JP2015224293A - Fluorine-containing coating agent and article treated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing coating agent which is improved in storage stability in a solution state before use and is capable of stable formation of a uniform coating film on a substrate.SOLUTION: A coating agent comprises (A) a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and/or its partially hydrolyzed condensate, (B) a solvent capable of dissolving ingredient (A) uniformly and (C) a 1-6C alcohol compound, in a content of ingredient (A) of 0.01-50 mass% and a content of ingredient (C) of 0.01-5 mass% relative to the whole of the coating agent.

Description

  The present invention relates to a coating agent containing a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer, and more particularly, storage stability in a solution state before use. In addition, it is possible to stably form a uniform coating film on a substrate, and to form a hydropolyether group-containing polymer modified with a fluoropolyether group-containing polymer that forms a film excellent in water and oil repellency and low dynamic friction. The present invention relates to a fluorine-containing coating agent containing a decomposable group-containing silane and / or a partial hydrolysis condensate thereof, and an article treated with the coating agent.

  In recent years, the touch panel of the screen including the display of the mobile phone has been accelerated. However, many touch panels have a bare screen, and there are many occasions where fingers, cheeks, etc. are in direct contact, and dirt such as sebum is likely to be attached. Therefore, there is an increasing demand for technology that makes it difficult to attach fingerprints to the surface of a display and technology that makes it easy to remove dirt in order to improve the appearance and visibility.

  In general, a fluoropolyether group-containing compound has very small surface free energy, and thus has water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties and the like. Utilizing its properties, it is widely used industrially for water and oil repellent and antifouling agents such as paper and fibers, lubricants for magnetic recording media, oil proofing agents for precision equipment, mold release agents, cosmetics and protective films. ing. However, its properties mean that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the substrate surface, it is difficult to make the coating adhere to the substrate. Met.

  On the other hand, silane coupling agents are well known as materials for bonding substrate surfaces such as glass and cloth and organic compounds, and are widely used as coating agents for various substrate surfaces. 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 with moisture in the air and forms a film. The coating becomes a strong coating having durability by chemically and physically bonding the hydrolyzable silyl group to the surface of glass or metal.

  Therefore, by introducing a hydrolyzable silyl group into the fluoropolyether group-containing compound, it is easy to adhere to the substrate surface, and on the substrate surface, water and oil repellency, chemical resistance, lubricity, releasability, Compositions capable of forming a film having antifouling properties and the like have been disclosed (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238777, Japanese Patent No. 2860979, Japanese Patent No. 4672095, and Special Table 2008-534696. No., JP-T 2008-537557, JP 2012-072722, JP 2012-157856, JP 2013-136833).

  These compositions are generally used after being diluted with a solvent capable of dissolving the fluoropolyether group-containing silane compound. The dilution concentration varies depending on the coating method, but in the case of spray coating or dipping coating, it is often used in the range of 0.03 to 5% by mass. These solvents are generally purchased from a solvent manufacturer and used, but usually contain a small amount of moisture. It is considered that such moisture is mixed during the production of the solvent, or absorbs moisture in the atmosphere or moisture attached to the wall surface of the container after the production. Moisture in the solvent reacts with the hydrolyzable silyl group, causing dimerization to multimerization between the polymers, and in some cases, causes gelation or precipitation of the polymer, which may cause a problem in storage stability.

  Even if gelation or polymer settling does not occur, increasing the molecular weight of the polymer may cause nozzle clogging problems in spray coating, inkjet coating, or dipping coating, In some cases, light and shade are likely to appear, a uniform film cannot be formed, sufficient performance cannot be obtained, and transparency and optical characteristics are impaired.

JP 2003-238777 A Japanese Patent No. 2860979 Japanese Patent No. 4672095 Special table 2008-534696 gazette JP 2008-537557 A JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A

  The present invention has been made in view of the above circumstances, and the fluorine-containing coating agent that can improve the storage stability in a solution state before use and can stably form a uniform coating film on a substrate. And an object surface-treated with the coating agent.

  As a result of intensive studies to achieve the above object, the present inventors have obtained (A) a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, (B) In the coating agent containing the solvent capable of uniformly dissolving the component (A), the content of the component (A) is 0.01 to 50% by mass with respect to the entire coating agent, and ( C) By containing the alcohol compound having 1 to 6 carbon atoms in an amount of 0.01 to 5% by mass with respect to the entire coating agent, the storage stability in a solution state before use is improved and the substrate is uniform on the substrate. The present inventors have found that it can be a fluorine-containing coating agent capable of stably forming a coating film, and has reached the present invention.

（式中、Ｒは炭素数１〜４のアルキル基、又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３である。）
で示される加水分解性シリル基を少なくとも１つ有するものであることを特徴とする〔１〕又は〔２〕記載の含フッ素コーティング剤。
〔４〕
式（２）の加水分解性基Ｘが、メトキシ基又はエトキシ基であることを特徴とする〔３〕記載の含フッ素コーティング剤。
〔５〕
（Ａ）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基含有シランが、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〕〜〔４〕のいずれかに記載の含フッ素コーティング剤。
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、ｄは独立に０〜５の整数であり、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、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い。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、Ｒは炭素数１〜４のアルキル基、又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３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基を有する基であり、αは１〜７の整数である。Ｙは加水分解性シリル基を側鎖に有する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。〕
〔６〕
Ｙが下記式（８）〜（１０）で示される〔５〕記載の含フッ素コーティング剤。

（式中、Ｒは炭素数１〜４のアルキル基、又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３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、Ｒ¹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。）
〔７〕
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〔５〕又は〔６〕記載の含フッ素コーティング剤。

（式中、ｂは２〜４の整数であり、ｃは１〜４の整数であり、ｊは１〜５０の整数であり、Ｍｅはメチル基である。）
〔８〕
Ｚが単結合又は下記式で示される２〜８価の基から選ばれるものである〔５〕〜〔７〕のいずれかに記載の含フッ素コーティング剤。

（式中、ｈは２〜４の整数であり、Ｍｅはメチル基である。）
〔９〕
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（Ｄ）を含有することを特徴とする〔１〕〜〔８〕のいずれかに記載の含フッ素コーティング剤。

（式中、Ｒｆは−（ＣＦ₂）_d−Ｏ−（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_q（ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_r（ＣＦ₂ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_s（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_t−（ＣＦ₂）_d−であり、ｄは独立に０〜５の整数であり、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、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い。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。）
〔１０〕
（Ｂ）成分の溶剤が、含フッ素溶剤である〔１〕〜〔９〕のいずれかに記載の含フッ素コーティング剤。
〔１１〕
〔１〕〜〔１０〕のいずれかに記載の含フッ素コーティング剤で処理された物品。
〔１２〕
〔１〕〜〔１０〕のいずれかに記載の含フッ素コーティング剤で処理されたタッチパネル。
〔１３〕
〔１〕〜〔１０〕のいずれかに記載の含フッ素コーティング剤で処理された反射防止処理物品。
〔１４〕
〔１〕〜〔１０〕のいずれかに記載の含フッ素コーティング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。 Accordingly, the present invention provides the following fluorine-containing coating agent and an article treated with the coating agent.
[1]
The following (A) to (C) components (A) hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partial hydrolysis condensate thereof,
(B) a solvent capable of uniformly dissolving the component (A),
(C) In the coating agent containing a C1-C6 alcohol compound, content of (A) component is 0.01-50 mass% with respect to the whole coating agent, and content of (C) component Is a fluorine-containing coating agent characterized by being 0.01 to 5% by mass with respect to the whole coating agent.
[2]
(C) Component is methanol or ethanol, The fluorine-containing coating agent as described in [1] characterized by the above-mentioned.
[3]
The hydrolyzable group-containing silane modified with the component (A) fluoropolyether group-containing polymer is represented by 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.)
10 to 200 repeating units represented by the following general formula (2)

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3.)
The fluorine-containing coating agent according to [1] or [2], which has at least one hydrolyzable silyl group represented by formula (1).
[4]
[3] The fluorine-containing coating agent according to [3], wherein the hydrolyzable group X of the formula (2) is a methoxy group or an ethoxy group.
[5]
The hydrolyzable group-containing silane modified with the component (A) fluoropolyether group-containing polymer is represented by the following general formulas (3), (4), (5) and (6) The fluorine-containing coating agent according to any one of [1] to [4], which is at least one selected from polymer-modified 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 formula, 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 - a and, d are independently integers of 0~5, p, q, r, s, t each independently 0 to 200 And p + q + r + s + t = an integer of 10 to 200, and each unit shown in parentheses may be bonded at random. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group, or —CFH ₂ group, and Q may be a single bond or fluorine-substituted. A divalent organic group, Z is a single bond, diorganosilylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, and a -Si≡. W is a group selected from a tetravalent group and a divalent to octavalent siloxane residue, and W represents the following general formulas (7a) to (7d)

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, f is an integer of 1 to 10, and D is (It is a single bond or a divalent organic group optionally substituted with fluorine having 1 to 20 carbon atoms, m is an integer of 2 to 6, and Me is a methyl group.)
And α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable silyl group in the side chain, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ]
[6]
The fluorine-containing coating agent according to [5], wherein Y is represented by the following formulas (8) to (10).

Wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and D is a single bond or fluorine having 1 to 20 carbon atoms. A divalent organic group that may be substituted; D ′ is a divalent organic group that may be substituted with fluorine having 1 to 10 carbon atoms; and R ¹ is a monovalent carbon group having 1 to 20 carbon atoms. A hydrogen group, and e is 1 or 2.)
[7]
The fluorine-containing coating agent according to [5] or [6], 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 1 to 4, j is an integer of 1 to 50, and Me is a methyl group.)
[8]
The fluorine-containing coating agent according to any one of [5] to [7], wherein Z is selected from a single bond or a divalent to octavalent group represented by the following formula.

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.)
[9]
The fluorine-containing coating agent according to any one of [1] to [8], further comprising a fluoropolyether group-containing polymer (D) represented by the following general formula (11).

(In the formula, 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 - a and, d are independently integers of 0~5, p, q, r, s, t each independently 0 to 200 And an integer of p + q + r + s + t = 10 to 200, and each unit shown in parentheses may be bonded at random.A is a fluorine atom, a hydrogen atom, or a terminal is a —CF ₃ group, — (It is a monovalent fluorine-containing group that is a CF ₂ H group or a —CFH ₂ group.)
[10]
(B) The fluorine-containing coating agent in any one of [1]-[9] whose solvent of a component is a fluorine-containing solvent.
[11]
Articles treated with the fluorine-containing coating agent according to any one of [1] to [10].
[12]
A touch panel treated with the fluorine-containing coating agent according to any one of [1] to [10].
[13]
An antireflective article treated with the fluorine-containing coating agent according to any one of [1] to [10].
[14]
A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with the fluorine-containing coating agent according to any one of [1] to [10].

  The fluorine-containing coating agent of the present invention contains an alcohol compound having 1 to 6 carbon atoms in a solution containing a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partial hydrolysis condensate thereof. By adding and blending, even if water is mixed in the solution, hydrolysis of the polymer terminal during storage until use is suppressed, or crosslinking reaction between hydrolyzable groups is suppressed. As a result, the storage stability is improved, troubles during coating can be prevented, and a uniform coating film can be stably formed on the substrate. Therefore, an excellent antifouling performance can be imparted without impairing the transparency and texture of various articles, the base material can be protected from intrusion of chemicals and the like, and the antifouling performance can be maintained for a long time.

  The fluorine-containing coating agent of the present invention comprises (A) a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, and (B) the component (A) uniformly. In the coating agent containing a solvent that can be dissolved and (C) an alcohol compound having 1 to 6 carbon atoms, the content of the component (A) is 0.01 to 50% by mass with respect to the entire coating agent. And content of (C) component is 0.01-5 mass% with respect to the whole coating agent, It is characterized by the above-mentioned.

（式中、Ｒは炭素数１〜４のアルキル基、又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３である。）
で示される加水分解性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。
更に、（Ａ）成分は、上記式（２）で示される加水分解性シリル基を少なくとも１個、好ましくは１〜１２個有するものであり、更にＸで示される加水分解性基を複数、好ましくは２〜３６個、より好ましくは２〜１８個有するものであることが望ましい。 As the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer of component (A), the fluoropolyether group of component (A) is represented by 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.)
10 to 200, preferably 20 to 100 repeating units represented by the following general formula (2) at least at one end, preferably at one end:

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3.)
Those having at least one hydrolyzable silyl group represented by the formula are preferably used.
Furthermore, the component (A) has at least one hydrolyzable silyl group represented by the above formula (2), preferably 1 to 12, and more preferably a plurality of hydrolyzable groups represented by X. Is preferably 2 to 36, more preferably 2 to 18.

Examples of the repeating unit represented by the general formula (1) which is a fluoropolyether group include the following units. In addition, the fluoropolyether group may be comprised by 1 type of these repeating units individually, may be a combination of 2 or more types, and each repeating unit may be couple | bonded at random.
-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 said Formula (2), R is alkyl groups, such as a C1-C4 methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.
X is a hydrolyzable group. Examples of the hydrolyzable group include alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group, trifluoromethoxy group, trifluoroethoxy group, and trichloroethoxy group. Such as a halogenated alkoxy group having 1 to 6 carbon atoms such as a group, an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, an acyloxy group having 1 to 10 carbon atoms such as an acetoxy group, and an isopropenoxy group Examples thereof include halogen groups such as alkenyloxy groups having 2 to 10 carbon atoms, chloro groups, bromo groups and iodo groups. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.

（式中、Ｒ、Ｘ、ａは上記の通りであり、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基を有する基であり、αは１〜７の整数である。Ｙは加水分解性シリル基を側鎖に有する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。〕 As the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer as the component (A), fluoropolyether groups represented by the following general formulas (3), (4), (5) and (6) At least one selected from the containing polymer-modified silane is more preferable.
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 formula, 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 - a and, d are independently integers of 0~5, p, q, r, s, t each independently 0 to 200 And p + q + r + s + t = an integer of 10 to 200, and each unit shown in parentheses may be bonded at random. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group, or —CFH ₂ group, and Q may be a single bond or fluorine-substituted. A divalent organic group, Z is a single bond, diorganosilylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, and a -Si≡. W is a group selected from a tetravalent group and a divalent to octavalent siloxane residue, and W represents the following general formulas (7a) to (7d)

(In the formula, R, X and a are as described above, f is an integer of 1 to 10, and D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may be substituted with fluorine. Yes, m is an integer from 2 to 6, and Me is a methyl group.)
And α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable silyl group in the side chain, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ]

In the above formulas (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 - a.
Here, d is independently an integer of 0 to 5, preferably 0 to 2, more preferably 1 or 2, and p, q, r, s, and t are each independently an integer of 0 to 200, preferably Is an integer of 5-100, q is an integer of 5-100, r is an integer of 0-100, s is an integer of 0-50, t is an integer of 0-100, and p + q + r + s + t is 10-200. , Preferably an integer of 20 to 100, and each unit shown in parentheses may be bonded at random.

（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の上限と同じである。） Specific examples of Rf include those shown below.

(Wherein d ′ is the same as d above, p ′, q ′, r ′, s ′, t ′ are each an integer of 1 or more, and the upper limit thereof is p, q, r, s, t above) (It is the same as the upper limit of.)

In the above formulas (3) and (5), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group, or —CFH ₂ group. Specific examples of the fluorine-containing group 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 single bond or a divalent organic group which may be substituted with fluorine, and is a linking group between an Rf group and a terminal group. Q is preferably an unsubstituted or substituted carbon number that may include one or more structures selected from the group consisting of an amide bond, an ether bond, an ester bond, or a diorganosilylene group such as a dimethylsilylene group. A divalent organic group having ˜12, preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, which may contain the above structure.

Here, as the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), 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 (an alkylene / arylene group, etc.). Examples thereof include those in which part or all are substituted with a halogen atom such as fluorine, among which an unsubstituted or substituted alkyl group having 2 to 4 carbon atoms and a phenyl group are preferred.
Examples of such Q include the following groups.

（式中、ｂは２〜４の整数であり、ｃは１〜４の整数であり、ｊは１〜５０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 1 to 4, j is an integer of 1 to 50, and Me is a methyl group.)

In the above formulas (3) and (4), Z is a single bond, preferably a diorganosilylene 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 group represented by a group, a hydroxyl group or K ₃ SiO— (K is independently a 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], trivalent group represented by -LSi = (L is preferably an alkyl group having 1 to 3 carbon atoms), tetravalent group represented by -C≡, -Si≡ And a group selected from siloxane residues having 2 to 8 and preferably 2 to 4 valences, and when it contains a siloxane bond, it has 2 to 13 silicon atoms, preferably silicon. Chain or cyclic o having 2 to 5 atoms It is preferably Ganoderma polysiloxane residues. 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 (wherein n is an integer of 2 to 6).
The organopolysiloxane residue preferably has 1 to 8 carbon atoms, more preferably 1 to 4 alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups. The alkylene group in the silalkylene structure 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、Ｒ、Ｘ、ａ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 having a hydrolyzable group represented by the following general formulas (7a) to (7d).

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

Here, R, X, and a are the same as described above, and the same examples as above can be exemplified.
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. , Methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group, octamethylene group, arylene group such as phenylene group, or Examples include combinations of two or more of these groups (alkylene / arylene groups, etc.), and those in which part or all of the hydrogen atoms of these groups are substituted with fluorine atoms. D is preferably an ethylene group, a propylene group, or a phenylene group.

（式中、ｆは上記と同じである。） Specific examples of W include those shown below.

(Wherein f is the same as above)

  In said formula (3), (4), (alpha) is an integer of 1-7, Preferably it is an integer of 1-3.

（式中、Ｒ、Ｘ、ａ、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、Ｒ¹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 in the side chain, and is preferably represented by the following general formula (8), (9) or (10). It is a group.

(In the formula, R, X, a and D are the same as above, D ′ is a C1-C10 fluorine-substituted divalent organic group, and R ¹ is C1-C20. And e is 1 or 2.)

Here, R, X, a, and D are the same as described above, and the same examples as described above can be exemplified.
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 (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group and octamethylene group, arylene group such as phenylene group, or these groups Or a combination of two or more of these groups (alkylene / arylene group, etc.), or a group in which some or all of the hydrogen atoms in these groups are substituted with fluorine atoms. D ′ is preferably an ethylene group or a propylene group.

R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group, allyl group and propenyl group and other alkenyl groups, phenyl group, An aryl group such as a tolyl group, and an aralkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group are exemplified. Among these, a methyl group is preferable.

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 said formula (5), (6), (beta) is an integer of 1-10, Preferably it is an integer of 1-4.
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, a bromine atom, A halogen atom such as an iodine atom.

とし、Ｚ基を

とし、加水分解性基を含む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シランでも本発明の効果は発揮できる。 As the fluoropolyether group-containing polymer-modified silane represented by the above formulas (3) and (4), the linking group Q is

And the Z group

And W group containing a hydrolyzable group

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

Further, the fluoropolyether group-containing polymer-modified silane represented by the above formulas (3) and (4) using a combination of these other than Q, Z, and W further has the following structure. Can be mentioned.

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒２３）

(Q1 / p1 = 0.9, p1 + q1≈45)

(Q1 / p1 = 0.9, p1 + q1≈45)

(Q1 / p1 = 0.9, p1 + q1≈45)

(Q1 / p1 = 0.9, p1 + q1≈23)

（Ｒｆａ＝−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５、ｆ＝３）

_{(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)

（ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 1.1, p1 + q1≈45)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 0.9, p1 + q1≈45)

（Ｒｆｂ：−ＣＦ₂Ｏ−（Ｃ₂Ｆ₄Ｏ）_q1（ＣＦ₂Ｏ）_p1−ＣＦ₂−、ｑ１／ｐ１＝１．１、ｐ１＋ｑ１≒５０、Ｒ＝−ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）−）

_{(Rfb: -CF 2 O- (C} 2 F 4 O) q1 (CF 2 O) p1 -CF 2 -, q1 / p1 = 1.1, p1 + q1 ≒ 50, R = -CH 2 CH 2 -, - CH (CH ₃ )-)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 0.9, p1 + q1≈45)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Examples of the fluoropolyether group-containing polymer-modified silane represented by the above formulas (5) and (6) include the following structures.

(Q1 / p1 = 0.9, p1 + q1≈45)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 0.9, p1 + q1≈45)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 0.9, p1 + q1≈45)

（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）

(Q1 / p1 = 0.9, p1 + q1≈45)

（ｑ１／ｐ１＝１．０、ｐ１＋ｑ１≒４０）

(Q1 / p1 = 1.0, p1 + q1≈40)

  In the fluorine-containing coating agent of the present invention, as the component (A), the terminal hydrolyzable group of the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer is partially hydrolyzed by a known method in advance. A partially hydrolyzed condensate obtained by decomposing and condensing may be contained.

  In addition, it is preferable that the weight average molecular weight of (A) component is 1,000-20,000, and it is more preferable that it is 2,000-10,000. If the weight average molecular weight is too small, the water / oil repellency and low dynamic friction of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated. In addition, in this invention, a weight average molecular weight can be measured as a standard polystyrene conversion value of the gel permeation chromatography (GPC) which used AK-225 (made by Asahi Glass) as a developing solvent.

  The solvent of (B) component will not be specifically limited if it can melt | dissolve (A) component uniformly. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluorohexane, perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, 1,3-trifluoromethylbenzene), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, Perfluorotripentylamine), partially fluorine-modified solvents (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 3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,3,3-pentafluorobutane), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) It can be illustrated. Among these, fluorine-modified fluorine-containing solvents are desirable in terms of solubility and wettability, and ethyl perfluorobutyl ether and decafluoropentane are particularly preferable. The said solvent may be used individually by 1 type, or may mix and use 2 or more types.

  The optimum concentration of the component (A) to be dissolved in the solvent varies depending on the coating method, but is an amount in which the content of the component (A) in the fluorine-containing coating agent is in the range of 0.01 to 50% by mass. It is preferable that it is the quantity used as the range of 0.03-25 mass%. If the concentration of component (A) is too low, sufficient antifouling and water / oil repellency will not be obtained after coating treatment, and if it is too high, the coating film will become non-uniform, resulting in reduced transparency and surface stickiness. To do.

Since the alcohol compound (C) is a polar compound, it is coordinated by hydrogen bonds or the like so as to surround the hydrolyzable group (A) in the coating agent. For this reason, it plays the role which protects a hydrolysable group from the water molecule mixed from the outside. Further, even if the hydrolyzable group of the component (A) is hydrolyzed into a silanol group by the mixed water molecules, the alcohol compound is coordinated around the silanol group, so that the silanol group is converted to other hydrolyzed groups. It functions to suppress reaction with degradable groups.
In addition, since (C) component does not melt | dissolve (A) component uniformly, it is not contained in (B) component.

  (C) A component is a C1-C6 alcohol compound. Examples of these are methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-methyl-2-propanol, 1,2-ethanediol, 1,3-propanediol, 1,2,3-propanetriol and the like can be mentioned. After applying the fluorine-containing coating agent on the substrate, it is desirable that the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer reacts quickly with the substrate. From this viewpoint, it is desirable that the component (C) volatilizes quickly from the substrate surface after coating, and methanol and ethanol having a low boiling point are preferable.

  (C) Content of a component is 0.01-5 mass% with respect to the whole coating agent, Preferably it is 0.05-3 mass%, More preferably, it is 0.05-1 mass%. When the content of the component (C) is too small, a sufficient storage stability effect in a solution state cannot be obtained, and when it is too large, appearance defects such as coating unevenness are likely to occur.

（式中、Ｒｆ及びＡは前記と同じである。）
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 of the present invention further comprises the following general formula (11) as component (D):

(In the formula, Rf and A are the same as described above.)
May be contained (hereinafter also referred to as non-functional polymer).

（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。）
が好ましく、またＡとしては、
−Ｆ
−ＣＦ₃
−ＣＦ₂ＣＦ₃
−ＣＦ₂ＣＦ₂ＣＦ₃
が好ましい。 In the above formula (11), Rf and A may be the same as Rf and A exemplified above, and Rf may be the same as or different from Rf in the component (A). as,

(Wherein 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 20 to 100, and t2 is an integer of 5 to 5. 200, preferably an integer of 10 to 100, t3 is an integer of 10 to 200, preferably 20 to 100, t2 + p2 is an integer of 10 to 200, preferably 20 to 100, q2 + p2 is 10 to 200, preferably 20 to 100 Is an integer.)
And A is preferably
-F
-CF ₃
-CF ₂ CF ₃
-CF ₂ CF ₂ CF ₃
Is preferred.

（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.

(Wherein p2, q2, r2, t2, and t3 are the same as above)

  The weight average molecular weight of the (D) component fluoropolyether group-containing polymer is preferably from 1,000 to 50,000, more preferably from 1,000 to 10,000, and further from 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.

  In addition, since the non-functional polymer of (D) component can use a commercial item, for example, since it is sold by the brand name of FOMBLIN, DOMNUM, KRYTOX, it can obtain easily. 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, 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 satisfying the 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, 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 satisfying the 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。） DENUM (trade name, DENNUM S20 (weight average molecular weight: 2,700), DENNUM S65 (weight average molecular weight: 4,500), DENNUM S100 (weight average molecular weight: 5,600) manufactured by Daikin Industries, Ltd.)

(In the formula, r2 is a number satisfying the 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 (trade name, manufactured by DuPont, 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 satisfying the weight average molecular weight.)

  Although the usage-amount in the case of mix | blending (D) component is not specifically limited, the range of 0-50 mass% is preferable with respect to the mass of (A) component, and when too large, the problem of adhesiveness may arise. In addition, it is preferable that the minimum in the case of mix | blending shall be 5 mass% or more from the point which exhibits the effect of (D) component effectively.

  Moreover, the fluorine-containing coating agent of this invention can mix | blend another additive in the range which does not impair this invention as needed. Specifically, hydrolysis condensation catalysts such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (fluorinated carboxylic acids, acetic acid, methane) Sulfonic acid, etc.) and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Of these, fluorine-based carboxylic acid, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. Although the addition amount of a hydrolysis-condensation catalyst is a catalyst amount, it is 0.01-5 mass parts normally with respect to 100 mass parts of said (A) component, Especially 0.1-1 mass part.

  The fluorine-containing coating agent of the present invention can suppress hydrolysis of the polymer terminal during storage in a solution state before use, thereby improving storage stability and preventing troubles during coating. A uniform coating film can be stably formed thereon.

The fluorine-containing coating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying or vapor deposition. The curing temperature varies depending on the curing method. For example, when applied by a spray method, an inkjet method, a dipping method, a brush coating, or a vacuum deposition method, the room temperature (20 ° C.) to 200 ° C., particularly 50 to 150 ° C. A 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 substrate, 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 the primer layer, or by performing vacuum plasma treatment, atmospheric pressure plasma treatment, or alkali treatment.

  The substrate to be treated with the fluorine-containing coating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The fluorine-containing coating agent of the present invention can impart water / oil repellency, chemical resistance, releasability, low dynamic friction and antifouling properties to these substrates. In particular, excellent antifouling performance can be imparted without impairing the transparency and texture of various articles, and the base material can be protected from intrusion of chemicals and the like, and the antifouling performance can be maintained for a long time. Articles to be treated with the fluorine-containing coating agent of the present invention include optical articles, films, glasses, quartz substrates, antireflection films and the like, and particularly used for touch panels, antireflection treatment articles, and tempered glass. .

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

（重量平均分子量：４，６００） The following compounds 1 to 4 were prepared as hydrolyzable group-containing silanes modified with a fluoropolyether group-containing polymer.
Compound 1

(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 2

_{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 3

_{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≒５０）
Ｒ：−ＣＨ₂ＣＨ₂−又は−ＣＨ（ＣＨ₃）−、
−ＣＨ₂ＣＨ₂−／−ＣＨ（ＣＨ₃）−≒０．６５／０．３５ Compound 4

_{Rfb: -CF 2 O- (C 2} F 4 O) q1 (CF 2 O) p1 -CF 2 -
(Q1 / p1 = 1.1, p1 + q1≈50)
R: —CH ₂ CH ₂ — or —CH (CH ₃ ) —,
-CH ₂ CH ₂ -/-CH (CH ₃ ) -≈0.65 / 0.35

The following were prepared as solvents for dissolving hydrolyzable group-containing silanes modified with fluoropolyether group-containing polymers.
Solvent A: Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M)
Solvent B: Vertrel XF (1,1,1,2,2,3,4,5,5,5-decafluoropentane, manufactured by DuPont)
Solvent C: Asahiklin AC-2000 (1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, manufactured by Asahi Glass Co., Ltd.)

When the water content in the solvent was measured with AQUACOUNTER AQ-2100 (Karl Fischer type trace moisture measuring device; manufactured by Hiranuma Sangyo Co., Ltd.), the results shown in Table 1 were obtained.

Preparation of coating agents Treatment agents AG:
Coating agent 100 so that the combination shown in Table 2 is 0.10 parts by mass of a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer, 0.20 parts by mass of an alcohol compound, and 99.70 parts by mass of a solvent. A mass part was prepared, put into a 100 mL brown bottle, and sealed.
Treatment agents H, I:
In the combinations shown in Table 2, 100 parts by mass of the coating agent was prepared so that the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer was 0.10 parts by mass, and the solvent was 99.90 parts by mass. Sealed in a brown bottle.
After these treatment agents A to I were placed in an oven at 50 ° C. for 72 hours, various tests were performed.

[Examples 1 to 7, Comparative Examples 1 and 2]
Preservation confirmation Gel Permeation Chromatography (GPC) was used to measure the treatment agents A to I, which were the coating agents, and the production ratio of a high molecular weight polymer of dimerization or higher was calculated. The measurement conditions are as follows. The results are shown in Table 3.
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector Column: TSKgel Multipore HXL-M manufactured by Tosoh Corporation
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (solution with a concentration of 0.1% by mass)

[Examples 8 to 14, Comparative Examples 3 and 4]
Formation of Cured Film and Evaluation of Transparency and Abrasion Resistance On the glass (Gorilla II manufactured by Corning), the treatment agents A to I, which are the coating agents prepared above, are applied by a spray coating apparatus (NST-51; T & K Corporation). And cured for 1 hour in an atmosphere of 80 ° C. and 80% humidity to form a cured film (film thickness: about 15 nm), and a test specimen was prepared.
The haze (transparency) measurement of this test body and the abrasion resistance test were performed under the following conditions. The results are shown in Table 4.

[Haze measurement conditions]
The haze of the test specimen prepared above was measured with the following apparatus according to JIS K 7136.
Device name: NDH-5000 (Nippon Denshoku)

[Abrasion resistance test conditions]
An abrasion test was performed 10,000 times under the following conditions, and the contact angle with water on the surface after the abrasion test was evaluated to be 100 ° or more as a pass.
Device name: Reciprocating wear test machine TRIBOGEAR 30S (manufactured by Shinto Kagaku)
Abrasion material: Bencott (Asahi Kasei Co., Ltd.)
Travel distance (one way): 30mm
Movement speed: 1,600 mm / min Load: 1 kg / cm ²
Contact angle meter name: Drop Master (manufactured by Kyowa Interface Science Co., Ltd.)

  From the above results, the treatment agents H and I to which no alcohol compound was added increased the proportion of the polymer that had been dimerized or more by hydrolysis during storage (Comparative Examples 1 and 2). Moreover, when a film was formed on the glass surface using these treatment agents, the surface uniformity was inferior, the haze value increased, and the wear durability also decreased (Comparative Examples 3 and 4). On the other hand, treatment agents A to G to which an alcohol compound has been added are unlikely to cause a high molecular weight of the polymer during storage (Examples 1 to 7), and the uniformity of the coating after coating is good, and transparency and wear durability. It was a result excellent in property (Examples 8 to 14).

Claims (14)

The following (A) to (C) components (A) hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partial hydrolysis condensate thereof,
(B) a solvent capable of uniformly dissolving the component (A),
(C) In the coating agent containing a C1-C6 alcohol compound, content of (A) component is 0.01-50 mass% with respect to the whole coating agent, and content of (C) component Is a fluorine-containing coating agent characterized by being 0.01 to 5% by mass with respect to the whole coating agent.   (C) Component is methanol or ethanol, The fluorine-containing coating agent of Claim 1 characterized by the above-mentioned. The hydrolyzable group-containing silane modified with the component (A) fluoropolyether group-containing polymer is represented by 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.)
10 to 200 repeating units represented by the following general formula (2)

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3.)
The fluorine-containing coating agent according to claim 1 or 2, which has at least one hydrolyzable silyl group represented by formula (1).   4. The fluorine-containing coating agent according to claim 3, wherein the hydrolyzable group X in the formula (2) is a methoxy group or an ethoxy group. The hydrolyzable group-containing silane modified with the component (A) fluoropolyether group-containing polymer is represented by the following general formulas (3), (4), (5) and (6) The fluorine-containing coating agent according to any one of claims 1 to 4, which is at least one selected from polymer-modified 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 formula, 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 - a and, d are independently integers of 0~5, p, q, r, s, t each independently 0 to 200 And p + q + r + s + t = an integer of 10 to 200, and each unit shown in parentheses may be bonded at random. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group, or —CFH ₂ group, and Q may be a single bond or fluorine-substituted. A divalent organic group, Z is a single bond, diorganosilylene group, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, and a -Si≡. W is a group selected from a tetravalent group and a divalent to octavalent siloxane residue, and W represents the following general formulas (7a) to (7d)

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, f is an integer of 1 to 10, and D is (It is a single bond or a divalent organic group optionally substituted with fluorine having 1 to 20 carbon atoms, m is an integer of 2 to 6, and Me is a methyl group.)
And α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable silyl group in the side chain, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ] The fluorine-containing coating agent according to claim 5, wherein Y is represented by the following formulas (8) to (10).

Wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and D is a single bond or fluorine having 1 to 20 carbon atoms. A divalent organic group that may be substituted; D ′ is a divalent organic group that may be substituted with fluorine having 1 to 10 carbon atoms; and R ¹ is a monovalent carbon group having 1 to 20 carbon atoms. A hydrogen group, and e is 1 or 2.) The fluorine-containing coating agent according to claim 5 or 6, 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 1 to 4, j is an integer of 1 to 50, and Me is a methyl group.) The fluorine-containing coating agent according to claim 5, 6 or 7, wherein Z is selected from a single bond or a divalent to octavalent group represented by the following formula.

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.) Furthermore, the fluoropolyether group containing polymer (D) represented by following General formula (11) is contained, The fluorine-containing coating agent of any one of Claims 1-8 characterized by the above-mentioned.

(In the formula, 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 - a and, d are independently integers of 0~5, p, q, r, s, t each independently 0 to 200 And an integer of p + q + r + s + t = 10 to 200, and each unit shown in parentheses may be bonded at random.A is a fluorine atom, a hydrogen atom, or a terminal is a —CF ₃ group, — (It is a monovalent fluorine-containing group that is a CF ₂ H group or a —CFH ₂ group.)   (B) The solvent of a component is a fluorine-containing solvent, The fluorine-containing coating agent of any one of Claims 1-9.   An article treated with the fluorine-containing coating agent according to any one of claims 1 to 10.   The touch panel processed with the fluorine-containing coating agent of any one of Claims 1-10.   The anti-reflective article processed with the fluorine-containing coating agent of any one of Claims 1-10. A glass, tempered glass, sapphire glass, quartz glass, or SiO ₂ treated substrate treated with the fluorine-containing coating agent according to any one of claims 1 to 10.