JP4383095B2 - Method for producing pattern forming body - Google Patents

Description

【０１１２】
ただし、ｎは２以上の整数であり、Ｒ¹，Ｒ²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、Ｒ¹、Ｒ²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。
【０１１３】
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ン化合物を混合してもよい。
【０１１４】
本実施態様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。
【０１１５】
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。
【０１１６】
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工液を調製し、この塗工液を後述する光触媒含有層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、ディップコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【０１１７】
本実施態様において、上述した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、１０Å〜１０００Å、中でも１０Å〜１００Åの範囲内であることが好ましい。
【０１１８】
▲２▼単分子膜である場合
次に、上記濡れ性変化層が単分子膜である場合について説明する。上記濡れ性変化層が単分子膜であることにより、上記濡れ性変化層を均一かつ緻密な層とすることができ、後述する機能性部を均一かつ高精細に形成することが可能となるのである。このような単分子膜としては、例えば自己組織化単分子膜が挙げられる。
【０１１９】
ここで、自己組織化単分子膜とは、固体／液体もしくは固体／気体界面で、有機分子同士が自発的に集合し、会合体を形成しながら自発的に単分子膜を形作っていく有機薄膜である。例として、ある特定の材料でできた基板を、その基板材料と化学的親和性の高い有機分子の溶液または蒸気にさらすと、有機分子は基板表面で化学反応し吸着する。その有機分子が、化学的親和性の高い官能基と、基板との化学反応を全く起こさない有機鎖との２つのパートからなり、親和性の高い官能基がその末端にある場合、分子は反応性末端が基板側を向き、有機鎖が外側を向いて吸着する。有機鎖同士が集合すると、全体として安定になるため、化学吸着の過程で有機分子同士は自発的に集合する。分子の吸着には、基板と末端官能基との間で化学反応が起こることが必要であることから、いったん基板表面が有機分子でおおわれ単分子膜ができあがると、それ以降は分子の吸着は起こらない。その結果、分子が密に集合し、配向性のそろった有機単分子膜ができるものである。
【０１２０】
本実施態様においては、上記濡れ性変化層が上記自己組織化単分子膜である場合、エネルギー照射に伴う光触媒の作用によって、濡れ性変化層表面に存在する撥水性を有する有機鎖が、エネルギー照射に伴う光触媒の作用によって除去されることにより、容易に表面を親水性とすることが可能であり、効率的に特性変化パターンの形成を行うことが可能となるのである。
【０１２１】
このような上記濡れ性変化層として用いられる単分子膜を構成する材料としては、上述した特性を有するものであれば、特に限定されるものではないが、本実施態様においては、有機鎖を有するシラン化合物であることが好ましい。これにより、単分子膜の形成が容易であり、かつ上述した特性を発揮することが可能となるからである。ここで、上記有機鎖を構成する炭素の数は、１〜２０の範囲内、中でも５〜１０の範囲内であることが好ましい。これにより、エネルギー照射前の濡れ性変化層を撥液性とすることができ、エネルギー照射に伴う光触媒の作用により上記有機鎖が分解等され、親液性とすることが可能となるのである。
【０１２２】
上記有機鎖を有するシラン化合物として、具体的には、上述したオルガノポリシロキサンの項で説明した材料等を用いることができ、中でもフルオロアルキルシランであることが好ましい。
【０１２３】
このような単分子膜からなる濡れ性変化層は、熱ＣＶＤ法やディップコート法、等により形成することができるが、本実施態様においては、熱ＣＶＤ法であることが製造効率等の面から好ましい。熱ＣＶＤ法の好ましい成膜条件としては、後述する透明基材等の耐熱温度以下であれば、原料となる物質の気化温度以上であり、かつ分解温度以下であれば特に限定されるものではないが、通常５０℃〜２００℃の範囲内であることが好ましい。
【０１２４】
また、本実施態様においては、公知である減圧熱ＣＶＤ法を用いてもよい。この減圧熱ＣＶＤ処理時における真空度として、十分な材料の蒸気圧が得られるように設定することができる。この蒸気圧は材料の種類により適宜選択されるものであるが、通常０．０１Ｔｏｒｒ〜１０Ｔｏｒｒ、中でも５Ｔｏｒｒ以下とすることができる。またこの際、透明基材表面との反応を促進するために、透明基材を加熱しながら減圧ＣＶＤ法を行い、濡れ性変化層を形成することが好ましい。この場合の加熱温度は、透明基材および濡れ性変化層の材料によって適宜選択されるものではあるが、通常４０℃〜１００℃の範囲内、中でも８０℃以下とされる。
【０１２５】
本実施態様において形成される濡れ性変化層の膜厚としては、その単分子膜の種類にもより決定されるものであるが、通常１ｎｍ〜５０ｎｍの範囲とされる。
【０１２６】
（分解除去層）
次に、本実施態様に用いられる特性変化層が分解除去層である場合について説明する。本実施態様に用いられる分解除去層は、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層である。このように分解除去層は、エネルギー照射され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とからなるパターン、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。
【０１２７】
なお、この分解除去層は、エネルギー照射による光触媒の作用により酸化分解され、気化等されることから、現像・洗浄工程等の特別な後処理なしに除去されるものであるが、分解除去層の材質によっては、洗浄工程等を行ってもよい。
【０１２８】
また、本実施態様に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、後述する透明基材と比較して、液体との接触角が高いことが好ましい。これにより、分解除去層が分解除去され、透明基材が露出した領域を親液性領域、上記分解除去層が残存する領域を撥液性領域とすることが可能となり、表面の凹凸だけでなく、濡れ性の差も利用して、機能性部を形成することが可能となるからである。
【０１２９】
ここで、親液性領域とは、液体との接触角が小さい領域であり、機能性部を形成する機能性部形成用塗工液に対する濡れ性の良好な領域をいうこととする。また、撥液性領域とは、液体との接触角が大きい領域であり、機能性部形成用塗工液に対する濡れ性が悪い領域をいうこととする。
【０１３０】
また、上記分解除去層は、４０ｍＮ／ｍの液体との接触角が、１０°以上、特に表面張力２０ｍＮ／ｍの液体との接触角が１０°以上の濡れ性を示すことが好ましい。これは、本実施態様は、残存する特性変化層が、撥液性が要求される部分であることから、液体との接触角が小さい場合は、撥液性が十分でなく、機能性部を形成しない撥液性領域にまで機能性部形成用塗工液が残存する可能性が生じるため好ましくないからである。
【０１３１】
また、本実施態様において、後述する透明基材は、４０ｍＮ／ｍの液体との接触角が、エネルギーが照射されていない部分において９°以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０°以下となるような層であることが好ましい。本実施態様においては透明基材が、親液性が要求される部分であることから、機能性部形成用塗工液の塗布に際して、親液性領域においても機能性部形成用塗工液をはじいてしまう可能性があり、親液性領域上に機能性部をパターニングすることが難しくなる可能性があるからである。ここで、液体との接触角は、上述した方法により測定した値である。
【０１３２】
この場合、後述する透明基材は表面を親液性となるように、表面処理したものであってもよい。材料の表面を親液性となるように表面処理した例としては、アルゴンや水などを利用したプラズマ処理による親液性表面処理が挙げられ、透明基材上に形成する親液性の層としては、例えばテトラエトキシシランのゾルゲル法によるシリカ膜等を挙げることができる。
【０１３３】
上記のような分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【０１３４】
また、本実施態様においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【０１３５】
ここで、本実施態様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。
【０１３６】
▲１▼自己組織化単分子膜
本実施態様に用いられ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、片方の分子末端に透明基材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）の高分子が一層透明基材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。本実施態様は、これらも自己組織化単分子膜に含める。
【０１３７】
▲２▼ラングミュア−ブロジェット膜
本実施態様に用いられるラングミュア−ブロジェット膜(Langmuir-Blodgett Film)は、透明基材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、これを適当な透明基材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。
【０１３８】
▲３▼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透明基材上に吸着・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。
【０１３９】
また、分解除去層の膜厚としては、エネルギーに伴う光触媒の作用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、１０Å〜１０００Å、中でも１０Å〜１００Åの範囲内とすることが好ましい。
【０１４０】
（２）透明基材
次に、本実施態様に用いられるパターン形成体用基板における基体について説明する。本実施態様に用いられる基体は、特性変化パターン形成の際に照射されるエネルギーに対して、透過性を有し、かつ上述した特性変化層が形成可能なものであれば特に限定されるものではないが、本実施態様においては、上述したように、パターン形成体用基板側からエネルギー照射が行われるものであることから、透明基材が照射されたエネルギーを吸収や散乱、干渉等させないことが好ましい。そのため、上述した照射されるエネルギーの透過率が５％〜９５％、中でも５０％〜９５％の範囲内であることが好ましい。これにより、照射されたエネルギーを光触媒含有層に効率よく到達させることが可能となるからである。
【０１４１】
このような透明基材としては、例えば石英ガラス、パイレックス（登録商標）ガラス、合成石英板等の可撓性のない透明なリジット材、あるいは透明樹脂フィルム、光学用樹脂板等の可撓性を有する透明なフレキシブル材等が挙げられる。
【０１４２】
本実施態様において、必要に応じてアルカリ溶出防止用やガスバリア性付与その他の目的の表面処理を施したものを用いてもよい。
【０１４３】
本実施態様においては、上記の中でも、エネルギーの透過性等の面から、パイレックス（登録商標）ガラスまたは透明樹脂フィルムであることが特に好ましい。
【０１４４】
２．第２実施態様
次に、本発明のパターン形成体の製造方法における第２実施態様について説明する。本発明のパターン形成体の製造方法における第２実施態様は、透明基材および、上記透明基材上に形成されたエネルギー照射に伴う光触媒の作用により特性が変化する特性変化層を有するパターン形成体用基板と、光触媒を含有する光触媒含有層および基体を有する光触媒含有層側基板とを、上記特性変化層および上記光触媒含有層が２００μｍ以下となるように間隙をおいて配置した後、上記透明基材側から光描画方式によりエネルギーを照射し、上記特性変化層の特性が変化した特性変化パターンを形成するものである。
【０１４５】
本実施態様のパターン形成体は、例えば図２に示すように、透明基材１と、その透明基材１上に形成された特性変化層２とを有するパターン形成体用基板３、および基体４と、その基体４上に形成された光触媒含有層５とを有する光触媒含有層側基板６を準備し、そのパターン形成体用基板３と光触媒含有層側基板６とを、所定の間隙をおいて配置する（図２（ａ））。次に、光描画方式により目的とするパターン状にのエネルギー８を上記パターン形成体用基板３の透明基材１側から照射する（図２（ｂ））。このエネルギー８により光触媒含有層５中の光触媒が励起され、対向する特性変化層２の特性が変化する。すなわち、エネルギー８に対応するパターン状に、特性変化層２の特性が変化した特性変化パターン９が形成されたパターン形成体を製造することができるのである（図２（ｃ））。
【０１４６】
本実施態様によれば、上述したように、光描画方式により、エネルギーを照射することから、目的とするパターン状に照射されたエネルギーによって、光触媒含有層に含有される光触媒を励起させることが可能となり、この光触媒の作用により特性変化層の特性が変化した高精細な特性変化パターンを形成することができるのである。
【０１４７】
ここで、本実施態様に用いられる光触媒含有層側基板およびパターン形成体用基板、およびパターン形成体用基板と光触媒含有層側基板との配置については、上述した第１実施態様と同様であるので、ここでの説明は省略し、以下、本実施態様のパターン形成体の製造方法の特徴である光描画方式によるエネルギー照射について説明する。
【０１４８】
（光描画方式によるエネルギー照射）
本実施態様においては、上記パターン形成体用基板および上記光触媒含有層側基板を、上述したような配置を維持した状態で、上記パターン形成体用基板の透明基材側から、光描画方式によりエネルギー照射が行われる。ここで、本実施態様でいう光描画方式とは、エキシマ、ＹＡＧ、遠紫外線等のレーザを用いて目的とするパターン状に描画照射する方法である。
【０１４９】
本実施態様においては、このような光描画方式を用いることにより、高精細なパターン状に、光触媒含有層にエネルギーを照射することが可能となり、このエネルギーが照射された領域の光触媒の作用により、特性変化層の特性を高精細なパターン状に変化させることが可能となるのである。
【０１５０】
ここで本実施態様においても、上記パターン形成体用基板における透明基材側からエネルギーの照射を行う。光触媒含有層側基板側からエネルギー照射を行った場合、投影露光によりパターン化されたエネルギーが、光触媒含有層を透過しなければならず、この光触媒含有層内部でのエネルギーの吸収や散乱等によって、高精細なパターンを形成することが困難となるからである。また、パターン形成体用基板側から、エネルギー照射を行うことにより、光触媒含有層側基板内におけるエネルギーの干渉等を考慮する必要がないことから、上述したように、上記光触媒含有層側基板における光触媒含有層の膜厚を、特性変化層の特性を変化させるために最適なものとすることができ、高精細な特性変化パターンが形成されたパターン形成体を効率よく製造することができるのである。
【０１５１】
Ｂ．機能性素子
次に、本発明の機能性素子について説明する。本発明の機能性素子は、上述したパターン形成体の製造方法により製造されたパターン形成体の特性変化パターンに沿って機能性部が形成されたものである。
【０１５２】
本発明においては、上述したパターン形成体の製造方法により製造されたパターン形成体の。特性の変化したパターンに沿って機能性部を形成することから、高精細な機能性部を形成することができるのである。
【０１５３】
ここで機能性とは、光学的（光選択吸収、反射性、偏光性、光選択透過性、非線形光学性、蛍光あるいはリン光等のルミネッセンス、フォトクロミック性等）、磁気的（硬磁性、軟磁性、非磁性、透磁性等）、電気・電子的（導電性、絶縁性、圧電性、焦電性、誘電性等）、化学的（吸着性、脱着性、触媒性、吸水性、イオン伝導性、酸化還元性、電気化学特性、エレクトロクロミック性等）、機械的（耐摩耗性等）、熱的（伝熱性、断熱性、赤外線放射性等）、生体機能的（生体適合性、抗血栓性等）のような各種の機能を意味するものである。
【０１５４】
本発明において用いられる機能性部を形成する機能性部形成用組成物としては、上述したように機能性素子の機能、機能性素子の形成方法等によって大きく異なるものであるが、例えば、紫外線硬化型モノマー等に代表される溶剤で希釈されていない組成物や、溶剤で希釈した液体状の組成物等を用いることができる。また、機能性部形成用組成物としては粘度が低いほど短時間にパターンが形成できることから特に好ましい。ただし、溶剤で希釈した液体状組成物の場合には、パターン形成時に溶剤の揮発による粘度の上昇、表面張力の変化が起こるため、溶剤が低揮発性であることが望ましい。
【０１５５】
本発明に用いられる機能性部形成用組成物としては、上記親液性領域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、また親液性領域上に配置された後、薬剤により処理され、もしくは紫外線、熱等により処理された後に機能性部となるものであってもよい。この場合、機能性部形成用組成物の結着剤として、紫外線、熱、電子線等で効果する成分を含有している場合には、硬化処理を行うことにより素早く機能性部が形成できることから好ましい。
【０１５６】
本発明においては、上記機能性部を形成する機能性部形成工程を行う方法としては、ディップコート、ロールコート、ブレードコート、スピンコート等の塗布手段、インクジェット、電界ジェット、ディスペンサーを用いる方法等を含むノズル吐出手段等の手段を用いることが好ましい。これらの方法を用いることにより、機能性部を均一かつ高精細に形成することが、可能となるからである。
【０１５７】
本発明の機能性素子としては、例えば機能性部として画素部を形成したカラーフィルタや、機能性部としてレンズを形成したマイクロレンズ、機能性部として金属配線を形成した導電性パターン形成体等が挙げられ、本発明においては、上記の中でも高精細なパターンが形成可能である本発明の利点を活用できる点から、後述する導電性パターン形成体であることが好ましい。
【０１５８】
Ｃ．導電性パターン形成体
次に、本発明の導電性パターン形成体について説明する。本発明の導電性パターン形成体は、上述した機能性素子における機能性部が、金属配線であるものである。本発明においては、上述したパターン形成体の製造方法により製造されたパターン形成体における特性変化パターンを、高精細なものとすることができることから、この特性変化パターンの例えば濡れ性等の差を利用して、例えばノズル吐出法等によって金属配線を形成することにより、高精細な金属配線が形成された導電性パターン形成体とすることができるのである。
【０１５９】
本発明においては、金属配線の形成方法は、上述したパターン形成体の特性変化パターンにおける特性の差を利用して、形成することが可能であれば、特に限定されるものではなく、一般的に金属配線を形成する際に用いられる材料を用いて、例えばインクジェット法や電界ジェット法、ディスペンサーを用いる方法等のノズル吐出法や、オフセット印刷法、スクリーン印刷法等により形成することができる。
【０１６０】
また、本発明においては、このように形成される金属配線の幅は、目的とする導電性パターン形成体の種類等により適宜選択されるものであるが、通常０．２μｍ〜５００μｍ、中でも１μｍ〜１００μｍの範囲内とすることができる。
【０１６１】
Ｄ．パターン形成体製造用光触媒含有層側基板
次に、本発明のパターン形成体製造用光触媒含有層側基板について説明する。本発明のパターン形成体製造用光触媒含有層側基板は、基体と、上記基体上に形成され、かつ光触媒を含有する光触媒含有層とを有し、パターン形成体の製造に際して照射されるエネルギーに対して反射防止機能を有するパターン形成体製造用光触媒含有層側基板であって、エネルギー照射に伴う光触媒の作用により特性が変化する特性変化層を有するパターン形成体用基板における上記特性変化層と、上記光触媒含有層とを所定の間隙をおいて配置し、上記パターン形成体用基板側から投影露光法によりエネルギー照射することにより、上記特性変化層の特性が変化したパターン形成体を形成するものである。
【０１６２】
すなわち、本発明のパターン形成体製造用光触媒含有層側基板は、パターン形成体を製造する際に用いられるものであり、パターン形成体用基板における上記特性変化層と、上記光触媒含有層とを対向して配置し、パターン形成体用基板側からエネルギーを照射することにより、特性変化層の特性が変化したパターン形成体を形成するものである。
【０１６３】
本発明においては、上記パターン形成体製造用光触媒含有層側基板がパターンの形成に際して照射されるエネルギーに対して、反射防止機能を有することから、照射されたエネルギーが反射されて、エネルギー照射されていない領域の光触媒含有層中の光触媒を励起させることがなく、高精細なパターンが形成されたパターン形成体を製造することができるのである。本発明においては、パターン形成体製造用光触媒含有層側基板に反射防止機能を付与することが可能であれば、その方法は特に限定されず、例えば基体がエネルギー吸収性を有するものであってもよく、また基体表面にエネルギー吸収層や、反射防止層を有するもの等であってもよい。
【０１６４】
また、本発明においては、上記光触媒含有層の膜厚が通常０．０１μｍ〜１０μｍの範囲内、中でも０．０５μｍ〜５μｍの範囲内、特に０．１μｍ〜２μｍの範囲内であることが好ましい。これにより、上記特性変化層の特性を効率よく変化させることができ、高精細なパターンを有するパターン形成体を効率よく製造することが可能なパターン形成体製造用光触媒含有層側基板とすることができるからである。
【０１６５】
ここで、本発明のパターン形成体製造用光触媒含有層側基板に用いられる基体や光触媒含有層、エネルギー吸収層、反射防止層等については、上述した「Ａ．パターン形成体の製造方法」の光触媒含有層側基板の項で説明したものと同様のものを用いることが可能であるので、ここでの説明は省略する。
【０１６６】
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。
【０１６７】
【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。
【０１６８】
[実施例１]
まず、フルオロアルキルシラン（ＧＥ東芝シリコーン社製 ＴＳＬ８２３３）５ｇに０．０１Ｎ塩酸を１．５ｇ添加して２４時間攪拌した後、イソプロピルアルコールにより１００倍に希釈して塗布液作製した。この塗布液を、スピンコート法により、無アルカリガラス基板上に塗布後乾燥させて、厚さ０．１μｍの濡れ性変化層を形成し、パターン形成体用基板とした。
【０１６９】
次に、ＰＥＴフィルム上に、光触媒含有層として、光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）を厚さ０．１５μｍとなるように塗布し、光触媒含有層側基板を形成した。
【０１７０】
続いて、上記濡れ性変化層と光触媒含有層側基板との間が、２５μｍとなるように配置し、パターン形成体用基板側から、遠紫外線固体レーザ（２６６ｎｍ、２５ｍＷ／ｃｍ^２）により５秒間照射した。この際、露光部の濡れ性変化層の表面の濡れ性は水との接触角が２０゜であり、未露光部の濡れ性変化層の表面の濡れ性は、水との接触角が１１０°であった。
【０１７１】
次に、ピエゾ駆動タイプのインクジェット装置を用いて、顔料５重量部、溶剤２０重量部、バインダ７５重量部を含むＲＧＢ各色の熱硬化型インク（着色インク）を、露光部に付着させ着色し、これにＵＶ処理を行い硬化させ、カラーフィルタを得た。
【０１７２】
[実施例２]
まず、デシルトリメトキシシラン（信越シリコーン（株）製 LS‐5258）３ｇに０．０１Ｎの塩酸を１．５ｇ添加して２４時間攪拌した後、イソプロピルアルコールにより１００倍に希釈して塗布液を作製した。この塗布液を、スピンコート法により、無アルカリガラス基板上に塗布後乾燥させて、厚さ５００Åの濡れ性変化層を形成し、パターン形成体用基板とした。
【０１７３】
次に、ＰＥＴフィルム上に、光触媒層として、光触媒コーティング剤であるST-K03（石原産業（株）製）を厚さ０．６μｍとなるように塗布し、光触媒層側基板を形成した。
【０１７４】
続いて、上記濡れ性変化層と光触媒含有層側基板との間が、５０μｍとなるように配置し、パターン形成体用基板側から、ステッパー露光機（I線＝３６５ｎｍ）により５分間照射した。この際、露光部の濡れ性変化層の表面の濡れ性は銀コロイド水溶液（濃度２０ｗｔ％）との接触角が１５°であり、未露光部接触角は１０４°であった。
【０１７５】
次に、上記パターン形成体用基板を銀コロイド水溶液（濃度２０ｗｔ％）に浸漬し、１０mm/sec.で引き上げることにより、親液性領域にのみに上記銀コロイド水溶液がパターン上に付着させた。この銀コロイド水溶液のパターンを３００℃で２０分間加熱することにより基板上に銀がパターニングされた導電性パターン形成体を得た。
【０１７６】
【発明の効果】
本発明によれば、投影露光方式によりエネルギーを照射することによって、光触媒含有層に含有される光触媒を高精細なパターン状に励起させることが可能となる。この励起された光触媒の作用により、対向されて配置されている特性変化層の特性を変化させることができ、高精細な特性変化パターンを有するパターン形成体を製造することができるのである。またこの際、パターン形成体用基板の透明基材側からエネルギー照射が行われることから、エネルギーが乱反射等することなく、光触媒含有層に到達することができ、高精細な特性変化パターンを形成することが可能となるのである。
【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】本発明のパターン形成体の製造方法の他の例を示す工程図である。
【符号の説明】
１ … 基材
２ … 特性変化層
３ … パターン形成体用基板
４ … 基体
５ … 光触媒含有層
６ … 光触媒含有層側基板
７ … フォトマスク
８ … エネルギー
９ … 特性変化パターン[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a high-definition pattern that can be used for various applications such as a conductive pattern forming body having fine metal wiring.
[0002]
[Prior art]
Conventionally, various methods for producing a pattern forming body for forming various patterns such as designs, images, characters, and circuits on a substrate have been produced.
[0003]
For example, when printing is described as an example, a lithographic printing plate used for lithographic printing, which is a kind of printing method, is a lithographic plate having a pattern composed of an oleophilic part that accepts ink and a part that does not accept printing ink. The lithographic printing plate is used to form an ink image to be printed on the lipophilic portion, and the formed image is transferred to paper or the like for printing. In such printing, a printing plate as a pattern forming body is produced by forming patterns such as characters and figures on the printing plate precursor as described above, and is used by being mounted on a printing press. Many printing plate precursors for offset printing, which are typical planographic printing plates, have been proposed.
[0004]
For example, a printing plate for offset printing is a method of exposing and developing through a mask on which a pattern is drawn on the printing plate precursor, a method of exposing directly by an electrophotographic method and making a plate directly on the printing plate precursor, etc. Can be produced. An electrophotographic offset printing plate precursor is provided with a photoconductive layer mainly composed of photoconductive particles such as zinc oxide and a binder resin on a conductive substrate, and this is exposed as a photoconductor by electrophotography. In this method, an offset original plate, that is, a pattern forming body is obtained by forming a highly lipophilic image on the surface of the photoreceptor and subsequently hydrophilizing the non-image portion by treatment with a desensitizing solution. The hydrophilic portion is immersed in water or the like to make it oleophobic, and the printing ink is received in the oleophilic image portion and transferred to paper or the like. However, in the pattern formation, various post-exposure treatments such as treatment with a desensitizing solution are required.
[0005]
In addition, as a method for forming a high-definition pattern, a photoresist layer coated on a substrate is subjected to pattern exposure, and after the exposure, the photoresist is developed, further etched, or a substance having functionality in the photoresist. 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 photoresist.
[0006]
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.
[0007]
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. .
[0008]
On the other hand, as a method for forming a high-definition pattern, a property changing layer whose properties are changed by the action of a photocatalyst is formed on a substrate, and energy irradiation is performed from the photocatalyst containing layer side using the photocatalyst containing layer containing the photocatalyst. The inventors have studied a method of manufacturing a pattern forming body that forms a characteristic pattern in which the characteristics of the characteristic change layer are changed by performing the process (for example, Patent Document 1).
[0009]
However, in this method, the proximity energy is applied to the characteristic change layer through the mask using parallel light as the irradiation energy, and mask alignment is required, and a pattern of about several tens of micrometers can be easily formed. Although it was possible to form by a simple process, for example, when a higher definition pattern such as a metal wiring is formed, there may be a problem in terms of accuracy.
[0010]
Here, when manufacturing a display or a semiconductor, a projection exposure method is known as a method for forming a finer pattern than the proximity method. According to this projection exposure method, since an image is formed using a lens or a mirror, alignment accuracy and resolution are excellent. However, when the projection exposure method is used in the method using the photocatalyst-containing layer, the energy patterned by the projection exposure must pass through the photocatalyst-containing layer, and the patterned energy is inside the photocatalyst-containing layer. It is difficult to form a high-definition pattern due to energy absorption and scattering at the surface.
[0011]
[Patent Document 1]
JP 2000-249821 A
[0012]
[Problems to be solved by the invention]
Therefore, it is desired to provide a method for producing a pattern forming body capable of forming a high-definition pattern by a simple method.
[0013]
  The present inventionA method for producing a pattern formed body, comprising:A substrate for a pattern forming body having a transparent base, a characteristic change layer whose characteristics are changed by the action of a photocatalyst formed by energy irradiation formed on the transparent base, a photocatalyst-containing layer containing the photocatalyst, and a photocatalyst having the base After placing the content layer side substrate with a gap so that the characteristic change layer and the photocatalyst content layer are 200 μm or less, energy is irradiated from the transparent substrate side by a projection exposure method, and the characteristic change layer Forms a characteristic change pattern that changes the characteristics ofThe characteristic change layer has a thickness in a range of 10 to 1000%, and the characteristic change layer has an energy transmittance of 70% to 99.5% in the energy to be irradiated. The photocatalyst-containing layer side substrate has an antireflection function for irradiated energy.The manufacturing method of the pattern formation body characterized by the above is provided.
[0014]
According to the present invention, it is possible to excite the photocatalyst contained in the photocatalyst-containing layer into a high-definition pattern by irradiating energy by the projection exposure method. By the action of the excited photocatalyst, the characteristics of the characteristic change layers arranged to face each other can be changed, and a pattern forming body having a high-definition characteristic change pattern can be manufactured. At this time, energy irradiation is performed from the transparent base material side of the substrate for the pattern forming body, and energy does not need to pass through the photocatalyst containing layer, so that the energy reaches the photocatalyst containing layer without irregular reflection or the like. This makes it possible to form a high-definition characteristic change pattern.
[0015]
In the present invention, the projection exposure method is preferably a mirror projection method or a stepper method. This is because pattern irradiation can be performed with high definition by performing energy irradiation by these methods.
[0016]
  The present invention also provides:A method for producing a pattern formed body, comprising:A substrate for a pattern forming body having a transparent base, a characteristic change layer whose characteristics are changed by the action of a photocatalyst formed by energy irradiation formed on the transparent base, a photocatalyst-containing layer containing the photocatalyst, and a photocatalyst having the base After placing the content layer side substrate with a gap so that the characteristic change layer and the photocatalyst content layer are 200 μm or less, energy is irradiated from the transparent substrate side by a light drawing method, and the characteristic change layer Forms a characteristic change pattern that changes the characteristics ofThe characteristic change layer has a thickness in a range of 10 to 1000%, and the characteristic change layer has an energy transmittance of 70% to 99.5% in the energy to be irradiated. The photocatalyst-containing layer side substrate has an antireflection function for irradiated energy.The manufacturing method of the pattern formation body characterized by the above is provided.
[0017]
According to the present invention, it is possible to excite the photocatalyst contained in the photocatalyst-containing layer in a desired high-definition pattern by irradiating energy using a light drawing method. It is possible to form a high-definition characteristic change pattern in which the characteristic of the characteristic change layer is changed. At this time, energy irradiation is performed from the transparent base material side of the substrate for the pattern forming body, and energy does not need to pass through the photocatalyst containing layer, so that the energy reaches the photocatalyst containing layer without irregular reflection or the like. Therefore, it is possible to form a high-definition characteristic change pattern.
[0018]
In the present invention, the characteristic change layer preferably has a thickness in the range of 10 to 1000 mm. This is because energy can be prevented from being irregularly reflected when passing through the characteristic change layer, and the energy can reach the photocatalyst-containing layer in a high-definition pattern.
[0019]
In the present invention, it is preferable that the characteristic change layer has an energy transmittance of 70% to 99.5%. This is because the irradiated energy can efficiently reach the photocatalyst-containing layer without being absorbed by the characteristic change layer.
[0020]
In the present invention, the property change layer can be a wettability change layer in which the wettability changes so that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying the energy irradiation. As a result, the lyophilic region where the wettability has changed and the liquid repellent region where the wettability has not changed can be formed by the action of the photocatalyst accompanying the energy irradiation. This is because, for example, a pattern forming body in which the functional portion can be easily formed can be obtained by an inkjet method or the like.
[0021]
At this time, the wettability changing layer can be a layer containing an organopolysiloxane. This is because it becomes possible to change the wettability of the wettability changing layer as described above.
[0022]
In the present invention, the organopolysiloxane is Y_nSiX_(4-n)(Where Y is an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group, chloroalkyl group, isocyanate group, or epoxy group, or an organic group containing these, and X is an alkoxyl group or halogen. N is an integer from 0 to 3.) It is preferably an organopolysiloxane which is one or two or more hydrolyzed condensates or cohydrolyzed condensates of a silicon compound represented by: This is because by using such an organopolysiloxane, it is possible to further exhibit the characteristics against the change in wettability as described above.
[0023]
Furthermore, it is preferable that the carbon number of Y which comprises the said organopolysiloxane exists in the range of 1-20. Thereby, the organopolysiloxane before energy irradiation can be made liquid repellent by the Y, and the Y can be made lyophilic by being decomposed and removed by the action of the photocatalyst by the energy irradiation. Because it can.
[0024]
In the present invention, the wettability changing layer can be a monomolecular film. As a result, the wettability changing layer can be formed into a dense and uniform film, and a high-definition and uniform functional part is formed in the characteristic change pattern in which the wettability is changed by the action of the photocatalyst accompanying the energy irradiation. This is because it becomes possible.
[0025]
At this time, the monomolecular film is preferably made of a silane compound having an organic chain. This is because the monomolecular film can be easily formed by using such a silane compound.
[0026]
Furthermore, it is preferable that the number of carbons constituting the organic chain is in the range of 1-20. The monomolecular film before energy irradiation can be made liquid-repellent by the organic chain, and the organic chain can be decomposed by the action of the photocatalyst accompanying energy irradiation to make it lyophilic. It is.
[0027]
In the present invention, the silane compound is preferably a fluoroalkylsilane. Thereby, since the liquid repellency of the non-energy-irradiated portion can be increased, the difference in wettability with the characteristic change pattern made lyophilic by the action of the photocatalyst accompanying the energy irradiation is increased. Because it can.
[0028]
In the present invention, the characteristic change layer may be a decomposition removal layer that is decomposed and removed by the action of a photocatalyst accompanying energy irradiation. Thereby, a concave portion can be formed as a characteristic change pattern on the surface of the characteristic change layer, and the functional portion can be easily formed by using, for example, an ink jet method or the like using the unevenness of the surface.
[0029]
At this time, the contact angle between the decomposition removal layer and the liquid having a surface tension of 40 mN / m is 10 ° or more, and the contact angle between the transparent substrate and the liquid having a surface tension of 40 mN / m is 9 ° or less. Is preferred. As a result, it becomes possible to make the area exposed by decomposing and removing the decomposition removal layer a lyophilic area and the decomposition removal layer on the liquid removal repellent area. This is because it is possible to form a functional part by utilizing the above-mentioned, and it is possible to obtain a pattern forming body capable of forming a higher-definition functional part.
[0030]
Here, the decomposition removal layer is preferably a monomolecular film. This is because the decomposition / removal layer can be a dense and uniform layer, and the decomposition / removal layer can be efficiently and uniformly decomposed and removed by the action of the photocatalyst accompanying the energy irradiation.
[0031]
Moreover, in this invention, it is preferable that the said photocatalyst content layer side board | substrate has a reflection preventing function with respect to the energy irradiated. As a result, it is possible to prevent the photocatalyst-containing layer side substrate from reflecting the irradiated energy and exciting the photocatalyst in the photocatalyst-containing layer in the region where no energy is irradiated. This is because it is possible to form a characteristic change pattern in which the characteristic of the change layer is changed.
[0032]
In the said invention, it is preferable that the width | variety of the said characteristic change pattern exists in the range of 0.2 micrometer-500 micrometers. Thereby, it is possible to obtain a pattern forming body capable of easily forming a functional part such as a metal wiring with high definition by using the characteristic change pattern.
[0033]
The present invention also provides a functional element characterized in that a functional part is formed along the characteristic change pattern of the pattern formed body manufactured by the method for manufacturing a pattern formed body described above.
[0034]
According to the present invention, a functional part can be easily formed by, for example, an ink-jet method or the like along the characteristic change pattern formed with high definition, and a functional part such as a metal wiring can be formed with high definition. It can be set as the functional element made.
[0035]
The present invention also provides a conductive pattern forming body, wherein the functional part of the functional element is a metal wiring.
[0036]
According to this invention, it can be set as the electroconductive pattern formation body which has the metal wiring formed in high definition easily by the nozzle discharge method etc. along the said characteristic change pattern.
[0037]
Furthermore, the present invention provides a pattern forming body having a base and a photocatalyst-containing layer formed on the base and containing a photocatalyst, and having an antireflection function with respect to energy irradiated in the production of the pattern forming body. A photocatalyst-containing layer side substrate for production, which has a characteristic change layer that has a characteristic change layer whose characteristics change due to the action of the photocatalyst upon energy irradiation, and the photocatalyst-containing layer having a predetermined gap And a photocatalyst for producing a pattern-forming body, wherein the pattern-forming body in which the characteristics of the property-changing layer are changed is formed by irradiating energy from the substrate side for the pattern-forming body by a projection exposure method. A layer side substrate is provided.
[0038]
According to the present invention, the photocatalyst-containing layer side substrate for producing a pattern forming body has an antireflection function, so that the energy irradiated when forming the pattern forming body is reduced by the photocatalyst containing layer side substrate for producing the pattern forming body. It is possible to prevent excitation of the photocatalyst in the photocatalyst containing layer in the region that is reflected and not irradiated with energy. Thereby, it can be set as the photocatalyst containing layer side board | substrate for pattern formation bodies manufacture which can manufacture the pattern formation body which has a high definition pattern.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a high-definition pattern that can be used for various applications such as a conductive pattern forming body having fine metal wiring, and a functional element using the pattern forming body. Furthermore, the present invention relates to a photocatalyst-containing layer side substrate for producing a pattern forming body used for producing a pattern forming body. Each will be described separately below.
[0040]
A. Method for producing pattern forming body
First, the manufacturing method of the pattern formation body of this invention is demonstrated. The manufacturing method of the pattern formation body of this invention has two embodiment with the method of energy irradiation. As a 1st embodiment, the substrate for pattern formation bodies which has a characteristic change layer in which a characteristic changes by the effect | action of the photocatalyst accompanying the energy irradiation formed on the transparent base material and the said transparent base material, and a photocatalyst are contained. After arranging the photocatalyst containing layer and the photocatalyst containing layer side substrate having a gap so that the characteristic change layer and the photocatalyst containing layer are 200 μm or less, energy is applied from the transparent substrate side by a projection exposure method. Is applied to form a characteristic change pattern in which the characteristics of the characteristic change layer are changed. Further, as a second embodiment, a substrate for a pattern forming body having a transparent base material, a property changing layer whose properties are changed by the action of the photocatalyst accompanying the energy irradiation formed on the transparent base material, and a photocatalyst. The photocatalyst-containing layer and the photocatalyst-containing layer side substrate having a substrate are arranged with a gap so that the characteristic change layer and the photocatalyst-containing layer are 200 μm or less, and then the optical drawing method from the transparent substrate side Is irradiated with energy to form a characteristic change pattern in which the characteristic of the characteristic change layer is changed.
[0041]
According to the present invention, energy is irradiated by a projection exposure method or a light drawing method, and therefore, in either embodiment, the photocatalyst contained in the photocatalyst-containing layer is excited by high-definition pattern energy. Therefore, a high-definition characteristic change pattern in which the characteristic of the characteristic change layer is changed by the action of the photocatalyst can be formed. Here, when energy is transmitted through the photocatalyst-containing layer side substrate, the photocatalyst-containing layer contains a photocatalyst or the like that is highly likely to cause energy absorption or scattering inside the photocatalyst-containing layer, so that a high-definition pattern is formed. It may be difficult to form. In this invention, since energy irradiation is performed from the transparent base material side of the substrate for pattern formation bodies, energy does not permeate | transmit a photocatalyst content layer side board | substrate. Thereby, it is possible to reach the photocatalyst-containing layer without irregularly reflecting energy, and it is possible to form a high-definition characteristic change pattern. In addition, since the photocatalyst-containing layer side substrate does not require energy transmission, the film thickness of the photocatalyst-containing layer, the type of the substrate, and the like are not limited, and the manufactured pattern forming body is manufactured at a low cost. It can also be preferred from the standpoint of efficiency.
[0042]
Hereinafter, each structure in the manufacturing method of the pattern formation body of this invention is each demonstrated for each embodiment.
[0043]
1. First embodiment
First, the 1st embodiment in the manufacturing method of the pattern formation object of the present invention is explained. The first embodiment of the method for producing a pattern forming body of the present invention is a pattern forming body having a transparent base material and a property changing layer whose properties are changed by the action of a photocatalyst accompanying energy irradiation formed on the transparent base material. After arranging the substrate for use, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the substrate with a gap so that the characteristic change layer and the photocatalyst-containing layer are 200 μm or less, the transparent group Energy is irradiated from the material side by a projection exposure method, and a characteristic change pattern in which the characteristic of the characteristic change layer is changed is formed.
[0044]
For example, as shown in FIG. 1, the pattern formed body of this embodiment includes a substrate 3 for a pattern formed body having a transparent base material 1 and a characteristic change layer 2 formed on the transparent base material 1, and a base body 4. And a photocatalyst containing layer side substrate 6 having a photocatalyst containing layer 5 formed on the substrate 4, and the pattern forming substrate 3 and the photocatalyst containing layer side substrate 6 are spaced apart from each other by a predetermined gap. It arrange | positions (FIG. 1 (a)). Next, using the mask 7 or the like on which the target pattern is formed, the energy 8 is projected and exposed through, for example, the projection exposure apparatus 11, and the pattern-shaped energy 8 ′ is applied to the transparent base material 1 of the pattern forming substrate 3. Irradiation from the side (FIG. 1B). The photocatalyst in the photocatalyst containing layer 5 is excited by this energy 8 ', and the characteristics of the opposing characteristic change layer 2 change. That is, it is possible to manufacture a pattern forming body in which the characteristic change pattern 9 in which the characteristic of the characteristic change layer 2 is changed is formed in a pattern corresponding to the energy 8 ′ (FIG. 1C).
[0045]
According to the present embodiment, as described above, since the energy is irradiated by the projection exposure method, it becomes possible to excite the photocatalyst contained in the photocatalyst containing layer by the energy of the high-definition pattern. A high-definition characteristic change pattern in which the characteristic of the characteristic change layer is changed by the action of the photocatalyst can be formed.
[0046]
Hereinafter, energy irradiation, which is a feature of the pattern forming body manufacturing method of the present embodiment, will be described first, and then the photocatalyst-containing layer side substrate and the pattern forming body substrate used in the present embodiment will be described.
[0047]
a. Energy irradiation
First, the energy irradiation in the manufacturing method of the pattern formation body of this embodiment is demonstrated. In the method for producing a pattern forming body according to this embodiment, a photocatalyst containing layer in a photocatalyst containing layer side substrate described later and a characteristic changing layer in a pattern forming substrate described later are arranged with a predetermined gap, and a pattern is formed. By irradiating energy by the projection exposure method from the transparent base material side of the formed body substrate, a pattern formed body on which a characteristic change pattern in which the characteristics of the characteristic change layer are changed can be manufactured.
[0048]
Hereinafter, the arrangement of the pattern forming body substrate and the photocatalyst-containing layer side substrate and the energy irradiation by the projection exposure method when performing such energy irradiation will be described.
[0049]
(Arrangement of pattern forming substrate and photocatalyst containing layer side substrate)
First, the arrangement of the pattern forming body substrate and the photocatalyst-containing layer side substrate upon energy irradiation in this embodiment will be described.
[0050]
In this embodiment, the characteristic change layer in the pattern forming body substrate described later and the photocatalyst containing layer in the photocatalyst containing layer side substrate described later are arranged with a predetermined gap, and energy is irradiated from a predetermined direction. Thus, a characteristic change pattern in which the characteristic of the characteristic change layer is changed can be formed.
[0051]
The above arrangement means a state where the action of the photocatalyst substantially extends to the surface of the property change layer, and in addition to a state where the photocatalyst is actually in contact, a predetermined interval is provided. Thus, the photocatalyst-containing layer and the characteristic change layer are arranged. This gap is preferably 200 μm or less.
[0052]
In the present embodiment, the above gap is preferably in the range of 0.2 μm to 10 μm, especially considering the fact that the pattern accuracy is very good, the photocatalyst sensitivity is high, and therefore the efficiency of property change of the property change layer is good. Is preferably in the range of 1 μm to 5 μm. Such a gap range is particularly effective for a small-area characteristic change layer capable of controlling the gap with high accuracy.
[0053]
On the other hand, when processing a large area characteristic change layer of, for example, 300 mm × 300 mm or more, there is no contact between the photocatalyst-containing layer side substrate and the characteristic change layer. It is extremely difficult to form. Therefore, when the characteristic change layer 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 does not occur in the characteristic change on the layer.
[0054]
Thus, when irradiating energy on the characteristic change layer having a relatively large area, the setting of the gap in the positioning device between the photocatalyst containing layer side substrate and the characteristic change layer in the energy irradiation device is within the range of 10 μm to 200 μm, In particular, it is preferable to set within a range of 25 μm to 75 μm. By setting the set value within such a range, it is possible to arrange the photocatalyst-containing layer side substrate and the characteristic change layer without contact with each other without causing a significant decrease in pattern accuracy and a significant deterioration in the sensitivity of the photocatalyst. Because it becomes possible.
[0055]
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, when 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, there is a possibility that the characteristic change rate may be slowed. Absent. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic change layer, and in this case as well, the speed of the characteristic change may be reduced.
[0056]
Moreover, as a method of forming such a very narrow gap uniformly and arranging the photocatalyst containing layer and the characteristic change layer, for example, a method using a spacer can be mentioned. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not intended for the photocatalytic action on the surface of the property change layer. By having a pattern similar to the characteristic change pattern, it is possible to form a predetermined characteristic change pattern on the characteristic change layer. Also, by using such a spacer, the active oxygen species generated by the action of the photocatalyst reaches the surface of the characteristic change layer at a high concentration without diffusing, and thus a high-definition characteristic change pattern is efficiently formed. be able to.
[0057]
In this embodiment, the arrangement state of the photocatalyst containing layer side substrate and the pattern forming body substrate only needs to be maintained at least during the energy irradiation.
[0058]
(Energy irradiation by projection exposure method)
Next, energy irradiation by the projection exposure method will be described. In the present embodiment, energy irradiation is performed by the projection exposure method from the transparent base material side of the pattern forming substrate while maintaining the above-described arrangement. Here, the projection exposure method in this embodiment is not particularly limited as long as it is a method generally used as a projection exposure method for forming an image in a target pattern through a lens or a mirror. Specifically, there are a mirror projection method, a stepper method, and the like. Here, the target patterned mask is usually placed between the light source and the lens or mirror. In this embodiment, by using such a projection exposure method, it becomes possible to irradiate the photocatalyst-containing layer with energy in a high-definition pattern, and by the action of the photocatalyst in the region irradiated with this energy, This makes it possible to change the characteristics of the characteristic change layer into a high-definition pattern.
[0059]
Here, in this embodiment, energy irradiation is performed from the transparent base material side in the substrate for a pattern forming body. When energy irradiation is performed from the photocatalyst containing layer side substrate side, the energy patterned by the projection exposure must pass through the photocatalyst containing layer, and by absorption or scattering of energy inside this photocatalyst containing layer, This is because it may be difficult to form a high-definition pattern. Moreover, since it is not necessary to consider interference of energy in the photocatalyst containing layer side substrate by performing energy irradiation from the pattern forming body substrate side, as described later, the photocatalyst in the photocatalyst containing layer side substrate will be described later. The film thickness of the containing layer can be optimized to change the characteristics of the characteristic change layer, and the pattern forming body can be manufactured efficiently. Furthermore, in this case, since the substrate in the photocatalyst-containing layer side substrate does not need to transmit the irradiated energy, the type of the substrate is not limited as will be described later, which is preferable from the viewpoint of cost and the like. It can be done.
[0060]
As described above, the energy projected by the projection exposure method is a concept that includes irradiation of any energy ray that can change the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is limited to irradiation of visible light. Is not to be done.
[0061]
Usually, the wavelength of light used for such energy irradiation is set in the range of 450 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.
[0062]
Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0063]
Further, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for the characteristic change layer surface to change the characteristics of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0064]
At this time, it is preferable in that the sensitivity can be increased by irradiating the photocatalyst-containing layer with energy while heating and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0065]
By performing the energy irradiation described above, in this embodiment, a pattern forming body having a characteristic change pattern in which the characteristic of the characteristic change layer is changed is manufactured.
[0066]
Here, the width of the characteristic change pattern formed in the pattern formed body formed in the present embodiment varies depending on the type and purpose of the pattern formed body, but is usually 0.2 μm to 500 μm, and particularly 1 μm to 100 μm. It is preferable to be within the range. Thereby, it is possible to obtain a pattern forming body capable of easily forming a functional part such as a metal wiring with high definition by using the characteristic change pattern.
[0067]
b. Photocatalyst containing layer side substrate
Next, the photocatalyst containing layer side substrate used in the above-described energy irradiation in this embodiment will be described. The photocatalyst-containing layer side substrate used in this embodiment has a photocatalyst-containing layer containing a photocatalyst and a substrate. Usually, the substrate and the photocatalyst-containing layer are formed on the substrate.
[0068]
Moreover, in this embodiment, it is preferable that this photocatalyst containing layer side board | substrate has an antireflection function with respect to the energy irradiated. Here, the antireflection function refers to a function that does not reflect the irradiated energy, for example, by absorbing or transmitting energy. This makes it possible to prevent the photocatalyst-containing layer side substrate from reflecting the irradiated energy during the above-described energy irradiation and exciting the photocatalyst in the photocatalyst-containing layer in the region where the energy is not irradiated. This is because it is possible to form a characteristic change pattern in which the characteristic of the characteristic change layer only in the irradiated region is changed. Hereinafter, each structure of the photocatalyst containing layer side board | substrate used for this process is demonstrated.
[0069]
(1) Photocatalyst containing layer
First, the photocatalyst containing layer used for the photocatalyst containing layer side substrate will be described. The photocatalyst-containing layer used in the present embodiment is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the opposing property-changing layer, and includes a photocatalyst and a binder. It may be a film formed with a photocatalyst alone. Further, the surface characteristics may be particularly lyophilic or lyophobic.
[0070]
As a photocatalyst used in this embodiment, 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.
[0071]
In this embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0072]
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.
[0073]
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 the photocatalyst of 20 nm or less is particularly preferable.
[0074]
The photocatalyst-containing layer in this embodiment may be formed of a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0075]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change of characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening of 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.
[0076]
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. Since it is possible and includes only the photocatalyst, it is possible to efficiently change the characteristics on the characteristic change layer as compared with the case where a binder is used.
[0077]
In addition, as another example of a method for forming a photocatalyst-containing layer comprising only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on a substrate and then changing the phase to crystalline titania by firing. Etc. 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.
[0078]
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.
[0079]
Thus, when using organopolysiloxane as a binder, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the organopolysiloxane as the binder in a solvent together with other additives as necessary. And it can form by apply | coating this coating liquid on a base material. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application 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.
[0080]
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, a hydrolyzate thereof, silanol, or a polysiloxane having an average molecular weight of 3000 or less.
[0081]
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.
[0082]
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.
[0083]
In this embodiment, as described above, since energy is irradiated from the pattern forming body substrate side, the photocatalyst-containing layer does not need to be permeable to the irradiated energy, and further, the photocatalyst-containing layer. There is no need to take into account energy interference in the interior. Therefore, the photocatalyst-containing layer used in the present embodiment can have a film thickness that can efficiently change the characteristics of the characteristic change layer in the pattern forming substrate described later. Specifically, such a film thickness is appropriately selected depending on the type and film thickness of the characteristic changing layer that changes the characteristics, but is usually within a range of 0.01 μm to 10 μm, preferably 0.05 μm. It can be in the range of ˜5 μm, particularly preferably in the range of 0.1 μm to 2 μm.
[0084]
In addition to the photocatalyst and the binder, the photocatalyst-containing layer used in the present embodiment 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, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0085]
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.
[0086]
(2) Substrate
Next, the base used for the photocatalyst-containing layer side substrate will be described. In this embodiment, as shown in FIG. 1, the photocatalyst containing layer side substrate 6 has at least a base 4 and a photocatalyst containing layer 5 formed on the base 4. In this embodiment, as described above, since the energy irradiation is performed from the pattern forming body substrate side, it is not necessary to have transparency with respect to the energy irradiated on the substrate, for example, a resinous film, A glass substrate, metal, or the like can be used. In the present embodiment, a resin film is preferable among the above because it can be preferable in terms of cost, strength, and the like. Further, the substrate used in this embodiment may be flexible or may not be flexible. Even opaque materials can be used.
[0087]
In this embodiment, as described above, the photocatalyst-containing layer side substrate preferably has an antireflection function with respect to the irradiated energy. For example, the substrate may absorb the energy described above. Examples of the method for causing the substrate to absorb the energy include a method for making the substrate black, and a method for incorporating an energy absorber into the substrate material.
[0088]
Furthermore, in this embodiment, an anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst-containing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0089]
(3) Other
In this embodiment, as described above, it is preferable that the substrate for a pattern forming body has an antireflection function with respect to irradiated energy. In order to provide the antireflection function, the substrate and the substrate In addition to the photocatalyst containing layer, the photocatalyst containing layer side substrate may have, for example, an energy absorbing layer or an antireflection layer.
[0090]
The energy absorbing layer used in the present embodiment is not particularly limited as long as it is a layer that absorbs irradiated energy, and examples thereof include a black layer and a layer containing an energy absorber. Such an energy absorbing layer may be formed between the substrate and the photocatalyst containing layer, or formed on the substrate surface opposite to the side on which the photocatalyst containing layer is formed. It may be. Furthermore, it may be formed on both surfaces of the substrate.
[0091]
In the present embodiment, the energy absorbing layer preferably absorbs the irradiated energy within the range of 1% to 100%, particularly within the range of 10% to 100%. This is because the irradiated energy can be prevented from being reflected and the like, and a high-definition pattern forming body can be manufactured.
[0092]
The antireflection layer used in the present embodiment is not particularly limited as long as it is a layer that prevents the irradiated energy from being reflected. For example, silica (SiO 2₂) And the like, or a layer of fine particles of polymers. Such an antireflection layer may also be formed between the substrate and the photocatalyst-containing layer, or may be formed on the surface of the substrate opposite to the side on which the photocatalyst-containing layer is formed. It may be a thing. Furthermore, it may be formed on both surfaces of the substrate.
[0093]
c. Pattern forming substrate
Next, the substrate for pattern forming bodies used in this embodiment will be described. The substrate for a pattern forming body used in the present embodiment has a transparent base material and a characteristic change layer whose characteristics change due to the action of a photocatalyst accompanying energy irradiation formed on the transparent base material. Hereinafter, each structure of the substrate for pattern formation bodies is demonstrated.
[0094]
(1) Characteristic change layer
First, the characteristic change layer used for the pattern forming body of this embodiment will be described. The characteristic change layer used in the pattern forming body of the present embodiment forms a characteristic change pattern in which the characteristic is changed by the action of the photocatalyst accompanying the energy irradiation of the photocatalyst-containing layers arranged opposite to each other during the energy irradiation described above. Is the layer to be played. In the present embodiment, a pattern capable of forming a functional part by, for example, an ink jet method using the difference in characteristics between the region where the characteristics of the property change layer have changed and the area where the characteristics have not changed. It can be a formed body.
[0095]
Here, in this embodiment, as described above, energy irradiation is performed from the pattern forming body substrate side. Therefore, the characteristic change layer of this embodiment is permeable to the irradiated energy, and it is preferable from the point of forming a high-definition characteristic change pattern that energy is not absorbed, scattered, or interfered. . Therefore, in this embodiment, the film thickness of the characteristic change layer is preferably in the range of 10 to 1000 mm, more preferably in the range of 10 to 100 mm, and the transmittance of the energy irradiated when forming the characteristic change pattern is 70%. It is preferable to be within a range of ˜99.5%. This is because the irradiated energy can efficiently reach the photocatalyst-containing layer, and energy scattering and interference can be prevented.
[0096]
Moreover, in this embodiment, it is preferable that a characteristic change layer is a layer which does not contain a photocatalyst. Thereby, there is no need to worry about the pattern formed body being affected by the photocatalyst over time, and the pattern formed body can be used without problems for a long period of time.
[0097]
The type of property change of the property change layer as described above is not particularly limited, but in this embodiment, the property change layer is wet so that the contact angle with the liquid is lowered by the action of the photocatalyst. In particular, the functional part is formed on the characteristic change pattern in the case of the wettability changing layer whose properties change and the case where the characteristic changing layer is a decomposition removal layer which is decomposed and removed by the action of the photocatalyst. Is preferable from the viewpoint of ease. Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0098]
(Wettability change layer)
First, the wettability changing layer used in this embodiment will be described. The wettability changing layer used in this embodiment is a layer whose wettability changes such that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying the energy irradiation. In this way, by using a wettability changing layer whose wettability changes so that the contact angle with the liquid is reduced by energy irradiation, the area irradiated with energy on the surface of the wettability changing layer is made a lyophilic region, energy An unirradiated region can be a liquid repellent region. This makes it possible to attach a functional part forming coating solution for forming a functional part such as a metal wiring only to a lyophilic region, for example, by an ink jet method or the like, and function in a high-definition pattern. This is because the sex part can be formed.
[0099]
Here, the lyophilic region is a region having a small contact angle with the liquid, and refers to a region having good wettability with respect to the functional part forming coating liquid that forms the functional part. Further, 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 forming coating liquid.
[0100]
The wettability changing layer has a contact angle with a liquid of 40 mN / m or more, particularly a liquid with a surface tension of 20 mN / m in a portion not irradiated with energy, that is, a liquid repellent region. It is preferable that the wettability is 10 ° or more. This is because the region where energy is not irradiated is a region where liquid repellency is required in the present embodiment, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient. This is because the functional part-forming coating liquid may remain on the liquid-repellent region when the functional part-forming coating liquid is applied, which is not preferable.
[0101]
Further, the wettability changing layer has a contact angle with a liquid of 40 mN / m or less, particularly a liquid with a surface tension of 60 mN / m, in a portion irradiated with energy, that is, a lyophilic region. It is preferable that it is a layer which becomes 10 degrees or less. When the contact angle with the liquid in the energy-irradiated part, that is, the lyophilic region is high, for example, when the functional part forming coating liquid is applied, the functional part forming also in the lyophilic region This is because the coating liquid may be repelled and it may be difficult to pattern the functional part on the lyophilic region.
[0102]
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.
[0103]
The wettability changing layer used in the present embodiment is not particularly limited as long as it has the above-described characteristics and has a main chain that is not easily deteriorated or decomposed by the action of the photocatalyst. In the embodiment, it is particularly preferable that (1) the organopolysiloxane is contained in the wettability changing layer and (2) the wettability changing layer is a monomolecular film. Hereinafter, each of these two cases will be described.
[0104]
(1) When organopolysiloxane is contained
First, the case where organopolysiloxane is contained in the wettability changing layer will be described. In this embodiment, by containing organopolysiloxane in the wettability changing layer, the wettability can be lowered by the action of the photocatalyst accompanying energy irradiation as described above.
[0105]
Examples of the organopolysiloxane contained in the present embodiment include (a) an organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (b) water repellency. And organopolysiloxanes such as organopolysiloxanes crosslinked with reactive silicones excellent in oil repellency.
[0106]
In the case of (a) above, the general formula:
Y_nSiX_{( 4-n )}
(Where Y is an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group, chloroalkyl group, isocyanate group, or epoxy group, or an organic group containing these, and X is an alkoxyl group, acetyl group, or Represents 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 alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Moreover, it is preferable that the carbon number of the whole organic group shown by Y exists in the range of 1-20, especially in the range of 5-10.
[0107]
As a result, when the wettability changing layer is formed, the surface can be made liquid-repellent by Y constituting the organopolysiloxane, and the Y is decomposed by the action of the photocatalyst accompanying the energy irradiation. This is because it can be made lyophilic.
[0108]
In particular, when an organopolysiloxane in which Y constituting the organopolysiloxane is a fluoroalkyl group is used, the wettability changing layer before energy irradiation can be made particularly high in liquid repellency. When high liquid repellency is required, it is preferable to use an organopolysiloxane having these fluoroalkyl groups. Specific examples of such organopolysiloxanes include one or more of the following hydroalkyl silanes, co-hydrolysis condensates, and are generally known as fluorine-based silane coupling agents. Can be used.
[0109]
CF_Three(CF₂)_ThreeCH₂CH₂Si (OCH_Three)_Three;
CF_Three(CF₂)_FiveCH₂CH₂Si (OCH_Three)_Three;
CF_Three(CF₂)₇CH₂CH₂Si (OCH_Three)_Three;
CF_Three(CF₂)₉CH₂CH₂Si (OCH_Three)_Three;
(CF_Three)₂CF (CF₂)_FourCH₂CH₂Si (OCH_Three)_Three;
(CF_Three)₂CF (CF₂)₆CH₂CH₂Si (OCH_Three)_Three;
(CF_Three)₂CF (CF₂)₈CH₂CH₂Si (OCH_Three)_Three;
CF_Three(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
CF_Three(CF₂)_Five(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
CF_Three(CF₂)₇(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
CF_Three(CF₂)_ThreeCH₂CH₂SiCH_Three(OCH_Three)₂;
CF_Three(CF₂)_FiveCH₂CH₂SiCH_Three(OCH_Three)₂;
CF_Three(CF₂)₇CH₂CH₂SiCH_Three(OCH_Three)₂;
CF_Three(CF₂)₉CH₂CH₂SiCH_Three(OCH_Three)₂;
(CF_Three)₂CF (CF₂)_FourCH₂CH₂SiCH_Three(OCH_Three)₂;
(CF_Three)₂CF (CF₂)₆CH₂CH₂Si CH_Three(OCH_Three)₂;
(CF_Three)₂CF (CF₂)₈CH₂CH₂Si CH_Three(OCH_Three)₂;
CF_Three(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
CF_Three(CF₂)_Five(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
CF_Three(CF₂)₇(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
CF_Three(CF₂)_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three;
CF_Three(CF₂)_FiveCH₂CH₂Si (OCH₂CH_Three)_Three;
CF_Three(CF₂)₇CH₂CH₂Si (OCH₂CH_Three)_Three;
CF_Three(CF₂)₉CH₂CH₂Si (OCH₂CH_Three)_Three;and
CF_Three(CF₂)₇SO₂N (C₂H_Five) C₂H_FourCH₂Si (OCH_Three)_Three.
[0110]
In addition, examples of the reactive silicone (b) include compounds having a skeleton represented by the following general formula.
[0111]
[Chemical 1]

[0112]
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.
[0113]
Moreover, you may mix the stable organosilicon compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0114]
The wettability changing layer in this embodiment 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.
[0115]
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.
[0116]
Such a wettability changing layer is prepared by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating liquid, and applying this coating liquid on a photocatalyst-containing layer described later. Can be formed. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0117]
In the present embodiment, the thickness of the wettability changing layer described above is preferably in the range of 10 to 1000 mm, and more preferably in the range of 10 to 100 mm, from the relationship of the wettability change rate by the photocatalyst.
[0118]
(2) Case of monomolecular film
Next, the case where the wettability changing layer is a monomolecular film will be described. Since the wettability changing layer is a monomolecular film, the wettability changing layer can be formed into a uniform and dense layer, and a functional part described later can be formed uniformly and with high definition. is there. Examples of such a monomolecular film include a self-assembled monomolecular film.
[0119]
Here, the self-assembled monomolecular film is an organic thin film that spontaneously forms a monomolecular film while organic molecules gather spontaneously at the solid / liquid or solid / gas interface to form an aggregate. It is. For example, when a substrate made of a specific material is exposed to a solution or vapor of an organic molecule having a high chemical affinity with the substrate material, the organic molecule chemically reacts and adsorbs on the substrate surface. If the organic molecule consists of two parts, a functional group with high chemical affinity and an organic chain that does not cause any chemical reaction with the substrate, the molecule reacts when the functional group with high affinity is at its end. The organic terminal is adsorbed with the substrate side facing and the organic chain facing the outside. When organic chains gather together, the whole becomes stable, so organic molecules gather spontaneously during the process of chemisorption. Since molecular adsorption requires a chemical reaction between the substrate and the terminal functional group, once the substrate surface is covered with organic molecules to form a monomolecular film, molecular adsorption does not occur thereafter. Absent. As a result, an organic monomolecular film in which molecules are closely gathered and aligned is formed.
[0120]
In this embodiment, when the wettability changing layer is the self-assembled monolayer, an organic chain having water repellency existing on the surface of the wettability changing layer is irradiated with energy by the action of a photocatalyst accompanying energy irradiation. By being removed by the action of the photocatalyst, the surface can be easily made hydrophilic and the characteristic change pattern can be efficiently formed.
[0121]
The material constituting the monomolecular film used as the wettability changing layer is not particularly limited as long as it has the above-described characteristics, but in this embodiment, it has an organic chain. A silane compound is preferred. This is because it is easy to form a monomolecular film and to exhibit the above-described characteristics. Here, the number of carbons constituting the organic chain is preferably in the range of 1 to 20, and more preferably in the range of 5 to 10. As a result, the wettability changing layer before energy irradiation can be made liquid repellent, and the organic chain can be decomposed by the action of the photocatalyst accompanying energy irradiation to make it lyophilic.
[0122]
As the silane compound having an organic chain, specifically, the materials described in the above-mentioned organopolysiloxane can be used, and among them, fluoroalkylsilane is preferable.
[0123]
Such a wettability changing layer made of a monomolecular film can be formed by a thermal CVD method, a dip coating method, or the like, but in this embodiment, the thermal CVD method is from the viewpoint of production efficiency and the like. preferable. Preferable film forming conditions for the thermal CVD method are not particularly limited as long as they are not higher than the heat-resistant temperature of a transparent base material to be described later, and are not lower than the vaporization temperature of the raw material and not higher than the decomposition temperature. However, it is preferable that it exists in the range of 50 to 200 degreeC normally.
[0124]
In this embodiment, a known low pressure thermal CVD method may be used. The degree of vacuum during the reduced pressure thermal CVD process can be set so that a sufficient vapor pressure of the material can be obtained. The vapor pressure is appropriately selected depending on the type of material, but is usually 0.01 Torr to 10 Torr, and in particular, 5 Torr or less. At this time, in order to promote the reaction with the surface of the transparent substrate, it is preferable to form a wettability changing layer by performing a low pressure CVD method while heating the transparent substrate. The heating temperature in this case is appropriately selected depending on the material of the transparent substrate and the wettability changing layer, but is usually in the range of 40 ° C. to 100 ° C., particularly 80 ° C. or less.
[0125]
The film thickness of the wettability changing layer formed in this embodiment is determined by the type of the monomolecular film, but is usually in the range of 1 nm to 50 nm.
[0126]
(Decomposition removal layer)
Next, the case where the characteristic change layer used in this embodiment is a decomposition removal layer will be described. The decomposition / removal layer used in this embodiment is a layer in which the decomposition / removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when irradiated with energy. In this way, the decomposed / removed layer is decomposed / removed by the action of the photocatalyst, so that the pattern including the portion with and without the decomposed / removed layer without the development process or the cleaning process, that is, the unevenness Can be formed.
[0127]
This decomposition / removal layer is oxidatively decomposed and vaporized by the action of the photocatalyst by energy irradiation, and is therefore removed without any special post-treatment such as development / washing process. Depending on the material, a cleaning process or the like may be performed.
[0128]
Moreover, it is preferable that the decomposition removal layer used for this embodiment not only forms an unevenness | corrugation, but this decomposition removal layer has a high contact angle with a liquid compared with the transparent base material mentioned later. As a result, the decomposition removal layer is decomposed and removed, and the area where the transparent substrate is exposed can be made lyophilic, and the area where the decomposition removal layer remains can be made a liquid repellent area. This is because the functional part can be formed by utilizing the difference in wettability.
[0129]
Here, the lyophilic region is a region having a small contact angle with the liquid, and refers to a region having good wettability with respect to the functional part forming coating liquid that forms the functional part. Further, the liquid repellent region is a region having a large contact angle with the liquid and means a region having poor wettability with respect to the functional part forming coating liquid.
[0130]
The decomposition removal layer preferably exhibits wettability with a contact angle with a liquid of 40 mN / m of 10 ° or more, particularly with a contact angle of 10 ° or more with a liquid with a surface tension of 20 mN / m. In this embodiment, since the remaining characteristic change layer is a portion where liquid repellency is required, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the functional portion is This is because the functional part forming coating liquid may remain in the liquid repellent region that is not formed, which is not preferable.
[0131]
In this embodiment, the transparent substrate described later has a contact angle with a liquid of 40 mN / m, which is 9 ° or less, particularly with a liquid with a surface tension of 60 mN / m, in a portion not irradiated with energy. The layer is preferably 10 ° or less. In the present embodiment, since the transparent substrate is a part that requires lyophilicity, the functional part forming coating liquid is applied even in the lyophilic area when the functional part forming coating liquid is applied. This is because it may be repelled and it may be difficult to pattern the functional part on the lyophilic region. Here, the contact angle with the liquid is a value measured by the method described above.
[0132]
In this case, the transparent base material to be described later may be surface-treated so that the surface becomes lyophilic. Examples of the surface treatment so that the surface of the material is lyophilic include lyophilic surface treatment by plasma treatment using argon, water, etc., and as a lyophilic layer formed on a transparent substrate Examples thereof include a silica film obtained by a sol-gel method of tetraethoxysilane.
[0133]
Specific examples of the film that can be used for the above-described decomposition removal layer include a film made of a fluorine-based or hydrocarbon-based resin having liquid repellency. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent, for example, a general composition such as a spin coating method. It can be formed by a film method.
[0134]
In this embodiment, a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, an alternating adsorption film, and the like can be used to form a film without defects. It can be said that it is more preferable to use such a film forming method.
[0135]
Here, the self-assembled monomolecular film, the Langmuir-Brocket film, and the alternating adsorption film used in the present embodiment will be specifically described.
[0136]
(1) Self-assembled monolayer
Examples of materials capable of forming a self-assembled film used in this embodiment include surfactant molecules such as fatty acids, organic silicon molecules such as alkyltrichlorosilanes and alkylalkoxides, and organic sulfur molecules such as alkanethiols. And organic phosphate molecules such as alkyl phosphates. The common commonality of molecular structure is that there is a functional group that has a relatively long alkyl chain and interacts with the surface of the transparent substrate 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 a transparent substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present embodiment, these are also included in the self-assembled monolayer.
[0137]
(2) Langmuir-Blodgett membrane
If the Langmuir-Blodgett film used in this embodiment is formed on a transparent substrate, there is no significant difference in form from the self-assembled monolayer described above. 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 transparent substrate and used. It is possible to form 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).
[0138]
(3) Alternate adsorption film
Alternating adsorption film (Layer-by-Layer Self-Assembled Film) generally adsorbs and binds at least two materials with positive or negative functional groups sequentially onto a transparent substrate. It is a film formed by stacking. 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 slightly biased towards materials with electrostatic interaction as the driving force, 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.
[0139]
In addition, the thickness of the decomposition removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the action of the photocatalyst associated with energy. 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 in general, it is preferably in the range of 10 to 1000 mm, particularly 10 to 100 mm. .
[0140]
(2) Transparent substrate
Next, the substrate in the substrate for pattern forming body used in this embodiment will be described. The substrate used in this embodiment is not particularly limited as long as it has transparency to the energy irradiated during the formation of the characteristic change pattern and can form the above-described characteristic change layer. However, in this embodiment, as described above, since the energy irradiation is performed from the pattern forming substrate side, the energy applied to the transparent base material may not be absorbed, scattered, or interfered. preferable. For this reason, it is preferable that the above-described transmittance of the irradiated energy is in the range of 5% to 95%, particularly 50% to 95%. This is because the irradiated energy can efficiently reach the photocatalyst containing layer.
[0141]
Examples of such a transparent substrate include inflexible transparent rigid materials such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plates, or flexibility such as transparent resin films and optical resin plates. The transparent flexible material etc. which have are mentioned.
[0142]
In the present embodiment, those subjected to surface treatment for preventing alkali elution, imparting gas barrier properties or other purposes may be used as necessary.
[0143]
In the present embodiment, among the above, Pyrex (registered trademark) glass or a transparent resin film is particularly preferable from the viewpoint of energy permeability.
[0144]
2. Second embodiment
Next, a second embodiment in the method for producing a pattern forming body of the present invention will be described. The second embodiment of the method for producing a pattern formed body of the present invention is a pattern formed body having a transparent base material and a property changing layer whose properties are changed by the action of a photocatalyst accompanying energy irradiation formed on the transparent base material. After arranging the substrate for use, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the substrate with a gap so that the characteristic change layer and the photocatalyst-containing layer are 200 μm or less, the transparent group Energy is irradiated from the material side by a light drawing method to form a characteristic change pattern in which the characteristic of the characteristic change layer is changed.
[0145]
For example, as shown in FIG. 2, the pattern forming body of this embodiment includes a substrate 3 for a pattern forming body having a transparent base material 1 and a characteristic change layer 2 formed on the transparent base material 1, and a base body 4. And a photocatalyst containing layer side substrate 6 having a photocatalyst containing layer 5 formed on the substrate 4, and the pattern forming substrate 3 and the photocatalyst containing layer side substrate 6 are spaced apart from each other by a predetermined gap. It arrange | positions (FIG. 2 (a)). Next, the target pattern-shaped energy 8 is irradiated from the transparent base material 1 side of the pattern forming substrate 3 by the optical drawing method (FIG. 2B). The photocatalyst in the photocatalyst containing layer 5 is excited by this energy 8, and the characteristics of the opposing characteristic change layer 2 change. That is, it is possible to manufacture a pattern forming body in which the characteristic change pattern 9 in which the characteristic of the characteristic change layer 2 is changed is formed in a pattern corresponding to the energy 8 (FIG. 2C).
[0146]
According to the present embodiment, as described above, since the energy is irradiated by the light drawing method, the photocatalyst contained in the photocatalyst containing layer can be excited by the energy irradiated in the target pattern. Thus, a high-definition characteristic change pattern in which the characteristic of the characteristic change layer is changed by the action of the photocatalyst can be formed.
[0147]
Here, the arrangement of the photocatalyst containing layer side substrate and the pattern forming body substrate used in this embodiment and the pattern forming body substrate and the photocatalyst containing layer side substrate is the same as in the first embodiment described above. The description here will be omitted, and energy irradiation by the optical drawing method, which is a feature of the method of manufacturing the pattern forming body of this embodiment, will be described below.
[0148]
(Energy irradiation by light drawing method)
In this embodiment, the pattern forming body substrate and the photocatalyst containing layer side substrate are maintained in the arrangement as described above, and the energy is drawn from the transparent base material side of the pattern forming body substrate by a light drawing method. Irradiation takes place. Here, the optical drawing method referred to in this embodiment is a method of drawing and irradiating in a target pattern using a laser such as excimer, YAG, or deep ultraviolet rays.
[0149]
In this embodiment, it is possible to irradiate the photocatalyst-containing layer with energy in a high-definition pattern by using such an optical drawing method, and by the action of the photocatalyst in the region irradiated with this energy, This makes it possible to change the characteristics of the characteristic change layer into a high-definition pattern.
[0150]
Here, also in this embodiment, energy irradiation is performed from the transparent base material side in the substrate for pattern forming body. When energy irradiation is performed from the photocatalyst containing layer side substrate side, the energy patterned by the projection exposure must pass through the photocatalyst containing layer, and by absorption or scattering of energy inside this photocatalyst containing layer, This is because it becomes difficult to form a high-definition pattern. Moreover, since it is not necessary to consider interference of energy in the photocatalyst containing layer side substrate by performing energy irradiation from the pattern forming substrate side, as described above, the photocatalyst in the photocatalyst containing layer side substrate The film thickness of the containing layer can be optimized to change the characteristics of the characteristic change layer, and a pattern forming body on which a high-definition characteristic change pattern is formed can be efficiently manufactured.
[0151]
B. Functional element
Next, the functional element of the present invention will be described. In the functional element of the present invention, a functional part is formed along the characteristic change pattern of the pattern forming body manufactured by the method for manufacturing a pattern forming body described above.
[0152]
In the present invention, the pattern forming body manufactured by the method for manufacturing a pattern forming body described above. Since the functional part is formed along the pattern having changed characteristics, a high-definition functional part can be formed.
[0153]
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.
[0154]
The functional part forming composition for forming the functional part used in the present invention varies greatly depending on the function of the functional element, the method of forming the functional element, etc. as described above. A composition not diluted with a solvent typified by a mold monomer or the like, a liquid composition diluted with a solvent, or the like can be used. Moreover, as a functional part formation composition, 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.
[0155]
The composition for forming a functional part used in the present invention may be a functional part by being attached to the lyophilic region or the like and disposed on the lyophilic region. Then, it may be treated with a medicine, or may be a functional part after being treated with ultraviolet rays, heat, or the like. In this case, as a binder of the composition for forming a functional part, when a component that is effective with ultraviolet rays, heat, electron beam, or the like is contained, the functional part can be quickly formed by performing a curing treatment. preferable.
[0156]
In the present invention, the functional part forming step for forming the functional part includes a coating means such as dip coating, roll coating, blade coating, and spin coating, a method using an inkjet, an electric field jet, a dispenser, and the like. It is preferable to use means such as nozzle discharge means. This is because by using these methods, the functional portion can be formed uniformly and with high definition.
[0157]
Examples of the functional element of the present invention include a color filter having a pixel portion as a functional portion, a microlens having a lens as a functional portion, and a conductive pattern forming body having a metal wiring as a functional portion. In the present invention, the conductive pattern forming body described later is preferable because the advantages of the present invention that can form a high-definition pattern can be used.
[0158]
C. Conductive pattern forming body
Next, the conductive pattern formed body of the present invention will be described. In the conductive pattern formed body of the present invention, the functional part in the functional element described above is a metal wiring. In the present invention, since the characteristic change pattern in the pattern formed body manufactured by the method for manufacturing a pattern formed body described above can be made high definition, the difference in wettability, for example, of the characteristic change pattern is used. Then, for example, by forming the metal wiring by a nozzle discharge method or the like, it is possible to obtain a conductive pattern forming body in which high-definition metal wiring is formed.
[0159]
In the present invention, the method for forming the metal wiring is not particularly limited as long as it can be formed by utilizing the difference in characteristics in the characteristic change pattern of the pattern forming body described above. By using a material used when forming the metal wiring, it can be formed by a nozzle discharge method such as an inkjet method, an electric field jet method, a method using a dispenser, an offset printing method, a screen printing method, or the like.
[0160]
In the present invention, the width of the metal wiring formed in this way is appropriately selected depending on the type of the conductive pattern forming body, etc., and is usually 0.2 μm to 500 μm, particularly 1 μm to It can be in the range of 100 μm.
[0161]
D. Photocatalyst-containing layer side substrate for pattern formation production
Next, the photocatalyst containing layer side substrate for producing the pattern forming body of the present invention will be described. The photocatalyst-containing layer side substrate for pattern-forming product production according to the present invention has a base and a photocatalyst-containing layer formed on the base and containing a photocatalyst. A pattern forming body-producing photocatalyst-containing layer side substrate having an antireflection function, wherein the characteristic changing layer in the pattern forming body substrate has a characteristic changing layer whose characteristics are changed by the action of a photocatalyst accompanying energy irradiation, and The photocatalyst-containing layer is disposed with a predetermined gap, and the pattern forming body in which the characteristics of the characteristic change layer are changed is formed by irradiating energy from the pattern forming substrate side by the projection exposure method. .
[0162]
That is, the photocatalyst-containing layer side substrate for producing a pattern forming body of the present invention is used when producing a pattern forming body, and the above-mentioned property changing layer and the above-mentioned photocatalyst containing layer in the substrate for a pattern forming body are opposed to each other. Thus, the pattern forming body in which the characteristics of the characteristic change layer are changed is formed by irradiating energy from the pattern forming body substrate side.
[0163]
In the present invention, since the photocatalyst-containing layer side substrate for producing a pattern forming body has an antireflection function with respect to the energy irradiated when the pattern is formed, the irradiated energy is reflected and irradiated. It is possible to produce a pattern forming body in which a high-definition pattern is formed without exciting the photocatalyst in the photocatalyst-containing layer in a region where there is no region. In the present invention, the method is not particularly limited as long as an antireflection function can be imparted to the photocatalyst-containing layer side substrate for producing a pattern-formed body. For example, even if the substrate has energy absorptivity. It may also be one having an energy absorption layer or an antireflection layer on the surface of the substrate.
[0164]
In the present invention, the film thickness of the photocatalyst-containing layer is usually in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 5 μm, and particularly preferably in the range of 0.1 μm to 2 μm. Thereby, the characteristics of the characteristic change layer can be changed efficiently, and a pattern forming body having a high-definition pattern can be efficiently manufactured. Because it can.
[0165]
Here, for the substrate, photocatalyst containing layer, energy absorbing layer, antireflection layer, etc. used in the photocatalyst containing layer side substrate for pattern forming product production of the present invention, the photocatalyst of “A. Pattern forming product producing method” described above is used. Since the thing similar to what was demonstrated by the term of the containing layer side board | substrate can be used, description here is abbreviate | omitted.
[0166]
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.
[0167]
【Example】
Hereinafter, the present invention will be described in more detail through examples.
[0168]
[Example 1]
First, 1.5 g of 0.01N hydrochloric acid was added to 5 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), stirred for 24 hours, and then diluted 100-fold with isopropyl alcohol to prepare a coating solution. This coating solution was applied on a non-alkali glass substrate by a spin coating method and then dried to form a wettability changing layer having a thickness of 0.1 μm to obtain a substrate for a pattern forming body.
[0169]
Next, as a photocatalyst containing layer, ST-K03 (Ishihara Sangyo Co., Ltd.), which is a photocatalyst inorganic coating agent, is applied on the PET film so as to have a thickness of 0.15 μm to form a photocatalyst containing layer side substrate. did.
[0170]
Then, it arrange | positions so that it may become 25 micrometers between the said wettability change layer and the photocatalyst containing layer side board | substrate, and a deep ultraviolet solid laser (266 nm, 25 mW / cm from the pattern formation board | substrate side.²) For 5 seconds. At this time, the wettability of the surface of the wettability changing layer in the exposed area is 20 ° in contact with water, and the wettability of the surface of the wettability changing layer in the unexposed area is 110 ° in contact with water. Met.
[0171]
Next, using a piezo drive type ink jet device, RGB thermosetting inks (colored inks) containing 5 parts by weight of pigment, 20 parts by weight of solvent, and 75 parts by weight of binder are attached to the exposed part and colored. This was subjected to UV treatment and cured to obtain a color filter.
[0172]
[Example 2]
First, 1.5 g of 0.01N hydrochloric acid was added to 3 g of decyltrimethoxysilane (LS-5258 manufactured by Shin-Etsu Silicone Co., Ltd.), stirred for 24 hours, and then diluted 100 times with isopropyl alcohol to prepare a coating solution. did. This coating solution was applied on a non-alkali glass substrate by a spin coating method and then dried to form a wettability changing layer having a thickness of 500 mm, thereby obtaining a substrate for a pattern forming body.
[0173]
Next, ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalyst coating agent, was applied as a photocatalyst layer to a thickness of 0.6 μm on the PET film to form a photocatalyst layer side substrate.
[0174]
Then, it arrange | positioned so that between the said wettability change layer and a photocatalyst containing layer side board | substrate might be set to 50 micrometers, and it irradiated for 5 minutes with the stepper exposure machine (I line | wire = 365 nm) from the pattern formation body substrate side. At this time, the wettability of the surface of the wettability changing layer in the exposed area was 15 ° with a silver colloid aqueous solution (concentration 20 wt%), and the contact angle with an unexposed area was 104 °.
[0175]
Next, the substrate for a pattern forming body was immersed in a silver colloid aqueous solution (concentration 20 wt%) and pulled up at 10 mm / sec., Thereby allowing the silver colloid aqueous solution to adhere onto the pattern only in the lyophilic region. By heating this silver colloid aqueous solution pattern at 300 ° C. for 20 minutes, a conductive pattern formed body in which silver was patterned on the substrate was obtained.
[0176]
【The invention's effect】
According to the present invention, it is possible to excite the photocatalyst contained in the photocatalyst-containing layer into a high-definition pattern by irradiating energy by the projection exposure method. By the action of the excited photocatalyst, the characteristics of the characteristic change layers arranged to face each other can be changed, and a pattern forming body having a high-definition characteristic change pattern can be manufactured. At this time, since the energy irradiation is performed from the transparent base material side of the substrate for the pattern forming body, the energy can reach the photocatalyst-containing layer without irregular reflection or the like, and a high-definition characteristic change pattern is formed. It becomes possible.
[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 process diagram showing another example of the method for producing a pattern-formed body of the present invention.
[Explanation of symbols]
1 ... Base material
2… Characteristic change layer
3 ... Pattern forming substrate
4 ... Base
5 ... Photocatalyst containing layer
6 ... Photocatalyst-containing layer side substrate
7 ... Photomask
8… Energy
9 ... Characteristic change pattern

Claims (18)

A method for producing a pattern formed body, comprising:
A substrate for a pattern forming body having a transparent base, a characteristic changing layer whose characteristics are changed by the action of a photocatalyst formed by energy irradiation formed on the transparent base, a photocatalyst-containing layer containing the photocatalyst, and a photocatalyst having the base After arranging the content layer side substrate with a gap so that the property change layer and the photocatalyst content layer are 200 μm or less, energy is irradiated from the transparent substrate side by a projection exposure method, and the property change layer A characteristic change pattern in which the characteristics of
The characteristic change layer has a thickness in a range of 10 to 1000 mm,
The characteristic change layer has an energy transmittance of 70% to 99.5% of the energy irradiated,
The said photocatalyst containing layer side board | substrate has a reflection preventing function with respect to the irradiated energy, The manufacturing method of the pattern formation body characterized by the above-mentioned .   The method of manufacturing a pattern forming body according to claim 1, wherein the projection exposure method is a mirror projection method or a stepper method. A method for producing a pattern formed body, comprising:
A substrate for a pattern forming body having a transparent base, a characteristic changing layer whose characteristics are changed by the action of a photocatalyst formed by energy irradiation formed on the transparent base, a photocatalyst-containing layer containing the photocatalyst, and a photocatalyst having the base After placing the inclusion layer side substrate with a gap so that the characteristic change layer and the photocatalyst containing layer are 200 μm or less, energy is irradiated from the transparent substrate side by a light drawing method, and the characteristic change layer A characteristic change pattern in which the characteristics of
The characteristic change layer has a thickness in a range of 10 to 1000 mm,
The characteristic change layer has an energy transmittance of 70% to 99.5% of the energy irradiated,
The said photocatalyst containing layer side board | substrate has a reflection preventing function with respect to the irradiated energy, The manufacturing method of the pattern formation body characterized by the above-mentioned . Said characteristic changing layer is, by the action of the photocatalyst accompanied by the energy irradiation, of claims 1, contact angle with a liquid is characterized in that it is a wettability variable layer that changes wettability so drops to claim 3 The manufacturing method of the pattern formation body in any one of Claims. The method for producing a pattern forming body according to claim 4 , wherein the wettability changing layer is a layer containing an organopolysiloxane. The organopolysiloxane is Y _n SiX _(4-n) (where Y is an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, a chloroalkyl group, an isocyanate group, or an epoxy group, or these) One or two or more hydrolyzed condensates or cohydrolyzed condensates of a silicon compound represented by: X represents an alkoxyl group or halogen, and n is an integer from 0 to 3. The method for producing a pattern forming body according to claim 5 , which is an organopolysiloxane. The method for producing a pattern forming body according to claim 6 , wherein the number of carbon atoms of Y constituting the organopolysiloxane is in the range of 1 to 20. The method for producing a pattern forming body according to claim 4 , wherein the wettability changing layer is a monomolecular film. The method for producing a pattern forming body according to claim 8 , wherein the monomolecular film is made of a silane compound having an organic chain. The number of carbon which comprises the said organic chain exists in the range of 1-20, The manufacturing method of the pattern formation body of Claim 9 characterized by the above-mentioned. The method for producing a pattern forming body according to claim 9 or 10 , wherein the silane compound is fluoroalkylsilane. The said characteristic change layer is a decomposition removal layer decomposed and removed by the effect | action of the photocatalyst accompanying energy irradiation, The manufacturing of the pattern formation body in any one of Claim 1 to 3 characterized by the above-mentioned. Method. The contact angle of the decomposition removal layer with a liquid having a surface tension of 40 mN / m is 10 ° or more, and the contact angle of the transparent substrate with a liquid having a surface tension of 40 mN / m is 9 ° or less. The manufacturing method of the pattern formation body of Claim 12 . Method for manufacturing a patterned member according to claim 14 or claim 13, wherein the decomposition removal layer is a monomolecular film. The width of the characteristic change pattern is in the range of 0.2 µm to 500 µm, and the method for producing a pattern forming body according to any one of claims 1 to 14 . A function part formed along a characteristic change pattern of a pattern forming body manufactured by the method for manufacturing a pattern forming body according to any one of claims 1 to 15. Sex element. 17. The conductive pattern forming body according to claim 16 , wherein the functional portion is a metal wiring.   The photocatalyst-containing layer side for producing a pattern forming body having a base and a photocatalyst-containing layer formed on the base and containing a photocatalyst and having an antireflection function with respect to energy irradiated in the production of the pattern forming body The substrate is a pattern forming body substrate having a property changing layer whose properties change due to the action of a photocatalyst associated with energy irradiation, and the photocatalyst-containing layer is disposed with a predetermined gap therebetween, A photocatalyst-containing layer-side substrate for producing a pattern-forming body, wherein the pattern-forming body in which the characteristics of the characteristic-changing layer are changed is formed by irradiating energy from the pattern-forming body substrate side by a projection exposure method.

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