JP4612994B2 - Pattern forming body, pattern forming body manufacturing method, and color filter - Google Patents

Description

【００６４】
ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１、Ｒ^２がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００６５】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコーン化合物を混合してもよい。
【００６６】
本発明においては、このようにオルガノポリシロキサン等の種々の材料を濡れ性変化層に用いることができるのであるが、上述したように、濡れ性変化層にフッ素を含有させることが、濡れ性のパターン形成に効果的である。したがって、光触媒の作用により劣化・分解しにくい材料にフッ素を含有させる、具体的にはオルガノポリシロキサン材料にフッ素を含有させて濡れ性変化層とすることが好ましいといえる。
【００６７】
本発明における濡れ性変化層には、さらに界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００６８】
また、濡れ性変化層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００６９】
このような濡れ性変化層は、上述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上の両面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。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【００７０】
本発明において、この濡れ性変化層の厚みは、光触媒による濡れ性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、特に好ましくは０．０１〜０．１μｍの範囲内である。
【００７１】
本発明において上述した成分の濡れ性変化層を用いることにより、光触媒含有層中の光触媒の作用により、上記成分の一部である有機基の酸化、分解等の作用を用いて、エネルギー照射部の濡れ性を変化させて親液性とし、エネルギー未照射部との濡れ性に大きな差を生じさせることができる。よって、例えば機能性部形成用塗布液を全面塗布した場合においても、比較的容易にエネルギー照射部である親液性領域内のみに機能性部形成用塗布液を付着させることが可能であり、高精細な機能性素子を低コストで製造することが可能なパターン形成体とすることができる。
【００７２】
なお、本発明に用いられる濡れ性変化層は、上述したように光触媒の作用により濡れ性の変化する層であれば特に限定されるものではないが、特に、光触媒を含まない層であることが好ましい。このように濡れ性変化層内に光触媒が含まれなければ、その後導電性パターン形成体として用いた場合に、経時的に影響を受ける心配をする必要がなく、長期間に渡り問題なく使用することが可能だからである。
【００７３】
（分解除去層）
次に分解除去層について説明する。本発明に用いられる分解除去層は、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層であれば、特に限定されるものではない。
【００７４】
このように分解除去層は、エネルギー照射した部分が光触媒の作用により分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分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。
【００７５】
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。
【００７６】
また、本発明に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、後述する基材と比較して、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、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、種々のパターンを形成することが可能となるからである。
【００７７】
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布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、上記機能性部形成用塗布液に対する濡れ性が悪い領域をいうこととする。
【００７８】
また、上記分解除去層は、４０ｍＮ／ｍの液体との接触角が、５０°以上、中でも９０°以上であることが好ましい。これは、本発明は、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、例えば機能性部を形成する機能性部形成用塗布液を塗布した場合に、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布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。
【００７９】
また、本発明において、後述する基材は、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４９°以下、中でも１０°以下であることが好ましい。本発明においては基材が、親液性が要求される部分であることから、例えば機能性部形成用塗布液を塗布した際に、親液性領域においても機能性部形成用塗布液をはじいてしまう可能性があり、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。
【００８０】
この場合、後述する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、基体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。
【００８１】
上記のような分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により基材の片面ずつに形成する方法であってもよいが、本発明においては、上述した濡れ性変化層の場合と同様に、乾式法により形成されることが、製造効率等の面から好ましい。
【００８２】
分解除去層の形成がプラズマＣＶＤ法により行なわれる場合には、原料ガスとして用いられる材料としては、炭化水素系材料や、フッ素含有有機材料等を挙げることができる。具体的に炭化水素系材料としては、ＣＨ_４、Ｃ_２Ｈ_２、Ｃ_２Ｈ_４、およびＣ_３Ｈ_８を挙げることができる。また、フッ素含有有機材料としては、ＣＦ_４、Ｃ_２Ｆ_４、Ｃ_２Ｆ_６、Ｃ_３Ｆ_６，Ｃ_３Ｆ_８，Ｃ_５Ｆ_８、ＰＴＦＥ（ポリテトラフルオロエチレン）、ＰＶＤＦ（ポリビニリデンフルオロエチレン）、ＰＶＦ（ポリビニルフルオリド）、ＥＴＦＥ（エチレン／テトラフルオロエチレン共重合体）等を挙げることができる。
【００８３】
分解除去層の形成が、熱ＣＶＤ法により行われる場合には、原料としては、通常の樹脂モノマー等を挙げることができる。
【００８４】
なお、プラズマＣＶＤ法および熱ＣＶＤ法の成膜条件、分解除去層の膜厚等については、上述した濡れ性変化層で説明したものと同様であるので、ここでの説明は省略する。
【００８５】
また、分解除去層がディップコート法等、他の方法により形成されてもよく、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てもよい。
【００８６】
ここで、本発明に用いられる自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜について具体的に説明する。
【００８７】
▲１▼自己組織化単分子膜
本発明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、片方の分子末端に基板表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基板表面に形成されたもの（後者はポリマーブラシと総称される）も自己組織化単分子膜と考えられる場合もあるようである。本発明は、これらも自己組織化単分子膜に含める。
【００８８】
▲２▼ラングミュア−ブロジェット膜
本発明に用いられるラングミュア−ブロジェット膜(Langmuir-Blodgett Film)は、基板上に形成されてしまえば形態上は上述した自己組織化単分子膜との大きな相違はない。ラングミュア−ブロジェット膜の特徴はその形成方法とそれに起因する高度な２次元分子パッキング性（高配向性、高秩序性）にあると言える。すなわち、一般にラングミュア−ブロジェット膜形成分子は気液界面上に先ず展開され、その展開膜がトラフによって凝縮されて高度にパッキングした凝縮膜に変化する。実際は、これを適当な基板に移しとって用いる。ここに概略を示した手法により単分子膜から任意の分子層の多層膜まで形成することが可能である。また、低分子のみならず、高分子、コロイド粒子なども膜材料とすることができる。様々な材料を適用した最近の事例に関しては宮下徳治らの総説“ソフト系ナノデバイス創製のナノテクノロジーへの展望” 高分子 50巻 9月号 644-647
(2001)に詳しく述べられている。
【００８９】
▲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基板上に吸着・結合させて積層することにより形成される膜である。多数の官能基を有する材料の方が膜の強度や耐久性が増すなど利点が多いので、最近ではイオン性高分子（高分子電解質）を材料として用いることが多い。また、タンパク質や金属や酸化物などの表面電荷を有する粒子、いわゆる“コロイド粒子”も膜形成物質として多用される。さらに最近では、水素結合、配位結合、疎水性相互作用などのイオン結合よりも弱い相互作用を積極的に利用した膜も報告されている。比較的最近の交互吸着膜の事例については、静電的相互作用を駆動力にした材料系に少々偏っているがPaula T. Hammondによる総説“Recent Explorations in Electrostatic Multilayer Thin Film Assembly”Current Opinion in Colloid & Interface Science, 4, 430-442 (2000)に詳しい。交互吸着膜は、最も単純なプロセスを例として説明すれば、正（負）電荷を有する材料の吸着−洗浄−負（正）電荷を有する材料の吸着−洗浄のサイクルを所定の回数繰り返すことにより形成される膜である。ラングミュア−ブロジェット膜のように展開−凝縮−移し取りの操作は全く必要ない。また、これら製法の違いより明らかなように、交互吸着膜はラングミュア−ブロジェット膜のような２次元的な高配向性・高秩序性は一般に有さない。しかし、交互吸着膜及びその作製法は、欠陥のない緻密な膜を容易に形成できること、微細な凹凸面やチューブ内面や球面などにも均一に成膜できることなど、従来の成膜法にない利点を数多く有している。
【００９０】
また、分解除去層の膜厚としては、後述する特性変化パターン形成工程において照射されるエネルギーにより分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、０．００１μｍ〜１μｍの範囲内、特に０．０１μｍ〜０．１μｍの範囲内とすることが好ましい。
【００９１】
２．基材
次に、本発明のパターン形成体に用いられる基材について説明する。本発明においては、この基材の両面に特性変化層が形成されるものである。
【００９２】
本発明に用いられる基材としては、最終的に得られるパターン形成体の用途等に応じて適宜選択されるものであり、例えば紙基材の樹脂積層板、ガラス布・ガラス不織布基材の樹脂積層板、セラミック、金属等を用いることができ、板状のものであることが好ましい。
【００９３】
また、本発明においては、基材を透明なものとすることができる。フォトリソグラフィー法等においては、フォトレジスト層を両面に形成した場合、基材が透明である場合には、露光により両面同時にフォトレジスト層が感光してしまうことから、フォトレジスト層の形成、露光、現像等の処理を片面ずつ行わなければならなかった。しかしながら、本発明においては、基材が透明であっても、上記特性変化層は、エネルギー照射のみによっては特性が変化せず、特性変化層表面の近傍に配置された光触媒を含有する層の光触媒の作用により特性が変化することから、基材をはさんで反対側の面に形成されている、光触媒を含有する層が近傍に配置されていない特性変化層の特性は変化しない。これにより、それぞれ片面ずつ特性変化層の特性を変化させることができ、目的とするパターンを両面にそれぞれ形成することができるのである。
【００９４】
また、基材が透明であることにより、エネルギー照射の方法等によっては、同時に両面の特性変化層の特性を変化させることが可能となり、それぞれ異なる特性変化パターンを同時に形成することができるのである。
【００９５】
ここで、両面の特性変化層を同時に変化させる場合には、基材の厚さは５０μｍ〜１００００μｍの範囲内であることが好ましい。
【００９６】
また、本発明においては、基材上に、上記特性変化層の形成が困難である場合や、基材と上記特性変化層との密着性が悪い場合には、基材上に、密着性向上させる密着性向上層を設けてもよい。このような密着性向上層としては、例えば、ポリイミド等が挙げられる。
【００９７】
なお、本発明に用いられる基材は、必要とされる部材、例えばカラーフィルタにおけるブラックマトリックス等が形成されているものであってもよい。
【００９８】
３．特性変化パターン
次に、本発明の特性変化パターンについて説明する。本発明の特性変化パターンは、エネルギー照射に伴う光触媒の作用により、上述した基材上に形成された両面の特性変化層の、特性が変化したパターンである。
【００９９】
本発明においては、この特性変化パターンは、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を用いて、エネルギー照射を行うことにより、上記特性変化層表面にパターンを形成することができる。
【０１００】
光触媒含有層における、後述するような二酸化チタンに代表される光触媒の作用機構は、必ずしも明確なものではないが、光の照射によって生成したキャリアが、近傍の化合物との直接反応、あるいは、酸素、水の存在下で生じた活性酸素種によって、有機物の化学構造に変化を及ぼすものと考えられている。本発明においては、このキャリアが光触媒含有層に隣接して配置される特性変化層中の化合物に作用を及ぼすものであると思われる。
【０１０１】
これにより、本発明においては、上記基材が透明性を有するものであった場合においても、例えば上記特性変化層の片面に上記光触媒含有層側基板を用いてエネルギー照射を行った際に、基材をはさんで裏側の面に形成されている特性変化層に、光触媒の影響を及ぼすことがなく、片面の特性変化層のみの特性を変化させることができ、目的とするパターンを両面にそれぞれ形成することができるのである。
【０１０２】
上記光触媒含有層側基板については、後述する「Ｂ．パターン形成体の製造方法」において詳しく説明するので、ここでの説明は省略する。
【０１０３】
４．パターン形成体
次に、本発明のパターン形成体について説明する。本発明のパターン形成体は、上述した基材と、その両面に形成された特性変化層とを有するものであって、その両面の特性変化層に、上記特性変化パターンが形成されたものである。
【０１０４】
本発明によれば、この特性変化パターンの特性の差を利用して、特性変化パターン上に様々な機能性部を形成することが可能であることから、種々の機能性素子を形成可能なパターン形成体とすることができる。
【０１０５】
ここで、本発明における上記特性変化パターンは、パターン形成体の両面において、同一のパターンであってもよく、また異なるパターンであってもよい。
【０１０６】
Ｂ．パターン形成体の製造方法
次に、本発明のパターン形成体の製造方法について説明する。本発明のパターン形成体の製造方法は、基材の両面に、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形成する特性変化層形成工程と、前記特性変化層の一面と、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、前記特性変化層および前記光触媒含有層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、前記特性変化層の特性が変化した第１特性変化パターンを形成する第１特性変化パターン形成工程と、前記第１特性変化パターンが形成された面と反対側の面の特性変化層と、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、前記特性変化層および前記光触媒含有層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、前記特性変化層の特性が変化した第２特性変化パターンを形成する第２特性変化パターン形成工程とを有することを特徴とする方法である。
【０１０７】
本発明のパターン形成体の製造方法は、例えば図２に示すように、まず、基材１の両面に特性変化層２を形成する特性変化層形成工程（図２（ａ））を行う。次に、基体４と、その基体４上に形成された光触媒を含有する光触媒含有層５とを有する光触媒含有層側基板６を準備し、その光触媒含有層５と上記特性変化層２の片面とを所定の間隙をおいて配置して、例えばフォトマスク７等を用いてエネルギー８の照射を行い（図２（ｂ））、特性変化層２の特性が変化した第１特性変化パターン３を形成する第１特性変化パターン形成工程を行う（図２（ｃ））。次に、上記と同様に、第１特性変化パターン３が形成された面と反対側の面の特性変化層２と、上記基体４および光触媒含有層５を有する光触媒含有層側基板６における光触媒含有層５とを所定の間隙をおいて配置し、フォトマスク７等を用いてエネルギー８を照射し（図２（ｄ））、特性変化層２の特性が変化した第２特性変化パターン３´を形成する第２特性変化パターン形成工程を行う（図２（ｅ））。
【０１０８】
ここで、上記第１特性変化パターン形成工程および第２特性変化パターン形成工程は、後述する「３．その他」の項で説明するように、上記光触媒含有層側基板の構造によっては、同時に行ってもよい。
【０１０９】
本発明によれば、上記特性変化層形成工程により、基材の両面に特性変化層が形成されることから、上記第１特性変化パターン形成工程および上記第２特性変化パターン形成工程において、上記光触媒含有層中の光触媒含有層の作用により、パターン形成体の両面に、特性の変化した特性変化パターンを形成することができる。また、本発明によれば、上記基材が透明である場合であっても、特性変化層は近傍に配置された光触媒含有層中の光触媒の作用により特性が変化することから、片面にエネルギー照射した際に、反対側の面の特性変化層に影響を及ぼすことがなく、それぞれ両面で異なる特性変化パターンを有するパターン形成体とすることができるのである。
【０１１０】
以下、本発明のパターン形成体の製造方法の各工程について説明する。
【０１１１】
１．特性変化層形成工程
まず、本発明のパターン形成体の製造方法における特性変化層形成工程について説明する。本発明のパターン形成体の製造方法における特性変化層形成工程は、基材の両面に、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形成する工程である。
【０１１２】
本発明においては、上記特性変化層を基材の両面に形成可能であれば、その形成方法等は特に限定されるものではなく、例えば片面ずつ一般的な方法により形成する方法であってもよいが、本発明においては、ディップコート法または乾式法により形成することが好ましい。これにより、特性変化層を両面同時に形成することができることから、製造効率等の面からも好ましいからである。
【０１１３】
本発明においては、上記の中でも乾式法により形成することが好ましい。これにより、短時間で両面に均一かつ膜厚の薄い層を形成することができることから、製造効率等の面で好ましいからである。本発明に用いられる乾式法として、具体的には、熱ＣＶＤ法やプラズマＣＶＤ法等を含むＣＶＤ法、または蒸着法やスパッタリング法、イオンプレーティング法等を含むＰＶＤ法等が挙げられ、中でも、プラズマＣＶＤ法や、熱ＣＶＤ法を含むＣＶＤ法を用いることが好ましい。これにより、特性変化層を均一かつ緻密な層とすることが可能となるからである。
【０１１４】
本工程における特性変化層の形成方法や材料、基材の種類等については、上述した「Ａ．パターン形成体」の特性変化層および基材の項で説明したものと同様であるので、ここでの説明は省略する。
【０１１５】
２．第１特性変化パターン形成工程
次に、本発明のパターン形成体の製造方法における第１特性変化パターン形成工程について説明する。本発明のパターン形成体の製造方法における第１特性変化パターン形成工程は、上述した特性変化層形成工程により形成された特性変化層の一面と、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、前記特性変化層および前記光触媒含有層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、前記特性変化層の特性が変化した第１特性変化パターンを形成する工程である。以下、本工程の各構成について説明する。
【０１１６】
（光触媒含有層側基板）
まず、本工程に用いられる光触媒含有層側基板について説明する。本工程に用いられる光触媒含有層側基板は、光触媒を含有する光触媒含有層および基体を有するものであり、通常、基体と、その基体上に光触媒含有層が形成されているものである。この光触媒含有層側基板は、例えばパターン状に形成された光触媒含有層側遮光部やプライマー層等を有していてもよい。以下、本工程に用いられる光触媒含有層側基板の各構成について説明する。
【０１１７】
ａ．光触媒含有層
まず、光触媒含有層側基板に用いられる光触媒含有層について説明する。本発明に用いられる光触媒含有層は、光触媒含有層中の光触媒が、隣接する特性変化層の特性を変化させるような構成であれば、特に限定されるものではなく、光触媒とバインダとから構成されているものであってもよく、光触媒単体で製膜されたものであってもよい。また、その表面の特性は特に親液性であっても撥液性であってもよい。
【０１１８】
本発明において用いられる光触媒含有層は、例えば図２に示すように、基材４上に全面に形成されたものであってもよいが、例えば図３に示すように、基材４上に光触媒含有層５がパターン上に形成されたものであってもよい。
【０１１９】
このように光触媒含有層をパターン状に形成することにより、後述するエネルギー照射において説明するように、光触媒含有層を特性変化層と所定の間隔をおいて配置させてエネルギーを照射する際に、フォトマスク等を用いるパターン照射をする必要がなく、全面に照射することにより、特性変化層上の特性が変化したパターンを形成することができる。
【０１２０】
この光触媒処理層のパターニング方法は、特に限定されるものではないが、例えばフォトリソグラフィー法等により行うことが可能である。
【０１２１】
また、実際に光触媒含有層に面する特性変化層上の部分のみの、特性が変化するものであるので、エネルギーの照射方向は上記光触媒含有層と特性変化層とが面する部分にエネルギーが照射されるものであれば、いかなる方向から照射されてもよく、さらには、照射されるエネルギーも特に平行光等の平行なものに限定されないという利点を有するものとなる。また、後述する「３．その他」の項で説明するように、このような光触媒含有層を有する光触媒含有層側基板を２つ用意し、上記特性変化層の両面に配置してエネルギー照射することにより、第１特性変化変化パターンおよび第２特性変化パターンを同時に形成することも可能となる。
【０１２２】
本発明で使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【０１２３】
本発明においては、特に二酸化チタンが、バンドギャップエネルギーが高く、化学的に安定で毒性もなく、入手も容易であることから好適に使用される。二酸化チタンには、アナターゼ型とルチル型があり本発明ではいずれも使用することができるが、アナターゼ型の二酸化チタンが好ましい。アナターゼ型二酸化チタンは励起波長が３８０ｎｍ以下にある。
【０１２４】
このようなアナターゼ型二酸化チタンとしては、例えば、塩酸解膠型のアナターゼ型チタニアゾル（石原産業（株）製ＳＴＳ−０２（平均粒径７ｎｍ）、石原産業（株）製ＳＴ−Ｋ０１）、硝酸解膠型のアナターゼ型チタニアゾル（日産化学（株）製ＴＡ−１５（平均粒径１２ｎｍ））等を挙げることができる。
【０１２５】
光触媒の粒径は小さいほど光触媒反応が効果的に起こるので好ましく、平均粒径が５０ｎｍ以下であることが好ましく、２０ｎｍ以下の光触媒を使用するのが特に好ましい。
【０１２６】
本発明における光触媒含有層は、上述したように光触媒単独で形成されたものであってもよく、またバインダと混合して形成されたものであってもよい。
【０１２７】
光触媒のみからなる光触媒含有層の場合は、特性変化層上の特性の変化に対する効率が向上し、処理時間の短縮化等のコスト面で有利である。一方、光触媒とバインダとからなる光触媒含有層の場合は、光触媒含有層の形成が容易であるという利点を有する。
【０１２８】
光触媒のみからなる光触媒含有層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒含有層を形成することにより、均一な膜でかつ光触媒のみを含有する光触媒含有層とすることが可能であり、これにより特性変化層上の特性を均一に変化させることが可能であり、かつ光触媒のみからなることから、バインダを用いる場合と比較して効率的に特性変化層上の特性を変化させることが可能となる。
【０１２９】
また、光触媒のみからなる光触媒含有層の形成方法の他の例としては、例えば光触媒が二酸化チタンの場合は、基材上に無定形チタニアを形成し、次いで焼成により結晶性チタニアに相変化させる方法等が挙げられる。ここで用いられる無定形チタニアとしては、例えば四塩化チタン、硫酸チタン等のチタンの無機塩の加水分解、脱水縮合、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン等の有機チタン化合物を酸存在下において加水分解、脱水縮合によって得ることができる。次いで、４００℃〜５００℃における焼成によってアナターゼ型チタニアに変性し、６００℃〜７００℃の焼成によってルチル型チタニアに変性することができる。
【０１３０】
また、バインダを用いる場合は、バインダの主骨格が上記の光触媒の光励起により分解されないような高い結合エネルギーを有するものが好ましく、例えばオルガノポリシロキサン等を挙げることができる。
【０１３１】
このようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒含有層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより光触媒含有層を形成することかできる。
【０１３２】
また、バインダとして無定形シリカ前駆体を用いることができる。この無定形シリカ前駆体は、一般式ＳｉＸ_４で表され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１３３】
具体的には、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−プロポキシシラン、テトラブトキシシラン、テトラメトキシシラン等が挙げられる。また、この場合には、無定形シリカの前駆体と光触媒の粒子とを非水性溶媒中に均一に分散させ、基材上に空気中の水分により加水分解させてシラノールを形成させた後、常温で脱水縮重合することにより光触媒含有層を形成できる。シラノールの脱水縮重合を１００℃以上で行えば、シラノールの重合度が増し、膜表面の強度を向上できる。また、これらの結着剤は、単独あるいは２種以上を混合して用いることができる。
【０１３４】
バインダを用いた場合の光触媒含有層中の光触媒の含有量は、５〜６０重量％、好ましくは２０〜４０重量％の範囲で設定することができる。また、光触媒含有層の厚みは、０．０５〜１０μｍの範囲内が好ましい。
【０１３５】
また、光触媒含有層には上記の光触媒、バインダの他に、界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、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。
【０１３６】
さらに、光触媒含有層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【０１３７】
ｂ．基体
次に、光触媒含有層側基板に用いられる基体について説明する。本発明においては、図２に示すように、光触媒含有層側基板は、少なくとも基体４とこの基体４上に形成された光触媒含有層５とを有するものである。この際、用いられる基体を構成する材料は、後述するエネルギーの照射方向や、得られるパターン形成体が透明性を必要とするか等により適宜選択される。
【０１３８】
また本発明に用いられる基体は、可撓性を有するもの、例えば樹脂製フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、エネルギー照射方法により適宜選択されるものである。
【０１３９】
なお、基体表面と光触媒含有層との密着性を向上させるために、基体上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１４０】
ｃ．光触媒含有層側遮光部
本発明に用いられる光触媒含有層側基板には、パターン状に形成された光触媒含有層側遮光部が形成されたものを用いても良い。このように光触媒含有層側遮光部を有する光触媒含有層側基板を用いることにより、エネルギー照射に際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒含有層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１４１】
このような光触媒含有層側遮光部を有する光触媒含有層側基板は、光触媒含有層側遮光部の形成位置により、下記の二つの態様とすることができる。
【０１４２】
一つが、例えば図４に示すように、基体４上に光触媒含有層側遮光部９を形成し、この光触媒含有層側遮光部９上に光触媒含有層５を形成して、光触媒含有層側基板とする態様である。もう一つは、例えば図５に示すように、基体４上に光触媒含有層５を形成し、その上に光触媒含有層側遮光部９を形成して光触媒含有層側基板とする態様である。
【０１４３】
いずれの態様においても、フォトマスクを用いる場合と比較すると、光触媒含有層側遮光部が、上記光触媒含有層と特性変化層との配置部分の近傍に配置されることになるので、基体内等におけるエネルギーの散乱の影響を少なくすることができることから、エネルギーのパターン照射を極めて正確に行うことが可能となる。
【０１４４】
ここで、本発明においては、図５に示すような光触媒含有層５上に光触媒含有層側遮光部９を形成する態様である場合には、光触媒含有層と特性変化層とを所定の位置に配置する際に、この光触媒含有層側遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記光触媒含有層側遮光部を上記間隙を一定のものとするためのスペーサとしても用いることができるという利点を有する。
【０１４５】
すなわち、所定の間隙をおいて上記光触媒含有層と特性変化層とを対向させた状態で配置する際に、上記光触媒含有層側遮光部と特性変化層とを密着させた状態で配置することにより、上記所定の間隙を正確とすることが可能となり、そしてこの状態でエネルギーを照射することにより、特性変化層と遮光部とが接触している部分の特性変化層は、特性が変化せず、特性変化パターンを精度良く形成することが可能となるのである。また、この際、エネルギーの照射方向は上記基体側からに限定されず、例えば基材の側面からであってもよい。この場合、後述する「３．その他」の項で説明するように、２つの光触媒含有層側基板を用意し、特性変化層の両面に配置して、基材の両面等からエネルギー照射を行うことにより、第１特性変化パターンおよび第２特性変化パターンを同時に形成することも可能である。
【０１４６】
このような光触媒含有層側遮光部の形成方法は、特に限定されるものではなく、光触媒含有層側遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１４７】
例えば、スパッタリング法、真空蒸着法等により厚み１０００〜２０００Å程度のクロム等の金属薄膜を形成し、この薄膜をパターニングすることにより形成されてもよい。このパターニングの方法としては、スパッタ等の通常のパターニング方法を用いることができる。
【０１４８】
また、樹脂バインダ中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層をパターン状に形成する方法であってもよい。用いられる樹脂バインダとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種または２種以上混合したものや、感光性樹脂、さらにはＯ／Ｗエマルジョン型の樹脂組成物、例えば、反応性シリコーンをエマルジョン化したもの等を用いることができる。このような樹脂製遮光部の厚みとしては、０．５〜１０μｍの範囲内で設定することができる。このよう樹脂製遮光部のパターニングの方法は、フォトリソ法、印刷法等一般的に用いられている方法を用いることができる。
【０１４９】
なお、上記説明においては、光触媒含有層側遮光部の形成位置として、基体と光触媒含有層との間、および光触媒含有層表面の二つの場合について説明したが、その他、基体の光触媒含有層が形成されていない側の表面に光触媒含有層側遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、特性変化パターンを小ロットで変更するような場合に好適に用いることができる。
【０１５０】
ｄ．プライマー層
次に、本発明の光触媒含有層側基板に用いられるプライマー層について説明する。本発明において、上述したように基体上に光触媒含有層側遮光部をパターン状に形成して、その上に光触媒含有層を形成して光触媒含有層側基板とする場合においては、上記光触媒含有層側遮光部と光触媒含有層との間にプライマー層を形成してもよい。
【０１５１】
このプライマー層の作用・機能は必ずしも明確なものではないが、光触媒含有層側遮光部と光触媒含有層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による特性変化層の特性変化を阻害する要因となる光触媒含有層側遮光部および光触媒含有層側遮光部間に存在する開口部からの不純物、特に、光触媒含有層側遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で特性変化の処理が進行し、その結果、高解像度のパターンを得ることが可能となるのである。
【０１５２】
なお、本発明においてプライマー層は、光触媒含有層側遮光部のみならず光触媒含有層側遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた光触媒含有層側遮光部全面にわたって形成されていることが好ましい。
【０１５３】
本発明におけるプライマー層は、光触媒含有層側基板の光触媒含有層側遮光部と光触媒含有層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１５４】
このプライマー層を構成する材料としては、特に限定されるものではないが、光触媒の作用により分解されにくい無機材料が好ましい。具体的には無定形シリカを挙げることができる。このような無定形シリカを用いる場合には、この無定形シリカの前駆体は、一般式ＳｉＸ_４で示され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物であり、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１５５】
また、プライマー層の膜厚は、０．００１μｍから１μｍの範囲内であることが好ましく、特に０．００１μｍから０．１μｍの範囲内であることが好ましい。
【０１５６】
（エネルギー照射）
次に、本工程におけるエネルギー照射について説明する。本工程においては、上記特性変化層と、上記光触媒含有層側基板における光触媒含有層とを、所定の間隙をおいて配置し、所定の方向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第１特性変化パターンを形成することができる。また、この際、特性変化層は近傍に配置された光触媒含有層中の光触媒の作用により特性が変化することから、基材をはさんで反対側の面の特性変化層は、エネルギー照射により特性が変化することなく、第１特性変化パターンのみを形成することができるのである。
【０１５７】
上記の配置とは、実質的に光触媒の作用が特性変化層表面に及ぶような状態で配置された状態をいうこととし、実際に物理的に接触している状態の他、所定の間隔を隔てて上記光触媒含有層と特性変化層とが配置された状態とする。この間隙は、２００μｍ以下であることが好ましい。
【０１５８】
本発明において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって特性変化層の特性変化の効率が良好である点を考慮すると特に０．２μｍ〜１０μｍの範囲内、好ましくは１μｍ〜５μｍの範囲内とすることが好ましい。このような間隙の範囲は、特に間隙を高い精度で制御することが可能である小面積の特性変化層に対して特に有効である。
【０１５９】
一方、例えば３００ｍｍ×３００ｍｍといった大面積の特性変化層に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒含有層側基板と特性変化層との間に形成することは極めて困難である。したがって、特性変化層が比較的大面積である場合は、上記間隙は、１０〜１００μｍの範囲内、特に５０〜７５μｍの範囲内とすることが好ましい。間隙をこのような範囲内とすることにより、パターンがぼやける等のパターン精度の低下の問題や、光触媒の感度が悪化して特性変化の効率が悪化する等の問題が生じることなく、さらに特性変化層上の特性変化にムラが発生しないといった効果を有するからである。
【０１６０】
このように比較的大面積の特性変化層をエネルギー照射する際には、エネルギー照射装置内の光触媒含有層側基板と特性変化層との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒含有層側基板と特性変化層とが接触することなく配置することが可能となるからである。
【０１６１】
このように光触媒含有層と特性変化層表面とを所定の間隔で離して配置することにより、酸素と水および光触媒作用により生じた活性酸素種が脱着しやすくなる。すなわち、上記範囲より光触媒含有層と特性変化層との間隔を狭くした場合は、上記活性酸素種の脱着がしにくくなり、結果的に特性変化速度を遅くしてしまう可能性があることから好ましくない。また、上記範囲より間隔を離して配置した場合は、生じた活性酸素種が特性変化層に届き難くなり、この場合も特性変化の速度を遅くしてしまう可能性があることから好ましくない。
【０１６２】
本発明においては、このような配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０１６３】
このような極めて狭い間隙を均一に形成して光触媒含有層と特性変化層とを配置する方法としては、例えばスペーサを用いる方法を挙げることができる。そして、このようにスペーサを用いることにより、均一な間隙を形成することができると共に、このスペーサが接触する部分は、光触媒の作用が特性変化層表面に及ばないことから、このスペーサを上述した特性変化パターンと同様のパターンを有するものとすることにより、特性変化層上に所定の特性変化パターンを形成することが可能となる。また、このようなスペーサを用いることにより、光触媒の作用により生じた活性酸素種が拡散することなく、高濃度で特性変化層表面に到達することから、効率よく高精細な特性変化パターンを形成することができる。
【０１６４】
本発明においては、このような光触媒含有層側基板の配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０１６５】
３．第２特性変化パターン形成工程
次に、本発明においては、第２特性変化パターン形成工程が行われる。本発明の第２特性変化パターン形成工程は、上述した第１特性変化パターン形成工程により第１特性変化パターンが形成された面と反対側の面の特性変化層と、上述した光触媒含有層側基板の光触媒含有層とを所定の間隙をおいて配置した後、エネルギーを照射し、特性変化層の特性が変化した第２特性変化パターンを形成する工程である。これにより、両面に特性の変化した特性変化パターンが形成されたパターン形成体とすることができるのである。この第２特性変化パターンのパターンは、そのパターン形成体の目的に応じて適宜選択されるものであり、第１特性変化パターンと異なるパターンであってもよく、また同じパターンであってもよい。
【０１６６】
ここで、本工程に用いられる光触媒含有層側基板や、エネルギーの照射等については、上述した第１特性変化パターン形成工程と同様であるので、ここでの説明は省略する。
【０１６７】
３．その他
本発明においては、上述した第１特性変化パターン形成工程と、第２特性変化パターン工程とを同時に行うことができる。この第１特性変化パターン形成工程と、第２特性変化パターン形成工程とを同時に行う方法としては、例えば図６に示すように、まず、基体４とその基体４の表面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および６´を準備する。この光触媒含有層側基板６および６´と、透明な基材１の両面に形成された特性変化層２および２´との間に、スペーサ１０それぞれ密着させて配置し、透明な基材１の側面からエネルギー８を照射する（図６（ａ））。これにより、スペーサ１０が接触していない部分のみの特性変化層２および２´の特性を変化させることができ、第１特性変化パターン３および第２特性変化パターン３´を同時に形成することができるのである（図６（ｂ））。この際、エネルギーの照射は側面からに限定されるものではなく、片面から、もしくは両面からであってもよいが、本発明においては、両面から行われることが、感度等の面から好ましい。
【０１６８】
このようなスペーサとしては、特性変化層の特性を変化させるパターン状に小孔を有するものであり、上記マスクの厚さは、２ｍｍ以下、中でも１００μｍ以下であることが好ましい。本発明においてマスクは、上記光触媒含有層と上記濡れ性変化層との間隔を決定するものであることから、上記値よりマスクの厚さが厚い場合は、生じた活性酸素種が特性変化層に届き難くなり、特性変化の速度を遅くしてしまう可能性があるからである。また、マスクの厚さの下限は１μｍである。これは、マスクの厚さが上記値より薄い場合には、高精細なマスクを形成することが困難となるからである。
【０１６９】
また、本発明のマスクに形成される小孔は、目的とするパターン形成体のパターンにより、その形状や大きさ等は適宜選択される。
【０１７０】
ここで、本発明に用いられるマスクは、その材料等はエネルギー照射による光触媒の作用により発生する活性酸素種を透過させるものでなければ、特に限定されるものではなく、透明なものでも不透明なものであってもよく、また可撓性を有するものであってもよい。
【０１７１】
本発明に用いられるマスクの材料として、具体的には金属、ガラスやセラミック等の無機物、またはプラスチック等の有機物等を挙げることができ、中でも金属であることが好ましい。本発明においては、上記マスクが金属からなるものであることにより、容易に特性変化層の特性を変化させるパターン状に小孔を形成することが可能であり、また繰り返し用いることが可能な強度を持ち合わせているからである。また、シャドウマスク等も用いることが可能である。
【０１７２】
ここで、マスクの小孔の形成方法は、マスクの材料により左右されるものであり、特に限定されるものではないが、例えばエッチング法等が挙げられる。
【０１７３】
また、上述したように光触媒含有層側基板の光触媒含有層がパターン状に形成されている場合には、光触媒含有層に面する特性変化層上の部分のみの、特性が変化するものであるので、シャドウマスク等を用いることなく、両面の特性変化層上に光触媒含有層側基板を配置することにより、第１特性変化パターンおよび第２特性変化パターンを同時に形成することができる。
【０１７４】
さらに、光触媒含有層上に光触媒含有層側遮光部が形成されている場合においても、光触媒含有層側基板を、光触媒含有層側遮光部を上記スペーサと同様に用いて両面の特性変化層に密着させて配置することにより、第１特性変化パターンおよび第２特性変化パターンを同時に形成することができる。
【０１７５】
なお、この際用いられるエネルギー等については、上述した第１特性変化パターン形成工程におけるエネルギー照射と同様であるので、ここでの説明は省略する。
【０１７６】
Ｃ．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、両面の特性変化パターン上に、機能性部が形成されたことを特徴とするものである。
【０１７７】
本発明によれば、上述し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、両面に高精細な機能性部を形成することができるのである。
【０１７８】
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。
【０１７９】
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。
【０１８０】
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。
【０１８１】
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。
【０１８２】
本発明の機能性素子は、例えば機能性部として片面に画素部を形成し、反対側の面にブラックマトリックスを形成したブラックマトリックス付きカラーフィルタや、機能性部として、片面に画素部を形成し、反対側の面にレンズを形成したレンズ付きカラーフィルタ、機能性部として両面に金属配線を形成した導電性パターン等が挙げられる。
【０１８３】
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。
【０１８４】
【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。
【０１８５】
[実施例１]
１．光触媒含有層側基板の形成
トリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）５ｇと０．５規定塩酸２．５ｇとを混合し、８時間攪拌した。これをイソプロピルアルコールにより１０倍に希釈しアンカー層用組成物とした。
【０１８６】
上記アンカー層用組成物を、１００μｍのライン＆スペースのフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明なアンカー層（厚み０．２μｍ）を形成した。
【０１８７】
次に、イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１８８】
上記光触媒含有層用組成物を、アンカー層が形成されたフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１８９】
２．分解除去層の形成
ポリカーボネートが主成分のユーピロンＺ４００（三菱ガス化学製）２ｇをジクロロメタン３０ｇと１１２トリクロロエタン７０ｇに溶解し分解層除去層用組成物とした。
【０１９０】
上記分解除去層用組成物を、ガラス基板上にディップコーターにより塗布し、１００℃で６０分間の乾燥処理を行うことにより、透明な分解除去層（厚み０．２μｍ）を形成した。
【０１９１】
３．第１パターン形成工程
前記分解除去層の第１面に光触媒含有層側基板を対向させた後、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で２００秒間露光した。これにより、第１面の前記分解除去層のエネルギー照射部が分解除去された。
【０１９２】
次いで、機能性部として遮光層組成物をディップコーターにより塗布した後、硬化することにより第１面上の前記分解除去層が分解除去された領域に、遮光層が形成された。
【０１９３】
４．第２パターン形成工程
前記分解除去層の第２面に光触媒含有層側基板を対向させた後、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で２００秒間露光した。これにより、第２面の前記分解除去層のエネルギー照射部が分解除去された。
【０１９４】
次いで、機能性部として着色層組成物をインクジェット法により塗布した後、硬化することにより第２面上の前記分解除去層が分解除去された領域に、着色層が形成されたカラーフィルタを得た。
【０１９５】
[実施例２]
１．光触媒含有層側基板の形成
トリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）５ｇと０．５規定塩酸２．５ｇとを混合し、８時間攪拌した。これをイソプロピルアルコールにより１０倍に希釈しアンカー層用組成物とした。
【０１９６】
上記アンカー層用組成物を、１００μｍのライン＆スペースのフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明なアンカー層（厚み０．２μｍ）を形成した。
【０１９７】
次に、イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１９８】
上記光触媒含有層用組成物を、アンカー層が形成されたフォトマスク基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１９９】
２．濡れ性変化層の形成
フルオロアルキルシランが主成分であるMF-160E（商品名、トーケムプロダクツ（株）製）の５％ＩＰＡ溶液を用意し、これを２４０℃に加熱してガラス基板上に付着させて、透明な濡れ性変化層（厚み０．１μｍ）を形成した。
【０２００】
３．第１パターン形成工程
前記濡れ性変化層の第１面に光触媒含有層側基板を対向させた後、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で１００秒間露光した。これにより、第１面の前記濡れ性変化層のエネルギー照射部が親液性領域となった。
【０２０１】
次いで、機能性部として遮光層組成物をディップコーターにより塗布した後、硬化することにより第１面上の前記親液性領域上に、遮光層を形成した。
【０２０２】
４．第２パターン形成工程
前記濡れ性変化層の第２面に光触媒含有層側基板を対向させた後、フォトマスク側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で１００秒間露光した。これにより、第２面の前記濡れ性変化層のエネルギー照射部が親液性領域となった。
【０２０３】
次いで、機能性部として着色層組成物をインクジェット法により塗布した後、硬化することにより第２面上の前記親液性領域に着色層を形成し、カラーフィルタを得た。
【０２０４】
【発明の効果】
本発明によれば、上記基材の両面に上記特性変化層が形成されていることから、エネルギー照射に伴う光触媒の作用によって、容易にパターン形成体の両面に、特性の変化した特性変化パターンを形成することができ、またこの特性変化パターンは両面で異なるものとすることができる。これにより、この特性が変化した特性変化パターンに沿って、容易に両面に様々な機能性部が形成可能なパターン形成体とすることができるのである。
【図面の簡単な説明】
【図１】本発明のパターン形成体の一例を示す概略断面図である。
【図２】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３】本発明における光触媒含有層側基板の一例を示す概略断面図である。
【図４】本発明における光触媒含有層側基板の他の例を示す概略断面図である。
【図５】本発明における光触媒含有層側基板の他の例を示す概略断面図である。
【図６】本発明のパターン形成体の製造方法におけるエネルギー照射の一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 … 特性変化パターン
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 … 光触媒含有層側遮光部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a high-definition pattern on both sides, which can be used for various applications such as a color filter and a printed board.
[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]
Here, when forming a high-definition pattern on both surfaces of the base material, it is necessary to perform the same process twice in any of the above methods. There was a problem of becoming enormous. In addition, when the photolithography method is used for a transparent substrate, if a photoresist is applied on both sides in advance, the photoresist layer is exposed on both sides by exposure, so the photoresist layer is formed simultaneously on both sides. However, it was necessary to form a photoresist layer on each side, and to perform exposure and development.
[0009]
On the other hand, as a method for forming a high-definition pattern, a method for producing a pattern forming body in which a substance that changes wettability by the action of a photocatalyst is formed on a substrate by a coating method, and a pattern is formed by performing energy irradiation Etc. have been studied by the present inventors (see, for example, Patent Document 1 and Patent Document 2).
[0010]
However, this method is a method of forming a pattern only on one side and not a pattern on both sides.
[0011]
[Patent Document 1]
JP 2001-272774 A
[Patent Document 2]
JP 2000-249821 A
[0012]
[Problems to be solved by the invention]
Therefore, it is desired to provide a manufacturing method of a pattern forming body capable of forming patterns with different high-definition surface characteristics on both sides by a simple method.
[0013]
[Means for Solving the Problems]
The present invention has a base material and a property change layer that is formed on both surfaces of the base material and changes properties due to the action of a photocatalyst associated with energy irradiation, and the two property change layers formed on both surfaces are Provided is a pattern forming body characterized by having a characteristic change pattern in which the characteristics are changed.
[0014]
According to the present invention, since the property change layer is formed on both surfaces of the base material, the property change pattern having the property changed easily on both surfaces of the pattern forming body by the action of the photocatalyst accompanying energy irradiation. It can be formed and the characteristic change pattern can be different on both sides. Thereby, it is possible to obtain a pattern forming body in which various functional parts can be easily formed on both sides along the characteristic change pattern in which the characteristic is changed.
[0015]
In the above invention, the property change layer may be a wettability change layer in which the wettability changes so that the contact angle with the liquid is lowered by the action of a photocatalyst accompanying energy irradiation. As a result, by the action of the photocatalyst accompanying energy irradiation, a lyophilic region where the wettability has changed and a liquid repellent region where the wettability has not changed can be formed. 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.
[0016]
In this case, the wettability changing layer is preferably a layer containing fluoroalkylsilane. As a result, the wettability changing layer can be a uniform monomolecular film, the wettability of the wettability changing layer surface can be changed efficiently, and the lyophilic region of the wettability changing layer can be repelled. This is because the difference in wettability with the liquid region can be increased.
[0017]
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, unevenness can be formed on the surface by the action of the photocatalyst accompanying the energy irradiation, and a pattern forming body capable of easily forming a functional part using the unevenness can be obtained.
[0018]
In the present invention, the substrate may be transparent. In the present invention, by using a layer whose characteristics change due to the action of the photocatalyst, even when energy irradiation is performed using a photocatalyst on one side, the opposite characteristic changing layer may be affected. This is because different patterns can be formed.
[0019]
The present invention also includes a property change layer forming step of forming a property change layer whose properties change due to the action of a photocatalyst associated with energy irradiation on both surfaces of the substrate,
After disposing one surface of the property change layer, the photocatalyst containing layer containing the photocatalyst and the photocatalyst containing layer side substrate having the substrate with a gap so that the property change layer and the photocatalyst containing layer are 200 μm or less. , A first characteristic change pattern forming step of forming a first characteristic change pattern by irradiating energy and changing the characteristic of the characteristic change layer;
The property change layer on the surface opposite to the surface on which the first property change pattern is formed, the photocatalyst containing layer containing the photocatalyst, and the photocatalyst containing layer side substrate having the substrate, the property change layer and the photocatalyst containing layer A second characteristic change pattern forming step of forming a second characteristic change pattern in which the characteristics of the characteristic change layer are changed by irradiating energy after being arranged with a gap so as to be 200 μm or less;
There is provided a method for producing a patterned body characterized by comprising:
[0020]
According to the present invention, since the characteristic change layer is formed on both surfaces of the substrate by the characteristic change layer forming step, the photocatalyst is used in the first characteristic change pattern forming step and the second characteristic change pattern forming step. Due to the action of the photocatalyst containing layer in the containing layer, it is possible to form a characteristic change pattern having changed characteristics on both sides of the pattern forming body, and the pattern of the first characteristic change pattern and the second characteristic change pattern. Can be different.
[0021]
In the said invention, it is preferable that the said characteristic change layer formation process is performed by the dry method. This is because the characteristic change layer can be efficiently formed on both surfaces in a short time, and a uniform and thin layer can be obtained.
[0022]
In this case, the dry method is preferably a CVD method. This is because a dense and uniform layer such as a self-assembled monolayer can be formed.
[0023]
In the present invention, the substrate may be transparent. In the present invention, the characteristic change layer changes its characteristics due to the action of the photocatalyst. Therefore, when forming the characteristic change pattern, energy irradiation does not affect the opposite characteristic change layer. A target pattern can be formed with high definition. Further, depending on the energy irradiation method, the first characteristic change pattern and the second characteristic change pattern can be formed simultaneously.
[0024]
Moreover, this invention provides the functional element characterized by the functional part being formed on the characteristic change pattern of both surfaces of the pattern formation body mentioned above. According to the present invention, it is possible to easily form a functional part on both sides using the difference in characteristics of the characteristic change pattern and to obtain a functional element having a high-definition functional part. Because.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a pattern forming body having a high-definition pattern on both sides that can be used for various applications including a color filter and a printed circuit board, a method for manufacturing the pattern forming body, and a functional part using the pattern. It relates to a functional element in which is formed. Each will be described in detail below.
[0026]
A. Pattern forming body
First, the pattern forming body of the present invention will be described. The pattern forming body of the present invention has a base material and a property change layer that is formed on both surfaces of the base material and whose properties change due to the action of a photocatalyst accompanying energy irradiation. The characteristic change layer has a characteristic change pattern in which the characteristic has changed.
[0027]
For example, as shown in FIG. 1, the pattern forming body of the present invention has a base material 1 and a characteristic change layer 2 formed on both surfaces of the base material 1, and on the surface of the characteristic change layer 2. A characteristic change pattern 3 having different characteristics is formed.
[0028]
According to the present invention, since the property change layer is formed on both surfaces of the base material, the property of the property change layer is easily formed on both surfaces of the pattern forming body by the action of the photocatalyst accompanying energy irradiation. A changed characteristic change pattern can be formed. In addition, according to the present invention, even if the substrate is transparent, the property changing layer does not change the property even if it is irradiated with energy unless the layer having the photocatalyst is arranged nearby. When energy is applied to one side, the pattern change body having different characteristic change patterns on both sides can be obtained without affecting the characteristic change layer on the opposite side. Thereby, it is possible to obtain a pattern forming body capable of forming a functional element having functional portions of different patterns on both surfaces by utilizing the characteristics of the characteristic change pattern.
[0029]
Hereinafter, each structure of the pattern formation body of this invention is demonstrated.
[0030]
1. Characteristic change layer
First, the characteristic change layer used for the pattern forming body of the present invention will be described. If the characteristic changing layer used in the pattern forming body of the present invention is a layer that is formed on both surfaces of the base material to be described later and the characteristic changes due to the action of the photocatalyst accompanying energy irradiation, the type of change in the characteristic, etc. It is not particularly limited.
[0031]
In the present invention, the property change layer is a wettability change layer in which the wettability changes so that the wettability is reduced by the action of the photocatalyst, and the property change layer is a decomposition removal layer that is decomposed and removed by the action of the photocatalyst. The two cases in some cases are particularly preferable from the viewpoint that the functional part can be easily formed on the pattern forming body. Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0032]
(Wettability change layer)
The wettability changing layer used in the present invention is not particularly limited as long as the wettability is changed so that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying energy irradiation.
[0033]
In this way, by forming a wettability changing layer in which the wettability changes so that the contact angle with the liquid is reduced by energy irradiation, the area irradiated with energy on the surface of the wettability changing layer is made a lyophilic region, energy The unirradiated region can be a liquid repellent region, and the functional part can be easily formed on the pattern forming body by utilizing this difference in wettability.
[0034]
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 or the like that forms the functional part. 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.
[0035]
The wettability changing layer preferably has a contact angle with a liquid of 40 mN / m of 50 ° or more, particularly 90 ° or more, in a portion not irradiated with energy, that is, a liquid repellent region. This is because the region where energy is not irradiated is a region where liquid repellency is required in the present invention, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient. This is because when the part forming coating solution is applied, the functional part forming coating solution may remain on the liquid repellent region, which is not preferable.
[0036]
In the wettability changing layer, the contact angle with a liquid of 40 mN / m is 49 ° or less, preferably 10 ° or less, in a portion irradiated with energy, that is, a lyophilic region. 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.
[0037]
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.
[0038]
Further, when the wettability changing layer as described above is used in the present invention, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer is more energy than the wettability changing layer. The wettability changing layer may be formed so as to be lower than that before energy irradiation by the action of the photocatalyst.
[0039]
In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of a lyophilic region in the liquid repellent region.
[0040]
Therefore, when such a wettability changing layer is used, a pattern of the lyophilic region can be easily formed in the lyophobic region by irradiating the pattern with energy. For example, a functional part-forming coating solution can be adhered only to the pattern part to easily form the functional part.
[0041]
As described above, the fluorine content contained in the wettability changing layer containing fluorine is the fluorine content in the lyophilic region having a low fluorine content formed by energy irradiation. When the fluorine content of the non-existing portion is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0042]
By setting it within such a range, it is possible to make a great difference in wettability between the energy irradiated portion and the unirradiated portion. Therefore, by applying, for example, a functional part forming coating liquid to such a wettability changing layer, it is possible to accurately form a functional part only in a lyophilic region having a reduced fluorine content. This is because a functional element can be obtained with high accuracy. This rate of decrease is based on weight.
[0043]
The fluorine content in such a wettability changing layer can be measured by various commonly used methods such as X-ray Photoelectron Spectroscopy, ESCA (Electron Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.
[0044]
In the present invention, such a wettability changing layer is formed on both surfaces of a substrate to be described later, and is applied to one surface of the substrate by a known coating method such as spin coating, spray coating, roll coating, bead coating or the like. Although it may be applied one by one, in the present invention, it is preferable to use dip coating or a dry method. Thereby, a wettability change layer can be formed simultaneously on both surfaces of a base material, and a pattern formation body can be manufactured efficiently. Moreover, in this invention, it is preferable to form by a dry method especially. Here, the dry method is a method in which a metal, metal oxide, organic substance or the like is gasified to form a film on the surface of the substrate, and a uniform thin film can be formed in a short time compared to the dip coating method. Because. Specific examples of the dry method used for forming the wettability changing layer used in the present invention include a CVD method including a thermal CVD method and a plasma CVD method, or a vapor deposition method, a sputtering method, an ion plating method and the like. PVD method etc. are mentioned.
[0045]
In the present invention, among the above, a CVD method such as a plasma CVD method or a thermal CVD method is preferable. This is because the wettability changing layer can be a uniform and dense layer.
[0046]
In addition, the plasma CVD method can form a desired material at a low temperature (approximately −10 to 200 ° C.) that does not cause thermal damage to the polymer base material. Since there is an advantage that the kind and physical properties of the film to be obtained can be controlled by the film pressure and input power, there is little possibility of causing thermal damage to the substrate for pattern formation described later. This is because, for example, a polymer base material having low heat resistance can be used as the pattern forming body substrate, and a pattern forming body that can be used for various applications can be obtained.
[0047]
As a film formation method by plasma CVD of a specific wettability changing layer in the present invention, first, the temperature of the substrate for pattern formation during film formation is in the range of -20 to 100 ° C, particularly -10 to 30 ° C. It is preferable to be within the range. Next, using any of the following materials as the source gas, the input power per unit area in the plasma generating means of the plasma CVD apparatus is set to a size that allows the organic thin film to be formed, and the film forming pressure is free from particles. The pressure is set within a range of high pressure (50 to 300 mTorr). Further, by forming a confined space for plasma such as a magnet and increasing its reactivity, the effect can be enhanced.
[0048]
Moreover, you may use a normal pressure plasma apparatus for formation of the wettability change layer in this invention. Thereby, since it can carry out by a normal pressure, it becomes possible to form a wettability change layer of a large area at low cost.
[0049]
Examples of the raw material gas for the wettability changing layer formed by the plasma CVD method of the present invention include a silicon compound having an organic chain. As a result, the region of the formed wettability changing layer that has not been irradiated with energy can be made a liquid repellent region by the organic chain, and the region that has been irradiated with the energy has an organic chain that is exposed to the action of the photocatalyst. It is because it can be set as the decomposed lyophilic region.
[0050]
Specific examples of these materials include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), tetramethylsilane (TMS), and vinyltrimethoxysilane. , Vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexamethyldisilazane Can be preferably used, and one or more conventionally known ones such as tetramethyldisiloxane and normal methyltrimethoxysilane can be used.
[0051]
In addition, when the wettability changing layer in the present invention is formed using a thermal CVD method, in the thermal CVD method, a material as a raw material is vaporized, and the material is fed so as to be uniform on the substrate, and then oxidized. Since reactions such as reduction and substitution are performed, for example, a self-assembled monolayer can be formed.
[0052]
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 alkyl group that does not cause a chemical reaction with the substrate at all, and the functional group with high affinity is at its end, the molecule Is adsorbed with the reactive end facing the substrate and the alkyl group or the like facing outward. For example, when alkyl groups are aggregated, the whole becomes stable, so that organic molecules spontaneously aggregate in 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.
[0053]
When the wettability changing layer is a self-assembled monolayer, in the characteristic change pattern forming step described later, for example, an alkyl group having water repellency existing on the surface of the wettability changing layer is substituted with a photocatalyst accompanying energy irradiation. By removing it by the action, the surface can be easily made hydrophilic, and the characteristic change pattern can be efficiently formed.
[0054]
As preferable film-forming conditions of the thermal CVD method in the present invention, the higher the heat resistance temperature of the pattern-forming body substrate described later, the better. However, it is preferably in the range of 50 ° C to 300 ° C.
[0055]
In the present invention, when the wettability changing layer is formed, preferred raw materials include fluoroalkyl silane, alkyl silane, thiol, etc. Among them, a layer containing fluoroalkyl silane is preferred. When the wettability changing layer is a layer containing a fluoroalkylsilane, it is possible to form the above-described self-assembled monolayer on the pattern forming substrate described later, and the energy unirradiated portion Because the liquid repellency can be increased by the action of the fluoroalkyl group present on the surface of the surface, it is possible to increase the difference in wettability between the lyophilic region and the liquid repellant region. is there.
[0056]
In addition, as a material used when the wettability changing layer as described above is formed by dip coating or the like, the characteristics of the wettability changing layer described above, that is, the wettability by the photocatalyst in the photocatalyst-containing layer facing by the energy irradiation The material is not particularly limited as long as it has a main chain that hardly deteriorates or decomposes due to the action of a photocatalyst, and specific examples include organopolysiloxane. In the present invention, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group.
[0057]
Examples of such an organopolysiloxane include (1) an organopolysiloxane that exerts great strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) water repellency and oil repellency. Mention may be made of organopolysiloxanes such as organopolysiloxanes crosslinked with excellent reactive silicones.
[0058]
In the case of (1) above, the general formula:
Y_nSiX_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolytic condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0059]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those known as fluorine-based silane coupling agents can be used.
[0060]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;and
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0061]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated part of the wettability changing layer is greatly improved. For example, when a coating liquid for forming a functional part is applied over the entire surface In addition, it is possible to prevent the adhesion of the functional part forming coating liquid, and it is possible to attach the functional part forming coating liquid only to the lyophilic region that is the energy irradiation part.
[0062]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0063]
[Chemical 1]

[0064]
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.
[0065]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0066]
In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
[0067]
The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0068]
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.
[0069]
Such a wettability changing layer is formed by preparing a coating liquid by dispersing the above-described components together with other additives in a solvent as required, and coating the coating liquid on both surfaces of the substrate. be able to. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. 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.
[0070]
In the present invention, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, from the relationship of the wettability change rate by the photocatalyst. is there.
[0071]
By using the wettability changing layer of the above-described component in the present invention, the action of the photocatalyst in the photocatalyst containing layer is used to oxidize, decompose, etc. the organic group that is a part of the above component, and It is possible to change the wettability to make it lyophilic and to make a large difference in wettability with the non-energy-irradiated part. Therefore, for example, even when the functional part forming coating liquid is applied over the entire surface, it is possible to attach the functional part forming coating liquid relatively easily only in the lyophilic region as the energy irradiation part, It can be set as the pattern formation body which can manufacture a high-definition functional element at low cost.
[0072]
In addition, the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. If the wettability changing layer does not contain a photocatalyst in this way, there is no need to worry about being affected over time when it is used as a conductive pattern formation body, and it should be used without problems over a long period of time. Because it is possible.
[0073]
(Decomposition removal layer)
Next, the decomposition removal layer will be described. The decomposition / removal layer used in the present invention is particularly limited as long as 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. is not.
[0074]
As described above, the decomposed / removed layer is decomposed and removed by the action of the photocatalyst, so that the pattern composed of the part with and without the decomposed / removed layer without performing the development process or the washing process, that is, the unevenness is formed. The pattern which has can be formed.
[0075]
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.
[0076]
Moreover, it is preferable that the decomposition removal layer used for this invention not only forms an unevenness | corrugation, but this decomposition removal layer has a high contact angle with a liquid compared with the base material mentioned later.
As a result, the decomposition / removal layer is decomposed and removed, and the region where the base material is exposed can be made a lyophilic region, and the region where the decomposition / removal layer remains can be made a liquid-repellent region, thereby forming various patterns. This is because it becomes possible.
[0077]
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. 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.
[0078]
Further, the decomposition removal layer preferably has a contact angle with a liquid of 40 mN / m of 50 ° or more, particularly 90 ° or more. In the present invention, 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. This is because when the functional part forming coating liquid to be formed is applied, there is a possibility that the functional part forming coating liquid may remain in the liquid repellent region where the functional part is not formed.
[0079]
In the present invention, the substrate described later preferably has a contact angle with a liquid of 40 mN / m of 49 ° or less, particularly 10 ° or less, in a portion where no energy is irradiated. In the present invention, since the substrate is a part that requires lyophilicity, for example, when the functional part forming coating solution is applied, the functional part forming coating solution is repelled even in the lyophilic region. This is because it may be difficult to pattern the functional portion. Here, the contact angle with the liquid is a value measured by the method described above.
[0080]
In this case, the substrate 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 or water, and the lyophilic layer formed on the substrate is as follows: For example, a silica film obtained by a sol-gel method of tetraethoxysilane can be used.
[0081]
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. Although it may be a method of forming each side of the substrate by a film method, in the present invention, as in the case of the wettability changing layer described above, it may be formed by a dry method in terms of production efficiency and the like. To preferred.
[0082]
When the decomposition removal layer is formed by the plasma CVD method, examples of the material used as the source gas include hydrocarbon materials and fluorine-containing organic materials. Specifically, as the hydrocarbon material, CH₄, C₂H₂, C₂H₄And C₃H₈Can be mentioned. As the fluorine-containing organic material, CF₄, C₂F₄, C₂F₆, C₃F₆, C₃F₈, C₅F₈, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoroethylene), PVF (polyvinyl fluoride), ETFE (ethylene / tetrafluoroethylene copolymer), and the like.
[0083]
When the decomposition / removal layer is formed by a thermal CVD method, examples of the raw material include ordinary resin monomers.
[0084]
Note that the film formation conditions of the plasma CVD method and the thermal CVD method, the film thickness of the decomposition removal layer, and the like are the same as those described in the wettability changing layer described above, and thus description thereof is omitted here.
[0085]
In addition, the decomposition removal layer may be formed by other methods such as a dip coating method, and by using a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, an alternating adsorption film, etc. Such a film formation method may be used because it is possible to form a film without any film.
[0086]
Here, the self-assembled monomolecular film, the Langmuir-Brocket film, and the alternating adsorption film used in the present invention will be specifically described.
[0087]
(1) Self-assembled monolayer
Examples of materials capable of forming a self-assembled film used in the present invention include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, and organic sulfur molecules such as alkanethiols, Examples thereof include organic phosphate molecules such as alkyl phosphates. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present invention, these are also included in the self-assembled monolayer.
[0088]
(2) Langmuir-Blodgett membrane
If the Langmuir-Blodgett film used in the present invention is formed on a substrate, there is no significant difference in form from the self-assembled monomolecular film 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 substrate for use. 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. For recent examples of various materials, Tokuharu Miyashita's review “Prospects for nanotechnology to create soft nanodevices” Polymer 50 vol. September 644-647
(2001).
[0089]
(3) Alternate adsorption film
Alternating adsorption film (Layer-by-Layer Self-Assembled Film) is generally laminated by adsorbing and bonding at least two materials with positive or negative functional groups sequentially onto the substrate. It is a film | membrane formed by doing. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is 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.
[0090]
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 energy irradiated in the characteristic change pattern forming step described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.
[0091]
2. Base material
Next, the base material used for the pattern forming body of the present invention will be described. In the present invention, characteristic change layers are formed on both surfaces of the substrate.
[0092]
The base material used in the present invention is appropriately selected according to the intended use of the finally obtained pattern formed body, for example, a resin laminate of a paper base, a resin of a glass cloth / glass nonwoven base Laminated plates, ceramics, metals, and the like can be used, and plate-like ones are preferable.
[0093]
In the present invention, the substrate can be transparent. In the photolithography method or the like, when the photoresist layer is formed on both sides, if the substrate is transparent, the photoresist layer is exposed simultaneously by exposure, so formation of the photoresist layer, exposure, Processing such as development had to be performed one side at a time. However, in the present invention, even if the base material is transparent, the characteristic change layer does not change its characteristic only by energy irradiation, and the photocatalyst is a layer containing a photocatalyst disposed in the vicinity of the surface of the characteristic change layer. Therefore, the characteristics of the characteristic change layer formed on the opposite surface across the base material and not including the photocatalyst containing layer are not changed. Thereby, the characteristic of the characteristic change layer can be changed on each side, and the target pattern can be formed on both sides.
[0094]
Further, since the base material is transparent, depending on the energy irradiation method and the like, it is possible to simultaneously change the characteristics of the characteristic change layers on both sides, and it is possible to simultaneously form different characteristic change patterns.
[0095]
Here, when simultaneously changing the characteristic change layers on both sides, the thickness of the base material is preferably in the range of 50 μm to 10000 μm.
[0096]
Further, in the present invention, when it is difficult to form the property change layer on the base material or when the adhesion between the base material and the property change layer is poor, the adhesion property is improved on the base material. An adhesion improving layer may be provided. Examples of such an adhesion improving layer include polyimide.
[0097]
The base material used in the present invention may be a member in which a required member, such as a black matrix in a color filter, is formed.
[0098]
3. Characteristic change pattern
Next, the characteristic change pattern of the present invention will be described. The characteristic change pattern of the present invention is a pattern in which the characteristic of the double-sided characteristic change layer formed on the substrate is changed by the action of the photocatalyst accompanying energy irradiation.
[0099]
In the present invention, this characteristic change pattern can be formed on the surface of the characteristic change layer by irradiating energy using a photocatalyst containing layer containing a photocatalyst and a photocatalyst containing layer side substrate having a substrate. it can.
[0100]
The action mechanism of the photocatalyst represented by titanium dioxide as described later in the photocatalyst containing layer is not necessarily clear, but the carrier generated by light irradiation reacts directly with a nearby compound, or oxygen, The reactive oxygen species generated in the presence of water is thought to change the chemical structure of organic matter. In the present invention, it is considered that this carrier acts on the compound in the property changing layer disposed adjacent to the photocatalyst containing layer.
[0101]
Thereby, in the present invention, even when the base material is transparent, for example, when energy irradiation is performed using the photocatalyst-containing layer side substrate on one side of the property change layer, The characteristic change layer formed on the back side of the material is not affected by the photocatalyst, and the characteristic of only the single side property change layer can be changed. It can be formed.
[0102]
The photocatalyst-containing layer side substrate will be described in detail in “B. Method for producing pattern forming body” to be described later, and will not be described here.
[0103]
4). Pattern forming body
Next, the pattern forming body of the present invention will be described. The pattern forming body of the present invention has the above-described base material and the characteristic change layers formed on both sides thereof, and the characteristic change pattern is formed on the characteristic change layers on both sides. .
[0104]
According to the present invention, it is possible to form various functional portions on the characteristic change pattern by utilizing the difference in characteristics of the characteristic change pattern, so that various functional elements can be formed. It can be a formed body.
[0105]
Here, the characteristic change pattern in the present invention may be the same pattern or a different pattern on both surfaces of the pattern forming body.
[0106]
B. Method for producing pattern forming body
Next, the manufacturing method of the pattern formation body of this invention is demonstrated. The method for producing a patterned product of the present invention comprises a property changing layer forming step of forming a property changing layer whose properties change due to the action of a photocatalyst accompanying energy irradiation on one side of the substrate, and one surface of the property changing layer, A photocatalyst-containing layer containing a photocatalyst and a 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 irradiated with energy, A first characteristic change pattern forming step for forming a first characteristic change pattern in which the characteristic of the change layer has changed, a characteristic change layer on a surface opposite to the surface on which the first characteristic change pattern is formed, and a photocatalyst After arranging the photocatalyst containing layer and the photocatalyst containing layer side substrate having a base with a gap so that the characteristic change layer and the photocatalyst containing layer are 200 μm or less, And a second characteristic change pattern forming step of forming a second characteristic change pattern in which the characteristic of the characteristic change layer is changed.
[0107]
In the method for producing a pattern formed body of the present invention, for example, as shown in FIG. 2, first, a characteristic change layer forming step (FIG. 2A) for forming the characteristic change layer 2 on both surfaces of the substrate 1 is performed. Next, a photocatalyst containing layer side substrate 6 having a base 4 and a photocatalyst containing layer 5 containing a photocatalyst formed on the base 4 is prepared, and the photocatalyst containing layer 5 and one side of the characteristic change layer 2 are Are arranged with a predetermined gap, and irradiation with energy 8 is performed using, for example, a photomask 7 or the like (FIG. 2B) to form a first characteristic change pattern 3 in which the characteristic of the characteristic change layer 2 is changed. A first characteristic change pattern forming step is performed (FIG. 2C). Next, in the same manner as described above, the photocatalyst containing layer in the photocatalyst containing layer side substrate 6 having the characteristic changing layer 2 on the surface opposite to the surface on which the first characteristic changing pattern 3 is formed, and the base 4 and the photocatalyst containing layer 5 is provided. The layer 5 is arranged with a predetermined gap, and energy 8 is irradiated using a photomask 7 or the like (FIG. 2D), and a second characteristic change pattern 3 ′ in which the characteristic of the characteristic change layer 2 is changed is obtained. A second characteristic change pattern forming step is formed (FIG. 2E).
[0108]
Here, the first characteristic change pattern formation step and the second characteristic change pattern formation step are performed simultaneously depending on the structure of the photocatalyst-containing layer side substrate, as will be described later in “3. Others”. Also good.
[0109]
According to the present invention, since the characteristic change layer is formed on both surfaces of the substrate by the characteristic change layer forming step, the photocatalyst is used in the first characteristic change pattern forming step and the second characteristic change pattern forming step. Due to the action of the photocatalyst containing layer in the containing layer, it is possible to form a characteristic change pattern having changed characteristics on both surfaces of the pattern forming body. In addition, according to the present invention, even when the base material is transparent, the property change layer changes its properties due to the action of the photocatalyst in the photocatalyst containing layer disposed in the vicinity, so that one side is irradiated with energy. In this case, it is possible to obtain a pattern-formed body having different characteristic change patterns on both sides without affecting the characteristic change layer on the opposite side.
[0110]
Hereinafter, each process of the manufacturing method of the pattern formation body of this invention is demonstrated.
[0111]
1. Characteristic change layer formation process
First, the characteristic change layer formation process in the manufacturing method of the pattern formation body of this invention is demonstrated. The characteristic change layer forming step in the method for producing a pattern formed body of the present invention is a step of forming a characteristic change layer whose characteristics change due to the action of a photocatalyst accompanying energy irradiation on both surfaces of the substrate.
[0112]
In the present invention, as long as the characteristic change layer can be formed on both surfaces of the base material, the forming method and the like are not particularly limited. For example, a method of forming each surface by a general method may be used. However, in the present invention, it is preferably formed by a dip coating method or a dry method. This is because the characteristic change layer can be formed on both sides simultaneously, which is preferable from the standpoint of manufacturing efficiency.
[0113]
In the present invention, the dry method is preferable among the above. This is because a uniform and thin layer can be formed on both surfaces in a short time, which is preferable in terms of manufacturing efficiency. Specific examples of the dry method used in the present invention include a CVD method including a thermal CVD method and a plasma CVD method, or a PVD method including a vapor deposition method, a sputtering method, an ion plating method, etc. It is preferable to use a plasma CVD method or a CVD method including a thermal CVD method. This is because the characteristic change layer can be a uniform and dense layer.
[0114]
About the formation method and material of the characteristic change layer in this process, the kind of the base material, etc., since they are the same as those described in the section of the characteristic change layer and the base material of “A. Description of is omitted.
[0115]
2. First characteristic change pattern forming step
Next, the 1st characteristic change pattern formation process in the manufacturing method of the pattern formation body of this invention is demonstrated. The first characteristic change pattern forming step in the method for producing a pattern forming body of the present invention includes a photocatalyst containing layer having a photocatalyst-containing layer and a substrate, one side of the characteristic change layer formed by the above-described characteristic change layer forming step A layer-side substrate is disposed with a gap so that the characteristic change layer and the photocatalyst-containing layer are 200 μm or less, and then irradiated with energy, and a first characteristic change pattern in which the characteristic of the characteristic change layer changes is obtained. It is a process of forming. Hereinafter, each structure of this process is demonstrated.
[0116]
(Photocatalyst containing layer side substrate)
First, the photocatalyst containing layer side substrate used in this step will be described. The photocatalyst-containing layer side substrate used in this step has a photocatalyst-containing layer containing a photocatalyst and a substrate. Usually, the substrate and the photocatalyst-containing layer are formed on the substrate. This photocatalyst containing layer side substrate may have a photocatalyst containing layer side light shielding part, a primer layer, etc. formed in the shape of a pattern, for example. Hereinafter, each structure of the photocatalyst containing layer side board | substrate used for this process is demonstrated.
[0117]
a. 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 invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the adjacent characteristic change layer, and is composed of a photocatalyst and a binder. It may be a film formed with a single photocatalyst. Further, the surface characteristics may be particularly lyophilic or lyophobic.
[0118]
The photocatalyst-containing layer used in the present invention may be formed on the entire surface of the substrate 4 as shown in FIG. 2, for example, but for example, as shown in FIG. The containing layer 5 may be formed on the pattern.
[0119]
By forming the photocatalyst-containing layer in a pattern like this, as will be described in the energy irradiation described later, when the photocatalyst-containing layer is irradiated with energy while being arranged at a predetermined interval from the characteristic change layer, It is not necessary to perform pattern irradiation using a mask or the like, and by irradiating the entire surface, it is possible to form a pattern whose characteristics on the characteristic change layer have changed.
[0120]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0121]
In addition, since the characteristics of only the portion on the characteristic change layer facing the photocatalyst containing layer actually changes, the energy irradiation direction is such that the portion where the photocatalyst containing layer and the characteristic change layer face is irradiated with energy. As long as it is applied, the irradiation may be performed from any direction, and the irradiation energy is not particularly limited to parallel light such as parallel light. Also, as described in “3. Others” described later, two photocatalyst-containing layer side substrates having such a photocatalyst-containing layer are prepared, arranged on both surfaces of the characteristic change layer, and irradiated with energy. Thus, the first characteristic change pattern and the second characteristic change pattern can be formed simultaneously.
[0122]
As the photocatalyst used in the present invention, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these.
[0123]
In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0124]
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.
[0125]
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.
[0126]
The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0127]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0128]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.
[0129]
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 can be modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0130]
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.
[0131]
When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this coating solution on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as the binder, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays and performing a curing treatment.
[0132]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, silanol as a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less.
[0133]
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.
[0134]
When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0135]
In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0136]
Furthermore, 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.
[0137]
b. Substrate
Next, the base used for the photocatalyst-containing layer side substrate will be described. In the present invention, as shown in FIG. 2, the photocatalyst-containing layer side substrate has at least a base 4 and a photocatalyst-containing layer 5 formed on the base 4. At this time, the material constituting the substrate to be used is appropriately selected depending on the energy irradiation direction to be described later and whether the pattern forming body to be obtained requires transparency.
[0138]
The substrate used in the present invention may be a flexible substrate such as a resin film, or may be a non-flexible substrate such as a glass substrate. This is appropriately selected depending on the energy irradiation method.
[0139]
In order to improve the adhesion between the substrate surface and the photocatalyst containing layer, an anchor layer may be formed on the substrate. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0140]
c. Photocatalyst containing layer side shading part
As the photocatalyst containing layer side substrate used in the present invention, a substrate on which a photocatalyst containing layer side light shielding portion formed in a pattern is formed may be used. Thus, by using the photocatalyst containing layer side substrate having the photocatalyst containing layer side light-shielding portion, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0141]
The photocatalyst-containing layer side substrate having such a photocatalyst-containing layer side light-shielding part can have the following two modes depending on the formation position of the photocatalyst-containing layer side light-shielding part.
[0142]
For example, as shown in FIG. 4, for example, a photocatalyst containing layer side light shielding portion 9 is formed on a substrate 4, and a photocatalyst containing layer 5 is formed on the photocatalyst containing layer side light shielding portion 9. It is an aspect to make. For example, as shown in FIG. 5, the photocatalyst containing layer 5 is formed on the substrate 4 and the photocatalyst containing layer side light-shielding portion 9 is formed thereon to form a photocatalyst containing layer side substrate.
[0143]
In any aspect, compared to the case of using a photomask, the photocatalyst-containing layer side light-shielding portion is arranged in the vicinity of the arrangement portion of the photocatalyst-containing layer and the characteristic change layer. Since the influence of energy scattering can be reduced, energy pattern irradiation can be performed very accurately.
[0144]
Here, in the present invention, when the photocatalyst containing layer side light shielding portion 9 is formed on the photocatalyst containing layer 5 as shown in FIG. 5, the photocatalyst containing layer and the characteristic change layer are placed at predetermined positions. When arranging, the photocatalyst containing layer side light shielding part is used as a spacer for keeping the gap constant by making the film thickness of the photocatalyst containing layer side light shielding part coincide with the width of the gap. Has the advantage of being able to.
[0145]
That is, when the photocatalyst containing layer and the characteristic change layer are arranged facing each other with a predetermined gap therebetween, the photocatalyst containing layer side light-shielding portion and the characteristic change layer are arranged in close contact with each other. Then, it becomes possible to make the predetermined gap accurate, and by irradiating energy in this state, the characteristic change layer of the part where the characteristic change layer and the light shielding part are in contact does not change in characteristics, This makes it possible to form the characteristic change pattern with high accuracy. At this time, the energy irradiation direction is not limited to the above-mentioned substrate side, and may be, for example, from the side surface of the substrate. In this case, as will be described later in “3. Others”, two photocatalyst-containing layer side substrates are prepared, arranged on both sides of the characteristic change layer, and irradiated with energy from both sides of the substrate. Thus, the first characteristic change pattern and the second characteristic change pattern can be formed simultaneously.
[0146]
The method for forming such a photocatalyst-containing layer side light-shielding part is not particularly limited, and is appropriately selected according to the characteristics of the formation surface of the photocatalyst-containing layer side light-shielding part, the shielding property against the required energy, and the like. Used.
[0147]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0148]
Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0149]
In the above description, the two positions of the photocatalyst containing layer side light shielding portion between the substrate and the photocatalyst containing layer and the surface of the photocatalyst containing layer have been described as the formation position of the photocatalyst containing layer side. It is also possible to adopt a mode in which the photocatalyst-containing layer side light shielding portion is formed on the surface that is not provided. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be preferably used when the characteristic change pattern is changed in a small lot.
[0150]
d. Primer layer
Next, the primer layer used for the photocatalyst containing layer side substrate of the present invention will be described. In the present invention, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate as described above, and the photocatalyst-containing layer is formed on the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side substrate is used. A primer layer may be formed between the side light shielding part and the photocatalyst containing layer.
[0151]
The function and function of this primer layer are not always clear, but by forming a primer layer between the photocatalyst-containing layer side light-shielding part and the photocatalyst-containing layer, the primer layer is characterized by the characteristics of the layer that changes the characteristics of the photocatalyst. Impurities from the openings existing between the photocatalyst containing layer side light shielding part and the photocatalyst containing layer side light shielding part, which are factors that hinder the change, in particular, residues generated when patterning the photocatalyst containing layer side light shielding part, metal, metal It is considered that it has a function of preventing diffusion of impurities such as ions. Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0152]
In the present invention, the primer layer prevents impurities existing in not only the photocatalyst containing layer side light shielding part but also the opening formed between the photocatalyst containing layer side light shielding parts from affecting the action of the photocatalyst. The primer layer is preferably formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.
[0153]
The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the photocatalyst containing layer side light-shielding portion of the photocatalyst containing layer side substrate is not in contact with the photocatalyst containing layer.
[0154]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX.₄X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0155]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0156]
(Energy irradiation)
Next, energy irradiation in this step will be described. In this step, the characteristic changing layer and the photocatalyst containing layer in the photocatalyst containing layer side substrate are arranged with a predetermined gap and irradiated with energy from a predetermined direction, whereby the characteristic changing layer has a characteristic. A changed first characteristic change pattern can be formed. At this time, the property change layer changes its properties due to the action of the photocatalyst in the photocatalyst containing layer arranged in the vicinity. Therefore, the property change layer on the opposite side across the base material has the property due to energy irradiation. Thus, only the first characteristic change pattern can be formed without changing.
[0157]
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.
[0158]
In the present invention, the gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good property change efficiency of the property change layer, particularly in the range of 0.2 μm to 10 μm, preferably It is preferable to be within a 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.
[0159]
On the other hand, when processing a characteristic change layer having a large area of, for example, 300 mm × 300 mm, a fine gap as described above is formed between the photocatalyst containing layer side substrate and the characteristic change layer without contact. It is extremely difficult to do. 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.
[0160]
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.
[0161]
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.
[0162]
In the present invention, such an arrangement state only needs to be maintained at least during energy irradiation.
[0163]
An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the property change layer. By having a pattern similar to the change pattern, a predetermined characteristic change pattern can be formed 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.
[0164]
In the present invention, such an arrangement state of the photocatalyst-containing layer side substrate only needs to be maintained at least during the energy irradiation.
[0165]
3. Second characteristic change pattern forming step
Next, in the present invention, a second characteristic change pattern forming step is performed. The second characteristic change pattern forming step of the present invention includes a characteristic change layer on a surface opposite to the surface on which the first characteristic change pattern is formed by the first characteristic change pattern forming step, and the photocatalyst-containing layer side substrate described above. This is a step of forming a second characteristic change pattern in which the characteristics of the characteristic change layer are changed by irradiating energy after arranging the photocatalyst containing layer with a predetermined gap. Thereby, it is possible to obtain a pattern forming body in which a characteristic change pattern having a characteristic change is formed on both surfaces. The pattern of the second characteristic change pattern is appropriately selected according to the purpose of the pattern forming body, and may be a pattern different from the first characteristic change pattern or the same pattern.
[0166]
Here, since the photocatalyst-containing layer side substrate used in this step, energy irradiation, and the like are the same as those in the first characteristic change pattern forming step described above, description thereof is omitted here.
[0167]
3. Other
In the present invention, the first characteristic change pattern forming step and the second characteristic change pattern step described above can be performed simultaneously. As a method for simultaneously performing the first characteristic change pattern forming step and the second characteristic change pattern forming step, for example, as shown in FIG. 6, first, a base 4 and a photocatalyst-containing layer formed on the surface of the base 4 5 and 5 ′ are prepared. Between the photocatalyst containing layer side substrates 6 and 6 ′ and the characteristic change layers 2 and 2 ′ formed on both surfaces of the transparent base material 1, the spacers 10 are arranged in close contact with each other, The energy 8 is irradiated from the side (FIG. 6A). As a result, it is possible to change the characteristics of the characteristic change layers 2 and 2 ′ only in the portion where the spacer 10 is not in contact, and the first characteristic change pattern 3 and the second characteristic change pattern 3 ′ can be formed simultaneously. (FIG. 6B). In this case, the irradiation of energy is not limited to the side surface, and may be performed from one side or both sides, but in the present invention, it is preferable to perform from both sides in terms of sensitivity and the like.
[0168]
Such a spacer has small holes in a pattern that changes the characteristics of the characteristic change layer, and the thickness of the mask is preferably 2 mm or less, more preferably 100 μm or less. In the present invention, the mask determines the distance between the photocatalyst-containing layer and the wettability changing layer. Therefore, when the thickness of the mask is thicker than the above value, the generated active oxygen species are in the characteristic changing layer. This is because it may become difficult to reach and slow down the characteristic change. The lower limit of the mask thickness is 1 μm. This is because it is difficult to form a high-definition mask when the mask thickness is thinner than the above value.
[0169]
Further, the shape, size, etc. of the small holes formed in the mask of the present invention are appropriately selected according to the pattern of the target pattern forming body.
[0170]
Here, the mask used in the present invention is not particularly limited as long as the material or the like is not capable of transmitting the active oxygen species generated by the action of the photocatalyst by energy irradiation, and is transparent or opaque. It may also be flexible.
[0171]
Specific examples of the mask material used in the present invention include metals, inorganic substances such as glass and ceramics, and organic substances such as plastics. Among these, metals are preferred. In the present invention, since the mask is made of a metal, it is possible to easily form small holes in a pattern that changes the characteristics of the characteristic change layer, and to have strength that can be used repeatedly. Because I have it. A shadow mask or the like can also be used.
[0172]
Here, the method for forming the small holes in the mask depends on the material of the mask and is not particularly limited, and examples thereof include an etching method.
[0173]
In addition, as described above, when the photocatalyst containing layer of the photocatalyst containing layer side substrate is formed in a pattern, the characteristics of only the portion on the characteristic changing layer facing the photocatalyst containing layer change. The first characteristic change pattern and the second characteristic change pattern can be formed simultaneously by disposing the photocatalyst-containing layer side substrate on the characteristic change layers on both sides without using a shadow mask or the like.
[0174]
Furthermore, even when the photocatalyst containing layer side light shielding part is formed on the photocatalyst containing layer, the photocatalyst containing layer side light shielding part is used to adhere to the characteristic change layers on both sides using the photocatalyst containing layer side light shielding part in the same manner as the spacer. By disposing them, the first characteristic change pattern and the second characteristic change pattern can be formed simultaneously.
[0175]
In addition, since the energy etc. which are used in this case are the same as the energy irradiation in the first characteristic change pattern forming step described above, the description here is omitted.
[0176]
C. Functional element
Next, the functional element of the present invention will be described. The functional element of the present invention is characterized in that a functional part is formed on the characteristic change patterns on both sides of the pattern forming body described above.
[0177]
According to the present invention, since the functional part is formed along the pattern of the above-described pattern formed body, the high-definition functional part can be formed on both sides.
[0178]
Here, the functionality is optical (light selective absorption, reflection, polarization, light selective transmission, nonlinear optical properties, luminescence such as fluorescence or phosphorescence, photochromic properties, 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.
[0179]
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.
[0180]
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.
[0181]
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.
[0182]
The functional element of the present invention has, for example, a color filter with a black matrix in which a pixel part is formed on one side as a functional part and a black matrix is formed on the opposite side, or a pixel part on one side as a functional part. And a color filter with a lens in which a lens is formed on the opposite surface, and a conductive pattern in which metal wiring is formed on both surfaces as a functional part.
[0183]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the same configuration as the technical idea described in the claims of the present invention. It is included in the technical scope of the invention.
[0184]
【Example】
Hereinafter, the present invention will be described in more detail through examples.
[0185]
[Example 1]
1. Formation of photocatalyst containing layer side substrate
5 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain an anchor layer composition.
[0186]
The anchor layer composition is applied onto a 100 μm line & space photomask substrate by a spin coater and dried at 150 ° C. for 10 minutes to form a transparent anchor layer (thickness 0.2 μm). did.
[0187]
Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, are mixed at 100 ° C. Stir for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0188]
A transparent photocatalyst-containing layer (thickness 0.15 μm) is obtained by applying the composition for a photocatalyst-containing layer onto a photomask substrate on which an anchor layer is formed using a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. Formed.
[0189]
2. Formation of decomposition removal layer
2 g of Iupilon Z400 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) mainly composed of polycarbonate was dissolved in 30 g of dichloromethane and 70 g of 112 trichloroethane to obtain a composition for a decomposition layer removal layer.
[0190]
The said composition for decomposition | disassembly removal layers was apply | coated with the dip coater on the glass substrate, and the transparent decomposition removal layer (thickness 0.2 micrometer) was formed by performing the drying process for 60 minutes at 100 degreeC.
[0191]
3. First pattern forming step
After making the photocatalyst containing layer side substrate face the first surface of the decomposition and removal layer, 40 mW / cm is applied from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm).²For 200 seconds. Thereby, the energy irradiation part of the decomposition removal layer on the first surface was decomposed and removed.
[0192]
Next, the light-shielding layer composition was applied as a functional part using a dip coater and then cured to form a light-shielding layer in the region where the decomposition removal layer on the first surface was decomposed and removed.
[0193]
4). Second pattern forming step
After making the photocatalyst-containing layer side substrate face the second surface of the decomposition removal layer, 40 mW / cm is applied from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm).²For 200 seconds. Thereby, the energy irradiation part of the decomposition removal layer on the second surface was decomposed and removed.
[0194]
Next, a colored layer composition was applied as a functional part by an inkjet method, and then cured to obtain a color filter in which a colored layer was formed in a region where the decomposition and removal layer on the second surface was decomposed and removed. .
[0195]
[Example 2]
1. Formation of photocatalyst containing layer side substrate
5 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain an anchor layer composition.
[0196]
The anchor layer composition is applied onto a 100 μm line & space photomask substrate by a spin coater and dried at 150 ° C. for 10 minutes to form a transparent anchor layer (thickness 0.2 μm). did.
[0197]
Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, are mixed at 100 ° C. Stir for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0198]
A transparent photocatalyst-containing layer (thickness 0.15 μm) is obtained by applying the composition for a photocatalyst-containing layer onto a photomask substrate on which an anchor layer is formed using a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. Formed.
[0199]
2. Formation of wettability changing layer
Prepare a 5% IPA solution of MF-160E (trade name, manufactured by Tochem Products Co., Ltd.), the main component of which is fluoroalkylsilane, and heat it to 240 ° C. to adhere it onto a glass substrate. A wettability changing layer (thickness 0.1 μm) was formed.
[0200]
3. First pattern forming step
After making the photocatalyst-containing layer side substrate face the first surface of the wettability changing layer, 40 mW / cm from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm).²For 100 seconds. Thereby, the energy irradiation part of the said wettability change layer of the 1st surface became a lyophilic region.
[0201]
Next, the light shielding layer composition was applied as a functional part by a dip coater and then cured to form a light shielding layer on the lyophilic region on the first surface.
[0202]
4). Second pattern forming step
After making the photocatalyst containing layer side substrate face the second surface of the wettability changing layer, 40 mW / cm from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm).²For 100 seconds. Thereby, the energy irradiation part of the said wettability change layer of the 2nd surface became a lyophilic area | region.
[0203]
Next, a colored layer composition was applied as a functional part by an ink jet method and then cured to form a colored layer in the lyophilic region on the second surface to obtain a color filter.
[0204]
【The invention's effect】
According to the present invention, since the property change layer is formed on both surfaces of the base material, the property change pattern having the property changed easily on both surfaces of the pattern forming body by the action of the photocatalyst accompanying energy irradiation. It can be formed and the characteristic change pattern can be different on both sides. Thereby, it is possible to obtain a pattern forming body in which various functional parts can be easily formed on both sides along the characteristic change pattern in which the characteristic is changed.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a pattern forming body of the present invention.
FIG. 2 is a process diagram showing an example of a method for producing a pattern formed body of the present invention.
FIG. 3 is a schematic cross-sectional view showing an example of a photocatalyst containing layer side substrate in the present invention.
FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate in the present invention.
FIG. 5 is a schematic sectional view showing another example of the photocatalyst containing layer side substrate in the present invention.
FIG. 6 is a process diagram showing an example of energy irradiation in the method for producing a patterned body of the present invention.
[Explanation of symbols]
1 ... Base material
2… Characteristic change layer
3 ... Characteristic change pattern
4 ... Base
5 ... Photocatalyst containing layer
6 ... Photocatalyst-containing layer side substrate
7 ... Photomask
8… Energy
9 ... Photocatalyst containing layer side light shielding part

Claims (9)

Formed on both sides of the substrate and a wettability changing layer that changes the wettability so that the contact angle with the liquid is reduced by the action of the photocatalyst accompanying energy irradiation and formed on both sides of the substrate. have been two of the wettability changing layer has a wettability changeable pattern wettability each has changed,
The substrate is transparent;
The said wettability change layer is a pattern formation body characterized by not containing a photocatalyst .   The pattern forming body according to claim 1, wherein the wettability changing layer is a layer containing a fluoroalkylsilane. The wettability change layer formation that forms wettability change layer that does not contain photocatalyst on both sides of transparent base material due to the action of photocatalyst accompanying energy irradiation so that the contact angle with liquid decreases. Process,
One surface of the wettability changing layer and a photocatalyst containing layer containing a photocatalyst and a photocatalyst containing layer side substrate having a substrate are arranged with a gap so that the wettability changing layer and the photocatalyst containing layer are 200 μm or less. Then, the first characteristic change pattern forming step of irradiating energy to form a first characteristic change pattern in which the wettability of the wettability change layer is changed,
The wettability changing layer on the surface opposite to the surface on which the first characteristic change pattern is formed, the photocatalyst containing layer containing the photocatalyst and the photocatalyst containing layer side substrate having the substrate, the wettability changing layer and the photocatalyst A second characteristic change pattern forming step of forming a second characteristic change pattern in which the wettability of the wettability change layer is changed by irradiating energy after disposing the inclusion layer with a gap of 200 μm or less;
A process for producing a pattern-forming body comprising: The method for producing a pattern forming body according to claim 3 , wherein the wettability changing layer forming step is performed by a dry method. The method for producing a pattern forming body according to claim 4 , wherein the dry method is a CVD method. The pattern formation according to any one of claims 3 to 5, wherein the photocatalyst-containing layer side substrate has a photocatalyst-containing layer side light-shielding portion formed in a pattern. Body manufacturing method. The photocatalyst-containing layer side substrate, which comprises a said substrate on the photocatalyst-containing layer side light-shielding portion formed in a pattern, and the photocatalyst-containing layer side light-shielding portion and the primer layer formed on said substrate, wherein characterized in that the photocatalyst-containing layer on the primer layer and is formed, the manufacturing method of pattern formation according to any one of claims from claims 3 to 6. 3. The pattern forming body according to claim 1 , wherein a pixel portion is formed on a wettability change pattern on one side and a light shielding portion is formed on the wettability change pattern on the opposite surface. Color filter. 3. A color according to claim 1 , wherein a pixel portion is formed on the wettability change pattern on one side and a lens is formed on the wettability change pattern on the opposite side. filter.

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