JP2005023381A - Thin-film-forming method, thin-film-forming apparatus, and body having thin film formed thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a thin film which does not exert influence on a substance to be treated, has superior water repellency, oil repellency, and wiping off properties for an oil ink, and has superior fretting resistance; and a body having the thin film. <P>SOLUTION: The method for forming the thin film comprises supplying a thin-film-forming gas including an organometallic compound having an organic group containing a fluorine atom, onto a body to be treated; and, introducing a discharge gas into a discharge space under ambient pressure or a pressure around ambient pressure, exciting it, and supplying the exited discharge gas onto the body to be treated. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５４】
等の基を表す。
ｋは０〜５０、好ましくは０〜３０の整数を表す。
【００５５】
Ｒｆ中にはフッ素原子のほか、他の置換基が置換されていてもよく、置換可能な基としては、前記Ｒ_１〜Ｒ_６において置換基として挙げられた基と同様の基が挙げられる。また、Ｒｆ中の骨格炭素原子が他の原子、例えば、−Ｏ−、−Ｓ−、−ＮＲ_０−（Ｒ_０は水素原子または置換もしくは非置換のアルキル基を表し、また前記一般式（Ｆ）で表される基であってもよい）、カルボニル基、−ＮＨＣＯ−、−ＣＯ−Ｏ−、−ＳＯ_２ＮＨ−等の基によって一部置換されていてもよい。
【００５６】
前記一般式（１）で表される化合物のうち、好ましいのは下記一般式（２）で表される化合物である。
【００５７】
一般式（２）
［Ｒｆ−Ｘ−（ＣＨ_２）_ｋ］_ｑ−Ｍ（Ｒ_１０）_ｒ（ＯＲ_１１）_ｔ
一般式（２）において、Ｍは前記一般式（１）と同様の金属原子を表し、Ｒｆ、Ｘは前記一般式（Ｆ）におけるＲｆ、Ｘと同様の基を表し、ｋについても同じ整数を表す。Ｒ_１０はアルキル基、アルケニル基を、またＲ_１１はアルキル基、アルケニル基、アリール基を表し、それぞれ、前記一般式（１）のＲ_１〜Ｒ_６の置換基として挙げた基と同様の基により置換されていてもよいが、好ましくは、非置換のアルキル基、アルケニル基を表す。また、ｑ＋ｒ＋ｔ＝４であり、ｑ≧１、またｔ≧１である。また、ｒ≧２の時２つのＲ_１０は連結して環を形成してもよい。
【００５８】
一般式（２）のうち、更に好ましいものものは下記一般式（３）で表される化合物である。
【００５９】
一般式（３）
Ｒｆ−Ｘ−（ＣＨ_２）_ｋ−Ｍ（ＯＲ_１２）_３
ここにおいて、Ｒｆ、Ｘまたｋは、前記一般式（２）におけるものと同義である。また、Ｒ_１２も、前記一般式（２）におけるＲ_１１と同義である。また、Ｍも前記一般式（２）におけるＭと同様であるが、特に、Ｓｉ、Ｔｉが好ましく、最も好ましいのはＳｉである。
【００６０】
本発明において、フッ素原子を有する有機金属化合物の他の好ましい例は、前記一般式（４）で表される化合物が挙げられる。
【００６１】
前記一般式（４）において、Ｒ_１〜Ｒ_６は、前記一般式（１）におけるＲ_１〜Ｒ_６と同義である。ここにおいても、Ｒ_１〜Ｒ_６の少なくとも１つは、前記フッ素原子を有する有機基であり、前記一般式（Ｆ）で表される基が好ましい。Ｒ_７は水素原子、または置換もしくは非置換のアルキル基を表す。また、ｊは０〜１５０の整数を表し、好ましくは０〜５０、最も好ましいのはｊが０〜２０の範囲である。
【００６２】
本発明において用いられる他の好ましいフッ素原子を有する化合物として、前記一般式（５）で表されるフッ素原子を有する有機金属化合物がある。
【００６３】
一般式（５）
［Ｒｆ−Ｘ−（ＣＨ_２）_ｋ−Ｙ］_ｍ−Ｍ（Ｒ_８）_ｎ（ＯＲ_９）_ｐ
一般式（５）において、ＭはＩｎ、Ａｌ、Ｓｂ、ＹまたはＬａを表す。Ｒｆ、Ｘは前記一般式（Ｆ）におけるＲｆ、Ｘと同様の基を表し、Ｙは単なる結合手または酸素を表す。ｋについても同じく０〜５０の整数を表し、好ましくは３０以下の整数である。Ｒ_９はアルキル基またはアルケニル基を、またＲ_８はアルキル基、アルケニル基またはアリール基を表し、それぞれ、前記一般式（１）のＲ_１〜Ｒ_６の置換基として挙げた基と同様の基により置換されていてもよい。また、一般式（５）において、ｍ＋ｎ＋ｐ＝３であり、ｍは少なくとも１であり、ｎは０〜２を、またｐも０〜２の整数を表す。ｍ＋ｐ＝３、即ちｎ＝０であることが好ましい。
【００６４】
本発明において用いられる他の好ましいフッ素原子を有する化合物として、下記一般式（６）で表されるフッ素原子を有する有機金属化合物がある。
【００６５】
一般式（６）
Ｒ^ｆ１（ＯＣ_３Ｆ_６）_ｍ１−Ｏ−（ＣＦ_２）_ｎ１−（ＣＨ_２）_ｐ１−Ｚ−（ＣＨ_２）_ｑ１−Ｓｉ−（Ｒ^２）_３
一般式（６）において、Ｒ^ｆ１は炭素数１〜１６の直鎖状又は分岐状のパーフルオロアルキル基、Ｒ^２は加水分解基、Ｚは−ＯＣＯＮＨ−又は−Ｏ−を表し、ｍ１は１〜５０の整数、ｎ１は０〜３の整数、ｐ１は０〜３の整数、ｑ１は１〜６の整数を表し、６≧ｎ１＋ｐ１＞０である。
【００６６】
Ｒ^ｆ１に導入しうる直鎖状又は分岐状のパーフルオロアルキル基の炭素数は、１〜１６がより好ましく、１〜３が最も好ましい。従って、Ｒ^ｆ１としては、−ＣＦ_３、−Ｃ_２Ｆ_５、−Ｃ_３Ｆ_７等が好ましい。
【００６７】
Ｒ^２に導入しうる加水分解基としては、−Ｃｌ、−Ｂｒ、−Ｉ、−ＯＲ^１１、−ＯＣＯＲ^１１、−ＣＯ（Ｒ^１１）Ｃ＝Ｃ（Ｒ^１２）_２、−ＯＮ＝Ｃ（Ｒ^１１）_２、−ＯＮ＝ＣＲ^１３、−Ｎ（Ｒ^１２）_２、−Ｒ^１２ＮＯＣＲ^１１などが好ましい。Ｒ^１１はアルキル基などの炭素数１〜１０の脂肪族炭化水素基を、またはフェニル基などの炭素数６〜２０の芳香族炭化水素基を表し、Ｒ^１２は水素原子またはアルキル基などの炭素数１〜５の脂肪族炭化水素を表し、Ｒ^１３はアルキリデン基などの炭素数３〜６の二価の脂肪族炭化水素基を表す。これらの加水分解基の中でも、−ＯＣＨ_３、−ＯＣ_２Ｈ_５、−ＯＣ_３Ｈ_７、−ＯＣＯＣＨ_３及び−ＮＨ_２が好ましい。
【００６８】
上記一般式（６）におけるｍ１は１〜３０あることがより好ましく、５〜２０であることが更に好ましい。ｎ１は１または２であることがより好ましく、ｐ１は１または２であることがより好ましい。また、ｑ１は１〜３であることがより好ましい。
【００６９】
本発明において用いられる他の好ましいフッ素原子を有する化合物として、前記一般式（７）で表されるフッ素原子を有する有機金属化合物がある。
【００７０】
前記一般式（７）において、Ｒｆは炭素数１〜１６の直鎖状または分岐状パーフルオロアルキル基、Ｘはヨウ素原子または水素原子、Ｙは水素原子または低級アルキル基、Ｚはフッ素原子またはトリフルオロメチル基、Ｒ^２１は加水分解可能な基、Ｒ^２２は水素原子または不活性な一価の有機基を表し、ａ、ｂ、ｃ、ｄはそれぞれ０〜２００の整数、ｅは０または１、ｍおよびｎは０〜２の整数、ｐは１〜１０の整数を表す。
【００７１】
前記一般式（７）において、Ｒｆは、通常、炭素数１〜１６の直鎖状または分岐状パーフルオロアルキル基であり、好ましくは、ＣＦ_３基、Ｃ_２Ｆ_５基、Ｃ_３Ｆ_７基である。Ｙにおける低級アルキル基としては、通常、炭素数１〜５のものが挙げられる。
【００７２】
Ｒ^２１の加水分解可能な基としては、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、Ｒ^２３Ｏ基、Ｒ^２３ＣＯＯ基、（Ｒ^２４）_２Ｃ＝Ｃ（Ｒ^２３）ＣＯ基、（Ｒ^２３）_２Ｃ＝ＮＯ基、Ｒ^２５Ｃ＝ＮＯ基、（Ｒ^２４）_２Ｎ基、及びＲ^２３ＣＯＮＲ^２４基が好ましい。ここで、Ｒ^２３はアルキル基等の通常は炭素数１〜１０の脂肪族炭化水素基またはフェニル基等の通常は炭素数６〜２０の芳香族炭化水素基、Ｒ^２４は水素原子またはアルキル基等の通常は炭素数１〜５の低級脂肪族炭化水素基、Ｒ^２５はアルキリデン基等の通常は炭素数３〜６の二価の脂肪族炭化水素基である。さらに好ましくは、塩素原子、ＣＨ_３Ｏ基、Ｃ_２Ｈ_５Ｏ基、Ｃ_３Ｈ_７Ｏ基である。
【００７３】
Ｒ^２２は水素原子または不活性な一価の有機基であり、好ましくは、アルキル基等の通常は炭素数１〜４の一価の炭化水素基である。ａ、ｂ、ｃ、ｄは０〜２００の整数であり、好ましくは１〜５０である。ｍおよびｎは、０〜２の整数であり、好ましくは０である。ｐは１または２以上の整数であり、好ましくは１〜１０の整数であり、さらに好ましくは１〜５の整数である。また、数平均分子量は５×１０^２〜１×１０^５であり、好ましくは１×１０^３〜１×１０^４である。
【００７４】
また、前記一般式（７）で表されるシラン化合物の好ましい構造のものとして、ＲｆがＣ_３Ｆ_７基であり、ａが１〜５０の整数であり、ｂ、ｃ及びｄが０であり、ｅが１であり、Ｚがフッ素原子であり、ｎが０である化合物である。
【００７５】
本発明において、フッ素原子を有するシラン化合物として好ましく用いられるフッ素を有する有機基を有する有機金属化合物、及び前記一般式（１）〜（７）で表される化合物の代表的化合物を以下に挙げるが、本発明ではこれらの化合物に限定されるものではない。
【００７６】
１：（ＣＦ_３ＣＨ_２ＣＨ_２）_４Ｓｉ
２：（ＣＦ_３ＣＨ_２ＣＨ_２）_２（ＣＨ_３）_２Ｓｉ
３：（Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２）Ｓｉ（ＯＣ_２Ｈ_５）_３
４：ＣＨ_２＝ＣＨ_２Ｓｉ（ＣＦ_３）_３
５：（ＣＨ_２＝ＣＨ_２ＣＯＯ）Ｓｉ（ＣＦ_３）_３
６：（ＣＦ_３ＣＨ_２ＣＨ_２）_２ＳｉＣｌ（ＣＨ_３）
７：Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（Ｃｌ）_３
８：（Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２）_２Ｓｉ（ＯＣ_２Ｈ_５）_２
９：ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
１０：ＣＦ_３ＣＨ_２ＣＨ_２ＳｉＣｌ_３
１１：ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２ＳｉＣｌ_３
１２：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２ＳｉＣｌ_３
１３：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
１４：ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２ＳｉＣｌ_３
１５：ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
１６：ＣＦ_３（ＣＦ_２）_８ＣＨ_２Ｓｉ（ＯＣ_２Ｈ_５）_３
１７：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＯＣ_２Ｈ_５）_３
１８：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＯＣ_３Ｈ_７）_３
１９：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＯＣ_４Ｈ_９）_３
２０：ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２Ｓｉ（ＯＣ_２Ｈ_５）_３
２１：ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２Ｓｉ（ＯＣ_３Ｈ_７）_３
２２：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＯＣ_２Ｈ_５）_３
２３：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＯＣ_３Ｈ_７）_３
２４：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）（ＯＣ_３Ｈ_７）_２
２５：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_２ＯＣ_３Ｈ_７
２６：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２ＳｉＣＨ_３（ＯＣＨ_３）_２
２７：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２ＳｉＣＨ_３（ＯＣ_２Ｈ_５）_２
２８：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２ＳｉＣＨ_３（ＯＣ_３Ｈ_７）_２
２９：（ＣＦ_３）_２ＣＦ（ＣＦ_２）_８（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_３
３０：Ｃ_７Ｆ_１５ＣＯＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
３１：Ｃ_８Ｆ_１７ＳＯ_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
３２：Ｃ_８Ｆ_１７（ＣＨ_２）_２ＯＣＯＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３
３３：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２
３４：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣ_２Ｈ_５）_２
３５：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣ_３Ｈ_７）_２
３６：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（Ｃ_２Ｈ_５）（ＯＣＨ_３）_２
３７：ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２Ｓｉ（Ｃ_２Ｈ_５）（ＯＣ_３Ｈ_７）_２
３８：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２
３９：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣ_２Ｈ_５）_２
４０：ＣＦ_３（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣ_３Ｈ_７）_２
４１：ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２
４２：ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２Ｓｉ（ＣＨ_３）（ＯＣ_３Ｈ_７）_２
４３：ＣＦ_３（ＣＦ_２）_２Ｏ（ＣＦ_２）_３（ＣＨ_２）_２Ｓｉ（ＯＣ_３Ｈ_７）_３
４４：Ｃ_７Ｆ_１５ＣＨ_２Ｏ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
４５：Ｃ_８Ｆ_１７ＳＯ_２Ｏ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
４６：Ｃ_８Ｆ_１７（ＣＨ_２）_２ＯＣＨＯ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３
４７：ＣＦ_３（ＣＦ_２）_５ＣＨ（Ｃ_４Ｈ_９）ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
４８：ＣＦ_３（ＣＦ_２）_３ＣＨ（Ｃ_４Ｈ_９）ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
４９：（ＣＦ_３）_２（ｐ−ＣＨ_３−Ｃ_６Ｈ_５）ＣＯＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
５０：ＣＦ_３ＣＯ−Ｏ−ＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
５１：ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２Ｓｉ（ＣＨ_３）Ｃｌ
５２：ＣＦ_３ＣＨ_２ＣＨ_２（ＣＨ_３）Ｓｉ（ＯＣＨ_３）_２
５３：ＣＦ_３ＣＯ−Ｏ−Ｓｉ（ＣＨ_３）_３
５４：ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＣＨ_３）Ｃｌ_２
５５：（ＣＦ_３）_２（ｐ−ＣＨ_３−Ｃ_６Ｈ_５）ＣＯＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
５６：（ＣＦ_３）_２（ｐ−ＣＨ_３−Ｃ_６Ｈ_５）ＣＯＣＨ_２ＣＨ_２Ｓｉ（ＯＣ_６Ｈ_５）_３
５７：（ＣＦ_３Ｃ_２Ｈ_４）（ＣＨ_３）_２Ｓｉ−Ｏ−Ｓｉ（ＣＨ_３）_３
５８：（ＣＦ_３Ｃ_２Ｈ_４）（ＣＨ_３）_２Ｓｉ−Ｏ−Ｓｉ（ＣＦ_３Ｃ_２Ｈ_４）（ＣＨ_３）_２
５９：ＣＦ_３（ＯＣ_３Ｆ_６）_２４−Ｏ−（ＣＦ_２）_２−ＣＨ_２−Ｏ−ＣＨ_２Ｓｉ（ＯＣＨ_３）_３
６０：ＣＦ_３Ｏ（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）_ｍＣＦ_２ＣＯＮＨＣ_３Ｈ_６Ｓｉ（ＯＣ_２Ｈ_５）_３ （ｍ＝１１〜３０）、
６１：（Ｃ_２Ｈ_５Ｏ）_３ＳｉＣ_３Ｈ_６ＮＨＣＯＣＦ_２Ｏ（ＣＦ_２Ｏ）_ｎ（ＣＦ_２ＣＦ_２Ｏ）_ｐＣＦ_２ＣＯＮＨＣ_３Ｈ_６Ｓｉ（ＯＣ_２Ｈ_５）_３ （ｎ／ｐ＝約０．５、数平均分子量＝約３０００）
６２：Ｃ_３Ｆ_７−（ＯＣＦ_２ＣＦ_２ＣＦ_２）ｑ−Ｏ−（ＣＦ_２）_２−［ＣＨ_２ＣＨ｛Ｓｉ−（ＯＣＨ_３）_３｝］_９−Ｈ （ｑ＝約１０）
６３：Ｆ（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）_１５ＣＦ（ＣＦ_３）ＣＯＮＨＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣ_２Ｈ_５）_３
６４：Ｆ（ＣＦ_２）_４［ＣＨ_２ＣＨ（Ｓｉ（ＯＣＨ_３）_３）］_２．０２ＯＣＨ_３
６５：（Ｃ_２Ｈ_５Ｏ）_３ＳｉＣ_３Ｈ_６ＮＨＣＯ−［ＣＦ_２（ＯＣ_２Ｆ_４）_１０（ＯＣＦ_２）_６ＯＣＦ_２］−ＣＯＮＨＣ_３Ｈ_６Ｓｉ（ＯＣ_２Ｈ_５）_３
６６：Ｃ_３Ｆ_７（ＯＣ_３Ｆ_６）_２４Ｏ（ＣＦ_２）_２ＣＨ_２ＯＣＨ_２Ｓｉ（ＯＣＨ_３）_３
６７：ＣＦ_３（ＣＦ_２）_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣＨ_３）_３
６８：（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２
６９：ＣＦ_３（ＣＦ_２）_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４ＳｉＣＨ_３（ＯＣＨ_３）_２
７０：ＣＦ_３（ＣＦ_２）_５（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣ_２Ｈ_５）_３
７１：ＣＦ_３（ＣＦ_２）_３Ｃ_２Ｈ_４Ｓｉ（ＮＣＯ）_３
７２：ＣＦ_３（ＣＦ_２）_５Ｃ_２Ｈ_４Ｓｉ（ＮＣＯ）_３
７３：Ｃ_９Ｆ_１９ＣＯＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
７４：Ｃ_９Ｆ_１９ＣＯＮＨ（ＣＨ_２）_３ＳｉＣｌ_３
７５：Ｃ_９Ｆ_１９ＣＯＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣ_２Ｈ_５）_３
７６：Ｃ_３Ｆ_７Ｏ（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）_２−ＣＦ（ＣＦ_３）−ＣＯＮＨ（ＣＨ_２）Ｓｉ（ＯＣ_２Ｈ_５）_３
７７：ＣＦ_３Ｏ（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）_６ＣＦ_２ＣＯＮＨ（ＣＨ_２）_３ＳｉＯＳｉ（ＯＣ_２Ｈ_５）_２（ＣＨ_２）_３ＮＨＣＯＣＦ_２（ＯＣＦ_２ＣＦ（ＣＦ_３））_６ＯＣＦ_３
７８：Ｃ_３Ｆ_７ＣＯＯＣＨ_２Ｓｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ_３）_２ＣＨ_２ＯＣＯＣ_３Ｆ_７
７９：ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２Ｏ（ＣＨ_２）_３Ｓｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ_３）_２（ＣＨ_２）_３ＯＣＨ_２ＣＨ_２（ＣＦ_２）_７ＣＦ_３
８０：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｏ（ＣＨ_２）_２Ｓｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ_３）_２（ＯＣ_２Ｈ_５）
８１：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｏ（ＣＨ_２）_２Ｓｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ_３）（ＯＣ_２Ｈ_５）_２
８２：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｏ（ＣＨ_２）_２Ｓｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ_３）_２ＯＳｉ（ＣＨ３）_２（ＯＣ_２Ｈ_５）
上記例示した化合物の他には、フッ素置換アルコキシシランとして、
８３：（パーフルオロプロピルオキシ）ジメチルシラン
８４：トリス（パーフルオロプロピルオキシ）メチルシラン
８５：ジメチルビス（ノナフルオロブトキシ）シラン
８６：メチルトリス（ノナフルオロブトキシ）シラン
８７：ビス（パーフルオロプロピルオキシ）ジフェニルシラン
８８：ビス（パーフルオロプロピルオキシ）メチルビニルシラン
８９：ビス（１，１，１，３，３，４，４，４−オクタフルオロブトキシ）ジメチルシラン
９０：ビス（１，１，１，３，３，３−ヘキサフルオロイソプロポキシ）ジメチルシラン
９１：トリス（１，１，１，３，３，３−ヘキサフルオロイソプロポキシ）メチルシラン
９２：テトラキス（１，１，１，３，３，３−ヘキサフルオロイソプロポキシ）シラン
９３：ジメチルビス（ノナフルオロ−ｔ−ブトキシ）シラン
９４：ビス（１，１，１，３，３，３−ヘキサフルオロイソプロポキシ）ジフェニルシラン
９５：テトラキス（１，１，３，３−テトラフルオロイソプロポキシ）シラン
９６：ビス〔１，１−ビス（トリフルオロメチル）エトキシ〕ジメチルシラン
９７：ビス（１，１，１，３，３，４，４，４−オクタフルオロ−２−ブトキシ）ジメチルシラン
９８：メチルトリス〔２，２，３，３，３−ペンタフルオロ−１，１−ビス（トリフルオロメチル）プロポキシ〕シラン
９９：ジフェニルビス〔２，２，２−トリフルオロ−１−（トリフルオロメチル）−１−トリルエトキシ〕シラン
等の化合物や、以下の化合物、
１００：（ＣＦ_３ＣＨ_２）_３Ｓｉ（ＣＨ_２−ＮＨ_２）
１０１：（ＣＦ_３ＣＨ_２）_３Ｓｉ−Ｎ（ＣＨ_３）_２
【００７７】
【化５】

【００７８】
更に、
【００７９】
【化６】

【００８０】
等のシラザン類や、
１０６：ＣＦ_３ＣＨ_２−ＣＨ_２ＴｉＣｌ_３
１０７：ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２ＴｉＣｌ_３
１０８：ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｔｉ（ＯＣＨ_３）_３
１０９：ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２ＴｉＣｌ_３
１１０：Ｔｉ（ＯＣ_３Ｆ_７）_４
１１１：（ＣＦ_３ＣＨ_２−ＣＨ_２Ｏ）_３ＴｉＣｌ_３
１１２：（ＣＦ_３Ｃ_２Ｈ_４）（ＣＨ_３）_２Ｔｉ−Ｏ−Ｔｉ（ＣＨ_３）_３
等のフッ素を有する有機チタン化合物、また、以下のようなフッ素含有有機金属化合物を例として挙げることができる。
【００８１】
１１３：ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２Ｏ（ＣＨ_２）_３ＧｅＣｌ
１１４：ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２ＯＣＨ_２Ｇｅ（ＯＣＨ_３）_３
１１５：（Ｃ_３Ｆ_７Ｏ）_２Ｇｅ（ＯＣＨ_３）_２
１１６：［（ＣＦ_３）_２ＣＨＯ］_４Ｇｅ
１１７：［（ＣＦ_３）_２ＣＨＯ］_４Ｚｒ
１１８：（Ｃ_３Ｆ_７ＣＨ_２ＣＨ_２）_２Ｓｎ（ＯＣ_２Ｈ_５）_２
１１９：（Ｃ_３Ｆ_７ＣＨ_２ＣＨ_２）Ｓｎ（ＯＣ_２Ｈ_５）_３
１２０：Ｓｎ（ＯＣ_３Ｆ_７）_４
１２１：ＣＦ_３ＣＨ_２ＣＨ_２Ｉｎ（ＯＣＨ_３）_２
１２２：Ｉｎ（ＯＣＨ_２ＣＨ_２ＯＣ_３Ｆ_７）_３
１２３：Ａｌ（ＯＣＨ_２ＣＨ_２ＯＣ_３Ｆ_７）_３
１２４：Ａｌ（ＯＣ_３Ｆ_７）_３
１２５：Ｓｂ（ＯＣ_３Ｆ_７）_３
１２６：Ｆｅ（ＯＣ_３Ｆ_７）_３
１２７：Ｃｕ（ＯＣＨ_２ＣＨ_２ＯＣ_３Ｆ_７）_２
１２８：Ｃ_３Ｆ_７（ＯＣ_３Ｆ_６）_２４Ｏ（ＣＦ_２）_２ＣＨ_２ＯＣＨ_２Ｓｉ（ＯＣＨ_３）_３
【００８２】
【化７】

【００８３】
これら具体例で挙げられた各化合物は、東レ・ダウコーニングシリコーン（株）、信越化学（株）、ダイキン化学（株）（例えば、オプツールＤＳＸ）また、Ｇｅｌｅｓｔ Ｉｎｃ．等により上市されており、容易に入手することができる他、例えば、Ｊ．Ｆｌｕｏｒｉｎｅ Ｃｈｅｍ．，７９（１）．８７（１９９６）、材料技術，１６（５），２０９（１９９８）、Ｃｏｌｌｅｃｔ．Ｃｚｅｃｈ．Ｃｈｅｍ．Ｃｏｍｍｕｎ．，４４巻，７５０〜７５５頁、Ｊ．Ａｍｅｒ．Ｃｈｅｍ．Ｓｏｃ．１９９０年，１１２巻，２３４１〜２３４８頁、Ｉｎｏｒｇ．Ｃｈｅｍ．，１０巻，８８９〜８９２頁，１９７１年、米国特許第３，６６８，２３３号明細書等、また、特開昭５８−１２２９７９号、特開平７−２４２６７５号、特開平９−６１６０５号、同１１−２９５８５号、特開２０００ー６４３４８号、同２０００−１４４０９７号公報等に記載の合成方法、あるいはこれに準じた合成方法により製造することができる。
【００８４】
本発明の薄膜形成方法は、上記フッ素原子を有する有機基を有する有機金属化合物を含有する薄膜形成ガスを被処理体に供給しながら、大気圧もしくは大気圧近傍の圧力下で、放電ガスを放電空間に導入して励起した励起放電ガスを、該被処理体に供給して薄膜を形成するものである。
【００８５】
更に好ましくは、励起放電ガスの放出口及び電極対を備えた固体誘電体容器内に放電ガスを流通させた状態で、電極と、該電極と対向して対をなす他の電極との間に電界を印加することにより、大気圧もしくは大気圧近傍の圧力下で、該放電ガスを放電空間に導入して励起放電ガスを発生させ、該励起放電ガスの供給方向と交差する方向から、被処理体に向けて薄膜形成ガスを供給する薄膜形成方法である。
【００８６】
本発明において、放電空間とは、所定の距離を有して対向配置された電極対により挟まれ、かつ前記電極対間へ放電ガスを導入して電界を印加することにより放電を起こす空間である。放電空間の形態は、特に制限はなく、例えば、対向する平板電極対により形成されるスリット状であっても、あるいは２つの円筒電極間に円周状に形成された空間であっても良い。
【００８７】
また、上記被処理体に励起した放電ガスあるいは薄膜形成ガス（両者を併せて処理ガスともいう）を供給する方法としては、特に限定されず、公知のガス供給方法により行うことができる。被処理体の近傍に励起した放電ガス放出口を設け、放電プラズマの放電方向と交差する方向から当該被処理体に向けて放電ガスを供給することにより、少量の処理ガスで効率よく処理を行うことができる。
【００８８】
本発明でいう大気圧又は大気圧近傍の圧力下とは、２０ｋＰａ〜２００ｋＰａの圧力下である。本発明において、電界を印加する電極間のさらに好ましい圧力は、７０ｋＰａ〜１４０ｋＰａである。
【００８９】
次いで、本発明の薄膜形成方法に用いる大気圧プラズマ放電処理装置、大気圧プラズマ放電処理方法及び大気圧プラズマ放電処理装置用の電極システムについて、以下にその実施の形態を図を用いて説明するが、本発明はこれに限定されない。また、以下の説明には、用語等に対し断定的な表現が含まれている場合があるが、本発明の好ましい例を示すものであって、本発明の用語の意義や技術的な範囲を限定するものではない。
【００９０】
図１は、本発明に有用な大気圧プラズマ放電処理装置の一例を示す断面図である。
【００９１】
以下、本発明でいう大気圧プラズマ放電処理装置とは、大気圧もしくは大気圧近傍の圧力下で、フッ素原子を有する有機基を有する有機金属化合物を含有する薄膜形成ガスを被処理体に供給しながら、大気圧もしくは大気圧近傍の圧力下で、放電ガスを放電空間に導入して励起した励起放電ガスを、該被処理体に供給して薄膜を形成する装置をいう。
【００９２】
図１において、大気圧プラズマ放電処理装置は、一方の第１電極２が外面に配設され、第１電極２と対応する位置の他の第２電極３が外面に配置され、第１電極２と第２電極３は、少なくとも対向する面に誘電体４が設けられ、かつ、放電ガス導入口５と励起放電ガス放出口６を備えた固体誘電体容器１、電界印加手段１０である対向電極間に高周波電界を印加する高周波電源１１、及び薄膜形成ガス供給部７からなる放電プラズマ処理装置であって、固体誘電体容器１に放電ガスを流通させた状態で対をなす電極の間に電界を印加することにより放電プラズマを発生させるものであり、かつ、励起放電ガスの供給方向と、薄膜形成ガスの供給方向が交差するように配置して、被処理体Ｓ上に薄膜形成を行う。
【００９３】
また、固体誘電体容器１と薄膜形成ガス供給部７とは、保持継ぎ手１４を介して可動治具１３により、各々が任意の交差角度となるように固定されている。また、図１においては図示していないが、上記構成の他に、放電ガスを固体誘電体容器１に、また薄膜形成ガスを薄膜形成ガス供給部７に導入するガス供給手段、前記電極温度を制御する電極温度調整手段等から構成されている。
【００９４】
本発明でいう励起放電ガスの供給方向と、薄膜形成ガスの供給方向が交差するとは、励起放電ガスの供給方向、すなわち固体誘電体容器１と、薄膜形成ガスの供給方向、すなわち薄膜形成ガス供給部７とのなす角度が、０度（平行）を超え、３６０度未満の範囲であることを意味し、両ガスの混合効率等を考慮すると０度（平行）を超え、１８０度以下であることが好ましく、より好ましくは１５〜１５０度である。
【００９５】
また、本発明の薄膜形成装置においては、少量の処理ガスで効率よく処理を行うためには、前記励起放電ガスの放出方向と薄膜形成ガスの放出方向が交差する領域が、励起放電ガスの放出口近傍にあるようになされており、当該交差する領域に被処理体を位置させることが好ましい。さらに、薄膜形成ガスの放出口も、上記交差する領域の近傍であることが好ましい。
【００９６】
また、前記被処理体Ｓと前記励起放電ガス放出口６との間の距離は、前記励起放電ガス放出口６から放出される放電プラズマの流速により適宜決められるが、空気と接触する確率が高くなり、大流速が必要となるので、好ましくは０．０１〜１０ｃｍである。
【００９７】
本発明の薄膜形成装置においては、固体誘電体容器と、前記薄膜形成ガス供給部とが可動治具により連結されており、該固体誘電体容器と該薄膜形成ガス供給部とが、略一定の相対位置を保ちながら移動可能であることが好ましい。
【００９８】
第１電極２と第２電極３とで挟まれ、かつ誘電体４を有する領域が放電空間である。この放電空間に、放電ガスＧを放電ガス導入口５より導入して励起させる。また、フッ素原子を有する有機基を有する有機金属化合物を含有する薄膜形成ガスＭは、薄膜形成ガス導入口８より、薄膜形成ガス供給部７に導入する。次いで、固体誘電体容器１の励起放電ガス放出口６より励起した放電ガスＧ′を、また薄膜形成ガス供給部７の薄膜形成ガス放出部９より薄膜形成ガスＭを、それぞれ交差する条件で、被処理体Ｓ表面に晒して薄膜を形成する。なお、被処理体Ｓは、支持体のようなシート状の被処理体のみでなく、様々な大きさ、形状のものを処理することが可能となる。例えば、レンズ形状、球状などの厚みを有するような形状の被処理体へも薄膜形成することができる。
【００９９】
本発明の薄膜形成方法においては、薄膜形成原料として、フッ素原子を有する有機基を有する有機金属化合物を用い、かつ励起した放電ガスと、薄膜形成ガスとを交差する関係にて接触させることにより、優れた撥水性、撥油性、皮脂やインクふき取り性及びその繰り返し耐久性を有し、かつ耐擦性が良好な薄膜を得ることができるものである。
【０１００】
一対の対向電極（第１電極２と第２電極３）は、金属母材と誘電体４で構成され、該金属母材をライニングすることにより無機質的性質の誘電体を被覆する組み合わせにより、また、金属母材に対しセラミックス溶射した後、無機質的性質の物質により封孔処理した誘電体を被覆する組み合わせにより構成されていてもよい。金属母材としては、銀、白金、ステンレススティール、アルミニウム、鉄、チタン、銅、金等の金属を使うことができる。また、誘電体のライニング材としては、ケイ酸塩系ガラス、ホウ酸塩系ガラス、リン酸塩系ガラス、ゲルマン酸塩系ガラス、亜テルル酸塩ガラス、アルミン酸塩ガラス、バナジン酸塩ガラス等を用いることができ、この中でもホウ酸塩系ガラスが加工し易く好ましい。また、誘電体の溶射に用いるセラミックスとしては、アルミナが良く、酸化珪素等で封孔処理することが好ましい。封孔処理としては、アルコキシラン系封孔材をゾルゲル反応させて無機化させることができる。
【０１０１】
また、図１では、対向電極は、第１電極２と第２電極３のように平板電極を用いてあるが、一方もしくは双方の電極を中空の円柱型電極あるいは角柱型電極としてもよい。この対向電極のうち一方の電極（第２電極３）に高周波電源１１が接続され、他方の電極（第１電極２）は、アース１２により接地され、対向電極間に電界を印加出来るように構成されている。また、図１に示した構成に対し、電界印加を第１電極２とし、他方の第２電極３をアースした構成でも良い。
【０１０２】
電界印加手段１０は高周波電源１１より、それぞれの電極対に電界を印加する。本発明に用いる高周波電源としては、特に限定はない。高周波電源としては、神鋼電機製高周波電源（３ｋＨｚ）、神鋼電機製高周波電源（５ｋＨｚ）、神鋼電機製高周波電源（１５ｋＨｚ）、神鋼電機製高周波電源（５０ｋＨｚ）、ハイデン研究所製高周波電源（連続モード使用、１００ｋＨｚ）、パール工業製高周波電源（２００ｋＨｚ）、パール工業製高周波電源（８００ｋＨｚ）、パール工業製高周波電源（２ＭＨｚ）、日本電子製高周波電源（１３．５６ＭＨｚ）、パール工業製高周波電源（２７ＭＨｚ）、パール工業製高周波電源（１５０ＭＨｚ）等を使用できる。また、４３３ＭＨｚ、８００ＭＨｚ、１．３ＧＨｚ、１．５ＧＨｚ、１．９ＧＨｚ、２．４５ＧＨｚ、５．２ＧＨｚ、１０ＧＨｚを発振する電源を用いてもよい。
【０１０３】
本発明に係る防汚膜を形成するする場合の対向電極間に印加する高周波電界の周波数としては、特に限定はないが、高周波電源として０．５ｋＨｚ以上、２．４５ＧＨｚ以下が好ましい。また、対向電極間に供給する電力は、好ましくは０．１Ｗ／ｃｍ^２以上、５０Ｗ／ｃｍ^２以下である。尚、対向電極における電界の印加面積（ｃｍ^２）は、放電が起こる範囲の面積のことを指す。
【０１０４】
対向電極間に印加する高周波電界は、断続的なパルス波であっても、連続したサイン波であっても構わない。パルス化された電界を印加する場合には、パルス電界波形の例としては、インパルス型、パルス型、変調型の波形が挙げられる。本発明におけるパルス電界波形は、ここで挙げた波形に限定されないが、パルスの立ち上がり時間が短いほどプラズマ発生の際のガスの電離が効率よく行われる。好ましくは、立ち上がり時間が１００μｓ以下である。更に、パルス波形、立ち上がり時間、周波数の異なるパルスを用いて変調を行ってもよい。このような変調は高速連続表面を行う上で有効である。
【０１０５】
本発明において、対向電極間の距離は、電極の金属母材上の誘電体の厚さ、印加電界の大きさ、プラズマを利用する目的等を考慮して決定される。上記電極の一方に誘電体を設置した場合の誘電体と電極の最短距離、上記電極の双方に誘電体を設置した場合の誘電体同士の距離を電極間の距離として、いずれの場合も均一な放電を行う観点から０．１ｍｍ〜２０ｍｍが好ましい。
【０１０６】
本発明に係る薄膜形成前、被処理体を別途設けた放電空間に晒して表面処理を施しても良い。また、薄膜形成前に、予め被処理体表面の除電処理を行い、更にゴミ除去を行っても良い。除電手段及び除電処理後のゴミ除去手段としては、通常のブロアー式や接触式以外に、複数の正負のイオン生成用除電電極と被処理体を挟むようにイオン吸引電極を対向させた除電装置とその後に正負の直流式除電装置を設けた高密度除電システム（特開平７−２６３１７３号）を用いてもよい。また、除電処理後のゴミ除去手段としては、非接触式のジェット風式減圧型ゴミ除去装置（特開平７−６０２１１号）等を挙げることが出来好ましく用いることも出来るが、これらに限定されない。
【０１０７】
また、本発明の薄膜形成装置においては、被処理体移動装置を有し、該被処理体移動装置上に設置した被処理体が、前記励起放電ガスの供給部近傍に移動して、励起放電ガスに晒されることが好ましい。図１に記載の１５が、本発明に係る被処理体移動装置で、その上に被処理体Ｓを保持した状態で、任意の方向に移動する。
【０１０８】
次に、放電空間に供給する放電ガスについて説明する。
放電ガスとは、放電を起こすことの出来るガスである。放電ガスとしては、窒素、希ガス、空気、水素、酸素などがあり、これらを単独で放電ガスとして用いても、混合して用いてもかまわない。その中でも、本発明においては、放電ガスが、希ガスを含有すること、または窒素ガスを含有することが好ましく、放電ガス中の希ガスまたは窒素ガスの含有量が５０体積％以上であることが好ましく、更に好ましくは全放電ガス量に対し５０〜１００体積％である。放電ガスの量は、放電空間に供給する全ガス量に対し、７０〜１００体積％含有することが好ましい。
【０１０９】
また、本発明に係る薄膜形成ガスとは、本発明に係る前述のフッ素原子を有する有機基を有する有機金属化合物を含有し、被処理体上に化学的に堆積して薄膜を形成するガスのことである。本発明においては、薄膜形成ガスに対する本発明に係る前述のフッ素原子を有する有機基を有する有機金属化合物の含有量としては、０．００１〜３０．０体積％の範囲であることが好ましい。
【０１１０】
本発明に係る薄膜形成ガスは、上述の放電ガスとして説明した窒素や希ガス等を含有することができる。なお、本発明に係る薄膜形成ガスは、水素ガス、酸素ガス、窒素ガス、空気等の補助ガスを０．００１体積％〜３０体積％混合させて使用してもよい。
【０１１１】
本発明の薄膜形成方法で処理される被処理体の材質は、特に限定はなく、酸化金属、プラスチック、金属、陶器、紙、木材、不織布、ガラス板、セラミック、建築材料等を挙げることができ、特に、被処理体表面が、無機化合物を含む表面、あるいは有機化合物を含む表面で構成されていることが、本発明の目的効果を発揮する観点から好ましいが、その中でも、更に好ましくはシリカ、チタニア等の酸化金属を主成分とする表面の被処理体である。また、被処理体の形態は、シート状でも成型品でもよく、ガラスとしては板ガラスやレンズ等、プラスチックとしては、プラスチックレンズ、プラスチックフィルム、プラスチックシート、あるいはプラスチック成型品等が挙げられる。被処理体が、このようなプラスチックを支持体とする場合には、その表面に酸化金属膜を形成したものが好ましい。
【０１１２】
本発明の薄膜形成方法により得られる薄膜形成体において、被処理体上に形成された薄膜表面の表面比抵抗値が、２３℃、５５％ＲＨ条件下で１×１０^１２Ω／□以下であることが好ましい。
【０１１３】
次いで、本発明に有用な大気圧プラズマ放電処理装置の他の例を以下に説明する。
【０１１４】
図２は、図１で示した本発明に有用な大気圧プラズマ放電処理装置の一例を示す斜視図である。
【０１１５】
図２に示す大気圧プラズマ放電処理装置は、薄膜形成する被処理体のほぼ幅手全域にわたり、励起放電ガス放出口及び薄膜形成ガス放出口を有し、固体誘電体容器及び薄膜形成ガス供給部を固定した状態で、連続して薄膜を形成することが可能な装置である。
【０１１６】
図２において、固体誘電体容器１には、各々長方形で同じ大きさである平板電極２１、２２が設けられており、平板電極２１と平板電極２２はそれぞれ対向電極を構成している。この一対の対向電極は平行に配置されている。また、各平板電極は四隅をそろえて配置されている。平板電極２１と２２のそれぞれの対向面には、図１で説明したのと同様の誘電体（不図示）が被覆されている。なお、本発明においては、平板電極２１、２２の少なくとも一方の電極の対向する面が誘電体で被覆されていればよい。
【０１１７】
対向する平板電極２１、２２間で形成される放電空間の幅手方向の端面（図中、手前面及び奥側面）は、蓋体２３、２３′によって塞がれている。蓋体は、放電空間と放電空間外との間で気体等が移動できないようにする。
【０１１８】
２４は、平板電極２１、２２間に放電ガスＧを導入するための放電ガス導入口であり、平板電極２１、２２の隙間のうち、蓋体２３、２３′で塞がれていない方向の一方の端部（図中上部）を、放電ガス導入口２４として用いている。
【０１１９】
図２の大気圧プラズマ処理装置においては、放電ガス導入口２４は、電極２１、２２の隙間の一部をそのまま放電ガス導入口２４として用いているが、該隙間にさらに部材を設けることで、放電ガス導入口２４を平板電極２１、２２間に放電ガスを効率よくかつ容易に導入することができる形状にしてもよい。
【０１２０】
２５は、電極２１、２２間で励起した放電ガスを平板電極２１、２２間の外に放出するための励起放電ガス放出口であり、平板電極２１、２２の隙間のうち、放電ガス導入口２４と向かい合う端部（図中下部）を励起放電ガス放出口２５として用いる。よって、放電ガス導入口２４と励起放電ガス放出口２５は同じ端部を用いることになる。
【０１２１】
薄膜形成ガス供給部７は、基本的には上記固体誘電体容器１が有する構造と同様のものが挙げられ、例えば、長方状の形態で、その内部にスリット状の薄膜形成ガスＭの導入路を有している。２６は、薄膜形成ガスＭを導入するための薄膜形成ガス導入口であり、導入された薄膜形成ガスＭは、薄膜形成ガス放出口２７より、前記励起放電ガスと交差する状態て、被処理体Ｓ表面に供給され、被処理体上に目的とする防汚膜を形成することができる。
【０１２２】
薄膜形成ガス放出口２７は、薄膜形成ガス導入口２６と向かい合う端部（図中下端部）を薄膜形成ガス放出口として用いている。また、励起放電ガス放出口と薄膜形成ガス放出口という構成を複数個並べた構造にしても良い。
【０１２３】
１１は平板電極２１、２２間に高周波電界を印加するための高周波電源である。１２はアースであり、平板電極２２はアース１２で接地されている。
【０１２４】
平板電極間２１、２２間に存在させる放電ガスは、大気圧又は大気圧近傍の圧力下で存在させ、高周波電源１１によって、平板電極間２１、２２間に電界を印加することで放電ガスを励起させ、励起放電ガスを発生させる。
【０１２５】
図２の大気圧プラズマ放電処理装置に用いられる電極システムは、平板電極２１、２２で構成され、平板電極２１、２２間に電界が印加され放電するようになっているのであるが、この電極システムを複数設け、さらに各電極システムに放電ガス導入口、薄膜形成ガス導入口、励起放電ガス放出口、薄膜形成ガス放出口を設けることで、被処理体への薄膜形成を複数回行うこともできる。これにより、被処理体Ｓ上に、同一成分、あるいは異なる成分の複数製膜を施したりすることができる。
【０１２６】
次に、図２に示した大気圧プラズマ放電処理装置を用いた薄膜形成方法を説明する。
【０１２７】
放電ガス導入口２４から平板電極２１、２２間に放電ガスＧを導入し、平板電極２１、２２間に大気圧又は大気圧近傍の圧力下で、放電ガスＧを存在させる。平板電極２１、２２間に高周波電源１１によって高周波電界が印加され、平板電極２１、２２間に存在する放電ガスＧを励起させ励起放電ガスＧ′を発生させる。平板電極２１、２２間で発生した励起放電ガスＧ′は、新たに放電ガス導入口２４から導入されてくる放電ガスＧに押され、また、蓋体２３、２３′によって電極の側面方向の隙間は塞がれていることから、放電ガス放出口２５より平板電極２１、２２間の外へと放出される。
【０１２８】
一方、薄膜形成ガスＭは、薄膜形成ガス導入口２６からが導入される。スリット間に導入された薄膜形成ガスＭは、新たに薄膜形成ガス導入口２６から導入されてくる薄膜形成ガスＭに押され、薄膜形成ガス放出口２７から外へと放出される。
【０１２９】
薄膜形成ガス放出口２７から放出される薄膜形成ガスＭは、励起放電ガス放出口２５から放出される励起放電ガスＧ′と、交差する形態で混合され、被処理体８上に薄膜が形成される。
【０１３０】
なお、図２には記載されていないが、図１と同様に、固体誘電体容器１と薄膜形成ガス供給部７とは、保持継ぎ手を介して可動治具により、各々が任意の交差角度となるように固定されている。
【０１３１】
図３は、本発明で用いることのできる他の大気圧プラズマ放電処理装置の一例を示す斜視図である。
【０１３２】
３３は内側電極であり、３２は外側電極であり、一対の対向電極を構成している。外側電極３２は、中空の円筒状電極であり、外側電極３２の筒管内に、円筒状の内側電極３３を同心配置している。
【０１３３】
本発明では、内側電極３３、外側電極３２の対向する面を共に誘電体で被覆しても良く、また内側電極３３、外側電極３２のうちどちらかの電極の対向する面に誘電体が被覆されていてもよい。そして、この対向面間で放電が発生する。
【０１３４】
内側電極３３、外側電極３２には、先ほど図１で説明した電極１、２に用いることができる電極、誘電体を用いることができる。
【０１３５】
３５は内側電極３３と外側電極３２の間に放電ガスＧを導入するための放電ガス導入口である。内側電極３３と外側電極３２の間とで放電空間が形成される。また、放電ガス導入口３５は内側電極３３と外側電極３２の間の端部の一方を用いる。
【０１３６】
図３の大気圧プラズマ処理装置においては、放電ガス導入口３５は、内側電極３３と外側電極３２の隙間の上端部をそのまま放電ガス導入口３５として用いているが、該隙間にさらに部材を設けることで、放電ガス導入口３５を内側電極３３と外側電極３２の間に放電ガスを効率よく容易に導入することができる形状にしてもよい。
【０１３７】
３６は、内側電極３３と外側電極３２の間で発生した励起放電ガスＧ′を内側電極３３と外側電極３２の間の外に放出するための励起放電ガス放出口であり、内側電極３３と外側電極３２の隙間において、放電ガス導入口３５として用いていないほうの下端部を用いる。
【０１３８】
図３の大気圧プラズマ処理装置に用いられる電極システムは、内側電極３３と外側電極３２で構成され、内側電極３３と外側電極３２の間に高周波電源１１で電界を印加されるようになっているのであるが、この電極システムを複数設け、さらに各電極システムに放電ガス導入口、励起放電ガス放出口、薄膜形成ガス導入口、薄膜形成ガス放出口を設けることで、被処理体へ薄膜形成を複数回行うこともできる。これにより、被処理体Ｓに、同一成分、あるいは異なる成分の複数製膜を施すことができる。
【０１３９】
次に、図３に示した大気圧プラズマ処理装置を用いた薄膜形成方法を説明する。
【０１４０】
放電ガス導入口３５から内側電極３３と外側電極３２の間に放電ガスＧを導入し、内側電極３３と外側電極３２の間に大気圧又は大気圧近傍の圧力下で放電ガスを存在させる。内側電極３３と外側電極３２の間に高周波電源１１によって高周波電界が印加され、内側電極３３と外側電極３２の間に存在する放電ガスＧを励起して励起放電ガスＧ′を発生させる。内側電極３３と外側電極３２の間で発生した励起放電ガスＧ′は、新たに放電ガス導入口３５から導入されてくる放電ガスＧに押し出されるようにして、励起放電ガス放出口３６より内側電極３３と外側電極３２の間から外部へと放出される。
【０１４１】
一方、薄膜形成ガス供給部７は、中空の円筒状構造を有し、上部に設けた薄膜形成ガス導入口３８から薄膜形成ガスＭを導入し、薄膜形成ガス放出口３９から薄膜形成ガスＭを放出する。薄膜形成ガス放出口３９から放出された薄膜形成ガスＭは、励起放電ガス放出口３６から放出された励起放電ガスＧ′と、被処理体Ｓ状で、交差する状態で混合され、被処理体Ｓ上に薄膜を形成する。
【０１４２】
本発明の薄膜形成方法においては、被処理体を放電空間、または励起放電ガスに晒して前処理を行った後、前記励起放電ガスと薄膜形成ガスとに被処理体を晒すこともできる。
【０１４３】
以下に、本発明に係る薄膜形成前、被処理体を放電空間に晒して薄膜形成する前処理に用いる大気圧プラズマ放電装置について説明する。
【０１４４】
図４は、本発明に係る前処理に用いる大気圧プラズマ放電装置の一例を示す概略図である。図４はプラズマ放電処理装置１３０、ガス供給手段１５０、電界印加手段１４０、及び電極温度調節手段１６０から構成されている。ロール回転電極１３５と角筒型固定電極群１３６として、被処理体Ｆをプラズマ放電処理するものである。ロール回転電極１３５はアース電極で、角筒型固定電極群１３６は高周波電源１４１に接続されている印加電極である。被処理体Ｆは、ガイドロール１６４を経てニップロール１６５で被処理体に同伴して来る空気等を遮断し、ロール回転電極１３５に接触したまま巻き回されながら角筒型固定電極群１３６との間を移送され、ニップロール１６６、ガイドロール１６７を経て、次工程である本発明に係る薄膜形成工程に移送する。前処理用ガスはガス供給手段１５０で、ガス発生装置１５１で発生させた前処理用のガスＧを、流量制御して給気口１５２より対向電極間（ここが放電空間になる）１３２のプラズマ放電処理容器１３１内に入れ、該プラズマ放電処理容器１３１内を前処理用のガスＧで充填し、放電処理が行われた処理排ガスＧ′を排気口１５３より排出するようにする。次に電界印加手段１４０で、高周波電源１４１により角筒型固定電極群１３６に電界を印加し、アース電極のロール回転電極１３５との電極間で放電プラズマを発生させる。ロール回転電極１３５及び角筒型固定電極群１３６を電極温度調節手段１６０を用いて媒体を加熱または冷却し電極に送液する。電極温度調節手段１６０で温度を調節した媒体を送液ポンプＰで配管１６１を経てロール回転電極１３５及び角筒型固定電極群１３６内側から温度を調節する。プラズマ放電処理の際、被処理体の温度によって得られる薄膜の物性や組成は変化することがあり、これに対して適宜制御することが好ましい。媒体としては、蒸留水、油等の絶縁性材料が好ましく用いられる。プラズマ放電処理の際、幅手方向あるいは長手方向での被処理体の温度ムラを出来るだけ生じさせないようにロール回転電極１３５の内部の温度を制御することが望ましい。なお、１６８及び１６９はプラズマ放電処理容器１３１と外界を仕切る仕切板である。
【０１４５】
また、本発明の薄膜形成方法においては、薄膜を形成する被処理体表面が、無機化合物を含むこと、あるいは被処理体表面の主成分が、酸化金属であることが好ましい。
【０１４６】
本発明において、被処理体表面に上記構成物を含む層を設ける方法の１つとして、大気圧プラズマ放電装置を用いることができる。
【０１４７】
大気圧プラズマ放電装置としては、例えば、放電ガスがヘリウムまたはアルゴンを主成分とする場合は、前述の図４で説明した大気圧プラズマ放電装置と同様の装置を用いることができるが、放電ガスが窒素を主成分とする場合は、図５に示す大気圧プラズマ放電装置を用いることがより好ましい。
【０１４８】
図５は、本発明に係る被処理体の表面処理に用いる大気圧プラズマ放電装置の一例を示す概略図である。
【０１４９】
装置の概略は、図４に示した構成とほぼ同様であるが、ロール回転電極（第１電極）１３５と角筒型固定電極群（第２電極）１３６との間の放電空間（対向電極間）１３２に、ロール回転電極（第１電極）１３５には第１電源１４１から周波数ω_１であって高周波電界Ｖ_１を、また角筒型固定電極群（第２電極）１３６には第２電源１４２から周波数ω_２であって高周波電界Ｖ_２をかけるようになっている。
【０１５０】
ロール回転電極（第１電極）１３５と第１電源１４１との間には、第１電源１４１からの電流がロール回転電極（第１電極）１３５に向かって流れるように第１フィルター１４３が設置されている。該第１フィルターは第１電源１４１からの電流をアース側へと通過しにくくし、第２電源１４２からの電流をアース側へと通過し易くするように設計されている。また、角筒型固定電極群（第２電極）１３６と第２電源１４２との間には、第２電源からの電流が第２電極に向かって流れるように第２フィルター１４４が設置されている。第２フィルター１４４は、第２電源１４２からの電流をアース側へと通過しにくくし、第１電源１４１からの電流をアース側へと通過し易くするように設計されている。
【０１５１】
なお、ロール回転電極１３５を第２電極、また角筒型固定電極群１３６を第１電極としてもよい。何れにしろ第１電極には第１電源が、また第２電極には第２電源が接続される。第１電源は第２電源より大きな高周波電界（Ｖ_１＞Ｖ_２）を印加出来る能力を有しており、また、周波数はω_１＜ω_２となる能力を有している。
【０１５２】
【実施例】
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
【０１５３】
《薄膜（防汚膜）形成体の作製》
〔被処理体１の作製〕
下記の手順に従って、セルローストリアセテートフィルム上に、帯電防止層、ハードコート層、反射防止層、また裏面にバックコート層を設けた被処理体１を作製した。
【０１５４】
（帯電防止層の形成）
厚さ８０μｍのセルローストリアセテートフィルム（コニカ社製、商品名：コニカタックＫＣ８０ＵＶＳＦ）の一方の面に、下記組成の帯電防止層１の塗布組成物を乾燥膜厚で０．２μｍとなるようにダイコートし、８０℃、５分間乾燥して、帯電防止層を設けた。
【０１５５】

（ハードコート層の形成）
上記帯電防止層を形成したフィルムに、下記ハードコート層組成物を、乾燥膜厚が３．５μｍとなるように塗布し、８０℃にて５分間乾燥した。次に８０Ｗ／ｃｍ高圧水銀灯を１２ｃｍの距離から４秒間照射して硬化させ、ハードコート層を有するハードコートフィルムを作製した。ハードコート層の屈折率は１．５０であった。
【０１５６】

【０１５７】
（バックコート層の塗設）
前記ハードコート層を塗設した面の反対面に、下記のバックコート層塗布組成物を、ウェット膜厚１４μｍとなるようにグラビアコーターで塗布し、乾燥温度８５℃にて乾燥させてバックコート層を塗設した。
【０１５８】

（反射防止層の形成）
図５に示した大気圧プラズマ放電処理装置を４基接続し、それぞれの装置の２個の電極の電極間隙を１ｍｍとし、各装置の放電空間に下記ガスをそれぞれ供給し、上記作製したハードコート層上に、順次薄膜を形成した。各装置の第１電極に第１の高周波電源として、神鋼電機社製（５０ｋＨｚ）の高周波電源を使用し、高周波電界１０ｋＶ／ｍｍ及び出力密度１Ｗ／ｃｍ^２で、また、第２電極に第２の高周波電源として、パール工業社製（１３．５６ＭＨｚ）の高周波電源を使用し、高周波電界０．８ｋＶ／ｍｍ及び出力密度５．０Ｗ／ｃｍ^２で印加し、プラズマ放電を行って酸化チタンを主成分とする薄膜及び酸化珪素を主成分とする反射防止層を形成した。このときの各装置の放電空間における窒素ガスの放電開始電界は３．７ｋＶ／ｍｍであった。なお、下記薄膜形成ガスは窒素ガス中で気化器によって蒸気とし、加温しながら放電空間に供給した。また、ロール電極はドライブを用いてセルロースエステルフィルムの搬送を同期して回転させた。両電極を８０℃になるように調節保温して行った。
【０１５９】

前記ハードコート層の上に、順に酸化チタン層、酸化珪素層、酸化チタン層、酸化珪素層を設け、帯電防止層、ハードコート層及び反射防止層を有する被処理体１（表１には、これをＴＡＣと記す）を作製した。なお、反射防止層を構成するそれぞれの層は、順に屈折率２．１（膜厚１５ｎｍ）、屈折率１．４６（膜厚３３ｎｍ）、屈折率２．１（膜厚１２０ｎｍ）、屈折率１．４６（膜厚７６ｎｍ）であった。
【０１６０】
〔試料１の作製〕
（大気圧プラズマ放電処理装置）
上記作製したセルローストリアセテートフィルム上にハードコート層及び反射防止層を有する被処理体１に、図２に示す大気圧プラズマ放電処理装置を用いて、防汚膜の形成を行った。放電ガス導入口２４より導入される放電ガスとして下記ガス種Ａ、薄膜形成ガス導入口２６より導入される薄膜形成ガスとしてガス種Ｂを用いた。
【０１６１】

電極２１、２２は、電極体にステンレスＳＵＳ３１６を用い、更に、電極の放電空間を構成する表面にアルミナセラミックを１ｍｍになるまで溶射被覆させた後、アルコキシシランモノマーを有機溶媒に溶解させた塗布液をアルミナセラミック被膜に塗布し、乾燥させた後に、１５０℃で加熱し封孔処理を行って誘電体を形成した。電極の誘電体を被覆していない部分に、高周波電源１１の接続やアース１２による接地を行った。なお、励起放電ガス放出口２５と被処理体との間隙は１０ｍｍとした。
【０１６２】
高周波電源１１には、パール工業製高周波電源（周波数：１３．５６ＭＨｚ）で、５Ｗ／ｃｍ^２の放電電力を印加した。なお、波形はサイン波である。
【０１６３】
〈薄膜形成〉
供給された薄膜形成ガス（ガス種Ｂ）と放電ガス（ガス種Ａ）は、各ガス放出口を出た後、被処理体１上で角度９０度で交差、混合する様にして、被処理体表面へ薄膜を形成して試料１を得た。この時、被処理体は、薄膜形成ガス放出角度に対して４５度の角度で、水平に配置した。また、薄膜形成装置は、水平に配置した被処理体に対し、図１中の左右方向及びそれに交差する方向（被処理体の移動方向）にそれぞれスキャンして行った。また、ガス種Ｂとガス種Ａとの使用量は、体積として１：１の比で用いた。
【０１６４】
〔試料２〜１１の作製〕
上記試料１の作製において、ガス種Ｂの原料として用いた例示化合物１５に代えて、表１に記載の各有機金属化合物を用いた以外は同様にして、試料２〜１１を作製した。
【０１６５】
〔試料１２の作製〕
前記試料１の作製において、高周波電源１１より、パルス電界６．４ｋＶ、周波数６．１ｋＨｚ、パルス幅１８０μｍの放電電力をパルス波で印加した以外は同様にして、試料１２を作製した。
【０１６６】
〔試料１３の作製〕
前記試料１の作製において、薄膜形成ガス（ガス種Ｂ）及び放電ガス（ガス種Ａ）で用いたアルゴンガスを、それぞれ窒素ガスに代え、更に、使用する高周波電源を、ハイデン研究所製高周波電源（周波数：４０ｋＨｚ）で、６Ｗ／ｃｍ^２の放電電力で放電した以外は同様にして、試料１３を作製した。
【０１６７】
〔試料１４の作製〕
前記試料１の作製において、被処理体を間接励起放電ガスに晒す前に、被処理体に下記前処理Ａを施した以外は同様にして、試料１４を作製した。
【０１６８】
前処理Ａ：被処理体を間接励起放電ガスに晒す前に、図１に記載の第１電極２と第２電極３とが対向する様に配置されている構成からなる放電空間に、放電ガスとしてアルゴンガス／酸素ガス＝９９：１（体積比）を流入し、被処理体１をその励起放電ガスに晒した。なお、高周波電源として、パール工業製高周波電源（周波数：１３．５６ＭＨＺ）、放電出力は１０ｗ／ｃｍ^２に設定して行った。
【０１６９】
〔試料１５の作製〕
前記試料１の作製において、被処理体を間接励起放電ガスに晒す前に、被処理体に下記前処理Ｂを施した以外は同様にして、試料１１を作製した。
【０１７０】
前処理Ｂ：被処理体を間接励起放電ガスに晒す前に、図４に示す１対のロール電極からなる放電装置を用いて、ロール電極対のギャップ間隙を１ｍｍ、放電ガスとして、アルゴンガス／酸素ガス＝９９／１（体積比）で、供給した放電空間に晒した。なお、高周波電源として、パール工業社製（１３．５６ＭＨｚ）の高周波電源を使用し、第２電極に出力密度５．０Ｗ／ｃｍ^２で印加した。
【０１７１】
〔試料１６の作製〕
前記試料１の作製において、被処理体として、被処理体１に代えてガラス板（製品名：日本板硝子社製 ０．５ｔソーダガラス 片面研磨品）を用いた以外は同様にして、試料１６を作製した。
【０１７２】
〔試料１７の作製〕
前記試料１の作製において、被処理体として、被処理体１に代えて厚さ１００μｍのポリエチレンテレフタレートフィルム（表１には、ＰＥＴと記す）を用いた以外は同様にして、試料１７を作製した。
【０１７３】
〔試料１８の作製〕
前記試料１７の作製において、高周波電源１１として、パール工業製高周波電源（周波数：１３．５６ＭＨｚ）に代えて、神鋼電機製高周波電源（１５ｋＨｚ）を用いた以外は同様にして、試料１８を作製した。
【０１７４】
〔試料１９の作製〕
前記試料１８の作製において、ガス種Ｂ（薄膜形成ガス）で用いた有機金属化合物（例示化合物１５）に代えて、６−フッ化プロピレンを用いた以外は同様にして、比較の試料１９を作製した。
【０１７５】
〔試料２０の作製〕
前記試料１９の作製において、被処理体として、厚さ１００μｍのポリエチレンテレフタレートフィルムにかえて、被処理体１（ＴＡＣ）を用いた以外は同様にして、比較の試料２０を作製した。
【０１７６】
各試料の薄膜形成方法の主な特徴を、表１に示す。
【０１７７】
【表１】

【０１７８】
《各試料の特性値の測定及び評価》
〔接触角の測定〕
各試料について、協和界面科学社製接触角計ＣＡ−Ｗを用いて、２３℃、５５％の環境下で、防汚膜表面の水に対する接触角とヘキサデカンに対する接触角を測定した。なお、測定はランダムに１０カ所について行い、その平均値を求めた。
【０１７９】
〔油性インク筆記性の評価：撥油性の評価〕
油性インク（ゼブラ社製 マッキー極細黒 ＭＯ−１２０−ＭＣ−ＢＫ）を用いて、試料表面を３ｍｍφ塗りつぶした後、油性インクによる表面上の筆記具合を目視観察し、下記の基準に則り油性インク筆記性の評価を行った。
【０１８０】
◎：油性インクを極めて良くはじき、ほとんど塗りつぶすことができず、撥油性が極めて良好である
○：一部で油性インクのはじきが発生し、全面を均一に塗りつぶすことができず、撥油性を有している
×：油性インクに対するなじみがよく、はじくことなく筆記できるため、撥油性を有していない
〔油性インク拭き取り性の評価〕
油性インク（ゼブラ社製 マッキー極細黒 ＭＯ−１２０−ＭＣ−ＢＫ）を用いて、試料表面を３ｍｍφ塗りつぶした後、柔らかい布（旭化成社製 ＢＥＭＣＯＴ Ｍ−３ ２５０ｍｍ×２５０ｍｍ）で油性インク画像を拭き取り、この操作を同一位置で２０回繰り返して行い、１回拭き取り後と２０回拭き取り後における油性インクの残り状況を目視観察し、下記の基準に則り油性インクの拭き取り性の評価を行った。
【０１８１】
◎：油性インクが、完全に拭き取れた
○：油性インクが、ほぼ拭き取れた
×：油性インクが、一部で拭き取られず残っている
〔耐擦過性の評価〕
各試料表面を、５００ｇの重りを載せたボンスター＃００００のスチールウールを用いて１０回擦って、発生する傷を目視で数え、下記の基準に則り耐擦過性の評価を行った。
【０１８２】
Ａ：傷が全く発生していない
Ｂ：発生している傷の本数が１〜５本未満
Ｃ：発生している傷の本数が５〜１５本未満
Ｄ：発生している傷の本数が１５本以上
〔表面比抵抗の測定〕
本発明の薄膜形成体について、下記の方法に従って表面比抵抗値を測定した結果、全て１×１０^１２Ω／□以下であった。
【０１８３】
（表面比抵抗の測定方法）
試料を、２３℃、５５％ＲＨの環境下で２４時間調湿した後、川口電機社製のテラオームメーターモデルＶＥ−３０を用いて測定した。測定に用いた電極は、２本の電極（試料と接触する部分が１ｃｍ×５ｃｍ）を１ｃｍの間隔で配置し、電極に試料を接触させて測定し、測定値を５倍にした値を表面比抵抗値（Ω／□）とした。
【０１８４】
以上により得られた表面比抵抗を除く結果を、表２に示す。
【０１８５】
【表２】

【０１８６】
表２より明らかなように、薄膜形成ガス原料としてフッ素原子を有する有機基を有する有機金属化合物を含有し、本発明の薄膜形成方法に従って防汚膜を形成した本発明の試料は、比較例に対し、撥水性、撥油性、油性インクの拭き取り性に優れ、かつ形成された防汚膜の耐擦過性が良好であることが分かる。また、試料１３と試料１を比較して明らかなように、放電ガス及び薄膜形成ガスで用いるアルゴンガスを窒素ガスに代えることで、油性インク拭き取りの繰り返し性が向上することも分かる。
【０１８７】
【発明の効果】
本発明により、被処理体への影響が無く、優れた撥水性、撥油性、油性インクの拭き取り性を有し、かつ耐擦過性が良好な薄膜形成方法、薄膜形成装置と薄膜形成体を提供することができた。
【図面の簡単な説明】
【図１】本発明に用いることのできる大気圧プラズマ放電処理装置の一例を示す断面図である。
【図２】本発明に用いることのできる大気圧プラズマ放電処理装置の一例を示す斜視図である。
【図３】本発明に用いることのできるの他の大気圧プラズマ放電処理装置の一例を示す斜視図である。
【図４】本発明に係る前処理に用いる大気圧プラズマ放電装置の一例を示す概略図である。
【図５】本発明に係る被処理体の表面処理に用いる大気圧プラズマ放電装置の他の一例を示す概略図である。
【符号の説明】
１、３１ 固体誘電体容器
２ 第１電極
３ 第２電極
４ 誘電体
５、２４、３５ 放電ガス導入口
６、２５、３６ 放電ガス放出口
７、３７ 薄膜形成ガス供給部
８、２６、３８ 薄膜形成ガス導入口
９、２７、３９ 薄膜形成ガス放出口
１０ 電界印加手段
１１ 高周波電源
１２ アース
１３ 可動治具
１４ 保持継ぎ手
１５ 被処理体移動装置
２１、２２ 平板電極
２３、２３′ 蓋体
３２ 外側電極
３３ 内側電極
Ｇ 放電ガス
Ｇ′励起放電ガス
Ｍ 薄膜形成ガス
Ｓ 被処理体
１３１ プラズマ放電処理容器
１３２ 放電空間
１３５ ロール電極（第１電極）
１３６ 角筒型電極群（第２電極）
１４０ 電界印加手段
１４１ 第１電源
１４２ 第２電源
１４３ 第１フィルター
１４４ 第２フィルター
１５０ ガス供給手段
１６０ 電極温度調節手段[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel method for forming an antifouling film, a thin film forming apparatus, and a thin film formed body, and more specifically, a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom, and an excited discharge gas. The present invention relates to a thin film forming method for forming a highly functional antifouling film on an object to be processed, a thin film forming apparatus, and a thin film forming body obtained thereby.
[0002]
[Prior art]
Currently, the surface of an image display device such as a touch panel directly touched by human fingers, the surface of an image display device such as a CRT or a liquid crystal display, the surface of a lens, the surface of a lens, or a transparent material such as a solar cell or window glass that is easily exposed to outside air It is known to provide an antifouling film on the surface that protects the surface, prevents adhesion of dirt and dust that impairs visibility, or easily removes adhering dirt and dust. It has been.
[0003]
Conventionally, as a method for forming an antifouling film, a method of applying a liquid material for forming an antifouling film to the surface of an article has been widely known and put into practical use (see Patent Document 1). As an example, there is a method of improving the antifouling property on the surface by coating the surface of an antireflection film used in a liquid crystal display or the like with a terminal silanol organic polysiloxane by a coating method (see Patent Document 2).
[0004]
However, the method of forming an antifouling film by a coating method requires chemical resistance to the solvent constituting the coating solution, so that the material of the base material that can be used is limited, and a drying process is required after coating Therefore, when the manufacturing process is costly loaded, and the target substrate surface has irregularities, leveling may occur in the drying process after coating, and the wettability of the coating liquid may vary depending on the material. There is a problem that it becomes inadequate, causing coating unevenness and repellency failure, and it is difficult to form an antifouling film having a uniform film thickness.
[0005]
Based on the above problems, a method of easily forming an antifouling film using atmospheric pressure plasma CVD has been proposed (see Patent Document 3). According to this method, it is possible to stably form an antifouling film having a uniform thickness even on a substrate having an uneven surface shape without requiring a drying step.
[0006]
[Patent Document 1]
JP 2000-144097 A (Claims)
[0007]
[Patent Document 2]
JP-A-2-36921 (Claims)
[0008]
[Patent Document 3]
JP 2003-98303 A (Claims)
[0009]
[Problems to be solved by the invention]
However, the above method is an atmospheric pressure plasma CVD method in which the target substrate is placed between the counter electrodes and the gas for forming a thin film is directly introduced into the discharge space, and antifouling performance (for example, water repellency, water repellency, etc.). Regarding oiliness, sebum and ink wiping properties, etc.), it has been found that the level is not always satisfactory.
[0010]
In addition, the method described in Japanese Patent Application Laid-Open No. 9-59777 is a discharge plasma processing method in which discharge plasma generated in an inert gas is projected toward the processing target while supplying the processing gas to the processing target. However, under the described processing conditions (inert gas conditions, processing gas conditions, applied electric field conditions, processing time, etc.), a highly reactive processing gas is uniformly decomposed and reacted with the surface of the object to be processed. Therefore, it is difficult to stably provide desired performance (hydrophilicity, water repellency, etc.).
[0011]
Accordingly, an object of the present invention is to provide a thin film forming method which has no influence on the object to be processed, has excellent water repellency, oil repellency, sebum and ink wiping properties and repeated durability, and has good scratch resistance. Another object of the present invention is to provide a thin film forming apparatus and a thin film forming body obtained thereby.
[0012]
[Means for Solving the Problems]
The above object of the present invention can be achieved by the following constitution.
[0013]
1. Excited discharge excited by introducing a discharge gas into the discharge space at or near atmospheric pressure while supplying a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom to the workpiece A method for forming a thin film, comprising supplying gas to the object to be processed.
[0014]
2. 2. The method for forming a thin film according to 1 above, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the general formula (1).
[0015]
3. 3. The method for forming a thin film as described in 2 above, wherein the compound represented by the general formula (1) is a compound represented by the general formula (2).
[0016]
4). 4. The method for forming a thin film as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3).
[0017]
5. 2. The method for forming a thin film according to 1 above, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the general formula (4).
[0018]
6). 2. The thin film forming method according to item 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the general formula (5).
[0019]
7). 2. The method for forming a thin film according to item 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the general formula (6).
[0020]
8). 2. The method for forming a thin film according to 1 above, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the general formula (7).
[0021]
9. An electric field is applied between the electrode and the other electrode in a pair facing the electrode in a state where the discharge gas is circulated in the solid dielectric container having the discharge port of the excited discharge gas and the electrode pair. In this way, the discharge gas is introduced into the discharge space under atmospheric pressure or a pressure close to atmospheric pressure to generate excited discharge gas, and from the direction intersecting the supply direction of the excited discharge gas to the object to be processed. The thin film forming method according to any one of 1 to 8 above, wherein the thin film forming gas is supplied toward the surface.
[0022]
10. 10. The thin film forming method according to any one of items 1 to 9, wherein the discharge space is formed by a high frequency electric field.
[0023]
11. 11. The method for forming a thin film according to any one of 1 to 10 above, wherein the discharge gas contains a rare gas.
[0024]
12 11. The method for forming a thin film according to any one of 1 to 10, wherein the discharge gas contains nitrogen gas.
[0025]
13. 13. The method for forming a thin film as described in any one of 1 to 12 above, wherein the discharge gas contains 50% by volume or more of a rare gas or a nitrogen gas.
[0026]
14 14. The method for forming a thin film as described in any one of 1 to 13 above, wherein the discharge space is formed by applying a pulsed electric field.
[0027]
15. 15. The thin film forming method according to any one of claims 1 to 14, wherein the thin film is formed after the pretreatment is performed by exposing the object to be discharged to the discharge space or the excited discharge gas.
[0028]
16. Forming a thin film containing a solid dielectric container having an excitation discharge gas discharge port disposed on the outer surface, another electrode paired opposite to the electrode, and an organometallic compound having an organic group having a fluorine atom A thin film forming apparatus for forming a thin film on a target object comprising a gas supply unit, wherein an electric field is applied between opposing electrodes in a state where a discharge gas is circulated through the solid dielectric container. The excited gas is generated by introducing the discharge gas into the discharge space at atmospheric pressure or near atmospheric pressure, and the thin film is formed from the supply direction of the excited discharge gas and the thin film forming gas supply unit. A thin film forming apparatus, wherein the gas supply direction intersects with the gas supply direction.
[0029]
17. 17. The thin film forming apparatus according to 16 above, wherein the organometallic compound having an organic group having a fluorine atom is at least one selected from the general formulas (1) to (7).
[0030]
18. The solid dielectric container and the thin film forming gas supply unit are connected by a movable jig, and the solid dielectric container and the thin film forming gas supply unit are movable while maintaining a substantially constant relative position. 18. The thin film forming apparatus as described in 16 or 17 above.
[0031]
19. A workpiece moving device is provided, and a workpiece to be processed installed on the workpiece moving device is moved to the vicinity of the excitation discharge gas supply unit and exposed to the excitation discharge gas. The thin film forming apparatus according to any one of 16 to 18 above.
[0032]
20. 20. The thin film forming apparatus according to any one of the items 16 to 19, wherein the electric field applied between the opposing electrodes is pulsed.
[0033]
21. 21. The thin film forming apparatus according to any one of claims 16 to 20, wherein a thin film is formed after a pretreatment is performed by exposing the object to be processed to a discharge space or the excited discharge gas.
[0034]
22. 16. A thin film formed body obtained by the thin film forming method according to any one of 1 to 15 above.
[0035]
23. A thin film forming body obtained by the thin film forming apparatus according to any one of 16 to 21.
[0036]
24. 24. The thin film forming body as described in 22 or 23 above, wherein the surface of the object to be processed for forming a thin film contains an inorganic compound.
[0037]
25. 25. The thin film formed body according to any one of the items 22 to 24, wherein a main component of a surface of an object to be thin film formed is a metal oxide.
[0038]
26. The surface specific resistance value of the surface of the thin film formed on the object to be processed is 1 × 10 5 at 23 ° C. and 55% RH.¹²26. The thin film forming body according to any one of the items 22 to 25, wherein the thickness is Ω / □ or less.
[0039]
Details of the present invention will be described below.
In the thin film forming method of the present invention, a discharge gas is discharged under atmospheric pressure or a pressure near atmospheric pressure while supplying a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom to an object to be processed. An excitation discharge gas introduced into the space and excited is supplied to the object to be processed.
[0040]
First, the details of the organometallic compound having an organic group having a fluorine atom contained in the thin film forming gas will be described.
[0041]
In the organometallic compound having an organic group having a fluorine atom according to the present invention, examples of the organic group having a fluorine atom include organic groups containing a fluorine atom-containing alkyl group, alkenyl group, aryl group, etc. The organometallic compound having an organic group having a fluorine atom used in the invention is an organic group having these fluorine atoms, such as silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium, It is an organometallic compound that is directly bonded to a metal such as lanthanum, iron, neodymium, copper, gallium, or half-new. Of these metals, silicon, titanium, germanium, zirconium, tin and the like are preferable, and silicon and titanium are more preferable. These fluorine-containing organic groups may be bonded to the metal compound in any form. For example, when a compound having a plurality of metal atoms such as siloxane has these organic groups, at least one metal atom is fluorine. It does not matter as long as it has an organic group having.
[0042]
According to the thin film forming method of the present invention, it is estimated that the organometallic compound having an organic group having a fluorine atom can easily form a bond with a substrate such as silica or glass, and can exert the excellent effect of the present invention. Yes.
[0043]
As the organometallic compound having an organic group having a fluorine atom used in the present invention, a compound represented by the general formula (1) is preferable.
[0044]
In the general formula (1), M represents Si, Ti, Ge, Zr or Sn. R₁~ R₆Each represents a hydrogen atom or a monovalent group, R₁~ R₆Is an organic group having a fluorine atom, for example, an alkyl group having a fluorine atom, an alkenyl group, or an organic group containing an aryl group is preferred, and the alkyl group having a fluorine atom is preferable. A group such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, 4,4,3,3,2,2,1,1-octafluorobutyl group is a fluorine atom Examples of the alkenyl group having a group include a group such as 3,3,3-trifluoro-1-propenyl group, and examples of the aryl group having a fluorine atom include a group such as a pentafluorophenyl group. . In addition, an alkyl group, an alkenyl group, an alkoxy group formed from an aryl group, an alkenyloxy group, an aryloxy group, or the like can also be used.
[0045]
Further, in the alkyl group, alkenyl group, aryl group, etc., any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, but preferably at least one is bonded. . The carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.
[0046]
R₁~ R₆Among the groups represented by formula (1), other than the organic group having a fluorine atom, a hydrogen atom or a monovalent group is represented. Examples of the monovalent group include a hydroxy group, an amino group, an isocyanate group, a halogen atom, and an alkyl group. Groups such as a group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, and an aryloxy group are exemplified, but not limited thereto. j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.
[0047]
Of the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. Among the alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, and aryloxy groups that are the monovalent groups, preferred are an alkoxy group, an alkenyloxy group, and an aryloxy group.
[0048]
Of the metal atoms represented by M, Si and Ti are preferable.
The monovalent group may be further substituted with other groups, and is not particularly limited. Preferred substituents include amino groups, hydroxyl groups, isocyanate groups, fluorine atoms, chlorine atoms, bromine atoms and the like. Atom, alkyl group, cycloalkyl group, aryl group such as alkenyl group, phenyl group, alkoxy group, alkenyloxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, alkaneamide group, arylamide group, alkylcarbamoyl And groups such as an arylcarbamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.
[0049]
In addition, the organic group having a fluorine atom, or other R₁~ R₆The group represented by¹R²R³M- (M represents the metal atom, R¹, R², R³Each represents a monovalent group, and the monovalent group is an organic group having the above fluorine atom or R₁~ R₆Represents a group other than the organic group having a fluorine atom. And a structure having a plurality of metal atoms further substituted with a group represented by Examples of these metal atoms include Si and Ti, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.
[0050]
R₁~ R₆Examples of the alkyl group, alkenyl group, and the alkoxy group formed from these, the alkyl group in the alkenyloxy group, and the alkenyl group are groups represented by the following general formula (F). preferable.
[0051]
Formula (F)
Rf-X- (CH₂)_k−
Here, Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted by a fluorine atom. For example, Rf represents a perfluoro group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, or a heptafluoropropyl group. Groups such as alkyl groups, groups such as 3,3,3-trifluoropropyl groups, 4,4,3,3,2,2,1,1-octafluorobutyl groups, and 1,1,1 -An alkenyl group substituted by a fluorine atom such as trifluoro-2-chloropropenyl group is preferred, among which a group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, a heptafluoropropyl group, 3,3,3-trifluoropropyl group, 4,4,3,3,2,2,1,1-octafluorobutyl group, etc. Alkyl group preferably has at least two or more fluorine atoms.
[0052]
X is a simple bond or a divalent group, and the divalent group is a group such as —O—, —S—, —NR— (where R represents a hydrogen atom or an alkyl group), —CO— , -CO-O-, -CONH-, -SO₂NH-, -SO₂-O-, -OCONH-,
[0053]
[Formula 4]

[0054]
Represents a group such as
k represents an integer of 0 to 50, preferably 0 to 30.
[0055]
In addition to the fluorine atom, other substituents may be substituted in Rf, and examples of the substitutable group include R₁~ R₆And the same groups as those mentioned as the substituent in In addition, the skeletal carbon atom in Rf is another atom, for example, -O-, -S-, -NR.₀-(R₀Represents a hydrogen atom or a substituted or unsubstituted alkyl group, and may be a group represented by the general formula (F)), a carbonyl group, —NHCO—, —CO—O—, —SO.₂It may be partially substituted with a group such as NH-.
[0056]
Of the compounds represented by the general formula (1), a compound represented by the following general formula (2) is preferable.
[0057]
General formula (2)
[Rf-X- (CH₂)_k]_q-M (R₁₀)_r(OR₁₁)_t
In general formula (2), M represents the same metal atom as in general formula (1), Rf and X represent the same groups as Rf and X in general formula (F), and k represents the same integer. To express. R₁₀Represents an alkyl group, an alkenyl group, and R₁₁Represents an alkyl group, an alkenyl group, or an aryl group, and each of R in the general formula (1)₁~ R₆May be substituted with the same groups as those mentioned above, but preferably represents an unsubstituted alkyl group or alkenyl group. Further, q + r + t = 4, q ≧ 1, and t ≧ 1. Two r when r ≧ 2₁₀May be linked to form a ring.
[0058]
Of the general formula (2), more preferred are compounds represented by the following general formula (3).
[0059]
General formula (3)
Rf-X- (CH₂)_k-M (OR₁₂)₃
Here, Rf, X and k are as defined in the general formula (2). R₁₂R in the general formula (2)₁₁It is synonymous with. Further, M is the same as M in the general formula (2), but Si and Ti are particularly preferable, and Si is most preferable.
[0060]
In the present invention, another preferred example of the organometallic compound having a fluorine atom is a compound represented by the general formula (4).
[0061]
In the general formula (4), R₁~ R₆Is R in the general formula (1)₁~ R₆It is synonymous with. Again, R₁~ R₆At least one of is an organic group having the fluorine atom, and a group represented by the general formula (F) is preferable. R₇Represents a hydrogen atom or a substituted or unsubstituted alkyl group. J represents an integer of 0 to 150, preferably 0 to 50, and most preferably j is in the range of 0 to 20.
[0062]
Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the general formula (5).
[0063]
General formula (5)
[Rf-X- (CH₂)_k-Y]_m-M (R₈)_n(OR₉)_p
In the general formula (5), M represents In, Al, Sb, Y, or La. Rf and X represent the same groups as Rf and X in formula (F), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, and is preferably an integer of 30 or less. R₉Represents an alkyl group or an alkenyl group, and R₈Represents an alkyl group, an alkenyl group or an aryl group, and each of R in the general formula (1)₁~ R₆It may be substituted with the same group as the group mentioned as the substituent. Moreover, in General formula (5), it is m + n + p = 3, m is at least 1, n represents 0-2, and p represents the integer of 0-2. It is preferable that m + p = 3, that is, n = 0.
[0064]
As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (6).
[0065]
General formula (6)
R^f1(OC₃F₆)_m1-O- (CF₂)_n1-(CH₂)_p1-Z- (CH₂)_q1-Si- (R²)₃
In the general formula (6), R^f1Is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R²Represents a hydrolytic group, Z represents —OCONH— or —O—, m1 represents an integer of 1 to 50, n1 represents an integer of 0 to 3, p1 represents an integer of 0 to 3, and q1 represents an integer of 1 to 6. 6 ≧ n1 + p1> 0.
[0066]
R^f1As for carbon number of the linear or branched perfluoroalkyl group which can be introduce | transduced into 1-16, 1-16 are more preferable, and 1-3 are the most preferable. Therefore, R^f1As -CF₃, -C₂F₅, -C₃F₇Etc. are preferred.
[0067]
R²Examples of the hydrolyzable group that can be introduced into the group include -Cl, -Br, -I, -OR¹¹, -OCOR¹¹, -CO (R¹¹) C = C (R¹²)₂, -ON = C (R¹¹)₂, -ON = CR¹³, -N (R¹²)₂, -R¹²NOCR¹¹Etc. are preferable. R¹¹Represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R¹²Represents an aliphatic hydrocarbon having 1 to 5 carbon atoms such as a hydrogen atom or an alkyl group, and R¹³Represents a C3-C6 divalent aliphatic hydrocarbon group such as an alkylidene group. Among these hydrolyzable groups, —OCH₃, -OC₂H₅, -OC₃H₇, -OCOCH₃And -NH₂Is preferred.
[0068]
As for m1 in the said General formula (6), it is more preferable that it is 1-30, and it is still more preferable that it is 5-20. n1 is more preferably 1 or 2, and p1 is more preferably 1 or 2. Further, q1 is more preferably 1 to 3.
[0069]
Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the general formula (7).
[0070]
In the general formula (7), Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trimethyl group. Fluoromethyl group, R²¹Is a hydrolyzable group, R²²Represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1, m and n are integers of 0 to 2, and p is 1 to 2. Represents an integer of 10.
[0071]
In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably CF₃Group, C₂F₅Group, C₃F₇It is a group. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms.
[0072]
R²¹As the hydrolyzable group, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, R²³O group, R²³COO group, (R²⁴)₂C = C (R²³) CO group, (R²³)₂C = NO group, R²⁵C = NO group, (R²⁴)₂N group and R²³CONR²⁴Groups are preferred. Where R²³Is usually an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group usually having 6 to 20 carbon atoms such as a phenyl group, R²⁴Is usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a hydrogen atom or an alkyl group, R²⁵Is usually a C 3-6 divalent aliphatic hydrocarbon group such as an alkylidene group. More preferably, a chlorine atom, CH₃O group, C₂H₅O group, C₃H₇O group.
[0073]
R²²Is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is 5 × 10.²~ 1x10⁵And preferably 1 × 10³~ 1x10⁴It is.
[0074]
Further, as a preferable structure of the silane compound represented by the general formula (7), Rf is C₃F₇A compound in which a is an integer of 1 to 50, b, c, and d are 0, e is 1, Z is a fluorine atom, and n is 0.
[0075]
In the present invention, typical examples of the organometallic compound having an organic group having fluorine, which is preferably used as the silane compound having a fluorine atom, and the compounds represented by the general formulas (1) to (7) are listed below. However, the present invention is not limited to these compounds.
[0076]
1: (CF₃CH₂CH₂)₄Si
2: (CF₃CH₂CH₂)₂(CH₃)₂Si
3: (C₈F₁₇CH₂CH₂) Si (OC₂H₅)₃
4: CH₂= CH₂Si (CF₃)₃
5: (CH₂= CH₂COO) Si (CF₃)₃
6: (CF₃CH₂CH₂)₂SiCl (CH₃)
7: C₈F₁₇CH₂CH₂Si (Cl)₃
8: (C₈F₁₇CH₂CH₂)₂Si (OC₂H₅)₂
9: CF₃CH₂CH₂Si (OCH₃)₃
10: CF₃CH₂CH₂SiCl₃
11: CF₃(CF₂)₃CH₂CH₂SiCl₃
12: CF₃(CF₂)₅CH₂CH₂SiCl₃
13: CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃
14: CF₃(CF₂)₇CH₂CH₂SiCl₃
15: CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃
16: CF₃(CF₂)₈CH₂Si (OC₂H₅)₃
17: CF₃(CH₂)₂Si (OC₂H₅)₃
18: CF₃(CH₂)₂Si (OC₃H₇)₃
19: CF₃(CH₂)₂Si (OC₄H₉)₃
20: CF₃(CF₂)₅(CH₂)₂Si (OC₂H₅)₃
21: CF₃(CF₂)₅(CH₂)₂Si (OC₃H₇)₃
22: CF₃(CF₂)₇(CH₂)₂Si (OC₂H₅)₃
23: CF₃(CF₂)₇(CH₂)₂Si (OC₃H₇)₃
24: CF₃(CF₂)₇(CH₂)₂Si (OCH₃) (OC₃H₇)₂
25: CF₃(CF₂)₇(CH₂)₂Si (OCH₃)₂OC₃H₇
26: CF₃(CF₂)₇(CH₂)₂SiCH₃(OCH₃)₂
27: CF₃(CF₂)₇(CH₂)₂SiCH₃(OC₂H₅)₂
28: CF₃(CF₂)₇(CH₂)₂SiCH₃(OC₃H₇)₂
29: (CF₃)₂CF (CF₂)₈(CH₂)₂Si (OCH₃)₃
30: C₇F₁₅CONH (CH₂)₃Si (OC₂H₅)₃
31: C₈F₁₇SO₂NH (CH₂)₃Si (OC₂H₅)₃
32: C₈F₁₇(CH₂)₂OCONH (CH₂)₃Si (OCH₃)₃
33: CF₃(CF₂)₇(CH₂)₂Si (CH₃) (OCH₃)₂
34: CF₃(CF₂)₇(CH₂)₂Si (CH₃) (OC₂H₅)₂
35: CF₃(CF₂)₇(CH₂)₂Si (CH₃) (OC₃H₇)₂
36: CF₃(CF₂)₇(CH₂)₂Si (C₂H₅) (OCH₃)₂
37: CF₃(CF₂)₇(CH₂)₂Si (C₂H₅) (OC₃H₇)₂
38: CF₃(CH₂)₂Si (CH₃) (OCH₃)₂
39: CF₃(CH₂)₂Si (CH₃) (OC₂H₅)₂
40: CF₃(CH₂)₂Si (CH₃) (OC₃H₇)₂
41: CF₃(CF₂)₅(CH₂)₂Si (CH₃) (OCH₃)₂
42: CF₃(CF₂)₅(CH₂)₂Si (CH₃) (OC₃H₇)₂
43: CF₃(CF₂)₂O (CF₂)₃(CH₂)₂Si (OC₃H₇)₃
44: C₇F₁₅CH₂O (CH₂)₃Si (OC₂H₅)₃
45: C₈F₁₇SO₂O (CH₂)₃Si (OC₂H₅)₃
46: C₈F₁₇(CH₂)₂OCHO (CH₂)₃Si (OCH₃)₃
47: CF₃(CF₂)₅CH (C₄H₉) CH₂Si (OCH₃)₃
48: CF₃(CF₂)₃CH (C₄H₉) CH₂Si (OCH₃)₃
49: (CF₃)₂(P-CH₃-C₆H₅COCH₂CH₂CH₂Si (OCH₃)₃
50: CF₃CO-O-CH₂CH₂CH₂Si (OCH₃)₃
51: CF₃(CF₂)₃CH₂CH₂Si (CH₃) Cl
52: CF₃CH₂CH₂(CH₃) Si (OCH₃)₂
53: CF₃CO-O-Si (CH₃)₃
54: CF₃CH₂CH₂Si (CH₃) Cl₂
55: (CF₃)₂(P-CH₃-C₆H₅COCH₂CH₂Si (OCH₃)₃
56: (CF₃)₂(P-CH₃-C₆H₅COCH₂CH₂Si (OC₆H₅)₃
57: (CF₃C₂H₄) (CH₃)₂Si-O-Si (CH₃)₃
58: (CF₃C₂H₄) (CH₃)₂Si-O-Si (CF₃C₂H₄) (CH₃)₂
59: CF₃(OC₃F₆)₂₄-O- (CF₂)₂-CH₂-O-CH₂Si (OCH₃)₃
60: CF₃O (CF (CF₃CF₂O)_mCF₂CONHC₃H₆Si (OC₂H₅)₃  (M = 11-30),
61: (C₂H₅O)₃SiC₃H₆NHCOCF₂O (CF₂O)_n(CF₂CF₂O)_pCF₂CONHC₃H₆Si (OC₂H₅)₃  (N / p = about 0.5, number average molecular weight = about 3000)
62: C₃F₇-(OCF₂CF₂CF₂) Q-O- (CF₂)₂-[CH₂CH {Si- (OCH₃)₃}]₉-H (q = about 10)
63: F (CF (CF₃CF₂O)₁₅CF (CF₃) CONHCH₂CH₂CH₂Si (OC₂H₅)₃
64: F (CF₂)₄[CH₂CH (Si (OCH₃)₃]]_2.02OCH₃
65: (C₂H₅O)₃SiC₃H₆NHCO- [CF₂(OC₂F₄)₁₀(OCF₂)₆OCF₂] -CONHC₃H₆Si (OC₂H₅)₃
66: C₃F₇(OC₃F₆)₂₄O (CF₂)₂CH₂OCH₂Si (OCH₃)₃
67: CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃
68: (CF₃)₂CF (CF₂)₆CH₂CH₂SiCH₃(OCH₃)₂
69: CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂
70: CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OC₂H₅)₃
71: CF₃(CF₂)₃C₂H₄Si (NCO)₃
72: CF₃(CF₂)₅C₂H₄Si (NCO)₃
73: C₉F₁₉CONH (CH₂)₃Si (OC₂H₅)₃
74: C₉F₁₉CONH (CH₂)₃SiCl₃
75: C₉F₁₉CONH (CH₂)₃Si (OC₂H₅)₃
76: C₃F₇O (CF (CF₃CF₂O)₂-CF (CF₃) -CONH (CH₂) Si (OC₂H₅)₃
77: CF₃O (CF (CF₃CF₂O)₆CF₂CONH (CH₂)₃SiOSi (OC₂H₅)₂(CH₂)₃NHCOCF₂(OCF₂CF (CF₃))₆OCF₃
78: C₃F₇COOCH₂Si (CH₃)₂OSi (CH₃)₂CH₂OCOC₃F₇
79: CF₃(CF₂)₇CH₂CH₂O (CH₂)₃Si (CH₃)₂OSi (CH₃)₂(CH₂)₃OCH₂CH₂(CF₂)₇CF₃
80: CF₃(CF₂)₅CH₂CH₂O (CH₂)₂Si (CH₃)₂OSi (CH₃)₂(OC₂H₅)
81: CF₃(CF₂)₅CH₂CH₂O (CH₂)₂Si (CH₃)₂OSi (CH₃) (OC₂H₅)₂
82: CF₃(CF₂)₅CH₂CH₂O (CH₂)₂Si (CH₃)₂OSi (CH₃)₂OSi (CH3)₂(OC₂H₅)
In addition to the compounds exemplified above, as fluorine-substituted alkoxysilanes,
83: (Perfluoropropyloxy) dimethylsilane
84: Tris (perfluoropropyloxy) methylsilane
85: Dimethylbis (nonafluorobutoxy) silane
86: Methyltris (nonafluorobutoxy) silane
87: Bis (perfluoropropyloxy) diphenylsilane
88: Bis (perfluoropropyloxy) methylvinylsilane
89: Bis (1,1,1,3,3,4,4,4-octafluorobutoxy) dimethylsilane
90: Bis (1,1,1,3,3,3-hexafluoroisopropoxy) dimethylsilane
91: Tris (1,1,1,3,3,3-hexafluoroisopropoxy) methylsilane
92: Tetrakis (1,1,1,3,3,3-hexafluoroisopropoxy) silane
93: Dimethylbis (nonafluoro-t-butoxy) silane
94: Bis (1,1,1,3,3,3-hexafluoroisopropoxy) diphenylsilane
95: Tetrakis (1,1,3,3-tetrafluoroisopropoxy) silane
96: Bis [1,1-bis (trifluoromethyl) ethoxy] dimethylsilane
97: Bis (1,1,1,3,3,4,4,4-octafluoro-2-butoxy) dimethylsilane
98: Methyltris [2,2,3,3,3-pentafluoro-1,1-bis (trifluoromethyl) propoxy] silane
99: Diphenylbis [2,2,2-trifluoro-1- (trifluoromethyl) -1-tolylethoxy] silane
And the following compounds,
100: (CF₃CH₂)₃Si (CH₂-NH₂)
101: (CF₃CH₂)₃Si-N (CH₃)₂
[0077]
[Chemical formula 5]

[0078]
Furthermore,
[0079]
[Chemical 6]

[0080]
Silazanes such as
106: CF₃CH₂-CH₂TiCl₃
107: CF₃(CF₂)₃CH₂CH₂TiCl₃
108: CF₃(CF₂)₅CH₂CH₂Ti (OCH₃)₃
109: CF₃(CF₂)₇CH₂CH₂TiCl₃
110: Ti (OC₃F₇)₄
111: (CF₃CH₂-CH₂O)₃TiCl₃
112: (CF₃C₂H₄) (CH₃)₂Ti-O-Ti (CH₃)₃
Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organometallic compounds as follows.
[0081]
113: CF₃(CF₂)₃CH₂CH₂O (CH₂)₃GeCl
114: CF₃(CF₂)₃CH₂CH₂OCH₂Ge (OCH₃)₃
115: (C₃F₇O)₂Ge (OCH₃)₂
116: [(CF₃)₂CHO]₄Ge
117: [(CF₃)₂CHO]₄Zr
118: (C₃F₇CH₂CH₂)₂Sn (OC₂H₅)₂
119: (C₃F₇CH₂CH₂) Sn (OC₂H₅)₃
120: Sn (OC₃F₇)₄
121: CF₃CH₂CH₂In (OCH₃)₂
122: In (OCH₂CH₂OC₃F₇)₃
123: Al (OCH₂CH₂OC₃F₇)₃
124: Al (OC₃F₇)₃
125: Sb (OC₃F₇)₃
126: Fe (OC₃F₇)₃
127: Cu (OCH₂CH₂OC₃F₇)₂
128: C₃F₇(OC₃F₆)₂₄O (CF₂)₂CH₂OCH₂Si (OCH₃)₃
[0082]
[Chemical 7]

[0083]
Each compound mentioned in these specific examples is Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Chemical Co., Ltd. (for example, OPTOOL DSX), and Gelest Inc. In addition to being easily marketed, for example, J.A. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J.M. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No. 3,668,233, etc., JP-A 58-122979, JP-A 7-242675, JP-A 9-61605, etc. 11-29585, JP-A Nos. 2000-64348, 2000-144097 and the like, or a synthesis method based on the synthesis method.
[0084]
The thin film forming method of the present invention discharges a discharge gas at atmospheric pressure or near atmospheric pressure while supplying a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom to a workpiece. An excited discharge gas introduced into the space and excited is supplied to the object to be processed to form a thin film.
[0085]
More preferably, in a state in which the discharge gas is circulated in a solid dielectric container having an excitation discharge gas discharge port and an electrode pair, the electrode is disposed between the electrode and the other electrode paired with the electrode. By applying an electric field, the discharge gas is introduced into the discharge space under atmospheric pressure or a pressure close to atmospheric pressure to generate excited discharge gas, and the treatment is performed from the direction intersecting the supply direction of the excited discharge gas. A thin film forming method for supplying a thin film forming gas toward a body.
[0086]
In the present invention, the discharge space is a space which is sandwiched between electrode pairs arranged to face each other at a predetermined distance, and causes discharge by introducing a discharge gas between the electrode pairs and applying an electric field. . The form of the discharge space is not particularly limited, and may be, for example, a slit formed by opposing plate electrode pairs or a space formed in a circumferential shape between two cylindrical electrodes.
[0087]
Further, the method for supplying the discharge gas or thin film forming gas (also referred to as processing gas together) excited to the object to be processed is not particularly limited, and can be performed by a known gas supply method. An excited discharge gas discharge port is provided in the vicinity of the object to be processed, and the discharge gas is supplied from the direction intersecting the discharge direction of the discharge plasma toward the object to be processed, thereby efficiently processing with a small amount of the processing gas. be able to.
[0088]
In the present invention, the atmospheric pressure or the pressure in the vicinity of the atmospheric pressure refers to a pressure of 20 kPa to 200 kPa. In the present invention, a more preferable pressure between electrodes to which an electric field is applied is 70 kPa to 140 kPa.
[0089]
Next, embodiments of an atmospheric pressure plasma discharge treatment apparatus, an atmospheric pressure plasma discharge treatment method, and an electrode system for an atmospheric pressure plasma discharge treatment apparatus used in the thin film forming method of the present invention will be described below with reference to the drawings. However, the present invention is not limited to this. In addition, the following explanation may include assertive expressions for terms and the like, but it shows preferred examples of the present invention, and the meaning and technical scope of the terms of the present invention are shown. It is not limited.
[0090]
FIG. 1 is a cross-sectional view showing an example of an atmospheric pressure plasma discharge treatment apparatus useful for the present invention.
[0091]
Hereinafter, the atmospheric pressure plasma discharge treatment apparatus referred to in the present invention supplies a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom to an object to be treated under atmospheric pressure or a pressure near atmospheric pressure. However, it refers to an apparatus for forming a thin film by supplying an excited discharge gas excited by introducing a discharge gas into a discharge space under atmospheric pressure or a pressure near atmospheric pressure.
[0092]
In FIG. 1, in the atmospheric pressure plasma discharge processing apparatus, one first electrode 2 is disposed on the outer surface, another second electrode 3 corresponding to the first electrode 2 is disposed on the outer surface, and the first electrode 2. The second electrode 3 is a solid dielectric container 1 provided with a dielectric 4 on at least opposite surfaces, and provided with a discharge gas introduction port 5 and an excited discharge gas discharge port 6, and a counter electrode which is an electric field applying means 10 A discharge plasma processing apparatus comprising a high-frequency power source 11 for applying a high-frequency electric field therebetween and a thin film forming gas supply unit 7, wherein an electric field is formed between electrodes paired in a state where a discharge gas is circulated through the solid dielectric container 1. Is applied to generate discharge plasma, and the supply direction of the excitation discharge gas and the supply direction of the thin film forming gas are arranged to cross each other, and a thin film is formed on the object S to be processed.
[0093]
The solid dielectric container 1 and the thin film forming gas supply unit 7 are fixed to each other at an arbitrary crossing angle by the movable jig 13 via the holding joint 14. Although not shown in FIG. 1, in addition to the above configuration, a gas supply means for introducing a discharge gas into the solid dielectric container 1 and a thin film formation gas into the thin film formation gas supply unit 7, and the electrode temperature It comprises electrode temperature adjusting means for controlling.
[0094]
The supply direction of the excitation discharge gas and the supply direction of the thin film forming gas referred to in the present invention intersect with each other in the supply direction of the excitation discharge gas, that is, the solid dielectric container 1, and the supply direction of the thin film formation gas, that is, supply of the thin film formation gas. This means that the angle formed with the part 7 is in the range of more than 0 degrees (parallel) and less than 360 degrees, and is more than 0 degrees (parallel) and 180 degrees or less considering the mixing efficiency of both gases. It is preferably 15 to 150 degrees.
[0095]
In the thin film forming apparatus of the present invention, in order to perform processing efficiently with a small amount of processing gas, the region where the discharge direction of the excited discharge gas and the discharge direction of the thin film forming gas intersect is the discharge of the excited discharge gas. It is preferably arranged in the vicinity of the exit, and the object to be processed is preferably located in the intersecting region. Furthermore, it is preferable that the thin film forming gas outlet is also in the vicinity of the intersecting region.
[0096]
Further, the distance between the object to be processed S and the excited discharge gas discharge port 6 is appropriately determined by the flow velocity of the discharge plasma discharged from the excited discharge gas discharge port 6, but the probability of contact with air is high. Since a large flow rate is required, it is preferably 0.01 to 10 cm.
[0097]
In the thin film forming apparatus of the present invention, the solid dielectric container and the thin film forming gas supply unit are connected by a movable jig, and the solid dielectric container and the thin film forming gas supply unit are substantially constant. It is preferable to be able to move while maintaining the relative position.
[0098]
A region sandwiched between the first electrode 2 and the second electrode 3 and having the dielectric 4 is a discharge space. A discharge gas G is introduced into the discharge space from the discharge gas inlet 5 and excited. A thin film forming gas M containing an organometallic compound having an organic group having a fluorine atom is introduced into the thin film forming gas supply unit 7 through the thin film forming gas inlet 8. Next, the discharge gas G ′ excited from the excited discharge gas discharge port 6 of the solid dielectric container 1 and the thin film formation gas M from the thin film formation gas discharge portion 9 of the thin film formation gas supply unit 7 are respectively crossed under the following conditions: A thin film is formed by exposing to the surface of the object to be processed S. In addition, the to-be-processed object S can process not only a sheet-like to-be-processed object like a support body but various sizes and shapes. For example, a thin film can be formed on an object to be processed having a lens shape or a spherical shape.
[0099]
In the thin film forming method of the present invention, an organic metal compound having an organic group having fluorine atoms is used as a thin film forming raw material, and the excited discharge gas and the thin film forming gas are brought into contact with each other in a crossing relationship. It is possible to obtain a thin film having excellent water repellency, oil repellency, sebum and ink wiping properties, repeated durability thereof, and good abrasion resistance.
[0100]
The pair of counter electrodes (the first electrode 2 and the second electrode 3) is composed of a metal base material and a dielectric 4, and by combining the metal base material with a dielectric material having an inorganic property, Further, it may be constituted by a combination in which a ceramic material is sprayed on a metal base material and then a dielectric material sealed with a substance having an inorganic property is coated. As the metal base material, metals such as silver, platinum, stainless steel, aluminum, iron, titanium, copper, and gold can be used. Dielectric lining materials include silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Of these, borate glass is preferable because it is easy to process. As the ceramic used for the thermal spraying of the dielectric, alumina is preferable, and it is preferable to perform a sealing treatment with silicon oxide or the like. As the sealing treatment, the alkoxysilane sealing material can be made inorganic by a sol-gel reaction.
[0101]
In FIG. 1, the counter electrode is a plate electrode like the first electrode 2 and the second electrode 3, but one or both electrodes may be a hollow cylindrical electrode or a prismatic electrode. The high frequency power supply 11 is connected to one electrode (second electrode 3) of the counter electrodes, and the other electrode (first electrode 2) is grounded by a ground 12 so that an electric field can be applied between the counter electrodes. Has been. In addition to the configuration shown in FIG. 1, a configuration in which electric field application is the first electrode 2 and the other second electrode 3 is grounded may be used.
[0102]
The electric field applying means 10 applies an electric field to each electrode pair from the high frequency power supply 11. There is no limitation in particular as a high frequency power supply used for this invention. As a high frequency power source, a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (15 kHz), a high frequency power source manufactured by Shinko Electric (50 kHz), a high frequency power source manufactured by HEIDEN Laboratory (continuous mode) Use, 100 kHz), Pearl Industrial High Frequency Power Supply (200 kHz), Pearl Industrial High Frequency Power Supply (800 kHz), Pearl Industrial High Frequency Power Supply (2 MHz), JEOL High Frequency Power Supply (13.56 MHz), Pearl Industrial High Frequency Power Supply (27 MHz) ), A high frequency power source (150 MHz) manufactured by Pearl Industries, Ltd. can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.
[0103]
The frequency of the high-frequency electric field applied between the counter electrodes when forming the antifouling film according to the present invention is not particularly limited, but is preferably 0.5 kHz or more and 2.45 GHz or less as the high-frequency power source. The power supplied between the counter electrodes is preferably 0.1 W / cm.²50 W / cm²It is as follows. In addition, the electric field application area (cm²) Refers to the area in which discharge occurs.
[0104]
The high frequency electric field applied between the counter electrodes may be an intermittent pulse wave or a continuous sine wave. In the case of applying a pulsed electric field, examples of the pulse electric field waveform include impulse type, pulse type, and modulation type waveforms. Although the pulse electric field waveform in the present invention is not limited to the waveform mentioned here, the shorter the pulse rise time, the more efficiently the ionization of gas during plasma generation. Preferably, the rise time is 100 μs or less. Furthermore, modulation may be performed using pulses having different pulse waveforms, rise times, and frequencies. Such modulation is effective for high speed continuous surfaces.
[0105]
In the present invention, the distance between the counter electrodes is determined in consideration of the thickness of the dielectric on the metal base material of the electrodes, the magnitude of the applied electric field, the purpose of using plasma, and the like. The shortest distance between the dielectric when the dielectric is placed on one of the electrodes and the distance between the dielectrics when the dielectric is placed on both of the electrodes is the distance between the electrodes. From the viewpoint of discharging, 0.1 mm to 20 mm is preferable.
[0106]
Before forming the thin film according to the present invention, the surface treatment may be performed by exposing the object to be processed to a discharge space provided separately. In addition, before the thin film is formed, the surface of the object to be processed may be previously subjected to charge removal, and further dust may be removed. As the charge removal means and the dust removal means after the charge removal process, in addition to a normal blower type or contact type, a charge removal device in which a plurality of positive and negative ion generation charge removal electrodes and an ion attracting electrode are opposed to each other to sandwich the object to be processed. Thereafter, a high-density static elimination system (Japanese Patent Laid-Open No. 7-263173) provided with a positive / negative DC type static elimination device may be used. Further, examples of the dust removal means after the static elimination treatment include a non-contact type jet-type depressurization type dust removal device (Japanese Patent Laid-Open No. 7-60211) and can be preferably used, but are not limited thereto.
[0107]
Further, in the thin film forming apparatus of the present invention, the target object moving device is provided, and the target object installed on the target object moving device moves to the vicinity of the excitation discharge gas supply unit to cause the excitation discharge. It is preferable to be exposed to gas. Reference numeral 15 shown in FIG. 1 denotes an object moving apparatus according to the present invention, which moves in an arbitrary direction while holding an object to be processed S thereon.
[0108]
Next, the discharge gas supplied to the discharge space will be described.
The discharge gas is a gas that can cause discharge. Examples of the discharge gas include nitrogen, rare gas, air, hydrogen, oxygen, and the like. These may be used alone as a discharge gas or may be mixed. Among them, in the present invention, the discharge gas preferably contains a rare gas or nitrogen gas, and the content of the rare gas or nitrogen gas in the discharge gas is 50% by volume or more. More preferably, it is 50-100 volume% with respect to the total discharge gas amount. The amount of discharge gas is preferably 70 to 100% by volume with respect to the total amount of gas supplied to the discharge space.
[0109]
Further, the thin film forming gas according to the present invention contains the above-mentioned organometallic compound having an organic group having a fluorine atom, and is a gas that is chemically deposited on an object to be processed to form a thin film. That is. In the present invention, the content of the organometallic compound having an organic group having a fluorine atom according to the present invention relative to the thin film forming gas is preferably in the range of 0.001 to 30.0% by volume.
[0110]
The thin film forming gas according to the present invention can contain nitrogen, a rare gas, or the like described as the discharge gas. The thin film forming gas according to the present invention may be used by mixing 0.001% to 30% by volume of auxiliary gas such as hydrogen gas, oxygen gas, nitrogen gas, air and the like.
[0111]
The material of the object to be processed to be processed by the thin film forming method of the present invention is not particularly limited, and examples thereof include metal oxide, plastic, metal, earthenware, paper, wood, nonwoven fabric, glass plate, ceramic, and building material. In particular, the surface of the object to be treated is preferably composed of a surface containing an inorganic compound or a surface containing an organic compound, from the viewpoint of exhibiting the object effect of the present invention. It is an object to be processed whose surface is mainly composed of metal oxide such as titania. The form of the object to be processed may be a sheet or a molded product. Examples of the glass include a plate glass and a lens, and examples of the plastic include a plastic lens, a plastic film, a plastic sheet, and a plastic molded product. When the object to be processed uses such a plastic as a support, one having a metal oxide film formed on the surface thereof is preferable.
[0112]
In the thin film formed body obtained by the thin film forming method of the present invention, the surface specific resistance value of the surface of the thin film formed on the object to be processed is 1 × 10 5 at 23 ° C. and 55% RH.¹²It is preferable that it is below Ω / □.
[0113]
Next, another example of an atmospheric pressure plasma discharge treatment apparatus useful for the present invention will be described below.
[0114]
FIG. 2 is a perspective view showing an example of an atmospheric pressure plasma discharge treatment apparatus useful for the present invention shown in FIG.
[0115]
The atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2 has an excitation discharge gas discharge port and a thin film formation gas discharge port over almost the entire width of the object to be thin film formed, and a solid dielectric container and a thin film formation gas supply unit. Is a device capable of continuously forming a thin film in a fixed state.
[0116]
In FIG. 2, the solid dielectric container 1 is provided with flat electrodes 21 and 22 each having a rectangular shape and the same size, and the flat electrode 21 and the flat electrode 22 each constitute a counter electrode. The pair of counter electrodes are arranged in parallel. Each flat plate electrode is arranged with four corners. The opposing surfaces of the plate electrodes 21 and 22 are covered with a dielectric (not shown) similar to that described in FIG. In the present invention, the opposing surface of at least one of the plate electrodes 21 and 22 only needs to be covered with a dielectric.
[0117]
End surfaces in the width direction of the discharge space formed between the opposed flat plate electrodes 21 and 22 (in the figure, the front and back sides of the hand) are closed by lids 23 and 23 '. The lid prevents gas or the like from moving between the discharge space and the outside of the discharge space.
[0118]
Reference numeral 24 denotes a discharge gas inlet for introducing the discharge gas G between the flat plate electrodes 21 and 22, and one of the gaps between the flat plate electrodes 21 and 22 in the direction not covered by the lid bodies 23 and 23 ′. Is used as the discharge gas introduction port 24.
[0119]
In the atmospheric pressure plasma processing apparatus of FIG. 2, the discharge gas introduction port 24 uses a part of the gap between the electrodes 21 and 22 as it is as the discharge gas introduction port 24, but by further providing a member in the gap, The discharge gas inlet 24 may have a shape that allows the discharge gas to be efficiently and easily introduced between the flat plate electrodes 21 and 22.
[0120]
Reference numeral 25 denotes an excited discharge gas discharge port for discharging the discharge gas excited between the electrodes 21 and 22 to the outside between the flat plate electrodes 21 and 22, and the discharge gas introduction port 24 in the gap between the flat plate electrodes 21 and 22. The end part (lower part in the figure) facing to is used as the excitation discharge gas discharge port 25. Therefore, the discharge gas inlet 24 and the excited discharge gas outlet 25 use the same end.
[0121]
The thin film forming gas supply unit 7 basically has the same structure as that of the solid dielectric container 1. For example, the thin film forming gas supply unit 7 has a rectangular shape and introduces a slit-shaped thin film forming gas M therein. Has a road. Reference numeral 26 denotes a thin film forming gas introduction port for introducing the thin film forming gas M. The introduced thin film forming gas M crosses the excitation discharge gas from the thin film forming gas discharge port 27 to be processed. The target antifouling film can be formed on the surface of the object to be processed by being supplied to the surface of S.
[0122]
The thin film forming gas discharge port 27 uses an end portion (lower end portion in the figure) facing the thin film forming gas introduction port 26 as a thin film forming gas discharge port. Further, a structure in which a plurality of configurations of an excitation discharge gas discharge port and a thin film forming gas discharge port are arranged may be used.
[0123]
Reference numeral 11 denotes a high-frequency power source for applying a high-frequency electric field between the plate electrodes 21 and 22. Reference numeral 12 denotes a ground, and the plate electrode 22 is grounded by the ground 12.
[0124]
The discharge gas that exists between the plate electrodes 21 and 22 is made to exist under atmospheric pressure or a pressure near atmospheric pressure, and the high-frequency power source 11 excites the discharge gas by applying an electric field between the plate electrodes 21 and 22. And excited discharge gas is generated.
[0125]
The electrode system used in the atmospheric pressure plasma discharge treatment apparatus of FIG. 2 is composed of flat plate electrodes 21 and 22, and an electric field is applied between the flat plate electrodes 21 and 22 to discharge. Furthermore, by providing a discharge gas inlet, a thin film forming gas inlet, an excited discharge gas outlet, and a thin film forming gas outlet in each electrode system, a thin film can be formed on the object to be processed multiple times. . Thereby, a plurality of films of the same component or different components can be formed on the workpiece S.
[0126]
Next, a thin film forming method using the atmospheric pressure plasma discharge processing apparatus shown in FIG. 2 will be described.
[0127]
The discharge gas G is introduced between the flat plate electrodes 21 and 22 from the discharge gas introduction port 24, and the discharge gas G is present between the flat plate electrodes 21 and 22 under atmospheric pressure or a pressure near atmospheric pressure. A high frequency electric field is applied between the flat plate electrodes 21 and 22 by the high frequency power supply 11 to excite the discharge gas G existing between the flat plate electrodes 21 and 22 to generate an excited discharge gas G ′. The excited discharge gas G ′ generated between the flat plate electrodes 21 and 22 is pushed by the discharge gas G newly introduced from the discharge gas introduction port 24, and the gaps in the lateral direction of the electrodes by the lids 23 and 23 ′. Is closed from the discharge gas discharge port 25 to the outside between the plate electrodes 21 and 22.
[0128]
On the other hand, the thin film forming gas M is introduced from the thin film forming gas inlet 26. The thin film forming gas M introduced between the slits is pushed by the thin film forming gas M newly introduced from the thin film forming gas introduction port 26 and is discharged to the outside from the thin film forming gas discharge port 27.
[0129]
The thin film forming gas M discharged from the thin film forming gas discharge port 27 is mixed with the excited discharge gas G ′ discharged from the excited discharge gas discharge port 25 in an intersecting manner, and a thin film is formed on the object 8 to be processed. The
[0130]
Although not shown in FIG. 2, as in FIG. 1, the solid dielectric container 1 and the thin film forming gas supply unit 7 are each set at an arbitrary crossing angle by a movable jig via a holding joint. It is fixed to become.
[0131]
FIG. 3 is a perspective view showing an example of another atmospheric pressure plasma discharge treatment apparatus that can be used in the present invention.
[0132]
33 is an inner electrode, 32 is an outer electrode, and constitutes a pair of counter electrodes. The outer electrode 32 is a hollow cylindrical electrode, and a cylindrical inner electrode 33 is concentrically disposed in a cylindrical tube of the outer electrode 32.
[0133]
In the present invention, the opposing surfaces of the inner electrode 33 and the outer electrode 32 may be covered with a dielectric, and the opposing surface of either the inner electrode 33 or the outer electrode 32 is covered with a dielectric. It may be. A discharge occurs between the opposing surfaces.
[0134]
As the inner electrode 33 and the outer electrode 32, an electrode or a dielectric that can be used for the electrodes 1 and 2 described above with reference to FIG. 1 can be used.
[0135]
Reference numeral 35 denotes a discharge gas inlet for introducing the discharge gas G between the inner electrode 33 and the outer electrode 32. A discharge space is formed between the inner electrode 33 and the outer electrode 32. The discharge gas inlet 35 uses one of the end portions between the inner electrode 33 and the outer electrode 32.
[0136]
In the atmospheric pressure plasma processing apparatus of FIG. 3, the discharge gas introduction port 35 uses the upper end portion of the gap between the inner electrode 33 and the outer electrode 32 as the discharge gas introduction port 35 as it is, but a member is further provided in the gap. Thus, the discharge gas introduction port 35 may be shaped so that the discharge gas can be efficiently and easily introduced between the inner electrode 33 and the outer electrode 32.
[0137]
Reference numeral 36 denotes an excitation discharge gas discharge port for discharging the excitation discharge gas G ′ generated between the inner electrode 33 and the outer electrode 32 to the outside between the inner electrode 33 and the outer electrode 32. In the gap between the electrodes 32, the lower end portion that is not used as the discharge gas inlet 35 is used.
[0138]
The electrode system used in the atmospheric pressure plasma processing apparatus of FIG. 3 includes an inner electrode 33 and an outer electrode 32, and an electric field is applied between the inner electrode 33 and the outer electrode 32 by the high frequency power supply 11. However, by providing a plurality of electrode systems, and by providing each electrode system with a discharge gas inlet, an excited discharge gas outlet, a thin film forming gas inlet, and a thin film forming gas outlet, a thin film can be formed on the workpiece. It can be done multiple times. Thereby, a plurality of films of the same component or different components can be formed on the workpiece S.
[0139]
Next, a thin film forming method using the atmospheric pressure plasma processing apparatus shown in FIG. 3 will be described.
[0140]
A discharge gas G is introduced between the inner electrode 33 and the outer electrode 32 from the discharge gas introduction port 35, and the discharge gas exists between the inner electrode 33 and the outer electrode 32 under atmospheric pressure or a pressure near atmospheric pressure. A high frequency electric field is applied between the inner electrode 33 and the outer electrode 32 by the high frequency power supply 11 to excite the discharge gas G existing between the inner electrode 33 and the outer electrode 32 to generate an excited discharge gas G ′. The excited discharge gas G ′ generated between the inner electrode 33 and the outer electrode 32 is pushed out to the discharge gas G newly introduced from the discharge gas introduction port 35, so that the inner electrode from the excitation discharge gas discharge port 36. It is emitted to the outside from between 33 and the outer electrode 32.
[0141]
On the other hand, the thin film forming gas supply unit 7 has a hollow cylindrical structure, and introduces the thin film forming gas M from the thin film forming gas inlet 38 provided at the upper portion, and receives the thin film forming gas M from the thin film forming gas discharge port 39. discharge. The thin film forming gas M discharged from the thin film forming gas discharge port 39 is mixed with the excited discharge gas G ′ discharged from the excited discharge gas discharge port 36 in a crossed state in the shape of the object S to be processed. A thin film is formed on S.
[0142]
In the thin film forming method of the present invention, the object to be treated can be exposed to the excitation discharge gas and the thin film forming gas after the object to be treated is exposed to the discharge space or the excitation discharge gas for pretreatment.
[0143]
Hereinafter, an atmospheric pressure plasma discharge apparatus used for pre-processing for forming a thin film by exposing a target object to a discharge space before forming a thin film according to the present invention will be described.
[0144]
FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma discharge apparatus used for the pretreatment according to the present invention. 4 includes a plasma discharge processing apparatus 130, a gas supply means 150, an electric field applying means 140, and an electrode temperature adjusting means 160. As the roll rotating electrode 135 and the rectangular tube type fixed electrode group 136, the object to be processed F is subjected to plasma discharge treatment. The roll rotation electrode 135 is a ground electrode, and the square tube type fixed electrode group 136 is an application electrode connected to the high frequency power source 141. The object to be processed F passes through the guide roll 164, blocks air or the like accompanying the object to be processed by the nip roll 165, and is wound between the rectangular tube-shaped fixed electrode group 136 while being wound while being in contact with the roll rotating electrode 135. Is transferred to the thin film forming process according to the present invention, which is the next process, through the nip roll 166 and the guide roll 167. The pretreatment gas is the gas supply means 150, and the plasma of the pretreatment gas G generated by the gas generator 151 is controlled between the counter electrodes (this is the discharge space) 132 from the air supply port 152 by controlling the flow rate. It is put in the discharge treatment vessel 131, the inside of the plasma discharge treatment vessel 131 is filled with the pretreatment gas G, and the treated exhaust gas G ′ subjected to the discharge treatment is discharged from the exhaust port 153. Next, the electric field applying means 140 applies an electric field to the rectangular tube fixed electrode group 136 from the high frequency power source 141 to generate discharge plasma between the electrode and the roll rotating electrode 135 of the ground electrode. The roll rotating electrode 135 and the rectangular tube type fixed electrode group 136 are heated or cooled using the electrode temperature adjusting means 160 and fed to the electrodes. The temperature of the medium whose temperature is adjusted by the electrode temperature adjusting means 160 is adjusted by the liquid feed pump P from the inside of the roll rotating electrode 135 and the rectangular tube type fixed electrode group 136 through the pipe 161. During the plasma discharge treatment, the properties and composition of the thin film obtained may vary depending on the temperature of the object to be treated, and it is preferable to appropriately control this. As the medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to control the temperature inside the roll rotation electrode 135 so that the temperature unevenness of the object to be processed in the width direction or the longitudinal direction does not occur as much as possible. Reference numerals 168 and 169 denote partition plates that partition the plasma discharge processing vessel 131 from the outside.
[0145]
Moreover, in the thin film formation method of this invention, it is preferable that the to-be-processed surface which forms a thin film contains an inorganic compound, or the main component of the to-be-processed surface is a metal oxide.
[0146]
In the present invention, an atmospheric pressure plasma discharge apparatus can be used as one method for providing a layer including the above-described component on the surface of the object to be processed.
[0147]
As the atmospheric pressure plasma discharge device, for example, when the discharge gas is mainly helium or argon, the same device as the atmospheric pressure plasma discharge device described in FIG. 4 can be used. When nitrogen is the main component, it is more preferable to use the atmospheric pressure plasma discharge apparatus shown in FIG.
[0148]
FIG. 5 is a schematic view showing an example of an atmospheric pressure plasma discharge apparatus used for surface treatment of an object to be processed according to the present invention.
[0149]
The outline of the apparatus is almost the same as the configuration shown in FIG. 4, but the discharge space (between the counter electrodes) between the roll rotating electrode (first electrode) 135 and the rectangular tube-shaped fixed electrode group (second electrode) 136. ) 132, the roll rotating electrode (first electrode) 135 is supplied with the frequency ω from the first power source 141.₁And the high frequency electric field V₁In addition, the square cylindrical fixed electrode group (second electrode) 136 is supplied with a frequency ω from the second power source 142.₂And the high frequency electric field V₂It comes to apply.
[0150]
A first filter 143 is installed between the roll rotation electrode (first electrode) 135 and the first power supply 141 so that the current from the first power supply 141 flows toward the roll rotation electrode (first electrode) 135. ing. The first filter is designed to make it difficult for the current from the first power supply 141 to pass to the ground side and to easily pass the current from the second power supply 142 to the ground side. Further, a second filter 144 is installed between the square tube type fixed electrode group (second electrode) 136 and the second power source 142 so that the current from the second power source flows toward the second electrode. . The second filter 144 is designed to make it difficult for the current from the second power source 142 to pass to the ground side and to easily pass the current from the first power source 141 to the ground side.
[0151]
Note that the roll rotating electrode 135 may be the second electrode, and the square tube fixed electrode group 136 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source has a higher high-frequency electric field (V₁> V₂) Can be applied, and the frequency is ω₁<Ω₂Has the ability to
[0152]
【Example】
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
[0153]
<< Preparation of thin film (antifouling film) formed body >>
[Preparation of object 1]
According to the following procedure, the to-be-processed object 1 which provided the antistatic layer, the hard-coat layer, the antireflection layer, and the backcoat layer in the back surface was produced on the cellulose triacetate film.
[0154]
(Formation of antistatic layer)
The coating composition of the antistatic layer 1 having the following composition was die-coated on one surface of a cellulose triacetate film (trade name: Konica Katak KC80UVSF, 80 μm thick) so as to have a dry film thickness of 0.2 μm. And dried at 80 ° C. for 5 minutes to provide an antistatic layer.
[0155]

(Formation of hard coat layer)
The following hard coat layer composition was applied to the film on which the antistatic layer was formed so that the dry film thickness was 3.5 μm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high-pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured, and a hard coat film having a hard coat layer was produced. The refractive index of the hard coat layer was 1.50.
[0156]

[0157]
(Coating back coat layer)
The backcoat layer coating composition described below was applied to the opposite side of the surface coated with the hard coat layer with a gravure coater to a wet film thickness of 14 μm and dried at a drying temperature of 85 ° C. Was applied.
[0158]

(Formation of antireflection layer)
The four atmospheric pressure plasma discharge treatment apparatuses shown in FIG. 5 are connected, the electrode gap between the two electrodes of each apparatus is set to 1 mm, the following gas is supplied to the discharge space of each apparatus, and the hard coat produced above A thin film was sequentially formed on the layer. A high frequency power source manufactured by Shinko Electric Co., Ltd. (50 kHz) is used as the first high frequency power source for the first electrode of each device, and the high frequency electric field is 10 kV / mm and the output density is 1 W / cm.²In addition, a high-frequency power source manufactured by Pearl Industrial Co., Ltd. (13.56 MHz) is used as the second high-frequency power source for the second electrode, and a high-frequency electric field of 0.8 kV / mm and an output density of 5.0 W / cm.²And a plasma discharge was performed to form a thin film mainly composed of titanium oxide and an antireflection layer mainly composed of silicon oxide. The discharge start electric field of nitrogen gas in the discharge space of each device at this time was 3.7 kV / mm. The following thin film forming gas was vaporized by a vaporizer in nitrogen gas and supplied to the discharge space while heating. The roll electrode was rotated in synchronization with the transport of the cellulose ester film using a drive. Both electrodes were adjusted and kept at 80 ° C.
[0159]

On the hard coat layer, a titanium oxide layer, a silicon oxide layer, a titanium oxide layer, and a silicon oxide layer are provided in this order, and an object to be treated 1 having an antistatic layer, a hard coat layer, and an antireflection layer (in Table 1, This is referred to as TAC). Each of the layers constituting the antireflection layer has a refractive index of 2.1 (film thickness of 15 nm), a refractive index of 1.46 (film thickness of 33 nm), a refractive index of 2.1 (film thickness of 120 nm), and a refractive index of 1. .46 (film thickness 76 nm).
[0160]
[Preparation of Sample 1]
(Atmospheric pressure plasma discharge treatment equipment)
An antifouling film was formed on the object 1 having a hard coat layer and an antireflection layer on the cellulose triacetate film produced using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. The following gas type A was used as the discharge gas introduced from the discharge gas introduction port 24, and gas type B was used as the thin film formation gas introduced from the thin film formation gas introduction port 26.
[0161]

The electrodes 21 and 22 are made of stainless steel SUS316 as an electrode body, and further coated with alumina ceramic on the surface constituting the discharge space of the electrode until the thickness becomes 1 mm, and then an alkoxysilane monomer dissolved in an organic solvent. Was applied to an alumina ceramic coating and dried, followed by heating at 150 ° C. and sealing treatment to form a dielectric. The portion of the electrode not covered with the dielectric was connected to the high frequency power supply 11 or grounded with the earth 12. The gap between the excited discharge gas discharge port 25 and the object to be processed was 10 mm.
[0162]
The high-frequency power source 11 is a Pearl high-frequency power source (frequency: 13.56 MHz), 5 W / cm.²The discharge power was applied. The waveform is a sine wave.
[0163]
<Thin film formation>
The supplied thin film forming gas (gas species B) and discharge gas (gas species A) cross each other at an angle of 90 degrees on the object to be processed 1 after exiting each gas discharge port. A thin film was formed on the body surface to obtain Sample 1. At this time, the object to be processed was disposed horizontally at an angle of 45 degrees with respect to the thin film forming gas discharge angle. In addition, the thin film forming apparatus performed scanning on the object to be processed arranged in the horizontal direction in the left-right direction in FIG. 1 and the direction intersecting it (moving direction of the object to be processed). Moreover, the usage-amount of the gas seed | species B and the gas seed | species A was used by the ratio of 1: 1 as a volume.
[0164]
[Preparation of Samples 2 to 11]
Samples 2 to 11 were prepared in the same manner except that each of the organometallic compounds shown in Table 1 was used in place of the exemplified compound 15 used as the raw material for the gas type B in the preparation of the sample 1.
[0165]
[Preparation of Sample 12]
Sample 12 was prepared in the same manner as in the preparation of Sample 1, except that a discharge electric power having a pulse electric field of 6.4 kV, a frequency of 6.1 kHz, and a pulse width of 180 μm was applied from the high-frequency power source 11 as a pulse wave.
[0166]
[Preparation of Sample 13]
In the preparation of the sample 1, the argon gas used in the thin film forming gas (gas type B) and the discharge gas (gas type A) is replaced with nitrogen gas, and the high-frequency power source used is a high-frequency power source manufactured by HEIDEN Laboratory. (Frequency: 40 kHz), 6 W / cm²Sample 13 was prepared in the same manner except that the battery was discharged at a discharge power of.
[0167]
[Preparation of Sample 14]
Sample 14 was prepared in the same manner as in preparation of Sample 1 except that the object to be processed was subjected to the following pretreatment A before the object to be processed was exposed to the indirectly excited discharge gas.
[0168]
Pretreatment A: Before exposing the object to be treated to the indirectly excited discharge gas, a discharge gas is formed in a discharge space having a configuration in which the first electrode 2 and the second electrode 3 shown in FIG. Then, argon gas / oxygen gas = 99: 1 (volume ratio) was introduced, and the object 1 was exposed to the excited discharge gas. In addition, as a high frequency power source, a high frequency power source (frequency: 13.56 MHz) manufactured by Pearl Industry, discharge output is 10 w / cm.²I went to set.
[0169]
[Preparation of Sample 15]
Sample 11 was prepared in the same manner as in preparation of Sample 1 except that the object to be processed was subjected to the following pretreatment B before the object to be processed was exposed to the indirectly excited discharge gas.
[0170]
Pretreatment B: Before exposing the object to be treated to the indirectly excited discharge gas, using a discharge device composed of a pair of roll electrodes shown in FIG. Oxygen gas was exposed to the supplied discharge space at 99/1 (volume ratio). In addition, a high frequency power source manufactured by Pearl Industrial Co., Ltd. (13.56 MHz) is used as the high frequency power source, and the output density is 5.0 W / cm for the second electrode.²Applied.
[0171]
[Preparation of Sample 16]
Sample 16 was prepared in the same manner except that a glass plate (product name: 0.5 t soda glass single-side polished product manufactured by Nippon Sheet Glass Co., Ltd.) was used as the object to be processed instead of the object 1 in the production of Sample 1. Produced.
[0172]
[Preparation of Sample 17]
Sample 17 was prepared in the same manner as in the preparation of Sample 1, except that a polyethylene terephthalate film having a thickness of 100 μm (referred to as PET in Table 1) was used instead of the object to be processed 1. .
[0173]
[Preparation of Sample 18]
Sample 18 was prepared in the same manner as in the preparation of Sample 17, except that Shinko Electric's high frequency power supply (15 kHz) was used instead of Pearl Industries' high frequency power supply (frequency: 13.56 MHz) as high frequency power supply 11. .
[0174]
[Preparation of Sample 19]
In the preparation of Sample 18, Comparative Sample 19 was prepared in the same manner except that 6-fluoropropylene was used instead of the organometallic compound (Exemplary Compound 15) used in Gas Type B (Thin Film Formation Gas). did.
[0175]
[Preparation of Sample 20]
In preparation of the sample 19, a comparative sample 20 was prepared in the same manner except that the object to be processed 1 (TAC) was used instead of the polyethylene terephthalate film having a thickness of 100 μm as the object to be processed.
[0176]
Table 1 shows the main characteristics of the thin film forming method for each sample.
[0177]
[Table 1]

[0178]
<< Measurement and evaluation of characteristic values of each sample >>
(Measurement of contact angle)
About each sample, the contact angle with respect to the water of the antifouling film surface and the contact angle with hexadecane were measured using a contact angle meter CA-W manufactured by Kyowa Interface Science Co., Ltd. in an environment of 23 ° C. and 55%. In addition, the measurement was performed at 10 locations at random and the average value was obtained.
[0179]
[Evaluation of oil-based ink writing performance: Evaluation of oil repellency]
Using oil-based ink (Mckey extra fine black MO-120-MC-BK manufactured by Zebra Co., Ltd.), the surface of the sample was filled with 3 mmφ, and then the writing condition on the surface with oil-based ink was visually observed. Sexuality was evaluated.
[0180]
A: The oil-based ink is repelled very well, almost cannot be painted, and the oil repellency is very good.
○: Some of the oil-based ink repels, the entire surface cannot be uniformly painted, and has oil repellency.
X: Familiar with oil-based ink, good writing without repelling, and no oil repellency
[Evaluation of oil-based ink wiping performance]
Using oil-based ink (Zebra Co., Ltd. Mackey extra fine black MO-120-MC-BK), the sample surface was painted 3 mmφ, and then the oil-based ink image was wiped off with a soft cloth (BEMCOT M-3 250 mm × 250 mm manufactured by Asahi Kasei Co., Ltd.) This operation was repeated 20 times at the same position, and the remaining state of the oil-based ink after wiping once and after wiping 20 times was visually observed, and the wiping property of the oil-based ink was evaluated according to the following criteria.
[0181]
A: Oil-based ink was completely wiped off
○: Oil-based ink was almost wiped off
X: Oil-based ink remains without being partially wiped off
[Evaluation of scratch resistance]
The surface of each sample was rubbed 10 times with Bonster # 0000 steel wool on which a 500 g weight was placed, the generated scratches were counted visually, and the scratch resistance was evaluated according to the following criteria.
[0182]
A: No scratches are generated
B: Number of scratches occurring is less than 1 to 5
C: Number of scratches occurring is less than 5-15
D: Number of scratches occurring is 15 or more
[Measurement of surface resistivity]
As a result of measuring the surface specific resistance value of the thin film-formed product of the present invention according to the following method, all the results were 1 × 10.¹²It was below Ω / □.
[0183]
(Measurement method of surface resistivity)
The sample was conditioned for 24 hours in an environment of 23 ° C. and 55% RH, and then measured using a Teraohm Meter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd. The electrodes used for the measurement were measured by placing two electrodes (1 cm x 5 cm in contact with the sample) at an interval of 1 cm, contacting the sample with the electrode, and multiplying the measured value by 5 times. The specific resistance value (Ω / □) was used.
[0184]
Table 2 shows the results excluding the surface specific resistance obtained as described above.
[0185]
[Table 2]

[0186]
As is apparent from Table 2, the sample of the present invention containing an organometallic compound having an organic group having a fluorine atom as a thin film forming gas raw material and forming an antifouling film according to the thin film forming method of the present invention is On the other hand, it can be seen that the water-repellent property, the oil-repellent property, the wiping property of the oil-based ink are excellent, and the antifouling film formed has good scratch resistance. Further, as apparent from comparison between Sample 13 and Sample 1, it can be seen that the repeatability of wiping oil-based ink is improved by replacing the argon gas used in the discharge gas and the thin film forming gas with nitrogen gas.
[0187]
【The invention's effect】
The present invention provides a thin film forming method, a thin film forming apparatus, and a thin film forming body that have no influence on the object to be processed, have excellent water repellency, oil repellency, oil-based ink wiping properties, and good scratch resistance. We were able to.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of an atmospheric pressure plasma discharge treatment apparatus that can be used in the present invention.
FIG. 2 is a perspective view showing an example of an atmospheric pressure plasma discharge treatment apparatus that can be used in the present invention.
FIG. 3 is a perspective view showing an example of another atmospheric pressure plasma discharge treatment apparatus that can be used in the present invention.
FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma discharge apparatus used for pretreatment according to the present invention.
FIG. 5 is a schematic view showing another example of an atmospheric pressure plasma discharge apparatus used for surface treatment of an object to be processed according to the present invention.
[Explanation of symbols]
1,31 Solid dielectric container
2 First electrode
3 Second electrode
4 Dielectric
5, 24, 35 Discharge gas inlet
6, 25, 36 Discharge gas outlet
7, 37 Thin film forming gas supply section
8, 26, 38 Thin film forming gas inlet
9, 27, 39 Thin film forming gas outlet
10 Electric field application means
11 High frequency power supply
12 Earth
13 Movable jig
14 Holding joint
15 Object moving device
21, 22 Flat plate electrode
23, 23 'lid
32 outer electrode
33 Inner electrode
G Discharge gas
G 'excited discharge gas
M Thin film forming gas
S object to be processed
131 Plasma discharge treatment vessel
132 Discharge space
135 Roll electrode (first electrode)
136 Square tube electrode group (second electrode)
140 Electric field applying means
141 First power supply
142 Second power supply
143 1st filter
144 Second filter
150 Gas supply means
160 Electrode temperature adjusting means

Claims (26)

Excited discharge excited by introducing a discharge gas into the discharge space at or near atmospheric pressure while supplying a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom to the workpiece A method for forming a thin film, comprising supplying gas to the object to be processed. The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (1).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. j represents an integer of 0 to 150. ] The thin film forming method according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group or an aryl group. K represents an integer of 0 to 50, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be linked to form a ring. ] The thin film forming method according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
[Wherein, M represents Si, Ti, Ge, Zr or Sn, Rf represents an alkyl group or an alkenyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom, and X represents a simple bond or a divalent group. Represents. R ₁₂ represents an alkyl group, an alkenyl group, or an aryl group, and k represents an integer of 0 to 50. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (4).

[Wherein, M represents Si, Ti, Ge, Zr or Sn, R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is And a group having a fluorine atom. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. j represents an integer of 0 to 150. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (5).
General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
[Wherein, M represents In, Al, Sb, Y, or La, and Rf represents an alkyl group or an alkenyl group in which at least one hydrogen atom is substituted with a fluorine atom. X represents a simple bond or a divalent group, and Y represents a simple bond or an oxygen atom. R ₈ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R ₉ represents a substituted or unsubstituted alkyl group or alkenyl group. k represents an integer of 0 to 50, m + n + p = 3, m is at least 1, and n and p each represent an integer of 0 to 2. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (6).
General formula (6)
^{_{R f1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3
[Wherein, R ^f1 represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1-50. An integer, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0. ] The method for forming a thin film according to claim 1, wherein the organometallic compound having an organic group having a fluorine atom is a compound represented by the following general formula (7).

[Wherein, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1, m and n Represents an integer of 0 to 2, and p represents an integer of 1 to 10. ] An electric field is applied between the electrode and the other electrode in a pair facing the electrode in a state where the discharge gas is circulated in the solid dielectric container having the discharge port of the excited discharge gas and the electrode pair. In this way, the discharge gas is introduced into the discharge space under atmospheric pressure or a pressure close to atmospheric pressure to generate excited discharge gas, and from the direction intersecting with the supply direction of the excited discharge gas, The thin film forming method according to claim 1, wherein the thin film forming gas is supplied toward the surface. The thin film forming method according to claim 1, wherein the discharge space is formed by a high frequency electric field. The thin film forming method according to claim 1, wherein the discharge gas contains a rare gas. The said discharge gas contains nitrogen gas, The thin film formation method of any one of Claims 1-10 characterized by the above-mentioned. The thin film forming method according to claim 1, wherein the discharge gas contains a rare gas or a nitrogen gas in an amount of 50% by volume or more. The method of forming a thin film according to claim 1, wherein the discharge space is formed by applying a pulsed electric field. The thin film formation method according to claim 1, wherein a thin film is formed after the pretreatment is performed by exposing the object to be processed to a discharge space or the excited discharge gas. Forming a thin film containing a solid dielectric container having an excitation discharge gas discharge port disposed on the outer surface, another electrode paired opposite to the electrode, and an organometallic compound having an organic group having a fluorine atom A thin film forming apparatus for forming a thin film on a target object comprising a gas supply unit, wherein an electric field is applied between opposing electrodes in a state where a discharge gas is circulated through the solid dielectric container. The excited gas is generated by introducing the discharge gas into the discharge space at atmospheric pressure or near atmospheric pressure, and the thin film is formed from the supply direction of the excited discharge gas and the thin film forming gas supply unit. A thin film forming apparatus, wherein the gas supply direction intersects with the gas supply direction. The thin film forming apparatus according to claim 16, wherein the organometallic compound having an organic group having a fluorine atom is at least one selected from the general formulas (1) to (7). The solid dielectric container and the thin film forming gas supply unit are connected by a movable jig, and the solid dielectric container and the thin film forming gas supply unit are movable while maintaining a substantially constant relative position. The thin film forming apparatus according to claim 16, wherein the thin film forming apparatus is provided. A workpiece moving device is provided, and a workpiece to be processed installed on the workpiece moving device is moved to the vicinity of the excitation discharge gas supply unit and exposed to the excitation discharge gas. The thin film forming apparatus according to any one of claims 16 to 18. The thin film forming apparatus according to any one of claims 16 to 19, wherein the electric field applied between the opposing electrodes is pulsed. 21. The thin film forming apparatus according to claim 16, wherein a thin film is formed after performing a pretreatment by exposing the object to be processed to a discharge space or the excited discharge gas. A thin film forming body obtained by the thin film forming method according to claim 1. A thin film forming body obtained by the thin film forming apparatus according to any one of claims 16 to 21. 24. The thin film forming body according to claim 22 or 23, wherein the surface of the object to be processed on which the thin film is formed contains an inorganic compound. 25. The thin film forming body according to any one of claims 22 to 24, wherein a main component of the surface of the object to be thin film formed is a metal oxide. The surface specific resistance value of the surface of the thin film formed on the object to be processed is 1 × 10 ¹² Ω / □ or less under the conditions of 23 ° C. and 55% RH. The thin film forming body according to item.

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