JP4506111B2 - Thin film forming method and thin film manufacturing apparatus - Google Patents

Description

【００５８】
上記一般式（１）において、ＭはＳｉ、Ｔｉ、Ｇｅ、ＺｒまたはＳｎを表す。
また、Ｒ₁〜Ｒ₆は各々水素原子または一価の基を表し、Ｒ₁〜Ｒ₆で表される基の少なくとも１つは、フッ素原子を有する有機基であり、例えば、フッ素原子を有するアルキル基、アルケニル基またはアリール基を含有する有機基が好ましく、フッ素原子を有するアルキル基としては、例えば、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、４，４，３，３，２，２，１，１−オクタフルオロブチル基等の基が、フッ素原子を有するアルケニル基としては、例えば、３，３，３−トリフルオロ−１−プロペニル基等の基が、また、フッ素原子を有するアリール基としては、例えば、ペンタフルオロフェニル基等の基が挙げられる。また、これらフッ素原子を有するアルキル基、アルケニル基、またアリール基から形成されるアルコキシ基、アルケニルオキシ基、アリールオキシ基等なども用いることができる。
【００５９】
また、フッ素原子は、前記アルキル基、アルケニル基、アリール基等においては、骨格中の炭素原子のどの位置に任意の数結合していてもよいが、少なくとも１個以上結合していることが好ましい。また、アルキル基、アルケニル基骨格中の炭素原子は、例えば、酸素、窒素、硫黄等他の原子、また、酸素、窒素、硫黄等を含む２価の基、例えば、カルボニル基、チオカルボニル基等の基で置換されていてもよい。
【００６０】
Ｒ₁〜Ｒ₆で表される基のうち、前記フッ素原子を有する有機基以外は、水素原子または１価の基を表し、１価の基としては、例えば、ヒドロキシ基、アミノ基、イソシアネート基、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルコキシ基、アルケニルオキシ基、アリールオキシ基等の基が挙げられるが、これに限定されない。ｊは０〜１５０の整数を表し、好ましくは０〜５０、更に好ましいのはｊが０〜２０の範囲である。
【００６１】
前記１価の基のうち、ハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子が好ましく、更に好ましいのは塩素原子である。また、前記１価の基である前記アルキル基、アルケニル基、アリール基、アルコキシ基、アルケニルオキシ基、アリールオキシ基のうち、好ましいのは、アルコキシ基、アルケニルオキシ基、アリールオキシ基であり、更に好ましいのはアルコキシ基である。
【００６２】
また、Ｍで表される金属原子のうち、好ましいのは、Ｓｉ、Ｔｉであり、更に好ましいのはＳｉである。
【００６３】
前記１価の基は、更にその他の基で置換されていてもよく、特に限定されないが、好ましい置換基としては、アミノ基、ヒドロキシル基、イソシアネート基、フッ素原子、塩素原子、臭素原子等のハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、フェニル基等のアリール基、アルコキシ基、アルケニルオキシ基、アリールオキシ基、アシル基、アシルオキシ基、アルコキシカルボニル基、アルカンアミド基、アリールアミド基、アルキルカルバモイル基、アリールカルバモイル基、シリル基、アルキルシリル基、アルコキシシリル基等の基が挙げられる。
【００６４】
また、前記フッ素原子を有する有機基、またはそれ以外のこれらＲ₁〜Ｒ₆で表される基は、Ｒ¹Ｒ²Ｒ³Ｍ−（Ｍは、前記金属原子を表し、Ｒ¹、Ｒ²、Ｒ³はそれぞれ１価の基を表し、１価の基としては前記フッ素原子を有する有機基またはＲ₁〜Ｒ₆として挙げられた前記フッ素原子を有する有機基以外の基を表す。）で表される基によって更に置換された複数の金属原子を有する構造であっても良い。これらの金属原子としては、Ｓｉ、Ｔｉなどが挙げられ、例えば、シリル基、アルキルシリル基、アルコキシシリル基等が挙げられる。
【００６５】
前記Ｒ₁〜Ｒ₆において挙げられたフッ素原子を有する基であるアルキル基、アルケニル基、またこれらから形成されるアルコキシ基、アルケニルオキシ基におけるアルキル基、アルケニル基としては、下記一般式（Ｆ）で表される基が好ましい。
【００６６】
一般式（Ｆ）
Ｒｆ−Ｘ−（ＣＨ₂）_k−
ここにおいてＲｆは、水素の少なくとも１つがフッ素原子により置換されたアルキル基、アルケニル基を表し、例えば、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロオクチル基、ヘプタフルオロプロピル基のようなパーフルオロアルキル基等の基、また、３，３，３−トリフルオロプロピル基、４，４，３，３，２，２，１，１−オクタフルオロブチル基等の基、また、１，１，１−トリフルオロ−２−クロルプロペニル基等のようなフッ素原子により置換されたアルケニル基が好ましく、中でも、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロオクチル基、ヘプタフルオロプロピル基等の基、また、３，３，３−トリフルオロプロピル基、４，４，３，３，２，２，１，１−オクタフルオロブチル基等の少なくとも２つ以上のフッ素原子有するアルキル基が好ましい。
【００６７】
また、Ｘは単なる結合手または２価の基である、２価の基としては−Ｏ−、−Ｓ−、−ＮＲ−（Ｒは水素原子またはアルキル基を表す）等の基、−ＣＯ−、−ＣＯ−Ｏ−、−ＣＯＮＨ−、−ＳＯ₂ＮＨ−、−ＳＯ₂−Ｏ−、−ＯＣＯＮＨ−、
【００６８】
【化２】

【００６９】
等の基を表す。
ｋは０〜５０、好ましくは０〜３０の整数を表す。
【００７０】
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Ｒ₁〜Ｒ₆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−、−ＮＲ₀−（Ｒ₀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−、−ＳＯ₂ＮＨ−等の基によって一部置換されていてもよい。
【００７１】
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。
【００７２】
一般式（２）
［Ｒｆ−Ｘ−（ＣＨ₂）_k］_q−Ｍ（Ｒ₁₀）_r（ＯＲ₁₁）_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。Ｒ₁₀はアルキル基、アルケニル基を、またＲ₁₁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Ｒ₁〜Ｒ₆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Ｒ₁₀は連結して環を形成してもよい。
【００７３】
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。
【００７４】
一般式（３）
Ｒｆ−Ｘ−（ＣＨ₂）_k−Ｍ（ＯＲ₁₂）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、Ｒ₁₂も、前記一般式（２）におけるＲ₁₁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。
【００７５】
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、下記一般式（４）で表される化合物が挙げられる。
【００７６】
【化３】

【００７７】
一般式（４）において、Ｒ₁〜Ｒ₆は、前記一般式（１）におけるＲ₁〜Ｒ₆と同義である。ここにおいても、Ｒ₁〜Ｒ₆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。Ｒ₇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。
【００７８】
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（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。
【００７９】
一般式（５）
［Ｒｆ−Ｘ−（ＣＨ₂）_k−Ｙ］_m−Ｍ（Ｒ₈）_n（ＯＲ₉）_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。Ｒ₉はアルキル基またはアルケニル基を、またＲ₈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Ｒ₁〜Ｒ₆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。
【００８０】
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。
【００８１】
一般式（６）
Ｒ^f1（ＯＣ₃Ｆ₆）_m1−Ｏ−（ＣＦ₂）_n1−（ＣＨ₂）_p1−Ｚ−（ＣＨ₂）_q1−Ｓｉ−（Ｒ²）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、Ｒ²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。
【００８２】
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、−ＣＦ₃、−Ｃ₂Ｆ₅、−Ｃ₃Ｆ₇等が好ましい。
【００８３】
Ｒ²に導入しうる加水分解基としては、−Ｃｌ、−Ｂｒ、−Ｉ、−ＯＲ¹¹、−ＯＣＯＲ¹¹、−ＣＯ（Ｒ¹¹）Ｃ＝Ｃ（Ｒ¹²）₂、−ＯＮ＝Ｃ（Ｒ¹¹）₂、−ＯＮ＝ＣＲ¹³、−Ｎ（Ｒ¹²）₂、−Ｒ¹²ＮＯＣＲ¹¹などが好ましい。Ｒ¹¹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、Ｒ¹²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、Ｒ¹³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、−ＯＣＨ₃、−ＯＣ₂Ｈ₅、−ＯＣ₃Ｈ₇、−ＯＣＯＣＨ₃及び−ＮＨ₂が好ましい。
【００８４】
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。
【００８５】
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（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。
【００８６】
【化４】

【００８７】
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、Ｒ²¹は加水分解可能な基、Ｒ²²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。
【００８８】
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、ＣＦ₃基、Ｃ₂Ｆ₅基、Ｃ₃Ｆ₇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。
【００８９】
Ｒ²¹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、Ｒ²³Ｏ基、Ｒ²³ＣＯＯ基、（Ｒ²⁴）₂Ｃ＝Ｃ（Ｒ²³）ＣＯ基、（Ｒ²³）₂Ｃ＝ＮＯ基、Ｒ²⁵Ｃ＝ＮＯ基、（Ｒ²⁴）₂Ｎ基、及びＲ²³ＣＯＮＲ²⁴基が好ましい。ここで、Ｒ²³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、Ｒ²⁴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、Ｒ²⁵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、ＣＨ₃Ｏ基、Ｃ₂Ｈ₅Ｏ基、Ｃ₃Ｈ₇Ｏ基である。
【００９０】
Ｒ²²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５×１０²〜１×１０⁵であり、好ましくは１×１０³〜１×１０⁴である。
【００９１】
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Ｃ₃Ｆ₇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。
【００９２】
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。
【００９３】
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−Ｃ₆Ｈ₅）ＣＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（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−Ｃ₆Ｈ₅）ＣＯＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃
５６：（ＣＦ₃）₂（ｐ−ＣＨ₃−Ｃ₆Ｈ₅）ＣＯＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₆Ｈ₅）₃
５７：（ＣＦ₃Ｃ₂Ｈ₄）（ＣＨ₃）₂Ｓｉ−Ｏ−Ｓｉ（ＣＨ₃）₃
５８：（ＣＦ₃Ｃ₂Ｈ₄）（ＣＨ₃）₂Ｓｉ−Ｏ−Ｓｉ（ＣＦ₃Ｃ₂Ｈ₄）（ＣＨ₃）₂５９：ＣＦ₃（ＯＣ₃Ｆ₆）₂₄−Ｏ−（ＣＦ₂）₂−ＣＨ₂−Ｏ−ＣＨ₂Ｓｉ（ＯＣＨ₃）₃
６０：ＣＦ₃Ｏ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_mＣＦ₂ＣＯＮＨＣ₃Ｈ₆Ｓｉ（ＯＣ₂Ｈ₅）₃ （ｍ＝１１〜３０）、
６１：（Ｃ₂Ｈ₅Ｏ）₃ＳｉＣ₃Ｈ₆ＮＨＣＯＣＦ₂Ｏ（ＣＦ₂Ｏ）_n（ＣＦ₂ＣＦ₂Ｏ）_pＣＦ₂ＣＯＮＨＣ₃Ｈ₆Ｓｉ（ＯＣ₂Ｈ₅）₃ （ｎ／ｐ＝約０．５、数平均分子量＝約３０００）
６２：Ｃ₃Ｆ₇−（ＯＣＦ₂ＣＦ₂ＣＦ₂）ｑ−Ｏ−（ＣＦ₂）₂−［ＣＨ₂ＣＨ｛Ｓｉ−（ＯＣＨ₃）₃｝］₉−Ｈ （ｑ＝約１０）
６３：Ｆ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）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（ＣＦ₃）ＣＦ₂Ｏ）₂−ＣＦ（ＣＦ₃）−ＣＯＮＨ（ＣＨ₂）Ｓｉ（ＯＣ₂Ｈ₅）₃
７７：ＣＦ₃Ｏ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）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）
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：（ＣＦ₃ＣＨ₂）₃Ｓｉ（ＣＨ₂−ＮＨ₂）
１０１：（ＣＦ₃ＣＨ₂）₃Ｓｉ−Ｎ（ＣＨ₃）₂
【００９４】
【化５】

【００９５】
更に、
【００９６】
【化６】

【００９７】
等のシラザン類や、
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
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。
【００９８】
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
【００９９】
【化７】

【０１００】
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。
【０１０１】
前記有機フッ素化合物、有機基を有する有機金属化合物、フッ素原子を有する有機基を有する有機金属化合物を、単独使用または適宜２種以上混合して使用してもよい。
【０１０２】
かかる防汚層を形成する有機フッ素化合物、有機基を有する有機金属化合物、または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ることによって、防汚層（防汚層の表面）の表面エネルギーを低くし、撥水性及び撥油性を兼ね備えた薄膜を得ることが出来る。
【０１０３】
尚、本発明に有機フッ素化合物、有機基を有する有機金属化合物、フッ素原子を有する有機基を有する有機金属化合物が常温、常圧で気体である場合は、混合ガスの構成成分として、そのまま使用出来るので最も容易に本発明の方法を遂行することが出来る。しかし、有機フッ素化合物、有機基を有する有機金属化合物、フッ素原子を有する有機基を有する有機金属化合物が常温・常圧で液体または固体である場合には、加熱、減圧等の方法により気化して使用すればよく、また、適切な溶剤に溶解して用いてもよい。
【０１０４】
本発明の薄膜形成方法は、前述のように、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、放電空間外で、前述の有機金属化合物を含有する薄膜形成ガスと放電空間外で接触させて間接励起ガスとし、間接励起ガスを基材に晒して薄膜を形成するものである。
【０１０５】
放電空間に直接晒した放電ガス（励起ガス）と薄膜形成ガスとを、放電空間外で接触させると、前記薄膜形成ガスが前記放電空間で励起した放電ガスからエネルギーを受け取り、間接的に励起すると推定している。本発明では、薄膜形成ガスをこのようにして処理したものを間接励起ガスと呼ぶ。
【０１０６】
原理は定かでないが、薄膜形成ガスを直接放電空間に晒して用いる場合に比して、非常に高性能に、かつ高速に防汚膜を形成出来ることを本発明者らは見出したものである。
【０１０７】
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圧印加することにより放電を起こす空間である。放電空間外とは、前記放電空間ではない空間のことをいう。
【０１０８】
放電空間の形態は、特に制限は無く、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。また、励起ガスと薄膜形成ガスは接触するように供給し、供給方向は並流でも向流でも、また斜めに交差するように流してもよい。
【０１０９】
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。
【０１１０】
本発明でいう大気圧または大気圧近傍の圧力下とは、２０ｋＰａ〜１１０ｋＰａの圧力下である。本発明において、電圧を印加する電極間の更に好ましい圧力は、７０ｋＰａ〜１４０ｋＰａである。
【０１１１】
図１は、本発明に係るジェット方式の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。
【０１１２】
図１において、大気圧プラズマ放電処理装置１は、主には、第１電極２と第２電極３とが各々対向する様に配置されている対向電極、電圧印加手段４である対向電極間に高周波電界を印加する高周波電源５の他に、図示していないが、放電ガスを放電空間に、薄膜形成ガスを放電空間外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。
【０１１３】
第１電極２と第２電極３とで挟まれ、かつ第一電極上の斜線で示した誘電体を有する領域Ａが放電空間である。この放電空間Ａに放電ガスＧを導入して、放電ガスを励起させる。また、電極が設置してある領域とは別の放電をしない領域に薄膜形成原料を含む薄膜形成ガスＭを導入する。次いで、電極が存在しない放電空間外Ｂの領域で、励起した放電ガスＧ′と、薄膜形成ガスＭとを接触させて間接励起ガスＮとして、この間接励起ガスＮが基材８表面に拡散し、薄膜を形成する。本発明では、励起した放電ガスは基材に直接接触せず、間接励起ガスが基材に接触することにより、励起した放電ガスが基材に直接接触する場合に比較し、基材に対するダメージを遙かに小さく出来る。
【０１１４】
尚、基材８は、支持体のようなシート状の基材のみでなく、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基材へも薄膜形成することが出来る。
【０１１５】
基材８は、例えば、図で示したような回転する多角形の供給装置の一辺上に設置され薄膜形成される。他の辺に他の基材を設置すれば連続的に薄膜形成体を得ることができる。
【０１１６】
本発明の薄膜形成方法においては、例えば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、薄膜形成ガスとを放電空間外の領域で接触させて間接励起ガスとすることにより、長期保存後でも優れた撥水性、撥油性、指紋拭き取り性を有し、かつ耐擦性、耐傷性が良好な防汚層用薄膜を得ることも出来る。
【０１１７】
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７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、チタン、銅、金、銀、白金、ステンレススティール、アルミニウム、鉄等の金属が使えるが、ステンレススティールまたはチタンが好ましい。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出来、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。また封孔処理としては、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。
【０１１８】
また、図１では、一対の対向電極は、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。この一対の対向電極のうち一方の電極（例えば、第１電極２）に高周波電源５が接続され、他方の電極（例えば、第２電極３）には、アース９により接地され、一対の対向電極間に電界を印加出来るように構成されている。
【０１１９】
電圧印加手段４は高周波電源５より、それぞれの電極の金属対に電圧を印加する。本発明に用いる高周波電源としては、特に限定は無い。防汚膜の形成に使用し得る高周波電源としては、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）等を好ましく使用出来る。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。
【０１２０】
本発明の有用な一例であ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、特に限定は無いが、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／ｃｍ²以上であり、好ましくは５０Ｗ／ｃｍ²以下である。
尚、対向電極における電圧の印加面積（ｃｍ²）は、放電が起こる範囲の面積のことを指す。対向電極間に印加する高周波電圧は、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。
【０１２１】
また、本発明においては電極間に２つ以上の高周波電界を印加し、放電空間を形成してもよい。
【０１２２】
本発明において、対向電極間の距離（図１のギャップ１）は、電極の金属母材上の誘電体の厚さ、印加電圧の大きさ、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が好ましく、より好ましくは０．２〜１０ｍｍである。
【０１２３】
本発明に係る薄膜形成前に、基材を放電空間または励起ガスに晒して基材の表面処理を行ってもよい。例えば、原料がアルコキシドの場合、放電空間または励起ガスに晒すことによる親水化処理が好ましく用いられる。また、薄膜形成前に予め基材表面の除電処理を行い、更にゴミ除去を行ってもよい。除電手段及び除電処理後のゴミ除去手段としては、前述装置のところでした手段と同様の手段を採用出来る。図示してないが、除電手段としては、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基材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が出来るが、これらに限定されない。
【０１２４】
本発明に係る薄膜形成方法で処理される基材の材質は、特に限定は無く、プラスチック、金属、陶器、紙、木材、不織布、ガラス板、セラミックス、建築材料等を挙げることが出来、その中でも、基材表面がシリカ等の酸化金属であることが好ましい。また、基材の形態は、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。基材がこのようなプラスチックを支持体とする場合には、その表面に反射防止膜のような金属酸化膜を形成したものが好ましく用いられる。
【０１２５】
図２は、比較のジェット方式の大気圧プラズマ放電処理装置の例を示す断面図である。
【０１２６】
図１で示した一対の対向電極（第一電極２と第２電極３）が、基材８が設置されている側の筒に配置されており、図１とは反対筒側の領域に放電ガスＧを導入して、放電空間Ａにおいてガス励起させる。また、対向電極が設置してある筒と反対側の筒には薄膜形成ガスＭを導入する。次いで、放電空間外Ｂの領域で、励起した放電ガスＧ′と薄膜形成ガスＭとを接触させて間接励起ガスＮとして、この間接励起ガスＮが基材８表面に拡散し薄膜形成される。このような配置の場合、励起した放電ガス及び間接励起ガスが基材上に直接接するため、励起した放電ガスによる基材表面のダメージが進行し易く、高性能で均一な薄膜が得られない。
【０１２７】
図３は、本発明に係る基材への反射防止膜の形成に用いた大気圧プラズマ放電処理装置の一例を示した概略図である。
【０１２８】
図３はプラズマ放電処理装置１３０、ガス供給手段１５０、電圧印加手段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、基材８をプラズマ放電処理をするものである。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ω₁であって高周波電圧Ｖ₁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ω₂であって高周波電圧Ｖ₂をかけるようになっている。
【０１２９】
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。
【０１３０】
尚、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圧（Ｖ₁＞Ｖ₂）を印加できる能力を有しており、周波数はω₁＜ω₂となる能力を有している。また、第１電源、第２電源は必ずしも両方とも使用する必要はなく、どちらか一方だけを使用することもできる。
【０１３１】
基材８は、ガイドロール１６４を経てニップロール１６５で基材に同伴してくる空気等を遮断し、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。処理ガスはガス供給手段１５０であるガス発生装置１５１で発生させた処理ガスＨ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内を処理ガスで充填し、放電処理が行われた処理排ガスＨ′を排気口１５３より排出するようにする。
【０１３２】
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、基材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基材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。尚、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。
【０１３３】
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処理装置の一例を示す概略図である。
【０１３４】
装置は、第１電極２と第２電極３とが対向するように配置されている対向電極、電圧印加手段４である対向電極間に高周波電界を印加する高周波電源５のほかに、図示していないが、ガス供給手段、電極温度調整手段等から構成されている。
【０１３５】
第１電極２と第２電極３とが対向している領域には、放電ガスＧを導入して、放電空間Ａにおいて励起される。そして励起した放電ガスＧ′を基材に晒すことによって、基材８の表面処理を行う。
【０１３６】
図５は、本発明に係る前処理に用いる大気圧プラズマ放電処理装置の別の一例を示す概略図である。
【０１３７】
装置は、第１電極２と第２電極３とが対向するように配置されている対向電極、電圧印加手段４である対向電極間に高周波電界を印加する高周波電源５のほかに、図示していないが、ガス供給手段、電極温度調整手段等から構成されている。
【０１３８】
第１電極２と第２電極３とが対向している領域に、基材８を配置し、放電ガスＧを導入して、放電空間Ａに基材８を晒すことによって、基材８の表面処理を行う。
【０１３９】
【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。
【０１４０】
《薄膜（防汚膜）形成試料の作製》
〔実施例試料１の作製：本発明〕
（大気圧プラズマ放電処理装置）
図１に示す大気圧プラズマ放電処理装置を用いて、１分間かけて、基材８上に防汚膜の製膜を行った。放電ガス導入口１３より導入される放電ガスにはガス種Ａ、薄膜形成ガス導入口１５より導入される薄膜形成ガスにはガス種Ｂを用いた。
【０１４１】
〈ガス種Ａ：放電ガス〉
窒素ガス ９８．５体積％
水素ガス １．５体積％
〈ガス種Ｂ：薄膜形成ガス〉
窒素ガス ９９．９体積％
有機金属化合物（表１記載） ０．１体積％
（エステック社製気化器により、窒素ガス中に表１記載化合物を気化）
〈ガス種供給比及び混合〉
ガス種Ａ：ガス種Ｂ＝２：１（体積比）で供給し、ガス吹き出し口１６を経て放電空間外Ｂで接触させた後、基材表面に供給した。
【０１４２】
電極２、３は、電極にステンレスＳＵＳ３１６を用い、更に、電極の表面にアルミナセラミックスを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ス被膜に塗布し、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５の接続やアース９接地を行った。尚、励起ガス吹き出し口及び薄膜形成ガス吹き出し口のギャップ１，２の間隙は表１に示した。
【０１４３】
高周波電源５には、ハイデン研究所製高周波電源（４０ＫＨｚ）で、７Ｗ／ｃｍ²の放電電力を印加した。
【０１４４】
基材８には、幅１０ｍｍ、長さ１０ｍｍ、厚み０．５ｍｍの日本板硝子製０．５ｔソーダライムガラス（片面研磨）を用いた。
【０１４５】
〔実施例試料２の作製：本発明〕
上記実施例試料１の作製において、ガス種Ａ、ガス種Ｂ、励起ガス側ギャップ１及び薄膜形成ガス側ギャップ２の間隙を下記に示すように変更した以外は同様にして、実施例試料２を作製した。
【０１４６】
〈ガス種Ａ：放電ガス〉
窒素ガス １００体積％
〈ガス種Ｂ：薄膜形成ガス〉
窒素ガス ９９．９体積％
有機金属化合物（表１記載） ０．１体積％
（エステック社製気化器により、窒素ガス中に表１記載化合物を気化）
ギャップ１、２は表１に記載した。
【０１４７】
〔実施例試料３の作製：本発明〕
上記実施例試料２の作製において、ガス種Ａ、ガス種Ｂ、励起ガス側ギャップ１及び薄膜形成ガス側ギャップ２の間隙を下記に示すよう変更した以外は同様にして、実施例試料３を作製した。
【０１４８】
〈ガス種Ａ：放電ガス〉
アルゴンガス ９８．５体積％
水素ガス １．５体積％
〈ガス種Ｂ：薄膜形成ガス〉
アルゴンガス ９９．９体積％
有機金属化合物（表１記載） ０．１体積％
（エステック社製気化器により、アルゴンガス中に表１記載化合物を気化）
ギャップ１、２は表１に記載した。
【０１４９】
高周波電源５はパール工業製高周波電源（１３．５６ＭＨｚ）で７Ｗ／ｃｍ²で印加した。
【０１５０】
〔実施例試料４の作製：本発明〕
実施例試料１で用いた基材を、前処理として下記前処理Ａを施した以外は実施例試料１と同様にして、実施例試料４を作製し同様に評価を行った。
【０１５１】
前処理Ａ：基材を間接励起ガスに晒す前に、図４に記載の第１電極２と第３電極３とが対向するように配置されている構成からなる放電空間に、放電ガスとして窒素：酸素＝９９：１（体積比）を流入し、基材をその励起放電ガスに３秒間晒した。尚、高周波電源として、ハイデン研究所製高周波電源（周波数：４０ｋＨｚ）、放電出力は１０Ｗ／ｃｍ²に設定して行った。
【０１５２】
〔実施例試料５の作製：本発明〕
実施例試料２で用いた基材を、前処理として下記前処理Ｂを施した以外は、実施例試料２と同様にして、実施例試料５を作製し同様に評価を行った。
【０１５３】
前処理Ｂ：基材を間接励起ガスに晒す前に、図５に記載の第１電極２と第２電極３とが対向するように配置されている構成からなる放電空間に、放電ガスとして窒素：酸素＝９９：１（体積比）を流入し、基材をその励起放電ガスに３秒間晒した。尚、高周波電源として、ハイデン研究所製高周波電源（周波数：４０ｋＨｚ）、放電出力は５Ｗ／ｃｍ²に設定して行った
〔実施例試料６の作製：本発明〕
実施例試料１の基材を、下記に示すセルロースエステルフィルム上に大気圧プラズマ法により反射防止層を形成した反射防止フィルムを使用した以外は、実施例試料１と同条件で薄膜形成し、実施例試料６を作製した。
【０１５４】
以上のようにして得られた実施例試料６について、表面比抵抗測定を下記に示す方法で行い、表面比抵抗値が１×１０¹²Ω／□以下であることを確認した。
【０１５５】
（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。
【０１５６】
〔基材の作製〕
（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。
【０１５７】
〈帯電防止層の塗布組成物〉
ダイヤナール（ＢＲ−８８ 三菱レーヨン社製） ０．５質量部
プロピレングリコールモノメチルエーテル ６０質量部
メチルエチルケトン １５質量部
乳酸エチル ６質量部
メタノール ８質量部
導電性ポリマー樹脂
ＩＰ−１６（特開平９−２０３８１０号公報記載） ０．５質量部
（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。
【０１５８】
〈ハードコート層組成物〉
ジペンタエリスリトールヘキサアクリレート単量体 ６０質量部
ジペンタエリスリトールヘキサアクリレート２量体 ２０質量部
ジペンタエリスリトールヘキサアクリレート３量体以上の成分
２０質量部
ジエトキシベンゾフェノン（ＵＶ光開始剤） ２質量部
メチルエチルケトン ５０質量部
酢酸エチル ５０質量部
イソプロピルアルコール ５０質量部
上記組成物を撹拌しながら溶解した。
【０１５９】
（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。
【０１６０】
〈バックコート層塗布組成物〉
アセトン ３０質量部
酢酸エチル ４５質量部
イソプロピルアルコール １０質量部
セルロースジアセテート ０．５質量部
アエロジル２００Ｖ ０．１質量部
（反射防止層の形成）
図３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、高周波電圧１０ｋＶ／ｍｍ及び出力密度１Ｗ／ｃｍ²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、高周波電圧０．８ｋＶ／ｍｍ及び出力密度５．０Ｗ／ｃｍ²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圧は３．７ｋＶ／ｍｍであった。尚、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。
【０１６１】
〈酸化チタン層形成用ガス組成〉
放電ガス：窒素 ９７．９体積％
薄膜形成ガス：テトライソプロポキシチタン ０．１体積％
添加ガス：水素 ２．０体積％
〈酸化珪素層形成用ガス組成〉
放電ガス：窒素 ９８．９体積％
薄膜形成ガス：テトラエトキシシラン ０．１体積％
添加ガス：酸素 １．０体積％
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基材（表１には、これをＴＡＣ−ＡＲと記す）を作製した。尚、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。
【０１６２】
〔比較試料１〜３の作製：比較例〕
図２に示す大気圧プラズマ放電処理装置を用いて、１分間かけて、基材８上に防汚膜の製膜を行った。表１に記載のように放電ガス導入口１３より導入される放電ガスにはガス種Ａ、薄膜形成ガス導入口１５より導入される薄膜形成ガスにはガス種Ｂを用いた。ガス種Ａ、ガス種Ｂ、励起ガス側ギャップ１及び薄膜形成ガス側ギャップ２の間隙、基材を表１に記載のように変更し、実施例試料１と同様にして薄膜形成し、比較試料１〜３を得た。
【０１６３】
各試料の薄膜形成方法の主な特徴を、表１に示す。
【０１６４】
【表１】

【０１６５】
次いで得られた試料について、下記に示す評価を実施した。
《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、防汚膜表面と水、及びヘキサデカンとの接触角を測定した。尚、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。
【０１６６】
〔拭き取り容易性の評価：油性インク〕
油性インク（ゼブラ社製 マッキー極細黒）で線を書き、柔らかい布（旭化成社製 ＢＥＭＣＯＴ Ｍ−３ ２５０ｍｍ×２５０ｍｍ）で５往復させて拭き取り、インクの残り状況を目視観察し、下記の基準に則り拭き取り容易性の評価を行った。
【０１６７】
◎：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
×：油性インクが基材表面に残っている
また、油性インクの拭き取りを２０回繰り返し、２０回目に上記の評価を実施した。
【０１６８】
〔灰付着試験〕
製膜した基材上をゴムロールで１０回転転がし、煙草の灰を近づけて、基材にくっつくかどうか試験した。
【０１６９】
◎：１ｃｍまで近づけても全く付着しない
○：１〜１０ｃｍまで近づけると付着する
×：１０ｃｍ以上でも付着する
以上により得られた結果を、表２に示す。
【０１７０】
【表２】

【０１７１】
表２より明らかなように本発明の薄膜形成方法及び薄膜製造装置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（接触角）、撥油性（拭き取り容易性の評価）が良好であることが分かる。
【０１７２】
また、帯電防止機能が付与されている本発明に係る実施例試料６は灰の付着がしにくくなっており、ゴミ付着に対して良好な性能を有することが分かった。
【０１７３】
【発明の効果】
本発明により、基材への影響が無く、優れた撥水性、撥油性を有する薄膜製造装置、それを用いた薄膜形成方法及び薄膜形成体を提供することが出来た。
【図面の簡単な説明】
【図１】本発明に係るジェット方式の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】比較のジェット方式の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３】基材上への反射防止膜の形成に用いた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】本発明に係る前処理に用いる大気圧プラズマ放電処理装置の一例を示す概略図である。
【図５】本発明に係る前処理に用いる大気圧プラズマ放電処理装置の別の一例を示す概略図である。
【符号の説明】
１ 大気圧プラズマ放電処理装置
２ 第１電極
３ 第２電極
４ 電圧印加手段
５ 高周波電源
７ 誘電体
８ 基材
９ アース
１３ 放電ガス導入口
１５ 薄膜形成ガス導入口
１６ ガス吹き出し口
Ｇ 放電ガス
Ｇ′ 励起した放電ガス
Ｍ 薄膜形成ガス
Ｎ 間接励起ガス
Ａ 放電空間
Ｂ 放電空間外
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 電圧印加手段
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
Ｈ 処理ガス
Ｈ′ 処理排ガス
Ｐ 送液ポンプ[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a thin film forming method.as well asThin film production equipmentIn placeMore specifically, a thin film forming method that reduces damage to the substrate as much as possible without directly contacting the excited discharge gas with the substrate.as well asThin film production equipmentIn placeRelated.
[0002]
[Prior art]
Conventionally, when a highly functional thin film such as an antireflection film, an antifouling film, an electrode film, a dielectric protective film, a semiconductor film, a transparent conductive film, an abrasion resistant film, or a barrier film is provided on a substrate, dry film formation As a method, a film forming method using a vacuum space such as a sputtering method, a vacuum vapor deposition method, a vacuum plasma CVD method, and an ion plating method has been mainly used.
[0003]
In the film forming method using such a vacuum space, a large-scale vacuum facility is required, so that the facility cost is high. Furthermore, it is unsuitable for continuous production and has a problem of low productivity.
[0004]
As a method for overcoming the disadvantages of using these vacuum spaces, Japanese Patent Application Laid-Open No. 61-238961, etc. discloses an atmospheric pressure plasma processing method in which discharge plasma is generated under atmospheric pressure and a high processing effect can be obtained by the discharge plasma. Proposed. The atmospheric pressure plasma treatment method can treat the substrate surface with a uniform composition, physical properties, and distribution. In addition, since the treatment can be performed under atmospheric pressure or pressure near atmospheric pressure, vacuum equipment is not required and equipment costs can be reduced. Furthermore, it is suitable for continuous production, and productivity can be improved.
[0005]
As an application example of this atmospheric pressure plasma processing method, a technique is disclosed in which a thin film forming gas is plasma-excited to form a thin film on a substrate (see, for example, Patent Documents 1 to 10).
[0006]
In such a thin film forming apparatus using atmospheric pressure plasma, a discharge gas and a thin film forming gas exist between the electrodes, and discharge plasma is generated between the electrodes. There are challenges. In particular, in a thin film manufacturing apparatus using atmospheric pressure plasma, the gap between the electrodes is often narrow, and the discharge or gas flow becomes non-uniform due to the deposition of the film forming material on the electrodes. There is a case where the gap is clogged.
[0007]
On the other hand, without using a thin film forming gas between the electrodes, an excitation gas generated by atmospheric pressure plasma discharge between the electrodes and a thin film forming gas not exposed to the atmospheric pressure plasma discharge are used as a base material. A technique for forming a thin film by spraying is disclosed (for example, see Patent Documents 11 and 12).
[0008]
[Patent Document 1]
JP-A-11-133205
[0009]
[Patent Document 2]
JP-A-11-61406
[0010]
[Patent Document 3]
JP 2000-147209 A
[0011]
[Patent Document 4]
JP 2000-121804 A
[0012]
[Patent Document 5]
JP 2001-98093 A
[0013]
[Patent Document 6]
JP 2001-185398 A
[0014]
[Patent Document 7]
JP 2002-110588 A
[0015]
[Patent Document 8]
Japanese Patent Laid-Open No. 2003-3266
[0016]
[Patent Document 9]
JP 2003-41372 A
[0017]
[Patent Document 10]
JP 2003-98303 A
[0018]
[Patent Document 11]
JP-A-9-59777
[0019]
[Patent Document 12]
JP 2003-49272 A
[0020]
[Problems to be solved by the invention]
These methods are one of the effective means for forming a high-performance thin film, and are particularly effective for forming an antifouling film using an organic metal compound having an organic group having a fluorine atom as a raw material. It is.
[0021]
However, in these methods, the excited discharge gas and the thin film forming gas are sprayed on the substrate, respectively, or the thin film forming gas is sprayed on the substrate while being in contact with the excited discharge gas. This is not necessarily a preferable method because it may be sprayed onto the material and as a result damage the substrate.
[0022]
  Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a thin film forming method in which damage to the substrate is reduced as much as possible without directly contacting the excited discharge gas with the substrate.as well asThin film production equipmentPlaceIt is to provide.
[0023]
[Means for Solving the Problems]
The above object of the present invention can be achieved by the following constitution.
[0024]
1. A discharge gas is introduced into a discharge space formed by applying a high-frequency voltage between electrodes facing each other under a pressure at or near atmospheric pressure, and the excited discharge gas is not directly brought into contact with the substrate. In addition,Organometallic compound having an organic group having a fluorine atomA thin film forming gas containing the substrate is sandwiched between the excited discharge gas and the thin film forming gas is indirectly excited by bringing the thin film forming gas into contact with the excited discharge gas outside the discharge space, and the substrate is exposed to the indirectly excited gas. The thin film formation method characterized by forming a thin film on this base material by this.
[0028]
2. Including an organometallic compound having an organic group having a fluorine atom so that a discharge gas is introduced into a discharge space under atmospheric pressure or a pressure near atmospheric pressure to be excited, and the excited discharge gas is not directly brought into contact with a substrate. By sandwiching a thin film forming gas between the substrate and the excited discharge gas, indirect excitation by bringing the thin film forming gas into contact with the excited discharge gas outside the discharge space, and exposing the substrate to the indirectly excited gas. A thin film forming method comprising forming a thin film on the substrate.
3. The discharge gas contains nitrogen and / or a rare gas.Or 2A method for forming a thin film according to 1.
[0029]
4. The above-mentioned 1 to 3, wherein the surface of the substrate contains an inorganic compound.3The thin film formation method of any one of claim | items.
[0030]
5. The main component of the surface of the substrate is a metal oxide,4The thin film formation method of any one of claim | items.
[0033]
6. Excited by introducing high-frequency voltage applying means for applying a high-frequency voltage between opposing electrodes under a pressure near or at atmospheric pressure, and introducing a discharge gas into the discharge space where the voltage is applied between the electrodes by the applying means So that the excited discharge gas is not in direct contact with the substrate,Organometallic compound having an organic group having a fluorine atomA thin film forming gas containing the substrate is sandwiched between the excited discharge gas and the excited discharge gas causes the thin film forming gas to indirectly excite the thin film forming gas, thereby forming a thin film on the substrate. A thin film manufacturing apparatus characterized in that
[0035]
7. The electrode is characterized in that at least one of the electrodes is covered with a dielectric.6The thin film manufacturing apparatus according to the item.
[0036]
8. The means for sandwiching the thin film forming gas between the substrate and the excited discharge gas contacts the means for supplying the thin film forming gas so as to exist on the surface of the substrate, and the excited discharge gas and the thin film forming gas. Characterized in that it comprises means for supplying6Or7The thin film manufacturing apparatus according to any one of the above.
[0039]
9. The surface specific resistance value is 1 × 10 at 23 ° C. and 55% RH.¹²Ω / □ or less5The thin film formation method of any one of these.
[0040]
Details of the present invention will be described below.
In the thin film forming method of the present invention, a discharge gas is introduced into a discharge space formed by applying a high-frequency voltage between opposing electrodes under a pressure of atmospheric pressure or near atmospheric pressure, and the excited discharge gas is excited. To avoid direct contact with the substrate.Organometallic compound having an organic group having a fluorine atomA thin film forming gas containing the substrate is sandwiched between the excited discharge gas and the thin film forming gas is indirectly excited by bringing the thin film forming gas into contact with the excited discharge gas outside the discharge space, and the substrate is exposed to the indirectly excited gas. Thus, a thin film is formed on the substrate. That is, the thin film forming gas and the indirectly excited gas are in direct contact with the substrate, and the discharge gas excited by the high-frequency voltage applying means does not directly contact the substrate. Therefore, the main feature is that the base material is less damaged by the excited discharge gas, and a high-performance and uniform thin film is formed.
[0041]
First, the discharge gas and the thin film forming gas according to the present invention will be described.
The gas used is basically a discharge gas containing no raw materials.Organometallic compound having an organic group having a fluorine atomA gas for forming a thin film, and an auxiliary gas for accelerating or controlling the reactivity may be used. A supply device and a supply method of the discharge gas and the thin film forming gas will be described later.
[0042]
A discharge gas is a gas that can cause a plasma discharge, and is a gas that itself functions as a medium for transferring energy, and is a gas necessary for generating a plasma discharge. Examples of the discharge gas include nitrogen, rare gas, air and the like, and these may be used alone as a discharge gas or may be used in combination. Examples of the rare gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and the like. In the present invention, the discharge gas is preferably nitrogen, argon or helium. It is preferable to contain 70-100 volume% of discharge gas amount with respect to the total gas amount supplied in discharge space. Note that hydrogen, oxygen, hydrocarbons, nitrogen oxides, ammonia, or moisture may be used as an auxiliary gas in the discharge gas by mixing 0.001% to 30% by volume with respect to the gas.
[0043]
The thin film forming gas receives the energy from the excited discharge gas and activates itself by itself to form a thin film chemically on the substrate.Organometallic compound having an organic group having a fluorine atomIt is a gas containing.
[0044]
The film forming gas isOrganometallic compound having an organic group having a fluorine atomHowever, it is preferable to contain at least one selected from nitrogen, rare gas, oxygen, hydrogen, hydrocarbon and nitrogen oxide in addition to the raw material. These may be used alone as a thin film forming gas, or may be used in combination. Examples of the rare gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and the like.
[0045]
Examples of the raw material contained in the thin film forming gas useful in the present invention include an organic metal compound, a metal halide, an organic fluorine compound, and the like, which are useful for forming a functional thin film.
[0046]
More specifically, when an organometallic compound or a metal halide is added to the raw material, for example, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, A metal selected from Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu can be included. Among them, it contains at least one element selected from Sn, In, Al, Ti, Zn, Si, Sb, Mg, Ba, Mo, V, Nb, P, B, W, Cs, Zr, Ga, and As. It is preferable. In the case of an organometallic compound, those selected from metal alkoxides, alkylated metals, and metal complexes are preferred.
[0047]
Various highly functional thin films can be obtained by appropriately selecting the above or other raw materials and forming the thin film. One example is shown below, but the present invention is not limited to this.
[0048]
Electrode film Au, Al, Ag, Ti, Ti, Pt, Mo, Mo-Si
Dielectric protective film SiO₂, SiO, Si_ThreeN_Four, Al₂O_Three, Al₂O_Three, Y₂O_Three
Transparent conductive film In₂O_Three, SnO₂ZnO
Electrochromic film WO_Three, IrO₂, MoO_Three, V₂O_Five
Fluorescent film ZnS, ZnS + ZnSe, ZnS + CdS
Magnetic recording film Fe-Ni, Fe-Si-Al, γ-Fe₂O_Three, Co, Fe_ThreeO_Four, Cr, SiO₂, Al₂O_Three
Superconductive film Nb, Nb-Ge, NbN
Solar cell film a-Si, Si
Reflective film Ag, Al, Au, Cu
Selective absorption membrane ZrC-Zr
Selective permeable membrane In₂O_Three, SnO₂
Anti-reflective coating SiO₂TiO₂, SnO₂, Ta₂O_Five
Shadow mask Cr
Abrasion resistant film Cr, Ta, Pt, TiC, TiN
Corrosion resistant film Al, Zn, Cd, Ta, Ti, Cr
Heat resistant film W, Ta, Ti
Lubricating film MoS₂
Decorative film Cr, Al, Ag, Au, TiC, Cu
For example, in the formation of the antireflection film, examples of the raw material for forming the low refractive index layer include organic silicon compounds, silicon hydrogen compounds, and silicon halide compounds. Examples of the organic silicon compounds include tetraethylsilane, tetramethyl, and the like. Silane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanediacetacetonate, methyltrimethoxysilane, methyltriethoxysilane, ethyl Examples of the silicon hydride compound such as triethoxysilane include tetrahydrogen silane and hexahydrogen disilane, and examples of the halogenated silicon compound include tetrachlorosilane, methyltrichlorosilane, and diethyldichlorosilane. It can, both can be preferably used in the present invention.
[0049]
In the formation of the antireflection film, a tin compound is used as a metal compound used as a raw material for forming a medium refractive index layer or a high refractive index layer. Preferred tin compounds include organic tin compounds, tin hydrogen compounds, tin halides, and the like. Examples of the organic tin compound include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, and triisopropylethoxy. Tin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyl Tin diacetacetonate, etc., tin hydride, etc., halogen As tin, tin chloride, can be mentioned tin tetrachloride, etc., all of which it can be used preferably in the present invention. Two or more of these reactive gases may be mixed and used at the same time. The tin oxide layer thus formed has a surface specific resistance value of 1 × 10.¹²Since it can be lowered to Ω / □ or less, it is also useful as an antistatic layer.
[0050]
In addition, the titanium compound used as a raw material for the reaction gas for forming the high refractive index layer in the antireflection film includes an organic titanium compound, a titanium hydrogen compound, a titanium halide, etc. Examples of the organic titanium compound include triethyl titanium. , Trimethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyldimethoxy Titanium hydrogen compound such as titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, tetradimethylamino titanium, dimethyl titanium diacetoacetonate, ethyl titanium triacetoacetonate, etc. Mono-titanium hydride, Jichitan hydrogen compound such as titanium halide, titanium trichloro, the titanium tetrachloride and the like. Alternatively, as the high refractive index layer, alkoxy tantalum such as tetraisopropoxy tantalum can be cited as a raw material for forming the tantalum oxide layer, and any of them can be preferably used in the present invention. These raw materials can be used by mixing two or more kinds at the same time, but are not limited thereto.
[0051]
Furthermore, a typical example of thin film formation is an article having a highly functional thin film such as an antifouling film. In the present invention, a thin film forming gas for producing an antifouling film will be described as a representative example.
[0052]
As the thin film forming gas for producing the antifouling film according to the present invention, an organic fluorine compound or an organic metal compound in which an organic group is directly bonded to a metal is used, and an organic metal compound having an organic group having a fluorine atom is particularly useful. is there.
[0053]
As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like can be preferably used. Examples of the fluorocarbon gas include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like. Examples of the fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, and trifluoropropylene. Further, for example, halogenated fluorocarbon compounds such as chlorotrifluoromethane, chlorodifluoromethane, dichlorotetrafluorocyclobutane, fluoroalcohols such as trifluoromethanol and pentafluoroethanol, fluorine such as trifluoroacetic acid and pentafluoropropionic acid Organic fluorine compounds such as fluorinated ketones such as fluorinated fatty acids and hexafluoroacetone can be used, but are not limited thereto. These compounds may have a fluorinated ethylenically unsaturated group in the molecule.
[0054]
In the organometallic compound having an organic group used in the present invention, examples of the organic group include an organic group containing an alkyl group, an alkenyl group, an aryl group, etc., and an organometallic compound having an organic group used in the present invention. These organic groups are directly bonded to metal atoms, for example, metals such as silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium, lanthanum, iron, neodymium, copper, gallium, and halfnium. It is an organometallic compound. 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 organic. It only needs to have a group, and the position is not limited.
[0055]
For example, silicon compounds having an organic group include methyltrichlorosilane, methyldichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, ethyldichlorosilane, n-propyltrichlorosilane, ethylmethyldichlorosilane, trimethylbromosilane, trimethylchlorosilane, n -Butyltrichlorosilane, i-butyltrichlorosilane, diethyldichlorosilane, methylpropyldichlorosilane, tetramethylsilane, diethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, pentyltrichlorosilane, butylmethyldichlorosilane, trimethyl Methoxysilane, ethyltrimethoxysilane, hexyltrichlorosilane, triethylchlorosilane, dimethyldiethoxysila , Propyltrimethoxysilane, heptyltrichlorosilane, hexamethyldichlorosilane, butyltrimethoxysilane, methyltriethoxysilane, octyltrichlorosilane, heptylmethyldichlorosilane, dibutyldichlorosilane, diethyldiethoxylane, ethyltriethoxysilane, tripropyl Chlorosilane, hexyltrimethoxysilane, propyltriethoxysilane, decyltrichlorosilane, dimethyloctylchlorosilane, pentyltriethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, octyltriethoxysilane, dodecylmethyldiethoxysilane, dodecyltriethoxysilane , Octadecylmethyldiethoxysilane, octadecyltriethoxysilane, 1,1,3,3-tetramethyl Rudisiloxane, 1,1,3,3-tetramethyldisilazane, hexamethyldisiloxane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3- Divinyl-1,1,3,3-tetramethyldisilazane, hexaethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisilazane, hexapropyldisiloxane, 1,1,3 3,5,5-hexamethyltricytoxane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, hexaethylcyclosiloxane, octamethylcyclotetrasiloxane, 1,1,1,3,5 , 7,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane, decamethyltetrasiloxane Any of these can be preferably used in the present invention.
[0056]
In the present invention, an organic metal compound containing a fluorine atom in the organic group, that is, having an organic group having a fluorine atom is preferable, and a compound represented by the following general formula (1) can be preferably used. .
[0057]
[Chemical 1]

[0058]
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.
[0059]
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.
[0060]
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.
[0061]
Of the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine 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. Preferred is an alkoxy group.
[0062]
Of the metal atoms represented by M, Si and Ti are preferable, and Si is more preferable.
[0063]
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.
[0064]
In addition, the organic group having a fluorine atom, or other R₁~ R₆The group represented by¹R²R^ThreeM- (M represents the metal atom, R¹, R², R^ThreeEach 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. It may be a structure having a plurality of metal atoms further substituted by 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.
[0065]
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.
[0066]
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.
[0067]
X is a simple bond or a divalent group. The divalent group is a group such as —O—, —S—, —NR— (R represents a hydrogen atom or an alkyl group), —CO—, and the like. , -CO-O-, -CONH-, -SO₂NH-, -SO₂-O-, -OCONH-,
[0068]
[Chemical 2]

[0069]
Represents a group such as
k represents an integer of 0 to 50, preferably 0 to 30.
[0070]
In addition to the fluorine atom, other substituents may be substituted in Rf, and examples of the substitutable group include R₁~ R₆Examples thereof include the same groups as those exemplified as the substituent in the above. 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-.
[0071]
Of the compounds represented by the general formula (1), a compound represented by the following general formula (2) is preferable.
[0072]
General formula (2)
[Rf-X- (CH₂)_k]_q-M (R_Ten)_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. R_TenRepresents 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~ R₆The substituent may be substituted with the same groups as those described 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 ≧ 2_TenMay be linked to form a ring.
[0073]
Of the general formula (2), more preferred are compounds represented by the following general formula (3).
[0074]
General formula (3)
Rf-X- (CH₂)_k-M (OR₁₂)_Three
Here, Rf, X and k are synonymous with those 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.
[0075]
In the present invention, another preferred example of the organometallic compound having a fluorine atom includes a compound represented by the following general formula (4).
[0076]
[Chemical Formula 3]

[0077]
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.
[0078]
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 (5).
[0079]
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 the general formula (F), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, 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.
[0080]
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).
[0081]
General formula (6)
R^f1(OC_ThreeF₆)_m1-O- (CF₂)_n1-(CH₂)_p1-Z- (CH₂)_q1-Si- (R²)_Three
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.
[0082]
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 -CF_Three, -C₂F_Five, -C_ThreeF₇Etc. are preferred.
[0083]
R²Examples of the hydrolyzable group that can be introduced into the group include -Cl, -Br, -I, and -OR.¹¹, -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, —OCH_Three, -OC₂H_Five, -OC_ThreeH₇, -OCOCH_ThreeAnd -NH₂Is preferred.
[0084]
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.
[0085]
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 (7).
[0086]
[Formula 4]

[0087]
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 trifluoro Methyl group, R^{twenty one}Is a hydrolyzable group, R^{twenty two}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 are integers of 0 to 2, and p is 1 to 2. Represents an integer of 10.
[0088]
In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably CF_ThreeGroup, C₂F_FiveGroup, C_ThreeF₇It is a group. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms.
[0089]
R^{twenty one}As the hydrolyzable group, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, R^{twenty three}O group, R^{twenty three}COO group, (R^{twenty four})₂C = C (R^{twenty three}) CO group, (R^{twenty three})₂C = NO group, R^{twenty five}C = NO group, (R^{twenty four})₂N group and R^{twenty three}CONR^{twenty four}Groups are preferred. Where R^{twenty three}Is 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, R^{twenty four}Is usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a hydrogen atom or an alkyl group, R^{twenty five}Is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. More preferably, a chlorine atom, CH_ThreeO group, C₂H_FiveO group, C_ThreeH₇O group.
[0090]
R^{twenty two}Is a hydrogen atom or an inert monovalent organic group, preferably a monovalent hydrocarbon group usually 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~ 1x10^FiveAnd preferably 1 × 10^Three~ 1x10^FourIt is.
[0091]
As a preferable structure of the silane compound represented by the general formula (7), Rf is C_ThreeF₇A 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.
[0092]
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.
[0093]
1: (CF_ThreeCH₂CH₂)_FourSi
2: (CF_ThreeCH₂CH₂)₂(CH_Three)₂Si
3: (C₈F₁₇CH₂CH₂) Si (OC₂H_Five)_Three
4: CH₂= CH₂Si (CF_Three)_Three
5: (CH₂= CH₂COO) Si (CF_Three)_Three
6: (CF_ThreeCH₂CH₂)₂SiCl (CH_Three)
7: C₈F₁₇CH₂CH₂Si (Cl)_Three
8: (C₈F₁₇CH₂CH₂)₂Si (OC₂H_Five)₂
9: CF_ThreeCH₂CH₂Si (OCH_Three)_Three
10: CF_ThreeCH₂CH₂SiCl_Three
11: CF_Three(CF₂)_ThreeCH₂CH₂SiCl_Three
12: CF_Three(CF₂)_FiveCH₂CH₂SiCl_Three
13: CF_Three(CF₂)_FiveCH₂CH₂Si (OCH_Three)_Three
14: CF_Three(CF₂)₇CH₂CH₂SiCl_Three
15: CF_Three(CF₂)₇CH₂CH₂Si (OCH_Three)_Three
16: CF_Three(CF₂)₈CH₂Si (OC₂H_Five)_Three
17: CF_Three(CH₂)₂Si (OC₂H_Five)_Three
18: CF_Three(CH₂)₂Si (OC_ThreeH₇)_Three
19: CF_Three(CH₂)₂Si (OC_FourH₉)_Three
20: CF_Three(CF₂)_Five(CH₂)₂Si (OC₂H_Five)_Three
21: CF_Three(CF₂)_Five(CH₂)₂Si (OC_ThreeH₇)_Three
22: CF_Three(CF₂)₇(CH₂)₂Si (OC₂H_Five)_Three
23: CF_Three(CF₂)₇(CH₂)₂Si (OC_ThreeH₇)_Three
24: CF_Three(CF₂)₇(CH₂)₂Si (OCH_Three) (OC_ThreeH₇)₂
25: CF_Three(CF₂)₇(CH₂)₂Si (OCH_Three)₂OC_ThreeH₇
26: CF_Three(CF₂)₇(CH₂)₂SiCH_Three(OCH_Three)₂
27: CF_Three(CF₂)₇(CH₂)₂SiCH_Three(OC₂H_Five)₂
28: CF_Three(CF₂)₇(CH₂)₂SiCH_Three(OC_ThreeH₇)₂
29: (CF_Three)₂CF (CF₂)₈(CH₂)₂Si (OCH_Three)_Three
30: C₇F₁₅CONH (CH₂)_ThreeSi (OC₂H_Five)_Three
31: C₈F₁₇SO₂NH (CH₂)_ThreeSi (OC₂H_Five)_Three
32: C₈F₁₇(CH₂)₂OCONH (CH₂)_ThreeSi (OCH_Three)_Three
33: CF_Three(CF₂)₇(CH₂)₂Si (CH_Three) (OCH_Three)₂
34: CF_Three(CF₂)₇(CH₂)₂Si (CH_Three) (OC₂H_Five)₂
35: CF_Three(CF₂)₇(CH₂)₂Si (CH_Three) (OC_ThreeH₇)₂
36: CF_Three(CF₂)₇(CH₂)₂Si (C₂H_Five) (OCH_Three)₂
37: CF_Three(CF₂)₇(CH₂)₂Si (C₂H_Five) (OC_ThreeH₇)₂
38: CF_Three(CH₂)₂Si (CH_Three) (OCH_Three)₂
39: CF_Three(CH₂)₂Si (CH_Three) (OC₂H_Five)₂
40: CF_Three(CH₂)₂Si (CH_Three) (OC_ThreeH₇)₂
41: CF_Three(CF₂)_Five(CH₂)₂Si (CH_Three) (OCH_Three)₂
42: CF_Three(CF₂)_Five(CH₂)₂Si (CH_Three) (OC_ThreeH₇)₂
43: CF_Three(CF₂)₂O (CF₂)_Three(CH₂)₂Si (OC_ThreeH₇)_Three
44: C₇F₁₅CH₂O (CH₂)_ThreeSi (OC₂H_Five)_Three
45: C₈F₁₇SO₂O (CH₂)_ThreeSi (OC₂H_Five)_Three
46: C₈F₁₇(CH₂)₂OCHO (CH₂)_ThreeSi (OCH_Three)_Three
47: CF_Three(CF₂)_FiveCH (C_FourH₉) CH₂Si (OCH_Three)_Three
48: CF_Three(CF₂)_ThreeCH (C_FourH₉) CH₂Si (OCH_Three)_Three
49: (CF_Three)₂(P-CH_Three-C₆H_FiveCOCH₂CH₂CH₂Si (OCH_Three)_Three
50: CF_ThreeCO-O-CH₂CH₂CH₂Si (OCH_Three)_Three
51: CF_Three(CF₂)_ThreeCH₂CH₂Si (CH_Three) Cl
52: CF_ThreeCH₂CH₂(CH_Three) Si (OCH_Three)₂
53: CF_ThreeCO-O-Si (CH_Three)_Three
54: CF_ThreeCH₂CH₂Si (CH_Three) Cl₂
55: (CF_Three)₂(P-CH_Three-C₆H_FiveCOCH₂CH₂Si (OCH_Three)_Three
56: (CF_Three)₂(P-CH_Three-C₆H_FiveCOCH₂CH₂Si (OC₆H_Five)_Three
57: (CF_ThreeC₂H_Four) (CH_Three)₂Si-O-Si (CH_Three)_Three
58: (CF_ThreeC₂H_Four) (CH_Three)₂Si-O-Si (CF_ThreeC₂H_Four) (CH_Three)₂59: CF_Three(OC_ThreeF₆)_{twenty four}-O- (CF₂)₂-CH₂-O-CH₂Si (OCH_Three)_Three
60: CF_ThreeO (CF (CF_ThreeCF₂O)_mCF₂CONHC_ThreeH₆Si (OC₂H_Five)_Three  (M = 11-30),
61: (C₂H_FiveO)_ThreeSiC_ThreeH₆NHCOCF₂O (CF₂O)_n(CF₂CF₂O)_pCF₂CONHC_ThreeH₆Si (OC₂H_Five)_Three  (N / p = about 0.5, number average molecular weight = about 3000)
62: C_ThreeF₇-(OCF₂CF₂CF₂) Q-O- (CF₂)₂-[CH₂CH {Si- (OCH_Three)_Three}]₉-H (q = about 10)
63: F (CF (CF_ThreeCF₂O)₁₅CF (CF_Three) CONHCH₂CH₂CH₂Si (OC₂H_Five)_Three
64: F (CF₂)_Four[CH₂CH (Si (OCH_Three)_Three]]_2.02OCH_Three
65: (C₂H_FiveO)_ThreeSiC_ThreeH₆NHCO- [CF₂(OC₂F_Four)_Ten(OCF₂)₆OCF₂] -CONHC_ThreeH₆Si (OC₂H_Five)_Three
66: C_ThreeF₇(OC_ThreeF₆)_{twenty four}O (CF₂)₂CH₂OCH₂Si (OCH_Three)_Three
67: CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSi (OCH_Three)_Three
68: (CF_Three)₂CF (CF₂)₆CH₂CH₂SiCH_Three(OCH_Three)₂
69: CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂
70: CF_Three(CF₂)_Five(C₆H_Four) C₂H_FourSi (OC₂H_Five)_Three
71: CF_Three(CF₂)_ThreeC₂H_FourSi (NCO)_Three
72: CF_Three(CF₂)_FiveC₂H_FourSi (NCO)_Three
73: C₉F₁₉CONH (CH₂)_ThreeSi (OC₂H_Five)_Three
74: C₉F₁₉CONH (CH₂)_ThreeSiCl_Three
75: C₉F₁₉CONH (CH₂)_ThreeSi (OC₂H_Five)_Three
76: C_ThreeF₇O (CF (CF_ThreeCF₂O)₂-CF (CF_Three) -CONH (CH₂) Si (OC₂H_Five)_Three
77: CF_ThreeO (CF (CF_ThreeCF₂O)₆CF₂CONH (CH₂)_ThreeSiOSi (OC₂H_Five)₂(CH₂)_ThreeNHCOCF₂(OCF₂CF (CF_Three))₆OCF_Three
78: C_ThreeF₇COOCH₂Si (CH_Three)₂OSi (CH_Three)₂CH₂OCOC_ThreeF₇
79: CF_Three(CF₂)₇CH₂CH₂O (CH₂)_ThreeSi (CH_Three)₂OSi (CH_Three)₂(CH₂)_ThreeOCH₂CH₂(CF₂)₇CF_Three
80: CF_Three(CF₂)_FiveCH₂CH₂O (CH₂)₂Si (CH_Three)₂OSi (CH_Three)₂(OC₂H_Five)
81: CF_Three(CF₂)_FiveCH₂CH₂O (CH₂)₂Si (CH_Three)₂OSi (CH_Three) (OC₂H_Five)₂
82: CF_Three(CF₂)_FiveCH₂CH₂O (CH₂)₂Si (CH_Three)₂OSi (CH_Three)₂OSi (CH3)₂(OC₂H_Five)
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: (CF_ThreeCH₂)_ThreeSi (CH₂-NH₂)
101: (CF_ThreeCH₂)_ThreeSi-N (CH_Three)₂
[0094]
[Chemical formula 5]

[0095]
Furthermore,
[0096]
[Chemical 6]

[0097]
Silazanes such as
106: CF_ThreeCH₂-CH₂TiCl_Three
107: CF_Three(CF₂)_ThreeCH₂CH₂TiCl_Three
108: CF_Three(CF₂)_FiveCH₂CH₂Ti (OCH_Three)_Three
109: CF_Three(CF₂)₇CH₂CH₂TiCl_Three
110: Ti (OC_ThreeF₇)_Four
111: (CF_ThreeCH₂-CH₂O)_ThreeTiCl_Three
112: (CF_ThreeC₂H_Four) (CH_Three)₂Ti-O-Ti (CH_Three)_Three
Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organometallic compounds as follows.
[0098]
113: CF_Three(CF₂)_ThreeCH₂CH₂O (CH₂)_ThreeGeCl
114: CF_Three(CF₂)_ThreeCH₂CH₂OCH₂Ge (OCH_Three)_Three
115: (C_ThreeF₇O)₂Ge (OCH_Three)₂
116: [(CF_Three)₂CHO]_FourGe
117: [(CF_Three)₂CHO]_FourZr
118: (C_ThreeF₇CH₂CH₂)₂Sn (OC₂H_Five)₂
119: (C_ThreeF₇CH₂CH₂) Sn (OC₂H_Five)_Three
120: Sn (OC_ThreeF₇)_Four
121: CF_ThreeCH₂CH₂In (OCH_Three)₂
122: In (OCH₂CH₂OC_ThreeF₇)_Three
123: Al (OCH₂CH₂OC_ThreeF₇)_Three
124: Al (OC_ThreeF₇)_Three
125: Sb (OC_ThreeF₇)_Three
126: Fe (OC_ThreeF₇)_Three
127: Cu (OCH₂CH₂OC_ThreeF₇)₂
128: C_ThreeF₇(OC_ThreeF₆)_{twenty four}O (CF₂)₂CH₂OCH₂Si (OCH_Three)_Three
[0099]
[Chemical 7]

[0100]
The compounds mentioned in these specific examples are 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. MoI. 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 and 2000-144097, and the like, or a synthesis method based thereon.
[0101]
You may use the said organic fluorine compound, the organometallic compound which has an organic group, and the organometallic compound which has an organic group which has a fluorine atom individually or in mixture of 2 or more types.
[0102]
By using an organic fluorine compound, an organic metal compound having an organic group, or an organic metal compound having an organic group having a fluorine atom, the surface energy of the antifouling layer (the surface of the antifouling layer) is reduced. A thin film having both water repellency and oil repellency can be obtained.
[0103]
In the present invention, when the organic fluorine compound, the organic metal compound having an organic group, or the organic metal compound having an organic group having a fluorine atom is a gas at normal temperature and normal pressure, it can be used as it is as a component of the mixed gas. Therefore, the method of the present invention can be performed most easily. However, when the organofluorine compound, the organometallic compound having an organic group, or the organometallic compound having an organic group having a fluorine atom is liquid or solid at room temperature and normal pressure, it is vaporized by a method such as heating or decompression. What is necessary is just to use, and you may melt | dissolve in a suitable solvent and use it.
[0104]
As described above, the thin film forming method of the present invention introduces and excites a discharge gas into the discharge space under atmospheric pressure or a pressure close to atmospheric pressure, and forms the thin film containing the aforementioned organometallic compound outside the discharge space. The gas is brought into contact with the outside of the discharge space to form an indirect excitation gas, and the thin film is formed by exposing the indirect excitation gas to the substrate.
[0105]
When the discharge gas (excitation gas) directly exposed to the discharge space is brought into contact with the thin film forming gas outside the discharge space, the thin film forming gas receives energy from the discharge gas excited in the discharge space and is indirectly excited. Estimated. In this invention, what processed the thin film formation gas in this way is called indirect excitation gas.
[0106]
Although the principle is not clear, the present inventors have found that the antifouling film can be formed at a very high performance and at a high speed as compared with the case where the thin film forming gas is directly exposed to the discharge space. .
[0107]
In the present invention, the discharge space is a space that 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 a voltage. The term “outside the discharge space” means a space that is not the discharge space.
[0108]
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. Further, the excitation gas and the thin film forming gas may be supplied so as to be in contact with each other, and the supply direction may be a parallel flow, a counter flow, or an oblique cross.
[0109]
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.
[0110]
In the present invention, the atmospheric pressure or the pressure in the vicinity of the atmospheric pressure is a pressure of 20 kPa to 110 kPa. In this invention, the more preferable pressure between the electrodes which apply a voltage is 70 kPa-140 kPa.
[0111]
FIG. 1 is a cross-sectional view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
[0112]
In FIG. 1, an atmospheric pressure plasma discharge treatment apparatus 1 mainly includes a counter electrode disposed so that a first electrode 2 and a second electrode 3 face each other, and a counter electrode which is a voltage applying means 4. In addition to the high-frequency power source 5 for applying a high-frequency electric field, although not shown, a gas supply means for introducing a discharge gas into the discharge space and a thin-film forming gas outside the discharge space, an electrode temperature adjusting means for controlling the electrode temperature, etc. It is composed of
[0113]
A region A that is sandwiched between the first electrode 2 and the second electrode 3 and has a dielectric shown by hatching on the first electrode is a discharge space. A discharge gas G is introduced into the discharge space A to excite the discharge gas. Further, a thin film forming gas M containing a thin film forming raw material is introduced into a region where discharge is not performed separately from the region where the electrodes are installed. Next, in the region outside the discharge space B where no electrode is present, the excited discharge gas G ′ and the thin film forming gas M are brought into contact with each other to form an indirect excitation gas N, which diffuses to the surface of the substrate 8. A thin film is formed. In the present invention, the excited discharge gas is not in direct contact with the base material, and the indirect excitation gas is in contact with the base material, thereby causing damage to the base material as compared with the case where the excited discharge gas is in direct contact with the base material. Can be much smaller.
[0114]
In addition, the base material 8 can process not only a sheet-like base material like a support body but various sizes and shapes. For example, a thin film can be formed on a substrate having a lens shape or a spherical shape.
[0115]
The base material 8 is installed on one side of a rotating polygonal supply device as shown in the figure, for example, and a thin film is formed. If another base material is installed on the other side, a thin film forming body can be obtained continuously.
[0116]
In the thin film forming method of the present invention, for example, an organometallic compound having an organic group having a fluorine atom is used as a thin film forming raw material, and the excited discharge gas and the thin film forming gas are brought into contact in a region outside the discharge space. By using an indirect excitation gas, it is possible to obtain a thin film for an antifouling layer having excellent water repellency, oil repellency and fingerprint wiping properties even after long-term storage, and having good abrasion resistance and scratch resistance.
[0117]
The pair of counter electrodes (the first electrode 2 and the second electrode 3) is composed of a metal base material and a dielectric 7, and by combining the metal base material to cover a dielectric 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 titanium, copper, gold, silver, platinum, stainless steel, aluminum, and iron can be used, but stainless steel or titanium is preferable. 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. Further, as the sealing treatment, the alkoxysilane-based sealing material can be made inorganic by a sol-gel reaction.
[0118]
In FIG. 1, the pair of counter electrodes are flat electrodes like the first electrode 2 and the second electrode 3, but one or both electrodes may be hollow cylindrical electrodes or prismatic electrodes. . The high-frequency power source 5 is connected to one electrode (for example, the first electrode 2) of the pair of counter electrodes, and the other electrode (for example, the second electrode 3) is grounded by the earth 9, and the pair of counter electrodes An electric field can be applied between them.
[0119]
The voltage applying means 4 applies a voltage from the high frequency power source 5 to the metal pair of each electrode. There is no limitation in particular as a high frequency power supply used for this invention. As a high frequency power source that can be used for forming an antifouling film, a high frequency power source (50 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by HEIDEN Laboratory (continuous mode use, 100 kHz), a high frequency power source manufactured by Pearl Industry (200 kHz), and a high frequency power source manufactured by Pearl Industry A power source (800 kHz), a pearl industry high frequency power supply (2 MHz), a JEOL high frequency power supply (13.56 MHz), a pearl industry high frequency power supply (27 MHz), a pearl industry high frequency power supply (150 MHz), and the like can be preferably 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.
[0120]
The frequency of the high-frequency electric field applied between the counter electrodes when forming the antifouling film which is a useful example of 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.²Or more, preferably 50 W / cm²It is as follows.
In addition, the voltage application area (cm²) Refers to the area in which discharge occurs. The high-frequency voltage applied between the counter electrodes may be an intermittent pulse wave or a continuous sine wave.
[0121]
In the present invention, a discharge space may be formed by applying two or more high-frequency electric fields between the electrodes.
[0122]
In the present invention, the distance between the counter electrodes (gap 1 in FIG. 1) is determined in consideration of the thickness of the dielectric on the metal base material of the electrode, the magnitude of the applied voltage, 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, the thickness is preferably 0.1 mm to 20 mm, more preferably 0.2 to 10 mm.
[0123]
Before forming the thin film according to the present invention, the substrate may be subjected to a surface treatment by exposing the substrate to a discharge space or an excitation gas. For example, when the raw material is an alkoxide, a hydrophilic treatment by exposure to a discharge space or an excitation gas is preferably used. Further, before the thin film is formed, the surface of the base material may be previously subjected to charge removal, and dust may be further removed. As the charge removal means and the dust removal means after the charge removal process, the same means as those used in the above apparatus can be employed. Although not shown in the drawing, as a charge removal means, besides a normal blower type or contact type, a plurality of positive and negative ion generation charge removal electrodes and a charge removal device in which an ion attracting electrode is opposed to sandwich the substrate, and then positive / negative Alternatively, a high-density static elimination system (Japanese Patent Laid-Open No. 7-263173) provided with the above-described DC type static elimination device may be used. Examples of the dust removal means after the charge removal treatment include a non-contact type jet-type depressurization type dust removal apparatus (Japanese Patent Laid-Open No. 7-60211) and can be preferably used, but are not limited thereto.
[0124]
The material of the base material processed by the thin film forming method according to the present invention is not particularly limited, and examples thereof include plastic, metal, earthenware, paper, wood, nonwoven fabric, glass plate, ceramics, and building materials. The substrate surface is preferably a metal oxide such as silica. The substrate may be in the form of a sheet or a molded product. Examples of glass include plate glass and lenses, and examples of plastic include plastic lenses, plastic films, plastic sheets, and plastic molded products. When the base material uses such a plastic as a support, one having a metal oxide film such as an antireflection film on its surface is preferably used.
[0125]
FIG. 2 is a cross-sectional view showing an example of a comparative jet type atmospheric pressure plasma discharge treatment apparatus.
[0126]
The pair of counter electrodes (first electrode 2 and second electrode 3) shown in FIG. 1 are arranged in the cylinder on the side where the base material 8 is installed, and discharge is performed in the area on the side of the cylinder opposite to FIG. The gas G is introduced and excited in the discharge space A. Further, the thin film forming gas M is introduced into the cylinder opposite to the cylinder where the counter electrode is installed. Subsequently, in the region outside the discharge space B, the excited discharge gas G ′ and the thin film forming gas M are brought into contact with each other to form an indirect excitation gas N, which is diffused on the surface of the substrate 8 to form a thin film. In such an arrangement, since the excited discharge gas and the indirectly excited gas are in direct contact with the substrate, the substrate surface is easily damaged by the excited discharge gas, and a high-performance and uniform thin film cannot be obtained.
[0127]
FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus used for forming an antireflection film on a substrate according to the present invention.
[0128]
FIG. 3 includes a plasma discharge processing apparatus 130, a gas supply unit 150, a voltage application unit 140, and an electrode temperature adjustment unit 160. As the roll rotating electrode 135 and the rectangular tube type fixed electrode group 136, the base material 8 is subjected to plasma discharge treatment. In the discharge space (between the counter electrodes) 132 between the roll rotating electrode (first electrode) 135 and the square tube type fixed electrode group (second electrode) 136, the roll rotating electrode (first electrode) 135 has the first power supply 141. To frequency ω₁The high frequency voltage V₁In addition, the square cylindrical fixed electrode group (second electrode) 136 is supplied with a frequency ω from the second power source 142.₂The high frequency voltage V₂It comes to apply.
[0129]
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.
[0130]
The roll rotating electrode 135 may be the second electrode, and the square tube type 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 supply has a higher high-frequency voltage (V₁> V₂) Can be applied, and the frequency is ω₁<Ω₂Has the ability to become. Further, it is not always necessary to use both the first power supply and the second power supply, and only one of them can be used.
[0131]
The base material 8 passes through the guide roll 164, blocks air or the like accompanying the base material with the nip roll 165, and moves between the rectangular tube fixed electrode group 136 while being wound while being in contact with the roll rotation electrode 135. Then, it passes through the nip roll 166 and the guide roll 167 and is transferred to the thin film forming process according to the present invention which is the next process. The processing gas H is generated in the gas generator 151 which is the gas supply means 150 and the flow rate is controlled so that the processing gas is in the plasma discharge processing vessel 131 between the counter electrodes (this is the discharge space) 132 from the air supply port 152. Then, the inside of the plasma discharge treatment vessel 131 is filled with the treatment gas, and the treatment exhaust gas H ′ subjected to the discharge treatment is discharged from the exhaust port 153.
[0132]
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-shaped 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 substrate, 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 rotating electrode 135 so that the temperature unevenness of the substrate 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.
[0133]
FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus used for the pretreatment according to the present invention.
[0134]
The apparatus is shown in addition to a high-frequency power source 5 that applies a high-frequency electric field between a counter electrode that is arranged so that the first electrode 2 and the second electrode 3 face each other and a counter electrode that is a voltage applying means 4. There are no gas supply means, electrode temperature adjustment means, and the like.
[0135]
A discharge gas G is introduced into a region where the first electrode 2 and the second electrode 3 face each other, and is excited in the discharge space A. Then, the substrate 8 is subjected to a surface treatment by exposing the excited discharge gas G ′ to the substrate.
[0136]
FIG. 5 is a schematic view showing another example of an atmospheric pressure plasma discharge treatment apparatus used for pretreatment according to the present invention.
[0137]
The apparatus is shown in addition to a high-frequency power source 5 that applies a high-frequency electric field between a counter electrode that is arranged so that the first electrode 2 and the second electrode 3 face each other and a counter electrode that is a voltage applying means 4. There are no gas supply means, electrode temperature adjustment means, and the like.
[0138]
The substrate 8 is disposed in a region where the first electrode 2 and the second electrode 3 are opposed to each other, the discharge gas G is introduced, and the substrate 8 is exposed to the discharge space A to thereby surface the substrate 8. Process.
[0139]
【Example】
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
[0140]
<< Preparation of thin film (antifouling film) formation sample >>
[Production of Example Sample 1: Present Invention]
(Atmospheric pressure plasma discharge treatment equipment)
Using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 1, an antifouling film was formed on the substrate 8 over 1 minute. Gas type A was used as the discharge gas introduced from the discharge gas inlet 13, and gas type B was used as the thin film forming gas introduced from the thin film forming gas inlet 15.
[0141]
<Gas type A: Discharge gas>
Nitrogen gas 98.5% by volume
Hydrogen gas 1.5% by volume
<Gas type B: Thin film forming gas>
Nitrogen gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in nitrogen gas by a vaporizer manufactured by STEC.)
<Gas supply ratio and mixing>
Gas species A: Gas species B = 2: 1 (volume ratio) was supplied, contacted outside the discharge space B via the gas outlet 16, and then supplied to the substrate surface.
[0142]
For electrodes 2 and 3, stainless steel SUS316 was used for the electrodes, and further, the surface of the electrode was spray-coated with alumina ceramic until the thickness became 1 mm, and then a coating solution in which an alkoxysilane monomer was dissolved in an organic solvent was applied to the alumina ceramic coating. Then, after drying, a dielectric was formed by heating at 150 ° C. and performing a sealing treatment. The portion of the electrode not covered with the dielectric was connected to the high frequency power source 5 or grounded 9. The gaps between the excitation gas outlet and the thin film forming gas outlet 1 and 2 are shown in Table 1.
[0143]
The high-frequency power source 5 is a high-frequency power source (40 KHz) manufactured by HEIDEN Laboratory, 7 W / cm.²The discharge power was applied.
[0144]
As the base material 8, 0.5 t soda lime glass (single side polishing) made of Japanese plate glass having a width of 10 mm, a length of 10 mm and a thickness of 0.5 mm was used.
[0145]
[Production of Example Sample 2: Present Invention]
In the production of Example Sample 1, Example Sample 2 was prepared in the same manner except that the gas type A, gas type B, excitation gas side gap 1 and thin film forming gas side gap 2 were changed as shown below. Produced.
[0146]
<Gas type A: Discharge gas>
Nitrogen gas 100% by volume
<Gas type B: Thin film forming gas>
Nitrogen gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in nitrogen gas by a vaporizer manufactured by STEC.)
The gaps 1 and 2 are shown in Table 1.
[0147]
[Production of Example Sample 3: Present Invention]
In the production of Example Sample 2, Example Sample 3 was produced in the same manner except that the gas type A, gas type B, excitation gas side gap 1 and thin film forming gas side gap 2 were changed as shown below. did.
[0148]
<Gas type A: Discharge gas>
Argon gas 98.5% by volume
Hydrogen gas 1.5% by volume
<Gas type B: Thin film forming gas>
Argon gas 99.9% by volume
Organometallic compound (described in Table 1) 0.1% by volume
(The compounds listed in Table 1 are vaporized in argon gas by a vaporizer manufactured by STEC.)
The gaps 1 and 2 are shown in Table 1.
[0149]
The high-frequency power source 5 is a high-frequency power source (13.56 MHz) manufactured by Pearl Industry, 7 W / cm.²Applied.
[0150]
[Production of Example Sample 4: Present Invention]
Example sample 4 was prepared and evaluated in the same manner as Example sample 1 except that the base material used in Example sample 1 was subjected to the following pretreatment A as a pretreatment.
[0151]
Pretreatment A: Before exposing the substrate to the indirect excitation gas, nitrogen is used as a discharge gas in a discharge space having a configuration in which the first electrode 2 and the third electrode 3 shown in FIG. : Oxygen = 99: 1 (volume ratio) was introduced, and the substrate was exposed to the excited discharge gas for 3 seconds. As a high frequency power source, a high frequency power source (frequency: 40 kHz) manufactured by HEIDEN Laboratory, discharge output is 10 W / cm.²I went to set.
[0152]
[Production of Example Sample 5: Present Invention]
Example sample 5 was prepared and evaluated in the same manner as Example sample 2 except that the base material used in Example sample 2 was subjected to the following pretreatment B as a pretreatment.
[0153]
Pretreatment B: Before exposing the substrate to the indirect excitation gas, nitrogen is used as a discharge gas in a discharge space having a configuration in which the first electrode 2 and the second electrode 3 shown in FIG. : Oxygen = 99: 1 (volume ratio) was introduced, and the substrate was exposed to the excited discharge gas for 3 seconds. As a high frequency power source, a high frequency power source (frequency: 40 kHz) manufactured by HEIDEN LABORATORY, discharge output is 5 W / cm²Set to
[Production of Example Sample 6: Present Invention]
The base material of Example Sample 1 was formed into a thin film under the same conditions as Example Sample 1 except that an antireflection film in which an antireflection layer was formed by the atmospheric pressure plasma method on the cellulose ester film shown below was used. Example sample 6 was prepared.
[0154]
With respect to Example Sample 6 obtained as described above, the surface resistivity measurement was performed by the method shown below, and the surface resistivity value was 1 × 10.¹²It confirmed that it was below ohm / square.
[0155]
(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. 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.
[0156]
[Preparation of substrate]
(Formation of antistatic layer)
On one surface of a cellulose triacetate film having a thickness of 80 μm (manufactured by Konica, trade name: Konicatak KC80UVSF), an antistatic layer coating composition having the following composition was die-coated so that the dry film thickness was 0.2 μm. It dried at 80 degreeC for 5 minute (s), and provided the antistatic layer.
[0157]
<Coating composition for antistatic layer>
Diamond (BR-88 manufactured by Mitsubishi Rayon Co., Ltd.) 0.5 parts by mass
60 parts by mass of propylene glycol monomethyl ether
Methyl ethyl ketone 15 parts by mass
6 parts by mass of ethyl lactate
8 parts by mass of methanol
Conductive polymer resin
IP-16 (described in JP-A-9-203810) 0.5 parts by mass
(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.
[0158]
<Hard coat layer composition>
60 parts by mass of dipentaerythritol hexaacrylate monomer
Dipentaerythritol hexaacrylate dimer 20 parts by mass
More than dipentaerythritol hexaacrylate trimer
20 parts by mass
Diethoxybenzophenone (UV photoinitiator) 2 parts by mass
50 parts by mass of methyl ethyl ketone
50 parts by mass of ethyl acetate
50 parts by mass of isopropyl alcohol
The composition was dissolved with stirring.
[0159]
(Coating back coat layer)
The backcoat layer coating composition described below was applied to the opposite surface of the surface coated with the hard coat layer with a gravure coater so as to have a wet film thickness of 14 μm, and dried at a drying temperature of 85 ° C. Was applied.
[0160]
<Backcoat layer coating composition>
30 parts by mass of acetone
45 parts by mass of ethyl acetate
10 parts by mass of isopropyl alcohol
Cellulose diacetate 0.5 parts by mass
Aerosil 200V 0.1 parts by mass
(Formation of antireflection layer)
The four atmospheric pressure plasma discharge treatment apparatuses shown in FIG. 3 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 as described 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, the high frequency voltage 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 the high frequency voltage is 0.8 kV / mm and the output density is 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 voltage 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.
[0161]
<Gas composition for titanium oxide layer formation>
Discharge gas: Nitrogen 97.9% by volume
Thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen
<Gas composition for forming silicon oxide layer>
Discharge gas: Nitrogen 98.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Addition gas: Oxygen 1.0% by volume
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 a substrate having an antistatic layer, a hard coat layer, and an antireflection layer (this is shown in Table 1). (Referred to as TAC-AR). Each layer 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).
[0162]
[Preparation of Comparative Samples 1-3: Comparative Example]
Using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2, an antifouling film was formed on the substrate 8 over 1 minute. As shown in Table 1, gas type A was used for the discharge gas introduced from the discharge gas inlet 13, and gas type B was used for the thin film forming gas introduced from the thin film forming gas inlet 15. The gas type A, gas type B, the gap between the excitation gas side gap 1 and the thin film forming gas side gap 2 and the base material were changed as shown in Table 1, and a thin film was formed in the same manner as in Example Sample 1. 1-3 were obtained.
[0163]
Table 1 shows the main characteristics of the thin film forming method for each sample.
[0164]
[Table 1]

[0165]
Subsequently, the evaluation shown below was implemented about the obtained sample.
<< Measurement and evaluation of characteristic values of each sample >>
(Measurement of contact angle)
About each sample, the contact angle with the antifouling film surface, water, and hexadecane was measured under an environment of 23 ° C. and 55% using a contact angle meter CA-W manufactured by Kyowa Interface Science Co., Ltd. In addition, the measurement was performed at 10 locations at random and the average value was obtained.
[0166]
[Evaluation of easy wiping: oil-based ink]
Write a line with oil-based ink (Mckey extra fine black made by Zebra), wipe it with a soft cloth (BEMCOT M-3 250mm x 250mm made by Asahi Kasei Co., Ltd.) 5 times, wipe the ink, and visually observe the remaining state of the ink. The ease of wiping was evaluated.
[0167]
A: Oil-based ink was completely wiped off
○: Oil-based ink was almost wiped off
Δ: Oil-based ink remains without being partially wiped off
X: Oil-based ink remains on the substrate surface
Moreover, wiping off of the oil-based ink was repeated 20 times, and the above evaluation was performed 20th time.
[0168]
[Ash adhesion test]
The film-formed base material was rolled 10 times with a rubber roll and brought close to the cigarette ash to test whether it adhered to the base material.
[0169]
◎: No adhesion even when close to 1cm
○: Adhere when close to 1-10cm
×: Adhering even at 10 cm or more
The results obtained as described above are shown in Table 2.
[0170]
[Table 2]

[0171]
As apparent from Table 2, the sample of the present invention in which the antifouling film was formed according to the thin film forming method and thin film production apparatus of the present invention was compared with the comparative example in terms of water repellency (contact angle) and oil repellency (ease of wiping). ) Is good.
[0172]
Moreover, it turned out that the Example sample 6 which concerns on this invention to which the antistatic function was provided becomes difficult to adhere ash, and has a favorable performance with respect to dust adhesion.
[0173]
【The invention's effect】
According to the present invention, it was possible to provide a thin film production apparatus having excellent water repellency and oil repellency without affecting the substrate, and a thin film forming method and a thin film formed body using the same.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus according to the present invention.
FIG. 2 is a cross-sectional view showing an example of a comparative jet type atmospheric pressure plasma discharge treatment apparatus.
FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge apparatus used for forming an antireflection film on a substrate.
FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus used for pretreatment according to the present invention.
FIG. 5 is a schematic view showing another example of an atmospheric pressure plasma discharge treatment apparatus used for pretreatment according to the present invention.
[Explanation of symbols]
1 Atmospheric pressure plasma discharge treatment equipment
2 First electrode
3 Second electrode
4 Voltage application means
5 High frequency power supply
7 Dielectric
8 Base material
9 Earth
13 Discharge gas inlet
15 Thin film forming gas inlet
16 Gas outlet
G Discharge gas
G 'excited discharge gas
M Thin film forming gas
N indirectly excited gas
A Discharge space
B Outside the discharge space
131 Plasma discharge treatment vessel
132 Discharge space
135 Roll electrode (first electrode)
136 Square tube electrode group (second electrode)
140 Voltage application means
141 First power supply
142 Second power supply
143 1st filter
144 Second filter
150 Gas supply means
160 Electrode temperature adjusting means
H Processing gas
H 'treated exhaust gas
P liquid pump

Claims (9)

The discharge gas is introduced into the discharge space formed by applying a high frequency voltage between the electrodes facing each other under the atmospheric pressure or near atmospheric pressure and excited, and the excited discharge gas is not directly brought into contact with the substrate. Indirectly, a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom is sandwiched between the substrate and the excited discharge gas, and the thin film forming gas is contacted with the excited discharge gas outside the discharge space. A thin film forming method comprising forming a thin film on a substrate by exciting and exposing the substrate to the indirectly excited gas. Including an organometallic compound having an organic group having a fluorine atom so that a discharge gas is introduced into a discharge space under atmospheric pressure or a pressure near atmospheric pressure to be excited, and the excited discharge gas is not directly brought into contact with a substrate. By sandwiching a thin film forming gas between the substrate and the excited discharge gas, indirect excitation by bringing the thin film forming gas into contact with the excited discharge gas outside the discharge space, and exposing the substrate to the indirectly excited gas. A thin film forming method comprising forming a thin film on the substrate. The thin film forming method according to claim 1, wherein the discharge gas contains nitrogen and / or a rare gas. The thin film forming method according to claim 1, wherein the surface of the base material contains an inorganic compound. The thin film forming method according to claim 1, wherein a main component of the surface of the base material is a metal oxide. Excited by introducing high-frequency voltage applying means for applying a high-frequency voltage between opposing electrodes under a pressure near or at atmospheric pressure, and introducing a discharge gas into a discharge space to which a voltage is applied between the electrodes by the applying means And a means for sandwiching a thin film forming gas containing an organometallic compound having an organic group having a fluorine atom between the substrate and the excited discharge gas so that the excited discharge gas does not directly contact the substrate. Then, the thin film manufacturing apparatus is characterized in that the discharge gas excited by the sandwiching causes the thin film forming gas to be indirectly excited to form a thin film on the substrate. The thin film manufacturing apparatus according to claim 6, wherein at least one of the electrodes is covered with a dielectric. The means for sandwiching the thin film forming gas between the substrate and the excited discharge gas contacts the means for supplying the thin film forming gas so as to exist on the surface of the substrate, and the excited discharge gas and the thin film forming gas. The thin film manufacturing apparatus according to claim 6, further comprising means for supplying the thin film. The surface specific resistance value is 1 × 10 at 23 ° C. and 55% RH. ¹² The thin film forming method according to claim 1, wherein the thickness is equal to or less than Ω / □.

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