JP4374210B2 - Method for producing pattern forming body - Google Patents

Description

【００５４】
ただし、ｎは２以上の整数であり、Ｒ¹，Ｒ²はそれぞれ炭素数１〜１０の置換もしくはハロゲンで水素が置換されていない非置換のアルキル、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、またはフェニルである。また、Ｒ¹、Ｒ²がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。本実施態様においては、上記Ｒ^１およびＲ^２がエネルギー照射に伴う光触媒の作用により、切断や分解等されて、濡れ性変化層表面の濡れ性を変化させることができる。したがって、このようなＲ^１およびＲ^２中にハロゲン（特にフッ素）を有しないものとすることにより、安定にパターン形成体を連続して製造することができるのである。
【００５５】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコン化合物を混合してもよい。この際、上記オルガノシリコン化合物についても、ハロゲン（特にフッ素）を分子中に有しないものであることが好ましい。
【００５６】
本実施態様における濡れ性変化層には、さらにハロゲンを含有しない界面活性剤を含有させることができる。界面活性剤としては、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ができる。
【００５７】
また、濡れ性変化層には上記の界面活性剤の他にも、ハロゲンを含有しない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、ポリアミド、ポリイミド、スチレンブタジエンゴム、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。
【００５８】
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、この塗布液を後述する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、ディップコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【００５９】
本実施態様において、上述した濡れ性変化層の厚みは、光触媒による濡れ性の変化速度等の関係より、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。
【００６０】
▲２▼単分子膜である場合
次に、上記濡れ性変化層が単分子膜である場合について説明する。上記濡れ性変化層が単分子膜であることにより、上記濡れ性変化層を均一かつ緻密な層とすることができ、例えば後述する特性変化パターン上に機能性部を形成する場合、機能性部を均一かつ高精細に形成することが可能となるのである。このような単分子膜としては、例えば自己組織化単分子膜が挙げられる。
【００６１】
ここで、自己組織化単分子膜とは、固体／液体もしくは固体／気体界面で、有機分子同士が自発的に集合し、会合体を形成しながら自発的に単分子膜を形作っていく有機薄膜である。例として、ある特定の材料でできた基板を、その基板材料と化学的親和性の高い有機分子の溶液または蒸気にさらすと、有機分子は基板表面で化学反応し吸着する。その有機分子が、化学的親和性の高い官能基と、基板との化学反応を全く起こさない有機鎖との２つのパートからなり、親和性の高い官能基がその末端にある場合、分子は反応性末端が基板側を向き、有機鎖が外側を向いて吸着する。有機鎖同士が集合すると、全体として安定になるため、化学吸着の過程で有機分子同士は自発的に集合する。分子の吸着には、基板と末端官能基との間で化学反応が起こることが必要であることから、いったん基板表面が有機分子でおおわれ単分子膜ができあがると、それ以降は分子の吸着は起こらない。その結果、分子が密に集合し、配向性のそろった有機単分子膜ができるものである。
【００６２】
本実施態様においては、上記濡れ性変化層が上記自己組織化単分子膜である場合、エネルギー照射に伴う光触媒の作用によって、濡れ性変化層表面に存在する撥液性を有するハロゲンを有しない有機鎖が、エネルギー照射に伴う光触媒の作用によって除去されることにより、容易に表面を親液性とすることが可能であり、効率的に特性変化パターンの形成を行うことが可能となるのである。本実施態様においては、撥液性を有する上記有機鎖を、ハロゲンを有しないものとすることにより、エネルギー照射に伴う光触媒の作用により、上記有機鎖が切断または分解等されて雰囲気中に放出された分子が、後述する光触媒含有層に影響を与えることがなく、安定にパターン形成体を連続して製造することが可能となるのである。
【００６３】
このような濡れ性変化層として用いられる単分子膜を構成する材料としては、上述した特性を有し、ハロゲンを含有しないものであれば、特に限定されるものではないが、本実施態様においては、ハロゲンを有しない有機鎖を有するシラン化合物であることが好ましい。ここで、上記ハロゲンを有しない有機鎖を構成する炭素の数は、５〜１６の範囲内、中でも６〜１２の範囲内であることが好ましい。これにより、エネルギー照射前の濡れ性変化層を撥液性とすることができ、エネルギー照射に伴う光触媒の作用により上記有機鎖が分解等され、親液性とすることが可能となるのである。また、本発明においては、上記有機鎖としては、アルキル基、フェニル基、アミノ基、フルオロ基、エポキシ基、ビニル基、スチリル基、メタクリロキシ基、アクリロキシ基、ウレイド基、クロロプロピル基、メルカプト基、スクシンイミド基、スルフィド基、イソシアネート基、カルボキシル基、ビシクロ基、イミダゾール基等が挙げられ、上記の中でもアルキル基であることが特に好ましい。
【００６４】
上記有機鎖を有するシラン化合物として、具体的には、上述したオルガノポリシロキサンの項で説明した材料等を用いることができる。
【００６５】
このような単分子膜からなる濡れ性変化層は、熱ＣＶＤ法やディップコート法、等により形成することができるが、本実施態様においては、熱ＣＶＤ法であることが製造効率等の面から好ましい。熱ＣＶＤ法の好ましい成膜条件としては、後述する基材等の耐熱温度以下であれば、原料となる物質の気化温度以上であり、かつ分解温度以下であれば特に限定されるものではないが、通常５０℃〜２００℃の範囲内であることが好ましい。
【００６６】
また、本実施態様においては、公知である減圧熱ＣＶＤ法を用いてもよい。この減圧熱ＣＶＤ処理時における真空度として、十分な材料の蒸気圧が得られるように設定することができる。この蒸気圧は材料の種類により適宜選択されるものであるが、通常０．０１Ｔｏｒｒ〜１０Ｔｏｒｒ、中でも５Ｔｏｒｒ以下とすることができる。またこの際、基材表面との反応を促進するために、基材を加熱しながら減圧ＣＶＤ法を行い、濡れ性変化層を形成することが好ましい。この場合の加熱温度は、基材および濡れ性変化層の材料によって適宜選択されるものではあるが、通常４０℃〜１００℃の範囲内、中でも８０℃以下とされる。
【００６７】
本実施態様において形成される濡れ性変化層の膜厚としては、その単分子膜の種類にもより決定されるものであるが、通常１ｎｍ〜５０ｎｍの範囲とされる。
【００６８】
（分解除去層）
次に、本発明に用いられる特性変化層が分解除去層である場合について説明する。本発明に用いられる分解除去層が単分子膜である場合には、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層である。このように分解除去層は、エネルギー照射された部分が光触媒の作用により分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分とからなるパターン、すなわち凹凸を有するパターンを形成することができる。
【００６９】
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。
【００７０】
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、分解除去層が分解除去されて露出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、表面の凹凸だけでなく、濡れ性の差も利用して、機能性部を形成することが可能となるからである。
【００７１】
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、例えば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、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。
【００７２】
また、上記分解除去層は、４０ｍＮ／ｍの液体との接触角が、１０°以上、中でも４０°以上であることが好ましい。これは、本発明は、残存する分解除去層が、撥液性が要求される部分であることから、液体との接触角が小さい場合は、撥液性が十分でなく、機能性部を形成しない撥液性領域にまで機能性部形成用塗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。
【００７３】
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９°以下、中でも５°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、機能性部形成用塗布液の塗布に際して、親液性領域においても機能性部形成用塗布液をはじいてしまう可能性があり、親液性領域上に機能性部をパターニングすることが難しくなる可能性があるからである。ここで、液体との接触角は、上述した方法により測定した値である。
【００７４】
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、ハロゲン（特にフッ素）を含有しない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。このような分解除去層に用いられる膜を、ハロゲンを有しないものとすることにより、エネルギー照射に伴う光触媒の作用により、上記分解除去層を構成する分子が切断または分解等されることによって、雰囲気中に放出される分子が、後述する光触媒含有層に影響を与えることがなく、安定にパターン形成体を連続して製造することが可能となるのである。このような炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【００７５】
また、本発明においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【００７６】
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。
【００７７】
▲１▼自己組織化単分子膜
本発明に用いられるハロゲン（特にフッ素）を含有しない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、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。
【００７８】
▲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。
【００７９】
▲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。
【００８０】
また、分解除去層の膜厚としては、エネルギーに伴う光触媒の作用により分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、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。
【００８１】
（２）基材
次に、本実施態様のパターン形成体に用いられる基材について説明する。本実施態様においては、上述した特性変化層が自己支持性を有しない場合や、強度が必要な場合、上記分解除去層である場合等に基材が用いられ、この基材上に特性変化層が形成されるものである。ここで、自己支持性とは、他の支持材無しで有形な状態で存在し得ることをいうこととする。
【００８２】
本実施態様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。
【００８３】
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。
【００８４】
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。
【００８５】
（３）その他
また、本実施態様においては、上述した基材上または特性変化層上に、パターン形成体の用途や種類に応じて、例えばカラーフィルタにおけるブラックマトリックスのような遮光部等、他の部材が形成されているものであってもよい。
【００８６】
本実施態様においては、例えば基材上に遮光部が形成され、かつ基材が透明である場合には、後述するエネルギーの照射をパターン形成体用基板の基材側から行うことも可能となり、フォトマスク等を用いることなく、遮光部が形成されていない領域上の特性変化層の特性のみを変化させることが可能となる。
【００８７】
ｂ．光触媒含有層側基板
次に、本実施態様に用いられる光触媒含有層側基板について説明する。本実施態様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、本実施態様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。
【００８８】
（１）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。本実施態様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、上述した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。
【００８９】
本実施態様において用いられる光触媒含有層は、例えば図１に示すように、基体４上に光触媒含有層５が全面に形成されたものであってもよいが、例えば図２に示すように、基体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。
【００９０】
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。
【００９１】
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。
【００９２】
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。
【００９３】
このよう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。本実施態様においては、このキャリアが光触媒含有層上で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。また、本実施態様においては、上述した特性変化層中にハロゲンが含有しないことから、光触媒含有層側基板を用いてエネルギー照射を行った場合であっても、ハロゲンにより発生したラジカル等が特性変化層に作用を及ぼすことがない。すなわち、光触媒含有層に繰り返しエネルギーを照射した場合にも、エネルギー照射により発生した一定量の活性酸素種のみが特性変化層の特性変化に寄与し、安定して同一の特性変化パターンを形成することができるのである。
【００９４】
本実施態様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。
【００９５】
本実施態様においては、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実施態様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。
【００９６】
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。
【００９７】
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８０ｎｍ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。
【００９８】
本実施態様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。
【００９９】
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。
【０１００】
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。
【０１０１】
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。
【０１０２】
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。
【０１０３】
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。
【０１０４】
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。
【０１０５】
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。
【０１０６】
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。
【０１０７】
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。
【０１０８】
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。
【０１０９】
（２）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。本実施態様においては、図１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。
【０１１０】
また本実施態様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。
【０１１１】
ここで、本実施態様においては、上述したパターン形成体用基板における特性変化層がハロゲンを含有しないことから、上記光触媒含有層を繰り返し使用した場合であっても、光触媒含有層の酸化分解力を一定のものとすることができる。したがって、光触媒含有層側基板を繰り返し使用するものとすることができることから、基体が所定の強度を有し、かつその表面が光触媒含有層との密着性が良好であることが好ましい。
【０１１２】
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。
【０１１３】
（３）光触媒含有層側遮光部
本実施態様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。
【０１１４】
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。
【０１１５】
一つが、例えば図３に示すように、基体４上に光触媒含有層側遮光部１０を形成し、この光触媒含有層側遮光部１０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４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１０を形成して光触媒含有層側基板とする態様である。
【０１１６】
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。
【０１１７】
ここで、本実施態様においては、図４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１０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。
【０１１８】
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、例えばパターン形成体用基板の基材の側面からであってもよい。
【０１１９】
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。
【０１２０】
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。
【０１２１】
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。
【０１２２】
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。
【０１２３】
（４）プライマー層
次に、本実施態様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。本実施態様において、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。
【０１２４】
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。
【０１２５】
なお、本実施態様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。
【０１２６】
本実施態様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。
【０１２７】
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。
【０１２８】
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。
【０１２９】
ｃ．光触媒含有層側基板の配置
次に、光触媒含有層側基板の配置について説明する。本実施態様においては、上述した特性変化層は、上述した光触媒含有層側基板における光触媒含有層が所定の間隙をおいて配置されて、エネルギー照射されることにより、表面の特性が変化する。この際の光触媒含有層側基板の配置とは、エネルギーの照射時に光触媒含有層と特性変化層とを光触媒の作用が及ぶように所定の間隔をおいて配置する必要があり、本実施態様においては、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向からエネルギーを照射する。この際、光触媒含有層および特性変化層を密着させてもよい。
【０１３０】
本実施態様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パターン形成体に対して特に有効である。
【０１３１】
一方、例えば３００ｍｍ×３００ｍｍといった大面積のパターン形成体に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒含有層側基板とパターン形成体用基板との間に形成することは極めて困難である。したがって、パターン形成体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。
【０１３２】
このように比較的大面積のパターン形成体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パターン形成体用基板との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒含有層側基板とパターン形成体用基板とが接触することなく配置することが可能となるからである。
【０１３３】
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。
【０１３４】
本実施態様においては、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。
【０１３５】
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。
【０１３６】
本実施態様においては、このようなスペーサを一つの部材として形成してもよいが、工程の簡略化等のため、上記光触媒含有層側基板の欄で説明したように、光触媒含有層側基板の光触媒含有層表面に形成することが好ましい。なお、上記光触媒含有層側基板における説明においては、光触媒含有層側遮光部として説明したが、本実施態様においては、このようなスペーサは特性変化層表面に光触媒の作用が及ばないように表面を保護する作用を有すればよいものであることから、特に照射されるエネルギーを遮蔽する機能を有さない材料で形成されたものであってもよい。
【０１３７】
ｄ．エネルギー照射
次に、本実施態様におけるエネルギー照射について説明する。本実施態様においては、上述したような配置を維持した状態で、対向する部分へのエネルギー照射が行われることにより、上述した特性変化層上に特性変化パターンが形成されるのである。
【０１３８】
なお、本実施態様でいうエネルギー照射（露光）とは、光触媒含有層による特性変化層表面の特性を変化させることが可能ないかなるエネルギー線の照射をも含む概念であり、可視光の照射に限定されるものではない。
【０１３９】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１４０】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１４１】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１４２】
また、エネルギー照射に際してのエネルギーの照射量は、特性変化層表面が光触媒含有層中の光触媒の作用により特性変化層表面の特性の変化が行われるのに必要な照射量とする。
【０１４３】
この際、光触媒含有層を加熱しながらエネルギー照射することにより、酸化分解力を上昇させることが可能となり、効率的な特性の変化を行うことができる点で好ましい。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１４４】
本実施態様におけるエネルギー照射方向は、光触媒含有層側遮光部もしくパターン形成体用基板側に遮光部が形成されているか否か等の特性変化パターンの形成方法や、光触媒含有層側基板もしくはパターン形成体用基板が透明であるか否かにより決定される。
【０１４５】
すなわち、光触媒含有層側遮光部が形成されている場合は、光触媒含有層側基板側からエネルギー照射が行なわれる必要があり、かつこの場合は光触媒含有層側基板が照射されるエネルギーに対して透明である必要がある。なお、この場合、光触媒含有層上に光触媒含有層側遮光部が形成され、かつこの光触媒含有層側遮光部を上述したようなスペーサとしての機能を有するように用いた場合においては、エネルギー照射方向は光触媒含有層側基板側からでもパターン形成体用基板側からであってもよい。
【０１４６】
一方、パターン形成体用基板側に遮光部が形成されている場合は、パターン形成体用基板側からエネルギー照射が行われる必要があり、かつこの場合は、パターン形成体用基板が照射されるエネルギーに対して透明である必要がある。なお、この場合も、特性変化層上にパターン形成体用基板側に遮光部が形成され、このパターン形成体用基板側の遮光部が上述したようなスペーサとしての機能を有するように用いられた場合、エネルギー照射方向は光触媒含有層側基板側からでもパターン形成体用基板側からであってもよい。
【０１４７】
フォトマスクを用いる場合は、フォトマスクが配置された側からエネルギーが照射される。この場合は、フォトマスクが配置された側の基板、すなわち光触媒含有層側基板もしくはパターン形成体側の基板のいずれかが透明である必要がある。
【０１４８】
上述したようなエネルギー照射が終了すると、光触媒含有層側基板が特性変化層との配置位置から離され、これにより特性変化パターンが形成され、その特性変化パターン内における特性変化の度合いが異なるパターン形成体となるのである。
【０１４９】
なお、本発明においては上述したように、光触媒含有層を繰り返し使用した場合であっても、酸化分解力が変化しないことから、連続して同様のパターン形成体用基板に対して、上記光触媒含有層側基板を用いてエネルギー照射を行い、パターン形成体を製造することが可能である。
【０１５０】
２．第２実施態様
次に、本発明のパターン形成体の製造方法における第２実施態様について説明する。本発明のパターン形成体の製造方法における第２実施態様は、エネルギー照射に伴う光触媒の作用により特性が変化する特性変化層を有するパターン形成体用基板と、光触媒を含有する光触媒含有層および基体を有する光触媒含有層側基板とを、上記特性変化層および上記光触媒含有層が２００μｍ以下となるように間隙をおいて配置した後、所定の方向からエネルギーを照射することにより、上記特性変化層表面に特性の変化した特性変化パターンを形成するパターン形成工程を、異なるパターン形成体用基板に１０回以上連続して行うパターン形成体の製造方法であって、１０回目に行われる上記パターン形成工程により形成される上記特性変化パターンの幅が、１回目に行われる上記パターン形成工程により形成される上記特性変化パターンの幅に対して、所定の範囲内である方法である。
【０１５１】
ここで、上記特性変化パターン形成工程を異なるパターン形成体用基板に１０回以上連続して行うとは、光触媒含有層を洗浄する工程あるいは上記特性変化層および光触媒含有層が充分に広くなるように間隔をおいて配置した後、所定の方向からエネルギーを照射する工程等、光触媒含有層の酸化分解力を変化させる工程を挟まずに、１０個以上のパターン形成体用基板における特性変化層に対して、上記光触媒含有層側基板を用いてエネルギーを照射する工程を行うことをいう。
【０１５２】
本実施態様によれば、１０回目に行われたパターン形成工程により形成された特性変化パターンの幅が、１回目に行われたパターン形成工程により形成された特性変化パターンの幅と比較して、所定の範囲内となることから、上記パターン形成工程を１０回以上連続して行った場合であっても、特性変化パターンの形状を一定のものとすることができ、安定にパターン形成体を製造することができるのである。これにより、連続して多量にパターン形成体を製造することができ、コストや製造効率の面からも好ましいものとすることができるのである。
【０１５３】
ここで、本実施態様においては、１０回目に行われる上記パターン形成工程により形成される上記特性変化パターンの幅が、１回目に行われる上記パターン形成工程により形成される上記特性変化パターンの幅に対して、０．７５倍〜１．２５倍の範囲内、中でも０．８倍〜１．２倍の範囲内であることが好ましく、また、±２０μｍの範囲内、中でも±１０μｍの範囲内であることが好ましい。
【０１５４】
本実施態様においては、上記パターン形成工程を、１０回以上、中でも５０回以上、特に５００回以上行うことが好ましく、また通常上限としては、１００００回以下とされる。
【０１５５】
本実施態様において、上述したような、１０回以上連続してパターン形成工程を行い、特性変化パターンの精度を上記範囲内とすることを実現可能とできるのは、通常上記特性変化層中にハロゲンが含有されない場合であり、この特性変化層中にハロゲンが含有されない場合のパターン形成体の製造方法については、第１実施態様と同様であるので、ここでの説明は省略する。
【０１５６】
Ｂ．機能性素子
次に、本発明の機能性素子について説明する。本発明の機能性素子は、上述したパターン形成体の製造方法により製造されたパターン形成体の特性変化パターン上に、機能性部が形成されたものである。
【０１５７】
本発明によれば、上記特性変化パターンの例えば濡れ性や、凹凸等の特性の差を利用して、容易に高精細な機能性部を形成することが可能となるのである。また、上述したパターン形成体の製造方法により連続して製造されたパターン形成体の特性変化パターンは、形状が一定であり、連続して製造することができることから、コストや製造効率の面でも好ましい機能性素子とすることができるのである。
【０１５８】
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。
【０１５９】
本発明における機能性部の形成方法は、上記特性変化パターンの特性の変化の種類により適宜選択させるものであるが、例えば上記特性変化層が濡れ性変化層である場合には、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、ディスペンサー等を含むノズル吐出手段等の手段を用いることが可能であり、本発明においては中でも、ノズル吐出手段を用いることが好ましい。上記ノズル吐出手段においては、目的とするパターン状に機能性部を形成する機能性部形成用組成物を塗布することが可能となり、より高精細に機能性部を形成することが可能となるからである。
【０１６０】
また、上記特性変化層が例えば分解除去層である場合には、インクジェット、ディスペンサー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く、これにより分解除去層の凹凸を利用して、高精細な機能性部を形成することが可能となるからである。
【０１６１】
また、上記特性変化層が例えば密着変化層である場合には、上記方法の他に、蒸着法、無電界めっき等も用いることが可能であり、機能性部形成用組成物を成膜後、密着阻害領域に付着した機能性部形成用組成物を除去することにより、密着性良好領域にのみ機能性部形成用組成物を密着させることができ、機能性部を形成することが可能となるのである。
【０１６２】
ここで、機能性部形成用組成物の材料としては、溶剤型材料および非溶剤型の材料のどちらも用いることが可能であるが、本発明においては溶剤型の材料であることが好ましい。本発明における機能性部は、上記特性変化パターンに沿って機能性部の膜厚が異なるものであることが好ましく、溶剤型の材料を用いることにより、溶剤が揮発する際に、この機能性部内の膜厚の差を大きいものとすることが可能となるからである。
【０１６３】
ここで、本発明により形成される機能性素子として、好ましいものは上記機能性部が画素部であるカラーフィルタ、上記機能性部がレンズであるマイクロレンズ、または上記機能性部が、生体分子付着性を有し、かつ生体分子の培地として用いることができる生体分子培養部等であることが好ましい。
【０１６４】
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、本実施態様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実施態様の技術的範囲に包含される。
【０１６５】
【実施例】
以下、本発明について、実施例および比較例を通じてさらに詳述する。
【０１６６】
[実施例１]
ドデシルアルキルシラン（東京化成工業（株）製）０．７ｇと０．００５ＮのＨＣｌ（水溶液）２．３６ｇとからなる溶液を２０℃で２４時間撹拌した後、溶液をイソプロピルアルコールで１００倍（質量基準）に希釈し、濡れ性変化層形成用組成物を得た。この濡れ性変化層形成用組成物を用いて、ガラス基板上にスピンコーティングし、１５０℃の温度で１０分間乾燥させ、透明で均一な濡れ性変化層を有するパターン形成体用基板を得た。
【０１６７】
次に、ガラス基板上に、Ｃｒの薄膜を幅が７０μｍでピッチが１００μｍのストライプ状に形成したマスクパターンを有するフォトマスクのマスクパターン側に、二酸化チタンの水分散液（石原産業（株）製、品名：「ST-K03」）をスピンコーティングし、加熱乾燥することにより透明な光触媒含有層を形成し、光触媒含有層側基板とした。
【０１６８】
上記光触媒含有層側基板における光触媒含有層と、上記光触媒含有層が上記濡れ性変化層とを、５０μｍのギャップを設けて対向させ、フォトマスク側から超高圧水銀ランプにて、波長が３６５ｎｍの紫外線を、２０ｍＷ／ｃｍ^２の照度で照射することにより露光し、濡れ性変化層の表面に濡れ性変化パターンを形成した。得られた濡れ性変化パターンは、未露光部における水との接触角が１０５°、および表面張力が４０ｍＮ／ｍの液体との接触角は６５°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに２１０秒を要した。また、未露光部の幅は６９μｍ、露光部の幅は３１μｍであった。
【０１６９】
続いて上述したものと同様のパターン形成体用基板に対して、２１０秒間の露光を、２０枚連続して行った。２０枚目のパターン形成体用基板において、未露光部の幅は６８μｍ、露光部の幅は３２μｍであった。
【０１７０】
[実施例２]
ドデシルアルキルシラン（東京化成工業（株）製）の変わりにヘキサアルキルシラン（G.E東芝シリコーン（株）製 TSL-8241）を用いた以外は、実施例１と同様にしてパターン形成体用基板を得て、実施例１と同様の光触媒含有層側基板を用いて露光を行った。得られた濡れ性変化パターンは、未露光部における水との接触角が９０°、および表面張力が４０ｍＮ／ｍの液体との接触角は４５°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１２０秒を要した。また、未露光部の幅は７０μｍ、露光部の幅は３０μｍであった。
【０１７１】
続いて上述したものと同様のパターン形成体用基板に対して、１２０秒間の露光を、２０枚連続して行った。２０枚目のパターン形成体用基板において、未露光部の幅は７１μｍ、露光部の幅は２９μｍであった。
【０１７２】
[実施例３]
ドデシルアルキルシラン（東京化成工業（株）製）の変わりにフェニルメトキシシラン（G.E東芝シリコーン（株）製 TSL-8172）を用いた以外は、実施例１と同様にしてパターン形成体用基板を得て、実施例１と同様の光触媒含有層側基板を用いて露光を行った。得られた濡れ性変化パターンは、未露光部における水との接触角が６０°、および表面張力が４０ｍＮ／ｍの液体との接触角は３０°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１５０秒を要した。また、未露光部の幅は７１μｍ、露光部の幅は２９μｍであった。
【０１７３】
続いて上述したものと同様のパターン形成体用基板に対して、１５０秒間の露光を、２０枚連続して行った。２０枚目のパターン形成体用基板において、未露光部の幅は６９μｍ、露光部の幅は３１μｍであった。
【０１７４】
[実施例４]
ドデシルアルキルシラン（東京化成工業（株）製）の変わりにγ-グリシドキシプロピルメチルジメトキシシラン（G.E東芝シリコーン（株）製 TSL-8355）を用いた以外は、実施例１と同様にしてパターン形成体用基板を得て、実施例１と同様の光触媒含有層側基板を用いて露光を行った。得られた濡れ性変化パターンは、未露光部における水との接触角が６０°、および表面張力が４０ｍＮ／ｍの液体との接触角は２５°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１８０秒を要した。また、未露光部の幅は７０μｍ、露光部の幅は３０μｍであった。
【０１７５】
続いて上述したものと同様のパターン形成体用基板に対して、１８０秒間の露光を、２０枚連続して行った。２０枚目のパターン形成体用基板において、未露光部の幅は７１μｍ、露光部の幅は２９μｍであった。
【０１７６】
[実施例５]
デシルアルキルシラン（信越シリコーン（株）製LS-5258）１．５ｇと、イソプロピルアルコール３０ｇとからなる溶液を容器に入れ、２４０℃に加熱したオーブンに投入し、デシルアルキルシランを気化させることにより、オーブン内をデシルアルキルシラン雰囲気にした。前記デシルアルキルシラン雰囲気のオーブン内にガラス基板を投入し、ガラス基板表面にデシルアルキルシランを蒸着させた。このようにして作成したパターン形成体用基板を用い、実施例１と同様に露光を行った。得られた濡れ性変化パターンは、未露光部における水との接触角が１００°、および表面張力が４０ｍＮ／ｍの液体との接触角は６５°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１８０秒を要した。また、未露光部の幅は７１μｍ、露光部の幅は２９μｍであった。
【０１７７】
続いて上述したものと同様のパターン形成体用基板に対して、１８０秒間の露光を、２０枚連続して行った。２０枚目のパターン形成体用基板において、未露光部の幅は６９μｍ、露光部の幅は３１μｍであった。
【０１７８】
[比較例１]
ヘプタデカフルオロデシルトリメトキシシラン（東芝シリコーン製 TSL−8233）１．５ｇとテトラメトキシシラン（東芝シリコーン製 TSL-8114）３．５ｇと０．００５ＮのＨＣｌ（水溶液）２．３６ｇとからなる溶液を２０℃で２４時間撹拌した後、溶液をイソプロピルアルコールで１００倍（質量基準）に希釈し、濡れ性変化層形成用組成物を得た。この濡れ性変化層形成用組成物を用いて、ガラス基板上にスピンコーティングし、１５０℃の温度で１０分間乾燥させ、透明で均一な濡れ性変化層を有するパターン形成体用基板を得た。
【０１７９】
前記パターン形成体用基板について実施例１と同様に濡れ性変化パターン形成を行った。得られた濡れ性変化パターンは、未露光部における水との接触角が１１０°、および表面張力が４０ｍＮ／ｍの液体との接触角は８０°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１８０秒を要した。また、１枚目露光時の未露光部の幅は７０μｍ、露光部の幅は３０μｍであった。
【０１８０】
続いて上述したものと同様のパターン形成体用基板に対して２０枚連続して行った場合、２０枚目のパターン形成体用基板において、未露光部の幅は２０μｍ、露光部の幅は８０μｍであり、露光部の幅の広がりが確認された。
【０１８１】
[比較例２]
ヘプタデカフルオロデシルトリメトキシシラン（東芝シリコーン製 TSL−8233）の代わりにトリデカフルオロオクチルトリメトキシシラン（東芝シリコーン製 TSL-8257）を用いた以外は比較例１と同様にしてパターン形成体用基板を作成し、実施例１と同様に露光して、濡れ性変化パターン形成を行った。得られた濡れ性変化パターンは、未露光部における水との接触角１１０°、および表面張力が４０ｍＮ／ｍの液体との接触角は８０°であり、露光部における水との接触角が１０°以下、および表面張力が４０ｍＮ／ｍの液体との接触角が９°以下になるのに１５０秒を要した。また、１枚目露光時の未露光部の幅は７１μｍ、露光部の幅は２９μｍであった。
【０１８２】
続いて上述したものと同様のパターン形成体用基板に対して２０枚連続して行った場合、２０枚目のパターン形成体用基板において、未露光部の幅は２２μｍ、露光部の幅は７８μｍであり、露光部の幅の広がりが確認された。
【０１８３】
【発明の効果】
本発明によれば、上記パターン形成体用基板が、上記特性変化層を有することから、光触媒含有層側基板を用いてエネルギー照射をすることによって、上記特性変化層の分子が分解等され、表面の特性が変化した上記特性変化パターンを形成することができる。ここで、本発明者等の研究により、上記特性変化層中にハロゲンが含有されている場合には、上記光触媒含有層側基板を連続して上記パターン形成工程に使用することにより、光触媒含有層の酸化分解力が変化するとの知見が得られた。本発明によれば、上記特性変化層中にハロゲンが含有されないことから、光触媒含有層側基板を連続して使用した場合であっても、光触媒含有層の酸化分解力を一定のものとすることができ、安定して高精細なパターン形成体を効率よく連続して製造することが可能となるのである。
【図面の簡単な説明】
【図１】本発明のパターン形成体の製造方法の一例を示す工程図である。
【図２】本発明のパターン形成体の製造方法に用いられる光触媒含有層側基板の一例を示す概略断面図である。
【図３】本発明のパターン形成体の製造方法に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【図４】本発明のパターン形成体の製造方法に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【符号の説明】
１ … 基材
２ … 特性変化層
３ … パターン形成体用基板
４ … 基体
５ … 光触媒含有層
６ … 光触媒含有層側基板
７ … フォトマスク
８ … エネルギー
９ … 特性変化パターン[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a pattern with different characteristics on the surface, which can be used for various applications including a color filter.
[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]
A printing plate for offset printing is produced by a method of exposing and developing through a mask on which a pattern is drawn on the printing plate precursor, or a method of exposing directly by an electrophotographic method and making a plate directly on the printing plate precursor. can do. 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]
There has also been proposed a method for producing a lithographic printing plate precursor using a heat mode recording material capable of forming a pattern composed of a portion having high receptivity to ink and a portion having ink repellency by laser irradiation. Yes. The heat mode recording material does not require a process such as development, and has a feature that a printing plate can be produced simply by forming an image with a laser beam. There were problems in the processing of residues such as solid substances and the printing durability.
[0006]
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.
[0007]
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.
[0008]
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. .
[0009]
On the other hand, as a method for forming a high-definition pattern, a characteristic changing layer or the like whose characteristics are changed by the action of a photocatalyst is formed on a substrate by a coating method, and a substrate having a photocatalyst-containing layer containing a photocatalyst is used. The inventors have studied a method for producing a pattern forming body that forms a pattern by irradiation (see, for example, Patent Document 1).
[0010]
According to the above method, a high-definition pattern can be easily formed. However, depending on the type of the characteristic change layer, the oxidative decomposition power of the photocatalyst-containing layer changes when the pattern forming body is continuously manufactured. There is a problem that it is difficult to control the width and the like of the formed pattern uniformly.
[0011]
[Patent Document 1]
JP 2000-249821 A
[0012]
[Problems to be solved by the invention]
From the above, it is possible to form a pattern with high definition, and the oxidative decomposition power of the photocatalyst-containing layer is constant even when the pattern-formed body is continuously produced. It is desired to provide a method for producing a pattern-formed body capable of controlling the shape.
[0013]
[Means for Solving the Problems]
The present invention relates to a substrate for a pattern forming body having a characteristic changing layer that does not contain a halogen, the characteristics of which are changed by the action of a photocatalyst accompanying energy irradiation, a photocatalyst-containing layer containing a photocatalyst, and a photocatalyst-containing layer side substrate having a substrate Are 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 from a predetermined direction, whereby the characteristic change whose characteristic has changed on the surface of the characteristic change layer There is provided a method for producing a pattern forming body, comprising a pattern forming step of forming a pattern.
[0014]
According to the present invention, since the substrate for the pattern forming body has the property change layer, by irradiating energy using the photocatalyst-containing layer side substrate, the molecules of the property change layer are decomposed, and the surface It is possible to form the above-described characteristic change pattern in which the characteristic is changed. Here, as a result of research by the present inventors, when the characteristic change layer contains halogen, the photocatalyst-containing layer is used by continuously using the photocatalyst-containing layer side substrate in the pattern forming step. It was found that the oxidative degradation power of selenium changed. According to the present invention, since the halogen is not contained in the property change layer, the oxidative decomposition power of the photocatalyst containing layer is made constant even when the photocatalyst containing layer side substrate is continuously used. Therefore, it is possible to efficiently and continuously produce a high-definition pattern forming body stably.
[0015]
Here, in the present invention, the characteristic change layer can be a wettability change layer in which a contact angle with a liquid is lowered by the action of a photocatalyst accompanying energy irradiation. Thereby, it can be set as the pattern formation body which can form a functional part easily using the wettability of the surface on the said characteristic change pattern by the inkjet method etc., for example.
[0016]
In the above invention, the wettability changing layer is Y_nSiX_(4-n)(Wherein Y represents an alkyl group, vinyl group, amino group, phenyl group or epoxy group, X represents an alkoxyl group, and n is an integer from 0 to 3). Or it can be set as the organopolysiloxane which is 2 or more types of hydrolysis-condensation products or a co-hydrolysis condensation product. This is because by using the layer as described above, the characteristics due to the wettability can be expressed.
[0017]
Under the present circumstances, it is preferable that the carbon number of Y which comprises the said organopolysiloxane exists in the range of 5-16. The above-mentioned wettability changing layer before energy irradiation can be made liquid-repellent by the above-mentioned Y, and the above-mentioned Y can be efficiently decomposed by the action of the photocatalyst accompanying the energy irradiation to make it lyophilic. Because it becomes.
[0018]
In the present invention, the wettability changing layer can be a monomolecular film. This is because the wettability changing layer can be a dense and uniform film, and the wettability can be changed uniformly and with high definition by the action of the photocatalyst accompanying the energy irradiation.
[0019]
At this time, the monomolecular film is preferably made of a silane compound having an organic chain. This is because the monomolecular film can be easily formed by using such a silane compound.
[0020]
Moreover, it is preferable that the carbon number which comprises the said organic chain exists in the range of 5-16. The organic chain can make the monomolecular film before energy irradiation liquid-repellent by the organic chain, and the organic chain can be efficiently decomposed by the action of the photocatalyst accompanying energy irradiation to make it lyophilic. Because it becomes.
[0021]
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, it is possible to obtain a pattern forming body on which the functional portion can be easily formed on the characteristic change pattern by using, for example, the surface unevenness by an ink jet method or the like.
[0022]
At this time, the contact angle of the decomposition removal layer with a liquid having a surface tension of 40 mN / m is 10 ° or more, and the contact with the liquid having a surface tension of 40 mN / m of the substrate exposed by decomposition removal of the decomposition removal layer. The angle is preferably 9 ° or less. As a result, it becomes possible to make the base material exposed by decomposing and removing the decomposition / removal layer a lyophilic region and the top of the decomposition / removal layer to be a liquid-repellent region. This is because the functional part can be formed using the difference, and a pattern forming body capable of forming a higher-definition functional part can be obtained.
[0023]
In the present invention, the decomposition removal layer may be a monomolecular film. This is because the decomposition / removal layer can be a dense and uniform layer, and the decomposition / removal layer can be efficiently and uniformly decomposed and removed by the action of the photocatalyst accompanying the energy irradiation.
[0024]
Further, the present invention provides a substrate for a pattern forming body having a characteristic changing layer whose characteristics are changed by the action of a photocatalyst accompanying energy irradiation, a photocatalyst containing layer containing a photocatalyst, and a photocatalyst containing layer side substrate having a substrate. After the characteristic change layer and the photocatalyst-containing layer are arranged with a gap so as to be 200 μm or less, a characteristic change pattern with changed characteristics is formed on the surface of the characteristic change layer by irradiating energy from a predetermined direction. The pattern forming process is a manufacturing method of a pattern forming body in which the pattern forming process is continuously performed 10 or more times on different pattern forming body substrates, and the width of the characteristic change pattern formed by the pattern forming process performed the 10th time is The width of the characteristic change pattern formed in the first pattern formation process is changed within a range of ± 20 μm. To provide a method for manufacturing a patterned member, characterized by.
[0025]
According to the present invention, the width of the characteristic change pattern formed by the pattern forming process performed for the tenth time is compared with the width of the characteristic change pattern formed by the pattern forming process performed for the first time. Since it is within the range, even if the pattern forming process is continuously performed 10 times or more, the shape of the characteristic change pattern can be made constant, and the pattern forming body can be manufactured stably and efficiently. It can be done.
[0026]
Furthermore, the present invention provides a function characterized in that a functional part is formed on a characteristic change pattern of a pattern forming body manufactured by the method of manufacturing a pattern forming body according to any one of the claims described above. Provide a sex element.
[0027]
According to the present invention, since the functional part is formed on the characteristic change pattern of the pattern formed body manufactured by the above-described method for manufacturing a pattern formed body, the characteristics of the characteristic change layer are utilized. The functional part can be easily formed uniformly and with high definition.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a pattern with different characteristics on the surface, which can be used for various applications including a color filter, and a functional element using the pattern forming body manufactured by the manufacturing method. Is. Each will be described in detail below.
[0029]
A. Method for producing pattern forming body
First, the manufacturing method of the pattern formation body of this invention is demonstrated. There are two embodiments of the method for producing a patterned body of the present invention. In the present invention, in either embodiment, for example, as shown in FIG. 1, a substrate 3 for a pattern forming body having a base material 1 and a characteristic change layer 2 formed on the base material 1, and a base material 4 and a photocatalyst-containing layer side substrate 6 having a photocatalyst-containing layer 5 formed on the substrate 4, and the characteristic change layer 2 and the photocatalyst-containing layer 5 are set to have a predetermined gap. Arrangement and irradiation of energy 8 using, for example, a photomask 7 (FIG. 1A) to form a characteristic change pattern 9 in which the characteristics of the characteristic change layer 2 are changed (FIG. 1B) pattern formation step It is what has.
[0030]
According to the present invention, in any embodiment, even when the photocatalyst-containing layer is used continuously and repeatedly, a predetermined pattern is formed without any change in the oxidative decomposition power of the photocatalyst-containing layer. It can be formed with high definition. Hereinafter, the manufacturing method of the pattern formation body of this invention is demonstrated for every embodiment, respectively.
[0031]
1. First embodiment
First, the 1st embodiment in the manufacturing method of the pattern formation object of the present invention is explained. The first embodiment of the method for producing a pattern forming body according to the present invention includes a substrate for a pattern forming body that has a characteristic change layer that does not contain a halogen and that has characteristics changed by the action of a photocatalyst accompanying energy irradiation, and a photocatalyst The photocatalyst containing layer and the photocatalyst containing layer side substrate having the 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 from a predetermined direction. The method includes a pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer.
[0032]
According to this embodiment, since the substrate for the pattern forming body has the property change layer, molecules on the property change layer are cut or decomposed by irradiating energy using the photocatalyst-containing layer side substrate. Thus, the characteristics of the characteristic change layer can be easily changed. Also, at this time, when halogen is contained in the characteristic change layer, the oxidative decomposition power of the photocatalyst containing layer can be improved by forming the pattern forming step continuously, thereby forming a constant characteristic change pattern. It can be difficult. This is not clear, but is considered to be caused by the following effects.
[0033]
When the property change layer is irradiated with energy using the photocatalyst-containing layer, on the property change layer, the photocatalyst that accompanies the energy irradiation causes the molecules constituting the property change layer to be cut or decomposed. The decomposed molecules are released into the atmosphere as gas such as radicals or ions. At this time, in the case where halogen, particularly fluorine, is contained in the characteristic change layer, a halogen gas atmosphere is formed by the decomposed halogen, and a part of the halogen gas is adsorbed on the photocatalyst containing layer. Therefore, when energy irradiation is continuously performed using the photocatalyst-containing substrate, the halogen is released to become radicals and the like, contributing to the characteristic change of the characteristic change layer. At this time, a halogen gas atmosphere containing the halogen adsorbed on the photocatalyst containing layer and the halogen generated from the new property change layer is formed, and these adsorb again on the photocatalyst containing layer. Therefore, when the pattern forming process is continuously performed, the amount of halogen radicals contributing to the characteristic change of the characteristic change layer gradually increases, and the oxidative decomposition ability of the photocatalyst containing layer is improved. Therefore, when the pattern formation process is continuously performed for the same time energy irradiation, or when the same energy amount is irradiated, the amount of radicals contributing to the molecular cutting or decomposition of the surface of the property change layer is reduced. Since they are different, it is considered difficult to form a constant characteristic change pattern continuously, for example, the pattern width increases.
[0034]
Here, in the present embodiment, since the halogen is not contained in the property change layer, when energy irradiation is performed using the photocatalyst containing layer, atoms released into the atmosphere are It is not adsorbed by the photocatalyst containing layer. Thereby, even if it is a case where the said photocatalyst containing layer side board | substrate is used continuously, the oxidative decomposition power of the said photocatalyst containing layer can be assumed to be unchanged. Therefore, it becomes possible to manufacture a large number of pattern forming bodies continuously, which is preferable from the viewpoint of manufacturing efficiency and cost. Furthermore, since there is no substance adsorbed on the photocatalyst-containing layer, the gap between the photocatalyst-containing layer and the characteristic change layer can be narrowed during energy irradiation. Thereby, the active oxygen species generated by the action of the photocatalyst accompanying the energy irradiation can reach the characteristic change layer without diffusing, and a pattern forming body in which a high-definition characteristic change pattern is formed is manufactured. Can do it.
[0035]
Hereinafter, each structure in the manufacturing method of the pattern formation body of this embodiment is demonstrated.
[0036]
a. Pattern forming substrate
First, the substrate for a pattern forming body used in this embodiment will be described. The substrate for the pattern forming body used in the present embodiment is not particularly limited as long as it has a property change layer that does not contain halogen, and the property is changed by the action of the photocatalyst accompanying energy irradiation. The characteristic change layer may be formed on a base material, or may be formed with a light shielding part or the like as necessary. Hereinafter, each member used for the substrate for pattern forming bodies of this embodiment is demonstrated.
[0037]
(1) Characteristic change layer
First, the characteristic change layer used in this embodiment will be described. The characteristic change layer used in this embodiment is a layer whose characteristics are changed by the action of the photocatalyst accompanying energy irradiation and does not contain halogen.
[0038]
Here, the characteristic change layer does not contain halogen means that the main chain, the side chain, or the additive in the molecule constituting the characteristic change layer does not contain halogen. It is preferable that a molecular chain in which molecules are cleaved or decomposed by the action of a photocatalyst accompanying irradiation does not contain halogen. Further, among the above halogens, it has been found that the oxidative decomposition power of the photocatalyst containing layer with respect to energy irradiation changes particularly when fluorine is contained. In this embodiment, fluorine is not particularly contained. It is preferable.
[0039]
In addition, the property change layer used in this embodiment is not particularly limited as long as the property changes due to the action of the photocatalyst associated with energy irradiation, and the type of property change is not particularly limited. The layer is not particularly limited, for example, a layer in which wettability is changed so that a contact angle with a liquid is lowered by the action of the photocatalyst, a layer to be decomposed and removed, or a layer in which adhesion to a biological substance is changed.
[0040]
In this embodiment, in particular, when 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 decomposition removal layer in which the property change layer is decomposed and removed by the action of the photocatalyst The two cases are particularly preferable from the viewpoint of easy formation of the functional part on the pattern forming body. Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0041]
(Wettability change layer)
The wettability changing layer used in this embodiment is a layer whose wettability changes so that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying energy irradiation, and does not contain halogen as described above. If there is, it will not be specifically limited.
[0042]
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.
[0043]
Here, the lyophilic region is a region having a small contact angle with the liquid, for example, 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.
[0044]
The wettability changing layer preferably has a contact angle with a liquid of 40 mN / m of 10 ° or more, particularly 40 ° 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 embodiment, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient. This is because the functional part forming coating liquid may remain on the liquid repellent region when the functional part forming coating liquid is applied, which is not preferable.
[0045]
The wettability changing layer preferably has a contact angle with a liquid of 40 mN / m of 9 ° or less, more preferably 5 ° 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.
[0046]
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.
[0047]
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.
[0048]
The wettability changing layer used in the present embodiment has the above-described characteristics and has a main chain that is not easily deteriorated by the action of the photocatalyst. In the molecules constituting the wettability changing layer, particularly accompanying energy irradiation. The side chain that is cleaved or decomposed by the action of the photocatalyst and contributes to the change in wettability is not particularly limited as long as it does not contain a halogen. The case where organopolysiloxane is contained in the wettability changing layer and (2) the case where the wettability changing layer is a monomolecular film are preferred. Hereinafter, each of these two cases will be described.
[0049]
(1) When organopolysiloxane is contained
First, the case where organopolysiloxane is contained in the wettability changing layer will be described. In this embodiment, by containing organopolysiloxane in the wettability changing layer, the wettability can be lowered by the action of the photocatalyst accompanying energy irradiation as described above.
[0050]
Examples of the organopolysiloxane contained in this embodiment include (a) an organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing an alkoxysilane that does not contain a halogen by sol-gel reaction or the like, and (b) Mention may be made of organopolysiloxanes such as organopolysiloxanes which are excellent in water repellency and crosslinked with halogen-free reactive silicones.
[0051]
In the case of (a) above, the general formula:
Y_nSiX_{( 4-n )}
(Here, Y includes an alkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3.)
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. In the silicon compound, organopolysiloxane is constituted by X being polycondensed or the like, and Y is a side chain of the organopolysiloxane. In this embodiment, the surface of the wettability changing layer before the energy irradiation can be made liquid repellent by the liquid repellency of Y in this side chain. Furthermore, when the Y is decomposed by the action of the photocatalyst accompanying energy irradiation, the energy irradiated region can be made lyophilic. Here, in the present embodiment, the photocatalyst described later is a molecule or atom released into the atmosphere by not having halogen (particularly fluorine) in Y that is decomposed by the action of the photocatalyst accompanying energy irradiation. The pattern forming body can be continuously produced stably without affecting the containing layer. Here, the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Moreover, it is preferable that carbon number of the group shown by said Y exists in the range of 5-16, especially in the range of 6-12. As a result, when the wettability changing layer is formed, the surface of the wettability changing layer can be made liquid repellent by the Y constituting the organopolysiloxane. This is because the region irradiated with energy can be made lyophilic by being decomposed. Further, when the number of carbon atoms of the group represented by Y is larger than the above range, the efficiency of decomposition of Y or the like decreases due to the action of the photocatalyst accompanying energy irradiation. In the present embodiment, the group represented by Y is particularly preferably an alkyl group among the above.
[0052]
Examples of the reactive silicone (b) include compounds having a skeleton represented by the following general formula.
[0053]
[Chemical 1]

[0054]
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 or a halogen in which hydrogen is not substituted, and 40% or less of the total is vinyl or phenyl. 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. In this embodiment, the above R¹And R²Can be cut or decomposed by the action of the photocatalyst accompanying energy irradiation, and the wettability of the wettability changing layer surface can be changed. Therefore, such R¹And R²By having no halogen (especially fluorine) therein, the pattern forming body can be stably produced continuously.
[0055]
Moreover, you may mix the stable organosilicon compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane. At this time, the organosilicon compound is also preferably one having no halogen (particularly fluorine) in the molecule.
[0056]
The wettability changing layer in this embodiment can further contain a surfactant not containing halogen. As the surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant can be used.
[0057]
In addition to the above surfactants, the wettability changing layer includes polyvinyl alcohol not containing halogen, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, Including melamine resin, polycarbonate, polyamide, polyimide, styrene butadiene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. be able to.
[0058]
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 necessary, and coating the coating liquid on a substrate described later. be able to. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0059]
In the present embodiment, the thickness of the wettability changing layer described above 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 due to the photocatalyst. Is within.
[0060]
(2) Case of monomolecular film
Next, the case where the wettability changing layer is a monomolecular film will be described. When the wettability changing layer is a monomolecular film, the wettability changing layer can be a uniform and dense layer. For example, when a functional part is formed on a characteristic change pattern described later, the functional part Can be formed uniformly and with high definition. Examples of such a monomolecular film include a self-assembled monomolecular film.
[0061]
Here, the self-assembled monomolecular film is an organic thin film that spontaneously forms a monomolecular film while organic molecules gather spontaneously at the solid / liquid or solid / gas interface to form an aggregate. It is. For example, when a substrate made of a specific material is exposed to a solution or vapor of an organic molecule having a high chemical affinity with the substrate material, the organic molecule chemically reacts and adsorbs on the substrate surface. If the organic molecule consists of two parts, a functional group with high chemical affinity and an organic chain that does not cause any chemical reaction with the substrate, the molecule reacts when the functional group with high affinity is at its end. The organic terminal is adsorbed with the substrate side facing and the organic chain facing the outside. When organic chains gather together, the whole becomes stable, so organic molecules gather spontaneously during the process of chemisorption. Since molecular adsorption requires a chemical reaction between the substrate and the terminal functional group, once the substrate surface is covered with organic molecules to form a monomolecular film, molecular adsorption does not occur thereafter. Absent. As a result, an organic monomolecular film in which molecules are closely gathered and aligned is formed.
[0062]
In this embodiment, when the wettability changing layer is the self-assembled monomolecular film, the organic compound having no liquid repellency existing on the surface of the wettability changing layer by the action of the photocatalyst accompanying energy irradiation. By removing the chain by the action of the photocatalyst accompanying energy irradiation, the surface can be easily made lyophilic, and the characteristic change pattern can be efficiently formed. In this embodiment, the organic chain having liquid repellency is free of halogen, so that the organic chain is cleaved or decomposed and released into the atmosphere by the action of the photocatalyst accompanying energy irradiation. Thus, it is possible to stably produce the pattern forming body continuously without affecting the photocatalyst containing layer described later.
[0063]
The material constituting the monomolecular film used as such a wettability changing layer is not particularly limited as long as it has the above-described characteristics and does not contain a halogen. A silane compound having an organic chain having no halogen is preferable. Here, the number of carbons constituting the organic chain having no halogen is preferably in the range of 5 to 16, more preferably in the range of 6 to 12. As a result, the wettability changing layer before energy irradiation can be made liquid repellent, and the organic chain can be decomposed by the action of the photocatalyst accompanying energy irradiation to make it lyophilic. In the present invention, the organic chain includes an alkyl group, phenyl group, amino group, fluoro group, epoxy group, vinyl group, styryl group, methacryloxy group, acryloxy group, ureido group, chloropropyl group, mercapto group, A succinimide group, a sulfide group, an isocyanate group, a carboxyl group, a bicyclo group, an imidazole group, and the like can be given. Among these, an alkyl group is particularly preferable.
[0064]
As the silane compound having an organic chain, specifically, the materials described in the above-mentioned organopolysiloxane section can be used.
[0065]
Such a wettability changing layer made of a monomolecular film can be formed by a thermal CVD method, a dip coating method, or the like, but in this embodiment, the thermal CVD method is from the viewpoint of production efficiency and the like. preferable. Preferable film forming conditions for the thermal CVD method are not particularly limited as long as they are equal to or lower than the heat resistance temperature of the base material to be described later, and are equal to or higher than the vaporization temperature of the raw material and are equal to or lower than the decomposition temperature. Usually, it is preferably within the range of 50 ° C to 200 ° C.
[0066]
In this embodiment, a known low pressure thermal CVD method may be used. The degree of vacuum during the reduced pressure thermal CVD process can be set so that a sufficient vapor pressure of the material can be obtained. The vapor pressure is appropriately selected depending on the type of material, but is usually 0.01 Torr to 10 Torr, and in particular, 5 Torr or less. At this time, in order to promote the reaction with the surface of the substrate, it is preferable to form a wettability changing layer by performing a low pressure CVD method while heating the substrate. The heating temperature in this case is appropriately selected depending on the material of the base material and the wettability changing layer, but is usually in the range of 40 ° C. to 100 ° C., particularly 80 ° C. or less.
[0067]
The film thickness of the wettability changing layer formed in this embodiment is determined by the type of the monomolecular film, but is usually in the range of 1 nm to 50 nm.
[0068]
(Decomposition removal layer)
Next, the case where the characteristic change layer used in the present invention is a decomposition removal layer will be described. When the decomposition / removal layer used in the present invention is a monomolecular film, it is a layer in which the decomposition / removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when irradiated with energy. is there. In this way, the decomposed / removed layer is decomposed / removed by the action of the photocatalyst, so that the pattern including the portion with and without the decomposed / removed layer without the development process or the cleaning process, that is, the unevenness Can be formed.
[0069]
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.
[0070]
In addition, the decomposition / removal layer used in the present invention not only forms irregularities, but the decomposition / removal layer has a higher contact angle with the liquid than the base material exposed by the decomposition / removal of the decomposition / removal layer. It is preferable. As a result, the decomposition removal layer is decomposed and removed, and the region where the base material is exposed can be made lyophilic, and the region where the decomposition removal layer remains can be made a liquid repellent region. This is because the functional part can be formed using the difference in wettability.
[0071]
Here, the lyophilic region is a region having a small contact angle with the liquid, for example, a region having good wettability with respect to the functional part forming coating liquid for forming the functional part. Further, the liquid repellent region is a region having a large contact angle with the liquid and means a region having poor wettability with respect to the functional part forming coating liquid.
[0072]
The decomposition removal layer preferably has a contact angle with a liquid of 40 mN / m of 10 ° or more, particularly 40 ° or more. In the present invention, since the remaining decomposition and removal layer is a part that requires liquid repellency, when the contact angle with the liquid is small, the liquid repellency is not sufficient and a functional part is formed. This is because the coating liquid for forming the functional part may remain in the liquid repellent region that is not used.
[0073]
In the present invention, the substrate described later preferably has a contact angle with a liquid of 40 mN / m of 9 ° or less, particularly 5 ° or less, in a portion where no energy is irradiated. In the present invention, since the base material is a part that requires lyophilicity, when the functional part forming coating solution is applied, the functional part forming coating solution may be repelled even in the lyophilic region. This is because it may be difficult to pattern the functional portion on the lyophilic region. Here, the contact angle with the liquid is a value measured by the method described above.
[0074]
Specific examples of the film that can be used for the decomposition removal layer as described above include a film made of a hydrocarbon-based resin having liquid repellency that does not contain halogen (particularly fluorine). By making the film used for such a decomposition / removal layer free of halogen, the molecules constituting the decomposition / removal layer are cleaved or decomposed by the action of the photocatalyst associated with the energy irradiation, so that the atmosphere Molecules released therein do not affect the photocatalyst-containing layer, which will be described later, and it becomes possible to continuously produce a pattern-forming body stably. Such a hydrocarbon-based resin is not particularly limited as long as it has liquid repellency, and these resins are dissolved in a solvent and, for example, a general film forming method such as a spin coating method is used. Can be formed.
[0075]
In the present invention, since a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, and an alternating adsorption film can be used, it is possible to form a film without defects. It can be said that it is more preferable to use such a film forming method.
[0076]
Here, the self-assembled monomolecular film, the Langmuir-Brocket film, and the alternating adsorption film used in the present invention will be specifically described.
[0077]
(1) Self-assembled monolayer
Examples of the material having the ability to form a self-assembled film not containing halogen (particularly fluorine) used in the present invention include, for example, surfactant molecules such as fatty acids, organic silicon molecules such as alkyl alkoxides, and organic materials such as alkanethiols. And organic phosphoric acid molecules such as sulfur molecules and 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 is the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, and a combination of these. Self-assembled monolayers composed of various molecules such as those of 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.
[0078]
(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).
[0079]
(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.
[0080]
In addition, the thickness of the decomposition removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the action of the photocatalyst associated with energy. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but 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.
[0081]
(2) Base material
Next, the base material used for the pattern forming body of this embodiment will be described. In the present embodiment, the base material is used when the above-described property change layer does not have self-supporting property, when strength is required, or when the property change layer is the decomposition removal layer, and the property change layer is formed on the base material. Is formed. Here, self-supporting means that it can exist in a tangible state without other supporting materials.
[0082]
The base material used in the present embodiment is appropriately selected according to the intended use of the finally obtained pattern forming body. For example, a paper laminate resin laminate, a glass cloth / glass nonwoven cloth base material, and the like. A resin laminate, ceramic, metal or the like can be used, and a plate-like one is preferable.
[0083]
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.
[0084]
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.
[0085]
(3) Other
Further, in the present embodiment, other members such as a light shielding portion such as a black matrix in a color filter are formed on the above-described base material or the characteristic change layer according to the use and type of the pattern forming body. It may be.
[0086]
In this embodiment, for example, when a light shielding part is formed on a base material and the base material is transparent, it becomes possible to perform irradiation of energy described later from the base material side of the substrate for the pattern forming body, Without using a photomask or the like, it is possible to change only the characteristics of the characteristic change layer on the region where the light shielding portion is not formed.
[0087]
b. Photocatalyst containing layer side substrate
Next, the photocatalyst containing layer side substrate used in this embodiment will be described. The photocatalyst-containing layer side substrate used in this embodiment has a photocatalyst-containing layer containing a photocatalyst and a substrate. Usually, the substrate and the photocatalyst-containing layer are formed on the substrate. 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 embodiment is demonstrated.
[0088]
(1) Photocatalyst containing layer
First, the photocatalyst containing layer used for the photocatalyst containing layer side substrate will be described. The photocatalyst-containing layer used in the present embodiment is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the above-described characteristic change layer, and includes a photocatalyst and a binder. It may be a film formed with a photocatalyst alone. Further, the surface characteristics may be particularly lyophilic or lyophobic.
[0089]
The photocatalyst-containing layer used in this embodiment may be one in which the photocatalyst-containing layer 5 is formed on the entire surface of the substrate 4 as shown in FIG. 1, for example, but as shown in FIG. The photocatalyst containing layer 5 may be formed on the pattern 4.
[0090]
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.
[0091]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0092]
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.
[0093]
In such a photocatalyst-containing layer, the mechanism of action of a photocatalyst represented by titanium dioxide as described later is not necessarily clear, but a carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In this embodiment, it is considered that this carrier acts on the compound in the property change layer on the photocatalyst containing layer. In the present embodiment, since the halogen is not contained in the above-described property changing layer, even when energy irradiation is performed using the photocatalyst containing layer side substrate, radicals generated by the halogen change the property. Does not affect the layer. That is, even when the photocatalyst-containing layer is repeatedly irradiated with energy, only a certain amount of active oxygen species generated by energy irradiation contributes to the characteristic change of the characteristic change layer, and stably forms the same characteristic change pattern. Can do it.
[0094]
As a photocatalyst used in this embodiment, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these.
[0095]
In this embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0096]
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.
[0097]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 80 nm or less, and the photocatalyst of 20 nm or less is particularly preferable.
[0098]
The photocatalyst-containing layer in this embodiment may be formed of a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0099]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change of characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening of the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0100]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst. Since it is possible and includes only the photocatalyst, it is possible to efficiently change the characteristics on the characteristic change layer as compared with the case where a binder is used.
[0101]
In addition, as another example of a method for forming a photocatalyst-containing layer comprising only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on a substrate and then changing the phase to crystalline titania by firing. Etc. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0102]
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.
[0103]
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.
[0104]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, a hydrolyzate thereof, silanol, or a polysiloxane having an average molecular weight of 3000 or less.
[0105]
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.
[0106]
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.
[0107]
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.
[0108]
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.
[0109]
(2) Substrate
Next, the base used for the photocatalyst-containing layer side substrate will be described. In this embodiment, as shown in FIG. 1, the photocatalyst-containing layer side substrate 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.
[0110]
The substrate used in this embodiment 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.
[0111]
Here, in this embodiment, since the characteristic change layer in the substrate for a pattern forming body does not contain a halogen, the oxidative decomposition power of the photocatalyst-containing layer is increased even when the photocatalyst-containing layer is repeatedly used. It can be constant. Accordingly, since the photocatalyst-containing layer side substrate can be repeatedly used, it is preferable that the substrate has a predetermined strength and the surface thereof has good adhesion to the photocatalyst-containing layer.
[0112]
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.
[0113]
(3) Photocatalyst containing layer side light shielding part
As the photocatalyst containing layer side substrate used in the present embodiment, 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.
[0114]
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.
[0115]
For example, as shown in FIG. 3, a photocatalyst-containing layer side light-shielding portion 10 is formed on a substrate 4, and a photocatalyst-containing layer 5 is formed on the photocatalyst-containing layer side light-shielding portion 10 to form a photocatalyst-containing layer side substrate. It is an aspect to make. For example, as shown in FIG. 4, the photocatalyst containing layer 5 is formed on the substrate 4 and the photocatalyst containing layer side light-shielding portion 10 is formed thereon to form a photocatalyst containing layer side substrate.
[0116]
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.
[0117]
Here, in this embodiment, when the photocatalyst containing layer side light-shielding portion 10 is formed on the photocatalyst containing layer 5 as shown in FIG. 4, the photocatalyst containing layer and the characteristic change layer are placed at predetermined positions. The photocatalyst-containing layer side light-shielding part is also 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. It has the advantage that it can be used.
[0118]
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. In this case, the direction of energy irradiation is not limited to the substrate side, and may be, for example, from the side surface of the substrate of the pattern forming substrate.
[0119]
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.
[0120]
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.
[0121]
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 part, a generally used method such as a photolithography method or a printing method can be used.
[0122]
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.
[0123]
(4) Primer layer
Next, the primer layer used for the photocatalyst containing layer side substrate of this embodiment will be described. In this embodiment, as described above, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate and the photocatalyst-containing layer is formed thereon to form the photocatalyst-containing layer side substrate, the photocatalyst-containing layer-side substrate is formed. A primer layer may be formed between the layer-side light shielding portion and the photocatalyst-containing layer.
[0124]
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.
[0125]
In this embodiment, the primer layer prevents impurities present in the opening formed between the photocatalyst containing layer side light shielding part as well as the photocatalyst containing layer side light shielding part from affecting the action of the photocatalyst. Therefore, it is preferable that the primer layer is formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.
[0126]
The primer layer in this embodiment 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 does not contact the photocatalyst containing layer.
[0127]
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.
[0128]
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.
[0129]
c. Arrangement of photocatalyst containing layer side substrate
Next, the arrangement of the photocatalyst-containing layer side substrate will be described. In this embodiment, the characteristic change layer described above changes the surface characteristics when the above-described photocatalyst containing layer on the photocatalyst containing layer side substrate is arranged with a predetermined gap and irradiated with energy. The arrangement of the photocatalyst-containing layer side substrate at this time requires that the photocatalyst-containing layer and the characteristic change layer be arranged at a predetermined interval so that the action of the photocatalyst is exerted during energy irradiation. After the photocatalyst containing layer and the characteristic change layer described above are arranged with a gap of 200 μm or less, energy is irradiated from a predetermined direction. At this time, the photocatalyst-containing layer and the characteristic change layer may be adhered to each other.
[0130]
In the present embodiment, the above gap is preferably in the range of 0.2 μm to 10 μm, especially considering the fact that the pattern accuracy is very good, the photocatalyst sensitivity is high, and therefore the efficiency of property change of the property change layer is good. Is preferably in the range of 1 μm to 5 μm. Such a gap range is particularly effective for a small-area pattern forming body capable of controlling the gap with high accuracy.
[0131]
On the other hand, when processing a pattern forming body having a large area of, for example, 300 mm × 300 mm, there is no contact between the photocatalyst-containing layer side substrate and the pattern forming body substrate. It is extremely difficult to form. Therefore, when the pattern forming body 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.
[0132]
When the pattern forming body having a relatively large area is irradiated with energy in this way, the setting of the gap in the positioning device between the photocatalyst containing layer side substrate and the pattern forming body substrate in the energy irradiation apparatus is in the range of 10 μm to 200 μm. Especially, it is preferable to set in the range of 25 micrometers-75 micrometers. By setting the set value within such a range, the pattern accuracy is not significantly reduced and the sensitivity of the photocatalyst is not greatly deteriorated, and the photocatalyst-containing layer side substrate and the pattern forming body substrate are not in contact with each other. This is because they can be arranged.
[0133]
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.
[0134]
In this embodiment, such an arrangement state only needs to be maintained at least during energy irradiation.
[0135]
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.
[0136]
In this embodiment, such a spacer may be formed as one member, but for simplification of the process, etc., as described in the column of the photocatalyst containing layer side substrate, It is preferable to form on the surface of the photocatalyst containing layer. In the above description of the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side light-shielding portion has been described. Since what is necessary is just to have the effect | action which protects, it may be formed with the material which does not have a function which shields especially the energy irradiated.
[0137]
d. Energy irradiation
Next, energy irradiation in this embodiment will be described. In the present embodiment, the characteristic change pattern is formed on the above-described characteristic change layer by irradiating energy to the facing portion while maintaining the arrangement as described above.
[0138]
The energy irradiation (exposure) referred to in the present embodiment is a concept including irradiation of any energy ray that can change the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is limited to irradiation with visible light. Is not to be done.
[0139]
Usually, the wavelength of light used for such energy irradiation is set in a range of 400 nm or less, preferably in a range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0140]
Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0141]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0142]
Further, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for the characteristic change layer surface to change the characteristics of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0143]
At this time, it is preferable in that the energy decomposition can be increased by irradiating energy while heating the photocatalyst-containing layer, and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0144]
The energy irradiation direction in the present embodiment is a method of forming a characteristic change pattern such as whether or not a light-shielding part is formed on the photocatalyst-containing layer side light-shielding part or pattern forming body substrate side, a photocatalyst-containing layer side substrate or pattern It is determined by whether or not the formed body substrate is transparent.
[0145]
That is, when the photocatalyst containing layer side light shielding portion is formed, it is necessary to irradiate energy from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate is transparent to the energy irradiated. Need to be. In this case, when the photocatalyst-containing layer side light-shielding part is formed on the photocatalyst-containing layer and this photocatalyst-containing layer side light-shielding part is used so as to function as a spacer as described above, the energy irradiation direction May be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.
[0146]
On the other hand, when the light shielding part is formed on the pattern forming substrate side, it is necessary to irradiate energy from the pattern forming substrate side, and in this case, the energy with which the pattern forming substrate is irradiated Must be transparent to In this case as well, a light shielding part is formed on the pattern forming body substrate side on the characteristic change layer, and the light shielding part on the pattern forming body substrate side has a function as a spacer as described above. In this case, the energy irradiation direction may be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.
[0147]
In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on the side where the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming body side substrate needs to be transparent.
[0148]
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is separated from the arrangement position with the characteristic change layer, thereby forming a characteristic change pattern, and pattern formation with different degree of characteristic change in the characteristic change pattern It becomes the body.
[0149]
In the present invention, as described above, even when the photocatalyst-containing layer is repeatedly used, the oxidative decomposition power does not change. It is possible to produce a pattern forming body by performing energy irradiation using a layer side substrate.
[0150]
2. Second embodiment
Next, a second embodiment in the method for producing a pattern forming body of the present invention will be described. The second embodiment of the method for producing a patterned product of the present invention comprises a substrate for a patterned product having a property changing layer whose properties are changed by the action of a photocatalyst accompanying energy irradiation, a photocatalyst-containing layer containing a photocatalyst, and a substrate. The photocatalyst-containing layer side substrate having the gap between the characteristic change layer and the photocatalyst containing layer is 200 μm or less, and then irradiating energy from a predetermined direction on the surface of the characteristic change layer. A pattern forming body manufacturing method in which a pattern forming process for forming a characteristic change pattern having changed characteristics is continuously performed 10 or more times on different pattern forming body substrates, and is formed by the pattern forming process performed at the 10th time. The width of the characteristic change pattern to be formed is the characteristic change pattern formed by the pattern forming process performed for the first time. The width of the over emissions, a method is within a predetermined range.
[0151]
Here, performing the characteristic change pattern forming step on the substrate for different pattern forming bodies 10 times or more continuously means that the photocatalyst containing layer is washed or the characteristic change layer and the photocatalyst containing layer are sufficiently widened. After arranging them at intervals, the step of changing the oxidative decomposition power of the photocatalyst-containing layer, such as a step of irradiating energy from a predetermined direction, is performed with respect to the characteristic change layer in the substrate for 10 or more pattern formers. Then, the step of irradiating energy using the photocatalyst-containing layer side substrate is performed.
[0152]
According to this embodiment, the width of the characteristic change pattern formed by the pattern formation process performed for the tenth time is compared with the width of the characteristic change pattern formed by the pattern formation process performed for the first time. Since it is within the predetermined range, even if the pattern forming process is continuously performed 10 times or more, the shape of the characteristic change pattern can be made constant, and the pattern forming body can be manufactured stably. It can be done. Thereby, a pattern formation body can be manufactured in large quantities continuously, and it can be preferable also from the surface of cost or manufacturing efficiency.
[0153]
Here, in this embodiment, the width of the characteristic change pattern formed by the pattern formation process performed for the tenth time is set to the width of the characteristic change pattern formed by the pattern formation process performed for the first time. On the other hand, it is preferably within a range of 0.75 times to 1.25 times, more preferably within a range of 0.8 times to 1.2 times, and within a range of ± 20 μm, particularly within a range of ± 10 μm. Preferably there is.
[0154]
In this embodiment, the pattern forming step is preferably performed 10 times or more, more preferably 50 times or more, and particularly preferably 500 times or more, and the upper limit is usually 10,000 times or less.
[0155]
In this embodiment, it is possible to realize that the pattern forming process is performed continuously 10 times or more and the accuracy of the characteristic change pattern is within the above range in the above-described characteristic change layer. Since the manufacturing method of the pattern forming body in the case where no halogen is contained in the characteristic change layer is the same as that in the first embodiment, the description thereof is omitted here.
[0156]
B. Functional element
Next, the functional element of the present invention will be described. In the functional element of the present invention, a functional part is formed on the characteristic change pattern of the pattern forming body manufactured by the method for manufacturing a pattern forming body described above.
[0157]
According to the present invention, it is possible to easily form a high-definition functional part using the difference in characteristics such as wettability and unevenness of the characteristic change pattern. Moreover, since the characteristic change pattern of the pattern formed body continuously manufactured by the above-described pattern formed body manufacturing method has a constant shape and can be manufactured continuously, it is preferable in terms of cost and manufacturing efficiency. It can be a functional element.
[0158]
Here, the term “functionality” means optical (light selective absorption, reflectivity, polarization, light selective transmission, nonlinear optical property, luminescence such as fluorescence or phosphorescence, photochromic property, etc.), magnetic (hard magnetism, soft magnetism, etc.). , Non-magnetic, magnetically permeable, etc.), electrical / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorptive, desorbable, catalytic, water-absorbing, ionic conductivity) , Redox, electrochemical properties, electrochromic, etc.), mechanical (wear resistance, etc.), thermal (heat transfer, heat insulation, infrared radiation, etc.), biofunctional (biocompatibility, antithrombotic, etc.) ) Means various functions.
[0159]
The method of forming the functional part in the present invention is appropriately selected according to the type of change in the characteristics of the above characteristic change pattern. For example, when the characteristic change layer is a wettability change layer, dip coating, roll It is possible to use means such as coating means, blade coating, spin coating, or other coating means, or nozzle ejection means including ink jet, dispenser, etc. Among them, it is preferable to use nozzle ejection means in the present invention. In the nozzle discharge means, it is possible to apply a functional part forming composition for forming a functional part in a target pattern, and it is possible to form the functional part with higher definition. It is.
[0160]
In addition, when the property change layer is, for example, a decomposition removal layer, it is preferable to use means such as a nozzle discharge means including an ink jet, a dispenser, etc., thereby making it possible to use the unevenness of the decomposition removal layer to achieve high definition. This is because the functional part can be formed.
[0161]
In addition, when the property change layer is, for example, an adhesion change layer, in addition to the above method, vapor deposition, electroless plating, or the like can be used, and after the functional part forming composition is formed, By removing the functional part forming composition attached to the adhesion-inhibiting region, the functional part forming composition can be brought into close contact only with the good adhesion region, and the functional part can be formed. It is.
[0162]
Here, as a material of the composition for forming a functional part, both a solvent type material and a non-solvent type material can be used. In the present invention, a solvent type material is preferable. The functional part in the present invention preferably has a functional part having a different film thickness along the characteristic change pattern. When the solvent is volatilized by using a solvent-type material, This is because the difference in film thickness can be made large.
[0163]
Here, as a functional element formed by the present invention, a preferable one is a color filter in which the functional part is a pixel part, a microlens in which the functional part is a lens, or the functional part is attached to a biomolecule. It is preferably a biomolecule culture section or the like that can be used as a biomolecule medium.
[0164]
The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and any structure that has substantially the same configuration as the technical idea described in the claims of the present embodiment and has the same effect can be used. It is included in the technical scope of this embodiment.
[0165]
【Example】
Hereinafter, the present invention will be described in more detail through examples and comparative examples.
[0166]
[Example 1]
A solution composed of 0.7 g of dodecylalkylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.36 g of 0.005N HCl (aqueous solution) was stirred at 20 ° C. for 24 hours, and then the solution was 100 times (by mass) with isopropyl alcohol. The composition for forming a wettability changing layer was obtained. Using this composition for forming a wettability changing layer, spin coating was performed on a glass substrate and dried at a temperature of 150 ° C. for 10 minutes to obtain a substrate for a pattern forming body having a transparent and uniform wettability changing layer.
[0167]
Next, an aqueous dispersion of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) is formed on the mask pattern side of a photomask having a mask pattern in which a Cr thin film is formed in a stripe shape having a width of 70 μm and a pitch of 100 μm on a glass substrate. The product name: “ST-K03”) was spin-coated and dried by heating to form a transparent photocatalyst-containing layer, which was a photocatalyst-containing layer side substrate.
[0168]
The photocatalyst-containing layer on the photocatalyst-containing layer side substrate and the photocatalyst-containing layer are opposed to the wettability changing layer with a gap of 50 μm. 20 mW / cm²The film was exposed by irradiating at an illuminance of 5 to form a wettability changing pattern on the surface of the wettability changing layer. In the obtained wettability change pattern, the contact angle with water in the unexposed part is 105 °, the contact angle with liquid with a surface tension of 40 mN / m is 65 °, and the contact angle with water in the exposed part is It took 210 seconds for the contact angle with a liquid having a surface tension of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. Moreover, the width | variety of the unexposed part was 69 micrometers and the width | variety of the exposed part was 31 micrometers.
[0169]
Subsequently, 20 exposures for 210 seconds were continuously performed on the same substrate for a pattern forming body as described above. In the 20th pattern forming substrate, the width of the unexposed portion was 68 μm and the width of the exposed portion was 32 μm.
[0170]
[Example 2]
A substrate for a pattern former was obtained in the same manner as in Example 1 except that hexaalkylsilane (GE Toshiba Silicone Co., Ltd. TSL-8241) was used instead of dodecylalkylsilane (Tokyo Chemical Industry Co., Ltd.). Then, exposure was performed using the same photocatalyst-containing layer side substrate as in Example 1. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 90 °, the contact angle with liquid with a surface tension of 40 mN / m is 45 °, and the contact angle with water in the exposed area is 45 °. It took 120 seconds for the contact angle with a liquid having a surface tension of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. Moreover, the width | variety of the unexposed part was 70 micrometers and the width | variety of the exposed part was 30 micrometers.
[0171]
Subsequently, 20 exposures for 120 seconds were continuously performed on the same substrate for a pattern forming body as described above. In the 20th substrate for pattern formation, the width of the unexposed portion was 71 μm and the width of the exposed portion was 29 μm.
[0172]
[Example 3]
A substrate for a pattern forming body was obtained in the same manner as in Example 1 except that phenylmethoxysilane (GE Toshiba Silicone Co., Ltd. TSL-8172) was used instead of dodecylalkylsilane (Tokyo Chemical Industry Co., Ltd.). Then, exposure was performed using the same photocatalyst-containing layer side substrate as in Example 1. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 60 °, the contact angle with liquid with a surface tension of 40 mN / m is 30 °, and the contact angle with water in the exposed area is 30 °. It took 150 seconds for the contact angle with a liquid having a surface tension of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. The width of the unexposed part was 71 μm and the width of the exposed part was 29 μm.
[0173]
Subsequently, 20 exposures for 150 seconds were continuously performed on the same substrate for a pattern forming body as described above. In the 20th substrate for pattern formation, the width of the unexposed portion was 69 μm and the width of the exposed portion was 31 μm.
[0174]
[Example 4]
A pattern was obtained in the same manner as in Example 1 except that γ-glycidoxypropylmethyldimethoxysilane (GE Toshiba Silicone Co., Ltd. TSL-8355) was used instead of dodecylalkylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.). The formed body substrate was obtained and exposed using the same photocatalyst-containing layer side substrate as in Example 1. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 60 °, the contact angle with liquid having a surface tension of 40 mN / m is 25 °, and the contact angle with water in the exposed area is 25 °. It took 180 seconds for the contact angle with a liquid of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. Moreover, the width | variety of the unexposed part was 70 micrometers and the width | variety of the exposed part was 30 micrometers.
[0175]
Subsequently, 20 exposures for 180 seconds were continuously performed on the same substrate for a pattern forming body as described above. In the 20th substrate for pattern formation, the width of the unexposed portion was 71 μm and the width of the exposed portion was 29 μm.
[0176]
[Example 5]
By putting a solution consisting of 1.5 g of decylalkylsilane (LS-5258 manufactured by Shin-Etsu Silicone Co., Ltd.) and 30 g of isopropyl alcohol into a container and putting it in an oven heated to 240 ° C. to vaporize the decylalkylsilane, The atmosphere in the oven was decylalkylsilane. A glass substrate was put in the oven in the decylalkylsilane atmosphere, and decylalkylsilane was deposited on the glass substrate surface. Exposure was performed in the same manner as in Example 1 using the pattern forming substrate thus prepared. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 100 °, the contact angle with liquid with a surface tension of 40 mN / m is 65 °, and the contact angle with water in the exposed area is It took 180 seconds for the contact angle with a liquid of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. The width of the unexposed part was 71 μm and the width of the exposed part was 29 μm.
[0177]
Subsequently, 20 exposures for 180 seconds were continuously performed on the same substrate for a pattern forming body as described above. In the 20th substrate for pattern formation, the width of the unexposed portion was 69 μm and the width of the exposed portion was 31 μm.
[0178]
[Comparative Example 1]
A solution comprising 1.5 g of heptadecafluorodecyltrimethoxysilane (TSL-8233 manufactured by Toshiba Silicone), 3.5 g of tetramethoxysilane (TSL-8114 manufactured by Toshiba Silicone) and 2.36 g of 0.005N HCl (aqueous solution) was prepared. After stirring at 20 ° C. for 24 hours, the solution was diluted 100 times (mass basis) with isopropyl alcohol to obtain a composition for forming a wettability changing layer. Using this composition for forming a wettability changing layer, spin coating was performed on a glass substrate and dried at a temperature of 150 ° C. for 10 minutes to obtain a substrate for a pattern forming body having a transparent and uniform wettability changing layer.
[0179]
The pattern forming body substrate was subjected to wettability change pattern formation in the same manner as in Example 1. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 110 °, the contact angle with liquid with a surface tension of 40 mN / m is 80 °, and the contact angle with water in the exposed area is It took 180 seconds for the contact angle with a liquid of 10 ° or less and a surface tension of 40 mN / m to be 9 ° or less. Further, the width of the unexposed portion at the time of the first exposure was 70 μm, and the width of the exposed portion was 30 μm.
[0180]
Subsequently, when 20 sheets are continuously formed on the same pattern forming substrate as described above, the width of the unexposed portion is 20 μm and the width of the exposed portion is 80 μm in the 20th pattern forming substrate. It was confirmed that the width of the exposed portion was widened.
[0181]
[Comparative Example 2]
Substrate for patterned body in the same manner as Comparative Example 1 except that tridecafluorooctyltrimethoxysilane (TSL-8257 made by Toshiba Silicone) was used instead of heptadecafluorodecyltrimethoxysilane (TSL-8233 made by Toshiba Silicone) Was exposed and exposed in the same manner as in Example 1 to form a wettability change pattern. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 110 °, the contact angle with liquid with a surface tension of 40 mN / m is 80 °, and the contact angle with water in the exposed area is 10 °. It took 150 seconds for the contact angle with the liquid having a surface tension of 40 mN / m or less to be 9 degrees or less. In addition, the width of the unexposed portion during the first exposure was 71 μm, and the width of the exposed portion was 29 μm.
[0182]
Subsequently, when 20 sheets are continuously formed on the same pattern forming substrate as described above, the width of the unexposed portion is 22 μm and the width of the exposed portion is 78 μm in the 20th pattern forming substrate. It was confirmed that the width of the exposed portion was widened.
[0183]
【The invention's effect】
According to the present invention, since the substrate for the pattern forming body has the property change layer, by irradiating energy using the photocatalyst-containing layer side substrate, the molecules of the property change layer are decomposed, and the surface It is possible to form the above-described characteristic change pattern in which the characteristic is changed. Here, as a result of research by the present inventors, when the characteristic change layer contains halogen, the photocatalyst-containing layer is used by continuously using the photocatalyst-containing layer side substrate in the pattern forming step. It was found that the oxidative degradation power of selenium changed. According to the present invention, since the halogen is not contained in the property change layer, the oxidative decomposition power of the photocatalyst containing layer is made constant even when the photocatalyst containing layer side substrate is continuously used. Therefore, it is possible to efficiently and continuously produce a high-definition pattern forming body stably.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an example of a method for producing a pattern-formed body of the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of a photocatalyst-containing layer side substrate used in the method for producing a pattern formed body of the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the method for producing a patterned body of the present invention.
FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the method for producing a pattern forming body of the present invention.
[Explanation of symbols]
1 ... Base material
2… Characteristic change layer
3 ... Pattern forming substrate
4 ... Base
5 ... Photocatalyst containing layer
6 ... Photocatalyst-containing layer side substrate
7 ... Photomask
8… Energy
9 ... Characteristic change pattern

Claims (14)

A pattern forming body substrate having a characteristic change layer that does not contain a halogen and that has characteristics changed by the action of a photocatalyst associated with energy irradiation, a photocatalyst-containing layer and a substrate, and further contacts the photocatalyst-containing layer After arranging the photocatalyst containing layer side substrate having the photocatalyst containing layer side light-shielding part formed as described above with a gap so that the characteristic change layer and the photocatalyst containing layer are 200 μm or less, energy is applied from a predetermined direction. And a pattern forming step of forming a characteristic change pattern having changed characteristics on the surface of the characteristic change layer by irradiating the pattern.   The photocatalyst-containing layer side substrate is formed by forming a photocatalyst-containing layer side light-shielding portion on the base and forming the photocatalyst-containing layer side light-shielding portion on the photocatalyst-containing layer side light-shielding portion. 2. A method for producing a pattern forming body according to 1.   The photocatalyst containing layer side substrate is a substrate in which a photocatalyst containing layer is formed on the substrate, and the photocatalyst containing layer side light shielding portion is formed on the photocatalyst containing layer. The manufacturing method of the pattern formation body of. The said characteristic change layer is a wettability change layer in which a contact angle with a liquid falls by the effect | action of the photocatalyst accompanying energy irradiation, The claim in any one of Claim 1 to 3 characterized by the above-mentioned. The manufacturing method of the pattern formation body of. The wettability changing layer is Y _n SiX _(4-n) (where Y includes an alkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or a halogen. n is an integer of 0 to 3.) claims, characterized in that the is an organopolysiloxane which is one or two or more hydrolytic condensate or cohydrolysis condensate of a silicon compound represented by the 4 The manufacturing method of the pattern formation body of description. The method for producing a pattern forming body according to claim 5 , wherein the number of carbon atoms of Y constituting the organopolysiloxane is in the range of 5 to 16. The method for producing a pattern forming body according to claim 4 , wherein the wettability changing layer is a monomolecular film. The method for producing a pattern forming body according to claim 7 , wherein the monomolecular film is made of a silane compound having an organic chain. The number of carbon which comprises the said organic chain exists in the range of 5-16, The manufacturing method of the pattern formation body of Claim 8 characterized by the above-mentioned. The said characteristic change layer is a decomposition removal layer decomposed and removed by the effect | action of the photocatalyst accompanying energy irradiation, The manufacturing of the pattern formation body in any one of Claim 1 to 3 characterized by the above-mentioned. Method. The contact angle with the liquid with a surface tension of 40 mN / m of the decomposition removal layer is 10 ° or more, and the contact angle with the liquid with a surface tension of 40 mN / m of the substrate exposed by the decomposition removal of the decomposition removal layer, It is 9 degrees or less, The manufacturing method of the pattern formation body of Claim 10 characterized by the above-mentioned. Method for manufacturing a patterned member according to claim 10 or claim 11, wherein the decomposition removal layer is a monomolecular film.   A substrate for a pattern forming body having a property change layer that does not contain a halogen, the property of which is changed by the action of a photocatalyst accompanying energy irradiation, and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a substrate, After the characteristic change layer and the photocatalyst-containing layer are arranged with a gap so as to be 200 μm or less, a characteristic change pattern with changed characteristics is formed on the surface of the characteristic change layer by irradiating energy from a predetermined direction. The pattern forming process is a method of manufacturing a pattern forming body that is performed continuously 10 times or more on different pattern forming body substrates, and the width of the characteristic change pattern formed by the pattern forming process performed the 10th time is: With respect to the width of the characteristic change pattern formed in the first pattern formation step, a range of ± 20 μm is obtained. Method for manufacturing a patterned member, wherein a change in the inner. A function part is formed on the characteristic change pattern of the pattern forming body manufactured by the method for manufacturing a pattern forming body according to any one of claims 1 to 13. Sex element.

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