JP5556822B2 - Fluorooxyalkylene group-containing polymer-modified silane, surface treatment agent containing the silane, and article surface-treated with the surface treatment agent - Google Patents

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, a silane coupling agent is well known as a material for bonding a substrate surface such as glass or cloth and an organic compound, and is widely used as a coating agent 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.

（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。） 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.

(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 linking group between a fluorooxyalkylene group and an alkoxysilyl group, such as an ether bond of —CF ₂ CH ₂ —O—CH ₂ —, is inferior in chemical resistance.
Therefore, as a result of intensive studies to solve the above problems, the present inventors have determined that the surface contains a fluoroxyalkylene group-containing polymer-modified silane in which an amide bond having a fluoroalkyl group on a nitrogen atom is introduced as the linking group. It has been found that the treatment agent can form a water / 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、Ｒｆ”は独立に炭素数１〜１０のフルオロアルキル基であり、Ｚは独立に単結合又はシロキサン結合を有する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、ｃは独立に０又は１、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。但し、Ｚが単結合の場合、ｃは０、αは１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。
〔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〔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。
〔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〔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は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。）
〔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〔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は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は独立に１〜３の整数である。）

（式中、Ｙは独立にＦ又はＣＦ₃基であり、ｆは独立に１〜３の整数、ｐ、ｑはそれぞれ０〜２００の整数で、ｐ＋ｑは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。）
〔５〕
前記式（１）のＺが、単結合、又はケイ素原子数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、〔１〕〜〔４〕のいずれか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。
〔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、〔１〕〜〔５〕のいずれか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。
〔７〕
〔１〕〜〔６〕のいずれか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。
〔８〕
〔７〕に記載の表面処理剤で処理された物品。
〔９〕
〔７〕に記載の表面処理剤で処理された光学物品。
〔１０〕
〔７〕に記載の表面処理剤で処理されたタッチパネル。
〔１１〕
〔７〕に記載の表面処理剤で処理された反射防止フイルム。
〔１２〕
〔７〕に記載の表面処理剤で処理されたＳｉＯ₂処理ガラス。
〔１３〕
〔７〕に記載の表面処理剤で処理された強化ガラス。
〔１４〕
〔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.
[1]
The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Rf ″ is independently a fluoroalkyl group having 1 to 10 carbon atoms, and Z is independently a single bond or a siloxane bond. R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b Is independently 2 or 3, c is independently 0 or 1, y is an integer of 1 to 5 independently for each unit, α is an integer of 1 to 5, and β is 1 or 2. However, Z is (In the case of a single bond, c is 0 and α is 1.)
A fluoroxyalkylene group-containing polymer-modified silane represented by:
[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 [1], comprising 3 to 201 repeating units represented by the formula:
[3]
[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) Fluorooxyalkylene 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 F or CF ₃ group, p and q are each an integer of 0 to 200, p + q is 3 to 200, and each repeating unit may be bonded at random. d is an integer of 1 to 3)
[4]
[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) Fluorooxyalkylene 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 each an integer of 0 to 200, and r + t + s is 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 independently.)

(In the formula, Y is independently F or CF ₃ group, f is independently an integer of 1 to 3, p and q are integers of 0 to 200, p + q is 3 to 200, and each repeating unit is (It may be combined randomly.)
[5]
The fluorooxyalkylene according to any one of [1] to [4], wherein Z in the formula (1) is a single bond or a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms. Group-containing polymer-modified silane.
[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 a fluorooxyalkylene group-containing polymer-modified silane according to any one of [1] to [5], selected from the group consisting of halogen groups.
[7]
[1] A surface treating agent comprising the fluorooxyalkylene group-containing polymer-modified silane according to any one of [1] to [6] and / or a partial hydrolysis-condensation product of the fluorooxyalkylene group-containing polymer-modified silane.
[8]
An article treated with the surface treatment agent according to [7].
[9]
An optical article treated with the surface treating agent according to [7].
[10]
A touch panel treated with the surface treatment agent according to [7].
[11]
An antireflection film treated with the surface treatment agent according to [7].
[12]
SiO ₂ treated glass treated with the surface treating agent according to [7].
[13]
Tempered glass treated with the surface treating agent according to [7].
[14]
A quartz substrate treated with the surface treating agent according to [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、Ｒｆ”は独立に炭素数１〜１０のフルオロアルキル基であり、Ｚは独立に単結合又はシロキサン結合を有する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、ｃは独立に０又は１、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。但し、Ｚが単結合の場合、ｃは０、αは１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, Rf ″ is independently a fluoroalkyl group having 1 to 10 carbon atoms, and Z is independently a single bond or a siloxane bond. R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b Is independently 2 or 3, c is independently 0 or 1, y is an integer of 1 to 5 independently for each unit, α is an integer of 1 to 5, and β is 1 or 2. However, Z is (In the case of a single bond, c is 0 and α is 1.)

The fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) of the present invention is a monovalent or divalent fluorooxyalkylene group-containing polymer residue (Rf) and a hydrolyzable silyl group such as an alkoxysilyl group ( -Si (R) _3-b (X) _b ) has a structure in which an amide bond having a fluoroalkyl group is introduced on a nitrogen atom as a linking group, and the above fluorooxyalkylene group The hydrolyzable silyl group (—Si (R) _{3 -b} (X) _b ) such as the containing polymer residue (Rf) and the alkoxy silyl group has an ether bond, —CF ₂ —CONH— bond, —CF ₂ —. The chemical resistance is excellent as compared with the case where they are connected via a CONCH ₃ —Ph— bond or the like.

（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, g of each repeating unit may mutually differ, Preferably it 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は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２又は３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.)

(In the formula, Y is independently F or CF ₃ group, p and q are each an integer of 0 to 200, preferably 10 to 100, p + q is 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 2 or 3.)

  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は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 is 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は独立に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, 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、ｆは独立に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は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, f is independently 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; p + q is 3 to 200, preferably 10 to 100, and each repeating unit may be bonded at random.)

In the above formula (1), Rf ″ is a fluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include the following groups.

（式中、Ｒｆ”、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）_c−Ｓｉ（Ｒ）_3-b（Ｘ）_b）との、シロキサン結合を有する２〜６価の連結基、又は単結合であり、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、単結合、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、特に好ましいＺとしては、単結合、ケイ素原子数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。該ポリシロキサン残基としては、例えば、下記の基が挙げられる。 In the above formula (1), Z is at the end.

(In the formula, Rf ″ and a are the same as above.)
And a hydrolyzable silylalkyl group containing a hydrolyzable silyl group such as an alkoxysilyl group (— (C _y H _2y ) _c —Si (R) _{3 -b} (X) _b ) It is desirable that a divalent to hexavalent linking group having a siloxane bond or a linking group having a 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 single bond, a linear, branched or cyclic organopolysiloxane residue having 2 to 10, preferably 2 to 9, particularly 2 to 6, silicon atoms, and particularly preferred Z Is a single bond, a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms. Examples of the polysiloxane residue 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 suitable especially. 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. c is 0 or 1. y is an integer of 1 to 5, preferably 1 to 3. Moreover, although α is an integer of 1 to 5, it represents the valence -1 of Z.

  Examples of the fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formula.

（式中、ｒ１＋ｔ１は６０（平均値）である。）

(In the formula, r1 + t1 is 60 (average value).)

（式中、ｍ１は３〜２００の整数である。）

(In the formula, m1 is an integer of 3 to 200.)

（式中、ｐ１＋ｑ１は３〜２００の整数である。）

(In the formula, p1 + q1 is an integer of 3 to 200.)

（式中、Ｒｆは上記と同じ、ＨａｌはＦ等のハロゲン原子である。）
で示される末端にハロゲン化アシル基が結合したフルオロオキシアルキレン基含有ポリマーに、下記一般式（ｃ）

（式中、Ｒｆ”は上記と同じ、ａ’は０〜３の整数である。）
で示されるフルオロアルキル基を有するアリルアミン等のアルケニルアミンを反応させ、下記一般式（ｄ）

（式中、Ｒｆ、Ｒｆ”、ａ’、βは上記と同じ。）
で示される末端にアリル基等のアルケニル基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。 The fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) can be prepared as follows.
The following general formula (a) or (b)

(In the formula, Rf is the same as described above, and Hal is a halogen atom such as F.)
A fluorooxyalkylene group-containing polymer having an acyl halide group bonded to the terminal represented by the following general formula (c):

(In the formula, Rf ″ is the same as above, and a ′ is an integer of 0 to 3.)
An alkenylamine such as allylamine having a fluoroalkyl group represented by the following general formula (d):

(In the formula, Rf, Rf ″, a ′, and β are the same as above.)
A fluorooxyalkylene group-containing polymer having an alkenyl group such as an allyl group at the terminal is obtained.

（式中、ｍ２は２〜１９９の整数であり、ｒ２は０〜２００の整数であり、ｔ２は０〜２００の整数であり、ｍ３は３〜２００の整数であり、ｐ２＋ｑ２は３〜２００の整数である。） Here, examples of the fluorooxyalkylene group-containing polymer having an acyl halide group bonded to the terminal include those shown below.

(In the formula, m2 is an integer of 2 to 199, r2 is an integer of 0 to 200, t2 is an integer of 0 to 200, m3 is an integer of 3 to 200, and p2 + q2 is 3 to 200. (It is an integer.)

（式中、ｎ１は１〜１０の整数である。） Examples of the alkenylamine having a fluoroalkyl group include those shown below.

(In the formula, n1 is an integer of 1 to 10.)

  The above reaction can be carried out in the presence of an acid acceptor such as triethylamine using an alkenylamine having a small excess of fluoroalkyl group with respect to a fluorooxyalkylene group-containing polymer to which an acyl halide group is bonded. The reaction conditions are 20 to 80 ° C. and about 1 to 10 hours. At this time, a solvent may be used. As the solvent, 1,3-bistrifluoromethylbenzene is preferable. In this manner, a fluorooxyalkylene group-containing polymer having an alkenyl group such as an allyl group at the end, represented by the general formula (d), can be obtained.

（式中、Ｚ、Ｒ、Ｘ、ｙ、ｂ、ｃ、αは上記と同じ。但し、Ｚが単結合の場合、ｃは０、αは１である。）
で示されるＳｉＨ基及びアルコキシシリル基を有する化合物のＳｉＨ基と、上記一般式（ｄ）で示される末端にアルケニル基を有するフルオロオキシアルキレン基含有ポリマーの末端アルケニル基とを反応させることにより、目的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を得ることができる。 Then, the following general formula (e)

(In the formula, Z, R, X, y, b, c, and α are the same as above. However, when Z is a single bond, c is 0 and α is 1.)
And a terminal alkenyl group of a fluorooxyalkylene group-containing polymer having an alkenyl group at the terminal represented by the general formula (d) by reacting the SiH group of the compound having an SiH group and an alkoxysilyl group represented by the general formula (d). The fluorooxyalkylene group-containing polymer-modified silane can be obtained.

Here, examples of the compound having a SiH group and an alkoxysilyl group include those shown below.

  The reaction of the compound having the SiH group and alkoxysilyl group represented by the general formula (e) with the fluorooxyalkylene group-containing polymer having an alkenyl group at the terminal represented by the general formula (d) is carried out in the presence of a catalyst. It can carry out by heating and mixing at 50-130 degreeC. As the catalyst, a toluene solution of chloroplatinic acid / vinylsiloxane complex is suitable.

（式中、Ｒ、Ｘ、ｂは上記と同じ。ｙ’は０〜３の整数である。）
で示される、ビニルトリメトキシシランなどのアルケニル基含有アルコキシシランを用いて反応させることによっても、目的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を得ることができる。 Further, the fluorooxyalkylene group-containing polymer having an alkenyl group at the terminal represented by the general formula (d) has 2 to 6 SiH groups in one molecule for deriving Z in the formula (1). After the terminal is modified with an excess of the compound, the following general formula (f)

(In the formula, R, X, and b are the same as above. Y ′ is an integer of 0 to 3.)
The target fluorooxyalkylene group-containing polymer-modified silane can also be obtained by reacting with an alkenyl group-containing alkoxysilane such as vinyltrimethoxysilane.

Here, examples of the compound having 2 to 6 SiH groups in one molecule for deriving Z in the formula (1) include those shown below.

  The reaction between the compound having 2 to 6 SiH groups in one molecule and the fluorooxyalkylene group-containing polymer having an alkenyl group at the terminal represented by the general formula (d) is performed at 50 to 130 ° C. in the presence of a catalyst. Can be carried out by heating and mixing. As the catalyst, a toluene solution of chloroplatinic acid / vinylsiloxane complex is suitable. At this time, the compound having 2 to 6 SiH groups in one molecule needs to be used in a large excess with respect to the fluorooxyalkylene group-containing polymer having an alkenyl group. It is preferable to use 2 to 10 moles of SiH groups in a compound having 2 to 6 SiH groups per molecule per mole of alkenyl groups. After completion of the reaction, the compound having an excess of SiH groups not bonded to the polymer is removed by distillation.

  Subsequently, an alkenyl group-containing alkoxysilane such as vinyltrimethoxysilane is reacted. The reaction at this time can be performed by heating and mixing at 50 to 100 ° C. for 30 minutes to 10 hours in the presence of a catalyst. As the catalyst, a toluene solution of chloroplatinic acid / vinylsiloxane complex is suitable. A solvent such as 1,3-bistrifluoromethylbenzene may be used. After completion of the reaction, the target fluorooxyalkylene group-containing polymer-modified silane can be obtained by removing the solvent and unreacted alkenyl group-containing alkoxysilane by distillation.

  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-bistrifluoromethylbenzene), 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 the fluorooxyalkylene group-containing polymer-modified silane (and its partially hydrolyzed condensate) is 100 parts by mass. On the other hand, it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass.

  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. Further, the curing temperature varies depending on the curing method, but for example, when applied by brushing or dipping, a range from room temperature to 200 ° C is desirable. 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（２３ｍｍｏｌ）と、下記式（ＩＩ）

で表される化合物３．５ｇ（２５ｍｍｏｌ）をフラスコに入れ、更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、６０℃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９５．７ｇを得た。 [Example 1]
In the reaction vessel, the following formula (I)

100 g (23 mmol) of a compound represented by the following formula (II)

Was added to a flask, and 2.5 g of triethylamine and 10 g of 1,3-bistrifluoromethylbenzene were mixed and placed in the flask, and reacted at 60 ° C. for 120 minutes. Then, neutralize with calcium carbonate, distill off the solvent, the following formula (III)

95.7 g of a fluorooxyalkylene group-containing polymer having an unsaturated bond at the terminal represented by

  Next, 50 g (11 mmol) of the compound represented by the formula (III) obtained in the above step, 10 g of 1,3-bistrifluoromethylbenzene, 2.7 g (22 mmol) of trimethoxysilane, and chloroplatinic acid / vinylsiloxane 0.02 g of a toluene solution of the complex (containing 0.1 mg of Pt) was mixed and stirred at 80 ° C. for 8 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 48 g of a liquid product.

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

[Example 2]
20 g (4.5 mmol) of the compound represented by the formula (III) used in Example 1 was dissolved in 15 g of 1,3-bistrifluoromethylbenzene, and 0.1 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (Pt And 0.5 g of 7.1 addition reaction product (HM-VMS) of tetramethyldisiloxane (HM) and vinyltrimethoxysilane (VMS) was added dropwise at 90 ° C. And the solvent and unreacted substances were distilled off under reduced pressure to obtain 19.7 g of a liquid product.

The HM-VMS was prepared by the following method.
Tetramethyldisiloxane (HM) 40 g (0.29 mol) and toluene 40 g were mixed and heated to 80 ° C. A mixture of 44.2 g (0.29 mol) of vinyltrimethoxysilane (VMS) and 2 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 10 mg of Pt) was slowly added dropwise. The obtained mixture was purified by distillation to obtain 48 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.

次に、上記工程で得られた式（ＩＶ）で表される生成物１５ｇ（３．２ｍｍｏｌ）を１，３−ビストリフルオロメチルベンゼン１０ｇに溶解させ、ビニルトリメトキシシラン（ＶＭＳ）１．８ｇ（１２ｍｍｏｌ）と塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．１０ｇ（Ｐｔとして０．５ｍｇ含有）を加えて、９０℃で２時間攪拌し、その後、溶剤及び未反応物を減圧溜去したところ、液状の生成物１５．３ｇを得た。 [Example 3]
Dissolve 20 g (4.5 mmol) of the compound represented by the formula (III) used in Example 1 and 5.5 g (23 mmol) of tetramethylcyclotetrasiloxane (cyclic siloxane H4) in 15 g of 1,3-bistrifluoromethylbenzene. And heated to 90 ° C. Thereafter, 0.07 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (containing 0.35 mg as Pt) was added dropwise and stirred at 90 ° C. for 4 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure. 20.3 g of a liquid product represented by the formula (IV) was obtained.

Next, 15 g (3.2 mmol) of the product represented by the formula (IV) obtained in the above step is dissolved in 10 g of 1,3-bistrifluoromethylbenzene, and 1.8 g of vinyltrimethoxysilane (VMS) ( 12 mmol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex (0.10 g) (containing 0.5 mg as Pt) and stirred at 90 ° C. for 2 hours, and then the solvent and unreacted materials were distilled off under reduced pressure. 15.3 g of liquid product was obtained.

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

（ｒ１＋ｔ１＝６０（平均値）。以下、同じ）
で表される化合物１００ｇ（９．６ｍｍｏｌ）と、下記式（ＩＩ）

で表される化合物２．９ｇ（２１．１ｍｍｏｌ）をフラスコに入れ、更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、６０℃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９６．７ｇを得た。

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

(R1 + t1 = 60 (average value). The same applies hereinafter)
100 g (9.6 mmol) of a compound represented by the following formula (II)

In a flask, 2.5 g of triethylamine and 10 g of 1,3-bistrifluoromethylbenzene were mixed and placed in the flask, and reacted at 60 ° C. for 120 minutes. Thereafter, the mixture was neutralized with calcium carbonate and the solvent was distilled off to obtain 96.7 g of a fluorooxyalkylene group-containing polymer having an unsaturated bond at the terminal represented by the following formula (VI).

  Next, 50 g (4.7 mmol) of the compound represented by the formula (VI) obtained in the above step, 20 g of 1,3-bistrifluoromethylbenzene, 2.2 g (19 mmol) of trimethoxysilane, chloroplatinic acid / vinyl A toluene solution of siloxane complex (0.1 g) (containing 0.5 mg as Pt) was mixed and stirred at 80 ° C. for 8 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 49.3 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 (“Himacy” 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% by 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 the structure which introduce | transduced the amide bond which has a fluoroalkyl group on a nitrogen atom as a coupling 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, Rf ″ is independently a fluoroalkyl group having 1 to 10 carbon atoms, and Z is independently a single bond or a siloxane bond. R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is independently an integer of 2 to 5, b Is independently 2 or 3, c is independently 0 or 1, y is an integer of 1 to 5 independently for each unit, α is an integer of 1 to 5, and β is 1 or 2. However, Z is (In the case of a single bond, c is 0 and α is 1.)
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 F or CF ₃ group, p and q are each an integer of 0 to 200, p + q is 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 each an integer of 0 to 200, and r + t + s is 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 independently.)

(In the formula, Y is independently F or CF ₃ group, f is independently an integer of 1 to 3, p and q are integers of 0 to 200, p + q is 3 to 200, and each repeating unit is (It may be combined randomly.)   The fluorooxyalkylene according to any one of claims 1 to 4, wherein Z in the formula (1) is a single bond or a linear or cyclic organopolysiloxane residue having 2 to 5 silicon atoms. Group-containing polymer-modified silane.   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.