JP2004061629A - Manufacturing method for functional element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a functional element easily manufactured and doubly having very accurate functional parts. <P>SOLUTION: The manufacturing method for the functional element includes the steps of: (1) forming an exposure part for a first functional part by radiating energy in a pattern after a characteristic changing layer whose characteristic is changed by the action of a photocatalyst associated with the radiation of energy and a photocatalyst incorporating layer incorporating the photocatalyst are arranged to be ≤200μm by leaving a gap between them; (2) forming the first functional part at the exposure part for the first functional part; (3) forming an exposure part for a second functional part by radiating the periphery of the first functional part with energy in a pattern after the characteristic changing layer where the first functional part is formed and the photocatalyst incorporating layer are arranged to be ≤200μm by leaving the gap between them; and (4) for forming the second functional part at the exposure part for the second functional part so as to cover over the first functional part. <P>COPYRIGHT: (C)2004,JPO

Description

【００６４】
ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１、Ｒ^２がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００６５】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコーン化合物を混合してもよい。
【００６６】
本発明においては、このようにオルガノポリシロキサン等の種々の材料を濡れ性変化層に用いることができるのであるが、上述したように、濡れ性変化層にフッ素を含有させることが、濡れ性のパターン形成に効果的である。したがって、光触媒の作用により劣化・分解しにくい材料にフッ素を含有させる、具体的にはオルガノポリシロキサン材料にフッ素を含有させて濡れ性変化層とすることが好ましいといえる。
【００６７】
本発明における濡れ性変化層には、さらに界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ　ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ　ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることかでき、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００６８】
また、濡れ性変化層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００６９】
このような濡れ性変化層は、上述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基板上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【００７０】
本発明において、この濡れ性変化層の厚みは、光触媒による濡れ性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、特に好ましくは０．０１〜０．１μｍの範囲内である。
【００７１】
また、上述したように、本発明の濡れ性変化層は自己支持性を有する材料であってもよく、自己支持性を有する材料としては、上述した材料を成膜したものが自己支持性を有するものであれば、これを用いることも可能であるが、例えば、ポリエチレン、ポリカーボネート、ポリプロピレン、ポリスチレン、ポリエステル、ポリビニルフロライド、アセタール樹脂、ナイロン、ＡＢＳ、ＰＴＦＥ、メタクリル樹脂、フェノール樹脂、ポリ弗化ビニリデン、ポリオキシメチレン、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレンテレフタレート、シリコーン等を挙げることができる。
【００７２】
（分解除去層）
次に分解除去層について説明する。本発明に用いられる分解除去層は、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層であれば、特に限定されるものではない。
【００７３】
このように分解除去層は、エネルギー照射した部分が光触媒の作用により分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分からなるパターン、すなわち凹凸を有するパターンを形成することができる。
【００７４】
なお、この分解除去層は、エネルギー照射による光触媒の作用により酸化分解され、気化等されることから、現像・洗浄工程等の特別な後処理なしに除去されるものであるが、分解除去層の材質によっては、洗浄工程等を行ってもよい。
【００７５】
また、本発明に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、上記基板表面と比較して、液体との接触角が高いことが好ましい。これにより、分解除去層が分解除去され、基板が露出した領域を親液性領域、上記分解除去層が残存する領域を撥液性領域とすることが可能となり、種々のパターンを形成することが容易となるからである。
【００７６】
ここで、上記エネルギー照射により基板が露出した領域である親液性領域と、エネルギー未照射の残存する分解除去層からなる領域である撥液性領域との特性が、その後塗布する機能性部形成用組成物が有する表面張力と同等の表面張力の液体に対する接触角において、少なくとも１°以上、好ましくは５°以上、特に１０°以上異なる親液性領域および撥液性領域から形成されたパターンであることが好ましい。
【００７７】
また、本発明の分解除去層表面の液体との接触角は、表面張力４０ｍＮ／ｍの液体との接触角が１０°以上、好ましくは表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、特に表面張力２０ｍＮ／ｍの液体との接触角が１０°以上の値を示すことが好ましい。
【００７８】
また、本発明において、特性変化層が分解除去層である場合には、後述する基板が親液性であることが好ましく、具体的には、表面張力４０ｍＮ／ｍの液体との接触角として９°以下であることが好ましく、さらに好ましくは、表面張力４０ｍＮ／ｍの液体との接触角として５°以下、特に好ましくは１°以下であることである。
【００７９】
分解除去層および基板の濡れ性が、上記範囲内であることにより、基板が露出した領域を親液性領域、分解除去層が残存する領域を撥液性領域とすることが可能となり、高精細なパターンの形成が容易となるからである。ここで、液体との接触角は、上述した方法により測定した値である。
【００８０】
この場合、後述する基板は表面を親液性となるように、表面処理したものであってもよい。材料の表面を親液性となるように表面処理した例としては、アルゴンや水などを利用したプラズマ処理による親液性表面処理が挙げられ、基板上に形成する親液性の層としては、例えばテトラエトキシシランのゾルゲル法によるシリカ膜等を挙げることができる。本発明においては、通常基板が露出した部分が親液性領域とされる。
【００８１】
上記のような分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【００８２】
また、本発明においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【００８３】
ここで、本発明に用いられる自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜について具体的に説明する。
【００８４】
（ｉ）自己組織化単分子膜
自己組織化単分子膜（Ｓｅｌｆ−Ａｓｓｅｍｂｌｅｄ　Ｍｏｎｏｌａｙｅｒ）の公式な定義の存在を発明者らは知らないが、一般的に自己組織化膜として認識されているものの解説文としては、例えばＡｂｒａｈａｍ　Ｕｌｍａｎによる総説“Ｆｏｒｍａｔｉｏｎ　ａｎｄ　Ｓｔｒｕｃｔｕｒｅ　ｏｆ　Ｓｅｌｆ−Ａｓｓｅｍｂｌｅｄ　Ｍｏｎｏｌａｙｅｒｓ”，　Ｃｈｅｍｉｃａｌ　Ｒｅｖｉｅｗ，　９６，　１５３３−１５５４　（１９９６）が優れている。本総説を参考にすれば、自己組織化単分子膜とは、適当な分子が適当な基板表面に吸着・結合（自己組織化）した結果生じた単分子層のことと言える。自己組織化膜形成能のある材料としては、例えば、脂肪酸などの界面活性剤分子、アルキルトリクロロシラン類やアルキルアルコキシド類などの有機ケイ素分子、アルカンチオール類などの有機イオウ分子、アルキルフォスフェート類などの有機リン酸分子などが挙げられる。分子構造の一般的な共通性は、比較的長いアルキル鎖を有し、片方の分子末端に基板表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基板表面に形成されたもの（後者はポリマーブラシと総称される）も自己組織化単分子膜と考えられる場合もあるようである。本発明は、これらも自己組織化単分子膜に含める。
【００８５】
（ｉｉ）ラングミュア−ブロジェット膜
本発明に用いられるラングミュア−ブロジェット膜（Ｌａｎｇｍｕｉｒ−Ｂｌｏｄｇｅｔｔ　Ｆｉｌｍ）は、基板上に形成されてしまえば形態上は上述した自己組織化単分子膜との大きな相違はない。ラングミュア−ブロジェット膜の特徴はその形成方法とそれに起因する高度な２次元分子パッキング性（高配向性、高秩序性）にあると言える。すなわち、一般にラングミュア−ブロジェット膜形成分子は気液界面上に先ず展開され、その展開膜がトラフによって凝縮されて高度にパッキングした凝縮膜に変化する。実際は、これを適当な基板に移しとって用いる。ここに概略を示した手法により単分子膜から任意の分子層の多層膜まで形成することが可能である。また、低分子のみならず、高分子、コロイド粒子なども膜材料とすることができる。様々な材料を適用した最近の事例に関しては宮下徳治らの総説“ソフト系ナノデバイス創製のナノテクノロジーへの展望”　高分子　５０巻　９月号　６４４−６４７
（２００１）に詳しく述べられている。
【００８６】
（ｉｉｉ）交互吸着膜
交互吸着膜（Ｌａｙｅｒ−ｂｙ−Ｌａｙｅｒ　Ｓｅｌｆ−Ａｓｓｅｍｂｌｅｄ　Ｆｉｌｍ）は、一般的には、最低２個の正または負の電荷を有する官能基を有する材料を逐次的に基板上に吸着・結合させて積層することにより形成される膜である。多数の官能基を有する材料の方が膜の強度や耐久性が増すなど利点が多いので、最近ではイオン性高分子（高分子電解質）を材料として用いることが多い。また、タンパク質や金属や酸化物などの表面電荷を有する粒子、いわゆる“コロイド粒子”も膜形成物質として多用される。さらに最近では、水素結合、配位結合、疎水性相互作用などのイオン結合よりも弱い相互作用を積極的に利用した膜も報告されている。比較的最近の交互吸着膜の事例については、静電的相互作用を駆動力にした材料系に少々偏っているがＰａｕｌａ　Ｔ．　Ｈａｍｍｏｎｄによる総説“Ｒｅｃｅｎｔ　Ｅｘｐｌｏｒａｔｉｏｎｓ　ｉｎ　Ｅｌｅｃｔｒｏｓｔａｔｉｃ　Ｍｕｌｔｉｌａｙｅｒ　Ｔｈｉｎ　Ｆｉｌｍ　Ａｓｓｅｍｂｌｙ”Ｃｕｒｒｅｎｔ　Ｏｐｉｎｉｏｎ　ｉｎ　Ｃｏｌｌｏｉｄ　＆　Ｉｎｔｅｒｆａｃｅ　Ｓｃｉｅｎｃｅ，　４，　４３０−４４２　（２０００）に詳しい。交互吸着膜は、最も単純なプロセスを例として説明すれば、正（負）電荷を有する材料の吸着−洗浄−負（正）電荷を有する材料の吸着−洗浄のサイクルを所定の回数繰り返すことにより形成される膜である。ラングミュア−ブロジェット膜のように展開−凝縮−移し取りの操作は全く必要ない。また、これら製法の違いより明らかなように、交互吸着膜はラングミュア−ブロジェット膜のような２次元的な高配向性・高秩序性は一般に有さない。しかし、交互吸着膜及びその作製法は、欠陥のない緻密な膜を容易に形成できること、微細な凹凸面やチューブ内面や球面などにも均一に成膜できることなど、従来の成膜法にない利点を数多く有している。
【００８７】
また、分解除去層の膜厚としては、後述するエネルギー照射工程において照射されるエネルギーにより分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、０．００１μｍ〜１μｍの範囲内、特に０．０１μｍ〜０．１μｍの範囲内とすることが好ましい。
【００８８】
（２）基板
次に、本発明における基板について説明する。本発明においては、上記特性変化層が自己支持性のない材料である場合、また分解除去層である場合に、例えば図１に示すように、基板１上に特性変化層２が設けられる。
【００８９】
この基板としては、上述した特性変化層が形成されるものであれば、特に限定されるものでなく、機能性素子の用途に応じて、可撓性を有するものであっても、可撓性を有さないものであってもよい。
【００９０】
また、特に材料等は限定されるものではなく、必要に応じて種々の材料を用いることができる。具体的には、ガラス、アルミニウム、およびその合金等の金属、プラスチック、織物、不織布等を挙げることができる。
【００９１】
（光触媒含有層側基板）
次に、本発明に用いられる光触媒含有層側基板について説明する。例えば図１（ａ）に示すように、本発明の機能性素子の製造方法に用いられる光触媒含有層側基板６は、少なくとも基材４と光触媒含有層５とを有するものであり、通常は基材４上に所定の方法で形成された薄膜状の光触媒含有層５が形成されてなるものである。また、この光触媒含有層側基板には、パターン状に形成された遮光部が形成されたものも用いることができ、この遮光部と光触媒含有層との間にプライマー層が形成されたものも用いることができる。以下、これらの各構成について説明する。
【００９２】
（１）光触媒含有層
本発明に用いられる光触媒含有層は、光触媒含有層中の光触媒が、対象とする特性変化層の特性を変化させるような構成であれば、特に限定されるものではなく、光触媒とバインダとから構成されているものであってもよく、光触媒単体で製膜されたものであってもよい。また、その表面の特性は特に親液性であっても撥液性であってもよい。
【００９３】
本発明において用いられる光触媒含有層は、例えば図２（ａ）に示すように、光触媒含有層側基板６の基材４上に、光触媒含有層５が全面に形成されたものであってもよいが、例えば図３に示すように、光触媒含有層側基板６の基材４上に光触媒含有層５がパターン上に形成されたものであってもよい。
【００９４】
このように光触媒含有層をパターン状に形成することにより、後述するエネルギー照射工程において説明するように、光触媒含有層を特性変化層と所定の間隔をおいて配置させてエネルギーを照射する際に、フォトマスク等を用いるパターン照射をする必要がなく、全面に照射することにより、特性変化層上に特性の変化したパターンを形成することができる。
【００９５】
この光触媒含有層のパターニング方法は、特に限定されるものではないが、例えばフォトリソ法等により行うことが可能である。
【００９６】
また、実際に光触媒含有層に面する特性変化層上の部分のみの特性が変化するものであるので、エネルギーの照射方向は上記光触媒含有層と特性変化層とが面する部分にエネルギーが照射されるものであれば、いかなる方向から照射されてもよく、さらには、照射されるエネルギーも特に平行光等の平行なものに限定されないという利点を有するものとなる。
【００９７】
このように光触媒含有層における、後述するような二酸化チタンに代表される光触媒の作用機構は、必ずしも明確なものではないが、光の照射によって生成したキャリアが、近傍の化合物との直接反応、あるいは、酸素、水の存在下で生じた活性酸素種によって、有機物の化学構造に変化を及ぼすものと考えられている。本発明においては、このキャリアが光触媒含有層近傍に配置される特性変化層中の化合物に作用を及ぼすものであると思われる。
【００９８】
本発明で使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【００９９】
本発明においては、特に二酸化チタンが、バンドギャップエネルギーが高く、化学的に安定で毒性もなく、入手も容易であることから好適に使用される。二酸化チタンには、アナターゼ型とルチル型があり本発明ではいずれも使用することができるが、アナターゼ型の二酸化チタンが好ましい。アナターゼ型二酸化チタンは励起波長が３８０ｎｍ以下にある。
【０１００】
このようなアナターゼ型二酸化チタンとしては、例えば、塩酸解膠型のアナターゼ型チタニアゾル（石原産業（株）製ＳＴＳ−０２（平均粒径７ｎｍ）、石原産業（株）製ＳＴ−Ｋ０１）、硝酸解膠型のアナターゼ型チタニアゾル（日産化学（株）製ＴＡ−１５（平均粒径１２ｎｍ））等を挙げることができる。
【０１０１】
光触媒の粒径は小さいほど光触媒反応が効果的に起こるので好ましく、平均粒径が５０ｎｍ以下が好ましく、２０ｎｍ以下の光触媒を使用するのが特に好ましい。
【０１０２】
本発明における光触媒含有層は、上述したように光触媒単独で形成されたものであってもよく、またバインダと混合して形成されたものであってもよい。
【０１０３】
光触媒のみからなる光触媒含有層の場合は、特性変化層上の特性の変化に対する効率が向上し、処理時間の短縮化等のコスト面で有利である。一方、光触媒とバインダとからなる光触媒含有層の場合は、光触媒含有層の形成が容易であるという利点を有する。
【０１０４】
光触媒のみからなる光触媒含有層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒含有層を形成することにより、均一な膜でかつ光触媒のみを含有する光触媒含有層とすることが可能であり、これにより特性変化層上の特性を均一に変化させることが可能であり、かつ光触媒のみからなることから、バインダを用いる場合と比較して効率的に特性変化層上の特性を変化させることが可能となる。
【０１０５】
また、光触媒のみからなる光触媒含有層の形成方法の他の例としては、例えば光触媒が二酸化チタンの場合は、基材上に無定形チタニアを形成し、次いで焼成により結晶性チタニアに相変化させる方法等が挙げられる。ここで用いられる無定形チタニアとしては、例えば四塩化チタン、硫酸チタン等のチタンの無機塩の加水分解、脱水縮合、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン等の有機チタン化合物を酸存在下において加水分解、脱水縮合によって得ることができる。次いで、４００℃〜５００℃における焼成によってアナターゼ型チタニアに変性し、６００℃〜７００℃の焼成によってルチル型チタニアに変性することができる。
【０１０６】
また、バインダを用いる場合は、バインダの主骨格が上記の光触媒の光励起により分解されないような高い結合エネルギーを有するものが好ましく、例えばオルガノポリシロキサン等を挙げることができる。
【０１０７】
このようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒含有層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより光触媒含有層を形成することかできる。
【０１０８】
また、バインダとして無定形シリカ前駆体を用いることができる。この無定形シリカ前駆体は、一般式ＳｉＸ_４で表され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１０９】
具体的には、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−プロポキシシラン、テトラブトキシシラン、テトラメトキシシラン等が挙げられる。また、この場合には、無定形シリカの前駆体と光触媒の粒子とを非水性溶媒中に均一に分散させ、基材上に空気中の水分により加水分解させてシラノールを形成させた後、常温で脱水縮重合することにより光触媒含有層を形成できる。シラノールの脱水縮重合を１００℃以上で行えば、シラノールの重合度が増し、膜表面の強度を向上できる。また、これらの結着剤は、単独あるいは２種以上を混合して用いることができる。
【０１１０】
バインダを用いた場合の光触媒含有層中の光触媒の含有量は、５〜６０重量％、好ましくは２０〜４０重量％の範囲で設定することができる。また、光触媒含有層の厚みは、０．０５〜１０μｍの範囲内が好ましい。
【０１１１】
また、光触媒含有層には上記の光触媒、バインダの他に、界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ　ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ　ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることかでき、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【０１１２】
さらに、光触媒含有層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【０１１３】
（２）基材
次に、本発明における光触媒含有層側基板の基材について説明する。本発明においては、例えば図２（ａ）に示すように、光触媒含有層側基板６は、少なくとも基材４とこの基材４上に形成された光触媒含有層５とを有するものである。この際、用いられる基材を構成する材料は、後述するエネルギー照射工程におけるエネルギーの照射方向や、得られる機能性素子が透明性を必要とするか等により適宜選択される。
【０１１４】
後述するように光触媒含有層側基板に遮光部を予め所定のパターンで形成しておき、この遮光部を用いてパターンを形成する場合や、パターンの形成を図２（ｂ）に示すように、光触媒含有層側基板６側に、フォトマスク７を用いてパターンの形成を行う場合には、光触媒含有層側基板６側からエネルギー照射をする必要がある。このような場合、基材４は透明性を有するものであることが必要となる。
【０１１５】
一方、機能性素子側基板にフォトマスクを配置してエネルギーを照射することも可能である。このような場合においては、基材の透明性は特に必要とされない。
【０１１６】
また本発明に用いられる基材は、可撓性を有するもの、例えば樹脂性フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、後述するエネルギー照射工程におけるエネルギー照射方法により適宜選択されるものである。
【０１１７】
このように、本発明における光触媒含有層側基板に用いられる基材は特にその材料を限定されるものではないが、本発明においては、この光触媒含有層側基板は、繰り返し用いられるものであることから、所定の強度を有し、かつその表面が光触媒含有層との密着性が良好である材料が好適に用いられる。具体的には、ガラス、セラミック、金属、プラスチック等を挙げることができる。
【０１１８】
なお、基材表面と光触媒含有層との密着性を向上させるために、基材上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１１９】
（３）遮光部
次に、本発明における光触媒含有層側基板の遮光部について説明する。本発明に用いられる光触媒含有層側基板には、パターン状に形成された遮光部が形成されたものを用いても良い。このように遮光部を有する光触媒含有層側基板を用いることにより、エネルギーをパターン状に照射するのに際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒含有層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１２０】
このような遮光部を有する光触媒含有層側基板は、遮光部の形成位置により、下記の二つの実施態様とすることができる。
【０１２１】
一つが、例えば図４に示すように、光触媒含有層側基板６の基材４上に遮光部１３を形成し、この遮光部１３上に光触媒含有層５を形成する実施態様である。もう一つは、例えば図５に示すように、光触媒含有層側基板６の基材４上に光触媒含有層５を形成し、その上に遮光部１３を形成する実施態様である。
【０１２２】
いずれの実施態様においても、フォトマスクを用いる場合と比較すると、遮光部が、上記光触媒含有層と特性変化層とが間隙をもって位置する部分の近傍に配置されることになるので、基材内等におけるエネルギーの散乱の影響を少なくすることができることから、エネルギーのパターン照射を極めて正確に行うことが可能となる。
【０１２３】
さらに、上記光触媒含有層上に遮光部を形成する実施態様においては、光触媒含有層と特性変化層とを所定の間隙をおいて配置する際に、この遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記遮光部を、一定の上記間隙を保つためのスペーサとしても用いることができるという利点を有する。
【０１２４】
すなわち、所定の間隙をおいて上記光触媒含有層と特性変化層とを接触させた状態で配置する際に、上記遮光部と特性変化層とを密着させた状態で配置することにより、上記所定の間隙を正確とすることが可能となり、そしてこの状態で光触媒含有層側基板からエネルギーを照射することにより、特性変化層上にパターンを精度良く形成することが可能となるのである。
【０１２５】
このような遮光部の形成方法は、特に限定されるものではなく、遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１２６】
このような本発明の遮光部の形成方法はとしては、例えばスパッタリング法、真空蒸着法等により、厚み１０００〜２０００Å程度のクロム等の金属薄膜を形成し、この薄膜をパターニングすることにより形成する方法等を挙げることができる。
【０１２７】
また、上記遮光部としては、樹脂バインダ中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層であってもよく、本発明においては、この樹脂性遮光部であることが好ましい。このような樹脂性遮光部の厚みとしては、０．５〜１０μｍの範囲内で設定することができ、一般的に金属薄膜を用いた場合より、厚さを高くすることが可能である。
【０１２８】
また、用いられる樹脂バインダとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種または２種以上混合したものや、感光性樹脂、さらにはＯ／Ｗエマルジョン型の樹脂組成物、例えば、反応性シリコーンをエマルジョン化したもの等を用いることができる。このような樹脂性遮光部のパターニングの方法は、フォトリソ法、印刷法等一般的に用いられている方法を用いることができる。
【０１２９】
なお、上記説明においては、遮光部の形成位置として、基材と光触媒含有層との間、および光触媒含有層表面の二つの場合について説明したが、その他、基材の光触媒含有層が形成されていない側の表面に遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、機能性素子を小ロットで変更するような場合に好適に用いることができる。
【０１３０】
（４）プライマー層
次に、本発明の光触媒含有層側基板に用いられるプライマー層について説明する。本発明において、上述したように基材上に遮光部をパターン状に形成して、その上に光触媒含有層を形成して光触媒含有層側基板とする場合においては、上記遮光部と光触媒含有層との間にプライマー層を形成してもよい。
【０１３１】
このプライマー層の作用・機能は必ずしも明確なものではないが、遮光部と光触媒含有層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による特性変化層の特性変化を阻害する要因となる遮光部および遮光部間に存在する開口部からの不純物、特に、遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で特性変化の処理が進行し、その結果、高解像度のパターンを得ることが可能となるのである。
【０１３２】
なお、本発明においてプライマー層は、遮光部のみならず遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた遮光部全面にわたって形成されていることが好ましい。
【０１３３】
図６はこのようなプライマー層を形成した光触媒含有層側基板の一例を示すものである。光触媒含有層側基板６の遮光部１３が形成された基材４の遮光部１３が形成されている側の表面にプライマー層１４が形成されており、このプライマー層１４の表面に光触媒含有層５が形成されている。
【０１３４】
本発明におけるプライマー層は、光触媒含有層側基板の遮光部と光触媒含有層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１３５】
このプライマー層を構成する材料としては、特に限定されるものではないが、光触媒の作用により分解されにくい無機材料が好ましい。具体的には無定形シリカを挙げることができる。このような無定形シリカを用いる場合には、この無定形シリカの前駆体は、一般式ＳｉＸ_４で示され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物であり、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１３６】
また、プライマー層の膜厚は、０．００１μｍから１μｍの範囲内であることが好ましく、特に０．００１μｍから０．１μｍの範囲内であることが好ましい。
【０１３７】
（エネルギー照射）
本発明においては、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向からエネルギーを照射する。この際、光触媒含有層および特性変化層を密着させてもよい。
【０１３８】
本発明において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって特性変化の効率が良好である点を考慮すると特に０．２μｍ〜１０μｍの範囲内、好ましくは１μｍ〜５μｍの範囲内とすることが好ましい。このような間隙の範囲は、特に間隙を高い精度で制御することが可能である小面積の機能性素子側基板に対して特に有効である。
【０１３９】
一方、例えば３００ｍｍ×３００ｍｍといった大面積の機能性素子側基板に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒含有層側基板と機能性素子側基板との間に形成することは極めて困難である。したがって、機能性素子側基板が比較的大面積である場合は、上記間隙は、１０〜１００μｍの範囲内、特に５０〜７５μｍの範囲内とすることが好ましい。間隙をこのような範囲内とすることにより、パターンがぼやける等のパターン精度の低下の問題や、光触媒の感度が悪化して特性変化の効率が悪化する等の問題が生じることなく、さらに特性変化層上の特性変化のムラが発生しないといった効果を有するからである。
【０１４０】
このように比較的大面積の機能性素子側基板をエネルギー照射する際には、エネルギー照射装置内の光触媒含有層側基板と機能性素子側基板との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒含有層側基板と機能性素子側基板とが接触することなく配置することが可能となるからである。
【０１４１】
上述したように、光触媒含有層と特性変化層表面とを所定の間隔で離して配置することにより、酸素と水および光触媒作用により生じた活性酸素種が脱着しやすくなる。すなわち、上記範囲より光触媒含有層と特性変化層との間隔を狭くした場合は、上記活性酸素種の脱着がしにくくなり、結果的に特性の変化速度を遅くしてしまう可能性があることから好ましくない。また、上記範囲より間隔を離して配置した場合は、生じた活性酸素種が特性変化層に届き難くなり、この場合も特性の変化速度を遅くしてしまう可能性があることから好ましくない。
【０１４２】
本発明においては、このような間隙をおいた配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０１４３】
このような極めて狭い間隙を均一に形成して光触媒含有層と特性変化層とを配置する方法としては、例えばスペーサを用いる方法を挙げることができる。そして、このようにスペーサを用いることにより、均一な間隙を形成することができると共に、このスペーサが接触する部分は、光触媒の作用が特性変化層表面に及ばないことから、このスペーサを上述したパターンと同様のパターンを有するものとすることにより、特性変化層上に所定のパターンを形成することが可能となる。
【０１４４】
本発明においては、このようなスペーサを一つの部材として形成してもよいが、工程の簡略化等のため、上記光触媒含有層側基板の欄で説明したように、光触媒含有層側基板の光触媒含有層表面に形成することが好ましい。なお、上記光触媒含有層側基板調製工程における説明においては、遮光部として説明したが、本発明においては、このようなスペーサは特性変化層表面に光触媒の作用が及ばないように表面を保護する作用を有すればよいものであることから、特に照射されるエネルギーを遮蔽する機能を有さない材料で形成されたものであってもよい。
【０１４５】
なお、本発明でいうエネルギー照射（露光）とは、光触媒含有層による特性変化層表面の特性を変化させることが可能ないかなるエネルギー線の照射をも含む概念であり、可視光の照射に限定されるものではない。
【０１４６】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１４７】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１４８】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１４９】
ここで、エネルギー照射に際してのエネルギーの照射量は、特性変化層表面が光触媒含有層中の光触媒の作用により特性変化層表面の特性の変化が行われるのに必要な照射量とする。
【０１５０】
またこの際、光触媒含有層を加熱しながらエネルギー照射することにより、感度を上昇させることが可能となり、効率的な特性の変化を行うことができる点で好ましい。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１５１】
本発明におけるエネルギー照射方向は、光触媒含有層側基板側からであってもよく、また機能性素子側基板側からであってもよい。ここで、光触媒含有層側基板に遮光部が形成されている場合は、光触媒含有層側基板側からエネルギー照射が行なわれる必要があり、かつこの場合は光触媒含有層側基板が照射されるエネルギーに対して透明である必要がある。なお、この場合、光触媒含有層上に遮光部が形成され、かつこの光触媒含有層側遮光部を上述したようなスペーサとしての機能を有するように用いた場合においては、エネルギー照射方向は光触媒含有層側基板側からでも機能性素子側基板側からであってもよい。
【０１５２】
さらに、光触媒含有層がパターン状に形成されている場合におけるエネルギー照射方向は、光触媒含有層と特性変化層とが接触する部分にエネルギーが照射されるのであればいかなる方向から照射されてもよい。同様に、上述したスペーサを用いる場合も、接触する部分にエネルギーが照射されるのであればいかなる方向から照射されてもよい。ここで、フォトマスクを用いる場合は、フォトマスクが配置された側からエネルギーが照射されることが必要である。
【０１５３】
上述したようなエネルギー照射が終了すると、光触媒含有層側基板が特性変化層との配置位置から離され、これにより図１（ｂ）に示すように特性が変化した第一機能性部用露光部９がパターン状に特性変化層２上に形成される。
【０１５４】
２．第一機能性部形成工程
次に、本発明における第一機能性部形成工程について説明する。本発明における第一機能性部形成工程は、例えば図１（ｂ）に示すように、上述した第一機能性部用露光部形成工程において、特性変化層２上のエネルギー照射により特性が変化した第一機能性部用露光部９に、第一機能性部１０を形成する工程である。この際、第一機能性部用露光部９の特性の変化した領域と、エネルギー未照射部の特性変化層２上の特性未変化領域との特性の差を利用して、容易に第一機能性部を形成することが可能となるのである。
【０１５５】
ここで機能性とは、光学的（光選択吸収、反射性、偏光性、光選択透過性、非線形光学性、蛍光あるいはリン光等のルミネッセンス、フォトクロミック性等）、磁気的（硬磁性、軟磁性、非磁性、透磁性等）、電気・電子的（導電性、絶縁性、圧電性、焦電性、誘電性等）、化学的（吸着性、脱着性、触媒性、吸水性、イオン伝導性、酸化還元性、電気化学特性、エレクトロクロミック性等）、機械的（耐摩耗性等）、熱的（伝熱性、断熱性、赤外線放射性等）、生体機能的（生体適合性、抗血栓性等）のような各種の機能を意味するものである。
【０１５６】
このような機能性部の第一機能性部用露光部のパターンに対応した部位への配置は、例えば親液性領域および撥液性領域の濡れ性の差を利用した方法や、密着性の差を利用した方法等が挙げられる。上記の中でも特に上述した特性変化層が濡れ性変化層または分解除去層である場合の、濡れ性の差を利用した方法であることが、機能性部形成用組成物等を用いて容易に第一機能性部を形成することが可能であること等から好ましい。
【０１５７】
本発明に用いられる機能性部形成用組成物としては、上述したように機能性素子の機能、機能性素子の形成方法等によって大きく異なるものであるが、例えば、紫外線硬化型モノマー等に代表される溶剤で希釈されていない組成物や、溶剤で希釈した液体状の組成物等を用いることができる。また、機能性部形成用組成物としては粘度が低いほど短時間にパターンが形成できることから特に好ましい。ただし、溶剤で希釈した液体状組成物の場合には、パターン形成時に溶剤の揮発による粘度の上昇、表面張力の変化が起こるため、溶剤が低揮発性であることが望ましい。さらに、後述するように、この第一機能性部上に第二機能性部を形成することから、第一機能性部を形成する機能性部形成用組成物は、親液性であることが好ましい。これにより、第二機能性部を均一に第一機能性部上に形成することが可能となるからである。また、第一機能性部を形成後、その表面を親液性とするように親液性処理を施してもよい。これにより、第二機能性部を第一機能性部上に均一に形成することが可能となるからである。
【０１５８】
本発明に用いられる機能性部形成用組成物としては、第一機能性部用露光部に付着等させて配置されることにより機能性部となるものであってもよく、また第一機能性部用露光部上に配置された後、薬剤により処理され、もしくは紫外線、熱等により処理された後に機能性部となるものであってもよい。この場合、機能性部形成用組成物の結着剤として、紫外線、熱、電子線等で効果する成分を含有している場合には、硬化処理を行うことにより素早く機能性部が形成できることから好ましい。
【０１５９】
このような機能性素子の形成方法を具体的に説明すると、機能性部形成用組成物は、ディップコート、ロールコート、ブレードコート、スピンコート等の塗布手段、インクジェット等を含むノズル吐出手段等の手段を用いて機能性素子上に形成された親液性領域のパターン上に機能性部を形成する。中でもノズル吐出手段を用いることが好ましく、特にインクジェット法であることが好ましい。
【０１６０】
また、上記の特性変化層が分解除去層であり、第一機能性部用露光部であるエネルギー照射部とエネルギー未照射部との特性の差が分解除去層の有無による凹凸のみである場合には、第一機能性部はノズル吐出法により形成することが好ましい。
【０１６１】
本実施態様において、好ましい第一機能性部としては、光導波路のコア層、ハードコート材により保護されるマイクロレンズ、絶縁層により被覆される金属配線等が挙げられる。
【０１６２】
３．第二機能性部用露光部形成工程
次に、第一機能性部が形成された特性変化層上に、第二機能性部用露光部を形成する工程について説明する。本発明における第二機能性部用露光部を形成する工程は、例えば図１（ｃ）に示すように、光触媒含有層側基板６の光触媒含有層５と、特性変化層２とを所定の間隙をおいて配置し、フォトマスク７を用いて、第一機能性部１０の周囲の第二機能性部を形成するパターン状に、エネルギー８を照射する。このエネルギー照射により、例えば図１（ｄ）に示すように、エネルギー８を照射した第二機能性部用露光部１１が特性変化領域とされ、エネルギー未照射である特性変化層２上は、特性未変化領域となる。この特性の差を利用して、容易に第二機能性部１２を形成することが可能となるのである。
【０１６３】
ここで、本発明における、第一機能性部の周囲とは、例えば図７に示すように、第二機能性部用露光部１２が第一機能性部１０の全ての周りを囲むものであるものや、図８または図９に示すように、第一機能性部１０の一部の周りを囲むものであるものも含むものとする。また、図１０に示すように、第一機能性部の両側に第二機能性部用露光部が形成されたものであってもよい。
【０１６４】
なお、本工程におけるエネルギーやこのパターン照射、さらにはパターン形成等については、第一機能性部用露光部形成工程と同様であるので、ここでの説明は省略する。
【０１６５】
４．第二機能性部形成工程
次に、第二機能性部を形成する工程について説明する。本発明において、第二機能性部形成工程は、例えば図１（ｄ）に示すように、上述した第二機能性部用露光部形成工程で特性変化領域とされた第二機能性部用露光部１１に第二機能性部１２を、第一機能性部１０の周囲、かつ第一機能性部１０を覆うように形成する工程である。これにより、機能性部が二重に形成された機能性素子とすることが可能となるのである。この機能性部の種類や、形成方法は特に限定されるものではなく、第一機能性部形成工程で述べたものと同様であるので、ここでの説明は省略する。
【０１６６】
ここで、本実施態様における、第二機能性部としては、封止材、光導波路のクラッド層、マイクロレンズのハードコート材、金属配線を覆う絶縁層等が挙げられ、中でも封止材、光導波路のクラッド層であることが好ましい。
【０１６７】
まず、第二機能性部が封止材である場合には、第一機能性部形成工程で形成した第一機能性部を封止することができ、高精細なパターンで第一機能性部を封止することが可能となるからである。
【０１６８】
また、機能性素子が光導波路である場合には、第一機能性部をコア層、第二機能性部をクラッド層とすることが可能となり、光導波路を容易に、かつ高精細に製造することができるからである。
【０１６９】
Ｂ．機能性素子
次に、本発明の機能性素子について説明する。本発明の機能性素子は、２つの態様がある。まず、第一の態様としては、例えば図１１に示すように、基板１と、上記基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、上記特性変化層２上にパターン状に形成された第一機能性部１０と、上記第一機能性部を覆うように形成された第二機能性部１２とを有することを特徴とする機能性素子である。基板上に光触媒の作用により特性変化層を有することにより、エネルギー照射により特性が変化した領域と、エネルギー未照射である特性未変化領域との、特性の差を利用して機能性素子を容易に形成することが可能であることから、結果的に低コストで高精細な機能性素子を形成することが可能である。また、上記の機能性素子においては、特性変化層中に光触媒を含有する必要がないことから、経時的に機能性部が光触媒の影響を受ける可能性がなく、高品質な機能性素子とすることが可能となるのである。
【０１７０】
また、この第一の態様においては、特性変化層が濡れ性変化層であることが好ましく、これにより、機能性素子の形成をエネルギー照射領域と、エネルギー未照射領域との濡れ性の差を利用して機能性素子を形成することが可能となることから、より容易に機能性素子を形成することが可能となるのである。ここで、上記エネルギー照射により形成される親液性領域と、エネルギー未照射の撥液性領域との特性が、その後塗布する機能性部形成用組成物が有する表面張力と同等の表面張力の液体に対する接触角において、少なくとも１°以上、好ましくは５°以上、特に１０°以上異なる親液性領域および撥液性領域から形成されたパターンであることが好ましい。また、本態様の機能性素子における撥液性領域は、その特性が表面張力４０ｍＮ／ｍの液体との接触角として１０°以上であることが好ましく、特に表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、中でも表面張力２０ｍＮ／ｍの液体との接触角が１０°以上であることが好ましい。
【０１７１】
さらに、本態様の機能性素子における親液性領域は、その特性が表面張力４０ｍＮ／ｍの液体との接触角として、９°以下であることが好ましく、特に表面張力５０ｍＮ／ｍの液体との接触角が１０°以下、中でも表面張力６０ｍＮ／ｍの液体との接触角が１０°以下であることが好ましい。
【０１７２】
本発明の機能性素子の第二の態様は、基板と、上記基板上に形成された光触媒の作用により分解除去される分解除去層と、上記基板上の上記分解除去層が分解除去された領域に、パターン状に形成された第一機能性部と、上記第一機能性部の周囲であり、かつ上記基板上の上記分解除去層が分解除去された領域に、上記第一機能性部を覆うように形成された第二機能性部とを有することを特徴とする機能性素子である。この第二の態様では、エネルギー照射に伴う光触媒の作用により分解除去される分解除去層が基板上に形成されていることから、エネルギー照射された領域と、エネルギー未照射の領域との凹凸を利用して機能性素子を形成することが可能となるのである。また、この際、分解除去層が分解除去されて露出する基板上と、分解除去層上との液体との接触角が異なることが好ましく、この場合には、分解除去層の有無による凹凸のみではなく、この濡れ性の差を利用することが可能となり、より容易に機能性素子を形成することが可能となるのである。具体的には、エネルギー照射により基板が露出した領域である親液性領域と、エネルギー未照射の残存する分解除去層からなる領域である撥液性領域との特性が、その後塗布する機能性部形成用組成物が有する表面張力と同等の表面張力の液体に対する接触角において、少なくとも１°以上、好ましくは５°以上、特に１０°以上異なる親液性領域および撥液性領域から形成されたパターンであることが好ましい。
【０１７３】
また、分解除去層からなる撥液性領域は、その特性が表面張力４０ｍＮ／ｍの液体との接触角として１０°以上であることが好ましく、特に表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、中でも表面張力２０ｍＮ／ｍの液体との接触角が１０°以上であることが好ましい。
【０１７４】
また、基板からなる親液性領域は、具体的には、表面張力４０ｍＮ／ｍの液体との接触角として９°以下であることが好ましく、さらに好ましくは、表面張力４０ｍＮ／ｍの液体との接触角として５°以下、特に好ましくは１°以下であることである。
【０１７５】
本発明における第一機能性部と第二機能性部は同じ機能性部であってもよく、異なる機能性部であってもよいが、異なる機能性部であることが一般的な機能発現上は好ましいといえる。
【０１７６】
ここで、本発明の上記の機能性素子を具体的に用いた機能性素子としては、第二機能性部を封止材とする機能性素子が挙げられ、例えば図７に示すように、まず、特性変化層上２にパターン上に第一機能性部１０を形成する。次にその第一機能性部１０が形成された部位の周囲を取り囲むようにエネルギー照射を行い第二機能性部用露光部１１を形成する。この第二機能性部用露光部１１上、かつ第一機能性部１０を覆うように封止材である第二機能性部を形成する。これにより、高精細な封止材で封止された機能性素子とすることが可能となるのである。
【０１７７】
また、上記の封止材の他に、第一機能性部がマイクロレンズであり、第二機能性部がそのマイクロレンズを保護するハードコート材である機能性素子や、第一機能性部が金属配線であり、第二機能性部がその金属配線を外部から遮蔽する絶縁層である機能性素子等が挙げられる。
【０１７８】
なお、本発明の機能性部、光触媒含有層、基材、エネルギー等の各構成および工程については、上述した機能性素子の製造方法の項で説明したものと同様であるので、ここでの説明は省略する。
【０１７９】
Ｃ．光導波路
また、本発明は上述した機能性素子を光導波路とすることが可能である。光導波路は、光を導波するコア層と、そのコア層を覆うように形成されるコア層より屈折率の小さいクラッド層とを有する構造である。このことから、本発明の機能性素子が光導波路として用いられる場合において、上記の機能性素子の第一機能性部としてコア層が用いられ、第二機能性部が上部クラッド層として用いられる。
【０１８０】
ここで、本発明の機能性素子には、上述したように２つの態様があり、上記機能性素子の第一の態様においては、例えば図１１に示すように第一機能性部であるコア層１０は、特性変化層２上に形成され、第二機能性部であるクラッド層１２が、そのコア層１０を覆うように形成される。また、上記機能性素子の第２の態様においては、例えば図１２に示すように第一機能性部であるコア層１０は、基板１上に形成され、第二機能性部であるクラッド層１２が、そのコア層１０を覆うように形成される。このことから、上述したコア層と直接接触する特性変化層、または基板が本発明の光導波路において下部クラッド層として用いられる。これらの光導波路における各構成について説明する。
【０１８１】
まず、本発明の機能性素子が光導波路として用いられる場合にその表面に直接コア層が形成される部位であり、特性変化層および基板のいずれかが該当する下部クラッド層について説明する。本発明における下部クラッド層として用いられる材料は、上記の機能性素子の製造方法において説明した特性変化層および基板に用いられるものと同様であるので、ここでの説明は省略するが、上述した材料の中でも屈折率が１．１〜１．７の範囲内、中でも１．１〜１．５の範囲内であることが下部クラッド層としての機能性を果たす面から好ましい。さらに、後述するコア層と屈折率の差が０．０３以上あることが好ましい。
【０１８２】
次に、本発明の機能性素子の第一機能性部として形成されるコア層について説明する。本発明によれば、上記の機能性素子の項で述べたように、上述した上記クラッド層上に、エネルギー照射に伴う光触媒の作用により濡れ性が変化したパターンや凹凸が形成されたパターンを利用して、容易にコア層を形成することが可能である。このようなコア層を形成するための材料としては、ポリイミド、ポリカーボネート、ポリメタクリル酸メチル、ポリスチレン、酸化ケイ素等が挙げられる。これらの材料をスピンコート法やディップコート法等の各種コーティング法やインクジェット法等のノズル吐出法、蒸着法および無電解メッキ法等を材料の特性に応じて選択し、コア層を形成する。選択する材料の種類や混合比率により屈折率を制御することが可能である。
【０１８３】
ここでコア層の形状に関しては、通常コア層内を導波する光のモード等を考慮して決定する。導波光としては、一般に赤外光を用いることから、コア層の頂部から底部までの膜厚が、０．８〜３００μｍの範囲内、好ましくは１〜１００μｍの範囲内が好ましい。またコア層底部の幅は０．８〜３００μｍの範囲内、好ましくは１〜１００μｍの範囲内が好ましい。上記範囲内のコア層とすることにより、コア層内を滞りなく光が導波し、効率の良好な光導波路を得ることができるからである。また、コア層の屈折率が１．１〜１．７の範囲内、好ましくは１．４〜１．７の範囲内とすることが好ましい。
【０１８４】
次に、第二機能性部として、上記コア層が形成された周囲、かつコア層を覆うように上部クラッド層が形成される。本発明によれば、上記の機能性素子の項で述べたように、第二機能性部である上部クラッド層を形成する領域に、エネルギー照射に伴う光触媒の作用により、濡れ性の異なるパターンや凹凸を有するパターンを形成することが可能であり、容易に上部クラッド層を形成することが可能となるのである。本発明における上部クラッド層は、コア層表面を被覆するような形状であれば、特に限定はされない。
【０１８５】
また、光導波路における上部クラッド層の役割としては、光導波路の光伝送損失を抑制することの他に、外部からの応力等による悪影響の防止や、光導波路端面を切断して端面研磨する際、高い寸法精度の加工を可能とすること等を挙げることができる。
【０１８６】
本発明において上部クラッド層は、透明性を有する材料で形成されている場合と、不透明である場合とのいずれの態様であってもよい。
【０１８７】
上部クラッド層が透明性を有する材料で形成されている場合に用いられる材料としては、例えば、シリコン樹脂、ポリメタクリレート樹脂、ポリカーボネート樹脂、酸化珪素、ＵＶ硬化型エポキシ樹脂、エポキシ樹脂、フッ素化ポリイミド、ポリイミド、ポリカーボネイト―ＭＭＡ、重水素化ポリフルオロメタクリレート等を挙げることができる。
【０１８８】
これらの材料は例えば蒸着法等により付着させることも可能であるが、好ましい方法としては、スピンコート、スプレーコート、ディップコート、ロールコート、ビードコート等の各種コーティング法やインクジェットなどの吐出法等により、塗工液とした上記材料を塗布することによって上部クラッド層を形成する方法を挙げることができる。また選択する材料の種類や材料の混合比率によって屈折率を容易に変化させることができるため、コア層の屈折率に応じて屈折率差を制御した上部クラッド層の形成が可能である。
【０１８９】
本発明において上部クラッド層の屈折率は１．１〜１．７の範囲内、好ましくは１．４〜１．７の範囲内であることが好ましい。上部クラッド層の屈折率を上記範囲内とすることにより、光伝送損失の一要因である吸収損失を効果的に防止することができるからである。また、上部クラッド層とコア層との屈折率の差は、０．０３以上、特に０．０５以上であることが好ましい。上記範囲程度にコア層の屈折率がクラッド層の屈折率よりも高ければ、吸収損失による光伝送損失を効率よく防止でき伝送効率の良好な光導波路が製造できるからである。
【０１９０】
なお、本発明の基材、エネルギー等の各構成および工程については、上述した機能性素子の製造方法の項で説明したものと同様であるので、ここでの説明は省略する。
【０１９１】
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
【０１９２】
例えば、上記説明においては、機能性素子の機能性部は二重構造を有するものであったが、本発明においては、機能性部を二重に有する機能性素子に限定されるものではなく、二重構造を有する機能性素子にさらに複数層の機能性部を同様にして形成した多重に機能性部を有する機能性素子も含まれるものとする。
【０１９３】
【実施例】
以下に実施例および比較例を示して、本発明をさらに具体的に説明する。
【０１９４】
［実施例１］
１．光触媒含有層側基板の形成
トリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）５ｇと０．５規定塩酸２．５ｇを混合し、８時間攪拌した。これをイソプロピルアルコールにより１０倍に希釈しプライマー層用組成物とした。
【０１９５】
上記プライマー層用組成物をフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明なプライマー層（厚み０．２μｍ）を形成した。
【０１９６】
次に、イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１９７】
上記光触媒含有層用組成物をプライマー層が形成されたフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１９８】
２．濡れ性変化層の形成
イソプロピルアルコール３０ｇとフルオロアルキルシラン（ＧＥ東芝シリコーン（株）製）０．４ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと０．５規定塩酸２．５ｇを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。
【０１９９】
上記濡れ性変化層用組成物を透明基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な濡れ性変化層（厚み０．１μｍ）を形成した。
【０２００】
３．第１機能性部用露光部の形成
光触媒含有層側基板と濡れ性変化層とを１００μｍのギャップを設けて対抗させて、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ^２の照度で６０秒間露光し、濡れ性変化層上に親液性領域からなる第１機能性部用露光部をパターン状に形成した。
【０２０１】
このとき、未露光部及び第１機能性部用露光部と表面張力４０ｍＮ／ｍの液体（純正化学株式会社製）との接触角を接触角測定器（協和界面科学（株）製ＣＡ−Ｚ型）を用いて測定（マイクロシリンジから液滴を滴下して３０秒後）した結果、それぞれ、７０°と７°であった。
【０２０２】
４．光導波路コア層の形成
上記親液性の第１機能性部用露光部にポリメタクリル酸メチルのＮ−メチル−２ピロリドン溶液をディップコート法にて塗布し、これを２５０℃で３０分間乾燥硬化させた。
【０２０３】
５．第２機能性部用露光部の形成
上記コア層を形成した基板にコア部の周囲にパターン状に上記３同様に露光し、第２機能性部用露光部を形成した。
【０２０４】
６．光導波路クラッド層の形成
上記親液性の第２機能性部用露光部及び第１機能性部上にポリスチレンのシクロヘキサノン溶液をディップコート法にて塗布し、これを２５０℃で３０分間乾燥硬化させた。
【０２０５】
［実施例２］
１．光触媒含有層側基板の形成
トリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）５ｇと０．５規定塩酸２．５ｇを混合し、８時間攪拌した。これをイソプロピルアルコールにより１０倍に希釈しプライマー層用組成物とした。
【０２０６】
上記プライマー層用組成物をフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明なプライマー層（厚み０．２μｍ）を形成した。
【０２０７】
次に、イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０２０８】
上記光触媒含有層用組成物をプライマー層が形成されたフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０２０９】
２．分解除去層の形成
カチオン性高分子であるポリジアリルジメチルアンモニウムクロライド（ＰＤＤＡ、平均分子量１００，０００−２００，０００、アルドリッチ）、アニオン性高分子であるポリスチレンスルホン酸ナトリウム塩（ＰＳＳ、平均分子量７０，０００、アルドリッチ）をガラス基材上に交互吸着させ厚さを約２ｎｍとした。
【０２１０】
３．第１機能性部用露光部の形成
光触媒含有層側基板と分解除去層とをアライメントをとり５０μｍのギャップを設けて対抗させて、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ^２の照度で１２０秒間露光し、分解除去層を分解除去し露出したガラス基材からなる第１機能性部用露光部をパターン状に形成した。
【０２１１】
このとき、未露光部及び画素部形成部と表面張力４０ｍＮ／ｍの濡れ指数標準液（純正化学株式会社製）との接触角を接触角測定器（協和界面科学（株）製ＣＡ−Ｚ型）を用いて測定（マイクロシリンジから液滴を滴下して３０秒後）した結果、それぞれ、３０°と６°であった。
【０２１２】
４．金属配線の形成
上記親液性の第１機能性部用露光部に銀コロイド溶液（濃度３０％）をディップコート法にて塗布し、これを５００℃で６０分間乾燥硬化させた。
【０２１３】
５．第２機能性部用露光部の形成
上記金属配線を形成した基板に金属配線の周囲にパターン状に上記３同様に露光し、第２機能性部用露光部を形成した。
【０２１４】
６．絶縁層の形成
トリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）５ｇと０．５規定塩酸２．５ｇを混合し、８時間攪拌した。これをイソプロピルアルコールにより１０倍に希釈し絶縁層用組成物とした。
【０２１５】
上記絶縁層用組成物を上記親液性の第２機能性部用露光部及び第１機能性部上にディップコート法にて塗布し、これを４００℃で３０分間乾燥硬化させた。
【０２１６】
【発明の効果】
本発明によれば、光触媒含有層側基板を用いて第一機能性部を形成するパターン状に、エネルギーの照射を行うことより、エネルギー照射部の特性変化層の特性が変化することから、エネルギー未照射部との特性の差を利用して、容易に第一機能性部を形成することが可能となるのである。次に、この第一機能性部が形成された特性変化層上に、光触媒含有層側基板を用いて第二機能性部を形成するパターン状にエネルギー照射することにより、第一機能性部の周囲に、パターン状に特性が変化した領域が得られる。上記と同様に、この特性が変化した領域と、エネルギー未照射の領域との特性の差を利用して、第一機能性部の周囲、かつ第一機能性部を覆うように特性変化層の特性が変化した第二機能性部用露光部を容易に形成することが可能となるのである。これにより、高精細な機能性部を二重に有する機能性素子を形成することが可能となる。
【図面の簡単な説明】
【図１】本発明の機能性素子の製造方法の一例を示す工程図である。
【図２】本発明の光触媒含有層側基板の一例を示す概略断面図である。
【図３】本発明の光触媒含有層側基板の他の例を示す概略断面図である。
【図４】本発明の光触媒含有層側基板の他の例を示す概略断面図である。
【図５】本発明の光触媒含有層側基板の他の例を示す概略断面図である。
【図６】本発明の光触媒含有層側基板の他の例を示す概略断面図である。
【図７】本発明の第二機能性部用露光部の一例を示す平面図である。
【図８】本発明の第二機能性部用露光部の他の例を示す平面図である。
【図９】本発明の第二機能性部用露光部の他の例を示す平面図である。
【図１０】本発明の第二機能性部用露光部の他の例を示す平面図である。
【図１１】本発明の機能性素子の一例を示す概略断面図である。
【図１２】本発明の機能性素子の他の例を示す概略断面図である。
【符号の説明】
１　…　基板
２　…　特性変化層
３　…　機能性素子側基板
４　…　基材
５　…　光触媒含有層
６　…　光触媒含有層側基板
７　…　フォトマスク
８　…　エネルギー
９　…　第一機能性部用露光部
１０…　第一機能性部
１１…　第二機能性部用露光部
１２…　第二機能性部
１３…　遮光部
１４…　プライマー層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a functional element sealed with a sealing material and a functional element used for an optical waveguide or the like and having a highly accurate and easy-to-manufacture functional part in duplicate.
[0002]
[Prior art]
Conventionally, as a method of forming a high-definition pattern, pattern exposure is performed on a photoresist layer applied on a substrate, and after exposure, the photoresist is developed and further etched, or the photoresist has functionality. 2. Description of the Related Art A method for manufacturing a functional element by photolithography, for example, by directly forming a target pattern by exposing a photoresist using a substance, is known.
[0003]
Further, for example, the production of a functional element having a dual structure, such as a sealing material or an optical waveguide, having a functional part of another type on the functional part so as to cover the functional part, It is necessary to perform the pattern formation by photolithography twice, that is, forming the second functional part after forming the one functional part, which requires many manufacturing steps, becomes complicated, and requires a high-precision device. There was a problem that costs were high. Further, it is difficult to adjust the position of the photomask when forming the second functional portion, and it is difficult to form a high-definition pattern. In addition, some of these methods require the use of a photoresist, development with a liquid developing solution after the exposure, and etching, so that it is necessary to treat a waste liquid. When a functional material is used as a material, there is a problem that the material is deteriorated by an alkali solution or the like used at the time of development.
[0004]
[Problems to be solved by the invention]
In view of the above, it is desired to provide a method for manufacturing a functional element which is easy to manufacture and has a double high-definition functional part.
[0005]
[Means for Solving the Problems]
The present invention, as described in claim 1,
(1) The photocatalyst-containing layer and the property-change layer include a property-change layer whose properties change due to the action of a photocatalyst accompanying energy irradiation, and a photocatalyst-containing layer-side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst. After arranging a gap so as to be 200 μm or less, a step of irradiating energy in a pattern shape to form an exposed portion for the first functional portion,
(2) forming a first functional part in the first functional part exposure part;
(3) After arranging the property changing layer on which the first functional portion is formed and the photocatalyst containing layer side substrate with a gap such that the photocatalyst containing layer and the property changing layer are 200 μm or less. A step of irradiating energy in a pattern around the first functional unit to form an exposure unit for the second functional unit,
(4) forming a second functional part on the exposure part for the second functional part so as to cover the first functional part;
The present invention provides a method for producing a functional element, comprising:
[0006]
According to the present invention, by irradiating energy in a pattern shape for forming the first functional portion using the photocatalyst-containing layer-side substrate, the characteristics of the characteristic change layer of the energy irradiation portion change. It is possible to easily form the first functional portion by utilizing the difference in characteristics from the unirradiated portion. Next, by irradiating energy on the characteristic change layer on which the first functional portion is formed by using the photocatalyst-containing layer-side substrate in a pattern for forming the second functional portion, the first functional portion is formed. Around the periphery, a region whose characteristics have changed in a pattern is obtained. Similarly to the above, utilizing the difference in characteristics between the region in which the characteristics have changed and the region in which energy has not been irradiated, the periphery of the first functional portion, and of the characteristic change layer so as to cover the first functional portion. This makes it possible to easily form the exposed portion for the second functional portion having changed characteristics. This makes it possible to form a functional element having a double high-definition functional part.
[0007]
In the first aspect of the present invention, as described in the second aspect, it is preferable that the characteristic change layer is formed on a substrate. In the present invention, the property change layer has self-supporting properties and may not require a substrate, but a material having good property change sensitivity usually has self-supporting properties. In many cases, it is necessary to form a coating film on a substrate. Therefore, as described above, it is preferable that the characteristic change layer is formed on the substrate.
[0008]
In the first or second aspect of the present invention, as described in the third aspect, the photocatalyst-containing layer is preferably a layer made of a photocatalyst. When the photocatalyst-containing layer is a layer composed of only the photocatalyst, the efficiency of changing the characteristics of the characteristic change layer can be improved, and the functional element can be manufactured efficiently.
[0009]
In the third aspect of the invention, as described in the fourth aspect, the photocatalyst-containing layer is preferably a layer formed by forming a photocatalyst on a substrate by a vacuum film formation method. By forming the photocatalyst by a vacuum film forming method, it is possible to form a uniform photocatalyst-containing layer having a uniform thickness with a small amount of unevenness on the surface, and to uniformly form a pattern in which the characteristics of the characteristic change layer have changed. This is because it can be performed with high efficiency.
[0010]
In the first or second aspect of the present invention, as described in the fifth aspect, the photocatalyst-containing layer may be a layer having a photocatalyst and a binder. When the photocatalyst-containing layer is a layer having a photocatalyst and a binder, the photocatalyst-containing layer can be easily formed, and as a result, a functional element can be manufactured at low cost.
[0011]
In the invention according to any one of the first to fifth aspects, as described in the sixth aspect, the photocatalyst comprises titanium oxide (TiO 2).₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃) Is preferably one or two or more substances selected from the group consisting of titanium oxide (TiO 2) and titanium oxide (TiO 2).₂) Is preferable. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, has low toxicity, and is easily available.
[0012]
In the invention according to any one of claims 1 to 7, it is preferable that the energy irradiation is performed while heating the photocatalyst-containing layer, as described in claim 8. By heating the photocatalyst-containing layer at the time of the energy irradiation, the effect of the photocatalyst can be enhanced, and the energy irradiation can be efficiently performed in a short time.
[0013]
In the invention according to any one of the first to eighth aspects, as described in the ninth aspect, the surface of the property change layer is irradiated with the energy by irradiating the photocatalyst containing layer with a gap. In doing so, it is preferable that the distance between the photocatalyst containing layer and the surface of the property change layer is in the range of 0.2 μm to 10 μm. By setting the gap within the above range, the characteristics of the characteristic change layer can be more effectively changed.
[0014]
In the invention described in any one of the first to eighth aspects, as described in the tenth aspect, it is preferable that the characteristic change layer is a layer containing no photocatalyst. This is because the property change layer does not need to contain a photocatalyst, so that it is possible to prevent the functional part from being affected by the photocatalyst over time.
[0015]
In the invention according to any one of the first to tenth aspects, as described in the eleventh aspect, the characteristic change layer is irradiated with energy by the action of a photocatalyst in the photocatalyst containing layer. It is preferable that the layer has a wettability changing layer in which the wettability changes so that the contact angle with the liquid decreases when the coating is performed. Since the property change layer is a wettability change layer, a region irradiated with energy can be a lyophilic region, and a region not irradiated with energy can be a lyophobic region. This is because the second functional part can be easily formed from the functional part-forming composition and the like.
[0016]
In the invention according to the eleventh aspect, as described in the twelfth aspect, the contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in a portion not irradiated with energy. And it is preferable that the angle is 9 ° or less in a portion irradiated with energy. When the contact angle with the liquid of the non-irradiated portion of the wettability changing layer is 10 ° or less, the liquid repellency is insufficient, and the contact angle with the liquid of the irradiated portion is If the angle is 10 ° or more, the spread of the functional part forming composition such as ink may be inferior.
[0017]
In the invention described in claim 11 or claim 12, as described in claim 13, the wettability changing layer is preferably a layer containing an organopolysiloxane. In the present invention, the properties required for the wettability changing layer are lyophobic when not irradiated with energy, and lyophilic due to the action of the photocatalyst in the photocatalyst containing layer that comes into contact when irradiated with energy. It is a characteristic of becoming. This is because organopolysiloxane is preferably used as a material that imparts such properties to the wettability changing layer.
[0018]
In the invention according to the thirteenth aspect, as described in the fourteenth aspect, it is preferable that the organopolysiloxane is an organopolysiloxane containing a fluoroalkyl group. The reason for this is that if the material contains a fluoroalkyl group, the difference in wettability between the energy-irradiated portion and the energy-unirradiated portion can be increased.
[0019]
In the invention described in claim 13 or claim 14, as described in claim 15, the organopolysiloxane comprises Y_nSix_(4-n)(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n is an integer of 0 to 3.) It is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound to be produced. By using such an organopolysiloxane, it is possible to exhibit the property against the change in wettability as described above.
[0020]
In the invention according to any one of claims 11 to 15, as described in claim 16, the wettability changing layer may have self-supporting properties. If the wettability changing layer has self-supporting properties, it is not necessary to use a substrate or the like. For example, if a commercially available resin film is used, a functional element can be easily manufactured.
[0021]
In the invention according to any one of the first to tenth aspects, as described in the seventeenth aspect, the characteristic change layer is irradiated with energy by the action of a photocatalyst in the photocatalyst containing layer. It is preferable that the layer is a decomposition-removed layer that is decomposed and removed when it is removed. This is because, when the property change layer is a decomposition removal layer, a pattern having irregularities on the surface of the decomposition removal layer can be formed by energy irradiation.
[0022]
In the seventeenth aspect of the invention, as described in the eighteenth aspect, the contact angle of the liquid with respect to the decomposition removal layer is such that the contact angle of the liquid with the substrate exposed when the decomposition removal layer is decomposed and removed. It is preferably different from the above. Because the contact angle between the decomposition removal layer and the liquid is different from the contact angle between the substrate and the liquid, the functional element can be more easily formed by utilizing the difference in wettability. .
[0023]
In the invention according to claim 17 or claim 18, as described in claim 19, the decomposition removal layer is any one of a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternate adsorption film. It is preferable that This is because, when the decomposition removal layer is the above-described film, a uniform film without defects can be formed.
[0024]
In the invention according to any one of the seventeenth to nineteenth aspects, as described in the twentieth aspect, the wettability on the substrate has a contact angle with a liquid having a surface tension of 40 mN / m. Is preferably 9 ° or less and 10 ° or more on the decomposition removal layer. When the wettability on the decomposition removal layer and the substrate is within the above range, the region where the energy is irradiated and the substrate is exposed is a lyophilic region, the region where the energy is not irradiated and the decomposition removal layer remains. Is a liquid-repellent region, and the functional portion can be easily formed by utilizing the difference in wettability.
[0025]
Further, according to the present invention, as described in claim 21, a substrate, a characteristic change layer whose characteristics are changed by the action of a photocatalyst formed on the substrate, and a pattern formed on the characteristic change layer in a pattern. There is provided a functional element having one functional part and a second functional part formed so as to cover the first functional part. This is because according to the present invention, it is possible to form the functional portion along with the change in the characteristics of the characteristic change layer, and as a result, it is possible to provide a low-cost functional element. Further, since it is not necessary to include a photocatalyst in the characteristic change layer, there is no possibility that the functional portion is affected by the photocatalyst over time, and a high-quality functional element can be obtained.
[0026]
In the invention described in claim 21, as described in claim 22, the property change layer is preferably a wettability change layer. Since the property change layer is a wettability change layer, it is possible to form the functional element more easily by utilizing the difference in wettability between the energy irradiated part and the non-irradiated part in forming the functional element. Because it becomes.
[0027]
Further, according to the present invention, as described in claim 23, the substrate, a decomposition removal layer that is decomposed and removed by the action of a photocatalyst formed on the substrate, and the decomposition removal layer on the substrate is decomposed and removed. In the region, the first functional portion formed in a pattern, and around the first functional portion, and in the region where the decomposition removal layer on the substrate is decomposed and removed, the first functional portion And a second functional part formed so as to cover the part. According to the present invention, since the decomposition removal layer is decomposed by energy irradiation, it is possible to form a functional part by using the irregularities of the energy irradiated part and the energy non-irradiated part, so that the production can be performed. It is easy, and as a result, a low-cost functional element can be obtained. Furthermore, since it is not necessary to include a photocatalyst in the decomposition removal layer, it is possible to reduce the possibility that the functional part is affected by the photocatalyst over time, and to provide a high-quality functional element. It becomes.
[0028]
In the invention described in any one of claims 21 to 23, as described in claim 24, the second functional portion may be a sealing material. This is because the second functional portion is a sealing material and the above-described functional element allows a functional element having a low-cost and high-definition sealing material to be obtained.
[0029]
Further, according to the present invention, the first functional portion of the functional element according to any one of claims 21 to 23 is a core layer, and the second functional portion is a cladding layer. An optical waveguide is provided. When the optical waveguide is the functional element, the functional element having a high-definition pattern can be obtained.
[0030]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a method for manufacturing a functional element and a functional element. Hereinafter, these will be described.
[0031]
A. Method for manufacturing functional element
The method for producing a functional element of the present invention,
(1) The photocatalyst-containing layer and the property-change layer, wherein the property-change layer whose properties change by the action of the photocatalyst accompanying energy irradiation and the photocatalyst-containing layer-side substrate having the photocatalyst-containing layer and the base material containing the photocatalyst, After arranging a gap so as to be 200 μm or less, a step of irradiating energy in a pattern shape to form an exposed portion for the first functional portion,
(2) forming a first functional part in the first functional part exposure part;
(3) After arranging the property changing layer on which the first functional portion is formed and the photocatalyst containing layer side substrate with a gap such that the photocatalyst containing layer and the property changing layer are 200 μm or less. A step of irradiating energy in a pattern around the first functional unit to form an exposure unit for the second functional unit,
(4) a step of forming a second functional part on the exposure part for the second functional part so as to cover the first functional part;
A method for producing a functional element, comprising:
[0032]
For example, as shown in FIG. 1, the present invention first includes a functional element side substrate 3 having a substrate 1 and a characteristic change layer 2 formed on the substrate 1 and having characteristics changed by the action of a photocatalyst accompanying energy irradiation. And a photocatalyst-containing layer-side substrate 6 having a base material 4 and a photocatalyst-containing layer 5 containing a photocatalyst formed on the base material 4, and a characteristic change layer 2 of the functional element-side substrate 3; The photocatalyst-containing layer 5 of the photocatalyst-containing layer-side substrate 6 is arranged at a predetermined gap, and energy 8 is irradiated using a photomask 7 in a pattern for forming the first functional portion (FIG. 1A )). As a result, the characteristics of the characteristic change layer 2 that has been subjected to the energy irradiation change, and the first functional portion exposing section 9 in which the characteristics have changed is provided with the first functional portion exposure difference 9 using the difference in the characteristics from the energy non-irradiated portion. The functional part 10 is formed (FIG. 1B). Further, the characteristic change layer 2 on which the first functional part 10 is formed and the photocatalyst-containing layer 5 are arranged at a predetermined gap, and the second functional part 10 is surrounded by the second functional part 10. Irradiation with energy 8 is performed using a photomask 7 in a pattern for forming a functional portion (FIG. 1C). Thereby, similarly to the above, the characteristics of the characteristic change layer in the portion irradiated with the energy change. Therefore, it becomes possible to form the second functional part 12 so as to cover the first functional part on the second functional part exposure part 11 whose characteristics have changed (FIG. 1D).
[0033]
Hereinafter, each of these steps will be described.
[0034]
1. Exposed part forming process for first functional part
In the step of forming an exposed portion for the first functional portion of the present invention, for example, as shown in FIG. 1A, a characteristic change in which characteristics are changed by the action of a photocatalyst accompanying the substrate 1 and energy irradiation formed on the substrate 1 A functional element side substrate 3 having a layer 2 and a photocatalyst containing layer side substrate 6 having a substrate 4 and a photocatalyst containing layer 5 containing a photocatalyst formed on the substrate 4 are prepared. The characteristic change layer 2 of the element-side substrate 3 and the photocatalyst-containing layer 5 of the photocatalyst-containing layer-side substrate 6 are arranged with a predetermined gap therebetween, and a photomask 7 is used to form a first functional portion. This is a step of irradiating energy 8 on the substrate. Each configuration of the first functional portion exposed portion forming step will be described.
[0035]
(Functional element side substrate)
The functional element-side substrate in the present invention refers to a functional element in the process of being manufactured in which a functional portion has not yet been formed in the characteristic change layer, and has a characteristic change layer. Hereinafter, each configuration of these functional element side substrates will be described.
[0036]
(1) Characteristic change layer
First, the characteristic change layer according to the present invention will be described. The property change layer of the present invention is not particularly limited as long as the property is changed by the action of a photocatalyst-containing layer described later.For example, a polymer material such as polyolefin such as polyethylene and polypropylene may be used. Due to the action of the photocatalyst, the part irradiated with energy can be a layer in which a polar group is introduced or the surface state is roughened to improve the adhesion with various substances as a property change layer. Good. By using the property change layer as the adhesive property change layer in which the adhesive property changes in this manner, it becomes possible to form a pattern having good adhesive property by energy irradiation, and it is possible to easily form the functional part. Because it becomes.
[0037]
Further, the property change layer in the present invention may have self-supporting properties or may have no self-supporting properties. In the present invention, having the self-supporting property means that it can exist in a tangible state without any other supporting material. When the property change layer has self-supporting properties, it is not necessary to form the property change layer on a substrate described later, and a commercially available resin film can be used, which is advantageous in cost. It can be said that.
[0038]
However, the property change layer formed of a material whose properties change significantly usually has few self-supporting materials, and in the case of such a material without self-support, the property change layer is formed on a substrate. It is necessary. Further, by forming the characteristic change layer on the substrate, the strength and the like are increased, and it is possible to use the layer as various pattern forming bodies.
[0039]
As a method of forming the above-described characteristic change layer on a substrate, a dry method, that is, a method formed by a vacuum deposition method or the like, or a wet method, that is, a method such as a spin coating method or a dip coating method may be used. It may be formed.
[0040]
As described above, the property change layer is not particularly limited as long as it is a layer having various properties that change by the action of the photocatalyst. In the present invention, however, the property change layer is changed in wettability by the action of the photocatalyst. The two functions are particularly obtained when the wettability changing layer is formed by a pattern due to the property and when the characteristic change layer is a decomposition removal layer formed by decomposing and removing the pattern by the action of a photocatalyst. It is preferable because the effect of the present invention is derived more from the relationship of the sex elements and the like.
[0041]
The property change layer used in the present invention is not particularly limited as long as the property is changed by the action of the photocatalyst as described above, but is preferably a layer containing no photocatalyst. If the photocatalyst is not contained in the wettability changing layer in this way, when used as a functional element thereafter, there is no need to worry about the effect of the photocatalyst over time, and it can be used for a long time without any problem. That's why.
[0042]
Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0043]
a. Variable wettability layer
The wettability changing layer in the present invention is not particularly limited as long as it is a layer whose surface wettability changes by the action of the photocatalyst. Generally, the wettability changing layer is formed by the action of the photocatalyst accompanying energy irradiation. The layer is preferably a layer whose wettability changes so that the contact angle with the liquid on the surface decreases.
[0044]
In this way, by forming a wettability changing layer in which the wettability changes so that the contact angle with the liquid is reduced by the energy irradiation, the wettability can be easily changed into a pattern by performing the energy irradiation in a pattern. Thus, it is possible to form a pattern of a lyophilic region having a small contact angle with a liquid, and to easily form a functional element by attaching a composition for forming a functional portion to the lyophilic region. Can be. Therefore, a functional element can be manufactured efficiently, which is advantageous in cost.
[0045]
Here, the lyophilic region is a region having a small contact angle with a liquid, and refers to, for example, a region having good wettability with a composition for forming a functional portion or the like. Further, the lyophobic region is a region having a large contact angle with a liquid, and is a region having poor wettability with the above-described composition for forming a functional part.
[0046]
In the present invention, when the contact angle with the liquid is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the lyophilic region, the contact angle with the liquid in the adjacent region, When the contact angle is higher than 1 °, the liquid repellent region is set.
[0047]
Here, the properties of the lyophilic region formed by the energy irradiation and the lyophobic region not irradiated with the energy have a surface tension equivalent to the surface tension of the functional part forming composition to be subsequently applied. It is preferable that the pattern is formed of a lyophilic region and a lyophobic region that differ by at least 1 ° or more, preferably 5 ° or more, and especially 10 ° or more in contact angle with respect to.
[0048]
The wettability changing layer has a contact angle of 10 ° or more with a liquid having a surface tension of 40 mN / m, preferably a liquid having a surface tension of 30 mN / m, in a portion not irradiated with energy, that is, in a water-repellent region. It is preferable to exhibit wettability with a contact angle of 10 ° or more, particularly a contact angle of 10 ° or more with a liquid having a surface tension of 20 mN / m. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency in the present invention. Therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and This is because the formation composition may possibly remain, which is not preferable.
[0049]
In addition, the contact angle with the liquid decreases when the energy change is applied to the wettability changing layer, and the contact angle with the liquid having a surface tension of 40 mN / m is 9 ° or less, preferably the contact angle with the liquid having a surface tension of 50 mN / m. The layer preferably has an angle of 10 ° or less, particularly a contact angle of 10 ° or less with a liquid having a surface tension of 60 mN / m. If the contact angle with the liquid in the energy-irradiated portion, that is, the lyophilic region, is high, the spread of the composition for forming a functional portion in this portion may be inferior, and problems such as chipping of the functional portion occur. This is because there is a possibility.
[0050]
In addition, the contact angle with the liquid referred to here is a contact angle with a liquid having various surface tensions measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (from the micro syringe to the liquid). 30 seconds after dropping) and obtained from the results or as a graph. In this measurement, wetting index standard solutions manufactured by Junsei Chemical Co., Ltd. were used as liquids having various surface tensions.
[0051]
Further, when the wettability changing layer as described above is used in the present invention, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer increases the energy relative to the wettability changing layer. The wettability changing layer may be formed such that when irradiated, the wettability changing layer is reduced by the action of the photocatalyst as compared with before the energy irradiation.
[0052]
With a wettability changing layer having such characteristics, a pattern composed of a portion having a low fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy, so that the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a low fluorine content is higher than the critical surface tension of the portion having a high fluorine content. This means that a portion having a low fluorine content is a lyophilic region as compared with a portion having a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a pattern of a lyophilic region in the lyophobic region.
[0053]
Therefore, when such a wettability changing layer is used, the pattern of the lyophilic region can be easily formed in the lyophobic region by pattern irradiation with energy. It is possible to easily form a functional part only on the functional element, and it is possible to provide a low-cost, high-quality functional element.
[0054]
As described above, as the content of fluorine contained in the wettability changing layer containing fluorine, the fluorine content in the low lyophilic region having a low fluorine content formed by energy irradiation is not irradiated with energy. When the fluorine content of the portion is 100, it is preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.
[0055]
By setting it in such a range, it is possible to cause a great difference in wettability between the energy-irradiated portion and the energy-unirradiated portion. Therefore, by forming a functional portion in such a wettability changing layer, it becomes possible to accurately form a functional portion only in a lyophilic region in which the fluorine content has been reduced, and a functional element can be accurately formed. Because it can be obtained. In addition, this reduction rate is based on weight.
[0056]
For the measurement of the fluorine content in such a wettability changing layer, it is possible to use various commonly-used methods, for example, X-ray photoelectron spectroscopy (X-ray \ Photoelectron \ Spectroscopy, ESCA (Electron). The method is not particularly limited as long as it is a method capable of quantitatively measuring the amount of fluorine on the surface, such as spectroscopy for chemical analysis), fluorescent X-ray analysis, or mass spectrometry.
[0057]
The material used for such a wettability changing layer is a material whose wettability changes due to the photocatalyst in the photocatalyst-containing layer that comes into contact with energy irradiation, that is, a material that changes due to the action of the photocatalyst. There is no particular limitation as long as it has a main chain that is not easily decomposed, but, for example, (1) an organo which exerts large strength by hydrolyzing or polycondensing chloro or alkoxysilane by a sol-gel reaction or the like. Polysiloxanes, and organopolysiloxanes such as (2) organopolysiloxanes obtained by crosslinking reactive silicones having excellent water repellency and oil repellency can be mentioned.
[0058]
In the case of the above (1), the general formula:
Y_nSix_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer of 0 to 3. )
Is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by Here, the carbon number of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0059]
Further, in particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or more hydrolytic condensates and co-hydrolytic condensates of the following fluoroalkylsilanes. What is generally known as a fluorine-based silane coupling agent can be used.
[0060]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;and
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0061]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the energy non-irradiated portion of the wettability changing layer is greatly improved. For example, the pixel portion in the case where the functional element is a color filter It exhibits a function of preventing adhesion of a functional part forming composition such as a coloring ink.
[0062]
Examples of the reactive silicone of the above (2) include compounds having a skeleton represented by the following general formula.
[0063]
Embedded image

[0064]
Here, n is an integer of 2 or more, and R¹, R²Is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and the vinyl, phenyl or halogenated phenyl accounts for 40% or less of the whole in a molar ratio. Also, R¹, R²Is preferably a group having a methyl group since the surface energy is minimized, and the molar ratio of the methyl group is preferably 60% or more. Further, the chain terminal or the side chain has at least one or more reactive group such as a hydroxyl group in the molecular chain.
[0065]
Further, a stable organosilicone compound which does not undergo a cross-linking reaction, such as dimethylpolysiloxane, may be mixed with the above-mentioned organopolysiloxane.
[0066]
In the present invention, various materials such as an organopolysiloxane can be used for the wettability changing layer as described above. It is effective for pattern formation. Therefore, it can be said that it is preferable that the material which is hardly deteriorated or decomposed by the action of the photocatalyst contain fluorine, specifically, the organopolysiloxane material contains fluorine to form the wettability changing layer.
[0067]
The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL @ BL, BC, BO, and BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL @ FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., and Dainippon Japan Megafac F-141 and 144 manufactured by Ink Chemical Industry Co., Ltd., Futagent F-200 and F251 manufactured by Neos Co., Ltd., Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd., and Florad FC-170 manufactured by 3M Corporation. 176 and the like, and a fluorine-based or silicone-based nonionic surfactant can be mentioned, and a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can also be used.
[0068]
Further, in addition to the above surfactant, the wettability changing layer, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate , Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, oligomers such as epichlorohydrin, polysulfide, polyisoprene, polymers, etc. Can be contained.
[0069]
Such a wettability changing layer can be formed by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating solution, and applying the coating solution on a substrate. . As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, and bead coating. When the composition contains an ultraviolet curable component, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0070]
In the present invention, the thickness of the wettability changing layer is preferably from 0.001 μm to 1 μm, and particularly preferably in the range of 0.01 to 0.1 μm, in view of the change rate of the wettability by the photocatalyst. is there.
[0071]
Further, as described above, the wettability changing layer of the present invention may be a material having self-supporting properties. As a material having self-supporting properties, a film formed of the above-described material has self-supporting properties. As long as it is used, it can be used, for example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride , Polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone and the like.
[0072]
(Decomposition removal layer)
Next, the decomposition removal layer will be described. The decomposition removal layer used in the present invention is not particularly limited as long as the decomposition removal layer of the part irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst containing layer when irradiated with energy. is not.
[0073]
As described above, since the decomposed and removed layer is decomposed and removed by the action of the photocatalyst at the portion irradiated with energy, it has a pattern consisting of a portion with and without the decomposed and removed portion without performing a developing step or a washing step, that is, has a concavo-convex pattern. A pattern can be formed.
[0074]
In addition, since this decomposition removal layer is oxidized and decomposed by the action of a photocatalyst by energy irradiation and is vaporized, it is removed without a special post-treatment such as a development / washing step. Depending on the material, a washing step or the like may be performed.
[0075]
Further, it is preferable that the decomposition removal layer used in the present invention not only forms irregularities, but also has a higher contact angle with a liquid than the substrate surface. Thereby, the decomposition removal layer is decomposed and removed, and the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition removal layer remains can be made a lyophobic region, so that various patterns can be formed. This is because it becomes easy.
[0076]
Here, the characteristics of the lyophilic region where the substrate is exposed by the above energy irradiation and the lyophobic region which is a region composed of the remaining decomposition and removal layer that has not been irradiated with the energy are changed to form the functional portion to be subsequently applied. In a pattern formed from a lyophilic region and a lyophobic region, the contact angle to a liquid having a surface tension equivalent to the surface tension of the composition for use is at least 1 ° or more, preferably 5 ° or more, particularly 10 ° or more. Preferably, there is.
[0077]
The contact angle between the decomposition removal layer surface and the liquid according to the present invention is such that the contact angle with the liquid having a surface tension of 40 mN / m is 10 ° or more, preferably the contact angle with the liquid having a surface tension of 30 mN / m is 10 ° or more. In particular, it is preferable that the contact angle with a liquid having a surface tension of 20 mN / m shows a value of 10 ° or more.
[0078]
Further, in the present invention, when the property change layer is a decomposition removal layer, it is preferable that a substrate described later is lyophilic, and specifically, the contact angle with a liquid having a surface tension of 40 mN / m is 9 The contact angle with a liquid having a surface tension of 40 mN / m is preferably 5 ° or less, more preferably 1 ° or less.
[0079]
When the wettability of the decomposition removal layer and the substrate is within the above range, the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition removal layer remains can be made a lyophobic region. This is because formation of a simple pattern becomes easy. Here, the contact angle with the liquid is a value measured by the method described above.
[0080]
In this case, a substrate described later may be surface-treated so that the surface becomes lyophilic. Examples of surface treatment of the surface of the material to be lyophilic include lyophilic surface treatment by plasma treatment using argon or water, as a lyophilic layer formed on the substrate, For example, a silica film formed by a sol-gel method of tetraethoxysilane can be used. In the present invention, a portion where the substrate is usually exposed is defined as a lyophilic region.
[0081]
Specific examples of the film that can be used for the decomposition removal layer as described above include a film made of a fluorine-based or hydrocarbon-based liquid-repellent resin or the like. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent and, for example, a common resin such as spin coating is used. It can be formed by a film method.
[0082]
Further, in the present invention, a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Blodgett film, and a layer having no defects can be formed by using a layer for alternate adsorption, and the like. It can be said that such a film forming method is more preferably used.
[0083]
Here, the self-assembled monomolecular film, the Langmuir-Blodgett film, and the alternating adsorption film used in the present invention will be specifically described.
[0084]
(I) Self-assembled monolayer
Although the inventors do not know the existence of an official definition of a self-assembled monolayer (Self-Assembled @ Monolayer), a commentary on what is generally recognized as a self-assembled monolayer is, for example, a review by Abraham @ Ulman. “Formation and Structure of the Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) are excellent. With reference to this review, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorption and binding (self-assembly) of appropriate molecules to an appropriate substrate surface. Materials capable of forming a self-assembled film include, for example, surfactant molecules such as fatty acids, organic silicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. Organic phosphoric acid molecule. The general commonality of molecular structures is that they have a relatively long alkyl chain and that at one molecular end there is a functional group that interacts with the substrate surface. The portion of the alkyl chain is a source of intermolecular force when the molecules are packed two-dimensionally. However, the example shown here is the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain having an oxyethylene chain, or a fluorocarbon chain. A self-assembled monolayer composed of various molecules, such as a complex-type chain, has been reported. There is also a composite self-assembled monolayer composed of a plurality of molecular species. Recently, a polymer having a plurality of functional groups (in some cases, one functional group) or a linear (in some cases having a branched structure) polymer in the form of particles, such as a dendrimer, has been developed. It seems that the one formed on the substrate surface (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. The present invention also includes these in self-assembled monolayers.
[0085]
(Ii) Langmuir-Blodgett membrane
The Langmuir-Blodgett (Film) film used in the present invention is not significantly different from the above-described self-assembled monomolecular film in form when formed on a substrate. The characteristics of the Langmuir-Blodgett film can be said to be its formation method and the resulting high two-dimensional molecular packing properties (high orientation and high ordering). That is, in general, Langmuir-Blodgett film-forming molecules are first developed on the gas-liquid interface, and the developed film is condensed by the trough and changes into a highly packed condensed film. In practice, this is transferred to an appropriate substrate and used. It is possible to form from a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. In addition, not only low molecules but also polymers, colloid particles, etc. can be used as the film material. For a review of recent applications of various materials, see Tokuharu Miyashita et al., "Prospects for Nanotechnology for Creating Soft Nanodevices", Polymer, Volume 50, September, 644-647.
(2001).
[0086]
(Iii) Alternating adsorption membrane
In general, an alternating adsorption film (Layer-by-Layer @ Self-Assembled @ Film) is formed by sequentially adsorbing and bonding at least two materials having a functional group having a positive or negative charge onto a substrate. This is a film formed by performing Since a material having a larger number of functional groups has more advantages such as an increase in the strength and durability of the membrane, an ionic polymer (polymer electrolyte) is often used recently as a material. Particles having a surface charge such as proteins, metals and oxides, so-called "colloidal particles" are also frequently used as film-forming substances. More recently, membranes have been reported that actively utilize weaker interactions than ionic bonds, such as hydrogen bonds, coordinate bonds, and hydrophobic interactions. In the case of a relatively recent alternately adsorbed film, although slightly biased toward a material system using electrostatic interaction as a driving force, Paula @ T. Review by Hammond, "Recent \ Explorations \ in \ Electrostatic \ Multilayer \ Thin \ Film \ Assembly" Current Current Opinion in Colloid & Interface Science, 4, 430-4. In the alternate adsorption film, taking the simplest process as an example, the cycle of adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge is repeated a predetermined number of times. It is a film to be formed. No development-condensation-transfer operation is required at all like a Langmuir-Blodgett membrane. Further, as is apparent from the difference between these production methods, the alternating adsorption film generally does not have a two-dimensional high orientation and high order unlike the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film forming methods, such as being able to easily form a dense film without defects and being able to uniformly form a film on a fine uneven surface, a tube inner surface, a spherical surface, and the like. Have many.
[0087]
The thickness of the decomposition removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the energy irradiated in the energy irradiation step described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but is generally in the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.1 μm. It is preferable that the thickness be in the range of 1 μm.
[0088]
(2) Substrate
Next, the substrate according to the present invention will be described. In the present invention, when the property change layer is a material having no self-supporting property or when it is a decomposition removal layer, the property change layer 2 is provided on the substrate 1 as shown in FIG. 1, for example.
[0089]
The substrate is not particularly limited as long as the above-described characteristic change layer is formed thereon. Depending on the use of the functional element, even if the substrate has flexibility, May not be provided.
[0090]
Further, the material and the like are not particularly limited, and various materials can be used as needed. Specific examples include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, and nonwoven fabrics.
[0091]
(Photocatalyst containing layer side substrate)
Next, the photocatalyst-containing layer-side substrate used in the present invention will be described. For example, as shown in FIG. 1A, the photocatalyst-containing layer-side substrate 6 used in the method for producing a functional element of the present invention has at least the base material 4 and the photocatalyst-containing layer 5, and is usually a substrate. The thin film-shaped photocatalyst containing layer 5 formed by a predetermined method is formed on the material 4. In addition, the photocatalyst-containing layer-side substrate may be one in which a light-shielding portion formed in a pattern is formed, and one in which a primer layer is formed between the light-shielding portion and the photocatalyst-containing layer may also be used. be able to. Hereinafter, each of these components will be described.
[0092]
(1) Photocatalyst containing layer
The photocatalyst-containing layer used in the present invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the target property-change layer, and includes a photocatalyst and a binder. Or a film formed of a single photocatalyst. In addition, the characteristics of the surface may be lyophilic or lyophobic.
[0093]
The photocatalyst-containing layer used in the present invention may be, for example, a photocatalyst-containing layer 5 formed on the entire surface of a base material 4 of a photocatalyst-containing layer-side substrate 6 as shown in FIG. However, for example, as shown in FIG. 3, the photocatalyst containing layer 5 may be formed in a pattern on the base material 4 of the photocatalyst containing layer side substrate 6.
[0094]
By forming the photocatalyst-containing layer in a pattern in this manner, as described in the energy irradiation step described below, when irradiating energy by arranging the photocatalyst-containing layer at a predetermined interval from the characteristic change layer, There is no need to perform pattern irradiation using a photomask or the like, and by irradiating the entire surface, a pattern with changed characteristics can be formed on the characteristic change layer.
[0095]
The method of patterning the photocatalyst-containing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0096]
In addition, since the characteristics of only the portion on the property change layer facing the photocatalyst containing layer change, the energy irradiation direction is that the portion where the photocatalyst containing layer and the property change layer face is irradiated with energy. Irradiation may be performed from any direction as long as it is possible, and furthermore, there is an advantage that the energy to be irradiated is not particularly limited to parallel light such as parallel light.
[0097]
In this way, the action mechanism of the photocatalyst represented by titanium dioxide as described later in the photocatalyst-containing layer is not necessarily clear, but the carrier generated by light irradiation is a direct reaction with a nearby compound, or It is considered that the reactive oxygen species generated in the presence of oxygen, water and water change the chemical structure of organic matter. In the present invention, it is considered that this carrier acts on the compound in the property change layer disposed near the photocatalyst containing layer.
[0098]
The photocatalyst used in the present invention includes, for example, titanium dioxide (TiO 2) which is known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃), And one or more of them may be used in combination.
[0099]
In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and any of them can be used in the present invention, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0100]
Examples of such anatase-type titanium dioxide include, for example, anatase-type titania sol of peptic hydrochloride type (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd .; ST-K01 manufactured by Ishihara Sangyo Co., Ltd.); Glue-type anatase titania sol (TA-15 (average particle diameter: 12 nm) manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
[0101]
The smaller the particle size of the photocatalyst is, the more effective the photocatalytic reaction takes place. It is preferable that the average particle size is 50 nm or less, and it is particularly preferable to use a photocatalyst having a mean particle size of 20 nm or less.
[0102]
The photocatalyst containing layer in the present invention may be formed by using only the photocatalyst as described above, or may be formed by mixing with a binder.
[0103]
In the case of the photocatalyst-containing layer composed of only the photocatalyst, the efficiency with respect to the change of the property on the property change layer is improved, which is advantageous in terms of cost such as shortening of the processing time. On the other hand, a photocatalyst-containing layer composed of a photocatalyst and a binder has an advantage that the photocatalyst-containing layer can be easily formed.
[0104]
Examples of a method for forming the photocatalyst-containing layer composed of only a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, and a vacuum evaporation method. By forming the photocatalyst-containing layer by a vacuum film forming method, it is possible to form a uniform film and a photocatalyst-containing layer containing only the photocatalyst, thereby uniformly changing the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it becomes possible to change the characteristics on the characteristic change layer more efficiently than when using a binder.
[0105]
Further, as another example of a method for forming a photocatalyst-containing layer composed of only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method in which amorphous titania is formed on a base material, and then the phase is changed to crystalline titania by firing And the like. As the amorphous titania used here, for example, titanium tetrachloride, hydrolysis and dehydration condensation of inorganic salts of titanium such as titanium sulfate, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be denatured to anatase type titania by baking at 400 ° C. to 500 ° C., and can be denatured to rutile type titania by baking at 600 ° C. to 700 ° C.
[0106]
When a binder is used, it is preferable that the binder has a high binding energy such that the main skeleton of the binder is not decomposed by the photoexcitation of the photocatalyst, and examples thereof include organopolysiloxane.
[0107]
When the organopolysiloxane is used as a binder in this manner, the photocatalyst-containing layer is prepared by dispersing a photocatalyst and an organopolysiloxane as a binder in a solvent together with other additives as necessary to prepare a coating solution. It can be formed by applying this coating liquid on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, and bead coating. When an ultraviolet-curable component is contained as a binder, the photocatalyst-containing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0108]
Further, an amorphous silica precursor can be used as a binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as a halogen, a methoxy group, an ethoxy group, or an acetyl group, a hydrolyzate of the compound, silanol, or a polysiloxane having an average molecular weight of 3000 or less.
[0109]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, tetramethoxysilane and the like. In this case, the precursor of the amorphous silica and the particles of the photocatalyst are uniformly dispersed in a non-aqueous solvent, and the substrate is hydrolyzed with moisture in the air to form silanol, and then cooled to room temperature. To form a photocatalyst-containing layer. If the dehydration-condensation polymerization of silanol is performed at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. These binders can be used alone or in combination of two or more.
[0110]
When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. Further, the thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0111]
The photocatalyst-containing layer may contain a surfactant in addition to the photocatalyst and the binder. Specifically, hydrocarbons such as NIKKOL @ BL, BC, BO, and BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL @ FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., and Dainippon Japan Megafac F-141 and 144 manufactured by Ink Chemical Industry Co., Ltd., Futagent F-200 and F251 manufactured by Neos Co., Ltd., Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd., and Florad FC-170 manufactured by 3M Corporation. 176 and the like, and a fluorine-based or silicone-based nonionic surfactant can be mentioned, and a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can also be used.
[0112]
Further, in addition to the above surfactant, the photocatalyst-containing layer, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Oligomers, polymers such as polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, etc. It can be contained.
[0113]
(2) Substrate
Next, the base material of the photocatalyst-containing layer-side substrate in the present invention will be described. In the present invention, for example, as shown in FIG. 2A, the photocatalyst-containing layer-side substrate 6 has at least the base material 4 and the photocatalyst-containing layer 5 formed on the base material 4. At this time, the material constituting the base material to be used is appropriately selected depending on the direction of energy irradiation in the energy irradiation step described later, whether the obtained functional element requires transparency, and the like.
[0114]
As described later, a light-shielding portion is formed in a predetermined pattern on the photocatalyst-containing layer-side substrate in advance, and when a pattern is formed using this light-shielding portion, or when the pattern is formed as shown in FIG. When a pattern is formed on the photocatalyst containing layer side substrate 6 side using the photomask 7, it is necessary to irradiate energy from the photocatalyst containing layer side substrate 6 side. In such a case, the base material 4 needs to have transparency.
[0115]
On the other hand, it is also possible to dispose a photomask on the functional element side substrate and irradiate energy. In such a case, the transparency of the substrate is not particularly required.
[0116]
The substrate used in the present invention may be a flexible substrate, for example, a resin film, or a non-flexible substrate, for example, a glass substrate. This is appropriately selected depending on an energy irradiation method in an energy irradiation step described later.
[0117]
As described above, the base material used for the photocatalyst-containing layer-side substrate in the present invention is not particularly limited in its material, but in the present invention, the photocatalyst-containing layer-side substrate is to be used repeatedly. Therefore, a material having a predetermined strength and having a surface having good adhesion to the photocatalyst-containing layer is preferably used. Specific examples include glass, ceramic, metal, plastic, and the like.
[0118]
Note that an anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst-containing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0119]
(3) Shading part
Next, the light-shielding portion of the photocatalyst-containing layer-side substrate in the present invention will be described. The photocatalyst-containing layer-side substrate used in the present invention may have a light-shielding portion formed in a pattern. By using the photocatalyst-containing layer-side substrate having the light-shielding portion as described above, it is not necessary to use a photomask or perform drawing irradiation with a laser beam when irradiating energy in a pattern. Therefore, since there is no need to align the photocatalyst-containing layer-side substrate with the photomask, it is possible to simplify the process, and it is not necessary to use an expensive apparatus required for drawing irradiation, thereby reducing cost. This is advantageous in that it is advantageous.
[0120]
The photocatalyst-containing layer-side substrate having such a light-shielding portion can be in the following two embodiments depending on the position where the light-shielding portion is formed.
[0121]
One is an embodiment in which, as shown in FIG. 4, for example, a light-shielding portion 13 is formed on the base material 4 of the photocatalyst-containing layer-side substrate 6, and the photocatalyst-containing layer 5 is formed on the light-shielding portion 13. The other is an embodiment in which the photocatalyst containing layer 5 is formed on the base material 4 of the photocatalyst containing layer side substrate 6 and the light shielding portion 13 is formed thereon, as shown in FIG. 5, for example.
[0122]
In any of the embodiments, as compared with the case where a photomask is used, the light-shielding portion is arranged near the portion where the photocatalyst-containing layer and the property-changing layer are located with a gap therebetween, so that the inside of the substrate or the like can be used. Can reduce the influence of the energy scattering in the above, so that the energy pattern irradiation can be performed very accurately.
[0123]
Further, in the embodiment in which the light-shielding portion is formed on the photocatalyst-containing layer, when the photocatalyst-containing layer and the property changing layer are arranged at a predetermined gap, the thickness of the light-shielding portion is set to the width of the gap. By making them coincide with each other, there is an advantage that the light-shielding portion can be used as a spacer for keeping the above-mentioned constant gap.
[0124]
That is, when the photocatalyst containing layer and the property changing layer are arranged in contact with each other with a predetermined gap therebetween, the light shielding section and the property changing layer are arranged in close contact with each other, whereby the predetermined The gap can be made accurate, and by irradiating energy from the photocatalyst-containing layer side substrate in this state, it becomes possible to form a pattern on the characteristic change layer with high accuracy.
[0125]
The method of forming such a light-shielding portion is not particularly limited, and is appropriately selected and used depending on the characteristics of the surface on which the light-shielding portion is formed, the shielding property against required energy, and the like.
[0126]
As a method for forming such a light-shielding portion of the present invention, for example, a method of forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 ° by sputtering, vacuum evaporation, or the like, and patterning the thin film. And the like.
[0127]
Further, the light-shielding portion may be a layer in which light-shielding particles such as carbon fine particles, a metal oxide, an inorganic pigment, and an organic pigment are contained in a resin binder. It is preferable that The thickness of such a resinous light-shielding portion can be set within a range of 0.5 to 10 μm, and can be generally thicker than when a metal thin film is used.
[0128]
In addition, as the resin binder used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, a mixture of two or more resins such as cellulose, and a photosensitive resin, An O / W emulsion type resin composition, for example, an emulsion of reactive silicone can be used. As a method of patterning such a resinous light-shielding portion, a commonly used method such as a photolithography method and a printing method can be used.
[0129]
In the above description, the light shielding portion is formed at two positions, that is, between the substrate and the photocatalyst-containing layer and on the surface of the photocatalyst-containing layer. However, in addition, the photocatalyst-containing layer of the substrate is formed. It is also possible to adopt a mode in which a light shielding portion is formed on the surface on the side where no light is present. In this embodiment, for example, a case where a photomask is brought into close contact with the surface to the extent that it can be detached or the like can be considered, and it can be suitably used when the functional element is changed in a small lot.
[0130]
(4) Primer layer
Next, the primer layer used in the photocatalyst-containing layer-side substrate of the present invention will be described. In the present invention, when the light-shielding portion is formed in a pattern on the substrate as described above, and the photocatalyst-containing layer is formed thereon to form a photocatalyst-containing layer-side substrate, the light-shielding portion and the photocatalyst-containing layer And a primer layer may be formed between them.
[0131]
Although the function and function of this primer layer are not always clear, by forming the primer layer between the light-shielding portion and the photocatalyst containing layer, the primer layer inhibits the property change of the property change layer due to the action of the photocatalyst. It is considered to exhibit a function of preventing diffusion of impurities such as impurities from the light-shielding portions and openings existing between the light-shielding portions, in particular, residues generated when patterning the light-shielding portions and impurities such as metals and metal ions. . Therefore, by forming the primer layer, the process of changing the characteristics proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0132]
In the present invention, since the primer layer is intended to prevent impurities existing not only in the light-shielding portions but also in the openings formed between the light-shielding portions from affecting the action of the photocatalyst, the primer layer includes the openings. It is preferable that it is formed over the entire light-shielding portion.
[0133]
FIG. 6 shows an example of a photocatalyst-containing layer-side substrate having such a primer layer formed thereon. A primer layer 14 is formed on the surface of the substrate 4 on which the light-shielding portion 13 is formed, of the substrate 4 on which the light-shielding portion 13 is formed, and the photocatalyst-containing layer 5 is formed on the surface of the primer layer 14. Is formed.
[0134]
The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the light-shielding portion of the photocatalyst-containing layer side substrate and the photocatalyst-containing layer do not come into contact with each other.
[0135]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of a photocatalyst is preferable. Specific examples include amorphous silica. When such an amorphous silica is used, the precursor of the amorphous silica has a general formula of SiX₄Wherein X is a silicon compound such as a halogen, a methoxy group, an ethoxy group, or an acetyl group. Silanol, which is a hydrolyzate thereof, or a polysiloxane having an average molecular weight of 3,000 or less is preferable.
[0136]
Further, the thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, and particularly preferably in the range of 0.001 μm to 0.1 μm.
[0137]
(Energy irradiation)
In the present invention, after arranging the photocatalyst containing layer and the property changing layer described above with a gap of 200 μm or less, energy is irradiated from a predetermined direction. At this time, the photocatalyst containing layer and the property change layer may be brought into close contact with each other.
[0138]
In the present invention, the gap is particularly good in the range of 0.2 μm to 10 μm, preferably 1 μm to 5 μm in consideration of the fact that the pattern accuracy is extremely good, the sensitivity of the photocatalyst is high, and the efficiency of the property change is good. It is preferable to be within the range. Such a range of the gap is particularly effective for a functional element side substrate having a small area capable of controlling the gap with high accuracy.
[0139]
On the other hand, when processing is performed on a functional element side substrate having a large area of, for example, 300 mm × 300 mm, without contact, and with the fine gap as described above, the photocatalyst containing layer side substrate and the functional element side substrate It is very difficult to form between them. Therefore, when the functional element-side substrate has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly preferably in the range of 50 to 75 μm. By setting the gap to be in such a range, a problem such as a decrease in pattern accuracy such as blurring of the pattern and a problem such as a decrease in sensitivity of the photocatalyst and a decrease in efficiency of characteristic change do not occur. This is because there is an effect that unevenness of the characteristic change on the layer does not occur.
[0140]
When the functional element-side substrate having a relatively large area is irradiated with energy as described above, the gap in the positioning device between the photocatalyst-containing layer-side substrate and the functional element-side substrate in the energy irradiation device is set to 10 μm to 200 μm. , Particularly preferably within the range of 25 μm to 75 μm. By setting the set value within such a range, without significantly lowering the pattern accuracy and significantly lowering the sensitivity of the photocatalyst, and without contact between the photocatalyst containing layer side substrate and the functional element side substrate. This is because they can be arranged.
[0141]
As described above, by arranging the photocatalyst-containing layer and the surface of the property change layer at a predetermined interval, oxygen and water and active oxygen species generated by the photocatalytic action are easily desorbed. That is, if the distance between the photocatalyst containing layer and the property change layer is narrower than the above range, the desorption of the active oxygen species becomes difficult, and as a result, the rate of change in properties may be reduced. Not preferred. Further, when the active oxygen species are arranged at an interval larger than the above range, it becomes difficult for the generated active oxygen species to reach the characteristic change layer, and also in this case, the change speed of the characteristic may be reduced, which is not preferable.
[0142]
In the present invention, such an arrangement with a gap only needs to be maintained at least during energy irradiation.
[0143]
As a method of forming such an extremely narrow gap uniformly and arranging the photocatalyst containing layer and the property changing layer, for example, a method using a spacer can be mentioned. By using such spacers, a uniform gap can be formed, and at the portion where the spacers come into contact, the action of the photocatalyst does not reach the surface of the characteristic change layer. By having the same pattern as described above, it becomes possible to form a predetermined pattern on the characteristic change layer.
[0144]
In the present invention, such a spacer may be formed as one member, but as described in the section of the photocatalyst containing layer side substrate, for the sake of simplification of the process, the photocatalyst containing layer side substrate It is preferably formed on the surface of the containing layer. In the above description of the photocatalyst-containing layer-side substrate preparation step, the light-shielding portion has been described. However, in the present invention, such a spacer acts to protect the surface of the property change layer so that the photocatalyst does not affect the surface. Therefore, it may be formed of a material having no function of shielding the irradiated energy.
[0145]
The term “energy irradiation (exposure)” in the present invention is a concept including irradiation of any energy ray capable of changing the properties of the surface of the property change layer by the photocatalyst-containing layer, and is limited to visible light irradiation. Not something.
[0146]
Usually, the wavelength of light used for such energy irradiation is set in a range of 400 nm or less, preferably in a range of 380 nm or less. This is because the preferable photocatalyst used for the photocatalyst-containing layer is titanium dioxide as described above, and light having the above-mentioned wavelength is preferable as the energy for activating the photocatalysis by the titanium dioxide.
[0147]
Examples of the light source that can be used for such energy irradiation include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and various other light sources.
[0148]
In addition to the above-described method using a light source and irradiating a pattern through a photomask, a method of drawing and irradiating a pattern using a laser such as excimer or YAG can also be used.
[0149]
Here, the energy irradiation amount at the time of the energy irradiation is an irradiation amount necessary for changing the characteristics of the surface of the characteristic change layer by the action of the photocatalyst in the photocatalyst containing layer.
[0150]
In this case, by irradiating energy while heating the photocatalyst-containing layer, the sensitivity can be increased, which is preferable in that the characteristics can be changed efficiently. Specifically, it is preferable to heat in the range of 30 ° C to 80 ° C.
[0151]
The energy irradiation direction in the present invention may be from the photocatalyst containing layer side substrate side or from the functional element side substrate side. Here, when the light-shielding portion is formed on the photocatalyst-containing layer side substrate, it is necessary to perform energy irradiation from the photocatalyst-containing layer side substrate side, and in this case, the energy applied to the photocatalyst-containing layer side substrate is reduced. It needs to be transparent. In this case, when a light-shielding portion is formed on the photocatalyst-containing layer and the photocatalyst-containing layer-side light-shielding portion is used so as to have a function as a spacer as described above, the energy irradiation direction is the photocatalyst-containing layer. It may be from the side substrate side or from the functional element side substrate side.
[0152]
Furthermore, when the photocatalyst-containing layer is formed in a pattern, the energy irradiation direction may be from any direction as long as the energy is applied to a portion where the photocatalyst-containing layer and the property changing layer are in contact. Similarly, in the case of using the above-described spacer, the irradiation may be performed from any direction as long as the energy is applied to the contact portion. Here, in the case of using a photomask, it is necessary to radiate energy from the side where the photomask is arranged.
[0153]
When the energy irradiation as described above is completed, the photocatalyst-containing layer-side substrate is separated from the position where the characteristic-changing layer is disposed, whereby the exposure unit for the first functional unit whose characteristics are changed as shown in FIG. 9 are formed on the characteristic change layer 2 in a pattern.
[0154]
2. First functional part forming process
Next, the first functional portion forming step in the present invention will be described. In the first functional portion forming step in the present invention, for example, as shown in FIG. 1B, in the above-described first functional portion exposing portion forming step, the characteristics were changed by the energy irradiation on the characteristic change layer 2. This is a step of forming the first functional unit 10 in the exposure unit 9 for the first functional unit. At this time, the first function can be easily performed by utilizing the difference in the characteristics between the region in which the characteristics of the exposure unit 9 for the first functional unit has changed and the region in which the characteristics have not changed on the characteristic change layer 2 in the unirradiated portion. It becomes possible to form a sex part.
[0155]
Here, the functionalities include optical (light selective absorption, reflectivity, polarization, light selective transmittance, nonlinear optical properties, luminescence such as fluorescence or phosphorescence, photochromic properties, etc.) and magnetic (hard magnetic, soft magnetic) , Non-magnetic, magnetic permeability, etc., electric / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorbing, desorbing, catalytic, water absorbing, ionic conductivity) , Redox properties, electrochemical properties, electrochromic properties, etc.), mechanical properties (abrasion resistance properties, etc.), thermal properties (thermal conductivity, thermal insulation properties, infrared radiation properties, etc.), biofunctional properties (biocompatibility, antithrombotic properties, etc.) ) Means various functions.
[0156]
Arrangement of such functional portions in a portion corresponding to the pattern of the exposed portion for the first functional portion is performed by, for example, a method using a difference in wettability between a lyophilic region and a lyophobic region, A method utilizing the difference is exemplified. Among the above, particularly when the above-mentioned property change layer is a wettability change layer or a decomposition removal layer, the method utilizing the difference in wettability can be easily performed using a functional part forming composition or the like. It is preferable because a single functional portion can be formed.
[0157]
The composition for forming a functional part used in the present invention, as described above, greatly differs depending on the function of the functional element, the method of forming the functional element, and the like, for example, is represented by an ultraviolet-curable monomer and the like. For example, a composition not diluted with a solvent, a liquid composition diluted with a solvent, or the like can be used. Further, as the composition for forming a functional part, a lower viscosity is particularly preferable because a pattern can be formed in a shorter time. However, in the case of a liquid composition diluted with a solvent, it is desirable that the solvent has low volatility, because the viscosity increases and the surface tension changes due to evaporation of the solvent during pattern formation. Furthermore, as described later, since the second functional part is formed on the first functional part, the functional part forming composition forming the first functional part may be lyophilic. preferable. Thereby, the second functional portion can be uniformly formed on the first functional portion. Further, after forming the first functional portion, a lyophilic treatment may be performed to make the surface lyophilic. Thereby, the second functional portion can be formed uniformly on the first functional portion.
[0158]
As the functional part forming composition used in the present invention, the functional part may be a functional part by being attached to the exposed part for the first functional part or the like, or the first functional part After being arranged on the exposure section, it may be treated with a chemical, or may be treated with ultraviolet rays, heat, or the like to become a functional section. In this case, as a binder of the composition for forming a functional part, when a component effective for ultraviolet rays, heat, electron beams, and the like is contained, the functional part can be quickly formed by performing a curing treatment. preferable.
[0159]
When the method for forming such a functional element is specifically described, the composition for forming a functional portion includes a coating means such as dip coating, a roll coating, a blade coating, and a spin coating, and a nozzle discharging means including an inkjet or the like. The functional part is formed on the pattern of the lyophilic region formed on the functional element by using the means. Among them, it is preferable to use a nozzle discharging means, and it is particularly preferable to use an inkjet method.
[0160]
Further, when the property change layer is a decomposition removal layer, and the difference in characteristics between the energy irradiated part and the energy non-irradiated part that is the exposed part for the first functional part is only the unevenness due to the presence of the decomposition removal layer. Preferably, the first functional portion is formed by a nozzle discharge method.
[0161]
In the present embodiment, preferable first functional portions include a core layer of an optical waveguide, a microlens protected by a hard coat material, a metal wiring covered with an insulating layer, and the like.
[0162]
3. Step of forming exposed part for second functional part
Next, the step of forming the exposed portion for the second functional portion on the characteristic change layer on which the first functional portion is formed will be described. In the step of forming the exposed portion for the second functional portion in the present invention, for example, as shown in FIG. 1C, the photocatalyst containing layer 5 of the photocatalyst containing layer side substrate 6 and the property changing layer 2 are separated by a predetermined gap. Then, using the photomask 7, the energy 8 is irradiated in a pattern shape forming the second functional portion around the first functional portion 10. By this energy irradiation, for example, as shown in FIG. 1D, the exposed portion 11 for the second functional portion irradiated with the energy 8 becomes a characteristic change region, and the characteristic change layer 2 on which the energy is not irradiated has the characteristic change region. The area remains unchanged. By utilizing the difference in the characteristics, the second functional portion 12 can be easily formed.
[0163]
Here, in the present invention, the periphery of the first functional unit refers to, for example, as shown in FIG. 7, the one where the second functional unit exposure unit 12 surrounds the entire periphery of the first functional unit 10. As shown in FIG. 8, FIG. 8 or FIG. 9, one that surrounds a part of the first functional unit 10 is also included. Further, as shown in FIG. 10, an exposure unit for a second functional unit may be formed on both sides of the first functional unit.
[0164]
The energy in this step, the pattern irradiation, and the pattern formation are the same as those in the first functional section exposure section forming step, and thus description thereof will be omitted.
[0165]
4. Second functional part forming step
Next, a step of forming the second functional portion will be described. In the present invention, the second functional part forming step is, for example, as shown in FIG. 1D, the second functional part exposing step which has been changed to the characteristic change area in the second functional part exposing part forming step described above. This is a step of forming the second functional portion 12 in the portion 11 so as to surround the first functional portion 10 and cover the first functional portion 10. This makes it possible to provide a functional element in which the functional portion is formed in a double manner. The type of the functional portion and the method of forming the functional portion are not particularly limited, and are the same as those described in the first functional portion forming step, and thus description thereof will be omitted.
[0166]
Here, in the present embodiment, examples of the second functional portion include a sealing material, a cladding layer of an optical waveguide, a hard coating material of a microlens, an insulating layer covering metal wiring, and the like. The cladding layer is preferably a waveguide cladding layer.
[0167]
First, when the second functional portion is a sealing material, the first functional portion formed in the first functional portion forming step can be sealed, and the first functional portion is formed in a high-definition pattern. This is because it is possible to seal
[0168]
Further, when the functional element is an optical waveguide, the first functional part can be a core layer and the second functional part can be a clad layer, so that the optical waveguide can be manufactured easily and with high definition. Because you can do it.
[0169]
B. Functional element
Next, the functional element of the present invention will be described. The functional element of the present invention has two modes. First, as a first mode, for example, as shown in FIG. 11, a substrate 1, a characteristic change layer 2 whose characteristics change by the action of a photocatalyst formed on the substrate 1, A functional element comprising: a first functional part formed in a pattern; and a second functional part formed to cover the first functional part. By having a characteristic change layer on the substrate by the action of a photocatalyst, a functional element can be easily formed by utilizing the difference in characteristics between the region whose characteristics have changed due to energy irradiation and the region where characteristics have not changed without energy irradiation. Since it can be formed, a high-definition functional element can be formed at low cost as a result. Further, in the above functional element, since it is not necessary to contain a photocatalyst in the property change layer, there is no possibility that the functional part is affected by the photocatalyst over time, and a high-quality functional element is obtained. It becomes possible.
[0170]
Further, in the first aspect, it is preferable that the property change layer is a wettability change layer, whereby the functional element is formed by utilizing the difference in wettability between the energy irradiated area and the energy non-irradiated area. As a result, the functional element can be formed, so that the functional element can be formed more easily. Here, the properties of the lyophilic region formed by the energy irradiation and the lyophobic region not irradiated with the energy have a surface tension equivalent to the surface tension of the functional part forming composition to be subsequently applied. It is preferable that the pattern is formed of a lyophilic region and a lyophobic region that differ by at least 1 ° or more, preferably 5 ° or more, and especially 10 ° or more in contact angle with respect to. The liquid-repellent region of the functional element of the present embodiment preferably has a characteristic of a contact angle of 10 ° or more with a liquid having a surface tension of 40 mN / m, and particularly a contact angle with a liquid having a surface tension of 30 mN / m. The contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 ° or more.
[0171]
Further, the lyophilic region in the functional element of this embodiment preferably has a contact angle of 9 ° or less as a contact angle with a liquid having a surface tension of 40 mN / m, and particularly has a contact angle with a liquid having a surface tension of 50 mN / m. The contact angle is preferably 10 ° or less, and particularly preferably the contact angle with a liquid having a surface tension of 60 mN / m is 10 ° or less.
[0172]
A second aspect of the functional element of the present invention comprises a substrate, a decomposed and removed layer which is decomposed and removed by the action of a photocatalyst formed on the substrate, and a region on the substrate where the decomposed and removed layer is decomposed and removed. In the first functional portion formed in a pattern, and around the first functional portion, and in the region where the decomposition removal layer is decomposed and removed on the substrate, the first functional portion, And a second functional part formed so as to cover the functional element. In the second aspect, since the decomposition removal layer that is decomposed and removed by the action of the photocatalyst accompanying the energy irradiation is formed on the substrate, the unevenness between the energy irradiated area and the energy unirradiated area is used. Thus, a functional element can be formed. Further, at this time, it is preferable that the contact angle between the liquid on the substrate where the decomposition removal layer is decomposed and removed and the liquid on the decomposition removal layer is different. In this case, only the unevenness due to the presence or absence of the decomposition removal layer is sufficient. Instead, this difference in wettability can be used, and a functional element can be formed more easily. Specifically, the characteristics of the lyophilic region, which is the region where the substrate is exposed by the energy irradiation, and the lyophobic region, which is the region composed of the remaining decomposition removal layer that has not been irradiated with the energy, are different from those of the functional part to be subsequently applied Patterns formed from lyophilic regions and lyophobic regions differing by at least 1 ° or more, preferably 5 ° or more, especially 10 ° or more in contact angle with a liquid having a surface tension equivalent to the surface tension of the forming composition It is preferable that
[0173]
The liquid repellent region composed of the decomposition removal layer preferably has a characteristic of a contact angle of 10 ° or more with a liquid having a surface tension of 40 mN / m, and particularly has a contact angle with a liquid having a surface tension of 30 mN / m. The contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 ° or more, especially 10 ° or more.
[0174]
Further, the lyophilic region formed of the substrate preferably has a contact angle with a liquid having a surface tension of 40 mN / m of 9 ° or less, more preferably a liquid having a surface tension of 40 mN / m. The contact angle is 5 ° or less, particularly preferably 1 ° or less.
[0175]
The first functional part and the second functional part in the present invention may be the same functional part or may be different functional parts. Is preferred.
[0176]
Here, as a functional element specifically using the above-described functional element of the present invention, a functional element using the second functional portion as a sealing material may be mentioned. For example, as shown in FIG. Then, the first functional portion 10 is formed on the pattern on the characteristic change layer 2. Next, energy irradiation is performed so as to surround the periphery of the portion where the first functional portion 10 is formed, thereby forming an exposure portion 11 for the second functional portion. A second functional part as a sealing material is formed on the second functional part exposure part 11 and so as to cover the first functional part 10. This makes it possible to obtain a functional element sealed with a high-definition sealing material.
[0177]
Further, in addition to the sealing material, the first functional portion is a microlens, and the second functional portion is a functional element that is a hard coat material that protects the microlens, and the first functional portion is Functional elements and the like are metal wirings, and the second functional part is an insulating layer that shields the metal wirings from the outside.
[0178]
In addition, since each structure and process of the functional part, the photocatalyst containing layer, the base material, the energy, and the like of the present invention are the same as those described in the section of the above-described method for manufacturing a functional element, the description here will be omitted. Is omitted.
[0179]
C. Optical waveguide
Further, in the present invention, the above-described functional element can be an optical waveguide. The optical waveguide has a structure having a core layer for guiding light and a clad layer formed to cover the core layer and having a smaller refractive index than the core layer. For this reason, when the functional element of the present invention is used as an optical waveguide, the core layer is used as the first functional part of the functional element, and the second functional part is used as the upper clad layer.
[0180]
Here, the functional element of the present invention has two aspects as described above. In the first aspect of the functional element, for example, as shown in FIG. Numeral 10 is formed on the characteristic change layer 2, and the cladding layer 12 as the second functional portion is formed so as to cover the core layer 10. In the second embodiment of the functional element, for example, as shown in FIG. 12, a core layer 10 as a first functional part is formed on a substrate 1 and a clad layer 12 as a second functional part. Is formed so as to cover the core layer 10. For this reason, the above-described characteristic change layer or substrate in direct contact with the core layer is used as the lower cladding layer in the optical waveguide of the present invention. Each configuration in these optical waveguides will be described.
[0181]
First, the lower clad layer, which is a portion where a core layer is directly formed on the surface of the functional element of the present invention when used as an optical waveguide, and which corresponds to either the characteristic change layer or the substrate, will be described. The material used as the lower cladding layer in the present invention is the same as that used for the characteristic change layer and the substrate described in the above-described method for manufacturing a functional element. Among them, the refractive index is preferably in the range of 1.1 to 1.7, and more preferably in the range of 1.1 to 1.5, from the viewpoint of achieving the function as the lower cladding layer. Further, it is preferable that the difference between the refractive index and the core layer described later is 0.03 or more.
[0182]
Next, the core layer formed as the first functional portion of the functional element of the present invention will be described. According to the present invention, as described in the section of the functional element, a pattern in which wettability is changed by the action of a photocatalyst accompanying energy irradiation or a pattern in which unevenness is formed on the clad layer is used. Thus, the core layer can be easily formed. Examples of a material for forming such a core layer include polyimide, polycarbonate, polymethyl methacrylate, polystyrene, and silicon oxide. These materials are selected from various coating methods such as a spin coating method and a dip coating method, a nozzle discharge method such as an ink jet method, a vapor deposition method, an electroless plating method, and the like according to the characteristics of the material to form a core layer. It is possible to control the refractive index by selecting the type of material and the mixing ratio.
[0183]
Here, the shape of the core layer is usually determined in consideration of the mode of light guided in the core layer. Since infrared light is generally used as the guided light, the thickness from the top to the bottom of the core layer is preferably in the range of 0.8 to 300 μm, and more preferably in the range of 1 to 100 μm. The width of the bottom of the core layer is preferably in the range of 0.8 to 300 μm, and more preferably in the range of 1 to 100 μm. By setting the core layer within the above range, light is guided without interruption in the core layer, and an efficient optical waveguide can be obtained. Further, the refractive index of the core layer is preferably in the range of 1.1 to 1.7, and more preferably in the range of 1.4 to 1.7.
[0184]
Next, an upper clad layer is formed as a second functional part so as to surround the core layer and cover the core layer. According to the present invention, as described in the section of the functional element above, in the region where the upper clad layer is formed as the second functional portion, by the action of the photocatalyst accompanying the energy irradiation, a pattern having a different wettability, It is possible to form a pattern having irregularities, and it is possible to easily form the upper cladding layer. The upper cladding layer in the present invention is not particularly limited as long as it has a shape covering the surface of the core layer.
[0185]
The role of the upper cladding layer in the optical waveguide, in addition to suppressing the optical transmission loss of the optical waveguide, to prevent adverse effects due to external stress and the like, when cutting the end face of the optical waveguide and polishing the end face, For example, it is possible to perform processing with high dimensional accuracy.
[0186]
In the present invention, the upper clad layer may be in any of a case where it is formed of a material having transparency and a case where it is opaque.
[0187]
As the material used when the upper cladding layer is formed of a material having transparency, for example, silicon resin, polymethacrylate resin, polycarbonate resin, silicon oxide, UV-curable epoxy resin, epoxy resin, fluorinated polyimide, Examples thereof include polyimide, polycarbonate-MMA, and deuterated polyfluoromethacrylate.
[0188]
These materials can be deposited by, for example, a vapor deposition method.A preferable method is, for example, spin coating, spray coating, dip coating, roll coating, various coating methods such as bead coating, or an ejection method such as inkjet. A method of forming the upper clad layer by applying the above-mentioned material as a coating liquid. Further, since the refractive index can be easily changed depending on the kind of the selected material and the mixing ratio of the materials, it is possible to form the upper clad layer in which the refractive index difference is controlled according to the refractive index of the core layer.
[0189]
In the present invention, the refractive index of the upper cladding layer is preferably in the range of 1.1 to 1.7, and more preferably in the range of 1.4 to 1.7. By setting the refractive index of the upper cladding layer within the above range, absorption loss, which is one factor of optical transmission loss, can be effectively prevented. The difference in the refractive index between the upper cladding layer and the core layer is preferably 0.03 or more, particularly preferably 0.05 or more. If the refractive index of the core layer is higher than the refractive index of the cladding layer within the above range, optical transmission loss due to absorption loss can be efficiently prevented, and an optical waveguide having good transmission efficiency can be manufactured.
[0190]
In addition, since each structure and process of the base material, energy, and the like of the present invention are the same as those described in the section of the above-described method for manufacturing a functional element, description thereof will be omitted.
[0191]
Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.
[0192]
For example, in the above description, the functional part of the functional element has a double structure, but in the present invention, the functional part is not limited to the functional element having the functional part doubly, It is assumed that a functional element having multiple functional parts in which a plurality of functional parts are formed in the same manner as the functional element having a double structure is also included.
[0193]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[0194]
[Example 1]
1. Formation of photocatalyst containing layer side substrate
5 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10-fold with isopropyl alcohol to obtain a primer layer composition.
[0195]
The composition for a primer layer was applied on a photomask substrate by a spin coater, and dried at 150 ° C. for 10 minutes to form a transparent primer layer (0.2 μm in thickness).
[0196]
Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, were mixed, and the mixture was mixed at 100 ° C. Stirred for 20 minutes. This was diluted three times with isopropyl alcohol to obtain a photocatalyst-containing layer composition.
[0197]
The composition for a photocatalyst-containing layer is applied on a photomask substrate on which a primer layer is formed by a spin coater, and dried at 150 ° C. for 10 minutes to form a transparent photocatalyst-containing layer (0.15 μm in thickness). Formed.
[0198]
2. Formation of wettability changing layer
30 g of isopropyl alcohol, 0.4 g of fluoroalkylsilane (manufactured by GE Toshiba Silicone Co., Ltd.), 3 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 2.5 g of 0.5N hydrochloric acid are mixed for 8 hours. Stirred. This was diluted 100 times with isopropyl alcohol to obtain a composition for a wettability changing layer.
[0199]
The composition for a wettability changing layer was applied on a transparent substrate by a spin coater, and dried at 150 ° C. for 10 minutes to form a transparent wettability changing layer (0.1 μm in thickness).
[0200]
3. Formation of exposure part for first functional part
The substrate on the photocatalyst containing layer side and the wettability changing layer were opposed to each other with a gap of 100 μm provided, and 40 mW / cm from the photomask side using an ultra-high pressure mercury lamp (wavelength 365 nm).²Exposure was performed at an illuminance of 60 seconds to form a first functional portion exposed portion composed of a lyophilic region in a pattern on the wettability changing layer.
[0201]
At this time, the contact angle between the unexposed portion and the exposed portion for the first functional portion and the liquid having a surface tension of 40 mN / m (manufactured by Junsei Chemical Co., Ltd.) was measured using a contact angle measuring device (CA-Z manufactured by Kyowa Interface Science Co., Ltd.). (30 minutes after the droplet was dropped from the micro syringe) as a result of the measurement using a mold).
[0202]
4. Formation of optical waveguide core layer
An N-methyl-2-pyrrolidone solution of poly (methyl methacrylate) was applied to the exposed portion for the first functional part having a lyophilic property by dip coating, and dried and cured at 250 ° C. for 30 minutes.
[0203]
5. Formation of exposure part for second functional part
The substrate on which the core layer was formed was exposed around the core portion in a pattern in the same manner as in 3 above, thereby forming an exposed portion for the second functional portion.
[0204]
6. Formation of optical waveguide cladding layer
A cyclohexanone solution of polystyrene was applied by dip coating on the lyophilic exposed portion for the second functional portion and the first functional portion, and dried and cured at 250 ° C. for 30 minutes.
[0205]
[Example 2]
1. Formation of photocatalyst containing layer side substrate
5 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10-fold with isopropyl alcohol to obtain a primer layer composition.
[0206]
The composition for a primer layer was applied on a photomask substrate by a spin coater, and dried at 150 ° C. for 10 minutes to form a transparent primer layer (0.2 μm in thickness).
[0207]
Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, were mixed, and the mixture was mixed at 100 ° C. Stirred for 20 minutes. This was diluted three times with isopropyl alcohol to obtain a photocatalyst-containing layer composition.
[0208]
The composition for a photocatalyst-containing layer is applied on a photomask substrate on which a primer layer is formed by a spin coater, and dried at 150 ° C. for 10 minutes to form a transparent photocatalyst-containing layer (0.15 μm in thickness). Formed.
[0209]
2. Formation of decomposition removal layer
Polydiallyldimethylammonium chloride (PDDA, average molecular weight 100,000-200,000, Aldrich) as a cationic polymer, and polystyrenesulfonic acid sodium salt (PSS, average molecular weight 70,000, Aldrich) as an anionic polymer were used. The film was alternately adsorbed on a glass substrate to have a thickness of about 2 nm.
[0210]
3. Formation of exposure part for first functional part
The substrate on the photocatalyst-containing layer side and the decomposition removal layer were aligned to be opposed to each other with a gap of 50 μm, and 40 mW / cm from the photomask side with an ultra-high pressure mercury lamp (wavelength 365 nm).²Exposure was performed at an illuminance of 120 seconds to decompose and remove the decomposed and removed layer, thereby forming an exposed portion for a first functional portion composed of an exposed glass substrate in a pattern.
[0211]
At this time, the contact angle between the unexposed portion and the pixel portion forming portion and a wetting index standard solution (manufactured by Junsei Chemical Co., Ltd.) having a surface tension of 40 mN / m was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.). ) (30 seconds after dropping the droplet from the microsyringe), the result was 30 ° and 6 °, respectively.
[0212]
4. Formation of metal wiring
A silver colloid solution (concentration: 30%) was applied to the lyophilic exposed portion for the first functional portion by a dip coating method, and dried and cured at 500 ° C. for 60 minutes.
[0213]
5. Formation of exposure part for second functional part
The substrate on which the metal wiring was formed was exposed around the metal wiring in a pattern in the same manner as in 3 above, thereby forming an exposed portion for the second functional portion.
[0214]
6. Formation of insulating layer
5 g of trimethoxymethylsilane (TSL8113, manufactured by GE Toshiba Silicone Co., Ltd.) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10-fold with isopropyl alcohol to obtain a composition for an insulating layer.
[0215]
The composition for an insulating layer was applied to the lyophilic exposed portion for the second functional portion and the first functional portion by a dip coating method, and dried and cured at 400 ° C. for 30 minutes.
[0216]
【The invention's effect】
According to the present invention, by irradiating energy in a pattern shape for forming the first functional portion using the photocatalyst-containing layer-side substrate, the characteristics of the characteristic change layer of the energy irradiation portion change. It is possible to easily form the first functional portion by utilizing the difference in characteristics from the unirradiated portion. Next, by irradiating energy on the characteristic change layer on which the first functional portion is formed by using the photocatalyst-containing layer-side substrate in a pattern for forming the second functional portion, the first functional portion is formed. Around the periphery, a region whose characteristics have changed in a pattern is obtained. Similarly to the above, utilizing the difference in characteristics between the region in which the characteristics have changed and the region in which energy has not been irradiated, the periphery of the first functional portion, and of the characteristic change layer so as to cover the first functional portion. This makes it possible to easily form the exposed portion for the second functional portion having changed characteristics. This makes it possible to form a functional element having a double high-definition functional part.
[Brief description of the drawings]
FIG. 1 is a process chart showing an example of a method for producing a functional element of the present invention.
FIG. 2 is a schematic sectional view showing an example of the photocatalyst-containing layer-side substrate of the present invention.
FIG. 3 is a schematic sectional view showing another example of the photocatalyst-containing layer-side substrate of the present invention.
FIG. 4 is a schematic sectional view showing another example of the photocatalyst-containing layer-side substrate of the present invention.
FIG. 5 is a schematic sectional view showing another example of the photocatalyst-containing layer-side substrate of the present invention.
FIG. 6 is a schematic sectional view showing another example of the photocatalyst-containing layer-side substrate of the present invention.
FIG. 7 is a plan view illustrating an example of an exposure unit for a second functional unit according to the present invention.
FIG. 8 is a plan view showing another example of the exposure unit for the second functional unit of the present invention.
FIG. 9 is a plan view showing another example of the exposure unit for the second functional unit of the present invention.
FIG. 10 is a plan view showing another example of the exposure unit for the second functional unit of the present invention.
FIG. 11 is a schematic sectional view showing an example of the functional element of the present invention.
FIG. 12 is a schematic sectional view showing another example of the functional element of the present invention.
[Explanation of symbols]
1… Substrate
2… Characteristic change layer
3 ... Functional element side substrate
4… Base material
5 ... Photocatalyst containing layer
6 ... Photocatalyst containing layer side substrate
7… Photo mask
8… Energy
9 ... Exposure section for first functional section
10 ... 1st functional department
11 ... Exposure unit for second functional unit
12… Second functional part
13 ... Light-shielding part
14 ... Primer layer

Claims (25)

(1) The photocatalyst-containing layer and the property-change layer include a property-change layer whose properties change due to the action of a photocatalyst accompanying energy irradiation, and a photocatalyst-containing layer-side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst. After arranging a gap so as to be 200 μm or less, a step of irradiating energy in a pattern shape to form an exposed portion for the first functional portion,
(2) forming a first functional part in the first functional part exposure part;
(3) After arranging the property changing layer on which the first functional portion is formed and the photocatalyst containing layer side substrate with a gap such that the photocatalyst containing layer and the property changing layer are 200 μm or less. A step of irradiating energy in a pattern around the first functional unit to form an exposure unit for the second functional unit,
(4) forming a second functional part on the second functional part exposure part so as to cover the first functional part. The method according to claim 1, wherein the characteristic change layer is formed on a substrate. The method according to claim 1, wherein the photocatalyst-containing layer is a layer made of a photocatalyst. 4. The method according to claim 3, wherein the photocatalyst-containing layer is a layer formed by forming a photocatalyst on a substrate by a vacuum film formation method. 3. The method according to claim 1, wherein the photocatalyst-containing layer is a layer having a photocatalyst and a binder. 4. The photocatalyst includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxidized The method for producing a functional element according to claim 1, wherein the functional element is one or more substances selected from iron (Fe ₂ O ₃ ). Method of manufacturing a functional device according to claim 6, wherein the photocatalyst is titanium oxide (TiO _2). The method for producing a functional element according to claim 1, wherein the energy irradiation is performed while heating the photocatalyst-containing layer. When irradiating the photocatalyst-containing layer with energy on the surface of the characteristic change layer with a gap therebetween, the distance between the photocatalyst-containing layer and the surface of the characteristic change layer is set to be in a range of 0.2 μm to 10 μm. The method for manufacturing a functional element according to claim 1, wherein the method comprises: The method according to any one of claims 1 to 9, wherein the characteristic change layer is a layer not containing a photocatalyst. The said property change layer is a wettability change layer which changes wettability by the action of the photocatalyst in the said photocatalyst containing layer so that the contact angle with a liquid may be reduced when irradiated with energy. A method for manufacturing a functional element according to any one of claims 1 to 10. The contact angle with a liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in a portion not irradiated with energy and 9 ° or less in a portion irradiated with energy. Item 12. The method for producing a functional element according to item 11. 13. The method according to claim 11, wherein the wettability changing layer is a layer containing an organopolysiloxane. The method according to claim 13, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The _{organopolysiloxane, Y n SiX (4-n} ) ( wherein, Y represents an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group or epoxy group, X represents an alkoxyl group or a halogen. n is an integer from 0 to 3.) An organopolysiloxane which is one or more hydrolytic condensates or co-hydrolytic condensates of a silicon compound represented by the following formula: A method for producing a functional element according to claim 14. The method according to any one of claims 11 to 15, wherein the wettability changing layer has a self-supporting property. 11. The layer according to claim 1, wherein the property change layer is a decomposition removal layer that is decomposed and removed when irradiated with energy by the action of a photocatalyst in the photocatalyst containing layer. 13. The method for producing a functional element according to item 10. 18. The functional element according to claim 17, wherein a contact angle of the liquid with respect to the decomposition removal layer is different from a contact angle of the liquid with respect to the substrate exposed when the decomposition removal layer is decomposed and removed. Production method. 19. The method according to claim 17, wherein the decomposition removal layer is one of a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternating adsorption film. 20. The wettability on the substrate is 9 ° or less as a contact angle with a liquid having a surface tension of 40 mN / m, and 10 ° or more on the decomposition removal layer. A method for manufacturing a functional element according to any one of claims 1 to 4. A substrate, a characteristic change layer having characteristics changed by the action of a photocatalyst formed on the substrate, a first functional part formed in a pattern on the characteristic change layer, and covering the first functional part And a second functional portion formed as described above. The functional element according to claim 21, wherein the property change layer is a wettability change layer. A substrate, a decomposition removal layer that is decomposed and removed by the action of a photocatalyst formed on the substrate, and a first functional portion formed in a pattern in a region on the substrate where the decomposition removal layer is decomposed and removed. And a second functional part formed around the first functional part and in a region where the decomposition removal layer is decomposed and removed on the substrate, so as to cover the first functional part. Functional element characterized by having. The functional element according to any one of claims 21 to 23, wherein the second functional part is a sealing material. 24. An optical waveguide, wherein the first functional part of the functional element according to any one of claims 21 to 23 is a core layer, and the second functional part is a cladding layer.

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