JP6888685B2 - Fluorine-containing coating composition, surface treatment agent and article - Google Patents

Description

The present invention relates to a coating agent containing a hydrolyzable alkoxy group or an aryloxy group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, and is particularly applied even in vacuum vapor deposition coating. A fluorine-containing coating agent composition capable of improving the subsequent curing rate and forming a stable film in a short time, a surface treatment agent containing the coating agent composition, and treatment with the surface treatment agent. Providing the goods that have been made.

In recent years, touch panels on screens, including mobile phone displays, are accelerating. However, many touch panels have a bare screen, and there are many opportunities for direct contact with fingers, cheeks, etc., and there is a problem that dirt such as sebum is easily attached. Therefore, there is an increasing demand for a technique for making it difficult for fingerprints to be attached to the surface of a display and a technique for making it easier to remove stains in order to improve the appearance and visibility.

In general, a fluoropolyether group-containing compound has water- and oil-repellent properties, chemical resistance, lubricity, mold releasability, antifouling property, and the like because its surface free energy is very small. Utilizing its properties, it is industrially widely used as a water- and oil-repellent antifouling agent for paper, fibers, etc., a lubricant for magnetic recording media, an oil-proof agent for precision equipment, a mold release agent, a cosmetic, a protective film, etc. ing. However, its properties also mean that it is non-adhesive and non-adhesive to other base materials, and even if it can be applied to the surface of the base material, it is difficult to make the film adhere to the base material. Met.

On the other hand, a silane coupling agent is well known as a substance for binding an organic compound to the surface of a base material such as glass or cloth, and is widely used as a coating agent on the surface of various base materials. The silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group causes a self-condensation reaction due to moisture in the air or the like to form a film. The film becomes a durable and strong film by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, or the like.

Therefore, by introducing a hydrolyzable silyl group into the fluoropolyether group-containing compound, it is easy to adhere to the surface of the base material, and the surface of the base material has water and oil repellency, chemical resistance, lubricity, and mold releasability. Compositions capable of forming a film having antifouling properties and the like are disclosed (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent No. 4672095, Japanese Patent Application Laid-Open No. 2008-534696). No., Japanese Patent Application Laid-Open No. 2008-537557, Japanese Patent Application Laid-Open No. 2012-072272, Japanese Patent Application Laid-Open No. 2012-157856, Japanese Patent Application Laid-Open No. 2013-136833).

These compositions are generally used after being diluted with a solvent capable of dissolving a fluoropolyether group-containing silane compound. The dilution concentration varies depending on the coating method, but in the case of vapor deposition coating, it is often used in the range of 10 to 50% by mass, and in the case of spray coating or dipping coating, it is 0.03 to 5% by mass. Often used in the range. As the fluoropolyether group-containing polymer used in these compositions, a compound containing an alkoxysilyl group such as a methoxy group or an ethoxy group is mainly used as a hydrolyzable silyl group. When applied to the surface of a base material such as glass, it is hydrolyzed by moisture in the air or adsorbed water on the base material, and crosslinks with active groups between polymers or on the surface of the base material to form chemical bonds. If this cross-linking reaction is fast, the formation of the coating film proceeds rapidly and a durable film can be formed, but the alkoxysilyl group should have a sufficient reaction rate from the viewpoint of hydrolyzability. However, faster curing was required.

Therefore, the prior art document describes a method of adding various inorganic acids, organic acids, amines and other basic compounds as catalysts for the purpose of accelerating the curing rate. However, if these catalyst components remain after coating, the crosslinked portion may be re-decomposed or the surface characteristics such as the contact angle and the friction coefficient may be adversely affected. Further, in the case of a touch panel surface application such as a smartphone, since it is directly touched with a finger, from these viewpoints, a compound that gradually volatilizes with time and does not remain on the surface is preferable.
On the other hand, the vapor deposition coating takes a step of heating and evaporating the polymer component in a vacuum to adhere it to the substrate, but if the additive is easily volatilized, it evaporates before the polymer and is drawn into the vacuum line side. There is a problem that a sufficient effect cannot be obtained because it is easy to be easily fixed to the base material.

Japanese Unexamined Patent Publication No. 2003-238577 Japanese Patent No. 2860979 Japanese Patent No. 4672095 Japanese Patent Application Laid-Open No. 2008-534696 Japanese Patent Application Laid-Open No. 2008-537557 Japanese Unexamined Patent Publication No. 2012-0727272 Japanese Unexamined Patent Publication No. 2012-157856 Japanese Unexamined Patent Publication No. 2013-136833

The present invention has been made in view of the above circumstances. Especially in vacuum-film deposition coating, by improving the curing rate after coating, performance such as wear durability is accelerated and a stable film is formed in a short time. It is an object of the present invention to provide a fluorine-containing coating agent composition which can be used, a surface treatment agent containing the coating agent composition, and an article treated with the surface treatment agent.

As a result of diligent studies to achieve the above object, the present inventors have (A) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof. A silane having a hydrolyzable silyl group in which the hydrolyzable silyl group is an alkoxysilyl group and / or an aryloxysilyl group, and (B) a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or its In a coating agent composition containing a partially hydrolyzed condensate containing a compound in which the hydrolyzable silyl group is an asyloxysilyl group and / or an aroyloxysilyl group, the components (A) and (B) The mass ratio should be (A) / (B) = 99.9 / 0.1 to 80/20 (the total mass of the components (A) and (B) is 100), specifically, the main agent. By adding a small amount of a compound having a hydrolyzable silyl group, which has a molecular weight distribution similar to that of the above and the compound having catalytic activity is removed by hydrolysis, the curing rate after coating can be increased, especially in vacuum vapor deposition coating. We have found that it is possible to obtain a fluorine-containing coating agent composition that can be improved and can form a stable film in a short time, and have completed the present invention.

（式中、Ｒ¹は炭素数１〜４のアルキル基、炭素数２〜４のアルコキシ置換アルキル基、又はフェニル基であり、Ｒは水素原子の一部がハロゲン原子で置換されていてもよい炭素数１〜６の１価炭化水素基であり、ａは２又は３である。）
で示される加水分解性アルコキシシリル基及び／又はアリーロキシシリル基を少なくとも１つ有するものである［１］記載の含フッ素コーティング剤組成物。
［３］
前記式（２ａ）において、Ｒ¹がメチル基又はエチル基である［２］記載の含フッ素コーティング剤組成物。
［４］
（Ｂ）成分のフルオロポリエーテル基含有ポリマーで変性された加水分解性シリル基を有するシランが、下記一般式（１）
−Ｃ_gＦ_2gＯ− （１）
（式中、ｇは単位毎に独立に１〜６の整数である。）
で表される繰り返し単位を分子中に１０〜２００個含み、かつフルオロポリエーテル基含有ポリマーの少なくとも１つの末端に下記一般式（２ｂ）

（式中、Ｒ²は炭素数１〜４のアルキル基、炭素数２〜４のアルコキシ置換アルキル基、又はフェニル基であり、Ｒは水素原子の一部がハロゲン原子で置換されていてもよい炭素数１〜６の１価炭化水素基であり、ａ’は１、２又は３である。）
で示される加水分解性アシロキシシリル基及び／又はアロイルオキシシリル基を少なくとも１つ有するものである［１］〜［３］のいずれかに記載の含フッ素コーティング剤組成物。
［５］
前記式（２ｂ）において、Ｒ²がメチル基又はエチル基であり、ａ’が１又は２である［４］記載の含フッ素コーティング剤組成物。
［６］
（Ａ）成分及び（Ｂ）成分のフルオロポリエーテル基含有ポリマーで変性された加水分解性シリル基を有するシランが、下記一般式（３）、（４）、（５）及び（６）で表されるフルオロポリエーテル基含有ポリマー変性加水分解性シランから選ばれる少なくとも１種であることを特徴とする［１］〜［５］のいずれかに記載の含フッ素コーティング剤組成物。
Ａ−Ｒｆ−ＱＺ（Ｗ）_α （３）
Ｒｆ−（ＱＺ（Ｗ）_α）₂ （４）
Ａ−Ｒｆ−Ｑ−（Ｙ）_βＢ （５）
Ｒｆ−（Ｑ−（Ｙ）_βＢ）₂ （６）
［式中、Ｒｆは−（ＣＦ₂）_d−Ｏ−（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_q（ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_r（ＣＦ₂ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_s（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_t−（ＣＦ₂）_d−であり、ｐ、ｑ、ｒ、ｓ、ｔはそれぞれ独立に０〜２００の整数であり、かつ、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝１０〜２００の整数であり、これらの括弧内に示される各単位はランダムに結合されていてよく、ｄは独立に０〜５の整数である。Ａはフッ素原子、水素原子、又は末端が−ＣＦ₃基、−ＣＦ₂Ｈ基もしくは−ＣＦＨ₂基である１価のフッ素含有基であり、Ｑは単結合、又はフッ素置換されていてもよい２価の有機基であり、Ｚは単結合、ジオルガノシリレン基、−ＪＣ＝〔Ｊはアルキル基、ヒドロキシル基もしくはＫ₃ＳｉＯ−（Ｋは独立に水素原子、アルキル基、アリール基又はアルコキシ基）で示されるシリルエーテル基〕で示される３価の基、−ＬＳｉ＝（Ｌはアルキル基）で示される３価の基、−Ｃ≡で示される４価の基、−Ｓｉ≡で示される４価の基、及び２〜８価のシロキサン残基から選ばれる基であり、Ｗは下記一般式（７ａ）〜（７ｄ）

〔式中、Ｘは下記一般式（２ａ）又は一般式（２ｂ）

（式中、Ｒ¹及びＲ²はそれぞれ独立に炭素数１〜４のアルキル基、炭素数２〜４のアルコキシ置換アルキル基、又はフェニル基であり、Ｒは水素原子の一部がハロゲン原子で置換されていてもよい炭素数１〜６の１価炭化水素基であり、ａは２又は３であり、ａ’は１、２又は３である。）
で示される基であり、ｆは１〜１０の整数であり、Ｄは単結合又は炭素数１〜２０のフッ素置換されていてもよい２価の有機基であり、ｍは２〜６の整数であり、Ｍｅはメチル基である。〕
で表される加水分解性シリル基を有する基から選ばれる基であり、αは１〜７の整数である。Ｙはアルコキシシリル基、アリーロキシシリル基、アシロキシシリル基又はアロイルオキシシリル基を有する２価の基であり、βは１〜１０の整数であり、Ｂは水素原子、炭素数１〜４のアルキル基、又はハロゲン原子である。］
［７］
Ｙが下記一般式（８）〜（１０）で示される基から選ばれる少なくとも１種である［６］記載の含フッ素コーティング剤組成物。

（式中、Ｘは上記一般式（２ａ）又は一般式（２ｂ）で示される基であり、Ｄは単結合又は炭素数１〜２０のフッ素置換されていてもよい２価の有機基であり、Ｄ’は炭素数１〜１０のフッ素置換されていてもよい２価の有機基であり、Ｒ³は炭素数１〜２０の１価炭化水素基であり、ｅは１又は２である。）
［８］
Ｑが単結合又は下記式で示される２価の基から選ばれるものである［６］又は［７］記載の含フッ素コーティング剤組成物。

（式中、ｂは２〜４の整数であり、ｃは２〜４の整数であり、Ｍｅはメチル基である。）
［９］
Ｚが単結合又は下記式で示される基から選ばれるものである［６］〜［８］のいずれかに記載の含フッ素コーティング剤組成物。

（式中、ｈは２〜４の整数であり、Ｍｅはメチル基である。）
［１０］
更に、下記一般式（１１）で表されるフルオロポリエーテル基含有ポリマー（Ｃ）を含有するものである［１］〜［９］のいずれかに記載の含フッ素コーティング剤組成物。

（式中、Ｒｆ’は２価のフルオロオキシアルキレン基含有ポリマー残基である。Ａはフッ素原子、水素原子、又は末端が−ＣＦ₃基、−ＣＦ₂Ｈ基もしくは−ＣＦＨ₂基である１価のフッ素含有基である。）
［１１］
［１］〜［１０］のいずれかに記載の含フッ素コーティング剤組成物を含む表面処理剤。
［１２］
更に、フッ素原子を含有する溶剤で希釈したものである［１１］記載の表面処理剤。
［１３］
［１１］又は［１２］記載の表面処理剤で処理された物品。
［１４］
［１１］又は［１２］記載の表面処理剤で処理されたタッチパネル。
［１５］
［１１］又は［１２］記載の表面処理剤で処理された反射防止処理物品。
［１６］
［１１］又は［１２］記載の表面処理剤で処理されたガラス、強化ガラス、サファイヤガラス、石英ガラス又はＳｉＯ₂処理基板。Therefore, the present invention provides the following fluorine-containing coating agent composition, a surface treatment agent containing the coating agent composition, and an article treated with the surface treatment agent.
[1]
It contains the following components (A) and (B), and the mass ratio of the components (A) and (B) is (A) / (B) = 99.9 / 0.1 to 80/20 ((A)). A fluorine-containing coating agent composition, wherein the total mass of the component and the component (B) is 100).
(A) A silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an alkoxysilyl group and / or an aryloxysilyl. Substituent compound,
(B) A silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an asyloxysilyl group and / or aroyl. A compound that is an oxysilyl group.
[2]
The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The following general formula (2a) is used at least one end of a fluoropolyether group-containing polymer containing 10 to 200 repeating units represented by.

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 2 or 3).
The fluorine-containing coating agent composition according to [1], which has at least one hydrolyzable alkoxysilyl group and / or allyloxysilyl group represented by.
[3]
The fluorine-containing coating agent composition according to [2] ^{, wherein R 1} is a methyl group or an ethyl group in the formula (2a).
[4]
The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (B) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The following general formula (2b) is used at least one end of a fluoropolyether group-containing polymer containing 10 to 200 repeating units represented by.

(In the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a'is 1, 2 or 3).
The fluorine-containing coating agent composition according to any one of [1] to [3], which has at least one hydrolyzable asyloxysilyl group and / or alloyloxysilyl group represented by.
[5]
^{The fluorine-containing coating agent composition according to [4], wherein R 2} is a methyl group or an ethyl group and a'is 1 or 2 in the formula (2b).
[6]
The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A) and the component (B) is represented by the following general formulas (3), (4), (5) and (6). The fluorine-containing coating agent composition according to any one of [1] to [5], which is at least one selected from the fluoropolyether group-containing polymer-modified hydrolyzable silanes.
A-Rf-QZ (W) _α (3)
Rf- (QZ (W) _α ) ₂ (4)
A-Rf-Q- (Y) _β B (5)
Rf- (Q- (Y) _β B) ₂ (6)
[In the equation, Rf is − (CF ₂ ) _d −O− (CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF (CF ₃ ) CF ₂ O) _t − (CF ₂ ) _d −, and p, q, r, s, and t are independently integers from 0 to 200, and p + q + r + s + t = 10 to 200. Each unit shown in these parentheses may be randomly combined, and d is an independently integer of 0-5. A fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, a monovalent fluorine-containing group is a -CF ₂ H group or -CFH ₂ group, Q is may be a single bond, or a fluorine-substituted It is a divalent organic group, Z is a single bond, a diorganosylylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is an independently hydrogen atom, alkyl group, aryl group or alkoxy group). ), The trivalent group represented by -LSi = (L is an alkyl group), the tetravalent group represented by -C≡, and -Si≡. It is a group selected from a tetravalent group and a 2 to 8 valent siloxane residue, and W is the following general formulas (7a) to (7d).

[In the formula, X is the following general formula (2a) or general formula (2b).

(In the formula, R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms, alkoxy-substituted alkyl groups having 2 to 4 carbon atoms, or phenyl groups, and R is a halogen atom in a part of hydrogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms which may be substituted, a is 2 or 3, and a'is 1, 2 or 3).
Is a group represented by, f is an integer of 1 to 10, D is a divalent organic group that may be monobonded or substituted with fluorine having 1 to 20 carbon atoms, and m is an integer of 2 to 6. And Me is a methyl group. ]
It is a group selected from the groups having a hydrolyzable silyl group represented by, and α is an integer of 1 to 7. Y is a divalent group having an alkoxysilyl group, an aryloxysilyl group, an asyloxysilyl group or an alloyloxysilyl group, β is an integer of 1 to 10, B is a hydrogen atom and the number of carbon atoms is 1 to 4. Alkoxy group or halogen atom. ]
[7]
The fluorine-containing coating agent composition according to [6], wherein Y is at least one selected from the groups represented by the following general formulas (8) to (10).

(In the formula, X is a group represented by the above general formula (2a) or general formula (2b), and D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may be substituted with fluorine. , D'is a divalent organic group having 1 to 10 carbon atoms which may be substituted with fluorine, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2. )
[8]
The fluorine-containing coating agent composition according to [6] or [7], wherein Q is selected from a single bond or a divalent group represented by the following formula.

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.)
[9]
The fluorine-containing coating agent composition according to any one of [6] to [8], wherein Z is selected from a single bond or a group represented by the following formula.

(In the formula, h is an integer of 2-4 and Me is a methyl group.)
[10]
Further, the fluorine-containing coating agent composition according to any one of [1] to [9], which contains a fluoropolyether group-containing polymer (C) represented by the following general formula (11).

(In the formula, Rf'is a divalent fluorooxyalkylene group-containing polymer residue. A is a fluorine atom, a hydrogen atom, or -CF ₃ groups, -CF ₂ H groups or -CFH ₂ groups at the end 1 Valuable fluorine-containing group.)
[11]
A surface treatment agent containing the fluorine-containing coating agent composition according to any one of [1] to [10].
[12]
The surface treatment agent according to [11], which is further diluted with a solvent containing a fluorine atom.
[13]
An article treated with the surface treatment agent according to [11] or [12].
[14]
A touch panel treated with the surface treatment agent according to [11] or [12].
[15]
An antireflection-treated article treated with the surface-treating agent according to [11] or [12].
[16]
_{Glass, tempered glass, sapphire glass, quartz glass or SiO 2} treated substrate treated with the surface treatment agent according to [11] or [12].

The fluorine-containing coating agent composition of the present invention contains a hydrolyzable alkoxysilyl group modified with a fluoropolyether group-containing polymer and / or a silane containing an aryloxysilyl group and / or a partially hydrolyzed condensate thereof. The coating agent composition contains a hydrolyzable asyloxysilyl group and / or an aloyloxysilyl group, which basically has a molecular weight distribution similar to that of the polymer and from which an acetic acid compound having catalytic activity is removed by hydrolysis. By adding a small amount of the compound, the two polymers are simultaneously evaporated during vacuum vapor deposition coating, uniformly dispersed and coated on the substrate, and then hydrolyzed to uniformly generate the catalyst compound. The curing rate after coating is improved, and a stable and uniform film is formed in a short time. Further, it exerts an effect of promoting curing not only in vacuum deposition coating but also in wet coating (spray coating, dipping coating).

The fluorine-containing coating agent composition of the present invention is (A) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzable condensate thereof, and the hydrolyzable silyl. A silane having a hydrolyzable silyl group modified with a compound whose group is an alkoxysilyl group and / or an aryloxysilyl group, and (B) a fluoropolyether group-containing polymer, and / or a partially hydrolyzed condensate thereof. In a coating agent composition containing a compound in which the hydrolyzable silyl group is an asyloxysilyl group and / or an aroyloxysilyl group, the mass ratio of the component (A) to the component (B) is (A) /. (B) = 99.9 / 0.1 to 80/20 (the total mass of the component (A) and the component (B) is 100).

The mass ratio of the component (A) to the component (B) is (A) / (B) = 99.9 / 0.1 to 80/20, preferably 99.8 / 0.2 to 85/15. Yes, more preferably 99.5 / 0.5 to 90/10 (the total mass of the components (A) and (B) is 100). If the amount of the component (B) is less than the above ratio, the effect of promoting curing may be difficult to be exhibited, and if it is more than the above ratio, the storage stability of the polymer at the time of uncuring may be lowered.

The component (A) and the component (B) have different hydrolyzable silyl groups bonded to silicon atoms (the component (A) is an alkoxysilyl group and / or an aryloxysilyl group, and the component (B)). Is an asyloxysilyl group and / or an alloyloxysilyl group), and the structure of the silane modified with the other fluoropolyether group-containing polymer has a similar molecular weight distribution. Often, those having the same structure or those having different structures may be used.

（式中、Ｒ¹は炭素数１〜４のアルキル基、炭素数２〜４のアルコキシ置換アルキル基、又はフェニル基であり、Ｒは水素原子の一部がハロゲン原子で置換されていてもよい炭素数１〜６の１価炭化水素基であり、ａは２又は３である。）
で示される加水分解性アルコキシシリル基及び／又はアリーロキシシリル基を少なくとも１つ有するものが好適に用いられる。As the silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A), the fluoropolyether group of the component (A) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The molecule contains 10 to 200, preferably 20 to 100 repeating units represented by, and at least one end, preferably one or two ends, more preferably one of the fluoropolyether group-containing polymer. The following general formula (2a) at the end

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 2 or 3).
Those having at least one hydrolyzable alkoxysilyl group and / or allyloxysilyl group represented by are preferably used.

Further, the component (A) has at least one hydrolyzable alkoxysilyl group and / or an aryloxysilyl group represented by the above formula (2a) in the molecule, preferably 1 to 12, more preferably. It is desirable to have 1 to 6 of.

（式中、Ｒ²は炭素数１〜４のアルキル基、炭素数２〜４のアルコキシ置換アルキル基、又はフェニル基であり、Ｒは水素原子の一部がハロゲン原子で置換されていてもよい炭素数１〜６の１価炭化水素基であり、ａ’は１、２又は３である。）
で示される加水分解性アシロキシシリル基及び／又はアロイルオキシシリル基を少なくとも１つ有するものが好適に用いられる。As the silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (B), the fluoropolyether group of the component (B) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The molecule contains 10 to 200, preferably 20 to 100 repeating units represented by, and at least one end, preferably one or two ends, more preferably one of the fluoropolyether group-containing polymer. The following general formula (2b) at the end

(In the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a'is 1, 2 or 3).
Those having at least one hydrolyzable asyloxysilyl group and / or alloyloxysilyl group represented by are preferably used.

Further, the component (B) has at least one hydrolyzable asyloxysilyl group and / or aloyloxysilyl group represented by the above formula (2b), preferably 1 to 12, and more preferably. It is desirable to have 1 to 6 pieces.

Examples of the repeating unit represented by the above general formula (1), which is a fluoropolyether group, include the following units. The fluoropolyether group may be composed of one of these repeating units alone, or may be a combination of two or more, and each repeating unit may be randomly bonded.
−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 O−
−CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O−
−C (CF ₃ ) ₂ O−

In the above formula (2a), R ¹ is an alkyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or the like, and the number of carbon atoms. It is an alkoxy-substituted alkyl group such as 2 to 4 methoxymethyl group, methoxyethyl group, ethoxymethyl group or ethoxyethyl group, or a phenyl group, and among them, a methyl group and an ethyl group are preferable.
R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of the hydrogen atom may be substituted with a halogen atom, and is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or sec. Examples thereof include an unsubstituted or halogen-substituted alkyl group such as a −butyl group, a tert-butyl group, a trifluoroethyl group, and a trichloroethyl group, and an unsubstituted or halogen-substituted aryl group such as a phenyl group. Of these, a methyl group and an ethyl group are preferable.

In the above formula (2b), R ² is an alkyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or the like, and the number of carbon atoms. It is an alkoxy-substituted alkyl group such as 2 to 4 methoxymethyl group, methoxyethyl group, ethoxymethyl group or ethoxyethyl group, or a phenyl group, and among them, a methyl group and an ethyl group are preferable.
R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of the hydrogen atom may be substituted with a halogen atom, and is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or sec. Examples thereof include an unsubstituted or halogen-substituted alkyl group such as a −butyl group, a tert-butyl group, a trifluoroethyl group, and a trichloroethyl group, and an unsubstituted or halogen-substituted aryl group such as a phenyl group. Of these, a methyl group and an ethyl group are preferable.

（式中、Ｘは上記一般式（２ａ）又は（２ｂ）で示される基であり、ｆは１〜１０の整数であり、Ｄは単結合又は炭素数１〜２０のフッ素置換されていてもよい２価の有機基であり、ｍは２〜６の整数であり、Ｍｅはメチル基である。）
で表される加水分解性シリル基を有する基から選ばれる基であり、αは１〜７の整数である。Ｙはアルコキシシリル基、アリーロキシシリル基、アシロキシシリル基及びアロイルオキシシリル基から選ばれる加水分解性シリル基を有する２価の基であり、βは１〜１０の整数であり、Ｂは水素原子、炭素数１〜４のアルキル基、又はハロゲン原子である。〕Hydrolyzable alkoxysilyl group modified with the fluoropolyether group-containing polymer of the component (A) and / or the hydrolyzable alkoxysilyl group modified with the allyloxysilyl group-containing silane and the fluoropolyether group-containing polymer of the component (B). The siloxysilyl group and / or alloyloxysilyl group-containing silane is derived from the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the following general formulas (3), (4), (5) and (6). At least one selected is more preferred.
A-Rf-QZ (W) _α (3)
Rf- (QZ (W) _α ) ₂ (4)
A-Rf-Q- (Y) _β B (5)
Rf- (Q- (Y) _β B) ₂ (6)
[In the equation, Rf is − (CF ₂ ) _d −O− (CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF (CF ₃ ) CF ₂ O) _t − (CF ₂ ) _d −, and p, q, r, s, and t are independently integers from 0 to 200, and p + q + r + s + t = 10 to 200. Each unit shown in these parentheses may be randomly combined, and d is an independently integer of 0-5. A fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, a monovalent fluorine-containing group is a -CF ₂ H group or -CFH ₂ group, Q is may be a single bond, or a fluorine-substituted It is a divalent organic group, Z is a single bond, a diorganosylylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is an independently hydrogen atom, alkyl group, aryl group or alkoxy group). ), The trivalent group represented by -LSi = (L is an alkyl group), the tetravalent group represented by -C≡, and -Si≡. It is a group selected from a tetravalent group and a 2 to 8 valent siloxane residue, and W is the following general formulas (7a) to (7d).

(In the formula, X is a group represented by the above general formula (2a) or (2b), f is an integer of 1 to 10, and D is a single bond or even if it is substituted with fluorine having 1 to 20 carbon atoms. It is a good divalent organic group, m is an integer of 2-6 and Me is a methyl group.)
It is a group selected from the groups having a hydrolyzable silyl group represented by, and α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable silyl group selected from an alkoxysilyl group, an aryloxysilyl group, an asyloxysilyl group and an alloyloxysilyl group, β is an integer of 1 to 10, and B is an integer of 1 to 10. It is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ]

In the above equations (3) to (6), Rf is − (CF ₂ ) _d −O− (CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF) ₂ CF ₂ CF ₂ O) _s (CF (CF ₃ ) CF ₂ O) _t − (CF ₂ ) _d −.
Here, p, q, r, s, and t are independently integers of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, and s is. An integer of 0 to 50, t is an integer of 0 to 100, and p + q + r + s + t is an integer of 10 to 200, preferably an integer of 20 to 100, and each unit shown in parentheses is randomly combined. You may be. d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 1 or 2.

（式中、ｄ’は上記ｄと同じであり、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’はそれぞれ１以上の整数であり、その上限は上記ｐ、ｑ、ｒ、ｓ、ｔの上限と同じであり、かつ、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’の合計は１〜２００である。ｕは１以上の整数、ｖは１以上の整数で、ｕ＋ｖ＝２〜１００の整数である。各繰り返し単位はランダムに結合されていてよい。）Specific examples of Rf include those shown below.

(In the formula, d'is the same as the above d, p', q', r', s', and t'are integers of 1 or more, respectively, and the upper limit thereof is the above p, q, r, s, t. Is the same as the upper limit of, and the total of p', q', r', s', and t'is 1 to 200. u is an integer of 1 or more, v is an integer of 1 or more, and u + v = 2. It is an integer of ~ 100. Each repeating unit may be randomly combined.)

The formula (3), in (5), A is a fluorine atom, a monovalent fluorine-containing group hydrogen atom, or a terminal is a -CF ₃ group, -CF ₂ H group or -CFH ₂ group, monovalent Specific examples of the fluorine-containing group of the above include those shown below.
−CF ₃
−CF ₂ CF ₃
−CF ₂ CF ₂ CF ₃
−CF ₂ H
-CFH ₂

In the above formulas (3) to (6), Q is a divalent organic group that may be single-bonded or fluorine-substituted, and is a linking group of an Rf group and a terminal group. As Q, preferably, a diorganosylylene group such as an amide bond, an ether bond, an ester bond or a dimethylsilylene group, −Si [OH] [(CH ₂ ) _b Si (CH ₃ ) ₃ ] − (b is 2 to 4). It is an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms, which may contain one or more structures selected from the group consisting of groups represented by (an integer of), and more preferably the above structure. It is an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms.

Here, as the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexa. It may be an alkylene group such as a methylene group or an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene-arylene group, etc.), and further, one of the hydrogen atoms of these groups. Examples thereof include those in which a part or the whole is substituted with a halogen atom such as fluorine or iodine, and among them, an unsubstituted or substituted alkyl group having 2 to 4 carbon atoms or a phenyl group is preferable.

Examples of such Q include the following groups.

（式中、ｂは２〜４の整数であり、ｃは２〜４の整数であり、Ｍｅはメチル基である。）

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.)

In each of the above formulas (3) and (4), Z is a single bond, preferably a diorganosylylene group such as a dialkylsilylene group having 1 to 3 carbon atoms, and −JC = [J is preferably an alkyl having 1 to 3 carbon atoms. A silyl represented by a group, a hydroxyl group or K ₃ SiO− (K is an independently hydrogen atom, preferably an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, or preferably an alkoxy group having 1 to 3 carbon atoms). Ether group], a trivalent group represented by −LSi = (L is preferably an alkyl group having 1 to 3 carbon atoms), a tetravalent group represented by −C≡, and −Si≡ It is a group selected from a tetravalent group represented by, and a siloxane residue of 2 to 8 valence, preferably 2 to 4 valent, and when it contains a siloxane bond, it has 2 to 13 silicon atoms, preferably silicon. It is preferably a chain, branched or cyclic organopolysiloxane residue having 2 to 5 atoms. Further, it may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group, that is, Si − (CH ₂ ) _{n −} Si (n is an integer of 2 to 6 in the above formula).
The organopolysiloxane residue preferably has an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, or a phenyl group. The alkylene group in the silalkylene bond preferably has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

Examples of such Z include those shown below.

（式中、ｈは２〜４の整数、Ｍｅはメチル基である。）

(In the formula, h is an integer of 2 to 4 and Me is a methyl group.)

（式中、Ｘは上記と同じであり、ｆは１〜１０、好ましくは２〜８の整数であり、Ｄは単結合又は炭素数１〜２０のフッ素置換されていてもよい２価の有機基であり、ｍは２〜６、好ましくは２〜４の整数であり、Ｍｅはメチル基である。）In the above formulas (3) and (4), W is a group selected from the groups having a hydrolyzable silyl group represented by the following general formulas (7a) to (7d).

(In the formula, X is the same as above, f is an integer of 1-10, preferably 2-8, and D is a divalent organic that may be single bond or fluorine substituted with 1-20 carbon atoms. It is a group, m is an integer of 2 to 6, preferably 2 to 4, and Me is a methyl group.)

Here, X is the same as above.
D is a single bond or a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms which may be substituted with fluorine, preferably a divalent hydrocarbon group, and the divalent hydrocarbon group may be used. , Methylene group, ethylene group, propylene group (trimethylethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, alkylene group such as octamethylene group, arylene group such as phenylene group, or Examples thereof include a combination of two or more of these groups (alkylene / arylene group, etc.) and those in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms. As D, an ethylene group, a propylene group, and a phenylene group are preferable.

（式中、ｆは上記と同じである。）Specifically, as W, the following can be exemplified.

(In the formula, f is the same as above.)

In the above equations (3) and (4), α is an integer of 1 to 7, preferably an integer of 1 to 3.

（式中、Ｘ、Ｄは上記と同じであり、Ｄ’は炭素数１〜１０のフッ素置換されていてもよい２価の有機基であり、Ｒ³は炭素数１〜２０の１価炭化水素基であり、ｅは１又は２である。）In the above formulas (5) and (6), Y is a divalent group having a hydrolyzable silyl group selected from an alkoxysilyl group, an aryloxysilyl group, an asyloxysilyl group and an aroyloxysilyl group, and is preferable. Is a group represented by the following general formula (8), (9) or (10).

(In the formula, X and D are the same as above, D'is a divalent organic group having 1 to 10 carbon atoms which may be substituted with fluorine, and R ³ is a monovalent hydrocarbon having 1 to 20 carbon atoms. It is a hydrogen group, and e is 1 or 2.)

Here, X and D are the same as above.
D'is a divalent organic group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms which may be substituted with fluorine, preferably a divalent hydrocarbon group, and the divalent hydrocarbon group is a methylene group. , Ethylene group, propylene group (trimethylethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, alkylene group such as octamethylene group, arylene group such as phenylene group, or groups thereof. Examples thereof include a combination of two or more of the above groups (alkylene / arylene group, etc.) and those in which a part or all of the hydrogen atoms of these groups are replaced with fluorine atoms. As D', an ethylene group and a propylene group are preferable.

Further, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Alkyl groups such as groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups and octyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups and propenyl groups, phenyl groups, Examples thereof include an aryl group such as a trill group, an aralkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group. Of these, a methyl group is preferred.

Specific examples of Y include the following groups.

（式中、Ｘは上記と同じであり、Ｍｅはメチル基である。）

(In the formula, X is the same as above and Me is a methyl group.)

In the above formulas (5) and (6), β is an integer of 1 to 10, preferably an integer of 1 to 4.
Further, in the above formulas (5) and (6), B is a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group, or a fluorine atom, a chlorine atom or a bromine atom. It is a halogen atom such as an iodine atom.

とし、Ｚ基を

とし、加水分解性シリル基を含むＷ基を

として表されるものを下記に例示する。これらＱ、Ｚ、Ｗの組み合わせは、これらに限られたものではなく、単純にＱ、Ｚ、Ｗを変更することで、数通りのフルオロポリエーテル基含有ポリマー変性加水分解性シランが得られる。いずれのフルオロポリエーテル基含有ポリマー変性加水分解性シランでも本発明の効果は発揮できる。As the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the above formulas (3) and (4), the linking group Q is used.

And the Z group

And the W group containing a hydrolyzable silyl group

What is represented as is illustrated below. These combinations of Q, Z, and W are not limited to these, and by simply changing Q, Z, and W, several fluoropolyether group-containing polymer-modified hydrolyzable silanes can be obtained. The effects of the present invention can be exhibited with any fluoropolyether group-containing polymer-modified hydrolyzable silane.

（式中、ｔ１、ｒ１はそれぞれｔ’、ｒ’と同じである。）

(In the formula, t1 and r1 are the same as t'and r', respectively.)

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

(In the formula, p1 and q1 are the same as p'and q', respectively.)

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

(In the formula, p1 and q1 are the same as p'and q', respectively.)

（式中、ｕ１、ｖ１は１以上の整数で、ｕ１＋ｖ１＝ｔ１であり、ｔ１はｔ’と同じである。）

(In the formula, u1 and v1 are integers of 1 or more, u1 + v1 = t1, and t1 is the same as t'.)

（式中、ｔ１はｔ’と同じである。）Further, the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the above formulas (3) and (4) using those other than the above Q, Z and W and combining them has the following structure. Can be mentioned. Xa is the same as above.

(In the formula, t1 is the same as t'.)

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

(In the formula, p1 and q1 are the same as p'and q', respectively.)

(In the formula, p1 and q1 are the same as p'and q', respectively.)

(In the formula, p1 and q1 are the same as p'and q', respectively.)

（式中、Ｒｆａ＝−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−であり、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。ｆ１は１〜１０の整数である。）

(In the equation, Rfa = −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _{p1 − CF 2} −, and p1 and q1 are the same as p'and q', respectively. F1 is 1. It is an integer of -10.)

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。ｆ１は１〜１０の整数である。）

(In the formula, p1 and q1 are the same as p'and q', respectively. F1 is an integer of 1 to 10.)

（式中、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

(In the formula, p1 and q1 are the same as p'and q', respectively.)

（式中、Ｒｆｂは−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−であり、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。Ｒ⁴は−ＣＨ₂ＣＨ₂−及び／又は−ＣＨ（ＣＨ₃）−である。）

（式中、Ｒｆｂは−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−であり、ｐ１、ｑ１はそれぞれｐ’、ｑ’と同じである。）

(In the equation, Rfb is −CF ₂ O − (C ₂ F ₄ O) _q1 (CF ₂ O) _{p1 − CF 2} −, and p1 and q1 are the same as p'and q', respectively. R ⁴ is −CH ₂ CH ₂ − and / or −CH (CH ₃ ) −)

(In the equation, Rfb is −CF ₂ O − (C ₂ F ₄ O) _q1 (CF ₂ O) _{p1 − CF 2} −, and p1 and q1 are the same as p'and q', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）Examples of the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the above formulas (5) and (6) have the following structure. Xa is the same as above.

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

（式中、ｐ１、ｑ１、ｔ１はそれぞれｐ’、ｑ’、ｔ’と同じである。）

(In the equation, p1, q1 and t1 are the same as p', q'and t', respectively.)

In the fluorine-containing coating agent composition of the present invention, as the component (A) or the component (B), a terminal hydrolyzable group of silane having a hydrolyzable silyl group modified with the above-mentioned fluoropolyether group-containing polymer is used. It may contain a partially hydrolyzed condensate obtained by partially hydrolyzing and condensing by a method known in advance.

The molecular weights of the components (A) and (B) are about the same (for example, the weight average molecular weight of the component (B) is 0.6 to 1.3 times the weight average molecular weight of the component (A), particularly 0.7. It is often in the range of about 1.2 times, particularly about 0.74 to 1.1 times), and these weight average molecular weights are preferably 1,000 to 20,000, respectively. More preferably, it is 000 to 10,000. If the weight average molecular weight is too small, the water and oil repellency and low dynamic friction property of the fluoropolyether group may not be exhibited, and if it is too large, the adhesion to the substrate may be deteriorated. In the present invention, the weight average molecular weight can be measured as a standard polystyrene-equivalent value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a developing solvent (hereinafter, the same).

（式中、Ａは前記と同じであり、Ｒｆ’は２価のフルオロオキシアルキレン基含有ポリマー残基である。）
で表されるフルオロポリエーテル基含有ポリマー（以下、無官能性ポリマーと称することもある）を含有してもよい。The fluorine-containing coating agent composition of the present invention further contains the following general formula (11) as the component (C).

(In the formula, A is the same as above, and Rf'is a divalent fluorooxyalkylene group-containing polymer residue.)
A fluoropolyether group-containing polymer represented by (hereinafter, may be referred to as a non-functional polymer) may be contained.

In the above formula (11), A can exemplify the same thing as A illustrated above, and as A,
-F
−CF ₃
−CF ₂ CF ₃
−CF ₂ CF ₂ CF ₃
Is preferable.

（式中、ｐ２は５〜２００、好ましくは１０〜１００の整数、ｑ２は５〜２００、好ましくは１０〜１００の整数、ｒ２は１０〜２００、好ましくは２０〜１００の整数、ｔ２は５〜２００、好ましくは１０〜１００の整数、ｔ３は１０〜２００、好ましくは２０〜１００の整数で、ｔ２＋ｐ２は１０〜２００、好ましくは２０〜１００の整数、ｑ２＋ｐ２は１０〜２００、好ましくは２０〜１００の整数である。）Rf'is a divalent fluorooxyalkylene group-containing polymer residue, which may be the same as or different from the Rf exemplified above, and the Rf'is preferably as shown below.

(In the formula, p2 is an integer of 5 to 200, preferably 10 to 100, q2 is an integer of 5 to 200, preferably 10 to 100, r2 is an integer of 10 to 200, preferably an integer of 20 to 100, and t2 is 5 to. 200, preferably an integer of 10 to 100, t3 is an integer of 10 to 200, preferably an integer of 20 to 100, t2 + p2 is an integer of 10 to 200, preferably an integer of 20 to 100, q2 + p2 is an integer of 10 to 200, preferably 20 to 100. Is an integer of.)

（式中、ｐ２、ｑ２、ｒ２、ｔ２、ｔ３は上記と同じである。）Examples of the non-functional polymer represented by the formula (11) include the following.

(In the formula, p2, q2, r2, t2, and t3 are the same as above.)

The weight average molecular weight of the fluoropolyether group-containing polymer of the component (C) is preferably 1,000 to 50,000, more preferably 1,000 to 10,000, and further the component (A). The weight average molecular weight is preferably in the range of 0.5 to 1.5 times the weight average molecular weight. If the weight average molecular weight is too small, the excellent slipperiness of the component (A) may be impaired, and if it is too large, the transparency of the coating film may be lowered.

As the non-functional polymer of the component (C), a commercially available product can be used, and for example, it is sold under the trade names of FOMBLIN, DEMNUM, and KRYTOX, so that it can be easily obtained. Examples of such a polymer include those having the following structure.

（式中、ｔ２’、ｐ２’は上記重量平均分子量を満足する数である。）FOMBLIN Y (trade name manufactured by Solvay Solexis, FOMBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100))

(In the formula, t2'and p2'are numbers that satisfy the above weight average molecular weight.)

（式中、ｑ２’、ｐ２’は上記重量平均分子量を満足する数である。）FOMBLIN Z (trade name manufactured by Solvay Solexis, FOMBLIN Z03 (weight average molecular weight: 4,000), FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight: 9,500))

(In the formula, q2'and p2'are numbers that satisfy the above weight average molecular weight.)

（式中、ｒ２’は上記重量平均分子量を満足する数である。）DEMNUM (trade name manufactured by Daikin Industries, Ltd., DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65 (weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))

(In the formula, r2'is a number that satisfies the above weight average molecular weight.)

（式中、ｔ３’は上記重量平均分子量を満足する数である。）KRYTOX (DuPont trade name, KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX (weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5,500), KRYTOX 143AD (weight average molecular weight) : 7,000)))

(In the formula, t3'is a number that satisfies the above weight average molecular weight.)

The amount used when the component (C) is blended is not particularly limited, but is preferably in the range of 0 to 50% by mass, more preferably in the range of 5 to 50% by mass with respect to the mass of the component (A).

Further, if necessary, other additives can be added to the fluorine-containing coating agent composition of the present invention as long as the present invention is not impaired. Specifically, hydrolysis and condensation catalysts, for example, organic tin compounds (dibutyltin dimethoxydo, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (fluorocarboxylic acid, acetic acid, methane, etc.) Basic organic compounds such as sulfonic acid), inorganic acids (hydrogen, sulfuric acid, etc.), compounds having a primary amino group, compounds having a secondary amino group, compounds having a tertiary amino group, compounds having a guanidyl group, etc. Examples thereof include compounds containing alkali metals such as lithium, sodium and potassium, and compounds containing alkaline earth metals such as magnesium and calcium. Among these, fluorocarboxylic acid, acetic acid, tetra n-butyl titanate, and dibutyl tin dilaurate are particularly desirable. The amount of the hydrolysis condensation catalyst added is the amount of the catalyst, but is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass with respect to 100 parts by mass of the component (A).

The fluorine-containing coating agent composition of the present invention can be prepared by uniformly mixing each of the above components by a conventional method.

The surface treatment agent of the present invention contains the above-mentioned fluorine-containing coating agent composition.
The surface treatment agent of the present invention, which comprises a fluorine-containing coating agent composition containing the component (A) and the component (B), is generally a solvent in which these polymers (components (A) and (B)) can be dissolved. It is used after being dissolved and diluted in a solvent. The diluting solvent is not particularly limited as long as it can be uniformly dissolved. Examples of such a solvent include a fluorine-modified aliphatic hydrocarbon solvent (perfluorohexane, perfluoroheptane, perfluorooctane, etc.), a fluorine-modified aromatic hydrocarbon solvent (m-xylenehexafluoride, benzotrifluoride, etc.). 1,3-Trifluoromethylbenzene, etc.), Fluorine-modified ether solvent (methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyl tetrahydrofuran), etc.), Fluorine-modified alkylamine solvent (Perfluorotributylamine, perfluorotripentylamine, etc.), partial fluorine-modified solvent (1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2 , 3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,5,5,6,6-tridecafluorohexane, 1,1, 1,2,2,3,3,4,5,5,6,6-tridecafluorooctane, 1,1,1,3,3-pentafluorobutane, etc.), hydrocarbon solvents (petroleum benzine) , Mineral spirits, toluene, xylene, etc.), solvents such as ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified. Among these, a fluorine-modified fluorine-containing solvent is desirable in terms of solubility, wettability, etc., and in particular, ethyl perfluorobutyl ether, decafluoropentane, and 1,1,1,3,3-pentafluorobutane are preferable. More preferred. The solvent may be used alone or in combination of two or more.

The optimum concentration of the component (A) and the component (B) to be dissolved in the solvent varies depending on the coating treatment method, but the component (A) is contained in the entire surface treatment agent containing the fluorine-containing coating agent composition and the solvent. The amount is in the range of 0.01 to 50% by mass, and particularly preferably in the range of 0.03 to 25% by mass. If the concentration of the component (A) is too low, sufficient antifouling property and water / oil repellency cannot be obtained after the coating treatment, and if it is too high, the coating film becomes non-uniform, the transparency is lowered, and the surface becomes sticky. To do.

The surface treatment agent containing the fluorine-containing coating agent composition of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, and vapor deposition treatment. The curing temperature varies depending on the curing method, but for example, when applied by a spray method, an inkjet method, a dipping method, a brush coating method, or a vacuum deposition method, the temperature is room temperature (20 ° C.) to 200 ° C., particularly 50 to 150 ° C. The range of is desirable. As the curing humidity, it is desirable to carry out under humidification in order to promote the reaction. The film thickness of the cured film is appropriately selected depending on the type of the base material, but is usually 0.1 to 100 nm, particularly 3 to 30 nm.
If the adhesion is poor, the adhesion _{can be improved by providing a SiO 2} layer as a primer layer, or performing vacuum plasma treatment, atmospheric pressure plasma treatment, or alkali treatment.

The base material treated with the surface treatment agent containing the fluorine-containing coating agent composition of the present invention is not particularly limited, and various materials such as paper, cloth, metal and oxides thereof, glass, plastic, ceramic, and quartz are used. It may be. The surface treatment agent containing the fluorine-containing coating agent composition of the present invention can impart water-repellent oil-repellent property, chemical resistance, mold releasability, low dynamic friction property, and antifouling property to these base materials. In particular, excellent antifouling performance can be imparted without impairing the transparency and texture of various articles, the base material can be protected from the intrusion of chemicals and the like, and the antifouling performance can be maintained for a long period of time. Examples of articles treated with a surface treatment agent containing the fluorine-containing coating agent composition of the present invention include optical articles, films, glass, quartz substrates, antireflection films, and particularly touch panels and antireflection films. Used for prevention treated articles, glass, tempered glass, sapphire glass, quartz glass, and SiO ₂ treated substrates.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

As the hydrolyzable alkoxysilyl group and / or allyloxysilyl group-containing silane (A) modified with a fluoropolyether group-containing polymer, the following compounds A1 to A4 are hydrolyzed with a fluoropolyether group-containing polymer. The following compounds B1 and B2 were prepared as the sex acyloxysilyl group and / or alloyloxysilyl group-containing silane (B).

（重量平均分子量：４，６００）Compound A1

(Weight average molecular weight: 4,600)

（Ｒｆａ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５、ｆ＝３）
（重量平均分子量：５，５００）Compound A2

(Rfa: −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _p1 −CF ₂ −, q1 / p1 = 0.9, p1 + q1 ≈ 45, f = 3)
(Weight average molecular weight: 5,500)

（Ｒｆｂ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒５０、ｆ＝３）
（重量平均分子量：４，８００）Compound A3

(Rfb: −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _p1 −CF ₂ −, q1 / p1 = 1.1, p1 + q1 ≈ 50, f = 3)
(Weight average molecular weight: 4,800)

（Ｒｆｂ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒４０）
（重量平均分子量：４，１００）Compound A4

(Rfb: −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _p1 −CF ₂ −, q1 / p1 = 1.1, p1 + q1 ≈ 40)
(Weight average molecular weight: 4,100)

（Ｒｆｂ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒５０、ｆ＝３）
（重量平均分子量：４，８００）Compound B1

(Rfb: −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _p1 −CF ₂ −, q1 / p1 = 1.1, p1 + q1 ≈ 50, f = 3)
(Weight average molecular weight: 4,800)

（Ｒｆｂ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒４０）
（重量平均分子量：４，１００）Compound B2

(Rfb: −CF ₂ O− (C ₂ F ₄ O) _q1 (CF ₂ O) _p1 −CF ₂ −, q1 / p1 = 1.1, p1 + q1 ≈ 40)
(Weight average molecular weight: 4,100)

The following C1 and C2 were prepared as curing catalysts for comparative examples.
C1: Trifluoroacetic acid C2: Acetic acid

[Examples 1 to 6 and Comparative Examples 1 to 6]
Preparation of Surface Treatment Agent In Examples 1 to 6, any of the above-mentioned A1 to A4 components and any of the B1 and B2 components are mixed with the compositions shown in Table 1 below (mixtures 1 to 6). A surface treatment agent was prepared by dissolving the mixture (total 100 parts by mass) in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration was 20% by mass. In Comparative Examples 1 to 6, any of the above-mentioned A1 to A4 components, or any of the curing catalysts C1 and C2 for Comparative Examples, were mixed with the compositions shown in Table 2 below (mixtures 7 to 12). ), A surface treatment agent was prepared by dissolving the mixture (total 100 parts by mass) in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration was 20% by mass.

Formation of hardened film by vacuum deposition Each surface treatment agent prepared above is _{vacuum-deposited on the outermost surface of glass (Gorilla 3 manufactured by Corning Inc.) treated with SiO 2} at 15 nm under the following conditions, and in an atmosphere of 25 ° C. and 50% humidity. A film (thickness: about 10 nm) formed by curing for 1 hour was used as a test piece in the following evaluation.
[Coating conditions and equipment by vacuum deposition]
Measuring device: Small vacuum vapor deposition device VPC-250F
Pressure: 2.0 x 10 ^-3 Pa to 3.0 x 10 ^{-2 Pa}
Deposition temperature (boat temperature): 500 ° C
Thin film deposition distance: 20 mm
Amount of treatment agent charged: 5 mg
Deposition amount: 5 mg

The cured film in the above test piece was evaluated by the following method.
[Water repellency]
The contact angle of the cured film with respect to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 3 below.

[Abrasion resistance]
Abrasion resistance to steel wool (# 0000):
Using Tribogear TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.), the cured film was reciprocally worn 5,000 times and 10,000 times under the following conditions, and then the contact angle of the cured film with water was measured by the contact angle meter DropMaster (Kyowa). It was measured using (manufactured by Interface Science Co., Ltd.). The results are shown in Table 3 below. If the water contact angle is less than 100 ° after 5,000 wears, the subsequent tests will not be carried out.
Contact area: 1 cm ²
Load: 1 kg
Travel distance (one way): 30 mm
Movement speed: 3,600 mm / min

Explanation of Table 3
Comparison of Examples 1 to 6 and Comparative Examples 1 to 4 In Examples 1 to 6, a polymer (A) having an alkoxysilyl group at the terminal and a polymer having an acyloxysilyl group at the end having a similar molecular weight distribution (A). This is the case when B) is added and blended. On the other hand, Comparative Examples 1 to 4 are cases where only the polymer (A) is blended and the polymer (B) is not blended. In Examples 1 to 6, when the polymer (A) and the polymer (B) are vapor-deposited on the substrate, curing is promoted by the acid (acetic acid) generated by the hydrolysis of the polymer (B). On the other hand, in Comparative Examples 1 to 4, since only the polymer of the terminal alkoxysilane (methoxysilane) is used, hydrolysis is slow, film curing on the substrate is slow, and wear durability is inferior to that of Examples.

Comparison of Example 6 and Comparative Examples 5 and 6 Comparative Examples 5 and 6 are examples in which an organic acidic compound was added as a catalyst instead of the component (B). In vacuum vapor deposition, since these additives have a low boiling point, they are easily sucked to the vacuum exhaust line side and can hardly be fixed on the surface of the base material, so that the effect of promoting curing is not seen and nothing is added. It was at the same level as Comparative Example 4.

Claims (16)

It contains the following components (A) and (B), and the mass ratio of the components (A) and (B) is (A) / (B) = 99.9 / 0.1 to 80/20 ((A)). A fluorine-containing coating agent composition, wherein the total mass of the component and the component (B) is 100).
(A) A silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an alkoxysilyl group and / or an aryloxysilyl. Substituent compound,
(B) A silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an asyloxysilyl group and / or aroyl. A compound that is an oxysilyl group. The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The following general formula (2a) is used at least one end of a fluoropolyether group-containing polymer containing 10 to 200 repeating units represented by.

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 2 or 3).
The fluorine-containing coating agent composition according to claim 1, which has at least one hydrolyzable alkoxysilyl group and / or allyloxysilyl group represented by. The fluorine-containing coating agent composition according to claim 2, wherein in the formula (2a), R ^{1 is a methyl group or an ethyl group.} The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (B) is the following general formula (1).
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The following general formula (2b) is used at least one end of a fluoropolyether group-containing polymer containing 10 to 200 repeating units represented by.

(In the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may have a part of hydrogen atoms substituted with halogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a'is 1, 2 or 3).
The fluorine-containing coating agent composition according to any one of claims 1 to 3, which has at least one hydrolyzable asyloxysilyl group and / or alloyloxysilyl group represented by. The fluorine-containing coating agent composition according to claim 4, wherein in the formula (2b), R ² is a methyl group or an ethyl group, and a'is 1 or 2. The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A) and the component (B) is represented by the following general formulas (3), (4), (5) and (6). The fluorine-containing coating agent composition according to any one of claims 1 to 5, wherein the composition is at least one selected from the fluoropolyether group-containing polymer-modified hydrolyzable silanes.
A-Rf-QZ (W) _α (3)
Rf- (QZ (W) _α ) ₂ (4)
A-Rf-Q- (Y) _β B (5)
Rf- (Q- (Y) _β B) ₂ (6)
[In the equation, Rf is − (CF ₂ ) _d −O− (CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF (CF ₃ ) CF ₂ O) _t − (CF ₂ ) _d −, and p, q, r, s, and t are independently integers from 0 to 200, and p + q + r + s + t = 10 to 200. Each unit shown in these parentheses may be randomly combined, and d is an independently integer of 0-5. A fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, a monovalent fluorine-containing group is a -CF ₂ H group or -CFH ₂ group, Q is may be a single bond, or a fluorine-substituted It is a divalent organic group, Z is a single bond, a diorganosylylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is an independently hydrogen atom, alkyl group, aryl group or alkoxy group). ), The trivalent group represented by -LSi = (L is an alkyl group), the tetravalent group represented by -C≡, and -Si≡. It is a group selected from a tetravalent group and a 2 to 8 valent siloxane residue, and W is the following general formulas (7a) to (7d).

[In the formula, X is the following general formula (2a) or general formula (2b).

(In the formula, R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms, alkoxy-substituted alkyl groups having 2 to 4 carbon atoms, or phenyl groups, and R is a halogen atom in a part of hydrogen atoms. It is a monovalent hydrocarbon group having 1 to 6 carbon atoms which may be substituted, a is 2 or 3, and a'is 1, 2 or 3).
Is a group represented by, f is an integer of 1 to 10, D is a divalent organic group that may be monobonded or substituted with fluorine having 1 to 20 carbon atoms, and m is an integer of 2 to 6. And Me is a methyl group. ]
It is a group selected from the groups having a hydrolyzable silyl group represented by, and α is an integer of 1 to 7. Y is a divalent group having an alkoxysilyl group, an aryloxysilyl group, an asyloxysilyl group or an alloyloxysilyl group, β is an integer of 1 to 10, B is a hydrogen atom and the number of carbon atoms is 1 to 4. Alkoxy group or halogen atom. ] The fluorine-containing coating agent composition according to claim 6, wherein Y is at least one selected from the groups represented by the following general formulas (8) to (10).

(In the formula, X is a group represented by the above general formula (2a) or general formula (2b), and D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may be substituted with fluorine. , D'is a divalent organic group having 1 to 10 carbon atoms which may be substituted with fluorine, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2. ) The fluorine-containing coating agent composition according to claim 6 or 7, wherein Q is selected from a single bond or a divalent group represented by the following formula.

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.) The fluorine-containing coating agent composition according to any one of claims 6 to 8, wherein Z is selected from a single bond or a group represented by the following formula.

(In the formula, h is an integer of 2-4 and Me is a methyl group.) The fluorine-containing coating agent composition according to any one of claims 1 to 9, further comprising a fluoropolyether group-containing polymer (C) represented by the following general formula (11).

(In the formula, Rf'is a divalent fluorooxyalkylene group-containing polymer residue. A is a fluorine atom, a hydrogen atom, or -CF ₃ groups, -CF ₂ H groups or -CFH ₂ groups at the end 1 Valuable fluorine-containing group.) A surface treatment agent containing the fluorine-containing coating agent composition according to any one of claims 1 to 10. The surface treatment agent according to claim 11, which is further diluted with a solvent containing a fluorine atom. An article treated with the surface treatment agent according to claim 11 or 12. A touch panel treated with the surface treatment agent according to claim 11 or 12. An antireflection-treated article treated with the surface-treating agent according to claim 11 or 12. A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with the surface treatment agent according to claim 11 or 12.