JP4231685B2 - Method for producing pattern forming body - Google Patents

Description

【００６４】
ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１、Ｒ^２がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００６５】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコーン化合物を混合してもよい。
【００６６】
本発明においては、このようにオルガノポリシロキサン等の種々の材料を濡れ性変化層に用いることができるのであるが、上述したように、濡れ性変化層にフッ素を含有させることが、濡れ性のパターン形成に効果的である。したがって、光触媒の作用により劣化・分解しにくい材料にフッ素を含有させる、具体的にはオルガノポリシロキサン材料にフッ素を含有させて濡れ性変化層とすることが好ましいといえる。
【００６７】
本発明における濡れ性変化層には、さらに界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００６８】
また、濡れ性変化層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００６９】
このような濡れ性変化層は、上述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基体上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【００７０】
また、上述したように、本発明の濡れ性変化層は自己支持性を有する材料であってもよく、自己支持性を有する材料としては、上述した材料を成膜したものが自己支持性を有するものであれば、これを用いることも可能であるが、例えば、ポリエチレン、ポリカーボネート、ポリプロピレン、ポリスチレン、ポリエステル、ポリビニルフロライド、アセタール樹脂、ナイロン、ABS、PTFE、メタクリル樹脂、フェノール樹脂、ポリ弗化ビニリデン、ポリオキシメチレン、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレンテレフタレート、シリコーン等を挙げることができる。
【００７１】
ｂ．分解除去層
次に分解除去層について説明する。本発明に用いられる分解除去層は、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層であれば、特に限定されるものではない。
【００７２】
このように分解除去層は、エネルギー照射した部分が光触媒の作用により分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分からなるパターン、すなわち凹凸を有するパターンを形成することができる。
【００７３】
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。
【００７４】
また、本発明に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、上記基体表面と比較して、液体との接触角が高いことが好ましい。これにより、分解除去層が分解除去され、基体が露出した領域を親液性領域、上記分解除去層が残存する領域を撥液性領域とすることが可能となり、種々のパターンを形成することが容易となるからである。
【００７５】
ここで、上記エネルギー照射により基体が露出した領域である親液性領域と、エネルギー未照射の残存する分解除去層からなる領域である撥液性領域との特性が、例えばパターン形成体上に機能性部を形成する場合、その機能性部を形成する機能性部用組成物が有する表面張力と同等の表面張力の液体に対する接触角において、少なくとも１°以上、好ましくは５°以上、特に１０°以上異なる親液性領域および撥液性領域から形成されたパターンであることが好ましい。
【００７６】
また、本発明の分解除去層表面の液体との接触角は、表面張力４０ｍＮ／ｍの液体との接触角が１０°以上、好ましくは表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、特に表面張力２０ｍＮ／ｍの液体との接触角が１０°以上の値を示すことが好ましい。
【００７７】
また、本発明において、特性変化層が分解除去層である場合には、後述する基体が親液性であることが好ましく、具体的には、表面張力４０ｍＮ／ｍの液体との接触角として９°以下であることが好ましく、さらに好ましくは、表面張力４０ｍＮ／ｍの液体との接触角として５°以下、特に好ましくは１°以下であることである。
【００７８】
分解除去層および基体の濡れ性が、上記範囲内であることにより、基体が露出した領域を親液性領域、分解除去層が残存する領域を撥液性領域とすることが可能となり、高精細なパターンの形成が容易となるからである。ここで、液体との接触角は、上述した方法により測定した値である。
【００７９】
この場合、後述する基体は表面を親液性となるように、表面処理したものであってもよい。材料の表面を親液性となるように表面処理した例としては、アルゴンや水などを利用したプラズマ処理による親液性表面処理が挙げられ、基体上に形成する親液性の層としては、例えばテトラエトキシシランのゾルゲル法によるシリカ膜等を挙げることができる。本発明においては、通常基体が露出した部分が親液性領域とされる。
【００８０】
上記のような分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【００８１】
また、本発明においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【００８２】
ここで、本発明に用いられる自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜について具体的に説明する。
【００８３】
（ｉ）自己組織化単分子膜
自己組織化単分子膜(Self-Assembled Monolayer)の公式な定義の存在を発明者らは知らないが、一般的に自己組織化膜として認識されているものの解説文としては、例えばAbraham Ulmanによる総説“Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996)が優れている。本総説を参考にすれば、自己組織化単分子膜とは、適当な分子が適当な基体表面に吸着・結合（自己組織化）した結果生じた単分子層のことと言える。自己組織化膜形成能のある材料としては、例えば、脂肪酸などの界面活性剤分子、アルキルトリクロロシラン類やアルキルアルコキシド類などの有機ケイ素分子、アルカンチオール類などの有機イオウ分子、アルキルフォスフェート類などの有機リン酸分子などが挙げられる。分子構造の一般的な共通性は、比較的長いアルキル鎖を有し、片方の分子末端に基体表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基体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。
【００８４】
（ii）ラングミュア−ブロジェット膜
本発明に用いられるラングミュア−ブロジェット膜(Langmuir-Blodgett Film)は、基体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、これを適当な基体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。
【００８５】
（iii）交互吸着膜
交互吸着膜(Layer-by-Layer Self-Assembled Film)は、一般的には、最低２個の正または負の電荷を有する官能基を有する材料を逐次的に基体上に吸着・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。
【００８６】
また、分解除去層の膜厚としては、後述するエネルギー照射工程において照射されるエネルギーにより分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、０．００１μｍ〜１μｍの範囲内、特に０．０１μｍ〜０．１μｍの範囲内とすることが好ましい。
【００８７】
（２）基体
次に、本発明における基体について説明する。本発明においては、上記特性変化層が自己支持性のない材料である場合、分解除去層である場合、またはパターン形成体用基板に強度が必要な場合等に、例えば図１に示すように、基体４上に特性変化層５が設けられる。
【００８８】
この基体としては、上述した特性変化層が形成されるものであれば、特に限定されるものでなく、パターン形成体の用途に応じて、可撓性を有するものであっても、可撓性を有さないものであってもよい。
【００８９】
また、特に材料等は限定されるものではなく、必要に応じて種々の材料を用いることができる。具体的には、ガラス、アルミニウム、およびその合金等の金属、プラスチック、織物、不織布等を挙げることができる。
【００９０】
２．光触媒含有層側基板
次に、本発明に用いられる光触媒含有層側基板について説明する。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は、少なくとも光触媒含有層と基材とを有するものであり、通常は基材上に所定の方法で形成された薄膜状の光触媒含有層が形成されてなるものである。以下、この光触媒含有層側基板の各構成について説明する。
【００９１】
（光触媒含有層）
本発明に用いられる光触媒含有層は、光触媒含有層中の光触媒が、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、光触媒単体で成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。
【００９２】
また、光触媒含有層と特性変化層との間にマスクを介在させてエネルギー照射を行うことにより、光触媒による作用が拡散せず、効率よく特性変化層の特性を変化させることができる。さらに、エネルギー照射方向は、上記光触媒含有層と特性変化層とがマスクを介して対向するマスク中の小孔部分にエネルギー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】
このような光触媒含有層における、後述するような二酸化チタンに代表される光触媒の作用機構は、必ずしも明確なものではないが、光の照射によって生成したキャリアが、近傍の化合物との直接反応、あるいは、酸素、水の存在下で生じた活性酸素種によって、有機物の化学構造に変化を及ぼすものと考えられている。本発明においては、このキャリアが光触媒含有層と対向する特性変化層中の化合物に作用を及ぼすものであると思われる。
【００９４】
本発明で使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【００９５】
本発明においては、特に二酸化チタンが、バンドギャップエネルギーが高く、化学的に安定で毒性もなく、入手も容易であることから好適に使用される。二酸化チタンには、アナターゼ型とルチル型とがあり本発明ではいずれも使用することができるが、アナターゼ型の二酸化チタンが好ましい。アナターゼ型二酸化チタンは励起波長が３８０ｎｍ以下にあるからである。
【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５０ｎｍ以下であることが好ましく、２０ｎｍ以下の光触媒を使用するのが特に好ましい。
【００９８】
本発明における光触媒含有層は、上述したように光触媒単独で形成されたものであってもよく、またバインダと混合して形成されたものであってもよい。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。
【００９９】
光触媒のみからなる光触媒含有層の他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成膜法を用いる方法を挙げることができる。真空成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。
【０１００】
また、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。
【０１０１】
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、例えば上述した特性変化層の、濡れ性変化層の説明の欄で詳しく説明したオルガノポリシロキサン等を挙げることができる。
【０１０２】
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。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ができる。
【０１０３】
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。
【０１０４】
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。
【０１０５】
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重量％〜６０重量％、好ましくは２０重量％〜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、０．０５μｍ〜１０μｍの範囲内が好ましい。
【０１０６】
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。
【０１０７】
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。
【０１０８】
（基材）
本発明においては、図１（ａ）に示すように、光触媒含有層側基板３は、少なくとも基材１とこの基材１上に形成された光触媒含有層２とを有するものである。
【０１０９】
この際、用いられる基材を構成する材料は、後述するパターンの形成におけ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】
すなわち、例えばパターン形成体用基板が、紙基材フェノール樹脂積層板といった不透明なものを基体として用いる場合においては、エネルギー照射方向は必然的に光触媒含有層側基板側からとなり、図１（ｂ）に示すように、エネルギー照射をする必要がある。このような場合においては、基材は透明性を有するものであることが必要となる。
【０１１１】
一方、パターン形成体用基板の基体が、例えば透明樹脂フィルムである場合等であれば、パターン形成体用基板側からエネルギー照射することも可能である。このような場合においては、基材の透明性は特に必要とされない。
【０１１２】
また、本発明に用いられる基材は、可撓性を有するもの、例えば樹脂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、後述する特性変パターンの形成におけるエネルギー照射方法により適宜選択される。
【０１１３】
このように、本発明における光触媒含有層側基板に用いられる基材は、特にその材料を限定されるものではないが、本発明においては、この光触媒含有層側基板は、繰り返し用いられるものであることから、所定の強度を有し、かつその表面と光触媒含有層との密着性が良好である材料が好適に用いられる。
【０１１４】
具体的には、ガラス、セラミック、金属、プラスチック等を挙げることができる。
【０１１５】
なお、基材表面と光触媒含有層との密着性を向上させるために、基材上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１１６】
３．マスク
次に、本発明に用いられるマスクについて説明する。本発明において用いられるマスクは、後述するエネルギー照射の際に、上述した光触媒含有層側基板における光触媒含有層と、上述したパターン形成体用基板における特性変化層との間に配置され、エネルギー照射による光触媒の作用により発生した活性酸素種を特性変化層にパターン状に到達させるためのものである。
【０１１７】
本発明に用いられるマスクは、特性変化層の特性を変化させるパターン状に小孔を有するものであり、上記マスクの厚さは、２ｍｍ以下、中でも１００μｍ以下であることが好ましい。本発明においてマスクは、上記光触媒含有層と上記濡れ性変化層との間隔を決定するものであることから、上記値よりマスクの厚さが厚い場合は、生じた活性酸素種が特性変化層に届き難くなり、特性変化の速度を遅くしてしまう可能性があるからである。また、マスクの厚さの下限は１μｍである。これは、マスクの厚さが上記値より薄い場合には、高精細なマスクを形成することが困難となるからである。
【０１１８】
また、本発明のマスクに形成される小孔は、目的とするパターン形成体のパターンにより、その形状や大きさ等は適宜選択される。
【０１１９】
ここで、本発明に用いられるマスクは、その材料等はエネルギー照射による光触媒の作用により発生する活性酸素種を透過させるものでなければ、特に限定されるものではなく、透明なものでも不透明なものであってもよく、また可撓性を有するものであってもよい。
【０１２０】
本発明に用いられるマスクの材料として、具体的には金属、ガラスやセラミック等の無機物、またはプラスチック等の有機物等を挙げることができ、中でも金属であることが好ましい。本発明においては、上記マスクが金属からなるものであることにより、容易に特性変化層の特性を変化させるパターン状に小孔を形成することが可能であり、また繰り返し用いることが可能な強度を持ち合わせているからである。また、シャドウマスク等も用いることが可能である。
【０１２１】
また、マスクの小孔の形成方法は、マスクの材料により左右されるものであり、特に限定されるものではないが、例えばエッチング法等が挙げられる。
【０１２２】
４．特性性変化層、光触媒含有層およびマスクの配置
次に、特性変化層、光触媒含有層およびマスクの配置について説明する。本発明においては、例えば図１（ｂ）に示すように、光触媒含有層２および特性変化層５の間にマスク８が配置される。
【０１２３】
これにより、後述するエネルギー照射時に、光触媒含有層中の光触媒の作用により発生した活性酸素種が、拡散することなく、小孔内を通じて特性変化層上に届き、高濃度の活性酸素種の存在下で特性変化層の特性が変化され、効率的にパターンの形成を行うことが可能となるのである。この際、マスクは、光触媒含有層および特性変化層の間に介在するように配置されていれば、光触媒含有層および特性変化層と密着して配置されてもよく、また密着しない状態で配置されてもよいが、本発明においては、光触媒含有層および特性変化層と密着して配置されることが好ましい。これにより、より活性酸素種の濃度が高い状態で、特性変化層の特性を変化させることができ、より効率よく特性の変化したパターンを有するパターン形成体とすることが可能となるからである。また、上記マスクが特性変化層と密着していることから、特性変化層上においてマスクと接触している面は、特性の変化が起こらず、マスクに形成された小孔のパターン状により高精細に特性の変化したパターンを形成することが可能となるのである。
【０１２４】
本発明においては、このような配置状態は、少なくとも露光の間だけ維持されればよい。
【０１２５】
４．パターンの形成
本発明においては、上述したような配置を維持した状態で、エネルギー照射が行われる。なお、本発明でいうエネルギー照射とは、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。
【０１２６】
通常このような露光に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１２７】
このような露光に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１２８】
また、露光に際してのエネルギーの照射量は、特性変化層表面が光触媒含有層中の光触媒の作用により特性変化層表面の特性の変化が行われるのに必要な照射量とする。
【０１２９】
この際、光触媒含有層を加熱しながら露光することにより、感度を上昇させ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。
【０１３０】
本発明においては、上記マスクの小孔が形成された部分の光触媒含有層にエネルギーを照射することが可能であれば、そのエネルギー照射方向は特に限定されるものではなく、パターン形成体用基板の基体や特性変化層の透明性、または光触媒含有層側基板の基材の透明性等により、適宜選択されるものである。
【０１３１】
５．光触媒含有層側基板およびマスクの取り外し
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およびマスクが特性変化層との接触位置から離され、これにより図１（ｃ）に示すように特性が変化したパターン１０を有するパターン形成体が得られる。
【０１３２】
なお、本発明は上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
【０１３３】
【実施例】
以下、本発明について、実施例を通じてさらに詳述する。
【０１３４】
[実施例１]
１．光触媒含有層側基板の形成
イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１３５】
上記光触媒含有層用組成物を、石英ガラス基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１３６】
２．分解除去層の形成
ポリカーボネートが主成分のユーピロンＺ４００（三菱ガス化学製）２ｇをジクロロメタン３０ｇと１１２トリクロロエタン７０ｇとに溶解し分解層除去層用組成物とした。
【０１３７】
上記分解除去層用組成物を、ガラス基板上にスピンコーターにより塗布し、１００℃で６０分間の乾燥処理を行うことにより、透明な分解除去層（厚み０．０１μｍ）を形成した。
【０１３８】
３．露光
１００μｍφの穴が２００μｍピッチで空いた厚さ５００μｍのステンレスを用意し、これを光触媒含有層側基板と分解除去層との間に介在させ配置した。次に光触媒含有層基板側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で６００秒間露光し、分解除去層を分解除去し、ガラス基板上にポリカーボネートをパターン状に形成した。
【０１３９】
[実施例２]
１．光触媒含有層側基板の形成
イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１４０】
上記光触媒含有層用組成物を、石英ガラス基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１４１】
２．分解除去層の形成
カチオン性高分子であるポリジアリルジメチルアンモニウムクロライド（PDDA、平均分子量100,000-200,000、アルドリッチ）と、アニオン性高分子であるポリスチレンスルホン酸ナトリウム塩（PSS、平均分子量70,000、アルドリッチ）とをガラス基材上に交互吸着させ厚さを約２ｎｍとした。
【０１４２】
３．露光
１００μｍφの穴が２００μｍピッチで空いた厚さ５００μｍのステンレスを用意し、これを光触媒含有層側基板と分解除去層との間に介在させ配置し、光触媒含有層側基板側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で１２０秒間露光し、分解除去層を分解除去し、ガラス基板上に交互吸着膜をパターン状に形成した。
【０１４３】
[実施例３]
１．光触媒含有層側基板の形成
イソプロピルアルコール３０ｇとトリメトキシメチルシラン（ＧＥ東芝シリコーン（株）製、ＴＳＬ８１１３）３ｇと光触媒無機コーティング剤であるＳＴ−Ｋ０３（石原産業（株）製）２０ｇとを混合し、１００℃で２０分間撹拌した。これをイソプロピルアルコールにより３倍に希釈し光触媒含有層用組成物とした。
【０１４４】
上記光触媒含有層用組成物を、石英ガラス基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な光触媒含有層（厚み０．１５μｍ）を形成した。
【０１４５】
２．濡れ性変化層の形成
イソプロピルアルコール３０ｇとフルオロアルキルシラン（ＧＥ東芝シリコーン（株））とテトラメトキシシラン（ＧＥ東芝シリコーン（株））３ｇと０．５規定塩酸２．５ｇとを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。
【０１４６】
上記濡れ性変化層用組成物を、ガラス基板上にスピンコーターにより塗布し、１５０℃で１０分間の乾燥処理を行うことにより、透明な濡れ性変化層（厚み０．１μｍ）を形成した。
【０１４７】
３．露光
１００μｍφの穴が２００μｍピッチで空いた厚さ５０μｍのポリイミドフィルムを用意し、これを光触媒含有層側基板と分解除去層との間に介在させて配置した後、光触媒含有層側基板側から超高圧水銀灯（波長３６５ｎｍ）により４０ｍＷ／ｃｍ²の照度で９０秒間露光し、ガラス基板上に濡れ性変化パターンを形成した。
【０１４８】
このとき、未露光部及び露光部とぬれ標準試薬（４０ｍＮ/ｍ）との接触角を接触角測定器（協和界面科学（株）製ＣＡ−Ｚ型）を用いて測定（マイクロシリンジから液滴を滴下して３０秒後）した結果、それぞれ、７５°と７°であった。
【０１４９】
【発明の効果】
本発明によれば、光触媒含有層および特性変化層の間に所定のパターンを有したマスクを介在させて配置した後、エネルギーを照射することにより、上記光触媒含有層から発生する活性酸素種が、上記マスクの小孔を通して拡散せずに上記特性変化層に到達する。これにより、活性酸素種が到達した部分のみの特性を変化させることが可能となる。また、発生した活性酸素種の濃度が高い状態で、特性変化層の特性を変化させることが可能であることから、短時間で効率よく、高精細に特性の変化したパターンを有するパターン形成体と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。
【符号の説明】
１ … 基材
２ … 光触媒含有層
３ … 光触媒含有層側基板
４ … 基体
５ … 特性変化層
６ … パターン形成体用基板
７ … 小孔
８ … マスク
９ … エネルギー
１０… 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]
As such a high-definition pattern forming body, a pattern forming body using a photocatalyst by the present inventors and a manufacturing method thereof have been proposed (for example, Patent Document 1). According to this, since it is possible to obtain a pattern formed body on which patterns having different characteristics are formed by pattern exposure, the pattern formed body can be obtained easily and accurately. Since various functional elements can be manufactured by utilizing the difference in characteristics of pattern forming bodies having patterns having different characteristics, functional elements such as color filters and microlenses can be efficiently and high-quality. There is an effect that it can be obtained.
[0004]
However, in the above method, since there is a gap between the photocatalyst and the pattern forming body, active oxygen species generated by the action of the photocatalyst diffuse, and the contrast or contour of the pattern obtained on the pattern forming body is blurred. In some cases, there were problems with accuracy.
[0005]
[Patent Document 1]
JP 2000-249821 A
[0006]
[Problems to be solved by the invention]
In view of the above, it is desired to provide a method for producing a pattern forming body capable of easily forming a high-definition pattern.
[0007]
[Means for Solving the Problems]
According to the present invention, a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst, and a characteristic change layer whose characteristics change due to the action of the photocatalyst in the photocatalyst-containing layer are provided. A substrate for a pattern forming body having a mask having a thickness of 2 mm or less having small holes in a desired pattern interposed between the photocatalyst-containing layer and the characteristic change layer, and then energy from a predetermined direction. By changing the characteristics of the characteristic change layer of the portion irradiated with energy, and then removing the photocatalyst-containing layer side substrate and the mask, a pattern with changed characteristics is formed on the characteristic change layer. Provided is a method for producing a pattern forming body, which is characterized by obtaining a pattern forming body.
[0008]
According to the present invention, the active oxygen species generated from the photocatalyst-containing layer by irradiating energy after arranging a mask having a predetermined pattern between the photocatalyst-containing layer and the characteristic change layer is The characteristic change layer is reached without being diffused through the small holes of the mask. This makes it possible to change the characteristics of only the portion where the active oxygen species has reached. In addition, since it is possible to change the characteristics of the characteristic change layer in a state where the concentration of the generated active oxygen species is high, a pattern forming body having a pattern whose characteristics have been changed with high definition in a short time efficiently It becomes possible to do.
[0009]
In the invention described in claim 1, as described in claim 2, it is preferable that the mask is disposed in close contact between the photocatalyst layer and the characteristic change layer. This is because the characteristics of the characteristic change layer can be changed in a state where the concentration of active oxygen species is higher, and a pattern forming body having a pattern whose characteristics have been changed more efficiently can be obtained.
[0010]
In the invention described in claim 1 or 2, as described in claim 3, the mask is preferably made of metal. This is because, if the mask is a metal, it is easy to form small holes in a desired pattern.
[0011]
In the invention described in any one of claims 1 to 3, as described in claim 4, the photocatalyst-containing layer may be a layer made of a photocatalyst. This is because if the photocatalyst-containing layer is a layer composed only of a photocatalyst, the characteristics of the characteristic change layer can be changed efficiently.
[0012]
In the invention described in claim 4, as described in claim 5, it is preferable that the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. By forming the photocatalyst-containing layer by the vacuum film formation method in this way, it is possible to obtain a homogeneous photocatalyst-containing layer having a uniform film thickness with few surface irregularities, and uniform and highly efficient characteristics of the surface of the property change layer This is because it is possible to change it.
[0013]
In the invention described in any one of claims 1 to 3, as described in claim 6, the photocatalyst-containing layer is a layer having a photocatalyst and a binder. Also good. By using the binder in this manner, it becomes possible to form the photocatalyst-containing layer relatively easily, and as a result, the pattern formed body can be manufactured at a low cost.
[0014]
In the invention described in any one of claims 1 to 6, as described in claim 7, the photocatalyst is made of titanium oxide (TiO 2).₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃It is preferable that it is 1 type, or 2 or more types of substances selected from the above, and as described in claim 8, the photocatalyst is titanium oxide (TiO 2).₂) Is preferable. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, non-toxic and easily available.
[0015]
In the invention described in any one of claims 1 to 8, as described in claim 9, the substrate for a pattern forming body is formed on a substrate and the substrate. It may have a characteristic change layer. This is because when the strength of the characteristic change layer is weak and the characteristic change layer does not have self-supporting property, it is preferably formed on the substrate.
[0016]
In the invention described in any one of claims 1 to 9, as described in claim 10, the characteristic change layer has energy generated by the action of the photocatalyst in the photocatalyst-containing layer. It may be a wettability changing layer in which the wettability changes so that the contact angle with the liquid decreases when irradiated. Since the characteristic change layer is a wettability change layer, the region irradiated with energy can be made a lyophilic region, and the region not irradiated with energy can be made a liquid repellent region. This is because, for example, a functional part composition that forms a functional part can be attached only to the lyophilic region by utilizing the difference in wettability.
[0017]
In the invention described in the tenth aspect, as described in the eleventh aspect, the contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° in a portion not irradiated with energy. It is above, and it is preferable that it is 9 degrees or less in the part irradiated with energy. When the contact angle between the wettability-changing layer and the portion where the energy is not irradiated is 10 ° or less, the liquid repellency is insufficient, and the contact angle between the portion where the energy is irradiated and the liquid However, when it is 9 ° or more, for example, when a functional element is formed on the pattern forming body using the difference in wettability, a composition for a functional part that forms a functional part, etc. This is because the spread may be inferior.
[0018]
In the invention described in the tenth or eleventh aspect, as described in the twelfth aspect, the wettability changing layer is preferably a layer containing an organopolysiloxane. In the present invention, the properties required for the wettability changing layer are liquid repellency when not irradiated with energy, and lyophilic by the action of the photocatalyst in the opposing photocatalyst containing layer when irradiated with energy. The characteristic is. This is because it is preferable to use organopolysiloxane as a material for imparting such characteristics to the wettability changing layer.
[0019]
In the invention described in claim 12, as described in claim 13, the organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. This is because if it contains a fluoroalkyl group, the difference in wettability between the energy-irradiated portion and the energy-unirradiated portion can be increased.
[0020]
In the invention described in claim 12 or claim 13, as described in claim 14, the organopolysiloxane is Y_nSiX_(4-n)Wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n is an integer from 0 to 3. It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolyzed condensate or cohydrolyzed condensate of the silicon compound. This is because by using such an organopolysiloxane, it is possible to exhibit the characteristics against the change in wettability as described above.
[0021]
In the invention described in any one of claims 10 to 14, as described in claim 15, the substrate for a pattern forming body is formed from a wettability changing layer having self-supporting property. It may be. If the wettability changing layer has a self-supporting property, it is not necessary to use a substrate or the like. For example, if a commercially available resin plate is used, a pattern-formed body can be produced at low cost.
[0022]
In the invention described in any one of claims 1 to 9, as described in claim 16, the characteristic change layer has energy generated by the action of the photocatalyst in the photocatalyst-containing layer. A decomposition removal layer that is decomposed and removed when irradiated is preferable. When the characteristic change layer is a decomposition removal layer, it is possible to form irregularities on the surface by the energy irradiation. Thereby, when forming a functional part on a pattern formation body using this unevenness | corrugation, it becomes possible to adhere the composition for functional parts easily by the inkjet method etc., for example.
[0023]
In the invention described in claim 16, as described in claim 17, the contact angle of the liquid with respect to the decomposition removal layer and the contact angle of the liquid with respect to the substrate exposed by the decomposition removal layer being decomposed and removed. Are preferably different from each other. As a result, for example, the substrate exposed by the energy irradiation can be made a lyophilic region, and the portion where the non-energy-irradiated decomposition and removal layer remains can be made a liquid repellent region. This is because the functional part can be formed on the pattern forming body by utilizing the difference in properties, for example.
[0024]
In the invention described in claim 16 or claim 17, as described in claim 18, the decomposition / removal layer is any of a self-assembled monolayer, a Langmuir-Blodgett film, and an alternating adsorption film. It is preferable that This is because, when the decomposition / removal layer is the film described above, a defect-free film having a relatively high strength can be easily formed.
[0025]
In the invention described in any one of claims 16 to 18, as described in claim 19, the wettability of the substrate exposed by the decomposition removal layer being decomposed and removed is The contact angle with a liquid having a surface tension of 40 mN / m is preferably 9 ° or less, and preferably 10 ° or more on the decomposition removal layer.
[0026]
In the present invention, the decomposition / removal layer is an area where liquid repellency is required. Therefore, when the contact angle with the liquid on the decomposition / removal layer is 10 ° or less, the liquid repellency is sufficient. It is not. In addition, the substrate exposed by decomposing and removing the decomposition removal layer by the action of the photocatalyst accompanying the irradiation of energy is a region where lyophilicity is required, and the contact angle with the liquid is 10 ° or more This is because, for example, when the functional part is formed on the pattern forming body, there is a high possibility that the composition for the functional part that forms the functional part in the lyophilic region is not spread and spread.
[0027]
In the invention described in any one of claims 1 to 19, as described in claim 20, it is preferable that the energy irradiation is performed while heating the photocatalyst containing layer. This is because by heating the photocatalyst, the sensitivity of the photocatalyst is improved and the characteristics on the characteristic change layer can be changed efficiently.
[0028]
In the invention described in any one of claims 1 to 20, it is preferable that the characteristic change layer is a layer not containing a photocatalyst as described in claim 21. This is because the characteristic change layer is a layer that does not contain a photocatalyst, so that the pattern forming body does not have to worry about being affected by the photocatalyst over time, and can be used without problems for a long period of time. .
[0029]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for producing a pattern formed body, and will be described in detail below.
[0030]
The method for producing a pattern forming body of the present invention comprises a photocatalyst-containing layer-side substrate having a photocatalyst-containing layer and a substrate, and a pattern having a characteristic-changing layer whose characteristics change due to the action of the photocatalyst in the photocatalyst-containing layer. The formed body substrate is disposed between the photocatalyst-containing layer and the property change layer with a mask having a small hole having a thickness of 2 mm or less in a desired pattern, and then irradiated with energy from a predetermined direction. By changing the characteristics of the characteristic change layer in the portion irradiated with energy, and then removing the photocatalyst-containing layer side substrate and the mask, a pattern having a pattern with a changed characteristic on the characteristic change layer is formed. It is characterized by obtaining a body.
[0031]
For example, as shown in FIG. 1, the method for producing a pattern forming body of the present invention includes a substrate 1 and a photocatalyst containing layer side substrate 3 having a photocatalyst containing layer 2 formed on the substrate 1, a substrate 4 and a substrate. 4 and a pattern forming body substrate 6 having the characteristic change layer 5 formed on the substrate 4 are prepared (FIG. 1A).
[0032]
Next, a mask 8 having a small hole 7 is disposed between the photocatalyst-containing layer 2 and the characteristic change layer 5, and energy 9 is irradiated from a predetermined direction (FIG. 1B). By irradiating this energy 9, the photocatalyst in the photocatalyst containing layer 2 is activated, and active oxygen species are generated. At this time, since the mask 8 is disposed between the photocatalyst containing layer 2 and the characteristic change layer 5, the active oxygen species generated on the photocatalyst containing layer 2 reach the characteristic change layer 5 without diffusing. And change the characteristics. Thereby, the characteristic of the characteristic change layer 5 can be changed in the presence of a high concentration of active oxygen species, and the characteristic of the characteristic change layer 5 can be changed efficiently. Further, when the mask 8 on the characteristic change layer 5 is brought into close contact, the active oxygen species does not reach other than the pattern formation portion of the small hole 7, so that a higher definition pattern can be formed. .
[0033]
Thereafter, by removing the photocatalyst-containing layer side substrate 3 and the mask 8, it is possible to obtain a pattern-formed body in which the pattern 10 having changed characteristics is formed on the characteristic change layer 5 (FIG. 1C).
[0034]
Hereinafter, each structure in the manufacturing method of the pattern formation body of this invention is demonstrated.
[0035]
1. Pattern forming substrate
First, the substrate for a pattern forming body used in the present invention will be described. The substrate for the pattern forming body used in the present invention is not particularly limited as long as it has a characteristic change layer whose characteristics change due to the action of the photocatalyst, and is formed of only the characteristic change layer. Alternatively, as shown in FIG. 1, the characteristic change layer 5 may be formed on the substrate 4. Hereinafter, each structure of the substrate for pattern formation bodies used for this invention is demonstrated.
[0036]
(1) Characteristic change layer
First, the characteristic change layer in the present invention will be described. The characteristic change layer of the present invention is not particularly limited as long as the characteristic changes by the action of the photocatalyst-containing layer described later. For example, a polymer material such as polyolefin such as polyethylene or polypropylene is used. As a result, a layer in which the part irradiated with energy is introduced with a polar group by the action of a photocatalyst or the surface state becomes rough and the adhesion to various substances is improved can be used as a characteristic change layer. Good. Thus, by making the characteristic change layer an adhesive change layer whose adhesiveness changes, it becomes possible to form a pattern with good adhesiveness by energy irradiation, and a functional part can be easily formed. This is because a pattern forming body can be obtained.
[0037]
In addition, the characteristic change layer in the present invention may be self-supporting or non-self-supporting. In addition, having self-supporting property as used in the field of this invention means that it can exist in a tangible state without another support material. When the characteristic change layer has a self-supporting property, it is not necessary to form the characteristic change layer on a substrate described later, and a commercially available resin film can be used, which is advantageous in terms of cost. It can be said.
[0038]
However, the characteristic change layer formed of a material whose characteristics change significantly is usually less self-supporting material. In such a non-self-supporting material, the characteristic change layer is formed on the substrate. It is necessary. Further, by forming the characteristic change layer on the substrate, the strength and the like are increased, and it can be used as various pattern forming bodies.
[0039]
As a method for forming the above-described property change layer on the substrate, it may be formed by a dry method, that is, a vacuum deposition method or the like, or by a wet method, that is, a method such as a spin coating method or a dip coating method. It may be formed.
[0040]
As described above, the characteristic change layer is not particularly limited as long as it has various characteristics that change due to the action of the photocatalyst. However, in the present invention, the characteristic change layer changes the wettability due to the action of the photocatalyst. Functions that can be obtained in particular are the wettability changing layer in which a pattern due to the property is formed and the decomposition changing layer in which the property changing layer is decomposed and removed by the action of the photocatalyst to form a pattern due to unevenness. This is preferable because the effectiveness of the present invention can be further extracted from the relationship of the active elements and the like.
[0041]
The characteristic change layer used in the present invention is not particularly limited as long as the characteristic change layer is changed by the action of the photocatalyst as described above, but is particularly preferably a layer not containing the photocatalyst. This is because if the photocatalyst is not contained in the wettability changing layer in this way, it is not necessary to worry about the influence of the photocatalyst over time, and the pattern formed body can be used without any problem for a long time.
[0042]
Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0043]
a. Wetting change layer
The wettability changing layer in the present invention is not particularly limited as long as the wettability of the surface is changed by the action of the photocatalyst, but in general, the wettability changing layer by the action of the photocatalyst accompanying energy irradiation. A layer whose wettability changes so that the contact angle with the liquid on the surface decreases is preferable.
[0044]
In this way, a pattern of a lyophilic region having a small contact angle with the liquid is formed by the energy irradiation by forming the wettability changing layer in which the wettability is changed so that the contact angle with the liquid is lowered by the energy irradiation. It becomes possible. Thus, for example, when a functional part is formed on a pattern forming body, a functional element can be easily formed by attaching a functional part composition or the like to the lyophilic region by, for example, an inkjet method. It becomes possible to do.
[0045]
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 composition or the like. The liquid repellent region is a region having a large contact angle with the liquid, and refers to a region having poor wettability with respect to the functional part composition or the like that forms the functional part.
[0046]
In the present invention, when the contact angle with the liquid in the adjacent region is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the contact with the liquid is determined from the contact angle with the liquid in the lyophilic region or the adjacent region. When the contact angle is higher than 1 °, the liquid repellent region is used.
[0047]
Here, the contact angle between the lyophilic region formed by energy irradiation and the liquid repellent region not irradiated with energy with respect to the functional part composition forming the functional part is at least 1 ° or more, preferably Is preferably 5 ° or more, and more preferably 10 ° or more.
[0048]
Further, the wettability changing layer has a contact angle with a liquid with a surface tension of 40 mN / m of 10 ° or more, preferably a liquid with a surface tension of 30 mN / m, in a portion not irradiated with energy, that is, in a water-repellent region. It is preferable to exhibit wettability with a contact angle of 10 ° or more, particularly 10 ° or more with a liquid having a surface tension of 20 mN / m. The portion not irradiated with energy is a portion that requires liquid repellency in the present invention. Therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient and, for example, functions on the pattern forming body. This is because the functional part composition may remain when forming the functional part, which is not preferable.
[0049]
Further, the wettability changing layer has a contact angle with a liquid that is lowered when irradiated with energy, and a contact angle with a liquid with a surface tension of 40 mN / m is 9 ° or less, preferably with a liquid with a surface tension of 50 mN / m. A layer having an angle of 10 ° or less, particularly a contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. When the contact angle with the energy irradiated part, that is, the liquid in the lyophilic region is high, for example, when the functional part is formed on the pattern forming body, the spread of the functional part composition in this part may be inferior. This is because there is a possibility that problems such as lack of functional parts may occur.
[0050]
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.
[0051]
Further, when the wettability changing layer as described above is used in the present invention, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer is more energy than the wettability changing layer. The wettability changing layer may be formed so that, when irradiated, the wettability changing layer is lowered by the action of the photocatalyst as compared with that before energy irradiation.
[0052]
In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a pattern of the lyophilic region in the liquid repellent region.
[0053]
Therefore, when such a wettability changing layer is used, the pattern of the lyophilic region can be easily formed in the liquid repellent region by irradiating the pattern with energy. When forming the functional part, it is possible to easily form the functional part only in the lyophilic region.
[0054]
As described above, the fluorine content contained in the wettability changing layer containing fluorine is not irradiated with energy in the lyophilic region having a low fluorine content formed by energy irradiation. When the fluorine content of the part is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0055]
By setting it within such a range, it is possible to make a great difference in wettability between the energy irradiated portion and the energy non-irradiated portion. Therefore, by forming, for example, a functional part in such a wettability changing layer, it is possible to accurately form the functional part only in the lyophilic region having a reduced fluorine content, and the functional element with high accuracy. It is because it can obtain. This rate of decrease is based on weight.
[0056]
The fluorine content in such a wettability changing layer can be measured by various commonly used methods. For example, X-ray photoelectron spectroscopy (ESCA) (Electron Spectroscopy, ESCA) Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.
[0057]
The material used for such a wettability changing layer is a material whose wettability changing layer has the characteristics described above, that is, a material whose wettability is changed by the photocatalyst in the photocatalyst-containing layer that is contacted by energy irradiation, and deteriorated by the action of the photocatalyst The main chain is not particularly limited as long as it has a main chain that is difficult to be decomposed. For example, (1) an organo group that exhibits high strength by hydrolysis and polycondensation of chloro or alkoxysilane by sol-gel reaction or the like Examples include polysiloxanes and (2) organopolysiloxanes such as organopolysiloxanes crosslinked with reactive silicones having excellent water and oil repellency.
[0058]
In the case of (1) above, the general formula:
Y_nSiX_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0059]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those known as fluorine-based silane coupling agents can be used.
[0060]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;and
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0061]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated part of the wettability changing layer is greatly improved. For example, a pixel part is formed on a pattern forming body, When used as a filter, it exhibits a function of preventing adhesion of a functional part composition such as a pixel part coloring ink.
[0062]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0063]
[Chemical 1]

[0064]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0065]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0066]
In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
[0067]
The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0068]
In addition to the above surfactants, the wettability changing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate. , Polyvinyl chloride, Polyamide, Polyimide, Styrene butadiene rubber, Chloroprene rubber, Polypropylene, Polybutylene, Polystyrene, Polyvinyl acetate, Polyester, Polybutadiene, Polybenzimidazole, Polyacrylonitrile, Epichlorohydrin, Polysulfide, Polyisoprene, etc. Can be contained.
[0069]
Such a wettability changing layer can be formed by preparing a coating solution by dispersing the above-described components in a solvent together with other additives as necessary, and coating the coating solution on a substrate. . As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0070]
Further, as described above, the wettability changing layer of the present invention may be a material having self-supporting property, and as the material having self-supporting property, a material obtained by depositing the above-described material has self-supporting property. However, for example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride , Polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone and the like.
[0071]
b. Decomposition removal layer
Next, the decomposition removal layer will be described. The decomposition / removal layer used in the present invention is particularly limited as long as the decomposition / removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when irradiated with energy. is not.
[0072]
As described above, since the portion irradiated with energy is decomposed and removed by the action of the photocatalyst, the decomposition / removal layer has a pattern composed of a portion with and without the decomposition / removal layer without performing a development process or a washing step, that is, has an unevenness A pattern can be formed.
[0073]
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.
[0074]
In addition, the decomposition / removal layer used in the present invention not only forms irregularities, but the decomposition / removal layer preferably has a higher contact angle with the liquid as compared with the surface of the substrate. As a result, the decomposition / removal layer is decomposed and removed, and the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition / removal layer remains can be made a liquid repellent region, thereby forming various patterns. This is because it becomes easy.
[0075]
Here, the characteristics of the lyophilic region, which is the region where the substrate is exposed by the energy irradiation, and the lyophobic region, which is the region composed of the remaining decomposition-removed layer that has not been irradiated with energy, function on the pattern forming body, for example When forming the functional part, the contact angle with respect to the liquid having a surface tension equivalent to the surface tension of the functional part composition forming the functional part is at least 1 °, preferably 5 ° or more, particularly 10 °. A pattern formed from different lyophilic regions and lyophobic regions is preferable.
[0076]
The contact angle with the liquid on the surface of the decomposition removal layer of the present invention is 10 ° or more, preferably 10 ° or more with a liquid with a surface tension of 40 mN / m, preferably 10 ° or more with a liquid with a surface tension of 30 mN / m. In particular, the contact angle with a liquid having a surface tension of 20 mN / m preferably exhibits a value of 10 ° or more.
[0077]
In the present invention, when the characteristic change layer is a decomposition removal layer, the substrate described later is preferably lyophilic, specifically, the contact angle with a liquid having a surface tension of 40 mN / m is 9 The contact angle with a liquid having a surface tension of 40 mN / m is more preferably 5 ° or less, and particularly preferably 1 ° or less.
[0078]
Since the wettability of the decomposition removal layer and the substrate is within the above range, the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition removal layer remains can be made a liquid repellent region. This is because a simple pattern can be easily formed. Here, the contact angle with the liquid is a value measured by the method described above.
[0079]
In this case, the substrate described later may be surface-treated so that the surface becomes lyophilic. Examples of the surface treatment so that the surface of the material is lyophilic include lyophilic surface treatment by plasma treatment using argon or water, and the lyophilic layer formed on the substrate is as follows: For example, a silica film obtained by a sol-gel method of tetraethoxysilane can be used. In the present invention, the portion where the substrate is usually exposed is regarded as the lyophilic region.
[0080]
Specific examples of the film that can be used for the above-described decomposition removal layer include a film made of a fluorine-based or hydrocarbon-based resin having liquid repellency. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent, for example, a general composition such as a spin coating method. It can be formed by a film method.
[0081]
In the present invention, since a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternating adsorption film can be used, a film having no defect can be formed. It can be said that it is more preferable to use such a film forming method.
[0082]
Here, the self-assembled monolayer film, the Langmuir-Blodgett film, and the alternating adsorption film used in the present invention will be specifically described.
[0083]
(I) Self-assembled monolayer
Although the inventors do not know the existence of an official definition of self-assembled monolayer, a commentary on what is generally recognized as a self-assembled membrane is, for example, a review by Abraham Ulman. “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. With reference to this review article, the self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and bonding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One layer 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.
[0084]
(Ii) 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 above-described self-assembled monolayer. 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 and used. It is possible to form a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).
[0085]
(Iii) 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.
[0086]
Further, the thickness of the decomposition / removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by energy irradiated in an energy irradiation step described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.
[0087]
(2) Substrate
Next, the substrate in the present invention will be described. In the present invention, when the characteristic change layer is a material having no self-supporting property, when it is a decomposition removal layer, or when the pattern forming body substrate requires strength, for example, as shown in FIG. A characteristic change layer 5 is provided on the substrate 4.
[0088]
The substrate is not particularly limited as long as the above-described characteristic change layer is formed. Even if the substrate has flexibility according to the use of the pattern forming body, the substrate is flexible. It may be a thing which does not have.
[0089]
In addition, the material and the like are not particularly limited, and various materials can be used as necessary. Specific examples include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, and nonwoven fabrics.
[0090]
2. Photocatalyst containing layer side substrate
Next, the photocatalyst containing layer side substrate used in the present invention will be described. The photocatalyst-containing layer side substrate used in the method for producing a pattern forming body of the present invention has at least a photocatalyst-containing layer and a base material, and is usually a thin film photocatalyst formed on the base material by a predetermined method. A content layer is formed. Hereinafter, each structure of this photocatalyst containing layer side board | substrate is demonstrated.
[0091]
(Photocatalyst containing layer)
The photocatalyst-containing layer used in the present invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the characteristic change layer, and includes a photocatalyst and a binder. It may be a thing, and the thing formed into a film by the photocatalyst simple substance may be used. The surface characteristics may be particularly lyophilic or lyophobic.
[0092]
In addition, by performing energy irradiation with a mask interposed between the photocatalyst-containing layer and the characteristic change layer, the action of the photocatalyst is not diffused, and the characteristic of the characteristic change layer can be changed efficiently. Furthermore, the energy irradiation direction may be applied from any direction as long as the photocatalyst-containing layer and the characteristic change layer are irradiated with energy to the small hole portion in the mask facing each other through the mask. The energy to be irradiated is not particularly limited to parallel light such as parallel light.
[0093]
The action mechanism of a photocatalyst represented by titanium dioxide as described later in such a photocatalyst-containing layer 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 the present invention, it is considered that this carrier acts on the compound in the characteristic change layer facing the photocatalyst containing layer.
[0094]
As the photocatalyst used in the present invention, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these.
[0095]
In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. This is because 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 50 nm or less, and the photocatalyst of 20 nm or less is particularly preferable.
[0098]
The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder. In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0099]
Examples of other methods for forming the photocatalyst-containing layer composed only of the 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 formation method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, and this can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.
[0100]
Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0101]
In the case of using a binder, it is preferable that the binder main skeleton has a high binding energy so that it is not decomposed by photoexcitation of the photocatalyst. For example, in the description of the wettability changing layer of the property changing layer described above, The described organopolysiloxane can be mentioned.
[0102]
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 application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0103]
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.
[0104]
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.
[0105]
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 μm to 10 μm.
[0106]
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.
[0107]
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.
[0108]
(Base material)
In this invention, as shown to Fig.1 (a), the photocatalyst containing layer side board | substrate 3 has the base material 1 and the photocatalyst containing layer 2 formed on this base material 1 at least.
[0109]
Under the present circumstances, the material which comprises the base material used is suitably selected by the irradiation direction of the energy in the pattern formation mentioned later, whether the pattern formation body obtained requires transparency, etc.
[0110]
That is, for example, when an opaque substrate such as a paper base phenolic resin laminate is used as the substrate for the pattern forming body, the energy irradiation direction is necessarily from the photocatalyst containing layer side substrate side, and FIG. As shown in Fig. 2, it is necessary to irradiate energy. In such a case, the base material needs to have transparency.
[0111]
On the other hand, if the substrate of the pattern forming substrate is, for example, a transparent resin film, it is possible to irradiate energy from the pattern forming substrate side. In such a case, the transparency of the substrate is not particularly required.
[0112]
In addition, the base material used in the present invention may be a flexible material such as a resin film, or may be a non-flexible material such as a glass substrate. This is appropriately selected depending on the energy irradiation method in forming the characteristic change pattern described later.
[0113]
Thus, the base material used for the photocatalyst-containing layer side substrate in the present invention is not particularly limited in its material, but in the present invention, this photocatalyst-containing layer side substrate is used repeatedly. For this reason, a material having a predetermined strength and good adhesion between the surface and the photocatalyst containing layer is preferably used.
[0114]
Specific examples include glass, ceramic, metal, and plastic.
[0115]
An anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst containing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0116]
3. mask
Next, the mask used in the present invention will be described. The mask used in the present invention is arranged between the photocatalyst-containing layer in the photocatalyst-containing layer side substrate described above and the characteristic change layer in the substrate for a pattern forming body described above during energy irradiation described later. This is to allow the active oxygen species generated by the action of the photocatalyst to reach the characteristic change layer in a pattern.
[0117]
The mask used in the present invention has small holes in a pattern that changes the characteristics of the characteristic change layer, and the thickness of the mask is preferably 2 mm or less, particularly preferably 100 μm or less. In the present invention, the mask determines the distance between the photocatalyst-containing layer and the wettability changing layer. Therefore, when the thickness of the mask is thicker than the above value, the generated active oxygen species are in the characteristic changing layer. This is because it may become difficult to reach and slow down the characteristic change. The lower limit of the mask thickness is 1 μm. This is because it is difficult to form a high-definition mask when the mask thickness is thinner than the above value.
[0118]
Further, the shape, size, etc. of the small holes formed in the mask of the present invention are appropriately selected according to the pattern of the target pattern forming body.
[0119]
Here, the mask used in the present invention is not particularly limited as long as the material or the like is not capable of transmitting the active oxygen species generated by the action of the photocatalyst by energy irradiation, and is transparent or opaque. It may also be flexible.
[0120]
Specific examples of the mask material used in the present invention include metals, inorganic substances such as glass and ceramics, and organic substances such as plastics. Among these, metals are preferred. In the present invention, since the mask is made of a metal, it is possible to easily form small holes in a pattern that changes the characteristics of the characteristic change layer, and to have strength that can be used repeatedly. Because I have it. A shadow mask or the like can also be used.
[0121]
The method for forming the small holes in the mask depends on the material of the mask and is not particularly limited, and examples thereof include an etching method.
[0122]
4). Arrangement of characteristic change layer, photocatalyst containing layer and mask
Next, the arrangement of the characteristic change layer, the photocatalyst containing layer, and the mask will be described. In the present invention, for example, as shown in FIG. 1B, a mask 8 is disposed between the photocatalyst-containing layer 2 and the characteristic change layer 5.
[0123]
This allows the active oxygen species generated by the action of the photocatalyst in the photocatalyst-containing layer to reach the characteristic change layer through the small holes without diffusing, and in the presence of a high concentration of active oxygen species. Thus, the characteristics of the characteristic change layer are changed, and the pattern can be formed efficiently. At this time, the mask may be disposed in close contact with the photocatalyst containing layer and the characteristic change layer, or may be disposed in a non-adherent state as long as the mask is disposed so as to be interposed between the photocatalyst containing layer and the characteristic change layer. However, in the present invention, it is preferably disposed in close contact with the photocatalyst-containing layer and the characteristic change layer. This is because the characteristics of the characteristic change layer can be changed in a state where the concentration of active oxygen species is higher, and a pattern forming body having a pattern whose characteristics have been changed more efficiently can be obtained. In addition, since the mask is in close contact with the characteristic change layer, the surface in contact with the mask on the characteristic change layer does not change the characteristic, and the pattern shape of the small holes formed in the mask increases the definition. Therefore, it is possible to form a pattern with changed characteristics.
[0124]
In the present invention, such an arrangement need only be maintained at least during exposure.
[0125]
4). Pattern formation
In the present invention, energy irradiation is performed while maintaining the above-described arrangement. The energy irradiation referred to in the present invention is a concept including irradiation of any energy ray capable of changing the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is not limited to visible light irradiation. Absent.
[0126]
Usually, the wavelength of light used for such exposure is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0127]
Examples of light sources that can be used for such exposure include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0128]
In addition, the irradiation amount of energy at the time of exposure is set to an irradiation amount necessary for the characteristic change layer surface to change the characteristic of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0129]
At this time, it is preferable in that the photocatalyst-containing layer is exposed while being heated, so that the sensitivity can be increased and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0130]
In the present invention, the energy irradiation direction is not particularly limited as long as it is possible to irradiate the photocatalyst-containing layer in the portion where the small holes of the mask are formed. It is appropriately selected depending on the transparency of the substrate and the property changing layer, the transparency of the substrate of the photocatalyst-containing layer side substrate, or the like.
[0131]
5). Removal of photocatalyst containing layer side substrate and mask
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate and the mask are separated from the contact position with the property change layer, thereby forming a pattern having a pattern 10 whose property is changed as shown in FIG. The body is obtained.
[0132]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
[0133]
【Example】
Hereinafter, the present invention will be described in more detail through examples.
[0134]
[Example 1]
1. Formation of photocatalyst containing layer side substrate
30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.) which is a photocatalytic inorganic coating agent are mixed and stirred at 100 ° C. for 20 minutes. did. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0135]
The said composition for photocatalyst containing layers was apply | coated with the spin coater on the quartz glass substrate, and the transparent photocatalyst containing layer (thickness 0.15 micrometer) was formed by performing a drying process for 10 minutes at 150 degreeC.
[0136]
2. Formation of decomposition removal layer
2 g of Iupilon Z400 (Mitsubishi Gas Chemical Co., Ltd.) mainly composed of polycarbonate was dissolved in 30 g of dichloromethane and 70 g of 112 trichloroethane to obtain a composition for a decomposition layer removal layer.
[0137]
The said composition for decomposition | disassembly removal layers was apply | coated with the spin coater on the glass substrate, and the transparent decomposition removal layer (thickness 0.01 micrometer) was formed by performing the drying process for 60 minutes at 100 degreeC.
[0138]
3. exposure
A stainless steel having a thickness of 500 μm in which holes of 100 μmφ were formed at a pitch of 200 μm was prepared, and this was interposed between the photocatalyst containing layer side substrate and the decomposition removal layer. Next, 40 mW / cm from the photocatalyst containing layer substrate side by an ultra high pressure mercury lamp (wavelength 365 nm).²The film was exposed for 600 seconds at an illuminance of, the decomposition removal layer was decomposed and removed, and a polycarbonate was formed in a pattern on the glass substrate.
[0139]
[Example 2]
1. Formation of photocatalyst containing layer side substrate
30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.) which is a photocatalytic inorganic coating agent are mixed and stirred at 100 ° C. for 20 minutes. did. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0140]
The said composition for photocatalyst containing layers was apply | coated with the spin coater on the quartz glass substrate, and the transparent photocatalyst containing layer (thickness 0.15 micrometer) was formed by performing a drying process for 10 minutes at 150 degreeC.
[0141]
2. Formation of decomposition removal layer
Polydiallyldimethylammonium chloride (PDDA, average molecular weight 100,000-200,000, Aldrich), a cationic polymer, and polystyrene sulfonate sodium salt (PSS, average molecular weight 70,000, Aldrich), an anionic polymer, on a glass substrate Were alternately adsorbed to a thickness of about 2 nm.
[0142]
3. exposure
A stainless steel with a thickness of 500 μm with holes of 100 μmφ formed at a pitch of 200 μm is prepared and placed between the photocatalyst containing layer side substrate and the decomposition removal layer. 365 nm) to 40 mW / cm²The film was exposed for 120 seconds at an illuminance of, the decomposition removal layer was decomposed and removed, and an alternating adsorption film was formed in a pattern on the glass substrate.
[0143]
[Example 3]
1. Formation of photocatalyst containing layer side substrate
30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.) which is a photocatalytic inorganic coating agent are mixed and stirred at 100 ° C. for 20 minutes. did. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0144]
The said composition for photocatalyst containing layers was apply | coated with the spin coater on the quartz glass substrate, and the transparent photocatalyst containing layer (thickness 0.15 micrometer) was formed by performing a drying process for 10 minutes at 150 degreeC.
[0145]
2. Formation of wettability changing layer
30 g of isopropyl alcohol, 3 g of fluoroalkylsilane (GE Toshiba Silicone), 3 g of tetramethoxysilane (GE Toshiba Silicone) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition.
[0146]
The said composition for wettability change layers was apply | coated with the spin coater on the glass substrate, and the transparent wettability change layer (thickness 0.1 micrometer) was formed by performing a drying process for 10 minutes at 150 degreeC.
[0147]
3. exposure
A polyimide film having a thickness of 50 μm in which holes of 100 μmφ are formed at a pitch of 200 μm is prepared and disposed between the photocatalyst containing layer side substrate and the decomposition removal layer, and then the ultra high pressure is applied from the photocatalyst containing layer side substrate side. 40 mW / cm with a mercury lamp (wavelength 365 nm)²Was exposed for 90 seconds to form a wettability change pattern on the glass substrate.
[0148]
At this time, the contact angle between the unexposed part and the exposed part and the wetting standard reagent (40 mN / m) was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping, the result was 75 ° and 7 °, respectively.
[0149]
【The invention's effect】
According to the present invention, the active oxygen species generated from the photocatalyst-containing layer by irradiating energy after arranging a mask having a predetermined pattern between the photocatalyst-containing layer and the characteristic change layer is The characteristic change layer is reached without being diffused through the small holes of the mask. This makes it possible to change the characteristics of only the portion where the active oxygen species has reached. In addition, since it is possible to change the characteristics of the characteristic change layer in a state where the concentration of the generated active oxygen species is high, a pattern forming body having a pattern whose characteristics have been changed with high definition in a short time efficiently It becomes possible to do.
[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.
[Explanation of symbols]
1 ... Base material
2 ... Photocatalyst containing layer
3 ... Photocatalyst containing layer side substrate
4 ... Base
5 ... Characteristic change layer
6 ... Substrate for pattern forming body
7 ... Small hole
8 ... Mask
9… Energy
10 ... Pattern

Claims (21)

A photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a base material, and a substrate for a pattern forming body having a characteristic changing layer whose characteristics change by the action of the photocatalyst in the photocatalyst-containing layer And a mask having a thickness of 2 mm or less having small holes in a desired pattern between the characteristic change layers, and then irradiating energy from a predetermined direction, whereby the energy irradiated portion A pattern forming body having a pattern with a changed characteristic on the characteristic changing layer is obtained by changing the characteristics of the characteristic changing layer and then removing the photocatalyst-containing layer side substrate and the mask. Manufacturing method. The method for producing a pattern forming body according to claim 1, wherein the mask is disposed in close contact between the photocatalyst layer and the characteristic change layer. The method for manufacturing a pattern forming body according to claim 1, wherein the mask is made of metal. The said photocatalyst containing layer is a layer which consists of photocatalysts, The manufacturing method of the pattern formation body in any one of Claim 1 to 3 characterized by the above-mentioned. The method for producing a pattern forming body according to claim 4, wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. The said photocatalyst containing layer is a layer which has a photocatalyst and a binder, The manufacturing method of the pattern formation body in any one of Claim 1- Claim 3 characterized by the above-mentioned. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. The method for producing a pattern forming body according to any one of claims 1 to 6, wherein the pattern forming body is one or more substances selected from iron (Fe ₂ O ₃ ). The photocatalyst is, the manufacturing method of the pattern forming member according to claim 7, characterized in that the titanium oxide (TiO _2). The pattern forming body according to any one of claims 1 to 8, wherein the substrate for the pattern forming body includes a base body and a characteristic change layer formed on the base body. Production method. The characteristic change layer is a wettability change layer whose wettability changes so that a contact angle with a liquid is lowered when irradiated with energy by the action of a photocatalyst in the photocatalyst-containing layer. The manufacturing method of the pattern formation body in any one of Claim 1-9. The contact angle with a liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in a portion not irradiated with energy and 9 ° or less in a portion irradiated. 10. A method for producing a pattern forming body according to 10. The method for producing a pattern forming body according to claim 10 or 11, wherein the wettability changing layer is a layer containing an organopolysiloxane. The method for producing a pattern forming body according to claim 12, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. 13. n is an integer from 0 to 3.) It is an organopolysiloxane which is one or two or more hydrolytic condensates or cohydrolytic condensates of a silicon compound represented by Or the manufacturing method of the pattern formation body of Claim 13. The method for producing a pattern forming body according to any one of claims 10 to 14, wherein the substrate for the pattern forming body includes a wettability changing layer having self-supporting property. The said characteristic change layer is a decomposition removal layer decomposed | disassembled and removed when energy is irradiated by the effect | action of the photocatalyst in the said photocatalyst containing layer, The any one of Claim 1-9 The manufacturing method of the pattern formation body of Claim. 17. The pattern forming body according to claim 16, wherein a contact angle of the liquid with respect to the decomposition / removal layer is different from a contact angle of the liquid with respect to the substrate exposed by the decomposition / removal layer. Manufacturing method. The method for producing a pattern forming body according to claim 16 or 17, wherein the decomposition / removal layer is any of a self-assembled monolayer, a Langmuir-Blodgett film, and an alternating adsorption film. The wettability of the substrate exposed by decomposing and removing the decomposition removal layer is 9 ° or less as a contact angle with a liquid having a surface tension of 40 mN / m, and is 10 ° or more on the decomposition removal layer. The method for producing a pattern forming body according to any one of claims 16 to 18, wherein: The method for producing a pattern forming body according to any one of claims 1 to 19, wherein the energy irradiation is performed while heating the photocatalyst-containing layer. The method for producing a pattern forming body according to any one of claims 1 to 20, wherein the characteristic change layer is a layer not containing a photocatalyst.

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