JPWO2019065035A1 - Fluorine-containing coating agent composition, surface treatment agent and article - Google Patents

Abstract

A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule and modified with a fluorooxyalkylene group-containing polymer and / or a portion thereof. A surface treatment agent containing a fluorine-containing coating agent composition in which a (hydrolyzed) condensate and perhydropolysilazane are mixed at a specific blending ratio is water repellent having excellent wear resistance to a resin or metal surface. It can form an oil repellent layer.

Description

The present invention relates to a fluorine-containing coating agent composition, and more particularly, a fluorine-containing coating agent composition that forms a film having excellent water and oil repellency and abrasion resistance, a surface treatment agent containing the composition, and the present invention. Regarding articles surface-treated with a surface treatment agent.

Many surface treatment agents have been used to show good water and oil repellency to glass, but they have good adhesion and water and oil repellency to surfaces other than glass such as resin and metal. None of them sufficiently exhibited surface characteristics such as abrasion resistance. Further, when the water- and oil-repellent layer is provided on the resin or metal surface, the performance is insufficient by directly applying the surface treatment agent.

In general, a fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, mold releasability, antifouling property, etc. because its surface free energy is very small. Utilizing its properties, it is industrially widely used as water and oil repellent antifouling agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, protective films, etc. ing. However, its properties mean that it is non-adhesive and non-adhesive to other base materials at the same time, and although it can be applied to the surface of the base material, it is difficult to adhere the coating film. ..

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 or metal.

Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into a 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 and resistance. A composition capable of forming a film having chemical properties, lubricity, mold releasability, antifouling property, etc. is disclosed (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238577, Japanese Patent Application Laid-Open No. 2860979, Patent). No. 4672095, JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-0727272, JP-A-2012-157856, JP-A-2013-136833).

When the substrate is surface-treated with the composition containing the above-mentioned fluoropolyether group-containing polymer-modified silane, a film is formed on the substrate using various coating methods. After coating, a hydrolyzable silyl group is formed. In the step of hydrolyzing and curing the film, the hydrolysis reaction is promoted by high temperature conditions such as 80 ° C. and 120 ° C. and conditions under humidification. Further, even at room temperature, a cured film can be formed by gradually reacting with moisture in the air. However, the curing step requires high-temperature humidification conditions, and it takes time to cure at room temperature, which may be a rate-determining factor (delay factor) in manufacturing. Further, the film (water- and oil-repellent layer) cured in a short time under mild conditions such as room temperature curing has a problem that wear resistance and antifouling performance deteriorate during use.

In Patent Document 9 (Japanese Unexamined Patent Publication No. 2008-14144), a fluorine-containing carboxylic acid is added to the coating composition as a curing catalyst to accelerate curing, so that film formation is performed in a short time under mild conditions. .. However, if the amount of catalyst is reduced, the wear resistance is inferior, and if the amount of catalyst is increased, the initial performance is lowered. In addition, there is a high possibility that the carboxyl group, which is a polar group, appears on the outermost surface of the coating film, and in that case, the performance deteriorates.

There is also a method of adding a catalyst in order to promote the hydrolysis reaction of the alkoxysilyl group. Conventionally known catalysts include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis (ethylacetoacetate) titanium; aluminum tris (acetylacetonate) and aluminum tris. Organic aluminum compounds such as (ethylacetacetate); organic zirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctate, dibutyltin dilaurate, dibutyltin di (2-ethylhexanoate), dioctyltin Organic tin compounds such as dilaurate, dioctyltin diacetate, dioctyltin dioctate; metal salts of organic carboxylic acids such as tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate, zinc stearate; hexylamine, phosphorus Amin compounds such as dodecylamine acid and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; tetra Examples thereof include guanidyl group-containing organic silicon compounds such as methylguanidylpropyltrimethoxysilane; organic acids (acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloride, sulfuric acid, etc.) and the like. However, these catalysts do not dissolve in a fluorine-based solvent, or even if they dissolve, they dissolve very little, so that the catalyst efficiency is poor. In addition, the residual metal content may cause deterioration of the characteristics of the cured film.

Further, Patent Document 10 (Japanese Unexamined Patent Publication No. 2004-145283) proposes a fluoropolyalkylene ether group-containing silane. The lens treated with the fluoropolyalkylene ether group-containing silane is excellent in oil repellency and fingerprint wiping property, but its abrasion resistance is not sufficient.

Further, various coating compositions have been studied as antifouling surface treatment agents for resins and metals. For example, Patent Document 11 (Japanese Unexamined Patent Publication No. 2012-017374) proposes a surface treatment composition containing polysilazane, polysiloxane, and a curing catalyst. However, the composition of this document contains a curing catalyst, and is not excellent in both water and oil repellency and the possibility of catalyst defects occurring during the formation of the cured film. It was.

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 Publication No. 2008-537557 Japanese Unexamined Patent Publication No. 2012-0727272 Japanese Unexamined Patent Publication No. 2012-157856 Japanese Unexamined Patent Publication No. 2013-136833 Japanese Unexamined Patent Publication No. 2008-14144 Japanese Unexamined Patent Publication No. 2004-145283 Japanese Unexamined Patent Publication No. 2012-017374

The present invention has been made in view of the above circumstances, and at least three siloxane bonds and / or at least 2 in a molecule capable of forming a water-repellent oil-repellent layer having excellent wear resistance, particularly on a resin or metal surface. A fluorine-containing coating agent composition containing a hydroxyl group or a hydrolyzable group-containing organic silicon compound containing sylphenylene bonds and modified with a fluorooxyalkylene group-containing polymer and / or a partial (hydrolyzed) condensate thereof. , A surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent.

As a result of diligent studies to solve the above object, the present inventors have contained at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule, and modified with a fluorooxyalkylene group-containing polymer. A hydroxyl group or hydrolyzable group-containing organic silicon compound and / or a partial (hydrolyzed) condensate thereof, preferably at least three siloxanes in the molecule represented by the general formula (1) or (2) described later. With a hydroxyl group or hydrolyzable group-containing organic silicon compound containing a bond and / or at least two silphenylene bonds and modified with a fluorooxyalkylene group-containing polymer and / or a partial (hydrolyzed) condensate thereof. A surface treatment agent containing a fluorine-containing coating agent composition using a mixture of perhydropolysilazane and a specific compounding ratio can form a water- and oil-repellent layer having excellent wear resistance to a resin or metal surface. The heading has led to the present invention.

（式中、Ｒｆは１価又は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り、Ａはシロキサン結合、シルフェニレン結合、及びＡと結合するＳｉと共にシロキサン結合又はシルフェニレン結合を形成する基から選ばれる１種又は２種以上を有する２〜１６価の有機基であり、Ｒは独立に炭素数１〜４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１〜３の整数であり、ｍは１〜１５の整数であり、αは１又は２である。）
で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び／又はその部分（加水分解）縮合物、又は下記一般式（２）

〔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−ポリシロキサン共重合体含有基であり、Ｑ、Ｑ’はそれぞれ単結合、又はエーテル結合を含んでいてもよく、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、−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、ｍ’は１〜７の整数であり、Ｘ、Ｒ、ｎは上記と同じである。）
で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマー−ポリシロキサン共重合体で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び／又はその部分（加水分解）縮合物であり、
（Ｂ）成分が、下記一般式（３）
−（ＳｉＨ₂−ＮＨ）_x− （３）
（式中、ｘは重合度を表す数である。）
で表されるパーヒドロポリシラザンである〔１〕に記載の含フッ素コーティング剤組成物。
〔３〕
式（１）で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物が、下記一般式（４ａ）又は（４ｂ）

［式中、Ｒｆは１価又は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り、Ｙは独立にケイ素原子、シロキサン結合、シルアルキレン構造及びシルアリーレン構造から選ばれる１種又は２種以上を有していてもよい２〜６価の有機基であり、Ｒは独立に炭素数１〜４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１〜３の整数であり、ａは１〜５の整数であり、Ｗは水素原子、又は下記式（４ａ’）

（式中、Ｙ’はケイ素原子及び／又はシロキサン結合を有していてもよい２〜６価の有機基であり、ｂは１〜５の整数であり、Ｒ、Ｘ、ｎは上記と同じである。）
で表される基であり、ＹとＹ’の合計中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を有する。αは１又は２である。］

（式中、Ｕは−（ＣＨ₂）_z1Ｏ−で、ｚ１は１〜２０の整数であり、Ａ¹は−（ＣＨ₂）_z2−で、ｚ２は１〜２０の整数であり、Ｖはシロキサン結合及び／又はシルフェニレン結合を有し、シルアルキレン構造及び／又はシルフェニレン結合以外のシルアリーレン構造を有していてもよい２〜６価の炭化水素基であり、ｃは１〜５の整数である。Ｒｆ、Ｘ、Ｒ、ｎ、αは上記と同じである。）
で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物である〔２〕に記載の含フッ素コーティング剤組成物。
〔４〕
前記式（１）、（４ａ）及び（４ｂ）において、αがそれぞれ１であり、Ｒｆが下記一般式（５）で表される１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〔２〕又は〔３〕に記載の含フッ素コーティング剤組成物。

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは１〜３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）
〔５〕
前記式（１）、（４ａ）及び（４ｂ）において、αがそれぞれ２であり、Ｒｆが下記一般式（６）で表される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〔２〕又は〔３〕に記載の含フッ素コーティング剤組成物。

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは１〜３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）
〔６〕
前記式（４ａ）において、Ｙが、炭素数５〜１０のアルキレン基、炭素数６〜８のアリーレン基を含むアルキレン基、アルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、及びケイ素原子数２〜１００個の直鎖状又は分岐状もしくは環状の２〜４価のオルガノポリシロキサン残基の結合手に炭素数２〜１０のアルキレン基が結合している２〜４価の基からなる群より選ばれる基である〔３〕〜〔５〕のいずれかに記載の含フッ素コーティング剤組成物。
〔７〕
前記式（４ａ’）において、Ｙ’が、炭素数２〜１０のアルキレン基、炭素数６〜８のアリーレン基を含むアルキレン基、ジオルガノシリレン基を含む炭素数２〜６のアルキレン基、アルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、及びケイ素原子数２〜１０個の直鎖状又はケイ素原子数３〜１０個の分岐状もしくは環状の２〜４価のオルガノポリシロキサン残基の結合手に炭素数２〜１０のアルキレン基が結合している２〜４価の基からなる群より選ばれる基である〔３〕〜〔６〕のいずれかに記載の含フッ素コーティング剤組成物。
〔８〕
式（２）中のＲｆ’が、下記一般式（７）又は（８）で示される２価のフルオロオキシアルキレン基含有ポリマー−ポリシロキサン共重合体含有基である〔２〕に記載の含フッ素コーティング剤組成物。
−（Ｚ’−Ｑ）_e−Ｒｆ¹−（Ｑ−Ｚ’）_e− （７）
−Ｒｆ¹−（Ｑ−Ｚ’−Ｑ−Ｒｆ¹）_f− （８）
（式中、Ｑは単結合、又はエーテル結合を含んでいてもよく、フッ素置換されていてもよい２価の有機基であり、Ｒｆ¹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り、Ｚ’は２価のポリシロキサン残基で、それぞれ同じでも異なってもよい。ｅは独立に０又は１であり、ｆは１〜３の整数である。）
〔９〕
式（７）及び（８）中のＺ’が、下記一般式（９）又は（１０）で示されるポリシロキサン鎖であり、Ｒｆ¹が下記一般式（６）で表される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〔８〕に記載の含フッ素コーティング剤組成物。

（式中、Ｒ’は同一又は異なってもよい炭素数１〜４のアルキル基、フェニル基又はフェニルエチル基である。ｔは１０〜２００の整数であり、ｙは１〜５の整数であり、ｗ１及びｗ２はそれぞれ１〜２００の整数で、同一又は異なっていてもよい。）

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは１〜３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）
〔１０〕
前記式（１）、（２）、（４ａ）及び／又は（４ｂ）において、Ｘがそれぞれ、水酸基、炭素数１〜１０のアルコキシ基、炭素数２〜１０のアルコキシアルコキシ基、炭素数１〜１０のアシロキシ基、炭素数２〜１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれるものである〔２〕〜〔９〕のいずれかに記載の含フッ素コーティング剤組成物。
〔１１〕
（Ａ）成分の分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物が、下記式のいずれかで表されるものである請求項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。

（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数で、ｐ１＋ｑ１は１０〜１０５の整数であり、これらの繰り返し単位はランダムに結合されていてよい。）

（式中、ｐ２は５〜１００の整数、ｑ２は５〜１００の整数で、ｐ２＋ｑ２は１０〜１０５の整数であり、ｔ１は４〜１９９の整数であり、ｔ２は０〜９９の整数である。括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
〔１２〕
（Ａ）成分の分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び／又はその部分（加水分解）縮合物が、ジブチルエーテルに可溶なものである〔１〕〜〔１１〕のいずれかに記載の含フッ素コーティング剤組成物。
〔１３〕
〔１〕〜〔１２〕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有する表面処理剤。
〔１４〕
〔１３〕に記載の表面処理剤の硬化物からなる硬化被膜。
〔１５〕
〔１３〕に記載の表面処理剤の硬化被膜を表面に有する物品。Therefore, the present invention provides the following fluorine-containing coating agent composition, a surface treatment agent containing the coating agent composition, and an article surface-treated with the surface treatment agent.
[1]
(A) A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule and modified with a fluorooxyalkylene group-containing polymer and / Or a partial (hydrolyzed) condensate thereof and (B) perhydropolysilazane, and the mixed mass ratio of the component (A) and the component (B) is 5:95 to 95: 5 (however, the component (A)). The total of the mixed mass ratios of the components (B) and (B) is 100)).
[2]
The component (A) is the following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and A is a group that forms a siloxane bond or a sylphenylene bond together with a siloxane bond, a sylphenylene bond, and Si that binds to A. It is a 2 to 16-valent organic group having one or more selected species, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms independently, and X is an independently hydroxyl group or a hydrolyzable group. , N is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2.)
A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by, and modified with a fluorooxyalkylene group-containing polymer. / Or a partial (hydrolyzed) condensate thereof, or the following general formula (2)

[In the formula, Rf'is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and Q and Q'may each contain a single bond or an ether bond, and are fluorine-substituted. May be a divalent organic group, where Z is a single bond, -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). Cyril ether group shown], trivalent group represented by -LSi = (L is an alkyl group), tetravalent group represented by -C≡, tetravalent group represented by -Si≡ , And a group selected from 2 to 8 valent siloxane residues, m'is an integer of 1 to 7, and X, R, n are the same as above. )
A hydroxyl group or hydrolyzable molecule containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer. A group-containing organic silicon compound and / or a partial (hydrolyzed) condensate thereof.
The component (B) is the following general formula (3)
− (SiH _2- NH) _x − (3)
(In the formula, x is a number representing the degree of polymerization.)
The fluorine-containing coating agent composition according to [1], which is perhydropolysilazane represented by.
[3]
The molecule represented by the formula (1) contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer. The organosilicon compound has the following general formula (4a) or (4b).

[In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and Y is one or more independently selected from a silicon atom, a siloxane bond, a sylalkylene structure and a sylarylene structure. It is a 2-6 valent organic group which may have, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms independently, X is an independently hydroxyl group or a hydrolyzable group, and n is 1. It is an integer of ~ 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a').

(In the formula, Y'is a 2-6 valent organic group that may have a silicon atom and / or a siloxane bond, b is an integer of 1-5, and R, X, n are the same as above. Is.)
It is a group represented by and has at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the total of Y and Y'. α is 1 or 2. ]

(In the equation, U is − (CH ₂ ) _z1 O−, z1 is an integer of 1 to 20, A ¹ is − (CH ₂ ) _z2 −, z2 is an integer of 1 to 20, and V is an integer of 1 to 20. It is a 2- to 6-valent hydrocarbon group having a siloxane bond and / or a silphenylene bond, and may have a silylene structure other than a silalkylene structure and / or a silphenylene bond, and c is 1 to 5. It is an integer. Rf, X, R, n, α are the same as above.)
A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer. The fluorine-containing coating agent composition according to [2].
[4]
In the formulas (1), (4a) and (4b), α is 1 and Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (5) [2]. Alternatively, the fluorine-containing coating agent composition according to [3].

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.)
[5]
In the formulas (1), (4a) and (4b), α is 2 and Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (6) [2]. Alternatively, the fluorine-containing coating agent composition according to [3].

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.)
[6]
In the formula (4a), Y has an alkylene group having 5 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, and the alkylene groups bonded to each other via a sylalkylene structure or a sill arylene structure. An alkylene group having 2 to 10 carbon atoms is bonded to a divalent group and a linear, branched or cyclic 2 to 4 valent organopolysiloxane residue having 2 to 100 silicon atoms. The fluorine-containing coating agent composition according to any one of [3] to [5], which is a group selected from the group consisting of 2 to 4 valent groups.
[7]
In the above formula (4a'), Y'is an alkylene group having 2 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms including a diorganosylylene group, and an alkylene group. A divalent group in which the groups are bonded to each other via a sylalkylene structure or a sylarylene structure, and a linear or cyclic 2- or cyclic group having 2 to 10 silicon atoms or 3 to 10 silicon atoms. Any of [3] to [6], which is a group selected from the group consisting of 2 to 4 valent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a tetravalent organopolysiloxane residue. The fluorine-containing coating agent composition according to.
[8]
Fluorine-containing according to [2], wherein Rf'in the formula (2) is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group represented by the following general formula (7) or (8). Coating agent composition.
− (Z'−Q) _e −Rf ¹ − (Q−Z') _e − (7)
^{-Rf 1 - (Q-Z'-} Q-Rf 1) f - (8)
(In the formula, Q is a divalent organic group which may contain a single bond or an ether bond and may be substituted with fluorine, and Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue. , Z'are divalent polysiloxane residues, which may be the same or different. E is independently 0 or 1, and f is an integer of 1-3.)
[9]
Z'in the formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), and Rf ¹ is a divalent fluoro represented by the following general formula (6). The fluorine-containing coating agent composition according to [8], which is an oxyalkylene group-containing polymer residue.

(In the formula, R'is an alkyl group, a phenyl group or a phenylethyl group having 1 to 4 carbon atoms which may be the same or different. T is an integer of 10 to 200 and y is an integer of 1 to 5. , W1 and w2 are integers of 1 to 200, respectively, and may be the same or different.)

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.)
[10]
In the formulas (1), (2), (4a) and / or (4b), X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, and 1 to 1 carbon atoms, respectively. The fluorine-containing coating agent composition according to any one of [2] to [9], which is selected from the group consisting of 10 asyloxy groups, alkoxyoxy groups having 2 to 10 carbon atoms and halogen groups.
[11]
A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. The fluorine-containing coating agent composition according to any one of claims 1 to 10, wherein the composition is represented by any of the following formulas.

(In the equation, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and these repeating units may be randomly combined.)

(In the formula, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, t1 is an integer of 4 to 199, and t2 is an integer of 0 to 99. Each repeating unit shown in parentheses may be randomly combined.)
[12]
A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. The fluorine-containing coating agent composition according to any one of [1] to [11], wherein and / or a partial (hydrolyzed) condensate thereof is soluble in dibutyl ether.
[13]
A surface treatment agent containing the fluorine-containing coating agent composition according to any one of [1] to [12].
[14]
A cured film made of a cured product of the surface treatment agent according to [13].
[15]
An article having a cured film of the surface treatment agent according to [13] on its surface.

The fluorine-containing coating composition of the present invention contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule, which is preferably soluble in dibutyl ether, and is hydroxyl group or hydrolyzed. Perhydropolysilazane can be used as a base material by mixing a fluorooxyalkylene group-containing polymer-modified organosilicon compound containing a sex group and / or a partial (hydrolyzed) condensate thereof with perhydropolysilazane in a specific blending ratio. Further, the hydroxyl group on the perhydropolysilazane layer reacts with the hydroxyl group or the hydrolyzable group portion of the fluorooxyalkylene group-containing polymer-modified organosilicon compound to strengthen the adhesion as a surface treatment agent. .. As a result, the article surface-treated with a surface treatment agent containing a fluorine-containing coating agent composition containing the organosilicon compound and / or a partial (hydrolyzed) condensate thereof and perhydropolysilazane is water- and oil-repellent. And has excellent wear resistance, especially cloth wear resistance.

The fluorine-containing coating agent composition of the present invention contains (A) at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule, and is a hydroxyl group modified with a fluorooxyalkylene group-containing polymer. Alternatively, it contains a hydrolyzable group-containing organic silicon compound and / or a partial (hydrolyzed) condensate thereof, and (B) perhydropolysilazane, and the mixed mass ratio of the component (A) and the component (B) is 5:95. A composition of ~ 95: 5, preferably 30:70 to 95: 5, particularly preferably 40:60 to 95: 5 (provided that the total mixed mass ratio of the components (A) and (B) is 100). By mixing these components in the above-mentioned specific compounding ratio, the adhesion to the base material is improved, and a cured film having excellent water and oil repellency and abrasion resistance, particularly cloth abrasion resistance, can be formed. It is characterized in that a surface treatment agent can be applied. In the above blending ratio, if the component (A) is too large, the adhesion to the substrate is poor, and as a result, a cured film having excellent wear durability cannot be obtained. If the component (A) is too small, the wear durability is poor. A cured film with excellent properties cannot be obtained.

Component (A) A hydroxyl group or hydrolyzable group containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. The contained organic silicon compound and / or its partial (hydrolyzed) condensate has at least 3 siloxane bonds (ie, Si—O—Si bonds) and / or at least 2 silphenylene bonds (ie, Si) in the molecule. -C ₆ H ₅ -Si bonds) containing, and containing a hydroxyl group or a hydrolyzable group in the molecule, preferably a soluble component dibutyl ether.

（式中、Ｒｆは１価又は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り、Ａはシロキサン結合、シルフェニレン結合、及びＡと結合するＳｉと共にシロキサン結合又はシルフェニレン結合を形成する基から選ばれる１種又は２種以上を有する２〜１６価の有機基であり、Ｒは独立に炭素数１〜４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１〜３の整数であり、ｍは１〜１５の整数であり、αは１又は２である。）
で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマーで変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び／又はその部分（加水分解）縮合物、又は下記一般式（２）

〔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−ポリシロキサン共重合体含有基であり、Ｑ、Ｑ’はそれぞれ単結合、又はエーテル結合を含んでいてもよく、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、−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、ｍ’は１〜７の整数であり、Ｘ、Ｒ、ｎは上記と同じである。）
で表される分子中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を含有し、かつ、フルオロオキシアルキレン基含有ポリマー−ポリシロキサン共重合体で変性された水酸基もしくは加水分解性基含有有機ケイ素化合物及び／又はその部分（加水分解）縮合物が挙げられる。At least 3, preferably 3 to 100, more preferably 3 to 40, more preferably 3 to 20 siloxane bonds in the molecule of the component (A) and / or at least 2 in the molecule, preferably 2. As a hydroxyl group- or hydrolyzable group-containing organic silicon compound containing 10 to 10 silphenylene bonds and modified with a fluorooxyalkylene group-containing polymer, the following general formula (1) is preferable.

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and A is a group that forms a siloxane bond or a sylphenylene bond together with a siloxane bond, a sylphenylene bond, and Si that binds to A. It is a 2 to 16-valent organic group having one or more selected species, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms independently, and X is an independently hydroxyl group or a hydrolyzable group. , N is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2.)
A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by, and modified with a fluorooxyalkylene group-containing polymer. / Or a partial (hydrolyzed) condensate thereof, or the following general formula (2)

[In the formula, Rf'is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and Q and Q'may each contain a single bond or an ether bond, and are fluorine-substituted. May be a divalent organic group, where Z is a single bond, -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). Cyril ether group shown], trivalent group represented by -LSi = (L is an alkyl group), tetravalent group represented by -C≡, tetravalent group represented by -Si≡ , And a group selected from 2 to 8 valent siloxane residues, m'is an integer of 1 to 7, and X, R, n are the same as above. )
A hydroxyl group or hydrolyzable molecule containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer. Examples include group-containing organic silicon compounds and / or partial (hydrolyzed) condensates thereof.

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは１〜３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）In the above formula (1), Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and when α is 1, Rf is a monovalent fluorooxyalkylene group-containing polymer residue, and Rf is It is preferably a monovalent fluorooxyalkylene group-containing polymer residue represented by the following formula (5).

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.)

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは単位毎にそれぞれ独立して１〜３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）Further, in the above formula (1), when α is 2, Rf is a divalent fluorooxyalkylene group-containing polymer residue, and Rf contains a divalent fluorooxyalkylene group represented by the following formula (6). It is preferably a polymer residue.

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, and d is an integer of 1 to 3 independently for each unit, and the unit may be linear or branched.)

In the above formulas (5) and (6), p, q, r, and s are integers of 0 to 200, respectively, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is 0 to 100. The integer of, s is an integer of 0 to 100, p + q + r + s = 3 to 200, preferably 10 to 105, and each repeating unit may be linear or branched, and each repeating unit may be used. May be randomly combined. More preferably, p + q is an integer of 10 to 105, particularly 15 to 60, and r = s = 0. If p + q + r + s is smaller than the upper limit value, the adhesion and curability are good, and if it is larger than the lower limit value, the characteristics of the fluoropolyether group can be sufficiently exhibited, which is preferable.

（式中、ｐ’、ｑ’、ｒ’、ｓ’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の上限と同じである。ｕは１〜２４の整数、ｖは１〜２４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。）Specifically, the following can be exemplified as the monovalent or divalent Rf.

(In the formula, p', q', r', and s'are integers of 1 or more, and the upper limit thereof is the same as the upper limit of p, q, r, and s. U is an integer of 1 to 24. v is an integer from 1 to 24. Each repeating unit may be randomly combined.)

In the above formula (1), A is a siloxane bond, silphenylene bond, and siloxane bond formation or silphenylene bond with Si to bind to A (i.e., the end -SiO- group or -SiC ₆ H ₅ - group It has 1 or 2 or more selected from the (having) groups, preferably 3 to 100 in the case of a siloxane bond, preferably 2 to 10 in the case of a sylphenylene bond, 2 to 16 valences, preferably 2. It is an organic group of ~ 8-valent, more preferably 2-7-valent, and is a linking group of a fluorooxyalkylene group-containing polymer residue and a hydroxyl group and / or a hydrolyzable group-containing silyl group. As the organic group of A, preferably, a hetero such as an oxygen atom (ether bond), an amide bond, a hydroxyl group, a linear, branched or cyclic organosiloxane residue, and a silialylene residue such as a silphenylene residue. A group that forms a siloxane bond and / or a sylphenylene bond, which may be substituted with an atom-containing structure, or a siloxane bond and / or a sylphenylene bond together with Si that is bonded to A, is preferably 3 in the case of a siloxane bond. Examples thereof include a 2 to 16 valent, particularly 2 to 8 valent, particularly 2 to 4 valent hydrocarbon groups having ~ 100, preferably 2 to 10 in the case of a silphenylene bond. Specific examples of A include the following groups.

Further, in the above formula (1), R is independently an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group having 1 to 4 carbon atoms, or a phenyl group, and a methyl group is preferable.
X is independently a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a methoxymethoxy group and a methoxyethoxy group. Alkoxy alkoxy group having 2 to 10 carbon atoms, asyloxy group having 1 to 10 carbon atoms such as acetoxy group, alkenyloxy group having 2 to 10 carbon atoms such as isopropenoxy group, halogen group such as chloro group, bromo group and iodo group. And so on. Of these, a methoxy group and an ethoxy group are preferable.
n is an integer of 1 to 3, preferably 3, m is an integer of 1 to 15, preferably an integer of 1 to 7, more preferably an integer of 1 to 6, and α is 1 or 2.

［式中、Ｒｆ、Ｒ、Ｘ、ｎ、αは上記と同じであり、Ｙは独立にケイ素原子、シロキサン結合、シルアルキレン構造及びシルアリーレン構造から選ばれる１種又は２種以上を有していてもよい２〜６価の有機基であり、ａは１〜５の整数であり、Ｗは水素原子、又は下記式（４ａ’）

（式中、Ｙ’はケイ素原子及び／又はシロキサン結合を有していてもよい２〜６価の有機基であり、ｂは１〜５の整数であり、Ｒ、Ｘ、ｎは上記と同じである。）
で表される基であり、ＹとＹ’の合計中に少なくとも３個のシロキサン結合及び／又は少なくとも２個のシルフェニレン結合を有する。］

（式中、Ｕは−（ＣＨ₂）_z1Ｏ−、ｚ１は１〜２０の整数であり、Ａ¹は−（ＣＨ₂）_z2−で、ｚ２は１〜２０の整数であり、Ｖはシロキサン結合及び／又はシルフェニレン結合を有し、シルアルキレン構造及び／又はシルフェニレン結合以外のシルアリーレン構造を有していてもよい２〜６価の炭化水素基であり、ｃは１〜５の整数である。Ｒｆ、Ｘ、Ｒ、ｎ、αは上記と同じである。）Further, a hydroxyl group or hydrolysis containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by the above general formula (1) and modified with a fluorooxyalkylene group-containing polymer. The group-containing organic silicon compound preferably contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by the following general formula (4a) or (4b), and , A hydroxyl group or hydrolyzable group-containing organic silicon compound modified with a fluorooxyalkylene group-containing polymer.

[In the formula, Rf, R, X, n, α are the same as above, and Y has one or more independently selected from a silicon atom, a siloxane bond, a sylalkylene structure, and a sill arylene structure. It may be a 2 to 6 valent organic group, a is an integer of 1 to 5, and W is a hydrogen atom or the following formula (4a').

(In the formula, Y'is a 2-6 valent organic group that may have a silicon atom and / or a siloxane bond, b is an integer of 1-5, and R, X, n are the same as above. Is.)
It is a group represented by and has at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the total of Y and Y'. ]

(In the equation, U is − (CH ₂ ) _z1 O−, z1 is an integer of 1 to 20, A ¹ is − (CH ₂ ) _z2 −, z2 is an integer of 1 to 20, and V is siloxane. It is a 2-6 valent hydrocarbon group having a bond and / or a silphenylene bond and may have a silylene structure other than a silalkylene structure and / or a silphenylene bond, and c is an integer of 1 to 5. Rf, X, R, n, α are the same as above.)

In the above formula (4a), Y may have one or more selected from a silicon atom, a siloxane bond, a sylalkylene structure and a sill arylene structure, and may have 2 to 6 valences, preferably 2 to 4 valences. It is more preferably a divalent organic group, and Y is specifically a butylene group (tetramethylene group, methylpropylene group), a hexamethylene group or other alkylene group having 4 to 10 carbon atoms, or a phenylene group or other carbon. An alkylene group containing an arylene group of number 6 to 8 (for example, an alkylene arylene group having 8 to 16 carbon atoms), a divalent group in which the alkylene groups are bonded to each other via a sylalkylene structure or a sylarylene structure, 2 to 100 silicon atoms, preferably 5 to 100, more preferably 10 to 50 carbon atoms in the bond of linear, branched or cyclic 2 to 6 valent organopolysiloxane residues. Examples thereof include a 2 to 6-valent group to which 10 alkylene groups are bonded, preferably an alkylene group having 5 to 10 carbon atoms and an arylene group having 6 to 8 carbon atoms, particularly an alkylene group containing a phenylene group and an alkylene group. A divalent group bonded to each other via a sylalkylene structure or a sylarylene structure, a linear group having 2 to 100 silicon atoms, or a branched or cyclic 2 to 4 valent group having 3 to 100 silicon atoms. It is a 2- to 4-valent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of the organopolysiloxane residue, and more preferably an alkylene group having 3 to 6 carbon atoms.

（式中、Ｒ¹はメチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４のアルキル基、フェニル基等の炭素数６〜１０のアリール基であり、Ｒ¹は同一でも異なっていてもよい。Ｒ²はメチレン基、エチレン基、プロピレン基（トリメチレン基、メチルエチレン基）等の炭素数１〜４のアルキレン基、フェニレン基等の炭素数６〜１０のアリーレン基である。）Here, examples of the sillalkylene structure and the sillarylene structure can be shown below.

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and an aryl group having 6 to 10 carbon atoms such as a phenyl group, and R ¹ is the same but different. R ² is an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group and a propylene group (trimethylethylene group and a methylethylene group), and an arylene group having 6 to 10 carbon atoms such as a phenylene group. )

（式中、Ｒ¹は上記と同じである。ｇは１〜９９、好ましくは４〜９９、好ましくは９〜４９の整数であり、ｈは２〜６、好ましくは２〜４の整数、ｊは０〜８の整数、好ましくは０又は１で、ｈ＋ｊは３〜１００、好ましくは５〜１００、より好ましくは１０〜５０の整数であり、ｋは１〜３の整数であり、好ましくは２又は３である。）The linear, branched or cyclic 2-hexavalent organopolysiloxane residues having 2 to 100 silicon atoms, preferably 5 to 100, more preferably 10 to 50 atoms are shown below. Can be illustrated.

(In the formula, R ¹ is the same as above. G is an integer of 1 to 99, preferably 4 to 99, preferably 9 to 49, h is an integer of 2 to 6, preferably 2 to 4, j. Is an integer of 0 to 8, preferably 0 or 1, h + j is an integer of 3 to 100, preferably 5 to 100, more preferably an integer of 10 to 50, and k is an integer of 1 to 3, preferably 2. Or 3)

（式中、ｇ１は２〜９９の整数、ｈ１は２〜１０の整数である。）
Ｙとして、好ましくはシロキサン結合及び／又はシルフェニレン結合を有する基である。Specific examples of Y include the following groups.

(In the formula, g1 is an integer of 2 to 99 and h1 is an integer of 2 to 10.)
As Y, it is preferably a group having a siloxane bond and / or a silphenylene bond.

（式中、Ｙ’はケイ素原子及び／又はシロキサン結合を有していてもよい２〜６価の有機基であり、ｂは１〜５の整数、好ましくは１〜３の整数であり、Ｒ、Ｘ、ｎは上記と同じである。）In the above formula (4a), W is a hydrogen atom or a group represented by the following formula (4a').

(In the formula, Y'is a 2-6 valent organic group which may have a silicon atom and / or a siloxane bond, b is an integer of 1 to 5, preferably an integer of 1 to 3, and R , X, n are the same as above.)

In the above formula (4a'), Y'is a 2-hexavalent, preferably 2-4-valent, more preferably divalent organic group, and may have a silicon atom and / or a siloxane bond.
Specifically, as Y', the number of carbon atoms of ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group and the like is 2 to 10, especially 3 carbon atoms. An alkylene group having 10 to 10 alkylene groups, a phenylene group and the like having 6 to 10 carbon atoms, particularly an alkylene group containing an arylene group having 6 to 8 carbon atoms (for example, an alkylene arylene group having 8 to 16 carbon atoms) and 2 to 10 carbon atoms. Oxyalkylene group, an alkylene group having 2 to 6 carbon atoms including a diorganosylylene group such as a dimethylsilylene group or a diethylsilylene group, and a divalent alkylene group in which the alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure. Group, alkylene group having 2 to 6 carbon atoms, including 2 to 10 linear, branched or cyclic organopolysiloxane residues, preferably 2 to 5 silicon atoms, silicon atom number 2 to 10 alkylene groups having 2 to 10 carbon atoms are bonded to the bonds of 2 to 10 linear, branched or cyclic 2 to 6 valent organopolysiloxane residues, preferably 2 to 5 Examples thereof include a hexavalent group, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group containing a phenylene group, an alkylene group having 2 to 6 carbon atoms containing a dimethylsilylene group, and a silalkylene group having a sylalkylene structure or a sill. A divalent group bonded via an arylene structure, an alkylene group having 2 to 6 carbon atoms containing a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, and a silicon atom number of 2 to 2. 2 to 4 in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of 10 linear or branched or cyclic 2 to 4 valent organopolysiloxane residues having 3 to 10 silicon atoms. It is a valent group, more preferably an alkylene group having 3 to 6 carbon atoms.

Here, the silalkylene structure, the silarylene structure, and the linear, branched, or cyclic 2-hexavalent organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 atoms are described above. An example is similar to that of the above.

Specific examples of Y'include the following groups.

In the above formula (4a), there are at least 3 siloxane bonds in the total of Y and Y', preferably 3 to 100, and at least 2 sylphenylene bonds in the total of Y and Y', preferably 2. It has 10 to 10 pieces.

In the above formula (4a), a is an integer of 1 to 5, preferably an integer of 1 to 3.

In the above formula (4b), U is − (CH ₂ ) _z1 O−, and z1 is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. Further, A ¹ is − (CH ₂ ) _z2 −, and z2 is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

In the above formula (4b), V preferably has 3 to 100 siloxane bonds and / or preferably 2 to 10 sylphenylene bonds, and has a sylalkylene structure and / or a sill-arylene structure other than the sylphenylene bond. It is a 2-hexavalent hydrocarbon group that may be used.
Specifically, an alkylene having 2 to 10 carbon atoms is bonded to a linear, branched or cyclic 2 to 4 valent organopolysiloxane residue having 3 to 100 silicon atoms, preferably 5 to 100 silicon atoms. An alkylene group having 2 to 10 carbon atoms is bonded to a 2- to 4-valent group to which the group is bonded and a linear organo (poly) silphenylene residue having 2 to 10 silicon atoms. divalent _{^{group, -Si (OSiR 3 2 -R 4}} -) a group represented by _3. Here, R ³ is an alkyl group or a phenyl group independently having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and R ⁴ is an independently methylene group having 1 to 4 carbon atoms. , Ethyl group, propylene group (trimethylene group, methylethylene group) or other alkylene group or phenylene group.
As V, those shown below are preferable.

In the above formula (4b), c is an integer of 1 to 5, preferably an integer of 1 to 3.

A fluorooxyalkylene group-containing polymer containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by the above formula (4a) or (4b) and having a hydrolyzable group. Specific examples of the modified organosilicon compound include the following structures. In the following formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105, and suitable values of p1 and q1 of each formula are shown in parentheses.

In the above general formula (2), Q and Q'are each divalent organic group which may contain a single bond or an ether bond and may be substituted with fluorine, and preferably contains an ether bond. An unsubstituted or fluorine-substituted divalent organic group having 2 to 12 carbon atoms, preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 2 to 12 carbon atoms which may contain an ether bond. is there.

Here, as the unsubstituted or fluorine-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), It may be an alkylene group such as a hexamethylene 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 or the like), and further, the hydrogen atom of these groups. Examples thereof include those in which a part or all thereof is substituted with a fluorine atom, and among them, an unsubstituted or substituted alkyl group having 2 to 4 carbon atoms and a phenyl group are preferable.

（式中、ｂ１は２〜４の整数である。）Examples of such Q and Q'include the following groups.

(In the formula, b1 is an integer of 2-4.)

In the above general formula (2), Rf'is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and is preferably divalent represented by the following general formula (7) or (8). Fluoroxyalkylene group-containing polymer-polysiloxane copolymer-containing group.
− (Z'−Q) _e −Rf ¹ − (Q−Z') _e − (7)
^{-Rf 1 - (Q-Z'-} Q-Rf 1) f - (8)
(In the formula, Q is the same as above, Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue, and Z'is a divalent polysiloxane residue, which may be the same or different. Is independently 0 or 1, and f is an integer of 1 to 3, preferably 1 or 2.)

In the above (7) and (8), Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue, and the same as the above formula (6) can be exemplified.

（式中、Ｒ’は同一又は異なってもよい炭素数１〜４のアルキル基、フェニル基又はフェニルエチル基である。ｔは１０〜２００の整数であり、ｙは１〜５の整数であり、ｗ１及びｗ２はそれぞれ１〜２００の整数で、同一又は異なっていてもよい。）In the above (7) and (8), Z'is a divalent polysiloxane residue, and is preferably a polysiloxane chain represented by the following general formula (9) or (10).

(In the formula, R'is an alkyl group, a phenyl group or a phenylethyl group having 1 to 4 carbon atoms which may be the same or different. T is an integer of 10 to 200 and y is an integer of 1 to 5. , W1 and w2 are integers of 1 to 200, respectively, and may be the same or different.)

In the above general formula (2), Z is a single bond, −JC = [J is preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or K ₃ SiO− (K is an independently hydrogen atom, preferably 1 carbon number). A trivalent group represented by an alkyl group of ~ 3, an aryl group such as a phenyl group, or a silyl ether group represented by preferably an alkoxy group having 1 to 3 carbon atoms), −LSi = (L is preferably 1 carbon number of carbon atoms). ~ 3 Alkyl groups), trivalent groups represented by −C≡, tetravalent groups represented by −Si≡, and 2-8 valent, preferably 2 to 4 valent siloxanes. It is a group selected from residues, and when it contains a siloxane bond, it is preferably a chain or cyclic organopolysiloxane residue having 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. ..
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.

（式中、ｌは１〜１２の整数、好ましくは１〜４の整数である。）Examples of such Z include those shown below.

(In the formula, l is an integer of 1 to 12, preferably an integer of 1 to 4.)

In the above general formula (2), m'is an integer of 1 to 7, preferably an integer of 1 to 3.

（式中、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。）Examples of the fluorooxyalkylene group-containing polymer-modified organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by the above formula (2) are as follows. Can be mentioned. In the following formula, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, and t1 is an integer of 4 to 199, preferably an integer of 9 to 99. , T2 is an integer of 0 to 99, preferably an integer of 4 to 49, but the more preferable values of p2, q2, t1, and t2 of each equation are shown in parentheses.

(In the formula, each unit shown in parentheses may be randomly combined.)

The component (A) contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the above-mentioned molecule, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer. Obtained by condensing the hydroxyl group of an organic silicon compound (hereinafter, also referred to as a fluoropolyether group-containing polymer) or the hydroxyl group in which the terminal hydrolyzable group of the fluoropolyether group-containing polymer is partially hydrolyzed by a known method in advance. It may contain a part (hydrolyzed) condensate to be used.

(B) Component The fluorine-containing coating agent composition of the present invention contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) described above, and is fluorooxyalkylene. Perhydropolysilazane as a component (B) is blended in combination with a hydroxyl group- or hydrolyzable group-containing organosilicon compound modified with a group-containing polymer in the above-mentioned specific ratio. As the perhydropolysilazane of the component (B), preferably, perhydropolysilazane represented by the following general formula (3) can be mentioned.
− (SiH _2- NH) _x − (3)
(In the formula, x is a number representing the degree of polymerization.)

The degree of polymerization of the component (B), perhydropolysilazane, is preferably about 800 to 8,000, more preferably about 1,000 to 5,000. This degree of polymerization can usually be measured as a weight average degree of polymerization in terms of standard polystyrene by gel permeation chromatography (GPC) analysis using toluene as a developing solvent.

As a specific example of the component (B), perhydropolysilazane, AZ NAX 120-20 (manufactured by Merck Performance Materials Manufacturing LLC) and the like are on the market.

The perhydropolysilazane component (B) may be blended with the component (A) in a specific mixed mass ratio in the form of a perhydropolysilazane solution previously dissolved in an organic solvent such as dibutyl ether.

The fluorine-containing coating agent composition of the present invention can be prepared by mixing the component (A) and the component (B), but the component (B) is previously added to the raw material for synthesizing the component (A). The component (A) may be synthesized in this state.

The present invention further relates to a hydroxyl group or hydrolyzable group containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule (A) and modified with a fluorooxyalkylene group-containing polymer. It contains an organosilicon compound and / or a partial (hydrolyzed) condensate thereof and (B) perhydropolysilazane, and the mixed mass ratio of the component (A) and the component (B) is 5:95 to 95: 5. A surface treatment agent containing a certain fluorine-containing coating agent composition is provided.

The surface treatment agent may contain, if necessary, a hydrolysis condensation catalyst, for example, an organic tin compound (dibutyltin dimethoxyde, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, etc.). Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acids (hydrogen, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid and the like are particularly desirable.
The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer and / or its partial (hydrolyzed) condensate. ~ 1 part by mass.

The surface treatment agent contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A), and is a hydroxyl group or a hydrolysis modified with a fluorooxyalkylene group-containing polymer. It may contain a suitable solvent for dissolving the organic silicon compound containing a sex group and / or a partial (hydrolyzed) condensate thereof. Examples of such a solvent include a fluorine-modified aliphatic hydrocarbon solvent (perfluoroheptane, perfluorooctane, etc.), a fluorine-modified aromatic hydrocarbon solvent (1,3-bis (trifluoromethyl) benzene, etc.), and fluorine. Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyl tetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (Petite benzine, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified. Among these, a fluorine-modified solvent is desirable in terms of solubility, wettability, etc., and in particular, 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyl tetrahydrofuran), and perfluorotri. Butylamine and ethylperfluorobutyl ether are preferred.

Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate. The optimum concentration of the fluoropolyether group-containing polymer to be dissolved in the solvent and its partial (hydrolyzed) condensate varies depending on the treatment method and may be an amount that is easy to weigh. However, in the case of direct coating, the solvent and The amount is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the fluoropolyether group-containing polymer (and its portion (hydrolyzed) condensate), and the vapor deposition treatment is performed. In this case, the amount is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, based on 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer (and its portion (hydrolyzed) condensate).

The surface treatment agent of the present invention can be applied to a substrate by a known method such as brush coating, dipping, or spraying. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the temperature is 25 to 200 ° C., particularly 50 to 150 ° C. for 30 minutes to 36 hours, particularly 1 It is preferably about 24 hours. Further, it may be cured under humidification. 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 1 to 20 nm.

The base material treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxides thereof, resins such as glass and plastic, ceramics, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the base material.

Articles treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game devices, eyeglass lenses, camera lenses, lens filters, and the like. Examples thereof include medical devices such as sunglasses and gastrocameras, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films and other optical articles. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and can further impart scratch resistance, it has particularly good adhesion to touch panel displays, resins and metals. Therefore, it is useful as a water- and oil-repellent layer for the housing of the smartphone.

The surface treatment agent of the present invention is used for antifouling coatings for sanitary products such as bathtubs and wash basins, windowpanes or tempered glasses for automobiles, trains, aircraft, etc., antifouling coatings for headlamp covers, and building materials for outer walls. Water and oil repellent coating, oil stain prevention coating for kitchen building materials, antifouling and sticker / graffiti prevention coating for telephone boxes, anti-fingerprint coating for fine arts, anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as a mold release agent or paint additive, a resin modifier, a fluidity modifier or a dispersibility modifier for an inorganic filler, and a lubricity improver for tapes, films and the like.

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.

A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. The following [Compound 1] to [Compound 3] were prepared as the following. All of [Compound 1] to [Compound 3] are components that are soluble in dibutyl ether at room temperature (25 ° C.). Also, for comparison, a fluoropolyether group-containing polymer that does not contain at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule and is insoluble in dibutyl ether at room temperature (25 ° C.). [Compound 4] and [Compound 5] were prepared as.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

As the component (B), perhydropolysilazane, AZ NAX 120-20 (manufactured by Merck Performance Materials Manufacturing LLC) was used.

[Examples 1 to 10, Comparative Examples 1 to 5]
Preparation of surface treatment agent and formation of cured film The fluorooxy of [Compound 1] to [Compound 3] which are the components (A) and [Compound 4] and [Compound 5] for comparison in the mixing ratio shown in Table 1. A hydrolyzable group-containing organosilicon compound modified with an alkylene group-containing polymer was mixed with a 10 mass% dibutyl ether solution of perhydropolysilazane as a component (B) or dibutyl ether as a solvent to prepare a surface treatment agent. Duralumin, PMMA (polymethylmethacrylate resin) or PC (polycarbonate resin) was Dip-coated with each surface treatment agent. The coating conditions were a pulling speed of 350 mm / min and a dipping time of 30 seconds. Immediately after coating, the glass was cured at 80 ° C. and a humidity of 50% RH for 1 hour to form a cured film having a thickness of about 100 nm. Comparative Examples 1 to 3 were dissolved in dibutyl ether as a solvent to prepare a 10% by mass solution. Further, in Comparative Examples 4 and 5, the components (A) [Compound 4] and [Compound 5] were not dissolved in the dibutyl ether in the component (B), and the coating liquid could not be prepared.

The cured coatings of Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated by the following methods. Both tests were performed at 25 ° C. and 40% RH humidity.

[Evaluation of solubility]
The component (A) and the component (B) were mixed, and the solubility was evaluated as "◯" if it was not visually clouded, and "x" if it was clouded. The results (solubility) are shown in Table 2.

Evaluation of water repellency [ Evaluation of initial water repellency]
The contact angle (water repellency) of the cured film with respect to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) for the substrate on which the cured film was formed as described above (droplets: 2 μl, Temperature: 25 ° C., Humidity: 40% RH). The water contact angle was measured 1 second after the 2 μl droplet was dropped on the sample surface. The results (initial contact angle) are shown in Table 2.
In the initial stage, both Examples and Comparative Examples showed good water repellency.

[Evaluation of wear resistance]
In the obtained cured film, the abrasion resistance to the cloth (Bencot) was measured using Tribogear TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.).
A cloth resistance test was carried out under the following conditions, and the contact angle (water repellency) of the cured coating with water after rubbing 4,000 times was measured in the same manner as above to evaluate the wear resistance. The results (contact angle after wear) are shown in Table 2.
Contact area: 10 mm x 30 mm
Load: 1 kg
Abrasion resistance Cloth: BEMCOT M-3II (manufactured by Asahi Kasei Corporation)
Travel distance (one way) 20 mm
Moving speed 3,600 mm / min Load: 0.5 kg / cm ²

The surface treatment agents of Examples 1 to 10 contained at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule described above, and were modified with a fluorooxyalkylene group-containing polymer. Adhesion to the metal substrate was improved by mixing the hydrophilic group-containing organosilicon compound and perhydropolysilazane dissolved in the dibutyl ether solution at a specific blending ratio. From this, the cured coatings of the surface treatment agents of Examples 1 to 10 contain at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecules of Comparative Examples 1 to 3, and are fluoro. Compared to the cured film of the surface treatment agent using only the hydrolyzable group-containing organic silicon compound modified with the oxyalkylene group-containing polymer, the contact angle is maintained at 100 ° or more even after 4,000 times of cloth wear, which is excellent. Demonstrated wear resistance.
Further, the hydrolyzable group-containing organosilicon compounds ([Compound 4] and [Compound 5]) modified with the fluorooxyalkylene group-containing polymer used in Comparative Examples 4 and 5 do not satisfy the above structure. It did not dissolve in the dibutyl ether solution and the coating solution could not be prepared.

Claims (15)

(A) A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule and modified with a fluorooxyalkylene group-containing polymer and / Or a partial (hydrolyzed) condensate thereof and (B) perhydropolysilazane, and the mixed mass ratio of the component (A) and the component (B) is 5:95 to 95: 5 (however, the component (A)). The total of the mixed mass ratios of the components (B) and (B) is 100)). The component (A) is the following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and A is a group that forms a siloxane bond or a sylphenylene bond together with a siloxane bond, a sylphenylene bond, and Si that binds to A. It is a 2 to 16-valent organic group having one or more selected species, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms independently, and X is an independently hydroxyl group or a hydrolyzable group. , N is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2.)
A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by, and modified with a fluorooxyalkylene group-containing polymer. / Or a partial (hydrolyzed) condensate thereof, or the following general formula (2)

[In the formula, Rf'is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and Q and Q'may each contain a single bond or an ether bond, and are fluorine-substituted. May be a divalent organic group, where Z is a single bond, -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). Cyril ether group shown], trivalent group represented by -LSi = (L is an alkyl group), tetravalent group represented by -C≡, tetravalent group represented by -Si≡ , And a group selected from 2 to 8 valent siloxane residues, m'is an integer of 1 to 7, and X, R, n are the same as above. )
A hydroxyl group or hydrolyzable molecule containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer. A group-containing organic silicon compound and / or a partial (hydrolyzed) condensate thereof.
The component (B) is the following general formula (3)
− (SiH _2- NH) _x − (3)
(In the formula, x is a number representing the degree of polymerization.)
The fluorine-containing coating agent composition according to claim 1, which is perhydropolysilazane represented by. The molecule represented by the formula (1) contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer. The organosilicon compound has the following general formula (4a) or (4b).

[In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and Y is one or more independently selected from a silicon atom, a siloxane bond, a sylalkylene structure and a sylarylene structure. It is a 2-6 valent organic group which may have, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms independently, X is an independently hydroxyl group or a hydrolyzable group, and n is 1. It is an integer of ~ 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a').

(In the formula, Y'is a 2-6 valent organic group that may have a silicon atom and / or a siloxane bond, b is an integer of 1-5, and R, X, n are the same as above. Is.)
It is a group represented by and has at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the total of Y and Y'. α is 1 or 2. ]

(In the equation, U is − (CH ₂ ) _z1 O−, z1 is an integer of 1 to 20, A ¹ is − (CH ₂ ) _z2 −, z2 is an integer of 1 to 20, and V is an integer of 1 to 20. It is a 2- to 6-valent hydrocarbon group having a siloxane bond and / or a silphenylene bond, and may have a silylene structure other than a silalkylene structure and / or a silphenylene bond, and c is 1 to 5. It is an integer. Rf, X, R, n, α are the same as above.)
A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer. The fluorine-containing coating agent composition according to claim 2. 2. Claim 2 in the formulas (1), (4a) and (4b), where α is 1 and Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (5). Or the fluorine-containing coating agent composition according to 3.

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.) 2. Claim 2 in the above formulas (1), (4a) and (4b), where α is 2 and Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (6). Or the fluorine-containing coating agent composition according to 3.

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.) In the formula (4a), Y has an alkylene group having 5 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, and the alkylene groups bonded to each other via a sylalkylene structure or a sill arylene structure. An alkylene group having 2 to 10 carbon atoms is bonded to a divalent group and a linear, branched or cyclic 2 to 4 valent organopolysiloxane residue having 2 to 100 silicon atoms. The fluorine-containing coating agent composition according to any one of claims 3 to 5, which is a group selected from the group consisting of 2 to 4 valent groups. In the above formula (4a'), Y'is an alkylene group having 2 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms including a diorganosylylene group, and an alkylene group. A divalent group in which the groups are bonded to each other via a silalkylene structure or a silarylene structure, and a linear or cyclic 2- or cyclic group having 2 to 10 silicon atoms or 3 to 10 silicon atoms. Any one of claims 3 to 6, which is a group selected from the group consisting of 2 to 4 valent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a tetravalent organopolysiloxane residue. The fluorine-containing coating agent composition according to. The fluorine-containing group according to claim 2, wherein Rf'in the formula (2) is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group represented by the following general formula (7) or (8). Coating agent composition.
− (Z'−Q) _e −Rf ¹ − (Q−Z') _e − (7)
^{-Rf 1 - (Q-Z'-} Q-Rf 1) f - (8)
(In the formula, Q is a divalent organic group which may contain a single bond or an ether bond and may be substituted with fluorine, and Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue. , Z'are divalent polysiloxane residues, which may be the same or different. E is independently 0 or 1, and f is an integer of 1-3.) Z'in the formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), and Rf ¹ is a divalent fluoro represented by the following general formula (6). The fluorine-containing coating agent composition according to claim 8, which is an oxyalkylene group-containing polymer residue.

(In the formula, R'is an alkyl group, a phenyl group or a phenylethyl group having 1 to 4 carbon atoms which may be the same or different. T is an integer of 10 to 200 and y is an integer of 1 to 5. , W1 and w2 are integers of 1 to 200, respectively, and may be the same or different.)

(In the formula, p, q, r, and s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, and each repeating unit may be branched. They may be randomly connected to each other, d is an integer of 1 to 3, and the unit may be linear or branched.) In the formulas (1), (2), (4a) and / or (4b), X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, and 1 to 1 carbon atoms, respectively. The fluorine-containing coating agent composition according to any one of claims 2 to 9, which is selected from the group consisting of 10 asyloxy groups, alkoxyoxy groups having 2 to 10 carbon atoms and halogen groups. A hydroxyl group or hydrolyzable group-containing organosilicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. However, the fluorine-containing coating agent composition according to any one of claims 1 to 10, which is represented by any of the following formulas.

(In the equation, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and these repeating units may be randomly combined.)

(In the formula, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, t1 is an integer of 4 to 199, and t2 is an integer of 0 to 99. Each repeating unit shown in parentheses may be randomly combined.) A hydroxyl group or hydrolyzable group-containing organic silicon compound containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule of the component (A) and modified with a fluorooxyalkylene group-containing polymer. The fluorine-containing coating agent composition according to any one of claims 1 to 11, wherein the condensate and / or a portion thereof (hydrolyzed) is soluble in dibutyl ether. A surface treatment agent containing the fluorine-containing coating agent composition according to any one of claims 1 to 12. A cured film made of a cured product of the surface treatment agent according to claim 13. An article having a cured film of the surface treatment agent according to claim 13 on the surface.