one of claims 1 to 14 , further comprising a solvent. The surface treatment agent according to any one of claims 1 to 15 , which is used as an antifouling coating agent or a waterproof coating agent. A pellet containing the surface treatment agent according to any one of claims 1 to 16 . An article comprising a substrate and a surface of the substrate, and a layer formed from the surface treatment agent according to any one of claims 1-16. 19. The article according to claim 18 , wherein the substrate is glass or sapphire glass. 19. The article of claim 18 , wherein the substrate 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 18 to 20 , which is an optical member. The article according to any one of claims 18 to 21 , which is a display.