JP4201162B2 - Method for manufacturing pattern formed body and photomask used therefor - Google Patents

Description

【０１２６】
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。
【０１２７】
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。
【０１２８】
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。
【０１２９】
このように、オルガノポリシロキサン材料にフッ素を含有させる方法としては、通常高い結合エネルギーを有する主剤に対し、フッ素化合物を比較的弱い結合エネルギーで結合させる方法、比較的弱い結合エネルギーで結合されたフッ素化合物を濡れ性変化層に混入させる方法等を挙げることができる。このような方法でフッ素を導入することにより、エネルギーが照射された場合に、まず結合エネルギーが比較的小さいフッ素結合部位が分解され、これによりフッ素を濡れ性変化層中から除去することができるからである。
【０１３０】
上記第１の方法、すなわち、高い結合エネルギーを有するバインダに対し、フッ素化合物を比較的弱い結合エネルギーで結合させる方法としては、上記オルガノポリシロキサンにフルオロアルキル基を置換基として導入する方法等を挙げることができる。
【０１３１】
例えば、オルガノポリシロキサンを得る方法として、上記（１）として記載したように、ゾルゲル反応等によりクロロまたはアルコキシシラン等を加水分解、重縮合して大きな強度を発揮するオルガノポリシロキサンを得ることができる。ここで、この方法においては、上述したように上記一般式：
Ｙ_ｎＳｉＸ_{（４−ｎ）}
（ここで、Ｙはアルキル基、フルオロアルキル基、ビニル基、アミノ基、フェニル基またはエポキシ基を示し、Ｘはアルコキシル基、アセチル基またはハロゲンを示す。ｎは０〜３までの整数である。）
で示される珪素化合物の１種または２種以上を、加水分解縮合物もしくは共加水分解縮合することによりオルガノポリシロキサンを得るのであるが、この一般式において、置換基Ｙとしてフルオロアルキル基を有する珪素化合物を用いて合成することにより、フルオロアルキル基を置換基として有するオルガノポリシロキサンを得ることができる。このようなフルオロアルキル基を置換基として有する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、エネルギーが照射された際、接触する光触媒含有層中の光触媒の作用により、フルオロアルキル基の炭素結合の部分が分解されることから、濡れ性変化層表面にエネルギーを照射した部分のフッ素含有量を低減させることができる。
【０１３２】
この際用いられるフルオロアルキル基を有する珪素化合物としては、フルオロアルキル基を有するものであれば特に限定されるものではないが、少なくとも１個のフルオロアルキル基を有し、このフルオロアルキル基の炭素数が４から３０、好ましくは６から２０、特に好ましくは６から１６である珪素化合物が好適に用いられる。このような珪素化合物の具体例は上述した通りであるが、中でも炭素数が６から８であるフルオロアルキル基を有する上記珪素化合物、すなわちフルオロアルキルシランが好ましい。
【０１３３】
本発明においては、このようなフルオロアルキル基を有する珪素化合物を上述したフルオロアルキル基を有さない珪素化合物と混合して用い、これらの共加水分解縮合物を上記オルガノポリシロキサンとして用いてもよいし、このようなフルオロアルキル基を有する珪素化合物を１種または２種以上用い、これらの加水分解縮合物、共加水分解縮合物を上記オルガノポリシロキサンとして用いてもよい。
【０１３４】
このようにして得られるフルオロアルキル基を有するオルガノポリシロキサンにおいては、このオルガノポリシロキサンを構成する珪素化合物の内、上記フルオロアルキル基を有する珪素化合物が０．０１モル％以上、好ましくは０．１モル％以上含まれていることが好ましい。
【０１３５】
フルオロアルキル基がこの程度含まれることにより、濡れ性変化層上の撥液性を高くすることができ、エネルギーを照射して親液性領域とした部分との濡れ性の差異を大きくすることができるからである。
【０１３６】
また、上記（２）に示す方法では、撥液牲に優れた反応性シリコーンを架橋することによりオルガノポリシロキサンを得るのであるが、この場合も同様に、上述した一般式中のＲ^１，Ｒ^２のいずれかもしくは両方をフルオロアルキル基等のフッ素を含有する置換基とすることにより、濡れ性変化層中にフッ素を含ませることが可能であり、またエネルギーが照射された場合に、シロキサン結合より結合エネルギーの小さいフルオロアルキル基の部分が分解されるため、エネルギー照射により濡れ性変化層表面におけるフッ素の含有量を低下させることができる。
【０１３７】
一方、後者の例、すなわち、バインダの結合エネルギーより弱いエネルギーで結合したフッ素化合物を導入させる方法としては、例えば、低分子量のフッ素化合物を導入させる場合は、例えばフッ素系の界面活性剤を混入する方法等を挙げることができ、また高分子量のフッ素化合物を導入させる方法としては、バインダ樹脂との相溶性の高いフッ素樹脂を混合する等の方法を挙げることができる。
【０１３８】
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。
【０１３９】
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。
【０１４０】
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かできる。
【０１４１】
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。
【０１４２】
本発明において上述した成分の濡れ性変化層を用いることにより、接触する光触媒含有層中の光触媒の作用により、上記成分の一部である有機基や添加剤の酸化、分解等の作用を用いて、露光部の濡れ性を変化させて親液性とし、未露光部との濡れ性に大きな差を生じさせることができる。よって、機能性部用組成物、例えば画素部着色用のインク等との受容性（親液性）および反撥性（撥液性）を高めることによって、品質の良好でかつコスト的にも有利なカラーフィルタ等の機能性素子を得ることができる。
【０１４３】
なお、本発明に用いられる濡れ性変化層は、上述したように光触媒の作用により濡れ性の変化する層であれば特に限定されるものではないが、特に、光触媒を含まない層であることが好ましい。このように濡れ性変化層内に光触媒が含まれなければ、その後機能性素子として用いた場合に、経時的な劣化を心配する必要がなく、長期間に渡り問題なく使用することが可能だからである。
【０１４４】
上述した濡れ性変化層は、通常基板上に形成されるものであるが、本発明におていは、この濡れ性変化層が自己支持性を有する材料で形成されており、基板を含まないものであってもよい。
【０１４５】
なお、本発明でいう自己支持性を有するとは、他の支持材無しで有形な状態で存在し得ることをいうこととする。
【０１４６】
このような本発明に用いられる濡れ性変化層の材料として、具体的には、光触媒含有層をその表面に接触させてエネルギーを照射させることにより、その後塗布する機能性部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が、少なくとも１°以上、好ましくは５°特に１０°以上変化する材料を挙げることができる。
【０１４７】
また、この濡れ性変化層は、照射されるエネルギーを透過することができる材料で形成されていることが必要である。
【０１４８】
このような材料としては、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。
【０１４９】
（分解除去層）
次に分解除去層について説明する。この分解除去層は、露光された際に光触媒含有層中の光触媒の作用により、露光された部分の分解除去層が分解除去される層である。
【０１５０】
このように分解除去層は、露光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。したがって各種印刷版原版等の凹凸のパターンを必要とする部材は、この方法により容易に形成することができる。また、スクリーン上にこの分解除去層を塗布し、光触媒含有層側基板と接触させてパターン露光することにより、露光された部分の分解除去層は分解除去されることから、スクリーン印刷の原版を現像・洗浄工程無しに形成することができる。さらに、レジスト特性を有する素材でこの分解除去層を形成した場合は、光触媒含有層側基板と接触させてパターン露光することにより、容易にレジストのパターンを形成することができる。したがって、現像・洗浄工程の無いフォトレジストとして、半導体製造工程等に用いることも可能である。
【０１５１】
なお、この分解除去層は、露光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。
【０１５２】
また、この分解除去層を用いた場合は、凹凸を形成するのみならず、分解除去されて露出する基材と分解除去層との特性の相違によりパターンを形成することも可能である。このような特性としては、接着性、発色性等種々のものを挙げることができるが、本発明においては中でも濡れ性を挙げることができ、この濡れ性の相違によりパターンを形成することが、最終的に素子を形成した場合の有効性の点で好ましい。
【０１５３】
すなわち、本発明においては、分解除去層とこの分解除去層が分解除去されて露出する基板との液体の接触角が異なるように構成されていることが好ましく、特に基板の液体との接触角より分解除去層上の液体との接触角が大きいことが好ましい。
【０１５４】
このような分解除去層表面に要求される撥液性としては、その後塗布する機能性部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が、３０°以上、特に４０°以上、中でも５０°以上となるものであることが好ましい。
【０１５５】
このような分解除去層に用いることができる材料としては、具体的には機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜等が好適に用いられ、その他フッ素系樹脂等を用いることができる。
【０１５６】
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−ブロケット膜、および交互吸着膜について具体的に説明する。
【０１５７】
ａ．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。
【０１５８】
ｂ．ラングミュア−ブロジェット膜
本発明に用いられるおけるラングミュア−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。
【０１５９】
ｃ．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。
【０１６０】
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。
【０１６１】
（２）基板
本発明のパターン形成体の製造方法において、特性変化層は強度との関係や最終的な機能性素子との関係から、図１に示すように基板４上に形成されることが好ましい。このような基板としては、パターン形成体もしくはパターン形成体により形成された機能性素子の用途に応じて、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。
【０１６２】
３．パターン形成工程
本発明においては、次に、光触媒含有層および特性変化層を２００μｍ以下であって、接触しないように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パターン形成工程が行われる。
【０１６３】
この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く、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のである。
【０１６４】
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パターン形成体用基板に対して特に有効である。
【０１６５】
一方、例えば３００ｍｍ×３００ｍｍといった大面積のパターン形成体用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パターン形成体用基板との間に設けることは極めて困難である。したがって、パターン形成体用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。
【０１６６】
このように比較的大面積のパターン形成体用基板を露光する際には、露光装置内の光触媒含有層側基板とパターン形成体用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パターン形成体用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。
【０１６７】
本発明においては、このような間隙をおいた配置状態は、少なくとも露光の間だけ維持されればよい。
【０１６８】
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。
【０１６９】
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。
【０１７０】
次に、上述したような接触状態を維持した状態で、接触する部分へのエネルギー照射が行われる。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。
【０１７１】
通常このような露光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。
【０１７２】
このような露光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。
【０１７３】
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。
【０１７４】
また、露光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。
【０１７５】
この際、光触媒含有層を加熱しながら露光することにより、感度を上昇させことが可能となり、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。
【０１７６】
本発明における露光方向は、光触媒含有層側基板に遮光部が形成されているか否か等のパターンの形成方法や、光触媒含有層側基板もしくはパターン形成体用基板が透明であるか否かにより決定される。
【０１７７】
すなわち、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露光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、露光方向は光触媒含有層側基板側からでもパターン形成体用基板側からであってもよい。
【０１７８】
また、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露光方向は、上述したように、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。
【０１７９】
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。
【０１８０】
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。この場合は、フォトマスクが配置された側の基板、すなわち光触媒含有層側基板もしくはパターン形成体用基板のいずれかが透明である必要がある。
【０１８１】
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接触位置から離され、これにより図１（ｄ）に示すように特性が変化した特性変化領域９からなるパターンが特性変化層５上に形成される。
【０１８２】
このようなパターン形成工程における、特性変化層表面の特性の変化は、大きく分けて二つのタイプに分けることが可能であり、一つがその表面の性質を変化させるものであり、もう一つが除去するものである。
【０１８３】
すなわち、表面の性質を変化する場合とは、特性変化層表面の化合物が光触媒の作用により変性して、その化学的性質、物理的性質を変化させるものである。例えば、表面の抵抗値を変化させる場合、表面の化学的な活性を変化させる場合、表面の粘着性を変化させる場合等がある。具体的には、上述した濡れ性変化層がその代表的な例である。
【０１８４】
一方、他の性質として、エネルギー照射に伴う光触媒の作用により、特性変化層が除去される場合も本発明でいう特性変化層の特性の変化に含まれるものである。例えば、基板上の特性変化層がエネルギーが照射された部分のみ除去される場合や、特性変化層表面において、エネルギーが照射された部分のみ凹部が形成される場合、さらには特性変化層表面においてエネルギーが照射されることにより部分的な除去が発生して凹凸が生じる場合等である。この場合の代表的な例が、上述した分解除去層である。
【０１８５】
４．機能性素子
上述したパターン形成体用基板に特性の変化したパターンを形成することによりパターン形成体を得ることができる。そしてこのパターンに沿って、機能性部形成用組成物を付着させることにより、種々の機能性素子を得ることができる。
【０１８６】
このような機能性素子は、上述したパターン形成体のパターンに沿って機能性部が形成されてなる点に特徴を有するものである。
【０１８７】
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）な各種の機能を意味するものである。
【０１８８】
このような機能性部のパターン形成体のパターンに対応した部位への配置は、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、親液性領域および撥液性領域の密着性の差を利用した方法等により行われる。
【０１８９】
例えば、濡れ性変化層上における濡れ性パターンの密着性の差を利用する場合としては、濡れ性変化層上に全面にわたって機能性部用組成物としての金属を蒸着させ、その後粘着剤等により引き剥がすことにより、密着性が良好な親液性領域のみ機能性部としての金属のパターンが形成される。これにより容易にプリント基板等を形成することができる。
【０１９０】
また、濡れ性変化層上における濡れ性パターンの濡れ性の差を利用する場合としては、機能性部用組成物をパターン形成体上に塗布することにより、濡れ性の良好な親液性領域のみ機能性部用組成物が付着することになり、容易にパターン形成体の親液性領域のパターン上にのみ機能性部を配置することができる。
【０１９１】
本発明に用いられる機能性部用組成物としては、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り、例えば上述した密着性の相違により金属のパターンを形成するような場合は、この機能性部用組成物は金属となり、また濡れ性の相違によりパターンを形成する場合には、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。
【０１９２】
溶剤で希釈した液体状組成物の場合は、溶剤が水、エチレングリコール等の高表面張力を示すものであることが好ましい。また、機能性部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。
【０１９３】
本発明に用いられる機能性部用組成物としては、パターン形成体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、またパターン形成体上に配置された後、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、機能性部用組成物の結着剤として、紫外線、熱、電子線等で硬化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。
【０１９４】
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、例えば機能性部用組成物をディップコート、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塗布することにより、パターン形成体表面の親液性領域パターン上に機能性部を形成する。
【０１９５】
さらに、無電解めっきによる金属膜形成方法に本発明のパターン形成体を用いることにより、機能性部として金属膜のパターンを有する機能性素子を得ることができる。具体的には、濡れ性の差を利用することにより、パターン形成体の濡れ性変化層表面における親液性領域にのみ化学めっきの前処理液によって処理を行い、次いで処理したパターン形成体を化学めっき液に浸漬することにより、所望の金属パターンを濡れ性変化層上に有する機能性素子を得ることができる。この方法によれば、レジストパターンを形成することなく、金属のパターンを形成することができるので、機能性素子として、プリント基板や電子回路素子を製造することができる。
【０１９６】
また、全面に機能性部用組成物を配置した後、撥液性領域と親液性領域との濡れ性の差異を利用して不要な部分を取り除くことにより、パターンに沿って機能性部を形成するようにしてもよい。これは濡れ性変化層上の親液性領域と撥液性領域との密着性の差を利用して、例えば、粘着テープを密着した後に引き剥がすことによる剥離、空気の吹き付け、溶剤による処理等の後処理により不要部分を除去して機能性部のパターンを得ることができる。
【０１９７】
この場合は、本発明のパターン形成体の濡れ性変化層表面に全面に機能性部用組成物を配置する必要があるが、この方法としては、例えばＰＶＤ、ＣＶＤ等の真空製膜手段を挙げることができる。
【０１９８】
このようにして得られる機能性素子として具体的には、カラーフィルタ、マイクロレンズ、プリント基板、電子回路素子等を挙げることができる。
【０１９９】
５．カラーフィルタ
カラーフィルタは、液晶表示装置等に用いられるものであり、赤、緑、青等の複数の画素部がガラス基板等上に高精細なパターンで形成されたものである。本発明のパターン形成体をこのカラーフィルタの製造に用いることにより、低コストで高精細なカラーフィルタとすることができる。
【０２００】
すなわち、上述したパターン形成体の親液性領域に、例えばインクジェット装置等によりインク（機能性部用組成物）を付着・硬化させることにより、容易に画素部（機能性部）を形成することができ、これにより少ない工程数で高精細なカラーフィルタを得ることができる。
【０２０１】
また、本発明においては、上記パターン形成体の遮光部をそのままカラーフィルタにおけるブラックマトリックスとして用いることが可能である。したがって、上述した本発明のパターン形成体上に機能性部としての画素部（着色層）を形成するれば、別途ブラックマトリックスを形成すること無しに、カラーフィルタを得ることが可能である。
【０２０２】
Ｂ．フォトマスク
次に、本発明のフォトマスクについて説明する。本発明のフォトマスクは、少なくとも以下の３つの態様がある。
【０２０３】
第１の態様のフォトマスクは、透明な基材と、０．２μｍ〜１０μｍの厚みで上記透明基材上にパターン状に形成された遮光部パターンと、上記透明な基材および上記遮光部パターン上に形成された光触媒含有層とからなることを特徴とするものであり、その具体例を、図３に示す。
【０２０４】
このように、本発明においては、上記パターン形成体の製造方法において、遮光部を有する光触媒含有層側基板の機能面に着目し、これをフォトマスクとしたものである。
【０２０５】
また、第２の態様のフォトマスクは、透明な基材と、上記透明な基材上に形成された光触媒含有層と、０．２μｍ〜１０μｍの厚みで上記光触媒含有層上にパターン状に形成された遮光部パターンとからなることを特徴とするものであり、その具体例を図４に示す。
【０２０６】
さらに、第３の態様のフォトマスクは、透明な基材と、上記透明な基材上にパターン状に形成された遮光部と、上記透明な基材および遮光部上に形成されたプライマー層と、上記プライマー層上に形成された光触媒含有層とからなることを特徴とするものであり、その具体例を図５に示す。
【０２０７】
いずれのフォトマスクの各要素とも、上記「パターン形成体の製造方法」の欄において説明したものと同様であり、かつ各態様が奏する作用効果も、上記「パターン形成体の製造方法」の欄において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。
【０２０８】
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。
【０２０９】
【実施例】
以下、本発明について、実施例を通じてさらに詳述する。
［実施例１］
100μmのラインアンドスペースで厚さ0.4μmのクロム製の遮光部パターンが形成された石英ガラス基板上に、テイカ（株）製の光触媒用酸化チタンコーティング剤TKC301をコーティングし、350℃で3時間乾燥させ、光触媒含有層付きフォトマスク（光触媒含有層側基板）を完成させた。
【０２１０】
次に、メチルトリメトキシシラン5gに0.1N塩酸水3gを添加し１時間室温にて攪拌した溶液をガラス基板上にコーティングし、150℃で10分間乾燥させ濡れ性変化層を形成した。
【０２１１】
これに、先のフォトマスクを密着させ、フォトマスク側から超高圧水銀ランプにて20mW/cm²（365nm）の照度で紫外線照射し濡れ性変化層表面に濡れ性のパターンを形成した。このとき、未露光部の水の接触角は72°であり、露光部の水の接触角が10°以下になるのに120秒かかった。また、濡れ性変化層表面上の未露光部は95μmで露光部は105μmであった。
【０２１２】
［実施例２］
実施例1のクロム製のパターン形成体の厚みが0.1μｍのものを使用する以外は実施例1同様にパターン形成を行った。その結果、露光部の水の接触角が10°以下になるのに370秒かかった。
【０２１３】
［実施例３］
実施例1のパターン形成体において、遮光部パターンをカーボンブラックが分散された樹脂バインダ製の厚さ20μｍのものとした以外は実施例1同様にパターン形成を行った。その結果、露光部の水の接触角が10°以下になるのに560秒かかった。
【０２１４】
［実施例４］
フォトマスクと濡れ性変化層の露光を密着させずに、遮光部パターン上の光触媒含有層と濡れ性変化層とのギャップを10μmに設定した以外は実施例1同様にパターン形成を行った。その結果、露光部の水の接触角が10°以下になるのに120秒掛かった。また、濡れ性変化表面上の未露光部は80μmで露光部は120μmであった。
【０２１５】
［実施例５］
50μmのラインアンドスペースで厚さ0.4μmのクロム製の遮光部のパターンが形成された石英ガラス製のフォトマスク上に、以下のような組成の成分を混合後２５℃で２４時間攪拌して調整したプライマー層用塗工液を塗布後、１２０℃で２０分間加熱し厚さ０．１μｍのプライマー層を形成した。
【０２１６】
＜プライマー層用塗工液の組成＞
・０．１規定塩酸水溶液 ５０ｇ
・テトラメトキシシラン １００ｇ
次いで、石原産業製の光触媒無機用コーティング剤ＳＴ−Ｋ０１をプライマー層上に塗布後、１５０℃で２０分間加熱し厚さ０．１５μｍの光触媒含有層を形成し、光触媒付きフォトマスク（光触媒含有層側基板）を形成した。
【０２１７】
次いで、ガラス基板上に以下のような組成の成分を混合後２５℃で２４時間攪拌して調整したフッ素系シリコーン用塗工液を塗布後、１２０℃で１５分間加熱し、厚さ０．０５μｍの特性変化層を形成した。
【０２１８】
＜フッ素系シリコーン塗工液の組成＞
・０．２規定塩酸水溶液 ２５ｇ
・フルオロアルキルシラン １５ｇ
・テトラメトキシシラン ５０ｇ
これに、先のフォトマスクを密着させ、フォトマスク側から超高圧水銀ランプにて、２０ｍＷ／ｃｍ^２（３６５ｎｍ）の照度で紫外線照射し特性変化層表面に濡れ性のパターンを形成した。このとき、未露光部の水との接触角は１０６°であり、露光部の水の接触角が１０°以下になるのに１２０秒かかった。また、このときの未露光部位の幅は、４９μｍ、露光部の幅は５１μｍであった。
【０２１９】
［参考例］
実施例５において、プライマー層を形成せず、光触媒付きフォトマスクを形成した以外は、上記実施例５と同様にパターン形成を行った。その結果、露光部の水との接触角が１０°以下になるのに２４０秒かかった。またこのときの未露光部位の幅は４０μｍ、露光部の幅は６０μｍであった。
【０２２０】
［実施例６］
５０μmのラインアンドスペースで厚さ0.4μmのクロム製の遮光層パターンが形成された石英ガラス製のフォトマスク上に、以下のような組成の成分を混合後25℃で24時間攪拌して調整したプライマー層用塗工液を塗布後、120℃で20分間加熱し厚さ0.1μｍのプライマー層を形成した。
【０２２１】
＜プライマー層用塗工液の組成＞
・0.1規定塩酸水溶液 ５０ｇ
・テトラメトキシシラン １００ｇ
次いで、石原産業製の光触媒無機用コーティング剤ST-K03をプライマー層上に塗布後、150℃で20分間加熱し厚さ0.15μｍの光触媒含有層を形成し、光触媒付きフォトマスク（光触媒含有層側基板）を完成させた。
【０２２２】
次いで、３７０×４７０mmのガラス基板上に、以下のような組成の成分を混合後25℃で24時間攪拌して調整したフッ素系シリコーン用塗工液を塗布後、120℃で15分間加熱し厚さ0.05μｍの特性変化層を形成した。
【０２２３】
＜フッ素系シリコーン塗工液の組成＞
・0.2規定塩酸水溶液 ２５ｇ
・フルオロアルキルシラン １５ｇ
・テトラメトキシシラン ５０ｇ
これに、大型自動露光機MA-6000シリーズ（（株）大日本科研製）を用いて、フォトマスクとのギャップを６0μｍに設定し、フォトマスク側から20mW/cm²（365nm）の照度で紫外線照射し特性変化層表面に濡れ性のパターンを形成した。このとき、面内における４点のギャップは実測で５３〜６４μｍの範囲であった。また、未露光部の濡れ標準試薬（４０ｍＮ／ｍ）の接触角は７５°であり、露光部の濡れ標準試薬（４０ｍＮ／ｍ）の接触角が9°以下になるのに150秒かかった。また、このときの未露光部位の幅は４９μm、露光部の幅は５１μｍであった。
【０２２４】
［実施例７］
実施例６のギャップを1５０μｍと設定した以外は実施例６同様にパターン形成を行った。このとき、面内における４点のギャップは実測で１４５μｍ〜１５２μｍの範囲であった。その結果、露光部の濡れ標準試薬（４０ｍＮ／ｍ）の接触角が9°以下になるのに２３０秒かかった。また、このときの未露光部位の幅は４７μｍ、露光部の幅は５３μｍであった。
【０２２５】
［比較例1］
実施例６のギャップを２５０μｍと設定した以外は実施例６同様にパターン形成を行った。その結果、露光部の濡れ標準試薬（４０ｍＮ／ｍ）の接触角が9°以下になるのに３6０秒かかった。また、このときの未露光部位の幅は１５μｍ、露光部の幅は８５μｍであった。
【０２２６】
［比較例２］
実施例６のギャップを5μｍと設定した以外は実施例６同様にパターン形成を行った。光触媒含有層と特性変化層とが接触している部分が生じ、その結果、面内で濡れ性の変化に差が生じてしまい、均一なパターンが得られなかった。
【０２２７】
［実施例８］
５０μmのラインアンドスペースで厚さ0.4μmのクロム製の遮光層パターンが形成された石英ガラス製のフォトマスク上に、以下のような組成の成分を混合後25℃で24時間攪拌して調整したプライマー層用塗工液を塗布後、120℃で20分間加熱し厚さ0.1μｍのプライマー層を形成した。
【０２２８】
＜プライマー層用塗工液の組成＞
・0.1規定塩酸水溶液 ５０ｇ
・テトラメトキシシラン １００ｇ
次いで、石原産業製の光触媒無機用コーティング剤ST-K03をプライマー層上に塗布後、150℃で20分間加熱し厚さ0.15μｍの光触媒含有層を形成し、光触媒付きフォトマスク（光触媒含有層側基板）を完成させた。
【０２２９】
次いで、ガラス基板上に金を蒸着した基板を、オクタデカンチオールをヘキサンにより溶解した自己組織化膜組成物に２４時間浸漬し、ガラス基板上に金を介して分解除去層を形成した。
【０２３０】
これに、先のフォトマスクを密着させ、フォトマスク側から超高圧水銀ランプにて20mW/cm²（365nm）の照度で紫外線照射し特性変化層表面に濡れ性のパターンを形成した。このとき、自己組織化膜を分解除去するのに150秒かかった。また、このときの未露光部位の幅は49μm、露光部の幅は51μｍであった。
【０２３１】
【発明の効果】
本発明によれば、特にエネルギー照射後の後処理も必要無く、種々の特性を有するパターンを高精細に形成することができる。また、エネルギー照射後、パターン形成体から光触媒含有層側基板を取り外すので、パターン形成体自体には光触媒含有層が含まれることがなく、したがってパターン形成体の光触媒の作用による経時的な劣化に対する心配がない。さらに、光触媒含有層と特性変化層との間隔が、上述した範囲内であるので、効率よくかつ精度の良好な特性の変化したパターンを有するパターン形成体を得ることができるといった効果を奏する。
【図面の簡単な説明】
【図１】本発明のパターン形成体の製造方法の一例を示す工程図である。
【図２】本発明に用いられる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】本発明に用いられる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】本発明に用いられる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】本発明に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【符号の説明】
１ … 基材
２ … 光触媒含有層
３ … 光触媒含有層側基板
４ … 基板
５ … 特性変化層
６ … パターン形成体用基板
９ … 特性変化領域
１０ … プライマー層
１３ … 遮光部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body that is less likely to deteriorate over time because there is no photocatalyst in the formed pattern forming body when changing the characteristics using the photocatalyst, and to this manufacturing method. The present invention also relates to a photomask that can be used.
[0002]
[Prior art]
Conventionally, as a method of forming a high-definition pattern, pattern exposure is performed on a photoresist layer coated on a substrate, and after exposure, the photoresist is developed and further etched, or the photoresist has functionality. There is known a method of manufacturing a pattern forming body by photolithography, such as directly forming a target pattern by exposing a photoresist using a substance.
[0003]
The formation of high-definition patterns by photolithography is used for the formation of colored patterns for color filters used in liquid crystal display devices, the formation of microlenses, the manufacture of fine electrical circuit boards, the manufacture of chromium masks used for pattern exposure, etc. However, depending on these methods, it is necessary to use a photoresist and develop with a liquid developer after exposure or to perform etching. In addition, when a functional substance is used as a photoresist, there is a problem that it deteriorates due to an alkali solution or the like used during development.
[0004]
A high-definition pattern such as a color filter is also formed by printing or the like, but the pattern formed by printing has problems such as positional accuracy, and it is difficult to form a high-precision pattern. .
[0005]
On the other hand, in order to solve such problems, the present inventors have studied a method for producing a pattern forming body in which a pattern is formed using a substance whose wettability is changed by the action of a photocatalyst. However, the conventional method for producing a pattern forming body by the action of a photocatalyst has a configuration in which the photo-catalyst is included in the manufactured pattern forming body itself, and depending on the type of the pattern forming body, this photocatalyst may cause deterioration. In some cases, there was a problem of having the property.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and can produce a pattern with high accuracy in the production of a pattern-formed body, and does not require post-treatment after exposure, and can produce a patterned pattern. Since a photocatalyst is not contained in the body, the main object is to provide a method for producing a pattern forming body that does not have to worry about deterioration of the pattern forming body itself.
[0007]
[Means for Solving the Problems]
  To achieve the above objective,The present inventionA pattern forming body substrate preparation step for preparing a pattern forming body substrate having a characteristic change layer in which the surface characteristics change by the action of the photocatalyst;A base material, a light-shielding portion formed in a pattern on the base material, a primer layer formed on the light-shielding portion and made of amorphous silica, and formed on the primer layerA photocatalyst-containing layer containing a photocatalyst;HaveAfter arranging the photocatalyst containing layer and the property change layer of the photocatalyst containing layer side substrate with a gap so as to be 200 μm or less, the above-mentioned from a predetermined directionPhotocatalyst containing layerBy irradiating energy,By the action of the photocatalyst contained in the photocatalyst containing layerIt has a pattern formation process which forms the pattern in which the characteristic changed on the surface of the above-mentioned characteristic change layer, and provides a manufacturing method of a pattern formation object characterized by things.
[0008]
According to the present invention, a post-treatment after energy irradiation is not particularly required, and a pattern having various characteristics can be formed with high definition. In addition, since the photocatalyst containing layer side substrate is removed from the pattern forming body after energy irradiation, the pattern forming body itself does not include the photocatalyst containing layer, and therefore there is a concern about deterioration over time due to the action of the photocatalyst of the pattern forming body. There is no. Furthermore, since the distance between the photocatalyst-containing layer and the characteristic change layer is within the above-described range, it is possible to obtain a pattern forming body having a pattern with a change in characteristics with good efficiency and accuracy.
[0009]
  In the present invention,It is preferable that the photocatalyst-containing layer and the characteristic change layer are arranged so as to be spaced from each other in a range of 0.2 μm to 10 μm. Since the distance between the photocatalyst-containing layer and the characteristic change layer is in the range of 0.2 μm to 10 μm, it is possible to obtain a pattern forming body having a pattern whose characteristics are changed by short-time energy irradiation.
[0010]
  In the present invention,The photocatalyst containing layer side substrate is preferably composed of a base material and a photocatalyst containing layer formed in a pattern on the base material. Thus, by forming the photocatalyst-containing layer in a pattern, it is possible to form patterns having different characteristics on the characteristic change layer without using a photomask. In addition, since the characteristics change only on the surface corresponding to the photocatalyst-containing layer, the energy to be irradiated is not particularly limited to parallel energy, and the energy irradiation direction is not particularly limited. This is because the type of energy source and the degree of freedom in arrangement are greatly increased.
[0011]
  In the present invention,The photocatalyst-containing layer side substrate is composed of a base material, a photocatalyst-containing layer formed on the base material, and a light-shielding portion formed in a pattern, and the irradiation of energy in the pattern forming step is a photocatalyst-containing layer. It is preferable to carry out from the side substrate.
[0012]
By having the light-shielding portion on the photocatalyst-containing layer side substrate in this way, it is not necessary to use a photomask or the like for energy irradiation, so that alignment with the photomask is unnecessary, and the process can be simplified. Because.
[0013]
  In the present invention,In the photocatalyst containing layer side substrate, the light shielding part may be formed in a pattern on the base material, and the photocatalyst containing layer may be further formed thereon,AlsoIn the photocatalyst containing layer side substrate, the photocatalyst containing layer may be formed on the base material, and the light shielding portion may be formed in a pattern on the photocatalyst containing layer.
[0014]
It can be said that it is preferable in terms of accuracy of the obtained characteristic pattern that the light shielding portion is disposed at a position close to the characteristic change layer. Therefore, it is preferable to dispose the light shielding portion at the position described above. Moreover, when the light-shielding part is formed on the photocatalyst containing layer, it has an advantage that it can be used as a spacer when arranging the photocatalyst containing layer and the characteristic change layer in the pattern forming step.
[0015]
  In the present invention,In the photocatalyst-containing layer-side substrate, a spacer having a thickness in the range of 0.2 μm to 10 μm is formed on the photocatalyst-containing layer in a pattern, and the spacer and the characteristic change layer are contacted to be exposed. It is preferable.
[0016]
Thus, by providing a spacer in a pattern on the photocatalyst containing layer and exposing it so as to contact the property changing layer, the distance between the photocatalyst containing layer and the property changing layer is in the range of 0.2 μm to 10 μm. It can be easily kept inside. Further, since the photocatalyst-containing layer is covered with the spacer in the portion where the spacer is formed, the property on the property changing layer does not change even when this portion is irradiated with energy. Therefore, it is possible to form a pattern having different characteristics on the characteristic change layer in the same pattern as the pattern in which the spacer is formed.
[0017]
  In the present invention,It is preferable that the spacer is a light shielding part formed of a light shielding material. This is because, since the spacer is the light shielding portion, it is possible to form a higher definition pattern by performing energy irradiation in a state where the light shielding portion is in close contact with the characteristic change layer.
[0018]
  The present invention also providesA photocatalyst-containing layer side substrate in which a photocatalyst-containing layer is formed on a photomask having a light-shielding portion formed in a pattern on a transparent substrate, and a photocatalyst in the photocatalyst-containing layer. A pattern forming body substrate having a characteristic change layer of which the photocatalyst-containing layer and the pattern formation body substrate are in contact with each other, or the action of the photocatalyst of the photocatalyst-containing layer acts on the characteristic change layer. After the above-mentioned photocatalyst-containing layer side substrate is arranged at a distance, the characteristics of the property change layer of the irradiated part are changed by irradiating energy, and then the photocatalyst-containing layer side substrate is removed. Provided is a method of manufacturing a pattern forming body, characterized by forming a changed pattern.
[0019]
According to the present invention, there is no need for post-processing particularly after energy irradiation, and a highly sensitive and high-definition pattern can be manufactured. In addition, since the photocatalyst containing layer side substrate is removed from the pattern after energy irradiation, the photocatalyst containing layer is not included in the characteristic change layer side substrate itself, and therefore there is no fear of deterioration over time due to the action of the photocatalyst. Further, due to the effect of the primer layer, a residue or the like that occurs when patterning the light shielding portion and exists in the light shielding portion or the opening between the light shielding portions does not affect the action of the photocatalyst. Therefore, it is possible to improve the sensitivity of the photocatalyst, and it is possible to obtain a pattern whose characteristics are changed by short-time energy irradiation.
[0020]
  In the present invention,The distance that the photocatalyst of the photocatalyst-containing layer reaches the property change layer is preferably in the range of 0.2 μm to 10 μm. This is because the distance between the photocatalyst-containing layer and the characteristic change layer is in the range of 0.2 μm to 10 μm, and thus a pattern forming body having a pattern whose characteristics are changed by short-time energy irradiation can be obtained.
[0021]
  In the present invention,The photocatalyst-containing layer is preferably a layer made of a photocatalyst. This is because, if the photocatalyst-containing layer is a layer composed only of a photocatalyst, it is possible to improve the efficiency of changing the characteristics of the characteristic change layer, and it is possible to efficiently produce a pattern forming body.
[0022]
  In the present inventionThe photocatalyst-containing layer is preferably a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. By forming the photocatalyst-containing layer by vacuum film formation in this way, it is possible to obtain a homogeneous photocatalyst-containing layer having a uniform film thickness with little surface irregularity, and forming a characteristic pattern on the surface of the characteristic change layer This is because it can be performed uniformly and with high efficiency.
[0023]
  In the present invention,The photocatalyst-containing layer may be a layer having a photocatalyst and a binder. By using the binder in this manner, it becomes possible to form the photocatalyst-containing layer relatively easily, and as a result, the pattern formed body can be manufactured at a low cost.
[0024]
  In the present invention,The photocatalyst is titanium oxide (TiO₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃It is preferable that it is 1 type, or 2 or more types of substances selected from the above, and as described in claim 15, the photocatalyst is 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, non-toxic and easily available.
[0025]
  In the present invention,It is preferable that the pattern forming body substrate is formed of at least a substrate and the characteristic change layer provided on the substrate. This is because the normal characteristic change layer has various characteristics, and is preferably formed as a thin film on the substrate in terms of strength, cost, and function.
[0026]
  In the present invention,It is preferable that the characteristic change layer is a wettability change layer in which wettability changes so that a contact angle with a liquid is lowered when irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer. There are various characteristics of the characteristic change layer, and among them, an important one is a change in wettability. By making the property change layer a wettability change layer in this way, it becomes possible to obtain a pattern formed body having a pattern in which the wettability has been changed by the action of a photocatalyst. This is because various functional elements such as a color filter and a microlens can be formed by attaching the composition for the sex part, as will be described later.
[0027]
  In the present invention,The contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is preferably 10 ° or more in the unexposed portion and 9 ° or less in the exposed portion. This is because the part that is not irradiated with energy is a part that requires liquid repellency, and the irradiated part is a part that requires lyophilicity, so it is necessary to have this level of wettability. .
[0028]
  In the present invention,The wettability changing layer is preferably a layer containing an organopolysiloxane,Above all,The organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. This is because such a wettability changing layer can obtain a significant change in wettability by energy irradiation in a state where the photocatalyst-containing layer is in contact.
[0029]
  In the present invention,The organopolysiloxane is Y_nSiX_(4-n)Wherein 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 from 0 to 3. It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolyzed condensate or cohydrolyzed condensate of the silicon compound. This is because by forming a wettability changing layer using such an organopolysiloxane as a material, a pattern forming body in which a wettability pattern having a large difference in wettability is formed can be obtained.
[0030]
  In the present invention,The pattern forming substrate is a film having self-supporting properties, and at least one surface thereof is wetted by the action of the photocatalyst in the photocatalyst-containing layer so that the contact angle with the liquid is lowered when irradiated with energy. It may be a film-like wettability changing layer whose properties change. Such a pattern forming body can obtain patterns with different wettability only by, for example, irradiating energy with one surface of a commercially available film made of a predetermined material in contact with the photocatalyst containing layer. This is because an inexpensive pattern forming body can be obtained.
[0031]
  In the present invention,The characteristic change layer may be a decomposition removal layer that is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer. Thus, by making the characteristic change layer into a decomposition removal layer that is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer, the part irradiated with energy is decomposed and removed by the action of the photocatalyst. Since the portion irradiated with energy can be completely decomposed and removed without the need for post-treatment, for example, the decomposition removal layer is a photoresist, and the photocatalyst-containing layer side substrate is brought into contact therewith. This is because there are various uses such as that a pattern can be formed on a photoresist without the necessity of performing a conventional development process.
[0032]
  In the present invention,It is preferable that the contact angle between the decomposition removal layer and the substrate exposed when the decomposition removal layer is decomposed and removed is different from that of the liquid.
[0033]
As described above, the contact angle between the decomposition and removal layer and the substrate exposed when the decomposition and removal layer is decomposed and removed is different, so that the portion subjected to the energy irradiation is decomposed by the action of the photocatalyst. As a result, the substrate is exposed on the surface. On the other hand, the decomposition removal layer remains in the portion where the energy is not irradiated. Here, when the contact angle between the decomposition removal layer and the exposed substrate is different, for example, the decomposition removal layer is formed of a liquid repellent material, and the substrate is formed of a lyophilic material. In some cases, the portion where the functional portion is previously formed is irradiated with energy and the photocatalyst is applied to remove the decomposition / removal layer of the portion. The irradiated portion is a recess and lyophilic. A region that is not irradiated with energy is a convex portion and a liquid repellent region. Thereby, the composition for a functional part can be accurately and easily attached to the concave part in which the functional part is provided and the part of the lyophilic region. Therefore, the functional part can be formed more accurately than in the case where the characteristic change layer described above is a wettability change layer, and it is not necessary to perform post-treatment after energy irradiation such as a development step or a washing step. For this reason, it is possible to easily simplify the process, and it is possible to obtain a functional element having an inexpensive and accurate functional part.
[0034]
  In the present invention,The decomposition removal layer is preferably a self-assembled monomolecular film, a Langmuir-Blodgett film, or an alternating adsorption film. This is because these materials are decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer and exhibit various functions.
[0035]
  In the present invention,The energy irradiation is preferably performed while heating the photocatalyst-containing layer. This is because by heating the photocatalyst, the sensitivity of the photocatalyst is improved and the characteristic change on the characteristic change layer can be efficiently performed.
[0036]
  In the present invention,A transparent substrate, a light-shielding portion formed in a pattern on the transparent substrate, a primer layer formed on the transparent substrate and the light-shielding portion, and a photocatalyst formed on the primer layer A photomask characterized by comprising a layer. By using such a photomask, it is possible to obtain a pattern with various characteristics changed simply by irradiating energy through this photomask, and to obtain a pattern formed body efficiently. .
[0037]
  Also,In the present invention,It consists of a transparent substrate, a photocatalyst containing layer formed on the transparent substrate, and a light shielding part pattern formed in a pattern on the photocatalyst containing layer with a thickness of 0.2 μm to 10 μm. 30. A photomask, a transparent substrate as described in claim 29, a light shielding part pattern formed in a pattern on the transparent substrate with a thickness of 0.2 μm to 10 μm, and the transparent substrate And a photocatalyst-containing layer formed on the light-shielding part pattern. In this case as well, by irradiating energy to the pattern forming substrate having the characteristic change layer as described above through this photomask, patterns having various characteristics can be obtained efficiently. This is because a pattern-formed body can be obtained.
[0038]
  The present invention further relates to the present invention.Provided is a functional element in which a functional part is arranged on a pattern forming body manufactured by a method for manufacturing a pattern forming body. Thus, a functional element can be easily obtained by using the pattern forming body of the present invention.
[0039]
  Of the present inventionExamples of the functional element include those in which the functional part is a metal. In this case, it can be applied to, for example, a high-definition electric circuit board.
[0040]
  The present invention provides the aboveProvided is a color filter, wherein the functional part of the functional element is a pixel part. Such a color filter has an extremely high quality because a high-definition pixel portion is formed with high accuracy.
[0041]
DETAILED DESCRIPTION OF THE INVENTION
First, the manufacturing method of the pattern formation body of this invention is demonstrated, Then, the photomask which can be used also for the manufacturing method of this pattern formation body is demonstrated.
[0042]
A. Method for producing pattern forming body
The pattern forming body manufacturing method of the present invention comprises a pattern forming body substrate preparation step of preparing a pattern forming body substrate having a characteristic change layer in which the surface characteristics change by the action of a photocatalyst,
After arranging the photocatalyst containing layer of the photocatalyst containing layer side substrate on which the photocatalyst containing layer is formed on the base material and the above characteristic change layer with a gap of 200 μm or less, a predetermined direction A pattern forming step of forming a pattern with a changed characteristic on the surface of the characteristic change layer by irradiating energy from
It is characterized by having.
[0043]
As described above, in the method for producing a pattern formed body of the present invention, the photocatalyst-containing layer and the characteristic change layer are arranged so as to have a predetermined gap, and then irradiated with energy from a predetermined direction, whereby Due to the action of the photocatalyst, the characteristics of the characteristic change layer facing the photocatalyst-containing layer and exposed are changed, and a pattern of the changed characteristic on the characteristic change layer is formed. Accordingly, post-processing such as development / washing after exposure is not required for pattern formation, so that patterns having different characteristics can be formed with fewer steps and at lower cost. And it can be set as the pattern formation body which can be used for various uses by selecting the material of this characteristic change layer.
[0044]
Furthermore, in the present invention, after the characteristics on the characteristic change layer are changed by the action of the photocatalyst in the photocatalyst containing layer, the photocatalyst containing layer side substrate is removed and the pattern forming body side substrate is used as the pattern forming body. The obtained pattern forming body does not necessarily contain a photocatalyst. Therefore, it is possible to prevent a problem that the obtained pattern forming body deteriorates with time due to the action of the photocatalyst.
[0045]
Such a method for producing a pattern forming body of the present invention will be specifically described with reference to the drawings. FIG. 1 shows an example of a method for producing a pattern forming body of the present invention.
[0046]
In this example, first, a photocatalyst containing layer side substrate 3 in which a photocatalyst containing layer 2 is formed on a substrate 1 and a pattern forming body substrate 6 in which a characteristic change layer 5 is formed on a substrate 4 are provided. It adjusts (refer FIG. 1 (a), the board | substrate preparation process for pattern formation bodies).
[0047]
Next, as shown in FIG. 1B, the photocatalyst containing layer side substrate 3 and the pattern forming body substrate 6 are arranged so that the photocatalyst containing layer 2 and the characteristic change layer 5 have a predetermined interval. After that, a photomask 7 on which a required pattern is drawn is used, and ultraviolet light 8 is irradiated from the photomask-containing layer side substrate 3 side through the photomask 7. Thereby, as shown in FIG.1 (c), the pattern which consists of the area | region 9 in which the characteristic changed on the surface of the characteristic change layer 5 is formed (pattern formation process).
[0048]
In the above example, the irradiation with ultraviolet rays is performed through the photomask 7. However, as will be described later, a photocatalyst containing layer is formed in a pattern, or a light shielding portion is formed in the photocatalyst containing layer side substrate. In this case, the entire surface is exposed without using the photomask 7 or the like.
[0049]
And the process of removing a photocatalyst content layer side substrate from the above-mentioned substrate 6 for pattern formations is performed (Drawing 1 (d)), and pattern formation object 6 which has pattern 9 in which the characteristic changed on the surface can be obtained.
[0050]
The method for producing the pattern forming body of the present invention will be described in detail for each element.
[0051]
1. Adjustment of photocatalyst containing layer side substrate
In the present invention, first, a photocatalyst-containing layer side substrate used in a pattern forming step described later is prepared. This photocatalyst containing layer side substrate has a base material and a photocatalyst containing layer containing a photocatalyst formed on the base material.
[0052]
Such a photocatalyst-containing layer side substrate has at least a photocatalyst-containing layer and a substrate, and is usually formed by forming a thin-film photocatalyst-containing layer formed by a predetermined method on the substrate. is there. Moreover, the thing in which the light shielding part formed in the pattern shape was formed can also be used for this photocatalyst containing layer side board | substrate.
[0053]
(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 characteristic change layer, and includes a photocatalyst and a binder. It may be formed, or it may be a film formed of a photocatalyst alone. Further, the wettability of the surface may be particularly lyophilic or lyophobic.
[0054]
The photocatalyst-containing layer used in the present invention may be formed on the entire surface of the substrate 1 as shown in FIG. 1 (a), for example, but for example, as shown in FIG. The photocatalyst containing layer 2 may be formed on the pattern on the material 1.
[0055]
By forming the photocatalyst-containing layer in a pattern like this, as described in the pattern forming step described later, when the photocatalyst-containing layer is arranged at a predetermined interval from the characteristic change layer and irradiated with energy, It is not necessary 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.
[0056]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0057]
In addition, since the characteristics of only the part on the characteristic change layer facing the photocatalyst containing layer actually change, the energy irradiation direction is such that the part where the photocatalyst containing layer and the characteristic change layer face is irradiated with energy. As long as it irradiates, it may irradiate from what direction, and also has the advantage that irradiation energy is not limited to parallel things, such as parallel light.
[0058]
Thus, 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 reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen 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 in the vicinity of the photocatalyst containing layer.
[0059]
As the photocatalyst used in the present invention, for example, titanium dioxide (TiO 2) 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 (Fe₂O₃1) or a mixture of two or more selected from these.
[0060]
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 an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0061]
Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0062]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.
[0063]
The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0064]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0065]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.
[0066]
Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, 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 modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0067]
Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by photoexcitation of said photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.
[0068]
When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this 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 or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0069]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, silanol as a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less.
[0070]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.
[0071]
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. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0072]
In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0073]
In addition to the above surfactants, the photocatalyst-containing layer includes 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, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.
[0074]
(Base material)
In the present invention, as shown in FIG. 1, the photocatalyst containing layer side substrate 3 has at least a base material 1 and a photocatalyst containing layer 2 formed on the base material 1.
[0075]
Under the present circumstances, the material which comprises the base material used is suitably selected by the irradiation direction of the energy in the pattern formation process mentioned later, whether the pattern formation body obtained requires transparency, etc.
[0076]
That is, for example, in the case where an opaque pattern forming body is used as a substrate, the energy irradiation direction is inevitably from the photocatalyst containing layer side substrate side, and as shown in FIG. It is necessary to arrange it on the layer side substrate 3 side and irradiate energy. In addition, as will be described later, a light-shielding portion is formed in a predetermined pattern on the photocatalyst-containing layer side substrate in advance, and energy is irradiated from the photocatalyst-containing layer side substrate side even when a pattern is formed using this light-shielding portion. There is a need. In such a case, the base material needs to have transparency.
[0077]
On the other hand, if the pattern forming body is transparent, it is possible to arrange the photomask on the pattern forming body substrate side and irradiate energy. Moreover, when forming the pattern formation body side light-shielding part in this pattern formation body substrate, it is necessary to irradiate energy from the pattern formation body substrate side. In such a case, the transparency of the substrate is not particularly required.
[0078]
The base material used in the present invention may be a flexible material such as a resin film, or may be a non-flexible material such as a glass substrate. This is appropriately selected depending on the energy irradiation method in the pattern forming process described later.
[0079]
As described above, the material used for the photocatalyst-containing layer side substrate in the present invention is not particularly limited, but in the present invention, the photocatalyst-containing layer side substrate is used repeatedly. Therefore, a material having a predetermined strength and having a surface having good adhesion to the photocatalyst containing layer is preferably used.
[0080]
Specific examples include glass, ceramic, metal, and plastic.
[0081]
In addition, in order to improve the adhesiveness between the substrate surface and the photocatalyst containing layer, a primer layer may be formed on the substrate. Examples of such a primer layer include silane-based and titanium-based coupling agents.
[0082]
(Shading part)
As the photocatalyst-containing layer side substrate used in the present invention, a substrate having a light-shielding portion formed in a pattern may be used. By using the photocatalyst containing layer side substrate having the light shielding portion in this manner, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0083]
The photocatalyst-containing layer side substrate having such a light shielding part can be made into the following two embodiments depending on the formation position of the light shielding part.
[0084]
For example, as shown in FIG. 3, one is an embodiment in which a light shielding part 13 is formed on a base material 1 and a photocatalyst containing layer 2 is formed on the light shielding part 13 to form a photocatalyst containing layer side substrate 3. . The other is an embodiment in which a photocatalyst containing layer 2 is formed on a base material 1 and a light shielding portion 13 is formed thereon to form a photocatalyst containing layer side substrate 3 as shown in FIG.
[0085]
In any embodiment, as compared with the case where a photomask is used, the light-shielding portion is disposed in the vicinity of the portion where the photocatalyst-containing layer and the characteristic change layer are located with a gap. Since it is possible to reduce the influence of energy scattering, the energy pattern irradiation can be performed very accurately.
[0086]
Furthermore, in the embodiment in which the light shielding part is formed on the photocatalyst containing layer, when the photocatalyst containing layer and the characteristic change layer are arranged with a predetermined gap, the thickness of the light shielding part is set to the width of the gap. By matching, the light-shielding portion can be used as a spacer for making the gap constant.
[0087]
That is, when the photocatalyst containing layer and the characteristic change layer are arranged in contact with each other with a predetermined gap, the light shielding part and the characteristic change layer are arranged in close contact with each other, thereby The gap can be made accurate, and in this state, by irradiating energy from the photocatalyst-containing layer side substrate, a pattern can be formed on the characteristic change layer with high accuracy.
[0088]
The method for forming such a light-shielding part is not particularly limited, and is appropriately selected and used depending on the characteristics of the surface where the light-shielding part is formed, the shielding property against the required energy, and the like.
[0089]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0090]
Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0091]
In the above description, the two light-shielding portions are formed between the base material and the photocatalyst-containing layer and on the surface of the photocatalyst-containing layer, but the photocatalyst-containing layer of the base material is formed. It is also possible to adopt a mode in which a light shielding portion is formed on the surface on the non-side. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be suitably used when the pattern forming body is changed in a small lot.
[0092]
(Primer layer)
In the present invention, when the light-shielding part is formed in a pattern on the substrate as described above and the photocatalyst-containing layer is formed on the substrate, the light-shielding part and the photocatalyst-containing layer are formed. It is preferable to form a primer layer between the two.
[0093]
The action and function of this primer layer are not necessarily clear, but by forming a primer layer between the light shielding part and the photocatalyst containing layer, the primer layer inhibits the characteristic change of the characteristic change layer due to the action of the photocatalyst. It is considered to exhibit a function to prevent diffusion of impurities such as light shielding portions and openings from the openings existing between the light shielding portions, particularly residues generated when the light shielding portions are patterned, and impurities such as metals and metal ions. . Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0094]
In the present invention, the primer layer prevents the impurities present in the openings formed between the light shielding portions as well as the light shielding portions from affecting the action of the photocatalyst. Therefore, the primer layer includes the openings. It is preferable that it is formed over the entire light shielding portion.
[0095]
FIG. 5 shows an example of the photocatalyst containing layer side substrate on which such a primer layer is formed. A primer layer 10 is formed on the surface of the substrate 1 on which the light shielding portion 13 is formed, on the side where the light shielding portion 13 is formed, and the photocatalyst-containing layer 2 is formed on the surface of the primer layer 10.
[0096]
The configuration in which the light shielding portion is formed in a pattern on the base material is a general photomask configuration. Therefore, it can be said that this primer layer is one in which the photocatalyst-containing layer is formed on the photomask via the primer layer.
[0097]
The primer layer in the present invention is not particularly limited as long as it has a structure in which the photocatalyst-containing layer and the photomask are arranged so as not to come into physical contact. That is, the primer layer only needs to be formed so that the light-shielding portion of the photomask and the photocatalyst-containing layer do not come into contact with each other.
[0098]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX.₄X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0099]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0100]
2. Substrate adjustment process for pattern forming body
In the method for producing a pattern forming body of the present invention, as shown in FIG. 1, first, a pattern forming body substrate 6 to be arranged at a position facing the above-described photocatalyst containing layer side substrate 3 is prepared.
[0101]
The substrate for pattern forming body is not particularly limited as long as it has at least a characteristic change layer, but it is preferable that the characteristic change layer is formed on the substrate from the viewpoint of strength and the like. Further, if necessary, other protective layers and the like may be formed, but it is necessary that the characteristic change layer is exposed at least on the entire surface or partially.
[0102]
In the present invention, the pattern forming substrate refers to a substrate in which the pattern due to the characteristic changing portion has not yet been formed on the characteristic changing layer, and the pattern forming substrate is exposed to light on the characteristic changing layer. A pattern formed body is formed with a pattern of the characteristic change portion.
[0103]
(1) Characteristic change layer
In the present invention, the property change layer may be any layer as long as the property is changed by the action of the photocatalyst. For example, an organic dye decomposed by the action of a photochromic material such as spiropyran or the action of the photocatalyst in the property change layer. Etc. may be mixed in the characteristic change layer, and the characteristic change layer may be a layer colored by the action of the photocatalyst.
[0104]
In addition, for example, by using a polymer material such as polyethylene such as polyethylene or polypropylene, a polar group is introduced into the exposed part due to the action of a photocatalyst, or the surface state becomes rough. A layer that is improved in adhesiveness may be used as a characteristic change layer. Thus, by making the characteristic change layer an adhesive change layer in which the adhesiveness changes, it becomes possible to form a pattern with good adhesiveness by pattern exposure. For example, a pattern forming body having such a pattern with a good adhesive property is formed by depositing a metal component on such a pattern forming body to form a metal thin film, and then utilizing the difference in adhesiveness to form a metal. By peeling the thin film with, for example, an adhesive or a drug, a metal thin film pattern can be formed. According to this method, it is possible to form a metal thin film pattern without forming a resist pattern, and it is possible to form a printed circuit board or an electronic circuit element having a finer pattern than that obtained by the printing method. it can.
[0105]
Further, in the present invention, such a characteristic change layer may be formed by a dry method, that is, a vacuum deposition method or the like, or by a wet method, that is, a method such as a spin coating method or a dip coating method. It may be formed.
[0106]
Thus, the characteristic change layer is not particularly limited as long as it has various characteristics that change due to the action of the photocatalyst. However, in the present invention, the characteristic change layer changes its wettability due to the action of the photocatalyst. Functions that can be obtained in particular are the wettability changing layer in which a pattern due to the property is formed and the decomposition changing layer in which the property changing layer is decomposed and removed by the action of the photocatalyst to form a pattern due to unevenness. It is preferable because the effectiveness of the present invention can be further extracted from the relationship of the characteristic elements.
[0107]
(Wettability change layer)
The wettability variable layer in the present invention is not particularly limited as long as the wettability of the surface is changed by the action of the photocatalyst, but in general, the wettability change is caused by the action of the photocatalyst accompanying irradiation of energy. A layer whose wettability changes so that the contact angle with the liquid on the surface of the layer decreases is preferable.
[0108]
In this way, the wettability is reduced so that the contact angle with the liquid is reduced by exposure (in the present invention, not only light is irradiated but also energy is applied). By changing the wettability changing layer, the wettability is easily changed into a pattern by irradiating energy through the light shielding part, and a pattern of a lyophilic region with a small contact angle with the liquid is formed. The functional element can be easily formed by attaching the functional part composition to the lyophilic region. Therefore, a functional element can be manufactured efficiently, which is advantageous in terms of cost.
[0109]
Here, the lyophilic region is a region having a small contact angle with the liquid, and if the functional part composition, for example, the functional element is a color filter, the pixel part (colored layer) coloring ink, In addition, when the functional element is a microlens, it means a region having good wettability with respect to a composition for forming a microlens. The liquid repellent region is a region having a large contact angle with the liquid and refers to a region having poor wettability with respect to the functional part composition described above.
[0110]
The wettability changing layer has a contact angle with a liquid with a surface tension of 40 mN / m of 10 ° or more, preferably a liquid with a surface tension of 30 mN / m, in a non-exposed portion, that is, a water-repellent region. It is preferable that the wettability is 10 ° or more, in particular, the contact angle with a liquid having a surface tension of 20 mN / m is 10 ° or more. This is because the non-exposed part is a part that requires liquid repellency in the present invention, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the functional part is formed. This is because there is a possibility that the composition for use will remain.
[0111]
Further, when the wettability changing layer is exposed to light, the contact angle with the liquid decreases, 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. Is preferably a layer such that the contact angle with a liquid having a surface tension of 60 mN / m is 10 ° or less. If the contact angle with the exposed portion, that is, the liquid in the lyophilic region is high, the spread of the composition for forming the functional part in this part may be inferior, and problems such as lack of the functional part may occur. Because there is sex.
[0112]
In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.
[0113]
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 is more energy than the wettability changing layer. The wettability changing layer may be formed so as to be lower than that before energy irradiation by the action of the photocatalyst.
[0114]
In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, 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 small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of a lyophilic region in the liquid repellent region.
[0115]
Therefore, when such a wettability changing layer is used, a pattern of the lyophilic region can be easily formed in the lyophobic region by irradiating the pattern with energy. Therefore, it is possible to easily form a functional part only, and a functional element with good quality can be obtained at low cost.
[0116]
As described above, the fluorine content contained in the wettability changing layer containing fluorine is the fluorine content in the lyophilic region having a low fluorine content formed by energy irradiation. When the fluorine content of the non-existing portion is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0117]
By setting it within such a range, it is possible to make a great difference in wettability between the energy irradiated portion and the unirradiated portion. Therefore, by forming the functional part in such a wettability changing layer, it becomes possible to accurately form the functional part only in the lyophilic region where the fluorine content is reduced, and the functional element can be accurately formed. Because it can be obtained. This rate of decrease is based on weight.
[0118]
The fluorine content in such a wettability changing layer can be measured by various commonly used methods such as X-ray Photoelectron Spectroscopy, ESCA (Electron Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.
[0119]
As a material used for such a wettability changing layer, the characteristics of the wettability changing layer described above, that is, a material whose wettability is changed by the photocatalyst in the photocatalyst-containing layer that is contacted by exposure, and deteriorated by the action of the photocatalyst, Although it is not particularly limited as long as it has a main chain that is difficult to decompose, for example, (1) an organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane or the like by a sol-gel reaction or the like Examples thereof include organosiloxanes such as siloxanes and (2) organopolysiloxanes crosslinked with reactive silicones having excellent water repellency and oil repellency.
[0120]
In the case of (1) above, 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 from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0121]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those known as fluorine-based silane coupling agents can be used.
[0122]
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.
[0123]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the unexposed portion of the wettability changing layer is greatly improved. For example, the pixel portion is colored when the functional element is a color filter. The function which prevents adhesion of the functional part composition such as the ink for use is developed.
[0124]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0125]
[Chemical 1]

[0126]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0127]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0128]
In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
[0129]
As described above, as a method for containing fluorine in the organopolysiloxane material, a method in which a fluorine compound is bonded with a relatively weak bond energy to a main agent that usually has a high bond energy, or a fluorine bonded with a relatively weak bond energy. Examples include a method of mixing a compound into the wettability changing layer. By introducing fluorine by such a method, when energy is irradiated, a fluorine bonding site having a relatively low binding energy is first decomposed, and thus fluorine can be removed from the wettability changing layer. It is.
[0130]
Examples of the first method, that is, a method of bonding a fluorine compound with a relatively weak binding energy to a binder having a high binding energy include a method of introducing a fluoroalkyl group as a substituent into the organopolysiloxane. be able to.
[0131]
For example, as described in (1) above, as a method for obtaining an organopolysiloxane, an organopolysiloxane exhibiting high strength can be obtained by hydrolyzing and polycondensing chloro or alkoxysilane or the like by a sol-gel reaction or the like. . Here, in this method, as described above, the above 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 from 0 to 3. )
An organopolysiloxane is obtained by hydrolyzing or co-hydrolyzing and condensing one or two or more of the silicon compounds represented by formula (1). In this general formula, silicon having a fluoroalkyl group as the substituent Y is obtained. By synthesizing using a compound, an organopolysiloxane having a fluoroalkyl group as a substituent can be obtained. When an organopolysiloxane having such a fluoroalkyl group as a substituent is used as a binder, the carbon bond portion of the fluoroalkyl group is caused by the action of the photocatalyst in the photocatalyst-containing layer that comes into contact when irradiated with energy. Since it is decomposed, it is possible to reduce the fluorine content in the portion where the wettability changing layer surface is irradiated with energy.
[0132]
The silicon compound having a fluoroalkyl group used at this time is not particularly limited as long as it has a fluoroalkyl group, but has at least one fluoroalkyl group, and the carbon number of the fluoroalkyl group A silicon compound in which is 4 to 30, preferably 6 to 20, particularly preferably 6 to 16, is preferably used. Specific examples of such a silicon compound are as described above, and among these, the above silicon compound having a fluoroalkyl group having 6 to 8 carbon atoms, that is, a fluoroalkylsilane is preferable.
[0133]
In the present invention, such a silicon compound having a fluoroalkyl group may be used in combination with the above-mentioned silicon compound having no fluoroalkyl group, and these cohydrolyzed condensates may be used as the organopolysiloxane. In addition, one or two or more silicon compounds having such a fluoroalkyl group may be used, and these hydrolyzed condensates and cohydrolyzed condensates may be used as the organopolysiloxane.
[0134]
In the organopolysiloxane having a fluoroalkyl group thus obtained, among the silicon compounds constituting the organopolysiloxane, the silicon compound having the fluoroalkyl group is 0.01 mol% or more, preferably 0.1%. It is preferable that it is contained in mol% or more.
[0135]
By including the fluoroalkyl group to such a degree, the liquid repellency on the wettability changing layer can be increased, and the difference in wettability with the portion that has been made lyophilic by irradiation with energy can be increased. Because it can.
[0136]
In the method shown in (2) above, organopolysiloxane is obtained by crosslinking reactive silicone having excellent liquid repellency. In this case as well, R in the above general formula is similarly used.¹, R²By making either or both of them a fluorine-containing substituent such as a fluoroalkyl group, it is possible to include fluorine in the wettability changing layer. Since the portion of the fluoroalkyl group having a low binding energy is decomposed, the fluorine content on the surface of the wettability changing layer can be reduced by energy irradiation.
[0137]
On the other hand, as a method for introducing a fluorine compound bonded with energy lower than the binding energy of the binder, for example, when introducing a low molecular weight fluorine compound, for example, a fluorine-based surfactant is mixed. Examples of the method of introducing a high molecular weight fluorine compound include a method of mixing a fluorine resin having high compatibility with the binder resin.
[0138]
The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0139]
In addition to the above surfactants, the wettability changing layer includes 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, Epichlorohydrin, Polysulfide, Polyisoprene, etc. Can be contained.
[0140]
Such a wettability changing layer can be formed by preparing a coating solution by dispersing the above-described components in a solvent together with other additives as necessary, and coating 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 or bead coating. In addition, in the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0141]
In the present invention, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, from the relationship of the wettability change rate by the photocatalyst. is there.
[0142]
By using the wettability changing layer of the above-described component in the present invention, by the action of the photocatalyst in the photocatalyst-containing layer in contact, the action of oxidation, decomposition or the like of the organic group or additive which is part of the above component By changing the wettability of the exposed part to make it lyophilic, a large difference in wettability with the unexposed part can be produced. Therefore, by improving the acceptability (lyophilicity) and repellent property (liquid repellency) of the functional part composition, for example, the ink for coloring the pixel part, the quality is favorable and the cost is advantageous. A functional element such as a color filter can be obtained.
[0143]
In addition, the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. If the photocatalyst is not included in the wettability changing layer in this way, there is no need to worry about deterioration over time when it is used as a functional element thereafter, and it can be used without problems for a long time. is there.
[0144]
The above-described wettability changing layer is usually formed on a substrate, but in the present invention, this wettability changing layer is formed of a self-supporting material and does not include a substrate. It may be.
[0145]
In addition, having self-supporting property as used in the field of this invention means that it can exist in a tangible state without another support material.
[0146]
Specifically, as the material of the wettability changing layer used in the present invention, the surface of the functional part composition to be applied thereafter by bringing the photocatalyst-containing layer into contact with the surface and irradiating energy. Examples thereof include a material whose contact angle with a liquid having a surface tension equivalent to the tension changes by at least 1 °, preferably 5 °, particularly 10 ° or more.
[0147]
In addition, the wettability changing layer needs to be formed of a material that can transmit irradiated energy.
[0148]
Examples of such materials include polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol, Examples thereof include polyvinyl chloride, polyethylene terephthalate, and silicone.
[0149]
(Decomposition removal layer)
Next, the decomposition removal layer will be described. This decomposition removal layer is a layer in which the exposed portion of the decomposition removal layer is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when exposed.
[0150]
As described above, the decomposed and removed layer is decomposed and removed by the action of the photocatalyst, so that the pattern including the portion with and without the decomposed / removed layer without performing the development process and the cleaning process, that is, the pattern having unevenness. Can be formed. Therefore, members that require uneven patterns such as various printing plate precursors can be easily formed by this method. In addition, by applying this decomposition / removal layer on the screen and bringing it into contact with the photocatalyst-containing layer side substrate for pattern exposure, the exposed portion of the decomposition / removal layer is decomposed and removed. -It can be formed without a cleaning step. Furthermore, when this decomposition / removal layer is formed of a material having resist characteristics, a resist pattern can be easily formed by exposing the pattern to contact with the photocatalyst-containing layer side substrate. Therefore, it can be used in a semiconductor manufacturing process or the like as a photoresist without a development / cleaning process.
[0151]
This decomposition / removal layer is oxidatively decomposed and vaporized by the action of the photocatalyst by exposure, and is therefore removed without any special post-treatment such as development / washing process. Depending on the case, a cleaning step or the like may be performed.
[0152]
Further, when this decomposition / removal layer is used, it is possible not only to form irregularities, but also to form a pattern based on the difference in characteristics between the base material that is decomposed and removed and the decomposition / removal layer. Examples of such properties include various properties such as adhesiveness and color developability, but in the present invention, wettability can be mentioned, and a pattern is formed by the difference in wettability. Therefore, it is preferable in terms of effectiveness when an element is formed.
[0153]
That is, in the present invention, it is preferable that the contact angle of the liquid between the decomposition / removal layer and the substrate exposed by decomposition / removal of the decomposition / removal layer is different, particularly from the contact angle of the substrate with the liquid. It is preferable that the contact angle with the liquid on the decomposition removal layer is large.
[0154]
The liquid repellency required for the surface of such a decomposition / removal layer is such that the contact angle with respect to a liquid having a surface tension equivalent to the surface tension of the functional part composition applied thereafter is 30 ° or more, particularly 40 ° or more. In particular, it is preferable that the angle is 50 ° or more.
[0155]
As a material that can be used for such a decomposition and removal layer, specifically, a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, an alternating adsorption film, and the like are preferably used. A resin or the like can be used.
[0156]
Here, the self-assembled monomolecular film, the Langmuir-Brocket film, and the alternating adsorption film used in the present invention will be specifically described.
[0157]
a. Self-assembled monolayer
Although the inventors do not know the existence of an official definition of self-assembled monolayer, a commentary on what is generally recognized as a self-assembled membrane is, for example, a review by Abraham Ulman. “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. Referring to this review article, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and binding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has 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 part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present invention, these are also included in the self-assembled monolayer.
[0158]
b. Langmuir-Blodgett membrane
The Langmuir-Blodgett film used in the present invention is not significantly different from the above-described self-assembled monomolecular film in form if it is formed on a substrate. It can be said that the Langmuir-Blodgett film is characterized by its formation method and the advanced two-dimensional molecular packing properties (high orientation and high order). 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 to change into a highly packed condensed film. In practice, this is transferred to a suitable substrate for use. It is possible to form from a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).
[0159]
c. Alternate adsorption film
Alternating adsorption film (Layer-by-Layer Self-Assembled Film) is generally laminated by adsorbing and bonding at least two materials with positive or negative functional groups sequentially onto the substrate. It is a film | membrane formed by doing. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is somewhat biased towards materials systems driven by electrostatic interactions, but a review by Paula T. Hammond “Recent Explorations in Electrostatic Multilayer Thin Film Assembly” Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). The alternate adsorption film can be described by taking the simplest process as an example, by repeating the adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge a predetermined number of times. It is a film to be formed. As with Langmuir-Blodgett membranes, no development-condensation-transfer operations are required. Further, as apparent from the difference in these production methods, the alternate adsorption film generally does not have a two-dimensional high orientation / high order like the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film formation methods, such as the ability to easily form a dense film without defects and the ability to form even fine irregular surfaces, tube inner surfaces, and spherical surfaces. Have many.
[0160]
Further, 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 energy irradiated in an 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 within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.
[0161]
(2) Substrate
In the method for producing a pattern formed body of the present invention, the characteristic change layer is preferably formed on the substrate 4 as shown in FIG. 1 from the relationship with the strength and the relationship with the final functional element. Examples of such a substrate include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, nonwoven fabrics, and the like, depending on the use of the pattern forming body or the functional element formed by the pattern forming body.
[0162]
3. Pattern formation process
In the present invention, a pattern forming step is next performed in which the photocatalyst-containing layer and the characteristic change layer are 200 μm or less and are arranged with a gap so as not to contact each other, and then irradiated with energy from a predetermined direction.
[0163]
Thus, by disposing the photocatalyst-containing layer and the property change layer surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, if the interval between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the characteristic change rate may be slowed down. It is not preferable, and it is not preferable that the active oxygen species generated are difficult to reach the property change layer when arranged at a distance from the above range. is there.
[0164]
In the present invention, in consideration of the fact that the pattern accuracy is very good, the photocatalyst sensitivity is high, and the efficiency of property change is good, the gap is particularly in the range of 0.2 μm to 10 μm, preferably 1 μm to 5 μm. It is preferable to be within the range. Such a range of the gap is particularly effective for a substrate for a pattern forming body having a small area in which the gap can be controlled with high accuracy.
[0165]
On the other hand, when processing is performed on a substrate for a pattern forming body having a large area of, for example, 300 mm × 300 mm, the photocatalyst-containing layer side substrate and the pattern forming body substrate are not contacted and the fine gap as described above is formed between It is extremely difficult to provide between the two. Therefore, when the pattern forming body substrate has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly in the range of 50 to 75 μm. By setting the gap within such a range, there is no problem of pattern accuracy deterioration such as blurring of the pattern or problems such as deterioration of photocatalyst sensitivity and deterioration of efficiency of characteristic change. This is because there is an effect that unevenness of the characteristic change on the layer does not occur.
[0166]
Thus, when exposing a pattern forming body substrate having a relatively large area, the setting of the gap in the positioning device between the photocatalyst containing layer side substrate and the pattern forming body substrate in the exposure apparatus is in the range of 10 μm to 200 μm. Especially, it is preferable to set in the range of 25 micrometers-75 micrometers. By setting the set value within such a range, the pattern accuracy is not significantly reduced and the sensitivity of the photocatalyst is not greatly deteriorated, and the photocatalyst-containing layer side substrate and the pattern forming body substrate are not in contact with each other. This is because they can be arranged.
[0167]
In the present invention, such an arrangement state with a gap need only be maintained at least during exposure.
[0168]
An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the characteristic change layer. It is possible to form a predetermined pattern on the characteristic change layer.
[0169]
In the present invention, such a spacer may be formed as one member. However, for simplification of the process, as described in the column of the photocatalyst containing layer side substrate, the photocatalyst of the photocatalyst containing layer side substrate is used. It is preferable to form on the surface of the containing layer. In the 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 so that the photocatalytic action does not reach the surface of the property change layer. Therefore, it may be formed of a material that does not have a function of shielding the irradiated energy.
[0170]
Next, in a state where the contact state as described above is maintained, energy irradiation is performed on the contacted portion. The energy irradiation (exposure) in the present invention is a concept including irradiation of any energy ray capable of changing the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is limited to irradiation with visible light. It is not something.
[0171]
Usually, the wavelength of light used for such exposure is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0172]
Examples of light sources that can be used for such exposure include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0173]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0174]
In addition, the irradiation amount of energy at the time of exposure is set to an irradiation amount necessary for the characteristic change layer surface to change the characteristic of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0175]
At this time, it is preferable in that the photocatalyst-containing layer is exposed while being heated, so that the sensitivity can be increased and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0176]
The exposure direction in the present invention is determined by the pattern formation method, such as whether or not the light-shielding part is formed on the photocatalyst-containing layer side substrate, and whether the photocatalyst-containing layer side substrate or the pattern forming body substrate is transparent. Is done.
[0177]
That is, when the light-shielding portion is formed on the photocatalyst containing layer side substrate, it is necessary to perform exposure from the photocatalyst containing layer side substrate side, and in this case, with respect to the energy irradiated to the photocatalyst containing layer side substrate It needs to be transparent. In this case, when the light shielding part is formed on the photocatalyst containing layer and the photocatalyst containing layer side light shielding part is used so as to function as the spacer as described above, the exposure direction is the photocatalyst containing layer side. It may be from the substrate side or from the pattern forming body substrate side.
[0178]
In addition, the exposure direction when the photocatalyst-containing layer is formed in a pattern is irradiated from any direction as long as energy is applied to the portion where the photocatalyst-containing layer and the property change layer are in contact as described above. May be.
[0179]
Similarly, in the case of using the above-described spacer, irradiation may be performed from any direction as long as energy is applied to the contact portion.
[0180]
In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming body substrate needs to be transparent.
[0181]
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is moved away from the contact position with the characteristic change layer, and as a result, a pattern consisting of the characteristic change region 9 whose characteristic has changed as shown in FIG. It is formed on the characteristic change layer 5.
[0182]
In such a pattern formation process, the change in characteristics of the surface of the characteristic change layer can be roughly divided into two types, one of which changes the properties of the surface and the other is removed. Is.
[0183]
That is, in the case of changing the surface property, the compound on the surface of the property changing layer is modified by the action of the photocatalyst to change its chemical property and physical property. For example, when the resistance value of the surface is changed, the chemical activity of the surface is changed, the adhesiveness of the surface is changed, and the like. Specifically, the wettability changing layer described above is a typical example.
[0184]
On the other hand, as another property, the case where the characteristic change layer is removed by the action of the photocatalyst accompanying energy irradiation is also included in the characteristic change of the characteristic change layer in the present invention. For example, when only the part irradiated with energy is removed from the characteristic change layer on the substrate, or when the concave part is formed only on the part irradiated with energy on the surface of the characteristic change layer, the energy is further changed on the surface of the characteristic change layer. This is a case in which partial removal occurs due to irradiating and unevenness occurs. A typical example in this case is the above-described decomposition removal layer.
[0185]
4). Functional element
A pattern formed body can be obtained by forming a pattern with changed characteristics on the above-described substrate for a pattern formed body. And various functional elements can be obtained by attaching the composition for functional part formation along this pattern.
[0186]
Such a functional element is characterized in that a functional part is formed along the pattern of the pattern forming body described above.
[0187]
Here, the term “functionality” means optical (light selective absorption, reflectivity, polarization, light selective transmission, nonlinear optical property, luminescence such as fluorescence or phosphorescence, photochromic property, etc.), magnetic (hard magnetism, soft magnetism, etc.). , Non-magnetic, magnetically permeable, etc.), electrical / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorptive, desorbable, catalytic, water-absorbing, ionic conductivity) , Redox, electrochemical properties, electrochromic, etc.), mechanical (wear resistance, etc.), thermal (heat transfer, heat insulation, infrared radiation, etc.), biofunctional (biocompatibility, antithrombotic, etc.) ) Means various functions.
[0188]
The arrangement of the functional part in the part corresponding to the pattern of the pattern forming body may be performed by a method using the difference in wettability between the lyophilic region and the lyophobic region, or the lyophilic region and the lyophobic region. It is performed by a method using the difference in adhesion between the two.
[0189]
For example, in order to utilize the difference in wettability pattern adhesion on the wettability changing layer, a metal as a functional part composition is vapor-deposited on the entire surface of the wettability changing layer and then drawn with an adhesive or the like. By peeling off, a metal pattern as a functional part is formed only in the lyophilic region having good adhesion. Thereby, a printed circuit board etc. can be formed easily.
[0190]
In addition, when utilizing the wettability difference of the wettability pattern on the wettability changing layer, only the lyophilic region having good wettability can be obtained by applying the functional part composition onto the pattern forming body. The functional part composition will adhere, and the functional part can be easily disposed only on the pattern of the lyophilic region of the pattern forming body.
[0191]
As described above, the functional part composition used in the present invention varies greatly depending on the function of the functional element, the method of forming the functional element, and the like. In the case of forming, this functional part composition is a metal, and in the case of forming a pattern due to a difference in wettability, a composition not diluted with a solvent typified by an ultraviolet curable monomer or the like A liquid composition diluted with a solvent can be used.
[0192]
In the case of a liquid composition diluted with a solvent, the solvent preferably exhibits a high surface tension such as water or ethylene glycol. Moreover, as a composition for functional parts, since a pattern can be formed in a short time, so that a viscosity is low, it is especially preferable. However, in the case of a liquid composition diluted with a solvent, it is desirable that the solvent has low volatility because an increase in viscosity and a change in surface tension occur due to volatilization of the solvent during pattern formation.
[0193]
As the functional part composition used in the present invention, it may be a functional part by being attached to the pattern forming body or the like, and after being placed on the pattern forming body, It may be a functional part after being treated with a drug or treated with ultraviolet rays, heat or the like. In this case, as a binder of the functional part composition, when it contains a component that is cured by ultraviolet rays, heat, electron beam or the like, it is preferable because the functional part can be formed quickly by performing a curing treatment. .
[0194]
A method for forming such a functional element will be specifically described. For example, means for applying a functional part composition, such as dip coating, roll coating, blade coating, spin coating and the like, nozzle ejection means including ink jet, etc. The functional part is formed on the lyophilic region pattern on the surface of the pattern forming body.
[0195]
Furthermore, the functional element which has a pattern of a metal film as a functional part can be obtained by using the pattern formation body of this invention for the metal film formation method by electroless plating. Specifically, by using the difference in wettability, only the lyophilic region on the wettability changing layer surface of the pattern formed body is treated with the chemical plating pretreatment liquid, and then the treated pattern formed body is chemically treated. By dipping in the plating solution, a functional element having a desired metal pattern on the wettability changing layer can be obtained. According to this method, since a metal pattern can be formed without forming a resist pattern, a printed circuit board or an electronic circuit element can be manufactured as a functional element.
[0196]
In addition, after the functional part composition is disposed on the entire surface, unnecessary parts are removed using the difference in wettability between the liquid-repellent region and the lyophilic region, so that the functional part is formed along the pattern. You may make it form. This utilizes the difference in adhesion between the lyophilic area and the liquid-repellent area on the wettability changing layer, for example, peeling by peeling after the adhesive tape is adhered, air blowing, treatment with a solvent, etc. Unnecessary portions can be removed by post-processing to obtain a functional portion pattern.
[0197]
In this case, it is necessary to dispose the functional part composition on the entire surface of the wettability changing layer of the pattern formed body of the present invention. Examples of this method include vacuum film forming means such as PVD and CVD. be able to.
[0198]
Specific examples of the functional element thus obtained include a color filter, a microlens, a printed board, and an electronic circuit element.
[0199]
5. Color filter
The color filter is used in a liquid crystal display device or the like, and has a plurality of pixel portions such as red, green, and blue formed on a glass substrate or the like with a high-definition pattern. By using the pattern formed body of the present invention for the production of this color filter, it is possible to obtain a high-definition color filter at low cost.
[0200]
That is, the pixel portion (functional portion) can be easily formed by adhering and curing the ink (composition for functional portion) to the lyophilic region of the pattern forming body described above using, for example, an ink jet apparatus. Thus, a high-definition color filter can be obtained with a small number of steps.
[0201]
In the present invention, the light-shielding portion of the pattern forming body can be used as it is as a black matrix in a color filter. Therefore, if a pixel portion (colored layer) as a functional portion is formed on the above-described pattern forming body of the present invention, a color filter can be obtained without forming a black matrix separately.
[0202]
B. Photo mask
Next, the photomask of the present invention will be described. The photomask of the present invention has at least the following three aspects.
[0203]
The photomask of the first aspect includes a transparent base material, a light shielding part pattern formed on the transparent base material in a thickness of 0.2 μm to 10 μm, the transparent base material, and the light shielding part pattern. The photocatalyst containing layer formed above is characterized in that a specific example is shown in FIG.
[0204]
Thus, in the present invention, in the method for producing a pattern forming body, attention is paid to the functional surface of the photocatalyst-containing layer side substrate having a light shielding portion, and this is used as a photomask.
[0205]
Further, the photomask of the second aspect is formed in a pattern on the photocatalyst-containing layer with a thickness of 0.2 μm to 10 μm with a transparent base material, a photocatalyst-containing layer formed on the transparent base material FIG. 4 shows a specific example of the light-shielding portion pattern.
[0206]
Furthermore, the photomask of the third aspect includes a transparent substrate, a light shielding portion formed in a pattern on the transparent substrate, and a primer layer formed on the transparent substrate and the light shielding portion. And a photocatalyst-containing layer formed on the primer layer, a specific example of which is shown in FIG.
[0207]
Each element of any of the photomasks is the same as that described in the above-mentioned “Method for Producing Pattern Formed Product”, and the effect of each aspect is also described in the “Method for producing Pattern Formed Product” column. Since it is the same as what was demonstrated, description here is abbreviate | omitted.
[0208]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
[0209]
【Example】
Hereinafter, the present invention will be described in more detail through examples.
[Example 1]
Coated with TKC301, a photocatalytic titanium oxide coating agent, made by Teika Co., Ltd. on a quartz glass substrate with a 0.4 μm thick light shielding part pattern of 100 μm line and space, and dried at 350 ° C. for 3 hours Thus, a photomask with a photocatalyst containing layer (photocatalyst containing layer side substrate) was completed.
[0210]
Next, a solution obtained by adding 3 g of 0.1N hydrochloric acid to 5 g of methyltrimethoxysilane and stirring at room temperature for 1 hour was coated on a glass substrate and dried at 150 ° C. for 10 minutes to form a wettability changing layer.
[0211]
The previous photomask is in close contact with this, and 20 mW / cm from the photomask side with an ultra-high pressure mercury lamp.²Ultraviolet rays were irradiated at an illuminance of (365 nm) to form a wettability pattern on the surface of the wettability changing layer. At this time, the contact angle of water in the unexposed area was 72 °, and it took 120 seconds for the contact angle of water in the exposed area to be 10 ° or less. The unexposed area on the wettability changing layer surface was 95 μm and the exposed area was 105 μm.
[0212]
[Example 2]
A pattern was formed in the same manner as in Example 1 except that the chromium pattern forming body of Example 1 having a thickness of 0.1 μm was used. As a result, it took 370 seconds for the contact angle of water in the exposed area to be 10 ° or less.
[0213]
[Example 3]
In the pattern formed body of Example 1, pattern formation was performed in the same manner as in Example 1 except that the light shielding part pattern was made of a resin binder having a thickness of 20 μm in which carbon black was dispersed. As a result, it took 560 seconds for the contact angle of water in the exposed area to be 10 ° or less.
[0214]
[Example 4]
A pattern was formed in the same manner as in Example 1 except that the gap between the photocatalyst containing layer and the wettability changing layer on the light-shielding part pattern was set to 10 μm without bringing the photomask and the wettability changing layer into exposure. As a result, it took 120 seconds for the contact angle of water in the exposed area to be 10 ° or less. The unexposed area on the wettability changed surface was 80 μm and the exposed area was 120 μm.
[0215]
[Example 5]
On a quartz glass photomask with a 50 μm line-and-space pattern of 0.4 μm thick chrome light-shielding part, the following components were mixed and stirred for 24 hours at 25 ° C. The applied primer layer coating solution was applied, and then heated at 120 ° C. for 20 minutes to form a primer layer having a thickness of 0.1 μm.
[0216]
<Composition of primer layer coating solution>
・ 0.1N hydrochloric acid aqueous solution 50g
・ Tetramethoxysilane 100g
Next, after applying the photocatalyst inorganic coating agent ST-K01 made by Ishihara Sangyo on the primer layer, it was heated at 150 ° C. for 20 minutes to form a photocatalyst containing layer having a thickness of 0.15 μm, and a photomask with a photocatalyst (photocatalyst containing layer) Side substrate) was formed.
[0217]
Next, after mixing the components of the following composition on the glass substrate, applying a coating solution for fluorine-based silicone prepared by stirring at 25 ° C. for 24 hours, heating at 120 ° C. for 15 minutes, and thickness of 0.05 μm The characteristic change layer was formed.
[0218]
<Composition of fluorine-based silicone coating solution>
・ 0.2N hydrochloric acid aqueous solution 25g
・ Fluoroalkylsilane 15g
・ Tetramethoxysilane 50g
The previous photomask is in close contact with this, and 20 mW / cm from the photomask side with an ultrahigh pressure mercury lamp.²Ultraviolet rays were irradiated at an illuminance of (365 nm) to form a wettability pattern on the surface of the property change layer. At this time, the contact angle with water in the unexposed area was 106 °, and it took 120 seconds for the contact angle with water in the exposed area to be 10 ° or less. At this time, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0219]
[Reference example]
In Example 5, pattern formation was performed in the same manner as in Example 5 except that the primer layer was not formed and a photomask with a photocatalyst was formed. As a result, it took 240 seconds for the contact angle of the exposed portion with water to be 10 ° or less. At this time, the width of the unexposed portion was 40 μm, and the width of the exposed portion was 60 μm.
[0220]
[Example 6]
On a quartz glass photomask having a 50 μm line and space 0.4 μm thick chromium light-shielding layer pattern formed, the following components were mixed and adjusted at 25 ° C. for 24 hours. After applying the primer layer coating solution, it was heated at 120 ° C. for 20 minutes to form a primer layer having a thickness of 0.1 μm.
[0221]
<Composition of primer layer coating solution>
・ 0.1N hydrochloric acid aqueous solution 50g
・ Tetramethoxysilane 100g
Next, the photocatalyst inorganic coating agent ST-K03 manufactured by Ishihara Sangyo Co., Ltd. was applied onto the primer layer, heated at 150 ° C. for 20 minutes to form a photocatalyst-containing layer having a thickness of 0.15 μm, and a photomask with a photocatalyst (photocatalyst-containing layer side) Substrate) was completed.
[0222]
Next, on a 370 × 470 mm glass substrate, the components of the following composition were mixed, and after coating with a coating solution for fluorine-based silicone prepared by stirring at 25 ° C. for 24 hours, the coating was heated at 120 ° C. for 15 minutes to obtain a thickness. A characteristic change layer having a thickness of 0.05 μm was formed.
[0223]
<Composition of fluorine-based silicone coating solution>
・ 0.2g hydrochloric acid aqueous solution 25g
・ Fluoroalkylsilane 15g
・ Tetramethoxysilane 50g
For this, using a large automatic exposure machine MA-6000 series (manufactured by Dainippon Kaken Co., Ltd.), the gap with the photomask is set to 60 μm, and 20 mW / cm from the photomask side.²Ultraviolet rays were irradiated at an illuminance of (365 nm) to form a wettability pattern on the surface of the property change layer. At this time, the gap at four points in the plane was in the range of 53 to 64 μm by actual measurement. The contact angle of the wet standard reagent (40 mN / m) in the unexposed area was 75 °, and it took 150 seconds for the contact angle of the wet standard reagent (40 mN / m) in the exposed area to be 9 ° or less. At this time, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0224]
[Example 7]
Pattern formation was performed in the same manner as in Example 6 except that the gap in Example 6 was set to 150 μm. At this time, the gaps at the four points in the plane were in the range of 145 μm to 152 μm by actual measurement. As a result, it took 230 seconds for the contact angle of the wet standard reagent (40 mN / m) in the exposed area to be 9 ° or less. At this time, the width of the unexposed portion was 47 μm, and the width of the exposed portion was 53 μm.
[0225]
[Comparative Example 1]
Pattern formation was performed in the same manner as in Example 6 except that the gap in Example 6 was set to 250 μm. As a result, it took 360 seconds for the contact angle of the wet standard reagent (40 mN / m) in the exposed area to be 9 ° or less. At this time, the width of the unexposed portion was 15 μm, and the width of the exposed portion was 85 μm.
[0226]
[Comparative Example 2]
A pattern was formed in the same manner as in Example 6 except that the gap in Example 6 was set to 5 μm. A portion in which the photocatalyst-containing layer and the property change layer are in contact with each other was generated. As a result, a difference in wettability change occurred in the surface, and a uniform pattern could not be obtained.
[0227]
[Example 8]
On a quartz glass photomask having a 50 μm line and space 0.4 μm thick chromium light-shielding layer pattern formed, the following components were mixed and adjusted at 25 ° C. for 24 hours. After applying the primer layer coating solution, it was heated at 120 ° C. for 20 minutes to form a primer layer having a thickness of 0.1 μm.
[0228]
<Composition of primer layer coating solution>
・ 0.1N hydrochloric acid aqueous solution 50g
・ Tetramethoxysilane 100g
Next, the photocatalyst inorganic coating agent ST-K03 manufactured by Ishihara Sangyo Co., Ltd. was applied onto the primer layer, heated at 150 ° C. for 20 minutes to form a photocatalyst-containing layer having a thickness of 0.15 μm, and a photomask with a photocatalyst (photocatalyst-containing layer side) Substrate) was completed.
[0229]
Next, the substrate on which gold was vapor-deposited on a glass substrate was immersed in a self-assembled film composition in which octadecanethiol was dissolved in hexane for 24 hours, and a decomposition removal layer was formed on the glass substrate via gold.
[0230]
The previous photomask is in close contact with this, and 20 mW / cm from the photomask side with an ultra-high pressure mercury lamp.²Ultraviolet rays were irradiated at an illuminance of (365 nm) to form a wettability pattern on the surface of the property change layer. At this time, it took 150 seconds to decompose and remove the self-assembled film. At this time, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm.
[0231]
【The invention's effect】
According to the present invention, a post-treatment after energy irradiation is not particularly required, and a pattern having various characteristics can be formed with high definition. In addition, since the photocatalyst containing layer side substrate is removed from the pattern forming body after energy irradiation, the pattern forming body itself does not include the photocatalyst containing layer, and therefore there is a concern about deterioration over time due to the action of the photocatalyst of the pattern forming body. There is no. Furthermore, since the distance between the photocatalyst-containing layer and the characteristic change layer is within the above-described range, there is an effect that it is possible to obtain a pattern forming body having a pattern with a changed characteristic with high efficiency and accuracy.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an example of a method for producing a pattern-formed body of the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of a photocatalyst-containing layer side substrate used in the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present invention.
FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate used in the present invention.
FIG. 5 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present invention.
[Explanation of symbols]
1 ... Base material
2 ... Photocatalyst containing layer
3 ... Photocatalyst containing layer side substrate
4 ... Board
5 ... Characteristic change layer
6 ... Substrate for pattern forming body
9 ... Characteristic change area
10… Primer layer
13 ... Shading part

Claims (21)

  A pattern forming body substrate preparing step for preparing a pattern forming body substrate having a characteristic changing layer whose surface characteristics are changed by the action of the photocatalyst, a base material, and a light shielding portion formed in a pattern on the base material A photocatalyst-containing layer of the photocatalyst-containing layer side substrate having a primer layer formed on the light-shielding portion and made of amorphous silica, and a photocatalyst-containing layer formed on the primer layer and containing a photocatalyst, and the characteristic change layer, Is disposed with a gap so as to be 200 μm or less, and then the photocatalyst-containing layer is irradiated with energy from a predetermined direction, so that the photocatalyst-containing layer has characteristics on the surface of the characteristic change layer. And a pattern forming step of forming a pattern having changed.   The method for producing a pattern forming body according to claim 1, wherein the photocatalyst-containing layer and the characteristic change layer are arranged so as to be within a range of 0.2 μm to 10 μm. The method for producing a pattern forming body according to claim 1 , wherein the photocatalyst-containing layer is a layer made of a photocatalyst. The said photocatalyst containing layer is a layer formed by film-forming a photocatalyst on a base material by a vacuum film-forming method, The manufacturing method of the pattern formation body of Claim 3 characterized by the above-mentioned. The photocatalyst-containing layer The method for producing a patterned member according to claim 1 or claim 2, characterized in that a layer having a photocatalyst and a binder. The photocatalyst is composed of 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 one or more substances selected from iron oxide (Fe ₂ O ₃ ), The pattern forming body according to any one of claims 1 to 5 Manufacturing method. The method for producing a pattern forming body according to claim 6, wherein the photocatalyst is titanium oxide (TiO ₂ ). The substrate for a pattern formation body is formed of at least a substrate and the characteristic change layer provided on the substrate, The claim 1 according to any one of claims 1 to 7 , A manufacturing method of a pattern formation object. The characteristic change layer is a wettability change layer whose wettability changes so that a contact angle with a liquid is lowered when irradiated with energy by the action of a photocatalyst in the photocatalyst-containing layer. The method for producing the pattern forming body according to 8 . The contact angle with a liquid having a surface tension of 40 mN / m in the variable wettability layer is, is 10 ° or more in the areas not exposed, claim 9, characterized in that at 9 ° or less in the exposed portion The manufacturing method of the pattern formation body of description. The method for producing a pattern forming body according to claim 9 or 10 , wherein the wettability changing layer is a layer containing an organopolysiloxane. The method for producing a pattern forming body according to claim 11, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. n is an integer of 0 to 3.) claim 11, characterized in that the is an organopolysiloxane which is one or more hydrolysis condensate or cohydrolysis condensate of a silicon compound represented by Or the manufacturing method of the pattern formation body of Claim 12 . The pattern forming substrate is a film having self-supporting properties, and at least one surface thereof is wetted by the action of the photocatalyst in the photocatalyst-containing layer so that the contact angle with the liquid is lowered when irradiated with energy. The method for producing a pattern forming body according to any one of claims 1 to 7 , wherein the wettability changing layer is a film-like layer whose properties change. The method for producing a pattern forming body according to claim 8 , wherein the characteristic change layer is a decomposition removal layer that is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer. 16. The method of manufacturing a pattern forming body according to claim 15, wherein the contact angle between the decomposition removal layer and the liquid exposed to the substrate exposed when the decomposition removal layer is decomposed and removed is different. The method for producing a pattern forming body according to any one of claims 1 to 16 , wherein the energy irradiation is performed while heating the photocatalyst-containing layer.   A transparent base material, a light-shielding portion formed in a pattern on the transparent base material, a primer layer formed on the transparent base material and the light-shielding portion and made of amorphous silica, and on the primer layer A photomask comprising a formed photocatalyst-containing layer. 18. A functional element, wherein a functional part is arranged on a pattern forming body manufactured by the method for manufacturing a pattern forming body according to any one of claims 1 to 17 . The functional element according to claim 19 , wherein the functional part is a metal. The color filter, wherein the functional part of the functional element according to claim 19 is a pixel part.

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