JP2011178835A - Perfluoroether-containing organopolysiloxane, surface treatment composition, and article and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a perfluoroether-containing organopolysiloxane which is used as a surface treatment agent giving a surface satisfying, in a well-balanced manner, three requirements: to have stain resistance; to have less conspicuous stains; and to be easily destained by wiping, to provide a surface treatment composition containing the same, and to provide an article and an optical component treated with the same. <P>SOLUTION: Perfluoroether-containing organopolysiloxane is represented by formula (1); Ay(R)xZ-Q-Rf-Q-W-Q-Rf-Q-Z(R)xAy, wherein Rf is a group containing a perfluoropolyether residue; W is a divalent organosiloxane group; Q is a divalent group; Z is an organopolysiloxane residue having three or more siloxane bonds; R is a monovalent hydrocarbon group; A is a group represented by formula (2), wherein X is a hydrolysable group, R<SP>1</SP>is an alkyl group or a phenyl group, a is 2 or 3, b is ≥2; x, y are 1-9, x+y=((valence of Z)-1). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a perfluoroether group-containing organopolysiloxane having a perfluorooxyalkylene group and a lipophilic group having a predetermined functional group, and a surface treatment agent containing the organopolysiloxane and / or a partial hydrolysis condensate thereof. Composition, specifically, a surface treatment agent composition comprising the siloxane and / or a partially hydrolyzed condensate thereof, which makes oil and sebum dirt adhering to the surface less noticeable and easily wipes off such dirt. About. In addition, the present invention relates to an antireflection filter, a hard coat film, a touch panel substrate, a polarizing plate, glass, a resin film, and other articles and optical components that are surface-treated with the treatment composition.

  In general, a perfluorooxyalkylene group (hereinafter referred to as “perfluoroether group”)-containing compound has water and oil repellency, releasability, antifouling property and the like because its surface free energy is very small. Utilizing this property, it is widely used industrially as a water / oil repellent / antifouling agent for paper and textiles, a water / oil repellent / antifouling agent for display surfaces, and an oil repellent for precision equipment.

It is known to use silane in order to bring the perfluoroether group into close contact with the substrate. For example, a fluoroaminosilane compound (Patent Document 1: Japanese Patent Application Laid-Open No. 11-29585), the following formula R _f — (OC ₃ F ₆ ) _n —O— (CF ₂ ) _m — (CH ₂ ) ₁ —O— (CH ₂ ) _s- Si (OR) ₃
(However, _Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, n is an integer of 1 to 50, m is an integer of 0 to 3, l is an integer of 0 to 3, and s is 0. An integer of ˜6, where 6 ≧ m + 1> 0, R represents an alkyl group having 1 to 10 carbon atoms.)
An antireflective film (Patent Document 2: Japanese Patent Application Laid-Open No. 2001-188102) using a silane coupling agent represented by the following formula is disclosed. However, the amount of the hydrolyzable group in one molecule cannot be said to be sufficient for the silane coupling agent, and there are problems such as requiring time for curing and poor adhesion to the substrate.

  A perfluoropolyether group-containing silane coupling agent having two or more hydrolyzable groups at the terminal is known (Patent Document 3: JP 2007-197425 A). The treatment agent is excellent in adhesion to the substrate, has a water- and oil-repellent surface, gives a surface having good slipperiness and easy to wipe off dirt.

  Each of the above-mentioned treatment agents is required to “make dirt less likely” and “easy to remove dirt”, while the former reduces water and oil repellency or surface energy of the surface, and the latter improves surface slipperiness. Have responded to each. However, recently, on surfaces such as antireflection films, protective films, and various filters that have been surface-treated with these treatment agents, deposits such as fingerprints and sweat appear to appear white, compared to untreated cases. The problem that these contaminations are easily noticeable has begun to be pointed out.

  In order to make the contamination inconspicuous, it is known that a surface treatment agent having a hydrocarbon group is used to expose the hydrocarbon group on the surface, thereby spreading the oil stain and making it inconspicuous (Patent Document 4: Special). No. 2002-367229). However, the entire surface becomes oleophilic, easily contaminated, and difficult to remove.

  In particular, in applications where fingerprint adhesion is a problem, the surface should be improved in water and oil repellency to reduce the amount of fingerprint adhesion, or a surface that is less noticeable even when fingerprints are attached and from which fingerprints can be removed. It is required to form.

JP-A-11-29585 JP 2001-188102 A JP 2007-197425 A JP 2002-367229 A

  The present invention has been made in view of the above circumstances, and is a perfluoroether group that is used as a surface treatment agent that provides a surface that balances the three requirements of being difficult to get dirty, less noticeable, and easy to wipe off. It is an object of the present invention to provide a containing organopolysiloxane, a surface treating agent composition containing the organopolysiloxane, and an article and an optical component treated with the composition.

  As a result of intensive studies in order to achieve the above object, the present inventors have a perfluoroether group-containing organopolysiloxane represented by the following formula (1) and / or a partially hydrolyzed condensate thereof as a main component. The surface treatment agent composition to be treated is treated on the surface of the base material and cured to provide a surface that balances the three requirements of being difficult to get dirty, less noticeable, and easy to wipe off. It came to make this invention.

［式中、Ｒｆはパーフルオロポリエーテル残基を含む基、Ｗはエステル基で置換されていてもよい炭素数８〜４０のケイ素原子に結合する１価炭化水素基を有する２価のオルガノシロキサン基、ＱはＲｆ基とＺ基、及びＲｆ基とＷ基とを連結する２価の基、Ｚはシロキサン結合を３個以上有する３〜１１価のオルガノポリシロキサン残基、Ｒはエステル基で置換されていてもよい炭素数８〜４０のケイ素原子に結合する１価炭化水素基、Ａは下記式（２）

（Ｘは独立に加水分解性基であり、Ｒ¹は炭素数１〜４のアルキル基又はフェニル基であり、ｂは２以上の整数であり、ａは２又は３である。）
で示される基であり、ｘは１〜９の整数、ｙは１〜９の整数、但し、ｘ＋ｙ＝（Ｚの価数−１）である。］
〔請求項２〕
式（１）において、Ｘがアルコキシ基、オキシアルコキシ基、アシロキシ基、アルケニルオキシ基、ハロゲン基から選ばれる加水分解性基であり、Ｒがエステル基で置換されていてもよい炭素数１０〜３０のケイ素原子に結合するアルキル基であり、ｘが１〜３である、請求項１記載のパーフルオロエーテル基含有オルガノポリシロキサン。
〔請求項３〕
式（１）において、Ｗが、下記一般式（３−１）〜（３−３）で表される基から選ばれるものである、請求項１又は２記載のパーフルオロエーテル基含有オルガノポリシロキサン。

（Ｒ²はエステル基で置換されていてもよい炭素数８〜４０の１価炭化水素基である。）
〔請求項４〕
式（１）において、Ｚが下記式（４−１）又は（４−２）で表される基である、請求項１〜３のいずれか１項記載のパーフルオロエーテル基含有オルガノポリシロキサン。

〔請求項５〕
式（１）において、Ｒｆが下記式で示される基であることを特徴とする請求項１〜４のいずれか１項記載のパーフルオロエーテル基含有オルガノポリシロキサン。
−（Ｃ_cＦ_2cＯ）_d−
（式中、ｃは１〜６の整数、ｄは１０〜４０の整数である。）
〔請求項６〕
下記式（１）で表されるパーフルオロエーテル基含有オルガノポリシロキサン。

［式中、Ｒｆは下記一般式（５）〜（８）で示される基から選ばれるパーフルオロポリエーテル残基を含む基：

（式中、Ｙはそれぞれ独立にＦ又はＣＦ₃基、ｅは１〜３の整数、ｇは２〜６の整数、ｆ、ｊはそれぞれ０〜１００の整数、但しｆ＋ｊは２〜１００の整数であり、ｈは０〜６の整数であり、かつｆ＋ｈ＋ｊ≦１００であり、各繰り返し単位の配列はランダムである。）

（式中、ｋは１〜１００の整数、ｅは１〜３の整数である。）

（式中、ＹはＦ又はＣＦ₃基、ｅは１〜３の整数、ｆ、ｍはそれぞれ０〜１００の整数、但しｆ＋ｍは２〜１００の整数であり、各繰り返し単位の配列はランダムである。）

（式中、ｎは０〜５０の整数、ｍは１〜５０の整数、但しｎ＋ｍは２〜６０の整数である。）
Ｗは下記一般式（３−１）〜（３−３）で表される基から選ばれるエステル基で置換されていてもよい炭素数８〜４０のケイ素原子に結合する１価炭化水素基を有する２価のオルガノシロキサン基：

（Ｒ²はエステル基で置換されていてもよい炭素数８〜４０の１価炭化水素基である。）
Ｑは下記式から選ばれる、Ｒｆ基とＺ基、及びＲｆ基とＷ基とを連結する２価の基：

Ｚは下記式（４−１）又は（４−２）で表されるオルガノポリシロキサン残基：

Ｒはエステル基で置換されていてもよい炭素数８〜４０の１価炭化水素基、Ａは下記式（２）で示される基：

（Ｘは独立に加水分解性基であり、Ｒ¹は炭素数１〜４のアルキル基又はフェニル基であり、ｂは２以上の整数であり、ａは２又は３である。）
ｘ，ｙはそれぞれ独立に１〜９の整数、但し、ｘ＋ｙ＝（Ｚの価数−１）であり、上記Ｒ及びＡがそれぞれ上記式（４−１）又は（４−２）の結合手に結合する。但し、該結合手のうち１個はＱと結合する。］
〔請求項７〕
請求項１〜６のいずれか１項記載のパーフルオロエーテル基含有オルガノポリシロキサン及び／又はその部分加水分解縮合物を含有する表面処理剤組成物。
〔請求項８〕
請求項７記載の表面処理剤組成物を硬化してなる硬化被膜を表面に有する物品。
〔請求項９〕
請求項７記載の表面処理剤組成物を硬化してなる硬化被膜を表面に有する光学部材。 That is, the present invention provides the following perfluoroether group-containing organopolysiloxane, surface treatment agent composition, article and optical member.
[Claim 1]
Perfluoroether group-containing organopolysiloxane represented by the following formula (1).

[Wherein Rf is a group containing a perfluoropolyether residue, W is a divalent organosiloxane having a monovalent hydrocarbon group bonded to a silicon atom of 8 to 40 carbon atoms which may be substituted with an ester group. Group, Q is a divalent group connecting Rf group and Z group, and Rf group and W group, Z is a 3-11 valent organopolysiloxane residue having 3 or more siloxane bonds, and R is an ester group A monovalent hydrocarbon group bonded to an optionally substituted silicon atom having 8 to 40 carbon atoms, A represents the following formula (2)

(X is independently a hydrolyzable group, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, b is an integer of 2 or more, and a is 2 or 3.)
Wherein x is an integer of 1 to 9, y is an integer of 1 to 9, provided that x + y = (valence of Z-1). ]
[Claim 2]
In Formula (1), X is a hydrolyzable group selected from an alkoxy group, an oxyalkoxy group, an acyloxy group, an alkenyloxy group, and a halogen group, and R is an optionally substituted carbon group having 10 to 30 carbon atoms. The perfluoroether group-containing organopolysiloxane according to claim 1, wherein x is 1 to 3 and is an alkyl group bonded to a silicon atom.
[Claim 3]
The perfluoroether group-containing organopolysiloxane according to claim 1 or 2, wherein in the formula (1), W is selected from the groups represented by the following general formulas (3-1) to (3-3). .

(R ² is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group.)
[Claim 4]
The perfluoroether group-containing organopolysiloxane according to any one of claims 1 to 3, wherein in the formula (1), Z is a group represented by the following formula (4-1) or (4-2).

[Claim 5]
The perfluoroether group-containing organopolysiloxane according to any one of claims 1 to 4, wherein in the formula (1), Rf is a group represented by the following formula.
− (C _c F _2c O) _d −
(In the formula, c is an integer of 1 to 6, and d is an integer of 10 to 40.)
[Claim 6]
Perfluoroether group-containing organopolysiloxane represented by the following formula (1).

[Wherein, Rf is a group containing a perfluoropolyether residue selected from the groups represented by the following general formulas (5) to (8):

(Wherein Y is independently F or CF ₃ group, e is an integer of 1 to 3, g is an integer of 2 to 6, f and j are each an integer of 0 to 100, provided that f + j is an integer of 2 to 100) H is an integer of 0 to 6 and f + h + j ≦ 100, and the arrangement of each repeating unit is random.)

(In the formula, k is an integer of 1 to 100, and e is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, e is an integer of 1 to 3, f and m are each an integer of 0 to 100, provided that f + m is an integer of 2 to 100, and the arrangement of each repeating unit is random. is there.)

(In the formula, n is an integer of 0 to 50, m is an integer of 1 to 50, and n + m is an integer of 2 to 60.)
W represents a monovalent hydrocarbon group bonded to a silicon atom having 8 to 40 carbon atoms which may be substituted with an ester group selected from the groups represented by the following general formulas (3-1) to (3-3). Divalent organosiloxane group:

(R ² is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group.)
Q is a divalent group connecting the Rf group and the Z group, and the Rf group and the W group, selected from the following formula:

Z is an organopolysiloxane residue represented by the following formula (4-1) or (4-2):

R is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group, and A is a group represented by the following formula (2):

(X is independently a hydrolyzable group, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, b is an integer of 2 or more, and a is 2 or 3.)
x and y are each independently an integer of 1 to 9, wherein x + y = (valence of Z-1), and R and A are bonds of the above formula (4-1) or (4-2), respectively. To join. However, one of the bonds is bonded to Q. ]
[Claim 7]
A surface treating agent composition comprising the perfluoroether group-containing organopolysiloxane and / or a partial hydrolysis condensate thereof according to any one of claims 1 to 6.
[Claim 8]
An article having on its surface a cured coating formed by curing the surface treating agent composition according to claim 7.
[Claim 9]
An optical member having on its surface a cured film formed by curing the surface treating agent composition according to claim 7.

  The perfluoroether group-containing organopolysiloxane of the present invention has a lipophilic group having a predetermined number of carbon atoms in the middle of a molecular chain (that is, a main chain represented by -Q-Rf-QWQRf-Q-). As a side chain substituent of a divalent organosiloxane group represented by -W- in the chain) and at least one at both ends of the molecular chain. The outermost surface of the substrate treated with the surface treating agent composition containing the compound (the substrate surface having a cured film of the composition) is water-repellent and lipophilic, hardly contaminated with sebum, sebum, etc. Since the outermost surface of the base material is covered with a fluorine group, the surface of the base material on which the fingerprint is easily attached is excellent in wiping off dirt. Can be used for coating applications.

1 is a ¹ H-NMR chart of Compound 1 obtained in Example 1.

  The perfluoroether group-containing organopolysiloxane of the present invention has a plurality of hydrolyzable silyl groups at each end of the molecular chain (2 to 27 at each end), so that both ends are firmly attached to the substrate. To do. Since the base material is covered with the perfluoropolyether chain between the fixed ends, it is difficult to get dirt and the wiping property is excellent. In addition, the oil repelled by the perfluoropolyether chain is absorbed by both ends and the lipophilic group (a silicon atom-bonded monovalent hydrocarbon group having a predetermined number of carbon atoms) in the molecular chain. So the dirt is not noticeable.

Hereinafter, the present invention will be described in more detail.
The perfluoroether group-containing organopolysiloxane having a lipophilic group of the present invention is represented by the following formula (1).

In the above formula (1), Rf is a group containing a perfluoropolyether residue, which may be linear or branched, but is preferably linear from the viewpoint of surface slipperiness. The structure of the perfluoro ethers such general formula _{- (C c F 2c O)} d - those containing a structure represented by and the like, wherein, c of the repeating units is an integer from 1 to 6, d is an integer of 1 to 100, preferably 2 to 50, more preferably 10 to 40.

Examples of the repeating unit —C _c F _2c O— represented by the above formula include the following units, and a combination of two or more of these may be used.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-C (CF _{3) 2} O-

Among these, the group shown below which contains a perfluorooxyalkylene group having 1 to 4 carbon atoms, particularly 1 to 3 carbon atoms as a repeating unit is preferable.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-

（式中、Ｙはそれぞれ独立にＦ又はＣＦ₃基、ｅは１〜３の整数、ｇは２〜６の整数、ｆ、ｊはそれぞれ０〜１００の整数、但しｆ＋ｊは２〜１００の整数であり、ｈは０〜６の整数であり、かつｆ＋ｈ＋ｊ≦１００であり、各繰り返し単位の配列はランダムである。）

（式中、ｋは１〜１００の整数、ｅは１〜３の整数である。）

（式中、ＹはＦ又はＣＦ₃基、ｅは１〜３の整数、ｆ、ｍはそれぞれ０〜１００の整数、但しｆ＋ｍは２〜１００の整数であり、各繰り返し単位の配列はランダムである。）

（式中、ｎは０〜５０の整数、ｍは１〜５０の整数、但しｎ＋ｍは２〜６０の整数である。） Rf is preferably selected from the groups represented by the following general formulas (5) to (8).

(Wherein Y is independently F or CF ₃ group, e is an integer of 1 to 3, g is an integer of 2 to 6, f and j are each an integer of 0 to 100, provided that f + j is an integer of 2 to 100) H is an integer of 0 to 6 and f + h + j ≦ 100, and the arrangement of each repeating unit is random.)

(In the formula, k is an integer of 1 to 100, and e is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, e is an integer of 1 to 3, f and m are each an integer of 0 to 100, provided that f + m is an integer of 2 to 100, and the arrangement of each repeating unit is random. is there.)

(In the formula, n is an integer of 0 to 50, m is an integer of 1 to 50, and n + m is an integer of 2 to 60.)

  The total number of repeating units in the chemical structural formulas (5) to (8) is preferably in the range of 2 to 50, more preferably 10 to 40.

  In the above formula (1), R is a monovalent hydrocarbon group bonded to a silicon atom having 8 to 40 carbon atoms, preferably 10 to 30, more preferably 10 to 20, which may be substituted with an ester group. Yes, it is a substituent bonded to the silicon atom in Z. Examples of R include saturated aliphatic monovalent hydrocarbon groups such as alkyl groups such as octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, and octadecyl group. Among these, a tetradecyl group and a hexadecyl group are particularly suitable. Further, these monovalent hydrocarbon groups may be, for example, ester-substituted (saturated aliphatic) monovalent hydrocarbon groups in which the terminal is substituted with an ester group. Examples of the ester-substituted monovalent hydrocarbon group include —R′—COO—R ″ (R ′ is a divalent hydrocarbon group such as an alkylene group having 1 to 38 carbon atoms, and R ″ is 1 to 38 carbon atoms). And monovalent hydrocarbon groups such as alkyl groups). The total number of carbon atoms of R ′ and R ″ is desirably 8 to 40 carbon atoms, preferably 10 to 30 carbon atoms, more preferably about 10 to 20 carbon atoms. The effect of making it inconspicuous is not sufficient, and if it exceeds the upper limit, it becomes difficult to wipe off dirt.

A is a group represented by the following formula (2).

  In formula (2), X is independently a hydrolyzable group, for example, a C1-C10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, a methoxymethoxy group, a methoxyethoxy group, or the like. C2-C10 alkenyloxy groups such as C2-C10 oxyalkoxy groups, acetoxy groups, etc., C2-C10 alkenyloxy groups such as isopropenoxy groups, halogen groups such as chloro groups, bromo groups, iodo groups, etc. Is mentioned. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable, and an alkoxy group (methoxy group, ethoxy group) is more preferable.

R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, specifically, a methyl group, an ethyl group, a phenyl group, or the like. Among them, a methyl group is preferable. a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. b is an integer of 2 or more, and an integer of 2 to 5 is preferable in terms of both adhesion to the substrate and surface characteristics.

The number x of R is an integer of 1 to 9, preferably 1 to 3, and may be different at both ends. When x is less than the lower limit value, the effect of making the stains inconspicuous is not sufficient, and when the upper limit value is exceeded, the amount of the group A is relatively reduced, and the adhesion to the substrate is lowered. The number y of A is an integer of 1 to 9, preferably 1 to 3, and may be different at both ends. However, x + y = (valence of Z-1).
The ratio x / y between the number x of R and the number y of A is preferably 1/5 to 5/1, more preferably 1/3 to 3/1. As a result, it is possible to achieve both characteristics of adhesion to the substrate and difficulty of conspicuous dirt.

In the formula (1), Z has 3 or more, preferably 3 to 4 siloxane bonds, which may contain one or more selected from oxygen, nitrogen, silicon and sulfur atoms. 3-11 valent, preferably 3-4 valent organopolysiloxane residues. However, it may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group (that is, Si— (CH ₂ ) _r —Si, where r is an integer of 1 to 4). The perfluoroether group-containing organopolysiloxane of the present invention can provide a coating excellent in abrasion resistance and scratch resistance by having a siloxane bond in the molecule.
In addition, examples of the substituent other than R, A, and Q bonded to the silicon atom in Z include an alkyl group having 1 to 4 carbon atoms or a phenyl group similar to R ¹ in Formula (2), and preferably It is a methyl group.

（式中、Ｍｅはメチル基である。） Examples of Z include the following.

(In the formula, Me is a methyl group.)

Among these, the group represented by the following formula (4-1) or (4-2) is preferable.

  In the formula (1), Q is a divalent group that connects the Rf group and the Z group, and the Rf group and the W group, and preferably one or more of silicon atoms, amides, ethers, and esters. Is an organic group having 2 to 12 carbon atoms, preferably 2 to 5 carbon atoms. Examples of Q include the following.

In the formula (1), W is a divalent organosiloxane group having a monovalent hydrocarbon group bonded to a silicon atom having 8 to 40 carbon atoms which may be substituted with an ester group. Monovalent carbonization bonded to an (aliphatic saturated) silicon atom such as an alkyl group having 8 to 40 carbon atoms, preferably 10 to 30 carbon atoms, more preferably about 10 to 20 carbon atoms, which may be substituted with an ester group A divalent organosiloxane group having a linear, branched or cyclic structure having about 4 to 8 silicon atoms, preferably having one or two hydrogen groups as side chain substituents (R ² ). More preferably, it is a divalent organosiloxane group having 4 or 5 silicon atoms and a branched or cyclic structure represented by the following formula (3-1), (3-2) or (3-3).

In addition, as R < ² > in W, the group similar to R in Formula (1) mentioned above can be illustrated, As a substituent other than R < ² > couple | bonded with the silicon atom in W, Formula (2) Examples thereof include an alkyl group having 1 to 4 carbon atoms or a phenyl group similar to R ^{1 in the} formula.

An example of the method for preparing the perfluoroether group-containing organopolysiloxane of the present invention is shown. First, organosiloxane W ′ having two SiH bonds and a long-chain hydrocarbon group (wherein both sides of W are blocked with SiH groups) and the following formula (i)
Q'RfQ '(i)
And a compound having an unsaturated group Q ′ on both sides of Rf described above is subjected to an addition reaction at a molar ratio of 1: 2.

Here, Q ′ is, for example, the following group.

（式中、Ｒ²は上記と同じ。） Examples of W ′ include the following.

(Wherein R ² is the same as above)

The following formula (ii) obtained thereby.
Q'RfQWQRfQ '(ii)
A fluorine compound having an unsaturated group Q ′ on both sides, and an organohydrogenpolysiloxane for deriving Z, wherein the compound Z ′ has a SiH bond at a position where Q, A and R are to be bonded. Are added in a 2: 1 molar ratio. Q ′ is the same as above.

Here, examples of the organohydrogenpolysiloxane Z ′ having a SiH bond include the following.

（Ｒ¹、Ｘ、ａ、ｂについては上述のとおりであるが、好ましくはｂは２〜５の整数である。）
で表される不飽和基（Ｃ_bＨ_2b-1基）を有する化合物Ａ’と、Ｒを誘導するためのＲの末端が不飽和結合になっている化合物Ｒ’、例えば１−テトラデセン、１０−ウンデセン酸エチルなどとを、上記オルガノハイドロジェンポリシロキサンの残りのＳｉＨ結合と付加反応させる。この際、式（ｉｉ）のフッ素化合物とＺ’との付加反応物，Ａ’及びＲ’の反応割合としては、式（ｉｉ）のフッ素化合物とＺ’との付加反応物１モルに対してＡ’とＲ’を合計して４〜６モル反応されるのがよく、またＡ’とＲ’とのモル比はＡ’／Ｒ’が１／３〜３／１が好ましい。
なお、付加反応は、常法に従い、８０〜１００℃程度の温度で、フッ素変性芳香族炭化水素系溶剤等のフッ素系溶剤や芳香族炭化水素系溶剤などの有機溶剤、及び付加反応触媒、例えば白金化合物の存在下で行うことができる。 Next, the following formula (iii) for deriving the structure (A) of formula (2)

(R ¹ , X, a, and b are as described above. Preferably, b is an integer of 2 to 5.)
A compound A ′ having an unsaturated group (C _b H _2b-1 group) and a compound R ′ having an unsaturated bond at the end of R for inducing R, such as 1-tetradecene, 10 -Addition of ethyl undecenoate or the like with the remaining SiH bonds of the organohydrogenpolysiloxane. At this time, the addition reaction product of the fluorine compound of formula (ii) and Z ′, and the reaction ratio of A ′ and R ′ are 1 mol of the addition reaction product of the fluorine compound of formula (ii) and Z ′. A ′ and R ′ are preferably added in a total of 4 to 6 moles, and the mole ratio of A ′ and R ′ is preferably 1/3 to 3/1.
In addition, the addition reaction is carried out according to a conventional method at a temperature of about 80 to 100 ° C., an organic solvent such as a fluorine-based solvent such as a fluorine-modified aromatic hydrocarbon solvent or an aromatic hydrocarbon solvent, and an addition reaction catalyst, for example, It can be carried out in the presence of a platinum compound.

  In the present invention, the perfluoroether group-containing organopolysiloxane obtained above or a partially hydrolyzed condensate thereof is used as the main component of the surface treatment agent composition.

If necessary, the surface treatment agent composition includes a hydrolysis condensation catalyst such as an organic titanium compound (such as tetra-n-butyl titanate), an organic tin compound (such as dibutyltin dimethoxide, dibutyltin dilaurate), an organic acid, or the like. (Acetic acid, methanesulfonic acid, carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added, and it is still preferred from the viewpoint of solubility that a hydrogen atom is substituted with a fluorine atom. Of these, acetic acid, tetra-n-butyl titanate, perfluorocarboxylic acid and the like are particularly desirable.
The addition amount of the hydrolysis-condensation catalyst is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the perfluoroether group-containing organopolysiloxane and / or its partial hydrolysis-condensation product. 1 part by mass.

Further, the surface treatment agent composition may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), fluorine Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (Petroleum benzine, mineral spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified. Of these, fluorine-modified solvents are desirable in terms of solubility, wettability, and the like, and in particular, ethyl perfluorobutyl ether, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotrimethyl. Such as butylamine.
The said solvent may be individual 1 type or may mix 2 or more types. The amount of the solvent used is such that the concentration of the perfluoroether group-containing organopolysiloxane of formula (1) and / or its partially hydrolyzed condensate is 0.01 to 50% by mass, particularly 0.05 to 20% by mass. It is preferable that the amount is small.

  As the surface treatment method and curing conditions using the surface treatment agent composition, brushing, dipping, spraying, spin coating, etc. are usually applied to the substrate with a thickness of about 0.1 nm to 5 μm, particularly about 1 to 100 nm. For example, in the case of brush coating or dipping, a cured film of the composition can be formed on the substrate surface by curing in the range of room temperature (23 ° C.) to 120 ° C. In order to accelerate the curing, it is preferably performed under humidification.

  The substrate to be treated with the surface treating agent composition is not particularly limited, and various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramics, and ceramic can be used. For example, the water-repellent oleophilic treatment can be performed on paper, cloth, metal, glass, plastic, ceramic, and the like. From the viewpoint of resistance to fingerprints, it is more effective to coat on a surface to which human fats and oils easily adhere.

  The surface treatment composition of the present invention is resistant to optical members such as touch panel displays, spectacle lenses, antireflection films, DVDs, Blu-ray discs, and the like, and main bodies such as ornaments, mobile phones, portable audio players, and digital cameras. Suitable for fingerprint coating.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this.

（ｐ／ｑ＝０．９、ｐ＋ｑ≒２３）
で示される両末端にα−不飽和結合を有するパーフルオロポリエーテル３０ｇ（０．０１４４ｍｏｌ）と、ｍ−キシレンヘキサフロライド６０ｇ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０４４２ｇ（Ｐｔ単体として１．１×１０^-6モルを含有）を入れて、９０℃に加熱撹拌した。そこへ、下記式（ＩＩ）

で示される両末端にＳｉＨ基を有し、かつ、１つの長鎖アルキル基を有するシロキサン３．５５ｇ（０．００７２ｍｏｌ）を滴下し、両末端にα−不飽和結合を有するパーフルオロポリエーテルを得た。 [Example 1]
In the reaction vessel, the following formula (I)

(P / q = 0.9, p + q≈23)
30 g (0.0144 mol) of a perfluoropolyether having an α-unsaturated bond at both ends, and 60 g of m-xylene hexafluoride, 0.0442 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (as a Pt simple substance) 1.1 × 10 ⁻⁶ mol), and the mixture was heated and stirred at 90 ° C. There, the following formula (II)

3.55 g (0.0072 mol) of a siloxane having SiH groups at both ends and having one long chain alkyl group is added dropwise, and a perfluoropolyether having α-unsaturated bonds at both ends is added. Obtained.

8.7 g (0.0360 mol) of tetramethylcyclotetrasiloxane was added and aged at 90 ° C. for 3 hours, and it was confirmed by ¹ H-NMR that the unsaturated group had disappeared. Subsequently, the reaction product was subjected to vacuum distillation to obtain 32 g of a cloudy liquid.

In a reaction vessel, put 30 g of the liquid obtained above, 30 g of m-xylene hexafluoride, 0.0442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone). The mixture was heated and stirred at 90 ° C. Thereto, 3.2 g (0.0216 mol) of vinyltrimethoxysilane and 4.2 g (0.0216 mol) of 1-tetradecene were added and aged at 90 ° C. for 3 hours. The reaction product was subjected to vacuum distillation to obtain 30.5 g of a cloudy liquid (referred to as “Compound 1”).

A ¹ H-NMR chart of Compound 1 is shown in FIG. 1, and chemical shift data is shown below.
¹ H-NMR (TMS standard, ppm)

（式中Ｒｆは上述のとおりである） From the above results, it was found that the structural formula of the main component of Compound 1 obtained was as follows.

(Wherein Rf is as described above)

[Example 2]
Compound 2 was obtained in the same manner as in Example 1, except that 1-tetradecene used in Example 1 was used in an equimolar amount (0.0216 mol) of ethyl 10-undecenoate.

（式中Ｒｆは上述のとおりである） It turned out that the structural formula of the main component of the obtained compound 2 is the following.

(Wherein Rf is as described above)

Preparation of surface treating agent composition Each of synthesized compounds 1 and 2 was dissolved in ethyl perfluorobutyl ether (HFE-7200, manufactured by Sumitomo 3M) to prepare a 0.1 mass% solution. A slide glass was immersed in each surface treatment composition obtained for 30 seconds and then pulled up at a speed of 150 mm / min, and left for 24 hours in an atmosphere of 25 ° C. and humidity 40% RH to form a cured film. Using this sample piece, evaluation was performed by the method described later. The results are shown in Table 1.

[Comparative Examples 1-6]
Sample pieces were prepared and evaluated in the same manner as in Examples except that 0.1% by mass solutions of the following compounds 3 to 8 were used instead of the compounds 1 and 2 synthesized in the examples. The results are shown in Table 1.

（ｐ／ｑ＝０．９、ｐ＋ｑ≒２３） Compound 3

(P / q = 0.9, p + q≈23)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒２３） Compound 4

(P / q = 0.9, p + q≈23)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） Compound 5

(P / q = 0.9, p + q≈45)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒２３） Compound 6

(P / q = 0.9, p + q≈23)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） Compound 7

(P / q = 0.9, p + q≈45)

Compound 8
Octadecyltrichlorosilane

[Comparative Example 7]
Evaluation was carried out by the following method in the same manner as in Examples using a slide glass without surface treatment. The results are shown in Table 1.

[Evaluation of water and oil repellency]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured coating and the contact angle with respect to oleic acid were measured.

[Evaluation A: Evaluation of Conspicuousness of Sebum Dirt]
After attaching sebum of the forehead to the finger and attaching the sebum on the treated surface of the substrate treated with each surface treating agent composition in a circular arc with the finger, whether the dirt is noticeable by visual inspection It was evaluated by.
○ Dirt is not noticeable.
△ Dirt is noticeable but I don't mind.
× Dirt is noticeable.

[Evaluation B: Evaluation of sebum dirt wiping property]
The above-mentioned sebum stain was wiped off using a tissue paper, and the surface after wiping was visually observed and evaluated according to the following criteria.
○ Dirt was completely removed.
Δ Dirt becomes inconspicuous, but it can be visually recognized when light is incident obliquely.
X Dirt is noticeable or dirt is not noticeable, but remains clearly attached.

[Evaluation C: Evaluation of wiping performance of magic ink]
On the treated surface, a line was drawn with magic ink (black, Himackey manufactured by Zebra Co., Ltd.), dried, wiped with tissue paper, and the surface after wiping was visually observed and evaluated according to the following criteria.
○ No trace of magic.
△ Magic marks remain thin after wiping.
× The traces of magic stand out.

[Evaluation D: Evaluation of slipperiness]
The treated surface was rubbed with tissue paper, and the slipperiness was evaluated according to the following criteria.
○ Glide well.
△ Slip.
× It gets caught.

  As is clear from the above results, compared to the comparative example, the examples are less noticeable of sebum stains, wiping properties of sebum stains, wiping properties of magic ink, and slippery, and are balanced as anti-fingerprint coating agents. Is good. On the other hand, the comparative example cannot satisfy any of the characteristics.

  The perfluoroether group-containing organopolysiloxane of the present invention gives a surface that is inconspicuous even if dirt is attached, and the attached dirt can be easily wiped off with a light force. It is suitable for surface treatment of devices such as cellular phones, PDAs, portable music players, car navigation systems, televisions, liquid crystal monitors, etc. where visibility is a problem due to dirt, and is particularly useful for touch panel applications.

Claims (9)

Perfluoroether group-containing organopolysiloxane represented by the following formula (1).

[Wherein Rf is a group containing a perfluoropolyether residue, W is a divalent organosiloxane having a monovalent hydrocarbon group bonded to a silicon atom of 8 to 40 carbon atoms which may be substituted with an ester group. Group, Q is a divalent group connecting Rf group and Z group, and Rf group and W group, Z is a 3-11 valent organopolysiloxane residue having 3 or more siloxane bonds, and R is an ester group A monovalent hydrocarbon group bonded to an optionally substituted silicon atom having 8 to 40 carbon atoms, A represents the following formula (2)

(X is independently a hydrolyzable group, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, b is an integer of 2 or more, and a is 2 or 3.)
Wherein x is an integer of 1 to 9, y is an integer of 1 to 9, provided that x + y = (valence of Z-1). ]   In Formula (1), X is a hydrolyzable group selected from an alkoxy group, an oxyalkoxy group, an acyloxy group, an alkenyloxy group, and a halogen group, and R is an optionally substituted carbon group having 10 to 30 carbon atoms. The perfluoroether group-containing organopolysiloxane according to claim 1, wherein x is 1 to 3 and is an alkyl group bonded to a silicon atom. The perfluoroether group-containing organopolysiloxane according to claim 1 or 2, wherein in the formula (1), W is selected from the groups represented by the following general formulas (3-1) to (3-3). .

(R ² is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group.) The perfluoroether group-containing organopolysiloxane according to any one of claims 1 to 3, wherein in the formula (1), Z is a group represented by the following formula (4-1) or (4-2).

The perfluoroether group-containing organopolysiloxane according to any one of claims 1 to 4, wherein in the formula (1), Rf is a group represented by the following formula.
− (C _c F _2c O) _d −
(In the formula, c is an integer of 1 to 6, and d is an integer of 10 to 40.) Perfluoroether group-containing organopolysiloxane represented by the following formula (1).

[Wherein, Rf is a group containing a perfluoropolyether residue selected from the groups represented by the following general formulas (5) to (8):

(Wherein Y is independently F or CF ₃ group, e is an integer of 1 to 3, g is an integer of 2 to 6, f and j are each an integer of 0 to 100, provided that f + j is an integer of 2 to 100) H is an integer of 0 to 6 and f + h + j ≦ 100, and the arrangement of each repeating unit is random.)

(In the formula, k is an integer of 1 to 100, and e is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, e is an integer of 1 to 3, f and m are each an integer of 0 to 100, provided that f + m is an integer of 2 to 100, and the arrangement of each repeating unit is random. is there.)

(In the formula, n is an integer of 0 to 50, m is an integer of 1 to 50, and n + m is an integer of 2 to 60.)
W represents a monovalent hydrocarbon group bonded to a silicon atom having 8 to 40 carbon atoms which may be substituted with an ester group selected from the groups represented by the following general formulas (3-1) to (3-3). Divalent organosiloxane group:

(R ² is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group.)
Q is a divalent group connecting the Rf group and the Z group, and the Rf group and the W group, selected from the following formula:

Z is an organopolysiloxane residue represented by the following formula (4-1) or (4-2):

R is a monovalent hydrocarbon group having 8 to 40 carbon atoms which may be substituted with an ester group, and A is a group represented by the following formula (2):

(X is independently a hydrolyzable group, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, b is an integer of 2 or more, and a is 2 or 3.)
x and y are each independently an integer of 1 to 9, wherein x + y = (valence of Z-1), and R and A are bonds of the above formula (4-1) or (4-2), respectively. To join. However, one of the bonds is bonded to Q. ]   A surface treating agent composition comprising the perfluoroether group-containing organopolysiloxane and / or a partial hydrolysis condensate thereof according to any one of claims 1 to 6.   An article having on its surface a cured coating formed by curing the surface treating agent composition according to claim 7.   An optical member having on its surface a cured film formed by curing the surface treating agent composition according to claim 7.

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