JP2013018743A - Fluorooxyalkylene group-containing polymer modified silane, surface treatment agent containing the silane, and article surface-treated with the surface treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorooxyalkylene group-containing polymer-modified silane for a surface treatment agent.SOLUTION: The fluorooxyalkylene group-containing polymer modified-silane is indicated by general formula (1) (in the formula, Rf is univalent or divalent fluorooxyalkylene group-containing polymer residue, Z is a divalent-hexavalent group which may independently have a siloxane bond, R is an alkyl group or a phenyl group of 1-4 carbons independently, X is a hydrolyzable group independently, (a) is an integer of 2-5 independently, b is 2 or 3 independently, y is an integer of 1-5 independently for each unit, α is an integer of 1-5, and β is 1 or 2).

Description

  The present invention relates to a fluoroxyalkylene group-containing polymer-modified silane, and more specifically, a fluorooxyalkylene group-containing polymer-modified silane that forms a film excellent in water and oil repellency and chemical resistance, and the silane or a partial hydrolysis thereof. The present invention relates to a surface treatment agent containing a condensate and an article treated with the surface treatment 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, and the like are directly attached, and there is a problem that dirt such as sebum is easily attached. Therefore, the demand for technology that makes it difficult to attach fingerprints to the surface of the display to improve the appearance and visibility, and technology that makes it easier to remove dirt is increasing year by year, and the development of materials that can meet these requirements has been developed. It is desired. However, the conventional water / oil repellent layer has high water / oil repellency and excellent dirt wiping property, but has a problem that the antifouling performance deteriorates during use. One of the causes of deterioration of the antifouling performance is chemical resistance.

  In general, a perfluorooxyalkylene group-containing compound has a 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 fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .

  On the other hand, silane coupling agents are well known as those for bonding a substrate surface such as glass or cloth and an organic compound, 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 an alkoxysilyl group) in one molecule. The alkoxysilyl 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 alkoxysilyl group to the surface of glass or metal.

  Patent Document 1 (Japanese Patent Laid-Open No. 2003-238777) proposes a perfluorooxyalkylene group-containing polymer-modified silane containing a linear perfluorooxyalkylene group represented by the following formula. Yes. The lens or antireflection film treated with the perfluorooxyalkylene group-containing polymer-modified silane is excellent in slipperiness, releasability, and abrasion resistance, but as a linking group between a perfluorooxyalkylene group and an alkoxysilyl group, Since allyl ether groups are used, chemical resistance is not sufficient.

（式中、Ｒｆは２価の直鎖型パーフルオロポリエーテル基、Ｒは炭素数１〜４のアルキル基又はフェニル基、Ｘは加水分解性基、ｌは０〜２、ｍは１〜５の整数、ａは２又は３である。）

(In the formula, Rf is a divalent linear perfluoropolyether group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, l is 0 to 2, and m is 1 to 5) , A is 2 or 3.)

JP 2003-238777 A

  The present invention has been made in view of the above circumstances, and includes a fluorooxyalkylene group-containing polymer-modified silane capable of forming a water- and oil-repellent layer excellent in chemical resistance, the silane and / or a partially hydrolyzed condensate thereof. It is an object of the present invention to provide a surface treatment agent containing the article and an article treated with the surface treatment agent.

The water / oil repellent layer coated on the surface of a touch panel display or the like is preferably resistant to acids, alkalis, and salt water contained in fingerprints and cleaning agents.
As described above, the present inventors have previously proposed a fluorooxyalkylene group-containing polymer having hydrolyzable groups at both ends (Japanese Patent Laid-Open No. 2003-238777: Patent Document 1). A film formed from an object does not have sufficient chemical resistance.
A polymer having a fluorooxyalkylene structure in the main chain and containing a hydrolyzable group at one or both ends of the molecular chain is firmly adhered to the base material when used as a surface treatment agent. However, a connecting group between a fluorooxyalkylene group and an alkoxysilyl group, for example, an ether bond of —CF ₂ CH ₂ —O—CH ₂ — is inferior in chemical resistance.
Accordingly, as a result of intensive studies to solve the above problems, the present inventors have obtained a fluorooxyalkylene group-containing polymer-modified silane using —CF ₂ —CONPh—CH ₂ — (Ph is a phenyl group) as the linking group. It has been found that a surface treatment agent containing can form a water- and oil-repellent layer excellent in chemical resistance, and 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、Ｚは独立にシロキサン結合を有してもよい２〜６価の基であり、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は独立に加水分解性基であり、ａは独立に２〜５の整数、ｂは独立に２又は３、ｙは単位毎に独立に１〜５の整数であり、αは１〜５の整数、βは１又は２である。）
で表されるフルオロオキシアルキレン基含有ポリマー変性シラン。
〔請求項２〕
前記フルオロオキシアルキレン基含有ポリマー残基が、下記一般式

（ｇは、単位毎に独立に、１〜６の整数である。）
で表される繰り返し単位３〜２０１個を含むことを特徴とする請求項１記載のフルオロオキシアルキレン基含有ポリマー変性シラン。
〔請求項３〕
前記式（１）のβが１であり、Ｒｆ基が下記一般式（２）、（３）及び（４）で示される基から選ばれることを特徴とする請求項１又は２記載のフルオロオキシアルキレン基含有ポリマー変性シラン。

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｍは３〜２００の整数、ｄは１〜３の整数である。）

（式中、ｍは３〜２００の整数、ｄは１〜３の整数である。）

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｐ、ｑはそれぞれ０〜２００の整数で、ｐ＋ｑ＝３〜２００であり、各繰り返し単位はランダムに結合されていてよい。また、ｄは１〜３の整数である。）
〔請求項４〕
前記式（１）のβが２であり、Ｒｆ基が下記一般式（５）、（６）及び（７）で示される基から選ばれることを特徴とする請求項１又は２記載のフルオロオキシアルキレン基含有ポリマー変性シラン。

（式中、Ｙはそれぞれ独立にＦ又はＣＦ₃基であり、ｄは独立に１〜３の整数、ｅは２〜６の整数、ｒ、ｔはそれぞれ０〜２００の整数で、ｒ＋ｔ＋ｓ＝３〜２００、ｓは０〜６の整数であり、各繰り返し単位はランダムに結合されていてよい。）

（式中、ｍは３〜２００の整数、ｄは１〜３の整数である。）

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｄは１〜３の整数、ｐ、ｑはそれぞれ０〜２００の整数で、ｐ＋ｑ＝３〜２００であり、各繰り返し単位はランダムに結合されていてよい。）
〔請求項５〕
前記式（１）のＺが、ケイ素原子２〜５個の直鎖状又は環状オルガノポリシロキサン残基である、請求項１〜４のいずれか１項に記載のフルオロオキシアルキレン基含有ポリマー変性シラン。
〔請求項６〕
前記式（１）の加水分解性基Ｘが、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、請求項１〜５のいずれか１項に記載のフルオロオキシアルキレン基含有ポリマー変性シラン。
〔請求項７〕
請求項１〜６のいずれか１項に記載のフルオロオキシアルキレン基含有ポリマー変性シラン及び／又は該フルオロオキシアルキレン基含有ポリマー変性シランの部分加水分解縮合物を含有する表面処理剤。
〔請求項８〕
請求項７に記載の表面処理剤で処理された物品。
〔請求項９〕
請求項７に記載の表面処理剤で処理された光学物品。
〔請求項１０〕
請求項７に記載の表面処理剤で処理されたタッチパネル。
〔請求項１１〕
請求項７に記載の表面処理剤で処理された反射防止フイルム。
〔請求項１２〕
請求項７に記載の表面処理剤で処理されたＳｉＯ₂処理ガラス。
〔請求項１３〕
請求項７に記載の表面処理剤で処理された強化ガラス。
〔請求項１４〕
請求項７に記載の表面処理剤で処理された石英基板。 Accordingly, the present invention provides a surface-treating agent containing the following fluorooxyalkylene group-containing polymer-modified silane and the silane and / or a partially hydrolyzed condensate thereof, and an article surface-treated with the surface-treating agent.
[Claim 1]
The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Z is independently a 2-6 valent group optionally having a siloxane bond, and R is independently carbon number. 1 to 4 alkyl groups or phenyl groups, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b is independently 2 or 3, y is 1 to 1 independently for each unit. 5 is an integer, α is an integer of 1 to 5, and β is 1 or 2.)
A fluoroxyalkylene group-containing polymer-modified silane represented by:
[Claim 2]
The fluorooxyalkylene group-containing polymer residue has the following general formula

(G is an integer of 1 to 6 independently for each unit.)
The fluorooxyalkylene group-containing polymer-modified silane according to claim 1, comprising 3 to 201 repeating units represented by the formula:
[Claim 3]
The fluorooxy according to claim 1 or 2, wherein β in the formula (1) is 1 and the Rf group is selected from the groups represented by the following general formulas (2), (3) and (4). An alkylene group-containing polymer-modified silane.

(In the formula, Y is independently an F or CF ₃ group, m is an integer of 3 to 200, and d is an integer of 1 to 3).

(In the formula, m is an integer of 3 to 200, and d is an integer of 1 to 3.)

(In the formula, Y is independently an F or CF ₃ group, p and q are each an integer of 0 to 200, and p + q = 3 to 200, and each repeating unit may be bonded at random. d is an integer of 1 to 3)
[Claim 4]
The fluorooxy according to claim 1 or 2, wherein β in the formula (1) is 2 and the Rf group is selected from the groups represented by the following general formulas (5), (6) and (7). An alkylene group-containing polymer-modified silane.

(Wherein Y is independently F or CF ₃ group, d is independently an integer of 1 to 3, e is an integer of 2 to 6, r and t are integers of 0 to 200, and r + t + s = 3 -200, s is an integer of 0-6, and each repeating unit may be bonded at random.

(In the formula, m is an integer of 3 to 200, and d is an integer of 1 to 3.)

(In the formula, Y is independently F or CF ₃ group, d is an integer of 1 to 3, p and q are integers of 0 to 200, respectively, p + q = 3 to 200, and each repeating unit is randomly selected. May be combined.)
[Claim 5]
The fluorooxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 4, wherein Z in the formula (1) is a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms. .
[Claim 6]
The hydrolyzable group X of the formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. And the fluoroxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 5, which is selected from the group consisting of halogen groups.
[Claim 7]
A surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 6 and / or a partial hydrolysis-condensation product of the fluorooxyalkylene group-containing polymer-modified silane.
[Claim 8]
An article treated with the surface treatment agent according to claim 7.
[Claim 9]
An optical article treated with the surface treating agent according to claim 7.
[Claim 10]
A touch panel treated with the surface treatment agent according to claim 7.
[Claim 11]
An antireflection film treated with the surface treatment agent according to claim 7.
[Claim 12]
SiO ₂ treated glass which has been treated with a surface treatment agent according to claim 7.
[Claim 13]
A tempered glass treated with the surface treating agent according to claim 7.
[Claim 14]
A quartz substrate treated with the surface treating agent according to claim 7.

  The film formed from the fluorooxyalkylene group-containing polymer-modified silane of the present invention has high water and oil repellency. By treating with the surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane and / or its partially hydrolyzed condensate of the present invention, excellent water and oil repellency can be imparted to various articles, High resistance and can keep antifouling performance for a long time.

（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、Ｚは独立にシロキサン結合を有してもよい２〜６価の基であり、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は独立に加水分解性基であり、ａは独立に２〜５の整数、ｂは独立に２又は３、ｙは単位毎に独立に１〜５の整数であり、αは１〜５の整数、βは１又は２である。） The fluorooxyalkylene group-containing polymer-modified silane of the present invention is represented by the following general formula (1).

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Z is independently a 2-6 valent group optionally having a siloxane bond, and R is independently carbon number. 1 to 4 alkyl groups or phenyl groups, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b is independently 2 or 3, y is 1 to 1 independently for each unit. 5 is an integer, α is an integer of 1 to 5, and β is 1 or 2.)

The fluorooxyalkylene group-containing polymer-modified silane of the present invention comprises a monovalent or divalent fluorooxyalkylene group-containing polymer residue (Rf) and a hydrolyzable silyl group (—Si (R) _3-b such as an alkoxysilyl group. (X) _b ) has a structure bonded via a linking group —CF ₂ —CONPh—CH ₂ — (Ph is a phenyl group, the same shall apply hereinafter), and the polymer residue containing the fluorooxyalkylene group The group (Rf) and a hydrolyzable silyl group such as an alkoxysilyl group (—Si (R) _{3 -b} (X) _b ) are bonded to an ether bond, —CF ₂ —CONH— bond, —CF ₂ —CONCH ₃ —. Compared with the case where it connects through Ph-bond etc., it is excellent in chemical resistance.

（ｇは、単位毎に独立に、１〜６の整数である。） In the formula, the monovalent or divalent fluorooxyalkylene group-containing polymer residue (Rf) is represented by 3 to 201 repeating units represented by the following general formula, preferably 6 to 101, more preferably 25 to 81. Including In addition, each repeating unit may mutually differ in the value of g, Preferably g is an integer of 1-4.

(G is an integer of 1 to 6 independently for each unit.)

Examples of the repeating unit represented by the above general formula include the following units. The Rf group may be composed of one type of these repeating units, or may be a combination of two or more types.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-C (CF _{3) 2} O-

  As Rf containing the repeating unit, when β is 1, a monovalent fluorooxyalkylene group selected from the groups represented by the following general formulas (2), (3) and (4) is preferable.

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｍは３〜２００、好ましくは１０〜１００の整数、ｄは１〜３の整数、好ましくは２又は３である。）

（式中、ｍは３〜２００、好ましくは１０〜１００の整数、ｄは１〜３の整数、好ましくは２又は３である。）

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｐ、ｑはそれぞれ０〜２００、好ましくは１０〜１００の整数で、ｐ＋ｑ＝３〜２００、好ましくは１０〜１００であり、各繰り返し単位はランダムに結合されていてよい。また、ｄは１〜３の整数、好ましくは１又は２である。）

(In the formula, Y is independently F or CF ₃ group, m is an integer of 3 to 200, preferably 10 to 100, and d is an integer of 1 to 3, preferably 2 or 3.)

(In the formula, m is an integer of 3 to 200, preferably 10 to 100, and d is an integer of 1 to 3, preferably 2 or 3.)

(Wherein Y is independently F or CF ₃ group, p and q are each an integer of 0 to 200, preferably 10 to 100, and p + q = 3 to 200, preferably 10 to 100, and each repetition. (The units may be randomly bonded, and d is an integer of 1 to 3, preferably 1 or 2.)

  As Rf containing the repeating unit, when β is 2, a divalent fluorooxyalkylene group selected from the groups represented by the following general formulas (5), (6) and (7) is preferable.

（式中、Ｙはそれぞれ独立にＦ又はＣＦ₃基であり、ｄは独立に１〜３の整数、好ましくは２又は３、ｅは２〜６の整数、好ましくは２又は３、ｒ、ｔはそれぞれ０〜２００、好ましくは１０〜１００の整数で、ｒ＋ｔ＋ｓ＝３〜２００、好ましくは１０〜１００、ｓは０〜６、好ましくは２〜４の整数であり、各繰り返し単位はランダムに結合されていてよい。）

Wherein Y is independently F or CF ₃ group, d is independently an integer of 1 to 3, preferably 2 or 3, e is an integer of 2 to 6, preferably 2 or 3, r, t Is an integer of 0 to 200, preferably 10 to 100, r + t + s = 3 to 200, preferably 10 to 100, s is an integer of 0 to 6, preferably 2 to 4, and each repeating unit is randomly bonded May be.)

（式中、ｍは３〜２００、好ましくは１０〜１００の整数、ｄは１〜３の整数、好ましくは２又は３である。）

(In the formula, m is an integer of 3 to 200, preferably 10 to 100, and d is an integer of 1 to 3, preferably 2 or 3.)

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｄは１〜３の整数、好ましくは１又は２、ｐ、ｑはそれぞれ０〜２００、好ましくは１０〜１００の整数で、ｐ＋ｑ＝３〜２００、好ましくは１０〜１００であり、各繰り返し単位はランダムに結合されていてよい。）

(Wherein Y is independently F or CF ₃ group, d is an integer of 1 to 3, preferably 1 or 2, p and q are each an integer of 0 to 200, preferably 10 to 100, and p + q = 3 to 200, preferably 10 to 100, and each repeating unit may be bonded at random.)

（式中、ａは上記と同じである。）
で示される構造を有するＲｆ基とアルコキシシリル基等の加水分解性シリル基を含む加水分解性シリルアルキル基（−Ｃ_yＨ_2y−Ｓｉ（Ｒ）_3-b（Ｘ）_b）との、シロキサン結合を有してもよい２〜６価の連結基であり、エーテル結合等の耐薬品性が悪い連結基は含まれないことが望ましい。分子中にシロキサン結合を有することにより耐摩耗性、耐擦傷性に優れたコーティングを与えることができる。好ましいＺとしては、ケイ素原子数が２〜１０個、好ましくは２〜９個、特に２〜６個の直鎖状、分岐状又は環状オルガノポリシロキサン残基であり、例えば下記の基が挙げられる。 In the above formula (1), Z is at the end.

(Wherein, a is the same as above)
In the Rf group and alkoxy hydrolyzable silyl group containing a hydrolyzable silyl group such as a silyl group _{(-C y H 2y -Si (R} ) 3-b (X) b) having the structure shown, siloxane It is a divalent to hexavalent linking group that may have a bond, and it is preferable that a linking group with poor chemical resistance such as an ether bond is not included. By having a siloxane bond in the molecule, a coating having excellent wear resistance and scratch resistance can be provided. Preferred Z is a linear, branched or cyclic organopolysiloxane residue having 2 to 10, preferably 2 to 9, particularly 2 to 6 silicon atoms, and examples thereof include the following groups. .

  In the above formula (1), X is a hydrolyzable group which may be different from each other. Examples of such X 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, an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, and an acetoxy group. And a halogen group such as an alkoxy group having 2 to 10 carbon atoms such as an acyloxy group having 1 to 10 carbon atoms and an isopropenoxy group, a chloro group, a bromo group and an iodo group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.

  In said formula (1), R is alkyl groups, such as a C1-C4 methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and a methyl group is especially suitable. a is an integer of 2 to 5, preferably 2 or 3, b is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. y is an integer of 1 to 5, preferably 1 to 3.

  Examples of the fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formula. In addition, in each formula, the repeating number (or polymerization degree) of each repeating unit constituting the fluorooxyalkylene group can take any number satisfying the above formulas (2) to (7).

で示されるＮ−［３−（ビニルジメチルシリル）プロピル］アニリンを酸フロライドと等モル量をフラスコに入れ、トリエチルアミンと溶剤、例えば１，３−ビストリフルオロメチルベンゼンを混合し、５０℃で１２０分反応させる。その後、炭酸カルシウムで中和し、溶剤を留去し、分子鎖両末端又は片末端に脂肪族不飽和結合を有するフルオロオキシアルキレン基含有ポリマーを得る。例えば、パーフルオロオキシアルキレン基含有ポリマーとして、

を使用した場合には、下記構造の末端ビニルジメチルシリル変性のフルオロオキシアルキレン基含有ポリマーが得られる。

Examples of the method for preparing the fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) include the following methods.
A perfluorooxyalkylene group-containing polymer having an acid fluoride group (—C (═O) —F) at both ends or one end of the molecular chain, and the following formula

N- [3- (vinyldimethylsilyl) propyl] aniline represented by formula (1) is placed in an equimolar amount with acid fluoride in a flask, and triethylamine and a solvent such as 1,3-bistrifluoromethylbenzene are mixed and mixed at 50 ° C. for 120 minutes. React. Then, it neutralizes with calcium carbonate, the solvent is distilled off, and a fluorooxyalkylene group-containing polymer having an aliphatic unsaturated bond at both ends or one end of the molecular chain is obtained. For example, as a perfluorooxyalkylene group-containing polymer,

When is used, a terminal vinyldimethylsilyl-modified fluorooxyalkylene group-containing polymer having the following structure is obtained.

Next, the compound obtained in the above step is dissolved in a solvent such as 1,3-bistrifluoromethylbenzene, and has one SiH group in the molecule, such as trimethoxysilane, and hydrolyzes an alkoxy group or the like. A silane compound having 2 or 3 functional groups is aged at 80 ° C. for 8 hours in the presence of a toluene solution of a chloroplatinic acid / vinylsiloxane complex. Then, the target compound as shown, for example by a following formula can be obtained by depressurizingly distilling a solvent and an unreacted substance.

  The present invention further provides a surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane. The surface treatment agent may contain a partially hydrolyzed condensate obtained by partially hydrolyzing and condensing a terminal hydrolyzable group of the fluorooxyalkylene group-containing polymer-modified silane in advance by a known method. .

If necessary, the surface treatment agent may be a hydrolysis-condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetran-butyl titanate, etc.), an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acid (hydrochloric acid, 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 addition amount of the hydrolysis-condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 100 parts by mass of the fluorooxyalkylene group-containing polymer-modified silane and / or its partial hydrolysis-condensation product. -1 part by mass.

  The surface treatment agent may contain a suitable solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (such as 1,3-trifluoromethylbenzene), and fluorine-modified ether-based solvents. Solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine) , Toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Of these, fluorine-modified solvents are desirable in terms of solubility and wettability, and in particular, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluoro Butyl ether is preferred.

  Two or more of these solvents may be mixed, and it is preferable to uniformly dissolve the fluorooxyalkylene group-containing polymer-modified silane and its partially hydrolyzed condensate. The optimum concentration of the fluorooxyalkylene group-containing polymer-modified silane to be dissolved in the solvent varies depending on the treatment method, but the total concentration of the solvent and fluorooxyalkylene group-containing polymer-modified silane (and its partially hydrolyzed condensate) is 100 parts by mass. 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass is preferable.

  The surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, when applied by brushing or dipping, the temperature is preferably in the range of room temperature to 200 ° C. As the curing humidity, it is desirable to carry out under humidification in order to promote the reaction. Moreover, although the film thickness of a cured film is suitably selected according to the kind of base material, it is 0.1-20 nm normally, and is especially 1-10 nm.

The substrate to be treated with the surface treating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, quartz and the like. The surface treating agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO ₂ -treated glass or film.

  Articles to be treated with the surface treatment agent of the present invention include car navigation, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, spectacle lenses, camera lenses, lens filters, sunglasses, Optical articles such as medical devices such as gastric cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The surface treatment agent of the present invention is particularly useful as a water and oil repellent layer for touch panel displays, antireflection films and the like because it can prevent fingerprints and sebum from adhering to the article and can further provide scratch resistance. .

  Further, the surface treatment agent of the present invention is an antifouling coating for sanitary products such as bathtubs and washstands, window glass or tempered glass for automobiles, trains, airplanes, etc., antifouling coating for headlamp covers, etc. Water- and oil-repellent coating, anti-stain coating for kitchen building materials, anti-fouling and anti-fouling coating for phone boxes, anti-fingerprint coating for artworks, anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as a lubricity improver for molds such as mold release agents or paint additives, resin modifiers, inorganic filler fluidity modifiers or dispersibility modifiers, tapes and films.

  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.

で表される化合物１００ｇ（２．３×１０^-2ｍｏｌ）と、下記式（II）

で表される化合物２．１ｇ（２．３×１０^-2ｍｏｌ）をフラスコに入れ、ここに、トリエチルアミン２．５ｇと１，３−ビストリフルオロメチルベンゼン１０ｇを混合してフラスコに入れ、５０℃で１２０分反応させた。その後、炭酸カルシウムで中和し、溶剤を留去し、下記式(III)

で表される末端に不飽和結合を有するフルオロオキシアルキレン基含有ポリマー（III）９７．８ｇを得た。 [Example 1]
In the reaction vessel, the following formula (I)

And 100 g (2.3 × 10 ⁻² mol) of the compound represented by the formula (II)

2.1 g (2.3 × 10 ⁻² mol) of the compound represented by formula (1) is placed in a flask, and 2.5 g of triethylamine and 10 g of 1,3-bistrifluoromethylbenzene are mixed and placed in the flask. For 120 minutes. Then, neutralize with calcium carbonate, distill off the solvent, the following formula (III)

97.8 g of a fluorooxyalkylene group-containing polymer (III) having an unsaturated bond at the terminal represented by

Next, 100 g (2.2 × 10 ⁻² mol) of a compound represented by the formula (III) obtained in the same manner as in the above step, 20 g of 1,3-bistrifluoromethylbenzene, 3.3 g of trimethoxysilane ( 2.7 × 10 ⁻² mol) and 0.05 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (containing 1.2 × 10 ⁻² mol as Pt alone) and aged at 80 ° C. for 8 hours. It was. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 100.2 g of a liquid product.

The obtained compound was confirmed to have the following structure by NMR.

[Example 2]
30 g (6.6 × 10 ⁻³ mol) of the compound represented by the formula (III) used in Example 1 is dissolved in 20 g of 1,3-trifluoromethylbenzene, and a toluene solution of a chloroplatinic acid / vinylsiloxane complex is used. 0.10 g (containing 2.5 × 10 ⁻⁸ mol as a simple substance of Pt), 2.5 g of 1: 1 addition reaction product (HM-VMS) of tetramethyldisiloxane (HM) and vinyltrimethoxysilane (VMS) (8.9 × 10 ⁻³ mol) was added dropwise, and the mixture was aged at 90 ° C. for 2 hours, and the solvent and unreacted substances were distilled off under reduced pressure to obtain ^30.8 g of a liquid product.

The HM-VMS was prepared by the following method.
Tetramethyldisiloxane (HM) 40 g (3.0 × 10 ⁻¹ mol) and toluene 40 g were mixed and heated to 80 ° C. A mixture of 44.2 g (3.0 × 10 ⁻¹ mol) of vinyltrimethoxysilane (VMS) and 2 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as a simple substance of Pt) It was dripped slowly. The resulting mixture was purified by distillation to obtain 84 g of an addition reaction product (HM-VMS) represented by the following formula.

The compound obtained in Example 2 was confirmed to have the following structure by NMR.

[Example 3]
30 g (6.6 × 10 ⁻³ mol) of the compound represented by the formula (III) used in Example 1 and 1 g of tetramethylcyclotetrasiloxane (cyclic siloxane H4) 8 g (3.3 × 10 ⁻² mol) , 3-trifluoromethylbenzene was dissolved in 20 g and heated to 90 ° C. Thereafter, 0.10 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.5 × 10 ⁻⁸ mol as a simple substance of Pt) was dropped, and the mixture was aged at 90 ° C. for 2 hours, and the solvent and unreacted substances were reduced in pressure. When distilled off, 30.5 g of a liquid product represented by the following formula (IV) was obtained.

Next, 30 g (6.3 × 10 ⁻³ mol) of the product represented by the formula (IV) obtained in the above step is dissolved in 20 g of 1,3-trifluoromethylbenzene, and vinyltrimethoxysilane (VMS) is dissolved. ) 3.4 g (2.3 × 10 ⁻² mol) and 0.10 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.5 × 10 ⁻⁸ mol as Pt alone) were added dropwise to 90 ° C. And the solvent and unreacted substances were distilled off under reduced pressure to obtain 29.5 g of a liquid product.

The compound obtained in Example 3 was confirmed to have the following structure by NMR.

で表される化合物１００ｇ（９．６×１０^-3ｍｏｌ）と、実施例１で用いた式（II）で表される化合物４．２ｇ（１．９×１０^-2ｍｏｌ）をフラスコに入れ、ここに、トリエチルアミン２．５ｇと１，３−ビストリフルオロメチルベンゼン１０ｇを混合してフラスコに入れ、５０℃で１２０分反応させた。その後、炭酸カルシウムで中和し、溶剤を留去し、下記式（ＶI）で表される末端に不飽和結合を有するフルオロオキシアルキレン基含有ポリマー１０３．５ｇを得た。

（ＶI） [Example 4]
In the reaction vessel, the following formula (V)

And 100 g (9.6 × 10 ⁻³ mol) of the compound represented by formula and 4.2 g (1.9 × 10 ⁻² mol) of the compound represented by the formula (II) used in Example 1 were put in a flask. Here, 2.5 g of triethylamine and 10 g of 1,3-bistrifluoromethylbenzene were mixed and placed in a flask, and reacted at 50 ° C. for 120 minutes. Thereafter, the mixture was neutralized with calcium carbonate, the solvent was distilled off, and 103.5 g of a fluorooxyalkylene group-containing polymer having an unsaturated bond at the terminal represented by the following formula (VI) was obtained.

(VI)

Next, 100 g (9.3 × 10 ⁻³ mol) of the compound represented by the formula (VI) obtained in the above step, 20 g of 1,3-bistrifluoromethylbenzene, 2.3 g of trimethoxysilane (1.9) × 10 ⁻² mol) and 0.05 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (containing 1.2 × 10 ⁻² mol as a simple substance of Pt) were mixed and aged at 80 ° C. for 8 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 98.6 g of a liquid product.

The compound obtained in Example 4 was confirmed to have the following structure by NMR.

[Comparative Examples 1-5]
The compounds of Comparative Examples 1 to 5 are shown below.

Comparative Example 1:

Comparative Example 2:

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） Comparative Example 3:

(P / q = 0.9, p + q≈45)

（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） Comparative Example 4:

(P / q = 0.9, p + q≈45)

Comparative Example 5:

Preparation of surface treatment agent and formation of cured film The fluorooxyalkylene group-containing polymer-modified silanes of Examples 1 to 3 and Comparative Examples 1 to 4 were dissolved in Novec 7200 (manufactured by 3M) so as to have a concentration of 20% by mass. Thus, a surface treatment agent was prepared. 10 mg of each surface treatment agent was vacuum-deposited on a glass (Gorilla made by Corning) with 10 nm of SiO ₂ treated on the outermost surface (treatment conditions: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.) The cured film was formed by curing for 2 hours in an atmosphere of 50 ° C. and 50% humidity.
The treatment bath was prepared by dissolving the fluorooxyalkylene group-containing polymer-modified silane of Example 4 and Comparative Example 5 in Novec 7200 (manufactured by 3M) so as to have a concentration of 0.1% by mass. Glass (Gorilla manufactured by Corning Co., Ltd.) treated with 10 nm of SiO ₂ on the outermost surface is immersed in a treatment bath for 30 seconds, then pulled up at a speed of 150 mm / min, and cured by curing for 24 hours in an atmosphere of 50 ° C. and 50% humidity. A film was formed.

The obtained cured film was evaluated by the following method. The results are shown in Table 1.
[Evaluation of water and oil repellency]
Using the glass produced as described above, the contact angle to water (water repellency) and the contact angle to oleic acid (oil repellency) of the cured coating were measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.).

[Magic ink wiping properties]
Oily magic (“Hi-Mackey” manufactured by Zebra Co., Ltd.) was applied to the treated surface, and the wiping property of the magic ink with tissue paper (Elmore manufactured by Kami Shoji Co., Ltd.) was visually evaluated using the following indicators.
◎ Easy and complete wiping by one wiping operation.
○: A little ink remains after one wiping operation.
Δ: About half remains after one wiping operation.
X: It cannot wipe off at all.

[Evaluation of chemical resistance]
The change in water repellency after immersion in the following chemicals was measured in the same manner as described above.
1. Saline test salt concentration: 5% by mass
Immersion time: 72 hours
2. Alkali resistance test Alkaline solution: 10% by mass NaOH aqueous solution Immersion time: 2 hours
3. Acid resistance test acid solution: 10 mass% HCl aqueous solution Immersion time: 5 hours

From the above results, the cured coatings of Comparative Examples 1, 3, and 4 having an ether bond as a linking group are inferior in chemical resistance. Further, Comparative Example 2 having a CONH bond in the linking group and Comparative Example 5 having a CON (CH ₃ ) bond are also inferior in chemical resistance. On the other hand, Examples 1-4 which have a CONPh bond in a connecting group were excellent in chemical resistance. Therefore, the surface treatment agents of Examples 1 to 4 have excellent water and oil repellency and excellent chemical resistance, and fingerprints and sebum adhere to the surface for a long period of time, and acid and alkaline cleaning agents adhere to it. In addition, the characteristics of the film can be maintained.

  The fluorooxyalkylene group-containing polymer-modified silane of the present invention can provide a cured film excellent in water / oil repellency and chemical resistance. For this reason, the surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane and / or its hydrolyzed condensate of the present invention, in particular, those that are assumed to be attached to oil and fat such as touch panel displays and antireflection films, and chemicals It is useful as a water- and oil-repellent layer for parts that need to be immersed in water.

Claims (14)

The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Z is independently a 2-6 valent group optionally having a siloxane bond, and R is independently carbon number. 1 to 4 alkyl groups or phenyl groups, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b is independently 2 or 3, y is 1 to 1 independently for each unit. 5 is an integer, α is an integer of 1 to 5, and β is 1 or 2.)
A fluoroxyalkylene group-containing polymer-modified silane represented by: The fluorooxyalkylene group-containing polymer residue has the following general formula

(G is an integer of 1 to 6 independently for each unit.)
The fluorooxyalkylene group-containing polymer-modified silane according to claim 1, comprising 3 to 201 repeating units represented by the formula: The fluorooxy according to claim 1 or 2, wherein β in the formula (1) is 1 and the Rf group is selected from the groups represented by the following general formulas (2), (3) and (4). An alkylene group-containing polymer-modified silane.

(In the formula, Y is independently an F or CF ₃ group, m is an integer of 3 to 200, and d is an integer of 1 to 3).

(In the formula, m is an integer of 3 to 200, and d is an integer of 1 to 3.)

(In the formula, Y is independently an F or CF ₃ group, p and q are each an integer of 0 to 200, and p + q = 3 to 200, and each repeating unit may be bonded at random. d is an integer of 1 to 3) The fluorooxy according to claim 1 or 2, wherein β in the formula (1) is 2 and the Rf group is selected from the groups represented by the following general formulas (5), (6) and (7). An alkylene group-containing polymer-modified silane.

(Wherein Y is independently F or CF ₃ group, d is independently an integer of 1 to 3, e is an integer of 2 to 6, r and t are integers of 0 to 200, and r + t + s = 3 -200, s is an integer of 0-6, and each repeating unit may be bonded at random.

(In the formula, m is an integer of 3 to 200, and d is an integer of 1 to 3.)

(In the formula, Y is independently F or CF ₃ group, d is an integer of 1 to 3, p and q are integers of 0 to 200, respectively, p + q = 3 to 200, and each repeating unit is randomly selected. May be combined.)   The fluorooxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 4, wherein Z in the formula (1) is a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms. .   The hydrolyzable group X of the formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. And the fluoroxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 5, which is selected from the group consisting of halogen groups.   A surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane according to any one of claims 1 to 6 and / or a partial hydrolysis-condensation product of the fluorooxyalkylene group-containing polymer-modified silane.   An article treated with the surface treatment agent according to claim 7.   An optical article treated with the surface treating agent according to claim 7.   A touch panel treated with the surface treatment agent according to claim 7.   An antireflection film treated with the surface treatment agent according to claim 7. SiO ₂ treated glass which has been treated with a surface treatment agent according to claim 7.   A tempered glass treated with the surface treating agent according to claim 7.   A quartz substrate treated with the surface treating agent according to claim 7.