JP2013018743A - Fluorooxyalkylene group-containing polymer modified silane, surface treatment agent containing the silane, and article surface-treated with the surface treatment agent - Google Patents
Fluorooxyalkylene group-containing polymer modified silane, surface treatment agent containing the silane, and article surface-treated with the surface treatment agent Download PDFInfo
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本発明は、フルオロオキシアルキレン基含有ポリマー変性シランに関し、詳細には、撥水撥油性、耐薬品性に優れた被膜を形成す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、及び該シランあるいはその部分加水分解縮合物を含む表面処理剤、並びに該表面処理剤で処理された物品に関する。 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.
近年、携帯電話のディスプレイをはじめ、画面のタッチパネル化が加速している。しかし、タッチパネルは画面がむき出しのものが多く、指や頬などが直接付着する機会が多く、皮脂等の汚れが付き易いことが問題となっている。そこで、外観や視認性をよくするためにディスプレイの表面に指紋を付きにくくする技術や、汚れを落とし易くする技術の要求が年々高まってきており、これらの要求に応えることのできる材料の開発が望まれている。しかし、従来の撥水撥油層は撥水撥油性が高く、汚れ拭取り性に優れるが、使用中に防汚性能が劣化してしまうという問題点があった。防汚性能の劣化原因のひとつとして、耐薬品性が挙げられる。 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.
一般に、パーフルオロオキシアルキレン基含有化合物は、その表面自由エネルギーが非常に小さいために、撥水撥油性、耐薬品性、潤滑性、離型性、防汚性などを有する。その性質を利用して、工業的には紙・繊維などの撥水撥油防汚剤、磁気記録媒体の滑剤、精密機器の防油剤、離型剤、化粧料、保護膜など、幅広く利用されている。しかし、その性質は同時に他の基材に対する非粘着性、非密着性であることを意味しており、基材表面に塗布することはできても、その被膜を密着させることは困難であった。 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. .
一方、ガラスや布などの基材表面と有機化合物とを結合させるものとして、シランカップリング剤が良く知られており、各種基材表面のコーティング剤として幅広く利用されている。シランカップリング剤は、１分子中に有機官能基と反応性シリル基（一般にはアルコキシシリル基）を有する。アルコキシシリル基が、空気中の水分などによって自己縮合反応を起こして被膜を形成する。該被膜は、アルコキシシリル基がガラスや金属などの表面と化学的・物理的に結合することにより耐久性を有する強固な被膜となる。 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.
これらを有するものとして、特許文献１（特開２００３−２３８５７７号公報）に、下記式で示される直鎖状のパーフルオロオキシアルキレン基を含有するパーフルオロオキシアルキレン基含有ポリマー変性シランが提案されている。該パーフルオロオキシアルキレン基含有ポリマー変性シランで処理したレンズや反射防止膜は、滑り性、離型性、及び耐摩耗性に優れるが、パーフルオロオキシアルキレン基とアルコキシシリル基との連結基として、アリルエーテル基が用いられているため、耐薬品性が十分でない。 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.
本発明は、上記事情に鑑みなされたもので、耐薬品性に優れた撥水撥油層を形成することができ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、該シラン及び／又はその部分加水分解縮合物を含む表面処理剤、及び該表面処理剤で処理された物品を提供することを目的とする。 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.
タッチパネルディスプレイ等の表面に被覆する撥水撥油層は、指紋や洗浄剤等に含まれる酸やアルカリ、塩水に対して耐性を有することが望ましい。
本発明者らは先に、上述したように、両末端に加水分解性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提案している（特開２００３−２３８５７７号公報：特許文献１）が、該組成物から形成される膜は、耐薬品性が十分でない。
主鎖にフルオロオキシアルキレン構造を有し、分子鎖の片末端又は両末端に加水分解性基を含有するポリマーは、これを表面処理剤として用いた場合に、基材と強固に密着し、布等による耐摩耗性に優れるものとなるが、フルオロオキシアルキレン基とアルコキシシリル基との連結基、例えば、−ＣＦ2ＣＨ2−Ｏ−ＣＨ2−のエーテル結合等は、耐薬品性に劣る。
そこで、本発明者らは、上記問題を解決すべく鋭意検討した結果、上記連結基として、−ＣＦ2−ＣＯＮＰｈ−ＣＨ2−（Ｐｈはフェニル基）を用いた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含有する表面処理剤が、耐薬品性に優れた撥水撥油層を形成し得ることを見出し、本発明をなすに至った。
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.
従って、本発明は、下記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該シラン及び／又はその部分加水分解縮合物を含む表面処理剤並びに該表面処理剤で表面処理された物品を提供する。
〔請求項１〕
下記一般式（１）
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
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。
〔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。
〔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)
A fluoroxyalkylene group-containing polymer-modified silane represented by:
[Claim 2]
The fluorooxyalkylene group-containing polymer residue has the following general formula
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.
[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.
[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.
本発明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から形成される被膜は、撥水撥油性が高い。本発明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／又はその部分加水分解縮合物を含有する表面処理剤で処理することによって、各種物品に優れた撥水撥油性を付与することができ、薬品に対する耐性が高く、長期に防汚性能を保つことができる。 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.
本発明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は、下記一般式（１）で示されるものである。
本発明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（Ｒｆ）とアルコキシシリル基等の加水分解性シリル基（−Ｓｉ（Ｒ）3-b（Ｘ）b）が、連結基−ＣＦ2−ＣＯＮＰｈ−ＣＨ2−（Ｐｈはフェニル基、以下同じ。）を介して結合した構造であることを特徴としており、上記フルオロオキシアルキレン基含有ポリマー残基（Ｒｆ）とアルコキシシリル基等の加水分解性シリル基（−Ｓｉ（Ｒ）3-b（Ｘ）b）が、エーテル結合や、−ＣＦ2−ＣＯＮＨ−結合、−ＣＦ2−ＣＯＮＣＨ3−Ｐｈ−結合等を介して連結している場合に比較して耐薬品性に優れている。 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.
前記式中、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（Ｒｆ）は、下記一般式で表される繰り返し単位３〜２０１個、好ましくは６〜１０１個、より好ましくは２５〜８１個を含む。なお、各繰り返し単位は互いにｇの値が異なっていてよく、好ましくはｇが１〜４の整数である。
上記一般式で示される繰り返し単位としては、例えば下記の単位等が挙げられる。なお、上記Ｒｆ基は、これらの繰り返し単位の１種単独で構成されていてもよいし、２種以上の組み合わせであってもよい。
−ＣＦ2Ｏ−
−ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−Ｃ（ＣＦ3）2Ｏ−
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-
上記繰り返し単位を含むＲｆとして、βが１の場合、下記一般式（２）、（３）及び（４）で示される基から選ばれる１価のフルオロオキシアルキレン基が好ましい。 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.
上記繰り返し単位を含むＲｆとして、βが２の場合、下記一般式（５）、（６）及び（７）で示される基から選ばれる２価のフルオロオキシアルキレン基が好ましい。 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.
上記式（１）において、Ｚは末端に
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（−ＣyＨ2y−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.
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. .
上記式（１）において、Ｘは互いに異なっていてよい加水分解性基である。このようなＸとしては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などの炭素数１〜１０のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基などの炭素数２〜１０のアルコキシアルコキシ基、アセトキシ基などの炭素数１〜１０のアシロキシ基、イソプロペノキシ基などの炭素数２〜１０のアルケニルオキシ基、クロル基、ブロモ基、ヨード基などのハロゲン基などが挙げられる。中でもメトキシ基、エトキシ基、イソプロペノキシ基、クロル基が好適である。 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.
上記式（１）において、Ｒは、炭素数１〜４のメチル基、エチル基、プロピル基、ブチル基等のアルキル基、又はフェニル基であり、中でもメチル基が好適である。ａは２〜５の整数、好ましくは２又は３であり、ｂは２又は３であり、反応性、基材に対する密着性の観点から、３が好ましい。ｙは１〜５、好ましくは１〜３の整数である。 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.
上記式（１）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としては、下記式で表されるものが例示できる。なお、各式において、フルオロオキシアルキレン基を構成する各繰り返し単位の繰り返し数（又は重合度）は、上記式（２）〜（７）を満足する任意の数をとり得るものである。 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).
上記式（１）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の調製方法としては、例えば下記のような方法が挙げられる。
分子鎖両末端又は片末端に酸フロライド基（−Ｃ（＝Ｏ）−Ｆ）を有するパーフルオロオキシアルキレン基含有ポリマーと、下記式
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
次に、上記工程で得られた化合物を溶剤、例えば、１，３−ビストリフルオロメチルベンゼンに溶解させ、トリメトキシシラン等の、分子中にＳｉＨ基を１個有すると共に、アルコキシ基等の加水分解性基を２個又は３個有するシラン化合物を、塩化白金酸／ビニルシロキサン錯体のトルエン溶液存在下、８０℃で８時間熟成させる。その後、溶剤及び未反応物を減圧留去することで、例えば下記式で示されるような目的の化合物を得ることができる。
本発明は、更に上記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含有する表面処理剤を提供する。該表面処理剤は、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末端加水分解性基を予め公知の方法により部分的に加水分解し、縮合させて得られる部分加水分解縮合物を含んでいてもよい。 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. .
表面処理剤には、必要に応じて、加水分解縮合触媒、例えば、有機錫化合物（ジブチル錫ジメトキシド、ジラウリン酸ジブチル錫など）、有機チタン化合物（テトラｎ−ブチルチタネートなど）、有機酸（酢酸、メタンスルホン酸、フッ素変性カルボン酸など）、無機酸（塩酸、硫酸など）を添加してもよい。これらの中では、特に酢酸、テトラｎ−ブチルチタネート、ジラウリン酸ジブチル錫、フッ素変性カルボン酸などが望ましい。
加水分解縮合触媒の添加量は触媒量であり、通常、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／又はその部分加水分解縮合物１００質量部に対して０．０１〜５質量部、特に０．１〜１質量部である。
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.
該表面処理剤は、適当な溶剤を含んでよい。このような溶剤としては、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタンなど）、フッ素変性芳香族炭化水素系溶剤（１，３−トリフルオロメチルベンゼンなど）、フッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２−ブチルテトラヒドロフラン）など）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミンなど）、炭化水素系溶剤（石油ベンジン、トルエン、キシレンなど）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）を例示することができる。これらの中では、溶解性、濡れ性などの点で、フッ素変性された溶剤が望ましく、特には、ｍ−キシレンヘキサフルオライド、パーフルオロ（２−ブチルテトラヒドロフラン）、パーフルオロトリブチルアミン、エチルパーフルオロブチルエーテルが好ましい。 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.
上記溶剤はその２種以上を混合してもよく、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その部分加水分解縮合物を均一に溶解させることが好ましい。なお、溶剤に溶解させ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の最適濃度は、処理方法により異なるが溶剤及びフルオロオキシアルキレン基含有ポリマー変性シラン（及びその部分加水分解縮合物）の合計１００質量部に対して０．０１〜１０質量部、特に０．０５〜５質量部であることが好ましい。 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.
本発明の表面処理剤は、刷毛塗り、ディッピング、スプレー、蒸着処理など公知の方法で基材に施与することができる。蒸着処理時の加熱方法は、抵抗加熱方式でも、電子ビーム加熱方式のどちらでもよく、特に限定されるものではない。また、硬化温度は、硬化方法によって異なるが、例えば、刷毛塗りやディッピングで施与した場合は、室温から２００℃の範囲が望ましい。硬化湿度としては、加湿下で行うことが反応を促進する上で望ましい。また、硬化被膜の膜厚は、基材の種類により適宜選定されるが、通常０．１〜２０ｎｍ、特に１〜１０ｎｍである。 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.
本発明の表面処理剤で処理される基材は特に制限されず、紙、布、金属及びその酸化物、ガラス、プラスチック、セラミック、石英など各種材質のものであってよい。本発明の表面処理剤は前記基板に撥水撥油性を付与することができる。特に、ＳｉＯ2処理されたガラスやフイルムの表面処理剤として好適に使用することができる。 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.
本発明の表面処理剤で処理される物品としては、カーナビゲーション、携帯電話、デジタルカメラ、デジタルビデオカメラ、ＰＤＡ、ポータブルオーディオプレーヤー、カーオーディオ、ゲーム機器、眼鏡レンズ、カメラレンズ、レンズフィルター、サングラス、胃カメラ等の医療用器機、複写機、ＰＣ、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ、保護フイルム、反射防止フイルムなどの光学物品が挙げられる。本発明の表面処理剤は前記物品に指紋及び皮脂が付着するのを防止し、更に傷つき防止性を付与することができるため、特にタッチパネルディスプレイ、反射防止フイルムなどの撥水撥油層として有用である。 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. .
また、本発明の表面処理剤は、浴槽、洗面台のようなサニタリー製品の防汚コーティング、自動車、電車、航空機などの窓ガラス又は強化ガラス、ヘッドランプカバー等の防汚コーティング、外壁用建材の撥水撥油コーティング、台所用建材の油汚れ防止用コーティング、電話ボックスの防汚及び貼り紙・落書き防止コーティング、美術品などの指紋付着防止付与のコーティング、コンパクトディスク、ＤＶＤなどの指紋付着防止コーティング、金型用に離型剤あるいは塗料添加剤、樹脂改質剤、無機質充填剤の流動性改質剤又は分散性改質剤、テープ、フイルムなどの潤滑性向上剤としても有用である。 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.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記実施例によって限定されるものではない。 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.
［実施例１］
反応容器に、下記式（Ｉ）
In the reaction vessel, the following formula (I)
次に、上記工程と同様にして得られた式（III）で表される化合物１００ｇ（２．２×１０-2ｍｏｌ）、１，３−ビストリフルオロメチルベンゼン２０ｇ、トリメトキシシラン３．３ｇ（２．７×１０-2ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０５ｇ（Ｐｔ単体として１．２×１０-2ｍｏｌを含有）を混合し、８０℃で８時間熟成させた。その後、溶剤及び未反応物を減圧留去したところ、液状の生成物１００．２ｇを得た。 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.
得られた化合物は、ＮＭＲにより下記構造であることが確認された。
［実施例２］
実施例１で用いた式（III）で表される化合物３０ｇ（６．６×１０-3ｍｏｌ）を１，３−トリフルオロメチルベンゼン２０ｇに溶解させ、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単体として２．５×１０-8ｍｏｌを含有）と、テトラメチルジシロキサン（ＨＭ）とビニルトリメトキシシラン（ＶＭＳ）の１：１付加反応物（ＨＭ−ＶＭＳ）２．５ｇ（８．９×１０-3ｍｏｌ）を滴下して、９０℃で２時間熟成し、溶剤及び未反応物を減圧留去したところ、液状の生成物３０．８ｇを得た。
[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.
なお、上記ＨＭ−ＶＭＳは下記の方法で調製した。
テトラメチルジシロキサン（ＨＭ）４０ｇ（３．０×１０-1ｍｏｌ）とトルエン４０ｇとを混合し、８０℃に加熱した。ビニルトリメトキシシラン（ＶＭＳ）４４．２ｇ（３．０×１０-1ｍｏｌ）と塩化白金酸／ビニルシロキサン錯体のトルエン溶液２ｇ（Ｐｔ単体として１．１×１０-7ｍｏｌを含有）の混合物をゆっくりと滴下した。得られた混合物を蒸留精製し、下記式に示す付加反応物（ＨＭ−ＶＭＳ）８４ｇを得た。
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.
実施例２で得られた化合物は、ＮＭＲにより下記構造であることが確認された。
［実施例３］
実施例１で用いた式（III）で表される化合物３０ｇ（６．６×１０-3ｍｏｌ）とテトラメチルシクロテトラシロキサン（環状シロキサンＨ４）８ｇ（３．３×１０-2ｍｏｌ）を１，３−トリフルオロメチルベンゼン２０ｇに溶解させ、９０℃まで加熱した。その後、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単体として２．５×１０-8ｍｏｌを含有）を滴下して、９０℃で２時間熟成し、溶剤及び未反応物を減圧留去したところ、下記式（IＶ）で表される液状の生成物３０．５ｇを得た。
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.
次に、上記工程で得られた式（IＶ）で表される生成物３０ｇ（６．３×１０-3ｍｏｌ）を１，３−トリフルオロメチルベンゼン２０ｇに溶解させ、ビニルトリメトキシシラン（ＶＭＳ）３．４ｇ（２．３×１０-2ｍｏｌ）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単体として２．５×１０-8ｍｏｌを含有）を滴下して、９０℃で２時間熟成し、溶剤及び未反応物を減圧留去したところ、液状の生成物２９．５ｇを得た。 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.
実施例３で得られた化合物は、ＮＭＲにより下記構造であることが確認された。
［実施例４］
反応容器に、下記式（Ｖ）
In the reaction vessel, the following formula (V)
次に、上記工程で得られた式（ＶI）で表される化合物１００ｇ（９．３×１０-3ｍｏｌ）、１，３−ビストリフルオロメチルベンゼン２０ｇ、トリメトキシシラン２．３ｇ（１．９×１０-2ｍｏｌ）、塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０５ｇ（Ｐｔ単体として１．２×１０-2ｍｏｌを含有）を混合し、８０℃で８時間熟成させた。その後、溶剤及び未反応物を減圧留去したところ、液状の生成物９８．６ｇを得た。 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.
実施例４で得られた化合物は、ＮＭＲにより下記構造であることが確認された。
［比較例１〜５］
比較例１〜５の化合物を以下に示す。
[Comparative Examples 1-5]
The compounds of Comparative Examples 1 to 5 are shown below.
比較例１：
比較例２：
比較例３：
比較例４：
比較例５：
表面処理剤の調製及び硬化被膜の形成
実施例１〜３及び比較例１〜４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、濃度２０質量％になるようにＮｏｖｅｃ ７２００（３Ｍ社製）に溶解させて表面処理剤を調製した。最表面にＳｉＯ2を１０ｎｍ処理したガラス（コーニング社製 Ｇｏｒｉｌｌａ）に、各表面処理剤１０ｍｇを真空蒸着し（処理条件は、圧力：２．０×１０-2Ｐａ、加熱温度：７００℃）、５０℃、湿度５０％の雰囲気下で２時間硬化させて硬化被膜を形成した。
実施例４及び比較例５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、濃度０．１質量％になるようにＮｏｖｅｃ ７２００（３Ｍ社製）に溶解させて処理浴を調製した。最表面にＳｉＯ2を１０ｎｍ処理したガラス（コーニング社製 Ｇｏｒｉｌｌａ）を、処理浴に３０秒間浸漬後、１５０ｍｍ／分の速度で引上げ、５０℃、湿度５０％の雰囲気下で２４時間硬化させて硬化被膜を形成した。
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.
得られた硬化被膜を下記の方法により評価した。結果を表１に示す。
［撥水撥油性の評価］
上記にて作製したガラスを用い、接触角計ＤｒｏｐＭａｓｔｅｒ（協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）及びオレイン酸に対する接触角（撥油性）を測定した。
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.).
［マジックインク拭取り性］
処理表面に油性マジック（ゼブラ株式会社製『ハイマッキー』）を塗り、ティッシュペーパー（カミ商事株式会社製エルモア）によるマジックインクの拭取り性を、下記指標を用い、目視により評価した。
◎：１回の拭取り操作で簡単に完全に拭取れる。
○：１回の拭取り操作では少しインクが残る。
△：１回の拭取り操作では半分ほど残る。
×：全く拭きとれない。
[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.
［耐薬品性の評価］
下記薬品に浸漬後の撥水性の変化を上記と同様に測定した。
１． 耐塩水試験
塩分濃度 ：５質量％
浸漬時間 ：７２時間
２． 耐アルカリ性試験
アルカリ液 ：１０質量％ＮａＯＨ水溶液
浸漬時間 ：２時間
３． 耐酸性試験
酸液 ：１０質量％ＨＣｌ水溶液
浸漬時間 ：５時間
[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
上記の結果より、エーテル結合を連結基に有する比較例１、３、４の硬化被膜は耐薬品性に劣る。また、連結基にＣＯＮＨ結合を有する比較例２や、ＣＯＮ（ＣＨ3）結合を有する比較例５も耐薬品性に劣る。一方、連結基にＣＯＮＰｈ結合を有する実施例１〜４は、耐薬品性に優れていた。そのため、実施例１〜４の表面処理剤は、撥水撥油性に優れ、且つ耐薬品性に優れており、長期に指紋や皮脂が付着したり、酸やアルカリ洗浄剤が付着したりしても、膜の特性を維持することができる。 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.
本発明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は、撥水撥油性、耐薬品性に優れた硬化被膜を与えることができる。このため、本発明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／又はその加水分解縮合物を含有する表面処理剤は、特に、タッチパネルディスプレイ、反射防止フイルムなど油脂の付着が想定されるものや、薬液に浸す必要がある部品の撥水撥油層として有用である。 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)
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。 The following general formula (1)
A fluoroxyalkylene group-containing polymer-modified silane represented by:
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。 The fluorooxyalkylene group-containing polymer residue has the following general formula
The fluorooxyalkylene group-containing polymer-modified silane according to claim 1, comprising 3 to 201 repeating units represented by the formula:
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