JP2004170463A - Method for manufacturing functional element and manufacturing apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a pattern formation body by an ink jet system which can form a high-definition pattern and has a wide selection range of the film thickness of a functional part, and a manufacturing apparatus for the same. <P>SOLUTION: The method for manufacturing the functional element includes: a pattern formation preparing process of preparing the pattern formation body having a pattern consisting of a lyophilic area and a water-repellent area on its surface; a cooling process of cooling the temperature of the surface of the pattern formation body to 0 to 25°C; a coating process of applying coating liquid for functional part formation forming the functional part; and a temperature raising process of raising the temperature of the pattern formation body surface coated with the coating liquid for functional part formation to 10 to 35°C. <P>COPYRIGHT: (C)2004,JPO

Description

【０１０３】
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。
【０１０４】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコン化合物をバインダに混合してもよい。
【０１０５】
（ｉｉｉ）分解物質
上記第２の形態および第３の形態においては、さらにエネルギー照射による光触媒の作用により分解され、これにより光触媒含有層上の濡れ性を変化させることができる分解物質を光触媒含有層に含有させる必要がある。すなわち、バインダ自体に光触媒含有層上の濡れ性を変化させる機能が無い場合、およびそのような機能が不足している場合に、上述したような分解物質を添加して、上記光触媒含有層上の濡れ性の変化を起こさせる、もしくはそのような変化を補助させるようにするのである。
【０１０６】
このような分解物質としては、光触媒の作用により分解し、かつ分解されることにより光触媒含有層表面の濡れ性を変化させる機能を有する界面活性剤を挙げることができる。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】
また、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、ナイロン、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、ポリマー等を挙げることができる。
【０１０８】
（ｉｖ）フッ素の含有
また、本実施態様においては、光触媒含有層がフッ素を含有し、さらにこの光触媒含有層表面のフッ素含有量が、光触媒含有層に対しエネルギーを照射した際に、上記光触媒の作用によりエネルギー照射前に比較して低下するように上記光触媒含有層が形成されていることが好ましい。
【０１０９】
このような特徴を有する光触媒含有層であれば、エネルギーをパターン照射することにより、後述するように容易にフッ素の含有量の少ない部分からなるパターンを形成することができる。ここで、フッ素は極めて低い表面エネルギーを有するものであり、このためフッ素を多く含有する物質の表面は、臨界表面張力がより小さくなる。したがって、フッ素の含有量の多い部分の表面の臨界表面張力に比較してフッ素の含有量の少ない部分の臨界表面張力は大きくなる。これはすなわち、フッ素含有量の少ない部分はフッ素含有量の多い部分に比較して親液性領域となっていることを意味する。よって、周囲の表面に比較してフッ素含有量の少ない部分からなるパターンを形成することは、撥液性域内に親液性領域のパターンを形成することとなる。
【０１１０】
したがって、このような光触媒含有層を用いた場合は、エネルギーをパターン照射することにより、撥液性領域内に親液性領域のパターンを容易に形成することができるので、例えばインクジェット法等により、機能性層形成用塗工液を塗布した場合に、高精細な機能性部を形成することが可能となるからである。
【０１１１】
上述したような、フッ素を含む光触媒含有層中に含まれるフッ素の含有量としては、エネルギーが照射されて形成されたフッ素含有量が低い親液性領域におけるフッ素含有量が、エネルギー照射されていない部分のフッ素含有量を１００とした場合に１０以下、好ましくは５以下、特に好ましくは１以下である。
【０１１２】
このような範囲内とすることにより、エネルギー照射部分と未照射部分との親液性に大きな違いを生じさせることができる。したがって、このような光触媒含有層に、例えば機能性層形成用塗工液を付着させることにより、フッ素含有量が低下した親液性領域のみに正確に機能性部を形成することが可能となり、精度の良い機能性素子を得ることができるからである。なお、この低下率は重量を基準としたものである。
【０１１３】
このような光触媒含有層中のフッ素含有量の測定は、一般的に行われている種々の方法を用いることが可能であり、例えばＸ線光電子分光法（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ， ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）とも称される。）、蛍光Ｘ線分析法、質量分析法等の定量的に表面のフッ素の量を測定できる方法であれば特に限定されるものではない。
【０１１４】
また、本実施態様においては、光触媒として上述したように二酸化チタンが好適に用いられるが、このように二酸化チタンを用いた場合の、光触媒含有層中に含まれるフッ素の含有量としては、Ｘ線光電子分光法で分析して定量化すると、チタン（Ｔｉ）元素を１００とした場合に、フッ素（Ｆ）元素が５００以上、このましくは８００以上、特に好ましくは１２００以上となる比率でフッ素（Ｆ）元素が光触媒含有層表面に含まれていることが好ましい。
【０１１５】
フッ素（Ｆ）が光触媒含有層にこの程度含まれることにより、光触媒含有層上における臨界表面張力を十分低くすることが可能となることから表面における撥液性を確保でき、これによりエネルギーをパターン照射してフッ素含有量を減少させたパターン部分における表面の親液性領域との濡れ性の差異を大きくすることができ、最終的に得られる機能性素子の精度を向上させることができるからである。
【０１１６】
さらに、このような機能性素子においては、エネルギーをパターン照射して形成される親インク領域におけるフッ素含有量が、チタン（Ｔｉ）元素を１００とした場合にフッ素（Ｆ）元素が５０以下、好ましくは２０以下、特に好ましくは１０以下となる比率で含まれていることが好ましい。
【０１１７】
光触媒含有層中のフッ素の含有率をこの程度低減することができれば、機能性素子を形成するためには十分な親液性を得ることができ、上記エネルギーが未照射である部分の撥液性との濡れ性の差異により、機能性素子を精度良く形成することが可能となり、利用価値の高い機能性素子を得ることができる。
【０１１８】
（ｖ）光触媒含有層の製造方法
上述したようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒含有層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより、光触媒含有層を形成することができる。
【０１１９】
ｂ．第二実施態様
次に、上記濡れ性変化層における第二実施態様について説明する。上記濡れ性変化層における第二実施態様は、少なくとも光触媒を含有する光触媒処理層と、上記光触媒処理層上に形成されたエネルギー照射に伴う光触媒の作用により、表面の液体との接触角が低下する層である表面変化型濡れ性変化層とからなる層である場合である。
【０１２０】
本実施態様においては、光触媒処理層上にエネルギー照射に伴う光触媒の作用により液体との接触角が低下する表面変化型濡れ性変化層が形成されていることから、エネルギー照射によって、光触媒処理層中の光触媒が表面変化型濡れ性変化層に作用し、表面変化型濡れ性変化層上のエネルギー照射された部分を、液体との接触角が低下するように変化させることが可能となるのである。以下、上記光触媒処理層および表面変化型濡れ性変化層について説明する。
【０１２１】
（ｉ）光触媒処理層
本実施態様に用いられる光触媒処理層は、少なくとも光触媒を含有するものであり、光触媒処理層がバインダを有する場合は、上記第一実施態様で説明した光触媒含有層と同様であるので、ここでの説明は省略する。ただし、本実施態様においては、光触媒処理層上の濡れ性は特に変化する必要がないことから、バインダ自体に光触媒が作用することによる濡れ性の変化が生じない場合であっても、第一実施態様のように分解物質を光触媒処理層に含有させる必要がない。また、バインダを有する場合の光触媒処理層の製造方法は、上述した第一実施態様と同様であるので、これについての説明も省略する。
【０１２２】
一方、バインダを有さない場合の光触媒処理層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒処理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処理層とすることが可能であり、これにより表面変化型濡れ性変化層上の濡れ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表面変化型濡れ性変化層上の濡れ性を変化させることが可能となる。
【０１２３】
また、光触媒のみからなる光触媒処理層の他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。
【０１２４】
（ｉｉ）表面変化型濡れ性変化層
次に、本実施態様に用いられる表面変化型濡れ性変化層について説明する。
【０１２５】
本実施態様に用いられる表面変化型濡れ性変化層は、上記光触媒処理層の作用により濡れ性が変化する層であれば特に限定されるものではないが、上述した第一実施態様の光触媒含有層中のバインダと同様の材料で形成することが好ましい。なお、このように上記第一実施態様の光触媒含有層中のバインダと同様の材料で形成した場合の表面変化型濡れ性変化層の材料および形成方法に関しては、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０１２６】
本実施態様において、この表面変化型濡れ性変化層の厚みは、光触媒による濡れ性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、特に好ましくは０．０１〜０．１μｍの範囲内である。
【０１２７】
本実施態様において上述した成分の表面変化型濡れ性変化層を用いることにより、隣接する光触媒処理層中の光触媒の作用により、上記成分の一部である有機基や添加剤の酸化、分解等の作用を用いて、エネルギー照射部分の濡れ性を変化させて親液性とし、エネルギー未照射部との濡れ性に大きな差を生じさせることができる。
【０１２８】
本実施態様に用いられる表面変化型濡れ性変化層は中でも、エネルギー照射していない部分、すなわち撥液性領域においては、４０ｍＮ／ｍの液体との接触角が、１０°以上、中でも表面張力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゜以上であることが好ましい。これは、エネルギー照射していない部分が、撥液性が要求される部分であることから、上記液体との接触角が小さい場合は、撥液性が十分でなく、上述した機能性部形成用塗工液をインクジェット方式により塗布し、硬化させて形成する場合に、撥液性領域にも機能性部形成用塗工液が付着する可能性があることから、高精細に機能性部を形成することが困難となるからである。
【０１２９】
また、上記表面変化型濡れ性変化層は、エネルギー照射された部分、すなわち親液性領域においては、４０ｍＮ／ｍの液体との接触角が９°未満、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０゜以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０゜以下となるような層であることが好ましい。エネルギー照射された部分、すなわち親液性領域における液体との接触角が高い場合は、例えば機能性部を形成する機能性部形成用塗工液を、親液性領域においてもはじいてしまう可能性があるからである。なお、ここでの表面変化型濡れ性変化層における液体との接触角も、上述した「１．パターン形成体準備工程」において説明した方法により測定された値である。
【０１３０】
なお、この表面変化型濡れ性変化層には、上記第一実施態様における光触媒含有層の説明中「フッ素の含有」の項で記載したものと同様にして同様のフッ素を含有させることができる。
【０１３１】
なお、本実施態様においては、表面変化型濡れ性変化層中に光触媒を含有する必要がなく、この場合には、経時的に機能性部が光触媒の影響を受ける可能性を少なくすることが可能である。
【０１３２】
ｃ．第三実施態様
次に、上記濡れ性変化層の第三実施態様について説明する。上記濡れ性変化層における第三実施態様は、光触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記濡れ性変化層と上記光触媒処理層とが２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより、表面の液体との接触角が低下するように濡れ性が変化する表面変化型濡れ性変化層である場合である。
【０１３３】
本実施態様における表面変化型濡れ性変化層は、例えば図５に示すように、表面変化型濡れ性変化層２１と、光触媒を含有する光触媒処理層２２および基体２３とを有する光触媒処理層側基板２０を準備する。次に、上記表面変化型濡れ性変化層２１と光触媒処理層２２とが、所定の間隙となるように配置された後、フォトマスク２４等を用いて、所定の方向からエネルギー２５を照射されることにより、表面変化型濡れ性変化層２１上におけるエネルギー照射された部分の液体との接触角が低下するように濡れ性が変化するものである。
【０１３４】
なお、上記光触媒処理層側基板は、エネルギー照射の間のみ、上記位置に配置されていればよい。
【０１３５】
本実施態様に用いられる表面変化型濡れ性変化層については、第二実施態様で説明した表面変化型濡れ性変化層と同様であるので、ここでの説明は省略し、光触媒処理層側基板のみについて説明する。
【０１３６】
本実施態様に用いられる光触媒処理層側基板は、少なくとも光触媒処理層と基体とを有するものであり、通常は基体上に所定の方法で形成された薄膜状の光触媒処理層が形成されてなるものである。また、この光触媒処理層側基板には、パターン状に形成された光触媒処理層側遮光部やプライマー層が形成されたものも用いることができる。
【０１３７】
本実施態様においては、エネルギーを照射する際に、上記表面変化型濡れ性変化層と、上記光触媒処理層側基板における光触媒処理層とを所定の間隙をおいて対向させ、光触媒処理層側基板の光触媒処理層の作用により、表面変化型濡れ性変化層の濡れ性を変化させ、エネルギー照射後、光触媒処理層側基板を取り外すことにより濡れ性パターンが形成されるのである。以下、この光触媒処理層側基板の各構成について説明する。
【０１３８】
（ｉ）光触媒処理層
本実施態様に用いられる光触媒処理層は、少なくとも光触媒を含有するものであり、バインダを有していても、有していなくてもよく、上述した第二実施態様の光触媒処理層と同様であるので、ここでの説明は省略する。
【０１３９】
ここで、本実施態様において用いられる光触媒処理層は、例えば図５に示すように、基体２３上に全面に形成されたものであってもよいが、例えば図６に示すように、基体２３上に光触媒処理層２２がパターン状に形成されたものであってもよい。
【０１４０】
このように光触媒処理層をパターン状に形成することにより、エネルギーを照射する際に、フォトマスク等を用いてパターン照射をする必要がなく、全面に照射することにより、表面変化型濡れ性変化層上に親液性領域と撥液性領域とからなる濡れ性パターンを形成することができる。
【０１４１】
この光触媒処理層のパターニング方法は、特に限定されるものではないが、例えばフォトリソグラフィー法等により行うことが可能である。
【０１４２】
また、光触媒処理層と表面変化型濡れ性変化層とを例えば密着させてエネルギー照射を行う場合には、実際に光触媒処理層の形成された部分のみの濡れ性が変化するものであるので、エネルギーの照射方向は上記光触媒処理層と表面変化型濡れ性変化層とが対向する部分にエネルギーが照射されるものであれば、いかなる方向から照射されてもよく、さらには、照射されるエネルギーも特に平行光等の平行なものに限定されないという利点を有するものとなる。
【０１４３】
（ｉｉ）基体
本実施態様においては、図５に示すように、光触媒処理層側基板は、少なくとも基体２３とこの基体２３上に形成された光触媒処理層２２とを有するものである。この際、用いられる基体を構成する材料は、後述するエネルギーの照射方向や、得られる機能性素子が透明性を必要とするか等により適宜選択される。
【０１４４】
また本実施態様に用いられる基体は、可撓性を有するもの、例えば樹脂製フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、エネルギー照射方法により適宜選択されるものである。
【０１４５】
なお、基体表面と光触媒処理層との密着性を向上させるために、基体上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１４６】
（ｉｉｉ）光触媒処理層側遮光部
本実施態様に用いられる光触媒処理層側基板には、パターン状に形成された光触媒処理層側遮光部が形成されたものを用いても良い。このように光触媒処理層側遮光部を有する光触媒処理層側基板を用いることにより、エネルギー照射に際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒処理層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１４７】
このような光触媒処理層側遮光部を有する光触媒処理層側基板は、光触媒処理層側遮光部の形成位置により、下記の二つの態様とすることができる。
【０１４８】
一つが、例えば図７に示すように、基体２３上に光触媒処理層側遮光部２６を形成し、この光触媒処理層側遮光部２６上に光触媒処理層２２を形成して、光触媒処理層側基板とする態様である。もう一つは、例えば図８に示すように、基体２３上に光触媒処理層２２を形成し、その上に光触媒処理層側遮光部２６を形成して光触媒処理層側基板２０とする態様である。
【０１４９】
いずれの態様においても、フォトマスクを用いる場合と比較すると、光触媒処理層側遮光部が、上記光触媒処理層と表面変化型濡れ性変化層との配置部分の近傍に配置されることになるので、基体内等におけるエネルギーの散乱の影響を少なくすることができることから、エネルギーのパターン照射を極めて正確に行うことが可能となる。
【０１５０】
さらに、上記光触媒処理層上に光触媒処理層側遮光部を形成する態様においては、光触媒処理層と表面変化型濡れ性変化層とを所定の位置に配置する際に、この光触媒処理層側遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記光触媒処理層側遮光部を上記間隙を一定のものとするためのスペーサとしても用いることができるという利点を有する。
【０１５１】
すなわち、所定の間隙をおいて上記光触媒処理層と表面変化型濡れ性変化層とを対向させた状態で配置する際に、上記光触媒処理層側遮光部と表面変化型濡れ性変化層とを密着させた状態で配置することにより、上記所定の間隙を正確とすることが可能となり、そしてこの状態で光触媒処理層側基板からエネルギーを照射することにより、表面変化型濡れ性変化層上に濡れ性変化パターンを精度良く形成することが可能となるのである。
【０１５２】
このような光触媒処理層側遮光部の形成方法は、特に限定されるものではなく、光触媒処理層側遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１５３】
例えば、スパッタリング法、真空蒸着法等により厚み１０００〜２０００Å程度のクロム等の金属薄膜を形成し、この薄膜をパターニングすることにより形成されてもよい。このパターニングの方法としては、スパッタ等の通常のパターニング方法を用いることができる。
【０１５４】
また、樹脂バインダ中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層をパターン状に形成する方法であってもよい。用いられる樹脂バインダとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種または２種以上混合したものや、感光性樹脂、さらにはＯ／Ｗエマルジョン型の樹脂組成物、例えば、反応性シリコーンをエマルジョン化したもの等を用いることができる。このような樹脂製遮光部の厚みとしては、０．５〜１０μｍの範囲内で設定することができる。このよう樹脂製遮光部のパターニングの方法は、フォトリソ法、印刷法等一般的に用いられている方法を用いることができる。
【０１５５】
なお、上記説明においては、光触媒処理層側遮光部の形成位置として、基体と光触媒処理層との間、および光触媒処理層表面の二つの場合について説明したが、その他、基体の光触媒処理層が形成されていない側の表面に光触媒処理層側遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、濡れ性変化パターンを小ロットで変更するような場合に好適に用いることができる。
【０１５６】
（ｉｖ）プライマー層
次に、本実施態様の光触媒処理層側基板に用いられるプライマー層について説明する。本実施態様において、上述したように基体上に光触媒処理層側遮光部をパターン状に形成して、その上に光触媒処理層を形成して光触媒処理層側基板とする場合においては、上記光触媒処理層側遮光部と光触媒処理層との間にプライマー層を形成してもよい。
【０１５７】
このプライマー層の作用・機能は必ずしも明確なものではないが、光触媒処理層側遮光部と光触媒処理層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による表面変化型濡れ性変化層の濡れ性変化を阻害する要因となる光触媒処理層側遮光部および光触媒処理層側遮光部間に存在する開口部からの不純物、特に、光触媒処理層側遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で濡れ性変化の処理が進行し、その結果、高解像度のパターンを得ることが可能となるのである。
【０１５８】
なお、本実施態様においてプライマー層は、光触媒処理層側遮光部のみならず光触媒処理層側遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた光触媒処理層側遮光部全面にわたって形成されていることが好ましい。
【０１５９】
本実施態様におけるプライマー層は、光触媒処理層側基板の光触媒処理層側遮光部と光触媒処理層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１６０】
このプライマー層を構成する材料としては、特に限定されるものではないが、光触媒の作用により分解されにくい無機材料が好ましい。具体的には無定形シリカを挙げることができる。このような無定形シリカを用いる場合には、この無定形シリカの前駆体は、一般式ＳｉＸ_４で示され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物であり、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１６１】
また、プライマー層の膜厚は、０．００１μｍから１μｍの範囲内であることが好ましく、特に０．００１μｍから０．１μｍの範囲内であることが好ましい。
【０１６２】
ｄ．第四実施態様
次に、上記濡れ性変化層の第四実施態様について説明する。上記濡れ性変化層の第四実施態様は、少なくとも光触媒を含有する光触媒処理層と、上記光触媒処理層上に形成されたエネルギー照射に伴う光触媒の作用により分解除去される分解除去型濡れ性変化層であり、かつ上記分解除去型濡れ性変化層に対する液体の接触角と、上記分解除去型濡れ性変化層が分解除去されて露出した前記光触媒処理層に対する液体の接触角とが異なる層とからなる層である場合である。
【０１６３】
本実施態様においては、上記光触媒処理層上にエネルギー照射に伴う光触媒の作用により分解除去される分解除去型濡れ性変化層が形成されていることから、エネルギー照射によって、光触媒処理層中の光触媒が分解除去型濡れ性変化層に作用し、分解除去型濡れ性変化層上のエネルギー照射された部分を、分解除去することが可能となるのである。
【０１６４】
ここで、上記光触媒処理層については、上述した第二実施態様に用いられる光触媒処理層と同様であるので、ここでの説明は省略し、本実施態様に用いられる分解除去型濡れ性変化層について、以下詳しく説明する。
【０１６５】
本実施態様に用いられる分解除去型濡れ性変化層は、エネルギー照射された際に光触媒処理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型濡れ性変化層が分解除去される層であり、かつこの分解除去型濡れ性変化層が、上記露出した光触媒処理層と比較して、液体との接触角が異なるものであれば、特に限定されるものではない。
【０１６６】
このように分解除去型濡れ性変化層は、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型濡れ性変化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。
【０１６７】
なお、この分解除去型濡れ性変化層は、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、分解除去型濡れ性変化層の材質によっては、洗浄工程等を行ってもよい。
【０１６８】
また、本実施態様には、凹凸を形成するのみならず、分解除去型濡れ性変化層と、この分解除去型濡れ性変化層が分解除去されて露出した光触媒処理層との液体との接触角が異なることから、パターン形成体上に撥液性領域と、親液性領域を形成することが可能となるのである。
【０１６９】
ここで、本実施態様に用いられる分解除去型濡れ性変化層は、上記の中でも、分解除去型濡れ性変化層が、上記露出した光触媒処理層と比較して、液体との接触角が高いことが好ましい。これにより、分解除去型濡れ性変化層が分解除去された領域を親液性領域、上記分解除去型濡れ性変化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、親液性領域と撥液性領域とからなるパターンを形成することが可能となるからである。
【０１７０】
ここで、本実施態様における分解除去型濡れ性変化層は、エネルギー照射後に残存している部分が撥液性領域となることから、４０ｍＮ／ｍの液体との接触角が、１０°以上、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０゜以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０゜以下となるような層であることが好ましい。これは、分解除去型濡れ性変化層が本実施態様においては撥液性が要求される部分であることから、液体との接触角が小さい場合は、撥液性が十分でなく、インクジェット方式により、機能性部形成用塗工液を塗布した際に、撥液性領域にまで機能性部形成用塗工液が付着する可能性が生じることから、高精細な機能性素子とすることが困難となるからである。
【０１７１】
また、エネルギー照射により露出した光触媒処理層、すなわち親液性領域においては、４０ｍＮ／ｍの液体との接触角が、４０ｍＮ／ｍの液体との接触角が９°未満、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０゜以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０゜以下となるような層であることが好ましい。これは光触媒処理層、すなわち親液性領域における機能性部形成用塗工液との接触角が高い場合は、機能性部形成用塗工液を塗布した場合に、親液性領域においても機能性部形成用塗工液をはじいてしまう可能性があり、インクジェット方式により親液性領域上に機能性部を形成することが難しくなる可能性があるからである。ここで、液体との接触角は、上述した「１．パターン形成体準備工程」において説明した方法により測定した値である。
【０１７２】
本実施態様の分解除去型濡れ性変化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。
【０１７３】
また、本実施態様においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【０１７４】
ここで、本実施態様に用いられる自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜について具体的に説明する。
【０１７５】
（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材表面に吸着・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材表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基材表面に形成されたもの（後者はポリマーブラシと総称される）も自己組織化単分子膜と考えられる場合もあるようである。本実施態様は、これらも自己組織化単分子膜に含める。
【０１７６】
（ｉｉ）ラングミュア−ブロジェット膜
本実施態様に用いられるラングミュア−ブロジェット膜（Ｌａｎｇｍｕｉｒ−Ｂｌｏｄｇｅｔｔ Ｆｉｌｍ）は、基材上に形成されてしまえば形態上は上述した自己組織化単分子膜との大きな相違はない。ラングミュア−ブロジェット膜の特徴はその形成方法とそれに起因する高度な２次元分子パッキング性（高配向性、高秩序性）にあると言える。すなわち、一般にラングミュア−ブロジェット膜形成分子は気液界面上に先ず展開され、その展開膜がトラフによって凝縮されて高度にパッキングした凝縮膜に変化する。実際は、これを適当な基材に移しとって用いる。ここに概略を示した手法により単分子膜から任意の分子層の多層膜まで形成することが可能である。また、低分子のみならず、高分子、コロイド粒子なども膜材料とすることができる。様々な材料を適用した最近の事例に関しては宮下徳治らの総説“ソフト系ナノデバイス創製のナノテクノロジーへの展望” 高分子 ５０巻 ９月号 ６４４−６４７ （２００１）に詳しく述べられている。
【０１７７】
（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材上に吸着・結合させて積層することにより形成される膜である。多数の官能基を有する材料の方が膜の強度や耐久性が増すなど利点が多いので、最近ではイオン性高分子（高分子電解質）を材料として用いることが多い。また、タンパク質や金属や酸化物などの表面電荷を有する粒子、いわゆる“コロイド粒子”も膜形成物質として多用される。さらに最近では、水素結合、配位結合、疎水性相互作用などのイオン結合よりも弱い相互作用を積極的に利用した膜も報告されている。比較的最近の交互吸着膜の事例については、静電的相互作用を駆動力にした材料系に少々偏っているがＰａｕｌａ Ｔ． Ｈａｍｍｏｎｄによる総説“Ｒｅｃｅｎｔ Ｅｘｐｌｏｒａｔｉｏｎｓ ｉｎ Ｅｌｅｃｔｒｏｓｔａｔｉｃ Ｍｕｌｔｉｌａｙｅｒ Ｔｈｉｎ Ｆｉｌｍ Ａｓｓｅｍｂｌｙ”Ｃｕｒｒｅｎｔ Ｏｐｉｎｉｏｎ ｉｎ Ｃｏｌｌｏｉｄ ＆ Ｉｎｔｅｒｆａｃｅ Ｓｃｉｅｎｃｅ， ４， ４３０−４４２ （２０００）に詳しい。交互吸着膜は、最も単純なプロセスを例として説明すれば、正（負）電荷を有する材料の吸着−洗浄−負（正）電荷を有する材料の吸着−洗浄のサイクルを所定の回数繰り返すことにより形成される膜である。ラングミュア−ブロジェット膜のように展開−凝縮−移し取りの操作は全く必要ない。また、これら製法の違いより明らかなように、交互吸着膜はラングミュア−ブロジェット膜のような２次元的な高配向性・高秩序性は一般に有さない。しかし、交互吸着膜及びその作製法は、欠陥のない緻密な膜を容易に形成できること、微細な凹凸面やチューブ内面や球面などにも均一に成膜できることなど、従来の成膜法にない利点を数多く有している。
【０１７８】
また、分解除去型濡れ性変化層の膜厚としては、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型濡れ性変化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。
【０１７９】
ｅ．第五実施態様
次に、上記濡れ性変化層の第五実施態様について説明する。上記濡れ性変化層の第五実施態様は、光触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記濡れ性変化層と上記光触媒処理層とが２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより、分解除去される分解除去型濡れ性変化層であり、上記分解除去型濡れ性変化層に対する液体の接触角と、上記分解除去型濡れ性変化層が分解除去されて露出した基材に対する液体の接触角とが異なる層である場合である。
【０１８０】
本実施態様においては、上述した第三実施態様と同様に、エネルギーを照射する際に、光触媒を含有する光触媒処理層を有する光触媒処理層側基板を用いて、上記分解除去型濡れ性変化層と、上記光触媒処理層とを所定の間隙をおいて対向させ、光触媒処理層側基板の光触媒処理層の作用により、分解除去型濡れ性変化層をパターン状に分解除去した後、光触媒処理層側基板を取り外すことにより、分解除去型濡れ性変化層が分解されたパターンが形成されるのである。この際、分解除去型濡れ性変化層が分解除去されて露出するのは後述する基材となる。この際、後述する基材は、表面を親液性となるように、表面処理したものであってもよい。材料の表面を親液性となるように表面処理した例としては、アルゴンや水などを利用したプラズマ処理による親液性表面処理が挙げられ、基体上に形成する親液性の層としては、例えばテトラエトキシシランのゾルゲル法によるシリカ膜等を挙げることができる。
【０１８１】
本実施態様に用いられる分解除去型濡れ性変化層については、上述した第四実施態様と同様であり、また光触媒処理層側基板については、上述した第三実施態様で説明した光触媒処理層側基板と同様であるので、ここでの説明は省略する。
【０１８２】
（２）基材
次に、本実施態様のパターン形成体に用いられる基材について説明する。本実施態様においては、上記濡れ性変化層が自己支持性を有しない場合、また機能性素子に強度が必要な場合、または上述した濡れ性変化層の第五実施態様である場合等に、基材上に上記濡れ性変化層が形成される。
【０１８３】
本実施態様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。
【０１８４】
また、本実施態様においては、上記濡れ性変化層の濡れ性が変化したパターンの形成に際してエネルギーを照射する必要性があるが、このエネルギーの照射において、基材側からエネルギーが照射される場合には、基材に透明性が必要とされる。
【０１８５】
なお、基材表面と濡れ性変化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。
【０１８６】
（３）その他
本実施態様においては、機能性素子の種類によって、パターン形成体中に遮光部が形成されていても良い。このように遮光部を有する場合は、エネルギー照射によるパターン形成に際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、簡便な工程とすることが可能となり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１８７】
このような遮光部の形成位置としては、基材上に形成し、その上から濡れ性変化層を形成する場合、すなわち基材と濡れ性変化層との間に形成する場合と、機能性部を形成する面と反対側の、濡れ性変化層またはパターン形成体が上記基材を有する場合には基材の表面にパターン状に形成する場合とがある。
【０１８８】
いずれの場合も、エネルギーの照射は、パターン形成体側からとなるが、全面に照射することにより、濡れ性変化層面にパターン状に濡れ性変化パターンを形成することができる。
【０１８９】
このような遮光部の形成方法は、特に限定されるものではなく、遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。この遮光部の形成方法については、上述した濡れ性変化層の第三実施態様における光触媒処理層側基板における光触媒処理層側遮光部の項において説明したものと同様のものを用いることが可能であるので、ここでの説明は省略する。
【０１９０】
（４）親液性領域および撥液性領域からなるパターンの形成
次に、上記濡れ性変化層への親液性領域および撥液性領域からなるパターン形成について説明する。本実施態様においては、所定の方向からエネルギーをパターン照射することにより、上記濡れ性変化層表面に濡れ性の違いによるパターンが形成され、このパターンに沿って、後述する機能性部が形成されるのである。
【０１９１】
なお、本実施態様でいうエネルギー照射（露光）とは、上記濡れ性変化層の濡れ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。
【０１９２】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒に二酸化チタンが好ましく用いられ、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。
【０１９３】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１９４】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１９５】
また、エネルギー照射に際してのエネルギーの照射量は、濡れ性変化層が光触媒の作用により濡れ性が変化するのに必要な照射量とする。
【０１９６】
この際、光触媒含有層を加熱しながらエネルギー照射することにより、感度を上昇させことが可能となり、効率的な濡れ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。
【０１９７】
ここで、上述したように、濡れ性変化層中に、光触媒含有層または光触媒処理層を有しない態様の場合には、上述した光触媒処理層側基板を、濡れ性変化層と所定の間隔をおいて配置し、所定の方向からエネルギー照射を行うことが必要である。
【０１９８】
上記の配置とは、実質的に光触媒の作用が濡れ性変化層表面に及ぶような状態で配置された状態をいうこととし、実際に物理的に接触している状態の他、所定の間隔を隔てて上記光触媒処理層と濡れ性変化層とが配置された状態とする。この間隙は、２００μｍ以下であることが好ましい。
【０１９９】
本実施態様において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって濡れ性変化層の濡れ性変化の効率が良好である点を考慮すると特に０．２μｍ〜１０μｍの範囲内、好ましくは１μｍ〜５μｍの範囲内とすることが好ましい。このような間隙の範囲は、特に間隙を高い精度で制御することが可能である小面積の濡れ性変化層に対して特に有効である。
【０２００】
一方、例えば３００ｍｍ×３００ｍｍといった大面積の濡れ性変化層に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒処理層側基板と濡れ性変化層との間に形成することは極めて困難である。したがって、濡れ性変化層が比較的大面積である場合は、上記間隙は、１０〜１００μｍの範囲内、特に５０〜７５μｍの範囲内とすることが好ましい。間隙をこのような範囲内とすることにより、パターンがぼやける等のパターン精度の低下の問題や、光触媒の感度が悪化して濡れ性変化の効率が悪化する等の問題が生じることなく、さらに濡れ性変化層上の濡れ性変化にムラが発生しないといった効果を有するからである。
【０２０１】
このように比較的大面積の濡れ性変化層をエネルギー照射する際には、エネルギー照射装置内の光触媒処理層側基板と濡れ性変化層との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒処理層側基板と濡れ性変化層とが接触することなく配置することが可能となるからである。
【０２０２】
このように光触媒処理層と濡れ性変化層表面とを所定の間隔で離して配置することにより、酸素と水および光触媒作用により生じた活性酸素種が脱着しやすくなる。すなわち、上記範囲より光触媒処理層と濡れ性変化層との間隔を狭くした場合は、上記活性酸素種の脱着がしにくくなり、結果的に濡れ性変化速度を遅くしてしまう可能性があることから好ましくない。また、上記範囲より間隔を離して配置した場合は、生じた活性酸素種が濡れ性変化層に届き難くなり、この場合も濡れ性変化の速度を遅くしてしまう可能性があることから好ましくない。
【０２０３】
本実施態様においては、このような配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０２０４】
このような極めて狭い間隙を均一に形成して光触媒処理層と濡れ性変化層とを配置する方法としては、例えばスペーサを用いる方法を挙げることができる。そして、このようにスペーサを用いることにより、均一な間隙を形成することができると共に、このスペーサが接触する部分は、光触媒の作用が濡れ性変化層表面に及ばないことから、このスペーサを上述した濡れ性変化パターンと同様のパターンを有するものとすることにより、濡れ性変化層上に所定の濡れ性変化パターンを形成することが可能となる。
【０２０５】
本実施態様においては、このような配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０２０６】
Ｂ．カラーフィルタ
次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した機能性素子の製造方法により形成されたカラーフィルタである。
【０２０７】
カラーフィルタにおける画素部の形状は、通常、マトリックス状やストライプ状であり、本発明においても同様である。本発明においては、このような画素部を形成する画素部形成用塗工液を塗布する前に、親液性領域のパターンが形成されたパターン形成体を冷却することにより、親液性領域上に精度良く、かつ所望の膜厚を有する画素部を形成することが可能となる。これにより、様々な用途に用いることが可能なカラーフィルタとすることが可能である。
【０２０８】
ここで、本発明のカラーフィルタは、上述した機能性素子の製造方法により製造することが可能であり、また一般的なカラーフィルタの製造に用いられる材料を用いることが可能である。
【０２０９】
Ｃ．機能性素子の製造装置
次に、本発明の機能性素子の製造装置について説明する。
【０２１０】
本発明の機能性素子の製造装置は、インクジェット方式により機能性部形成用塗工液を吐出させる吐出手段と、前記吐出手段から吐出された機能性部形成用塗工液が着弾する基板を固定する固定手段と、前記固定手段に固定される基板の表面温度を０℃〜２５℃の範囲内とする冷却手段とを有することを特徴とするものである。
【０２１１】
本発明においては、このような機能性素子の製造装置とすることにより、機能性部形成用塗工液を安定に吐出させることができ、従来よりも機能性部形成用塗工液の塗布量を多く確保することができるため、機能性部形成用塗工液から形成される機能性部の膜厚の選択範囲を広くすることができ、かつ高精細なパターンの形成を容易に可能とすることができる。
【０２１２】
本発明の機能性素子の製造装置について図面を用いて説明する。図２は本発明の機能性素子の製造装置の一例を示した概略図である。
【０２１３】
まず、本発明の機能性素子の製造装置は、インクジェット方式により基板１１表面に機能性部形成用塗工液を塗布するヘッド１０を有する。さらに、このようなヘッド１０により機能性部形成用塗工液が塗布される基板１１を固定する固定手段１２を有する。このような固定手段１２としては、基板１１を水平状態に安定に保持することが可能な手段であれば特に限定はされない。例えば、ステージ上で吸引することにより基板１１を固定する手段等を挙げることができる。さらに、このような固定手段１２により固定された基板１１の表面温度を上述した範囲内に冷却する冷却手段１３を有する。本発明における冷却手段１３としては、基板１１表面の温度を上述した範囲内とすることができる手段であれば特に限定はされない。具体的には、上述したように冷媒を基板１１と接触する部材内で循環させる方法や、低温状態に基板１１を曝す方法等を挙げることができる。その中でも冷媒を基板１１と接触する部材内で循環させる方法であることが好ましい。例えば、冷媒を循環させ冷却したステージ上に基板１１を配置する方法等である。この際用いる冷媒としては液体窒素等を挙げることができる。
【０２１４】
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。
【０２１５】
【実施例】
以下に実施例を示し、本発明をさらに説明する。
【０２１６】
［実施例］
（１）光触媒含有層用塗工液の調整
下記の成分を混合し、１００℃で２０分間攪拌して、光触媒含有層用塗工液を調製した。
光触媒含有層用塗工液の組成
・イソプロピルアルコール：３ｇ
・フルオロアルキルシラン（トーケムプロダクツ製、ＭＦ−１６０Ｅ：Ｎ−［３−（トリメトキシシリル）プロピル］−Ｎ−エチル−パーフルオロオクタンスルホンアミドのイソプロピルエーテル５０重量％溶液）：０．０７ｇ
・酸化チタンゾル（石原産業製、ＳＴＫ−０１）：３ｇ
・シリカゾル（日本合成ゴム製、グラスカＨＰＣ７００２）：０．６ｇ
・アルキルアルコキシシラン（日本合成ゴム製、ＨＰＣ４０２Ｃ）：０．２ｇ
（２）光触媒含有層の形成
開口部７６μｍ×２５９μｍで線幅が２３μｍのクロム薄膜パターンからなるブラックマトリックスを有するソーダガラス製の透明基板上に、上記の光触媒含有層用塗工液をスピンコーターにより塗布し、１５０℃、１０分間の乾燥処理後、加水分解、重縮合反応を進行させて、光触媒がオルガノポリシロキサン中に強固に固定された厚み０．５μｍの透明な光触媒含有層を形成した。
【０２１７】
この光触媒含有層にマスクを介して水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ^２の照度で３分間、光線を照射し、非照射部位と照射部位の水に対する接触角を測定した。接触角の測定は、接触角測定器（協和界面科学（株）製、ＣＡ−Ｚ型）を用い、非照射部位又は照射部位にマイクロシリンジから水滴を滴下して３０秒後に行った。その結果、非照射部位における水の接触角は７０゜であるのに対して、照射部位における水の接触角は１０゜以下であり、照射部位が高親水性となって、照射部位と非照射部位との濡れ性の差を利用してパターン形成が可能なことが確認された。
【０２１８】
さらに、ＪＩＳ Ｋ６７６８に規定する濡れ性試験において示された標準液を用い、光触媒含有層の非照射部位に液滴を接触させて３０秒後の接触角（θ）を測定し、ジスマンプロット（横軸：標準液の表面張力、縦軸：ｃｏｓθ）を作成し、グラフを外挿したところ、ｃｏｓθ＝０となる点が示す表面張力、すなわち非照射部位の臨界表面張力は３０ｍＮ／ｍだった。同じ方法で、照射部位における臨界表面張力を測定したところ、７０ｍＮ／ｍだった。
【０２１９】
（３）光触媒含有層の露光
パターンピッチが７６μｍ×２５９μｍで、且つ、上記ブラックマトリックスの線幅（２３μｍ）よりも狭い幅（１０μｍ）の遮光パターンを有するマスクを、上記透明基板の光触媒含有層上に配置し、ブラックマトリックスと重なるように位置合わせした後、このマスクを介して水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ^２の照度で５０秒間、光触媒含有層を露光して、照射部位を高親水性とした。各照射部位は、ブラックマトリックス上に存在する幅１０μｍの非照射部により区画され、ブラックマトリックスに囲まれた７６μｍ×２５９μｍの大きさの画素部形成領域と、その周囲のブラックマトリックスと重なる領域を有していた。
【０２２０】
（４）画素部用着色インクの調整
カラーフィルタ用ＵＶ硬化型インク 青色画素部用着色インク組成
・顔料（Ｃ．Ｉ．ピグメントブルー１５：６）：５重量部
・高分子分散剤（ＡＶＥＣＩＡ社製、ソルスパース２４０００）：２重量部
・バインダー（ベンジルメタクリレート−メタクリル酸共重合体）：３重量部
・モノマー１（ジペンタエリスリトールペンタアクリレート）：２重量部
・モノマー２（トリプロピレングリコールジアクリレート）：５重量部
・開始剤（２−メチル−１−［４−（メチルチオ）フェニル］−２−モンフォリノプロパン）−１−オン：２重量部
・溶剤（ジエチレングリコールモノブチルエーテルアセテート、２９．９ｄｙｎ／ｃｍ）：８１重量部
さらに、前記組成中のＣ．Ｉ．ピグメントブルー１５：６に代えてＣ．Ｉ．ピグメントレッド２５４を同量用いるほかは青色画素部用着色インクの場合と同様にして赤色画素部用着色インクを調整した。さらに、前記組成中のＣ．Ｉ．ピグメントブルー１５：６に代えてＣ．Ｉ．ピグメントグリーン３６を同量用いるほかは青色画素部用着色インクの場合と同様にして緑色画素部用着色インクを調整した。
【０２２１】
（５）カラーフィルタの製造
インクジェットヘッドに各色の画素用着色インクを充填した。次に、当該ヘッドから各色画素用着色インクを、基板上に点在する青色用の画素部形成領域の中心部にドロップ径３０μｍで滴下した。
【０２２２】
滴下した各色の画素部用着色インクは、ブラックマトリックス上の非照射部においてはじかれ、各色の画素部形成領域においては均一に拡散して選択的に付着された。
【０２２３】
その後、各色の着色インク層を８０℃、３分間乾燥させて、水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ^２の照度で３０秒間、光を照射して、さらに、２３０℃で３０分間熱処理を行なって画素部を形成した。
【０２２４】
ここで基板を５℃で冷却する冷却工程を取り入れた場合には、インクジェットから塗布を行なったインク液滴が冷却基板の親液性領域上に着弾後、径が広がりにくく、かつ速やかに濡れ広がることが抑制された。また流動性の関係から親液性領域に塗布される塗布量が増えても、連続的に吐出される液滴の影響から生じる波が機能性部形成用塗工液内に伝播しにくいため、このような波の物理的な影響を受けにくい。これにより十分な塗布量を確保することが可能となった。また、インクジェットでの塗布した後、５℃の状態から常温にゆっくりと戻しながら十分なレベリングを行なった後に、８０℃、３分間の乾燥を行なった。その結果、基板の表面温度を冷却する工程を取り入れなかった場合の最大塗布膜厚が２．５μｍであったのに対し、３．５μｍの塗布膜厚を形成することができるようになった。
【０２２５】
ここで、インクの温度と粘度との関係を図９、インクの温度と接触角との関係を図１０、インクの温度と表面張力との関係を図１１に示す。
【０２２６】
【発明の効果】
本発明によれば、パターン形成体の表面温度を上記範囲に冷却しているので、インクジェット装置により吐出された機能性部形成用塗工液は、パターン形成体の親液性領域上に着弾後、パターン形成体の表面温度の影響から粘度が上昇し流動性が低下する。また、パターン形成体を冷却すると、その表面の濡れ性は、全体的に機能性部形成用塗工液に対する接触角が高くなる方向に変化する傾向にある。従って、機能性部形成用塗工液は、親液性領域上に着弾後、径が広がりにくく、かつ速やかに濡れ広がることが抑制される。また流動性の関係から親液性領域に塗布される塗布量が増えても、連続的に吐出される液滴の影響から生じる波が機能性部形成用塗工液内を伝播しにくいため、このような波の物理的な影響を受けにくい。これにより十分な塗布量を確保することが可能となる。従って、インクジェット方式により形成される機能性部の膜厚の選択範囲を広げることができ、かつ微細なパターンを形成することができる。さらに、塗布工程後は昇温工程によりパターン形成体の表面温度を上記範囲内に戻しているので、機能性部形成用塗工液の粘度は元に戻り流動性が回復する。従って、機能性部形成用塗工液は親液性領域内に良好に濡れ広がり、親液性領域のパターンに沿って、高精細なパターンとすることができるといった効果を奏する。
【図面の簡単な説明】
【図１】本発明のインクジェット方式による機能性素子の製造方法の一例を示した工程図である。
【図２】本発明の機能性素子の製造装置の一例を示した概略図である。
【図３】従来のインクジェット方式による機能性素子の製造方法の一例を示した工程図である。
【図４】光触媒含有層を用いたパターン形成体において、温度変化に伴う溶媒系塗工液における接触角の変化を示したグラフである。
【図５】本発明における濡れ性変化層の一例を示す概略断面図である。
【図６】本発明における光触媒処理層側基板の一例を示す概略断面図である。
【図７】本発明における光触媒処理層側基板の他の例を示す概略断面図である。
【図８】本発明における光触媒処理層側基板の他の例を示す概略断面図である。
【図９】本発明の実施例におけるインクの温度と粘度との関係を示したグラフである。
【図１０】本発明の実施例におけるインクの温度と接触角との関係を示したグラフである。
【図１１】本発明の実施例におけるインクの温度と表面張力との関係を示したグラフである。
【符号の説明】
１ … パターン形成体
２ … 親液性領域
３ … 撥液性領域
４ … インクジェット装置
５ … 機能性部形成用塗工液[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method of manufacturing a functional element of an ink jet system capable of forming a high-definition pattern with a wide selection range of a film thickness, and an apparatus for manufacturing the same.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, an ink-jet patterning method, in which an ink liquid is formed into small particles called droplets and then sprayed onto an object to form a pattern by forming an image point, forms a pattern of a functional element such as a color filter. It is used for The patterning method using the ink jet method has advantages in that noise is less than other patterning methods and processing such as development and fixing is unnecessary.
[0003]
In such an ink jet system, droplets are ejected from a nozzle to apply the ink to a target object.Therefore, the ink is applied to a tip portion of the nozzle by minute ink, static electricity, and bubbles contained in the ink. When the ink is ejected from the nozzles, the landing position of the ink is shifted from the target position, and a problem such as mixing of patterns occurs with a small probability. In order to solve such a problem, means for precisely adjusting the viscosity and surface tension of the ink have been developed.
[0004]
For example, Patent Literature 1 discloses a technique in which a PTC heater is fixed between an ink holding container and a nozzle, and heated ink is supplied to the nozzle.
[0005]
Patent Literature 2 discloses that an ink supply tank is integrated adjacent to a recording head, an ink viscosity is converted into an electric signal, and the ink temperature is controlled by the electric signal. There is disclosed a technique of discharging from a liquid.
[0006]
Patent Document 3 discloses a technology in which a temperature sensor for directly detecting the temperature of an ink liquid is provided in the ink liquid chamber, and the temperature of the ink liquid in the ink liquid chamber is controlled to an appropriate temperature in accordance with the output of the temperature sensor. Have been.
[0007]
Patent Literature 4 discloses an arithmetic unit that calculates a rate of change of the temperature of ink in an ink tank per unit time, and starts adjusting the viscosity of the ink after confirming that the rate of change reaches a predetermined range. Thus, an ink jet printer provided with a control means for controlling the viscosity adjusting means is disclosed.
[0008]
Patent Literature 5 discloses that a temperature control system that controls the temperature of ink is provided, and information that enables an optimal operating temperature for the ink to be determined is read into the ink container by the temperature control system, thereby providing a physical control. Is disclosed.
[0009]
An example of a conventional method for manufacturing a functional element using such an ink-jet method will be described with reference to FIG. First, as shown in FIG. 3A, a lyophilic region 2 that exhibits good wettability with respect to a functional part forming coating liquid discharged from an ink jet device and a function that is better than the lyophilic region 2 A pattern forming body 1 having a pattern formed of a liquid-repellent region 3 having a large contact angle with respect to the coating liquid for forming a hydrophilic part and having a lower wettability than the lyophilic region 2 is prepared. Next, as shown in FIG. 3B, a coating liquid 5 for forming a functional part is applied to the lyophilic region 2 using an inkjet device 4. At this time, by adjusting the temperature of the functional part forming coating liquid 5 in the vicinity of the nozzle of the inkjet device 4, the viscosity of the temperature-dependent functional part forming coating liquid 5 is adjusted to a suitable range. And good ejection is possible. Thus, the droplets of the functional part forming coating liquid 5 discharged from the inkjet device 4 can be accurately applied to the lyophilic region 2. After the functional part forming coating liquid 5 discharged from the nozzle of the ink jet device 4 lands on the lyophilic region 2 of the pattern forming body 1, as shown in FIG. And spreads into the lyophilic region 2.
[0010]
In such a conventional method of manufacturing a functional element using an ink-jet method, a problem arises in that the landing position of a droplet is shifted from a target position by lowering the viscosity of a coating liquid for forming a functional portion. Has been prevented. Therefore, since the coating liquid for forming a functional portion used in the ink jet method has high fluidity due to its viscosity, it swiftly spreads in the lyophilic region after landing on the pattern forming body. On the other hand, since the droplets are continuously discharged, a wave is generated on the surface of the coating liquid for forming the functional portion in the lyophilic region. When the coating liquid for forming a functional part is rich in fluidity, this wave propagates well on the surface of the coating liquid for forming a functional part in the lyophilic region. If the wave propagates well in this manner, it is possible to actually apply the liquid in the lyophilic region rather than the application amount theoretically derived from the difference in surface energy between the lyophilic region and the lyophobic region. The possible coating amount is reduced. As described above, in the method of manufacturing a functional element using the conventional inkjet method, it is difficult to prevent inconveniences such as mixing of patterns and to secure a certain film thickness. Further, a method of forming a partition wall to achieve a desired film thickness has been developed, but the formation of the partition wall requires complicated labor, which is disadvantageous in manufacturing efficiency.
[0011]
[Patent Document 1]
JP-A-07-137294
[Patent Document 2]
JP-A-2002-148426
[Patent Document 3]
JP-A-2000-71442
[Patent Document 4]
JP-A-2002-59563 public information
[Patent Document 5]
JP-A-2002-192745
[0012]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and provides a method and apparatus for manufacturing a functional element capable of forming a high-definition pattern and having a wide selection range of the thickness of a functional section. The main purpose is to do so.
[0013]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a pattern forming body preparing step of preparing a pattern forming body having a pattern composed of a lyophilic region and a lyophobic region on the surface, as described in claim 1.
A cooling step of cooling the temperature of the surface of the pattern forming body to a range of 0 ° C to 25 ° C;
An application step of applying a functional part forming coating liquid for forming a functional part using an inkjet method in a lyophilic area of the pattern formed body surface cooled in the cooling step,
A temperature raising step of setting the temperature of the surface of the pattern-formed body on which the coating liquid for forming a functional portion is applied to be in a range of 10 ° C to 35 ° C;
The present invention provides a method for producing a functional element, comprising:
[0014]
In the present invention, since the surface temperature of the pattern formed body is cooled to the above range, the coating liquid for forming a functional portion discharged by the ink jet device lands on the lyophilic region of the pattern formed body, The viscosity increases and the fluidity decreases due to the influence of the surface temperature of the pattern forming body. Further, when the pattern formed body is cooled, the wettability of the surface thereof tends to change in a direction in which the contact angle with the coating liquid for forming a functional portion becomes higher as a whole. Accordingly, the diameter of the coating liquid for forming a functional part after landing on the lyophilic region is difficult to spread, and it is suppressed that the coating liquid spreads quickly. In addition, even if the application amount applied to the lyophilic region increases from the fluidity relationship, since waves generated from the influence of continuously ejected droplets are difficult to propagate into the functional part forming coating liquid, It is less susceptible to the physical effects of such waves. This makes it possible to secure a sufficient coating amount. Therefore, the selection range of the film thickness of the functional portion formed by the ink jet method can be widened, and a fine pattern can be formed. Furthermore, since the surface temperature of the pattern forming body is returned to the above range by the temperature raising step after the application step, the viscosity of the functional part forming coating liquid returns to its original state and the fluidity is restored. Therefore, the coating liquid for forming a functional part can be satisfactorily wetted and spread in the lyophilic region, and a high-definition pattern can be formed along the pattern in the lyophilic region.
[0015]
In the first aspect of the present invention, as described in the second aspect, the pattern forming body has a wettability changing layer whose contact angle with respect to a liquid is reduced by an external stimulus, and It is preferable that a pattern composed of the lyophilic region and the lyophobic region is formed by applying an external stimulus in a pattern. Thereby, it is possible to easily form a pattern due to a difference in wettability on the pattern forming body, which is preferable in terms of manufacturing efficiency and the like.
[0016]
In the second aspect of the present invention, as described in the third aspect, the pattern forming body may have a base material and a wettability changing layer formed on the base material. . When the wettability changing layer has a self-supporting property, the wettability changing layer may not be formed on a base material. This is because when the element requires strength, the wettability changing layer may be formed on a substrate.
[0017]
According to the second or third aspect of the present invention, as described in the fourth aspect, the external stimulus is energy irradiation, and the wettability changing layer contains at least a photocatalyst and a binder. A photocatalyst-containing layer in which the contact angle with the liquid is reduced by the action of the photocatalyst accompanying irradiation can be obtained.
[0018]
Since the wettability changing layer is the photocatalyst-containing layer, it is easy to form a lyophilic region having a reduced contact angle with a liquid due to the action of the photocatalyst of the photocatalyst-containing layer itself with energy irradiation. This is possible.
[0019]
In the fourth aspect of the invention, as described in the fifth aspect, the binder is preferably a layer containing an organopolysiloxane. In the present invention, the property required for the photocatalyst-containing layer is, when energy is not irradiated, liquid repellency, and when energy is irradiated, the photocatalyst in the photocatalyst-containing layer becomes lyophilic. It is such a characteristic. This is because organopolysiloxane is preferably used as a material for imparting such characteristics to the photocatalyst-containing layer.
[0020]
In the fifth aspect of the present invention, as described in the sixth aspect, the organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. It is preferable that the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. This is because the difference in wettability between the energy-irradiated portion and the non-irradiated portion can be increased if the material contains a fluoroalkyl group.
[0021]
In the invention described in claim 5 or claim 6, as described in claim 7, the organopolysiloxane is 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 or a halogen, and n is an integer of 0 to 3.) It is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound to be produced. By using such an organopolysiloxane, it is possible to exhibit the property against the change in wettability as described above.
[0022]
In the invention described in claim 2 or claim 3, as described in claim 8, the external stimulus is energy irradiation, and the wettability changing layer includes a photocatalyst treatment layer containing at least a photocatalyst. Alternatively, it may be a layer composed of a surface-change-type wettability-change layer, which is a layer in which the contact angle with the liquid on the surface is reduced by the action of the photocatalyst accompanying the energy irradiation formed on the photocatalyst-treated layer. Since the wettability changing layer is composed of the photocatalyst treatment layer and the surface change type wettability change layer, the surface of the surface change type wettability change layer due to the action of the photocatalyst in the photocatalyst treatment layer with energy irradiation. This is because it becomes possible to form a lyophilic region in the first step. Further, since the photocatalyst treatment layer does not come into contact with the functional part to be formed, the functional part is less likely to be affected by the photocatalyst over time, and a high-quality functional element can be obtained. This is because
[0023]
According to the second or third aspect of the present invention, as described in the ninth aspect, the external stimulus is energy irradiation, and the wettability changing layer is a photocatalyst-treated layer and a substrate containing a photocatalyst. After the photocatalyst treatment layer side substrate having the above is disposed with a gap such that the wettability changing layer and the photocatalyst treatment layer are 200 μm or less, the liquid on the surface is irradiated with energy from a predetermined direction. It may be a surface-changeable wettability changing layer in which the wettability changes so as to decrease the contact angle with the surface. Since the wettability changing layer is the surface changing type wettability changing layer, the contact angle with the liquid on the surface decreases due to the action of the photocatalyst in the photocatalyst processing layer side substrate due to the energy irradiation, and the lyophilicity changes. This is because the conductive region can be formed.
[0024]
In the invention described in claim 8 or claim 9, as described in claim 10, it is preferable that the surface-changeable wettability-change layer is a layer containing an organopolysiloxane. In the present invention, the properties required for the surface-change-type wettability-change layer include liquid-repellency when energy is not irradiated, and parent property due to the action of the photocatalyst in the photocatalyst treatment layer when energy is irradiated. It is characteristic that it becomes liquid. This is because it is preferable to use organopolysiloxane as a material for imparting such properties to the surface-change-type wettability-change layer.
[0025]
In the tenth aspect, as described in the eleventh aspect, the organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. It is preferable that the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. This is because the difference in wettability between the energy-irradiated portion and the non-irradiated portion can be increased if the material contains a fluoroalkyl group.
[0026]
In the invention according to claim 11, as described in claim 12, the organopolysiloxane is 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 or a halogen, and n is an integer of 0 to 3.) It is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound to be produced. By using such an organopolysiloxane, it is possible to exhibit the property against the change in wettability as described above.
[0027]
In the invention described in claim 2 or claim 3, as described in claim 13, the external stimulus is energy irradiation, and the wettability changing layer includes a photocatalyst treatment layer containing at least a photocatalyst. A decomposition-removal type wettability changing layer that is decomposed and removed by the action of a photocatalyst accompanying energy irradiation formed on the photocatalyst treatment layer, and a contact angle of a liquid with the decomposition-removal type wettability change layer; It may be a layer composed of a layer having a different contact angle of the liquid with the photocatalyst treatment layer exposed after the removal type wettability changing layer is decomposed and removed. The wettability changing layer, the photocatalyst treatment layer, by comprising the decomposition removal type wettability change layer formed thereon, with energy irradiation, by the action of the photocatalyst in the photocatalyst treatment layer, for example, The photocatalyst treatment layer exposed after the decomposition-removal type wettability changing layer is decomposed and removed can be a lyophilic region, and the decomposition-removal type wettability variable layer can be a lyophobic region. This is because a pattern including the liquid region can be formed.
[0028]
According to the second or third aspect of the present invention, as described in the fourteenth aspect, the external stimulus is energy irradiation, and the wettability changing layer is a photocatalyst-treated layer and a substrate containing a photocatalyst. After the photocatalyst treatment layer side substrate having the above is disposed with a gap such that the wettability changing layer and the photocatalyst treatment layer are 200 μm or less, the substrate is decomposed and removed by energy irradiation from a predetermined direction. The contact angle of the liquid with respect to the decomposition-removal type wettability changing layer, and the contact angle of the liquid with respect to the substrate exposed after the decomposition-removal type wettability change layer is decomposed and removed. Different layers may be used.
[0029]
Since the wettability changing layer is the decomposition-removal type wettability changing layer, the action of the photocatalyst in the photocatalyst processing layer on the photocatalyst processing layer side substrate causes the decomposition removal type wettability change with energy irradiation. It becomes possible to decompose and remove the layer, for example, wetting the base material exposed by decomposing and removing the decomposition-removal type wettability changing layer as a lyophilic region and the decomposition-removal type wettability variable layer as a lyophobic region. This is because it is possible to form a pattern depending on the gender.
[0030]
In the invention according to claim 13 or claim 14, as described in claim 15, the decomposition removal type wettability changing layer is formed of a self-assembled monomolecular film, a Langmuir-Blodgett film, or an alternate adsorption. Preferably, it is one of the membranes. This is because the decomposition-removal-type wettability changing layer is formed of the above-described film, so that a relatively high-strength, defect-free film can be formed.
[0031]
In the invention according to any one of claims 4 to 15, as described in claim 16, the photocatalyst comprises 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 (Fe₂O₃) Is preferably one or two or more substances selected from the group consisting of titanium oxide (TiO 2) and titanium oxide (TiO 2).₂) Is preferable. This is because titanium dioxide has a high bandgap energy, is effective as a photocatalyst, is chemically stable, has no toxicity, and is easily available.
[0032]
The present invention also provides a color filter manufactured by the method for manufacturing a functional element according to any one of claims 1 to 17.
[0033]
According to the present invention, since the functional layer is a pixel portion, a color filter having a high-definition pixel portion can be obtained, and the shape and thickness of the pixel portion can be adjusted. Therefore, the color filter can be used for various purposes.
[0034]
Further, in the present invention, as set forth in claim 19, a discharging means for discharging the functional part forming coating liquid by an ink jet method, and the functional part forming coating liquid discharged from the discharging means lands. A fixing device for fixing a substrate to be fixed, and a cooling device for setting a surface temperature of the substrate fixed to the fixing device within a range of 0 ° C. to 25 ° C. .
[0035]
In the present invention, by using such a functional element manufacturing apparatus, it is possible to stably discharge the functional part forming coating liquid, and to apply the functional part forming coating liquid more than before. It is possible to widen the selection range of the thickness of the functional part formed from the functional part forming coating liquid, and to easily form a high-definition pattern. can do.
[0036]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a method for manufacturing a functional element and an apparatus for manufacturing the functional element of the present invention will be described in detail.
[0037]
A. Method for manufacturing functional element
The method of manufacturing a pattern-formed body of the present invention includes a pattern-formed body preparing step of preparing a pattern-formed body having a pattern composed of a lyophilic region and a lyophobic region on its surface,
A cooling step of cooling the temperature of the surface of the pattern forming body to a range of 0 ° C to 25 ° C;
An application step of applying a functional part forming coating liquid for forming a functional part using an inkjet method in a lyophilic area of the pattern formed body surface cooled in the cooling step,
A temperature raising step of setting the temperature of the surface of the pattern-formed body on which the coating liquid for forming a functional portion is applied to be in a range of 10 ° C to 35 ° C;
Which is characterized by having
[0038]
According to the method for producing a functional element of the present invention, a high-definition pattern having a desired film thickness can be easily formed. In general, in a patterning method in which a coating liquid is discharged by an inkjet method and the liquid is landed on a substrate, a pattern formed body having a pattern formed by a difference in wettability on a substrate is used, and the wettability to the coating liquid is good. A method of discharging a coating liquid to a lyophilic region, a method of providing a partition and discharging the coating liquid into the partition, and the like are known. In such a patterning method by the ink jet method, it is preferable to keep the viscosity of the ink low to some extent in order to apply the coating liquid stably from the nozzle, and the coating liquid having such a low viscosity is placed on the lyophilic region. It shows good wet spread after impact. On the other hand, a wave is generated on the surface of the coating liquid in the lyophilic region due to the physical action of the droplets continuously discharged, and the lyophilic region and the lyophobic property are affected by the wave. Even within the range of the theoretical coating amount that can be applied to the lyophilic region calculated by the difference in surface energy in the region, the coating liquid may erode the lyophobic region, It was difficult to secure a sufficient film thickness.
[0039]
Therefore, in the present invention, the above-described problem is solved by providing a cooling step before the step of applying the functional part forming coating liquid. That is, in the pattern forming body whose surface temperature is within a predetermined range due to the cooling step, the coating liquid for forming the functional portion applied on the lyophilic region has a viscosity due to the influence of the surface temperature of the pattern forming body. Rise and fluidity decreases. In addition, the wettability of the surface of the pattern formed body due to the cooling step tends to change in the direction in which the contact angle with the coating liquid for forming a functional portion becomes higher as a whole. Therefore, the coating liquid for forming the functional part is difficult to spread in diameter after landing on the lyophilic area, is prevented from spreading quickly, and is applied to the lyophilic area due to fluidity. Even if the amount increases, waves generated by the influence of continuously ejected droplets are difficult to propagate into the functional part forming coating liquid, so that the coating amount of the functional part forming coating liquid can be easily increased. Become. Therefore, it is possible to widen the selection range of the thickness of the functional part formed by applying the functional part forming coating liquid by the ink jet method. In addition, since the contact angle of the functional part forming coating liquid on the surface of the pattern forming body tends to be large due to the cooling step, the functional part forming coating liquid after landing on the lyophilic region is used. Since the diameter is difficult to spread, a fine pattern can be formed.
[0040]
Further, after the application step, the temperature of the surface of the pattern forming body is returned to the above range by the temperature raising step, so that the viscosity of the coating liquid for forming the functional part is reduced and the fluidity is recovered. Therefore, the coating liquid for forming a functional part can be satisfactorily wetted and spread in the lyophilic region, and a high-definition pattern can be formed along the pattern in the lyophilic region.
[0041]
The method for manufacturing the functional element of the present invention having such advantages will be described with reference to the drawings. FIG. 1 is a process chart showing an example of a method for producing a functional element of the present invention.
[0042]
First, as shown in FIG. 1A, a lyophilic region 2 having good wettability with respect to the coating liquid for forming a functional part on the surface, and a coating liquid for forming a functional part than the lyophilic region 2 A pattern-formed body 1 having a pattern formed by a difference in wettability composed of a liquid-repellent region 3 having a large contact angle with the liquid-repellent region 3 is prepared, and liquid nitrogen is circulated near the pattern-formed body 1 so that the pattern-formed body 1 Is lowered to a predetermined temperature.
[0043]
Next, as shown in FIG. 1B, a functional part forming coating liquid 5 is applied onto the lyophilic area 2 of the pattern forming body 1 by using an ink jet device 4. After the functional portion forming coating liquid 5 lands on the lyophilic region 2 of the pattern forming body 1, the temperature decreases and the viscosity increases due to the influence of the surface temperature of the pattern forming body 1. Since the fluidity decreases with this, the physical influence exerted by the functional part forming coating liquid 5 continuously discharged from the ink jet device 4 can be reduced, and as shown in FIG. Thus, a sufficient amount of coating can be ensured. In addition, since the surface of the pattern forming body 1 changes in the direction in which the contact angle with the functional part forming coating liquid 5 becomes larger as a whole by cooling, the functional part forming coating after landing on the lyophilic region 2 is applied. The diameter of the liquid 5 becomes smaller than that when the liquid 5 is applied at room temperature, and a fine pattern can be formed.
[0044]
Next, when the temperature of the pattern forming body 1 on which the functional part forming coating liquid 5 is applied is increased to within a predetermined range, the viscosity of the functional part forming coating liquid 5 recovers and the fluidity increases. . Therefore, as shown in FIG. 1D, the functional part forming coating liquid 5 spreads well in the lyophilic area 2. In the present invention, even if the viscosity of the functional part forming coating liquid 5 is recovered by the temperature raising step, the coating amount is such that the functional part forming coating liquid 5 does not erode the lyophobic region 3. Since the coating is performed in the liquid region 2, the functional portion forming coating liquid 5 does not spread to the liquid repellent region 3, so that a high-definition pattern can be formed and a desired film thickness can be obtained. It can be.
[0045]
The method for manufacturing the functional element of the present invention will be described for each step.
[0046]
1. Pattern forming body preparation process
The pattern forming body preparing step in the present invention is a step of preparing a pattern forming body having a pattern formed on its surface by a difference in wettability composed of a lyophilic region and a lyophobic region.
[0047]
The pattern forming body prepared in this step includes a lyophilic property in which the functional part forming coating liquid wets and spreads according to the pattern to which the functional part forming coating liquid discharged by the inkjet apparatus is applied. There is no particular limitation as long as a pattern comprising a region and a lyophobic region having a lower wettability to the functional part forming coating liquid than the lyophilic region is formed on the surface.
[0048]
As for the wettability of the lyophilic region and the lyophobic region formed on the surface of such a pattern forming body, if the functional part forming coating liquid can be applied in a pattern with high accuracy. Although not particularly limited, specifically, it is preferably within the following range.
[0049]
First, in the liquid-repellent region, the contact angle of the coating liquid for forming a functional portion described later is preferably 30 ° or more at room temperature, and more preferably 40 ° or more. Furthermore, at room temperature, the contact angle with a liquid having a surface tension of 40 mN / m is 10 ° or more, preferably the contact angle with a liquid having a surface tension of 30 mN / m is 10 ° or more, and particularly, a contact with a liquid having a surface tension of 20 mN / m. Preferably, the angle is at least 10 °. Since the liquid-repellent area is a part where liquid-repellency is required, when the contact angle with the liquid is small, the liquid-repellent property is not sufficient, and the coating liquid for forming the liquid-repellent part may remain. This is because it is not preferable because of high properties.
[0050]
Further, in the lyophilic region, the contact angle of the coating liquid for forming a functional part described below is 20 ° or less at room temperature, and preferably 10 ° or less. Furthermore, at room temperature, the contact angle with a liquid having a surface tension of 40 mN / m is less than 9 °, preferably, the contact angle with a liquid having a surface tension of 50 mN / m is 10 ° or less, particularly, a liquid having a surface tension of 60 mN / m. It is preferable that the contact angle is 10 ° or less. This is because if the contact angle with the liquid in the lyophilic region is high, the wetting and spreading of the functional part forming coating liquid in this part may be inferior.
[0051]
In addition, the contact angle with the liquid referred to here is a contact angle with a liquid having various surface tensions measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (from the micro syringe to the liquid). 30 seconds after dropping) and obtained from the results or as a graph. In this measurement, wetting index standard solutions manufactured by Junsei Chemical Co., Ltd. were used as liquids having various surface tensions.
[0052]
In such a pattern formed body, in the present invention, since a pattern composed of a lyophilic region and a lyophobic region can be formed with high definition, wettability is reduced in a direction in which a contact angle with respect to a liquid is reduced by an external stimulus. It is preferable that the wettability changing layer be capable of forming a pattern composed of a lyophilic region and a lyophobic region by changing and applying an external stimulus in a pattern. The pattern formed body having the wettability changing layer in which the contact angle with respect to the liquid is reduced by the external stimulus will be described later in detail.
[0053]
2. Cooling process
Next, a cooling step which is a particularly characteristic step in the present invention will be described. The cooling step in the present invention is a step of cooling the temperature of the surface of the pattern forming body having a pattern having a difference in wettability comprising a lyophilic region and a lyophobic region on the surface to a predetermined temperature by a cooling means. .
[0054]
In this step, the temperature of the surface of the pattern forming body needs to be in the range of 0 ° C. to 25 ° C., and among them, cooling is preferably performed in the range of 0 ° C. to 15 ° C. If the surface temperature is lower than the above range, water droplets adhere to the surface of the pattern forming body due to a phenomenon such as dew condensation, which is not preferable because it causes deterioration. On the other hand, if the surface temperature is higher than the above range, a change such as a rise in viscosity or a decrease in fluidity due to a decrease in the temperature of the coating liquid for forming a functional portion cannot be sufficiently obtained, and it is difficult to obtain the effects of the present invention. Because it becomes. Further, the surface temperature of the pattern formed body is set to be within the above range at least until the coating step described later. Thereby, in the coating step described later, a sufficient amount of the functional part forming coating liquid can be obtained.
[0055]
Further, it has been found that the wettability of the pattern-formed body surface tends to change in the direction in which the contact angle with the coating liquid for forming a functional portion increases as a whole by this step. FIG. 4 is a graph showing a change in the contact angle in a solvent-based coating liquid when the temperature of the photocatalyst-containing layer surface is lowered using a photocatalyst-containing layer substrate having a photocatalyst-containing layer described later formed on the substrate. . In addition, the surface tension of the solvent-based coating liquid is 29 mN / m. The graph shown in FIG. 4 suggests that the wettability of the surface of the photocatalyst-containing layer changes as the temperature decreases, so that the contact angle with the solvent-based coating liquid increases.
[0056]
For this reason, after the pattern formed body is cooled in this step, the wettability to the functional part forming coating liquid is reduced overall, so that the functional part formed on the lyophilic area is reduced. The diameter of the application coating liquid is smaller than that when the coating liquid is applied under general application conditions. Therefore, a fine pattern can be formed.
[0057]
In the present step, the cooling means for keeping the surface temperature of the pattern formed body within the above range is not particularly limited as long as it is a means capable of cooling the surface of the pattern formed body without unevenness. Specifically, a method of circulating a coolant in a member that contacts the pattern forming body, a method of exposing the pattern forming body to a low temperature state, and the like can be given. Among them, a method in which a refrigerant is circulated in a member that contacts the pattern forming body is preferable. Specifically, there is a method of arranging a pattern forming body on a cooled stage by circulating a coolant. Further, the coolant is not particularly limited as long as it can cool the surface temperature of the pattern forming body within the above range by being circulated, and specific examples thereof include liquid nitrogen. .
[0058]
3. Coating process
Next, the coating step in the present invention will be described. The application step in the present invention is a step of applying a functional part forming coating liquid by an ink jet method on the lyophilic area of the pattern formed body cooled by the cooling step described above and having a surface temperature within the above range. is there.
[0059]
In the present invention, before applying the coating liquid for forming a functional portion, since the surface temperature of the pattern formed body is set in advance within the above range, the liquid droplet lands on the lyophilic region of the pattern formed body. The temperature of the coating liquid for forming a functional portion after the impact drops is lowered, and a change such as an increase in viscosity and a decrease in fluidity is caused by the temperature change. As a result, the coating liquid for forming the functional portion is prevented from spreading quickly into the lyophilic region, and a sufficient coating amount can be secured. This is for the following reason.
[0060]
That is, from the relationship between the surface energy difference between the lyophilic region and the lyophobic region, the amount of coating that can be applied to the lyophilic region without eroding the coating liquid for forming a functional part in the lyophobic region Can be calculated theoretically, but conventionally, physical factors, such as the physical impact of droplets continuously ejected from the nozzle of the inkjet apparatus, than the theoretically derived coating amount The actual amount of application was greatly reduced due to factors such as high energy. However, in the present invention, by providing the above-mentioned cooling step, the coating liquid for forming a functional portion applied in this step increases in viscosity after landing on the lyophilic region, and the fluidity decreases. Such an effect can be obtained. By such a change, the physical influence can be reduced. Accordingly, it is possible to apply the coating amount up to a theoretically possible amount which can be applied on the lyophilic region. Therefore, since the upper limit of the amount of application that can be applied on the lyophilic region is increased as compared with the related art, the selection range of the thickness of the functional part formed from the functional part forming coating liquid is reduced. Can be spread. In addition, since the contact angle of the liquid on the surface of the pattern formed body tends to be large due to the cooling step described above, the diameter of the functional part forming coating liquid after landing on the lyophilic region is unlikely to spread, A fine pattern can be formed.
[0061]
Such a functional part forming coating liquid applied in this step is a coating liquid for forming the functional part of the functional element finally obtained by the present invention, The functional part is formed by applying the composition on the lyophilic area and curing the composition. The material and the like of such a coating liquid for forming a functional part in the present invention are selected according to the type of the functional element finally obtained.
[0062]
The term “functionality” as used herein means optical (light selective absorption, reflection, polarization, light selective transmission, nonlinear optical properties, luminescence such as fluorescence or phosphorescence, photochromic properties, etc.), magnetic (hard magnetic , Soft magnetic, non-magnetic, magnetically permeable, etc., electric / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorbing, desorbing, catalytic, water absorbing, Ion conductivity, redox properties, electrochemical properties, electrochromic properties, etc., mechanical (wear resistance, etc.), thermal (thermal conductivity, heat insulation, infrared radiation, etc.), biofunctional (biocompatible, anti- (Thrombotic properties, etc.).
[0063]
In the present invention, the functional element finally obtained includes a color filter, an electroluminescent element and the like, and among them, a color filter is preferable. For example, when the functional element is a color filter, the functional portion may include a pixel portion, and the functional portion forming coating liquid generally includes a material for forming the pixel portion. Can be.
[0064]
Further, in the present invention, since the coating liquid for forming a functional portion is applied using an ink jet method, a liquid suitable for the ink jet method is used. The properties of the coating liquid used in such an ink-jet method include a solvent-containing, low-viscosity, high-boiling point, and the like. By using the functional part forming coating liquid having the above properties, the functional part forming coating liquid can be rapidly discharged from the nozzle without delay, and the functional part forming coating on the nozzle inner wall can be performed. This is because the remaining of the liquid can be prevented, and the application accuracy of the ink jet device can be improved.
[0065]
In such a functional part forming coating liquid, as for the viscosity, in the cooling step described above, the viscosity is increased before and after cooling, and the viscosity increases, and when applied on the lyophilic area. However, there is no particular limitation as long as it can be prevented from spreading immediately.
[0066]
In the functional part forming coating liquid used in the present invention, when the solvent based functional part forming coating liquid is used, the viscosity at room temperature is in the range of 5 cps to 20 cps, and among them, the viscosity is in the range of 7 cps to 14 cps. Is preferably within the range. On the other hand, when the aqueous functional part forming coating liquid is used, the viscosity at room temperature is preferably in the range of 3 cps to 10 cps, and particularly preferably in the range of 4 cps to 7 cps. In the case of a functional part forming coating liquid having a viscosity within the above range, when the coating liquid is ejected from a nozzle by an ink jet method, inconvenience such that the landing position of the droplet is shifted from the target position occurs. Is prevented.
[0067]
The viscosity in the present invention uses a value measured at a measurement temperature of 20 ° C. by a viscometer VIBROVISCOMMETER CJV5000 (manufactured by A & D).
[0068]
Further, the coating liquid for forming a functional part may be a thermosetting type or an ultraviolet curable type, and the curing method and the like are not particularly limited.
[0069]
The thickness of the functional portion formed in this step varies depending on the surface energy difference in the lyophilic region and the lyophobic region, but is generally defined by the surface energy difference. And a film thickness in the range of 5 μm to 20 μm.
[0070]
4. Heating process
The temperature raising step is a step of raising the temperature of the surface of the pattern forming body on which the above-described functional part forming coating liquid has been applied to a predetermined temperature. By this process, the temperature of the functional part forming coating liquid which has been in a cooled state rises, and the fluidity is restored. As a result, the coating liquid for forming a functional portion is satisfactorily wet-spread in the lyophilic region, so that a high-definition pattern can be formed.
[0071]
The temperature of the surface of the pattern forming body in this step is in the range of 10 ° C. to 35 ° C., and preferably in the range of 25 ° C. to 30 ° C. If the surface temperature is lower than the above range, the fluidity of the coating liquid for forming a functional part is not sufficiently recovered, and good wet spread cannot be obtained.On the other hand, the surface temperature is lower than the above range. This is because if the value of is increased, the composition of the functional part-forming coating liquid may change.
[0072]
The method for keeping the temperature of the surface of the pattern-formed body within the above-described range is not particularly limited as long as a rapid temperature change does not occur. For example, there is a method of leaving the pattern formed body at room temperature.
[0073]
In the present invention, the functional part forming coating liquid is applied within the range of the coating amount that can be applied to the lyophilic area at the maximum from the difference in surface energy between the lyophilic area and the lyophobic area. Therefore, even if the viscosity of the functional part forming coating liquid is recovered by the temperature raising step, the functional part forming coating liquid does not spread to the liquid repellent region. Therefore, a high-definition pattern can be formed along the pattern of the lyophilic region of the pattern forming body. In addition, since the upper limit of the amount of application that can be applied to the lyophilic region is increased as compared with the related art, the selection range of the thickness of the functional portion can be widened.
[0074]
5. Other
Here, a description will be given of a pattern formed body in the case where the pattern formed body has a wettability changing layer in which the contact angle with respect to a liquid is reduced by an external stimulus.
[0075]
The pattern forming body prepared in the above-described pattern forming body preparing step includes, as described above, the functional part forming coating liquid ejected by the inkjet method according to the pattern to be applied. A pattern formed of a lyophilic region in which the coating liquid spreads and a lyophobic region having less wettability to the functional part forming coating liquid than the lyophilic region is formed on the surface. There is no particular limitation.
[0076]
In such a pattern formed body, in the present invention, since a pattern composed of a lyophilic region and a lyophobic region can be formed with high definition, wettability is reduced in a direction in which a contact angle with respect to a liquid is reduced by an external stimulus. It is preferable that the wettability changing layer be capable of forming a pattern composed of a lyophilic region and a lyophobic region by changing and applying an external stimulus in a pattern.
[0077]
Here, the wettability changing layer may be formed on a base material, or a light-shielding portion or the like may be formed on the pattern forming body. Hereinafter, each component constituting the pattern formed body when the pattern formed body has the wettability changing layer will be described.
[0078]
(1) wettability changing layer
First, the wettability changing layer used in the present invention will be described. The wettability changing layer used in the present invention is not particularly limited as long as the contact angle with respect to the liquid is reduced by an external stimulus, such as a physical stimulus or a chemical stimulus. From the viewpoint of manufacturing efficiency and cost, it is preferable that the external stimulus is such that the contact angle with the liquid is reduced by irradiation with energy such as ultraviolet light. This makes it possible to efficiently form a pattern including a lyophilic region and a lyophobic region using a photocatalyst or the like without requiring a large-scale device or a special material. .
[0079]
The wettability changing layer having such characteristics is a photocatalyst-containing layer that contains at least a photocatalyst and a binder, and whose contact angle with a liquid is reduced by the action of the photocatalyst accompanying energy irradiation (hereinafter referred to as a first embodiment). Surface-change type wetting, which is a layer in which the contact angle with the liquid on the surface is reduced by the action of the photocatalyst treatment layer containing at least the photocatalyst and the photocatalyst accompanying the energy irradiation formed on the photocatalyst treatment layer. In the case of a layer composed of a property change layer (hereinafter, referred to as a second embodiment), a photocatalyst treatment layer containing a photocatalyst and a photocatalyst treatment layer side substrate having a substrate are separated from the wettability change layer and the photocatalyst treatment layer. Is arranged so as to be 200 μm or less, and is irradiated with energy from a predetermined direction so that the contact angle with the liquid on the surface is reduced. When the wettability changing layer is a surface-change type wettability changing layer in which wettability changes (hereinafter, referred to as a third embodiment), the wettability changing layer is formed on at least a photocatalyst treatment layer containing a photocatalyst and the photocatalyst treatment layer. Is a decomposition-removal type wettability changing layer that is decomposed and removed by the action of the photocatalyst accompanying the irradiated energy irradiation, and the contact angle of the liquid with the decomposition-removal type wettability change layer and the decomposition-removal type wettability change layer are decomposed. A layer composed of a layer having a different contact angle of the liquid with the photocatalyst treatment layer that has been removed and exposed (hereinafter, referred to as a fourth embodiment), or the wettability changing layer is a photocatalyst treatment containing a photocatalyst. After arranging the photocatalyst treatment layer side substrate having the layer and the base with a gap such that the wettability changing layer and the photocatalyst treatment layer are 200 μm or less, energy irradiation is performed from a predetermined direction. Is a decomposition-removable wettability changing layer that is decomposed and removed, and a contact angle of the liquid to the decomposition-removable wettability-variable layer, and a substrate that is exposed after the decomposition-removable wettability-change layer is decomposed and removed. It is preferable that the layer has a different contact angle with the liquid (hereinafter, referred to as a fifth embodiment).
[0080]
Hereinafter, each embodiment will be described in detail.
[0081]
a. First embodiment
First, a first embodiment of the wettability changing layer will be described. The first embodiment of the wettability changing layer is a case where the wettability changing layer is a photocatalyst-containing layer containing at least a photocatalyst and a binder, and a contact angle with a liquid is reduced by the action of the photocatalyst accompanying energy irradiation. It is.
[0082]
The photocatalyst-containing layer used in the present embodiment is a layer whose contact angle with a liquid is reduced by the action of the photocatalyst accompanying energy irradiation, and is not particularly limited as long as it is a layer containing at least a photocatalyst and a binder. Instead, this makes it possible to make the portion irradiated with energy a lyophilic region and the portion not irradiated with energy a lyophobic region.
[0083]
Among the photocatalyst-containing layers used in the present embodiment, especially, in the portion not irradiated with energy, that is, in the liquid-repellent region, the contact angle with the liquid of 40 mN / m is 10 ° or more, especially the liquid having a surface tension of 30 mN / m. It is preferable that the contact angle with the liquid having a surface tension of 20 mN / m is 10 ° or more. This is because the part that is not irradiated with energy is a part that is required to have liquid repellency, and is formed by applying a functional part forming coating liquid that forms a functional part by an ink jet method and curing it. This is because, in some cases, there is a possibility that the coating liquid for forming a functional portion may adhere to the lyophobic region, and it becomes difficult to form the functional portion with high definition.
[0084]
The photocatalyst-containing layer has a contact angle with a liquid of 40 mN / m less than 9 °, preferably a contact angle with a liquid of surface tension of 50 mN / m, in a portion irradiated with energy, that is, a lyophilic region. The layer preferably has a contact angle of 10 ° or less, particularly 10 ° or less, with a liquid having a surface tension of 60 mN / m. When the contact angle with the liquid in the energy-irradiated portion, that is, the lyophilic region is high, there is a possibility that the functional portion forming coating liquid that forms the functional portion may be repelled in the lyophilic region. There is a possibility that, when the coating liquid for forming a functional part is applied by the inkjet method in the present embodiment, the coating liquid for forming a functional part does not spread sufficiently, and it becomes difficult to form a functional part. Because there is.
[0085]
Here, the contact angle with the liquid is measured by the same method as the measurement method described in the above-mentioned “1.
[0086]
The photocatalyst-containing layer used in the present embodiment contains fluorine in the photocatalyst-containing layer, and furthermore, the fluorine content on the surface of the photocatalyst-containing layer, when the photocatalyst-containing layer is irradiated with energy, the action of the photocatalyst The photocatalyst-containing layer may be formed such that the photocatalyst-containing layer is reduced as compared to before the energy irradiation, and is decomposed by the action of the photocatalyst by the energy irradiation, whereby the wettability on the photocatalyst-containing layer can be changed. It may be formed to contain a decomposed substance.
[0087]
In the photocatalyst-containing layer as described above, the action mechanism of the photocatalyst represented by titanium dioxide as described below is not necessarily clear, but the carrier generated by light irradiation is a direct reaction with a nearby compound, Alternatively, it is considered that active oxygen species generated in the presence of oxygen and water change the chemical structure of an organic substance. In the present embodiment, it is considered that the carrier acts on the binder compound in the photocatalyst-containing layer to change the wettability of the surface.
[0088]
Hereinafter, the photocatalyst, the binder, and other components constituting such a photocatalyst-containing layer will be described.
[0089]
(I) Photocatalyst
First, the photocatalyst used in the present embodiment will be described. The photocatalyst used in the present embodiment is, for example, titanium dioxide (TiO 2) which is 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 (Fe₂O₃), And one or more of them may be used in combination.
[0090]
In this embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and any of them can be used in the present embodiment. Anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0091]
Examples of such anatase-type titanium dioxide include, for example, anatase-type titania sol of peptized hydrochloric acid (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd .; ST-K01 manufactured by Ishihara Sangyo Co., Ltd.); Glue-type anatase titania sol (TA-15 (average particle diameter: 12 nm) manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
[0092]
The smaller the particle size of the photocatalyst is, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.
[0093]
The content of the photocatalyst in the photocatalyst containing layer used in the present embodiment can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. Further, the thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0094]
(Ii) Binder
Next, the binder used in the present embodiment will be described. In the present embodiment, when the wettability on the photocatalyst-containing layer is changed by the action of the photocatalyst on the binder itself (first embodiment), it is decomposed by the action of the photocatalyst due to energy irradiation, whereby the photocatalyst-containing layer is decomposed. The photocatalyst-containing layer contains a decomposable substance capable of changing the wettability of the photocatalyst-containing layer (second embodiment), and a combination thereof (third embodiment). Can be divided. The binder used in the first embodiment and the third embodiment needs to have a function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst. In the second embodiment, such a binder is used. No special function is required.
[0095]
Hereinafter, the binder used in the second embodiment, that is, the binder that does not particularly require the function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst will be described. Next, the first embodiment and the third embodiment will be described. The binder used, that is, the binder having a function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst will be described.
[0096]
The binder used in the second embodiment, which does not particularly require the function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst, has such a high binding energy that the main skeleton is not decomposed by the photoexcitation of the photocatalyst. It is not particularly limited as long as it is one. Specific examples include polysiloxanes having no organic substituents or having some organic substituents, and these can be obtained by hydrolysis and polycondensation of tetramethoxysilane, tetraethoxysilane, and the like. .
[0097]
When such a binder is used, the photocatalyst-containing layer may contain a decomposed substance that is decomposed by the action of the photocatalyst due to energy irradiation as an additive, thereby changing the wettability on the photocatalyst-containing layer. Required.
[0098]
Next, a binder used in the first and third embodiments, which requires a function of changing the wettability on the photocatalyst-containing layer by the action of the photocatalyst, will be described. As such a binder, those having a high binding energy such that the main skeleton is not decomposed by the photoexcitation of the photocatalyst described above, and those having an organic substituent that is decomposed by the action of the photocatalyst are preferable. (1) Organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction, etc. (2) Organopolysiloxane cross-linked with reactive silicone having excellent water repellency and oil repellency And the like.
[0099]
In the case of the above (1), 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 of 0 to 3. )
Is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by Here, the carbon number of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0100]
In addition, as the binder, a polysiloxane containing a fluoroalkyl group can be particularly preferably used. Specifically, one or more hydrolyzed condensates and co-hydrolyzed condensates of the following fluoroalkylsilanes are preferably used. For example, those generally known as a fluorine-based silane coupling agent can be used.
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-energy-irradiated portion of the photocatalyst-containing layer is greatly improved, and a functional layer-forming coating liquid for forming a functional portion is provided. It exhibits the function of preventing adhesion of
[0101]
Examples of the reactive silicone of the above (2) include compounds having a skeleton represented by the following general formula.
[0102]
Embedded image

[0103]
Here, n is an integer of 2 or more, and R¹, R²Is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and the vinyl, phenyl or halogenated phenyl accounts for 40% or less of the whole in a molar ratio. Also, R¹, R²Is preferably a group having a methyl group since the surface energy is minimized, and the molar ratio of the methyl group is preferably 60% or more. Further, the chain terminal or the side chain has at least one or more reactive group such as a hydroxyl group in the molecular chain.
[0104]
In addition, a stable organosilicon compound that does not undergo a cross-linking reaction such as dimethylpolysiloxane may be mixed with the binder together with the above-mentioned organopolysiloxane.
[0105]
(Iii) decomposition substances
In the above-described second and third embodiments, it is necessary to cause the photocatalyst-containing layer to further contain a decomposed substance that can be decomposed by the action of the photocatalyst due to energy irradiation and thereby change the wettability on the photocatalyst-containing layer. is there. That is, when the binder itself has no function of changing the wettability on the photocatalyst-containing layer, and when such a function is insufficient, the above-described decomposition substance is added, and It causes a change in wettability or assists such a change.
[0106]
Examples of such a decomposed substance include a surfactant that is decomposed by the action of a photocatalyst and has a function of changing the wettability of the surface of the photocatalyst-containing layer by being decomposed. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, and BB series manufactured by Nikko Chemicals Co., Ltd .; ZONYL FSN and FSO manufactured by DuPont; Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd .; Megafac F-141 and 144 manufactured by Ink Chemical Industry Co., Ltd., Futagent F-200 and F251 manufactured by Neos Co., Ltd., Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd., and Florad FC-170 manufactured by 3M Corporation. 176 and the like, and a fluorine-based or silicone-based nonionic surfactant, and a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can also be used.
[0107]
In addition to the surfactant, 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 And oligomers and polymers such as styrene-butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene.
[0108]
(Iv) Fluorine content
Further, in the present embodiment, the photocatalyst containing layer contains fluorine, furthermore, when the content of fluorine on the surface of the photocatalyst containing layer is irradiated with energy to the photocatalyst containing layer, the action of the photocatalyst before the energy irradiation. It is preferable that the photocatalyst-containing layer is formed so as to be lower than the above.
[0109]
With a photocatalyst-containing layer having such characteristics, a pattern composed of a portion having a low fluorine content can be easily formed by pattern irradiation with energy as described later. Here, fluorine has an extremely low surface energy, so that 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 content of fluorine is higher than the critical surface tension of the surface of the portion having a large content of fluorine. This means that a portion having a low fluorine content is a lyophilic region as compared with a portion having 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 a lyophilic region in the lyophobic region.
[0110]
Therefore, when such a photocatalyst-containing layer is used, the pattern of the lyophilic region can be easily formed in the lyophobic region by irradiating the pattern with energy. This is because when a coating liquid for forming a functional layer is applied, a high-definition functional portion can be formed.
[0111]
As described above, as the content of fluorine contained in the fluorine-containing photocatalyst containing layer, the fluorine content in the low lyophilic region where the fluorine content formed by irradiation with energy is low, the energy is not irradiated When the fluorine content of the portion is 100, it is 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0112]
By setting it in such a range, a large difference can be made in the lyophilicity between the energy-irradiated portion and the non-irradiated portion. Therefore, by attaching a coating liquid for forming a functional layer, for example, to such a photocatalyst-containing layer, it becomes possible to accurately form a functional portion only in the lyophilic region where the fluorine content has been reduced, This is because a highly accurate functional element can be obtained. In addition, this reduction rate is based on weight.
[0113]
For the measurement of the fluorine content in the photocatalyst-containing layer, it is possible to use various methods generally used, and for example, X-ray photoelectron spectroscopy (ESCA (Electron Spectroscopy)). It is also not particularly limited as long as it is a method capable of quantitatively measuring the amount of fluorine on the surface such as X-ray fluorescence analysis, mass spectrometry, and the like.
[0114]
In this embodiment, titanium dioxide is preferably used as the photocatalyst as described above. When titanium dioxide is used in this manner, the content of fluorine contained in the photocatalyst-containing layer may be an X-ray. When analyzed by photoelectron spectroscopy and quantified, when the titanium (Ti) element is taken as 100, the fluorine (F) element has a fluorine (F) element ratio of 500 or more, preferably 800 or more, and particularly preferably 1200 or more. It is preferable that the element F) is contained on the surface of the photocatalyst containing layer.
[0115]
When fluorine (F) is contained in the photocatalyst-containing layer to this extent, the critical surface tension on the photocatalyst-containing layer can be sufficiently reduced, so that the liquid repellency on the surface can be ensured. This is because the difference in wettability with the lyophilic region on the surface in the pattern portion in which the fluorine content has been reduced can be increased, and the accuracy of the functional element finally obtained can be improved. .
[0116]
Furthermore, in such a functional element, the fluorine content in the parent ink region formed by irradiating the energy with the pattern is 50 or less, preferably 100 or less, when the titanium (Ti) element is 100. Is preferably 20 or less, more preferably 10 or less.
[0117]
If the content of fluorine in the photocatalyst-containing layer can be reduced to this extent, sufficient lyophilicity for forming a functional element can be obtained, and the lyophobic property of the part where the energy is not irradiated is obtained. Due to the difference in wettability, the functional element can be formed with high accuracy, and a functional element with high utility value can be obtained.
[0118]
(V) Method for producing photocatalyst-containing layer
When the organopolysiloxane is used as a binder as described above, the photocatalyst-containing layer is prepared by dispersing a photocatalyst and an organopolysiloxane as a binder in a solvent together with other additives as necessary. Then, it can be formed by applying this coating liquid 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, and bead coating. When an ultraviolet-curable component is contained as a binder, the photocatalyst-containing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0119]
b. Second embodiment
Next, a second embodiment of the wettability changing layer will be described. In the second embodiment of the wettability changing layer, the photocatalyst treatment layer containing at least a photocatalyst, and the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer reduces the contact angle with the liquid on the surface. This is the case where the layer is composed of a surface-change-type wettability-change layer.
[0120]
In the present embodiment, since the surface change type wettability change layer in which the contact angle with the liquid is reduced by the action of the photocatalyst accompanying the energy irradiation is formed on the photocatalyst treatment layer, This photocatalyst acts on the surface-change-type wettability-change layer, and the energy-irradiated portion on the surface-change-type wettability-change layer can be changed so that the contact angle with the liquid decreases. Hereinafter, the photocatalyst treatment layer and the surface change type wettability change layer will be described.
[0121]
(I) Photocatalyst treatment layer
The photocatalyst-treated layer used in the present embodiment contains at least a photocatalyst. When the photocatalyst-treated layer has a binder, the photocatalyst-containing layer is the same as the photocatalyst-containing layer described in the first embodiment. Description is omitted. However, in this embodiment, since the wettability on the photocatalyst treatment layer does not need to be particularly changed, even if the wettability does not change due to the photocatalyst acting on the binder itself, the first embodiment There is no need to include a decomposition material in the photocatalyst treatment layer as in the embodiment. In addition, since the method for manufacturing the photocatalyst treatment layer having a binder is the same as that of the first embodiment described above, description thereof will be omitted.
[0122]
On the other hand, examples of a method for forming the photocatalyst treatment layer having no binder include a method using a vacuum film forming method such as a sputtering method, a CVD method, and a vacuum evaporation method. By forming the photocatalyst treatment layer by the vacuum film formation method, it is possible to form a uniform film and a photocatalyst treatment layer containing only the photocatalyst, thereby making the wettability on the surface change type wettability change layer uniform. , And only the photocatalyst, it is possible to change the wettability on the surface-change-type wettability changing layer more efficiently than in the case of using a binder.
[0123]
Further, as another method for forming a photocatalyst treatment layer composed of only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on a base material and then changing the phase to crystalline titania by firing, or the like. No. As the amorphous titania used here, for example, titanium tetrachloride, hydrolysis and dehydration condensation of inorganic salts of titanium such as titanium sulfate, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, 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 denatured to anatase type titania by baking at 400 ° C. to 500 ° C., and can be denatured to rutile type titania by baking at 600 ° C. to 700 ° C.
[0124]
(Ii) Surface change type wettability change layer
Next, the surface variable wettability variable layer used in the present embodiment will be described.
[0125]
The surface-change-type wettability changing layer used in the present embodiment is not particularly limited as long as the wettability changes by the action of the photocatalyst treatment layer, but the photocatalyst-containing layer of the first embodiment described above. It is preferable to form with the same material as the binder inside. The material and the method of forming the surface-change-type wettability-change layer when formed with the same material as the binder in the photocatalyst-containing layer of the first embodiment are the same as those of the first embodiment. Therefore, the description here is omitted.
[0126]
In the present embodiment, the thickness of the surface-change-type wettability-changing layer is preferably from 0.001 μm to 1 μm, particularly preferably from 0.01 to 0.1 μm, from the relation of the change rate of the wettability by the photocatalyst. Is within the range.
[0127]
In the present embodiment, by using the surface change type wettability changing layer of the above-described components, the action of the photocatalyst in the adjacent photocatalyst treatment layer causes the oxidation, decomposition, etc. of the organic groups and additives which are a part of the above components. By using the action, the wettability of the energy-irradiated portion can be changed to make the portion lyophilic, and a large difference can be produced in the wettability with the energy-unirradiated portion.
[0128]
Among the surface-change-type wettability changing layers used in the present embodiment, the contact angle with a liquid of 40 mN / m with a liquid of 40 mN / m is 10 ° or more, especially the surface tension of 30 mN, in a portion not irradiated with energy, that is, in a lyophobic region. The contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 ° or more. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency, so if the contact angle with the liquid is small, the liquid repellency is not sufficient, and the above-described functional portion forming When a coating liquid is applied by an inkjet method and cured, the functional part is formed with high definition because the coating liquid for forming the functional part may adhere to the lyophobic area. It becomes difficult to do so.
[0129]
The surface-changeable wettability changing layer has a contact angle with a liquid of 40 mN / m less than 9 °, preferably a liquid of a surface tension of 50 mN / m, in a portion irradiated with energy, that is, a lyophilic region. Is preferably a layer having a contact angle of 10 ° or less, particularly a liquid having a surface tension of 60 mN / m. When the contact angle with the liquid in the energy-irradiated portion, that is, the lyophilic region, is high, for example, the functional portion-forming coating liquid that forms the functional portion may be repelled in the lyophilic region. Because there is. Here, the contact angle with the liquid in the surface-change-type wettability changing layer is also a value measured by the method described in the above-mentioned “1.
[0130]
The surface-changeable wettability changing layer may contain the same fluorine in the same manner as that described in the section of “fluorine content” in the description of the photocatalyst-containing layer in the first embodiment.
[0131]
In the present embodiment, it is not necessary to include a photocatalyst in the surface-change-type wettability changing layer. In this case, it is possible to reduce the possibility that the functional portion is affected by the photocatalyst over time. It is.
[0132]
c. Third embodiment
Next, a third embodiment of the wettability changing layer will be described. In the third embodiment of the wettability changing layer, a photocatalyst treatment layer containing a photocatalyst and a photocatalyst treatment layer side substrate having a substrate are separated by a gap such that the wettability change layer and the photocatalyst treatment layer are 200 μm or less. This is a case where the surface is changed to a surface-change type wettability change layer in which the wettability changes so that the contact angle with the liquid on the surface is reduced by irradiating energy from a predetermined direction.
[0133]
As shown in FIG. 5, for example, as shown in FIG. 5, the surface-change-type wettability change layer in the present embodiment is a photocatalyst-treatment-layer-side substrate having a photocatalyst-containing photocatalyst treatment layer 22 and a base 23 containing a photocatalyst. Prepare 20. Next, after the surface change type wettability change layer 21 and the photocatalyst treatment layer 22 are arranged so as to have a predetermined gap, energy 25 is irradiated from a predetermined direction using a photomask 24 or the like. Thereby, the wettability is changed so that the contact angle with the liquid at the energy-irradiated portion on the surface-changeable wettability changing layer 21 decreases.
[0134]
Note that the photocatalyst processing layer side substrate may be disposed at the above position only during energy irradiation.
[0135]
The surface change type wettability change layer used in the present embodiment is the same as the surface change type wettability change layer described in the second embodiment, and thus description thereof will be omitted, and only the photocatalyst treatment layer side substrate will be described. Will be described.
[0136]
The photocatalyst treatment layer side substrate used in the present embodiment has at least a photocatalyst treatment layer and a substrate, and usually has a thin film photocatalyst treatment layer formed by a predetermined method on the substrate. It is. The photocatalyst-treated layer-side substrate may be a substrate on which a photocatalyst-treated layer-side light-shielding portion or a primer layer formed in a pattern is formed.
[0137]
In the present embodiment, when irradiating energy, the surface change type wettability change layer and the photocatalyst treatment layer in the photocatalyst treatment layer side substrate are opposed with a predetermined gap, and the photocatalyst treatment layer side substrate By the action of the photocatalyst treatment layer, the wettability of the surface-change-type wettability changing layer is changed, and after the energy irradiation, the photocatalyst treatment layer side substrate is removed to form a wettability pattern. Hereinafter, each configuration of the photocatalyst processing layer side substrate will be described.
[0138]
(I) Photocatalyst treatment layer
The photocatalyst treatment layer used in the present embodiment contains at least a photocatalyst and may or may not have a binder, and is the same as the photocatalyst treatment layer of the second embodiment described above. Therefore, the description here is omitted.
[0139]
Here, the photocatalyst treatment layer used in the present embodiment may be formed on the entire surface of the substrate 23 as shown in FIG. 5, for example, but may be formed on the substrate 23 as shown in FIG. Alternatively, the photocatalyst treatment layer 22 may be formed in a pattern.
[0140]
By forming the photocatalyst treatment layer in a pattern as described above, when irradiating energy, it is not necessary to irradiate the pattern using a photomask or the like. A wettability pattern including a lyophilic region and a lyophobic region can be formed thereon.
[0141]
The method of patterning the photocatalyst treatment layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0142]
Further, in the case where the photocatalyst treatment layer and the surface-change-type wettability change layer are brought into close contact with each other and energy irradiation is performed, for example, the wettability of only the portion where the photocatalyst treatment layer is formed is changed. Irradiation direction of the photocatalyst treatment layer and the surface change type wettability change layer may be irradiated from any direction as long as the energy is irradiated to the portion facing the changeable wettability change layer. This has the advantage that it is not limited to parallel light such as parallel light.
[0143]
(Ii) Substrate
In this embodiment, as shown in FIG. 5, the photocatalyst processing layer side substrate has at least a base 23 and a photocatalyst processing layer 22 formed on the base 23. At this time, a material constituting the base to be used is appropriately selected depending on, for example, a direction of irradiation of energy described later and whether the obtained functional element requires transparency.
[0144]
The substrate used in the present embodiment may be a substrate having flexibility, for example, a resin film, or a substrate having no flexibility, for example, a glass substrate. This is appropriately selected depending on the energy irradiation method.
[0145]
Note that an anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst treatment layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0146]
(Iii) Light-shielding portion on the photocatalyst treatment layer side
The photocatalyst processing layer side substrate used in the present embodiment may be a substrate on which a photocatalyst processing layer side light shielding portion formed in a pattern is formed. By using the photocatalyst processing layer side substrate having the photocatalyst processing layer side light-shielding portion as described above, it is not necessary to use a photomask or perform drawing irradiation with a laser beam when irradiating energy. Therefore, since it is not necessary to align the photocatalyst processing layer side substrate and the photomask, it is possible to simplify the process, and it is not necessary to use an expensive apparatus required for drawing irradiation. This is advantageous in that it is advantageous.
[0147]
The photocatalyst processing layer side substrate having such a photocatalyst processing layer side light shielding portion can be in the following two modes depending on the formation position of the photocatalyst processing layer side light shielding portion.
[0148]
One is, for example, as shown in FIG. 7, a photocatalyst processing layer side light shielding portion 26 is formed on a substrate 23, and a photocatalyst processing layer 22 is formed on the photocatalyst processing layer side light shielding portion 26. It is an aspect to make it. The other is a mode in which a photocatalyst processing layer 22 is formed on a substrate 23, and a photocatalyst processing layer side light-shielding portion 26 is formed thereon to form a photocatalyst processing layer side substrate 20, as shown in FIG. 8, for example. .
[0149]
In any of the embodiments, as compared with the case of using a photomask, the photocatalyst-treated layer-side light-shielding portion is arranged near the arrangement portion of the photocatalyst treatment layer and the surface-change-type wettability-change layer, Since the influence of energy scattering inside the base or the like can be reduced, it is possible to perform energy pattern irradiation extremely accurately.
[0150]
Further, in the aspect in which the photocatalyst-treated layer-side light-shielding portion is formed on the photocatalyst-treated layer, the photocatalyst-treated layer-side light-shielding portion is provided when the photocatalyst-treated layer and the surface-change-type wettability changing layer are arranged at predetermined positions. By making the film thickness of the film coincide with the width of the gap, there is an advantage that the light-shielding portion on the photocatalyst treatment layer side can be used as a spacer for making the gap constant.
[0151]
That is, when the photocatalyst treatment layer and the surface-change-type wettability-change layer are arranged facing each other with a predetermined gap therebetween, the photocatalyst-treatment-layer-side light-shielding portion and the surface-change-type wettability-change layer are in close contact with each other. By arranging in this state, it is possible to make the predetermined gap accurate, and in this state, by irradiating energy from the photocatalyst processing layer side substrate, the wettability on the surface change type wettability change layer This makes it possible to accurately form the change pattern.
[0152]
The method of forming such a photocatalyst treatment layer side light-shielding portion is not particularly limited, and is appropriately selected according to the characteristics of the formation surface of the photocatalyst treatment layer-side light-shielding portion, the shielding property against required energy, and the like. Used.
[0153]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 ° by a sputtering method, a vacuum evaporation method, or the like, and patterning the thin film. As the patterning method, a normal patterning method such as sputtering can be used.
[0154]
Alternatively, a method in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder may be formed in a pattern. As the resin binder to be used, one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, photosensitive resin, and O / O A W emulsion type resin composition, for example, an emulsion of reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. A commonly used method such as a photolithography method and a printing method can be used as a method for patterning the resin light-shielding portion.
[0155]
In the above description, the case where the photocatalyst treatment layer side light-shielding portion is formed is described between the base and the photocatalyst treatment layer and the surface of the photocatalyst treatment layer. It is also possible to adopt a mode in which a photocatalyst treatment layer-side light-shielding portion is formed on the surface on the side that is not provided. In this embodiment, for example, a case where a photomask is brought into close contact with the surface to the extent that the photomask can be detached is considered, and the method can be suitably used when the wettability change pattern is changed in a small lot.
[0156]
(Iv) Primer layer
Next, the primer layer used for the photocatalyst processing layer side substrate of the present embodiment will be described. In the present embodiment, as described above, when the photocatalyst treatment layer side light-shielding portion is formed in a pattern on the substrate and the photocatalyst treatment layer is formed thereon to form the photocatalyst treatment layer side substrate, A primer layer may be formed between the layer-side light shielding portion and the photocatalyst treatment layer.
[0157]
The function and function of this primer layer are not always clear, but by forming the primer layer between the light-shielding part on the photocatalyst treatment layer side and the photocatalyst treatment layer, the primer layer has a surface-change wettability due to the action of the photocatalyst. Impurities from the photocatalyst-treated layer-side light-shielding portion and the openings existing between the photocatalyst-treatment-layer-side light-shielding portions, which are factors that hinder the change in wettability of the variable layer, particularly residues generated when patterning the photocatalyst-treated layer-side light-shielding portion It is also considered to have a function of preventing diffusion of impurities such as metals and metal ions. Therefore, by forming the primer layer, the process of changing the wettability proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0158]
In this embodiment, the primer layer is intended to prevent impurities present not only in the photocatalyst-treated layer-side light-shielding portion but also in the opening formed between the photocatalyst-treatment layer-side light-shielded portions from affecting the action of the photocatalyst. Therefore, it is preferable that the primer layer is formed over the entire light-shielding portion on the photocatalyst treatment layer side including the opening.
[0159]
The primer layer in the present embodiment is not particularly limited as long as the primer layer is formed so that the light-shielding portion on the photocatalyst treatment layer side of the substrate on the photocatalyst treatment layer side does not contact the photocatalyst treatment layer.
[0160]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of a photocatalyst is preferable. Specific examples include amorphous silica. When such an amorphous silica is used, the precursor of the amorphous silica has a general formula of SiX₄Wherein X is a silicon compound such as a halogen, a methoxy group, an ethoxy group, or an acetyl group. Silanol, which is a hydrolyzate thereof, or a polysiloxane having an average molecular weight of 3000 or less is preferable.
[0161]
Further, the thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, and particularly preferably in the range of 0.001 μm to 0.1 μm.
[0162]
d. Fourth embodiment
Next, a fourth embodiment of the wettability changing layer will be described. The fourth embodiment of the wettability changing layer includes a photocatalyst treatment layer containing at least a photocatalyst, and a decomposition removal type wettability change layer formed on the photocatalyst treatment layer and decomposed and removed by the action of the photocatalyst accompanying energy irradiation. And a contact angle of the liquid with respect to the decomposition-removal type wettability changing layer, and a layer having a different contact angle of the liquid with the photocatalyst treatment layer exposed after the decomposition-removal type wettability change layer is decomposed and removed. This is the case when it is a layer.
[0163]
In the present embodiment, since the decomposition removal type wettability changing layer which is decomposed and removed by the action of the photocatalyst accompanying the energy irradiation is formed on the photocatalyst treatment layer, the photocatalyst in the photocatalyst treatment layer is irradiated by the energy irradiation. It acts on the decomposition-removal-type wettability changing layer, and it becomes possible to decompose and remove the energy-irradiated portion on the decomposition-removal-type wettability change layer.
[0164]
Here, since the photocatalyst treatment layer is the same as the photocatalyst treatment layer used in the second embodiment described above, the description is omitted here, and the decomposition removal type wettability changing layer used in the present embodiment is described. The details will be described below.
[0165]
The decomposition removal type wettability change layer used in the present embodiment is a layer in which the energy removal is performed on the portion of the photocatalyst treated layer where the decomposition removal type wettability change layer is decomposed and removed by the action of the photocatalyst in the photocatalyst treatment layer. There is no particular limitation as long as the decomposition removal type wettability changing layer has a different contact angle with a liquid as compared with the exposed photocatalyst treatment layer.
[0166]
In this manner, the decomposed / removable type wettability changing layer is decomposed and removed by the action of the photocatalyst, so that the portion having the decomposed / removable type wettability changing layer and the portion without the decomposed / removable type wettability changing layer are not subjected to the developing step or the washing step. , That is, a pattern having irregularities.
[0167]
The decomposition removal type wettability changing layer is oxidized and decomposed by the action of a photocatalyst due to energy irradiation, and is vaporized or the like, so that it is removed without a special post-treatment such as a development / washing step. Depending on the material of the decomposition removal type wettability changing layer, a washing step or the like may be performed.
[0168]
In addition, in the present embodiment, not only the unevenness is formed, but also the contact angle of the liquid between the decomposition removal type wettability changing layer and the photocatalyst treatment layer exposed after the decomposition removal type wettability change layer is decomposed and removed. Therefore, it is possible to form a lyophobic region and a lyophilic region on the pattern forming body.
[0169]
Here, the decomposition removal type wettability change layer used in the present embodiment is, among the above, the decomposition removal type wettability change layer, the contact angle with the liquid is higher than the exposed photocatalyst treatment layer. Is preferred. This makes it possible to make the region where the decomposition removal type wettability changing layer is decomposed and removed a lyophilic region and the region where the decomposition removal type wettability changing layer remains as a lyophobic region. This is because it becomes possible to form a pattern composed of a liquid repellent region and a liquid repellent region.
[0170]
Here, in the decomposition removal type wettability changing layer in the present embodiment, since the portion remaining after the energy irradiation becomes the liquid repellent region, the contact angle with the liquid of 40 mN / m is preferably 10 ° or more, more preferably Is preferably a layer having a contact angle of 10 ° or less with a liquid having a surface tension of 50 mN / m, particularly 10 ° or less with a liquid having a surface tension of 60 mN / m. This is because the decomposition-removal type wettability changing layer is a portion where liquid repellency is required in the present embodiment, so if the contact angle with the liquid is small, the liquid repellency is not sufficient, and When the coating liquid for forming a functional part is applied, the coating liquid for forming a functional part may adhere to the lyophobic region, so that it is difficult to obtain a high-definition functional element. This is because
[0171]
In the photocatalyst treatment layer exposed by the energy irradiation, that is, in the lyophilic region, the contact angle with the liquid of 40 mN / m is less than 9 °, preferably the surface tension is 50 mN / m. The layer preferably has a contact angle of 10 ° or less with a liquid having a m of 10 m or less, particularly 10 ° or less with a liquid having a surface tension of 60 mN / m. This is because when the contact angle between the photocatalyst treatment layer and the functional part forming coating liquid in the lyophilic area is high, when the functional part forming coating liquid is applied, the function also functions in the lyophilic area This is because the coating liquid for forming a functional part may be repelled, and it may be difficult to form a functional part on the lyophilic region by an inkjet method. Here, the contact angle with the liquid is a value measured by the method described in “1.
[0172]
Specific examples of the film that can be used for the decomposition removal type wettability changing layer of this embodiment include a film made of a fluorine-based or hydrocarbon-based liquid-repellent resin. 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 and, for example, a common resin such as spin coating is used. It can be formed by a film method.
[0173]
Further, in the present embodiment, a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, and an alternately adsorbed film can be used to form a defect-free film. It can be said that such a film forming method is more preferably used.
[0174]
Here, the self-assembled monolayer, the Langmuir-Brocket film, and the alternating adsorption film used in the present embodiment will be specifically described.
[0175]
(I) Self-assembled monolayer
The inventors do not know the existence of an official definition of a self-assembled monolayer (Self-Assembled Monolayer), but as a commentary on what is generally recognized as a self-assembled monolayer, a review by Abraham Ulman "Formation and Structure of Self-Assembled Monolayers", Chemical Review, 96, 1533-1554 (1996). With reference to this review, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorption and binding (self-assembly) of appropriate molecules to an appropriate substrate surface. Materials capable of forming a self-assembled film include, for example, surfactant molecules such as fatty acids, organic silicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. Organic phosphoric acid molecule. A general commonality of molecular structures is that they have a relatively long alkyl chain, and a functional group that interacts with the substrate surface is present at one molecular end. The portion of the alkyl chain is a source of intermolecular force when the molecules are packed two-dimensionally. However, the example shown here is the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain having an oxyethylene chain, or a fluorocarbon chain. A self-assembled monolayer composed of various molecules, such as a complex-type chain, has been reported. There is also a composite self-assembled monolayer composed of a plurality of molecular species. Recently, a polymer having a plurality of functional groups (in some cases, one functional group) or a linear (in some cases having a branched structure) polymer in the form of particles, such as a dendrimer, has been developed. It seems that the one formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present embodiment, these are also included in the self-assembled monolayer.
[0176]
(Ii) Langmuir-Blodgett membrane
The Langmuir-Blodgett film used in the present embodiment is not significantly different from the above-described self-assembled monomolecular film in terms of morphology as long as it is formed on a substrate. The characteristics of the Langmuir-Blodgett film can be said to be its formation method and the resulting high two-dimensional molecular packing properties (high orientation and high ordering). 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 and changes into a highly packed condensed film. In practice, this is transferred to a suitable substrate and used. It is possible to form from a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. In addition, not only low molecules but also polymers, colloid particles, etc. can be used as the film material. A recent example of applying various materials is described in detail in a review by Tokuharu Miyashita et al., "Prospects for Nanotechnology for Creating Soft Nanodevices", Polymer, Vol. 50, September, 644-647 (2001).
[0177]
(Iii) Alternating adsorption membrane
An alternating adsorption film (Layer-by-Layer Self-Assembled Film) generally has a material having at least two functional groups having positive or negative charges sequentially adsorbed and bound on a substrate. This is a film formed by stacking. Since a material having a larger number of functional groups has more advantages such as an increase in the strength and durability of the membrane, an ionic polymer (polymer electrolyte) is often used recently as a material. Particles having a surface charge such as proteins, metals and oxides, so-called "colloidal particles" are also frequently used as film-forming substances. More recently, membranes have been reported that actively utilize weaker interactions than ionic bonds, such as hydrogen bonds, coordinate bonds, and hydrophobic interactions. Regarding the case of a relatively recent alternately adsorbed film, it is slightly biased toward a material system using electrostatic interaction as a driving force, but Paula T. et al. Review by Hammond "Recent Explorations in Electrostatic Multilayer Thin Film Assembly" Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). In the alternate adsorption film, taking the simplest process as an example, the cycle of adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge is repeated a predetermined number of times. It is a film to be formed. No development-condensation-transfer operations are required at all as with Langmuir-Blodgett membranes. Further, as is apparent from the difference between these production methods, the alternating adsorption film generally does not have a two-dimensional high orientation and high order unlike the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film forming methods, such as being able to easily form a dense film without defects and being able to uniformly form a film on a fine uneven surface, a tube inner surface, a spherical surface, and the like. Have many.
[0178]
Further, the thickness of the decomposition removal type wettability changing layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the energy irradiated in the 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 type wettability changing layer, and the like, but is generally in the range of 0.001 μm to 1 μm, particularly 0.1 μm. It is preferable that the thickness be in the range of 01 μm to 0.1 μm.
[0179]
e. Fifth embodiment
Next, a fifth embodiment of the wettability changing layer will be described. The fifth embodiment of the wettability changing layer, the photocatalyst treatment layer containing a photocatalyst and a photocatalyst treatment layer side substrate having a substrate, the gap between the wettability change layer and the photocatalyst treatment layer is 200μm or less. After being disposed in the above-mentioned manner, it is a decomposition removal type wettability changing layer that is decomposed and removed by energy irradiation from a predetermined direction, and the contact angle of the liquid with the decomposition removal type wettability changing layer and the decomposition removal This is the case where the mold wettability changing layer is a layer having a different contact angle of the liquid to the exposed substrate after being decomposed and removed.
[0180]
In this embodiment, as in the third embodiment described above, when irradiating energy, using the photocatalyst processing layer side substrate having a photocatalyst processing layer containing a photocatalyst, the decomposition removal type wettability changing layer and The photocatalyst treatment layer is opposed to the photocatalyst treatment layer with a predetermined gap therebetween, and by the action of the photocatalyst treatment layer on the photocatalyst treatment layer side substrate, the decomposition removal type wettability changing layer is decomposed and removed in a pattern form. By removing the layer, a pattern in which the decomposition removal type wettability changing layer is decomposed is formed. At this time, what is exposed after being decomposed and removed from the decomposition removal type wettability changing layer is a base material described later. At this time, the base material described later may be surface-treated so that the surface becomes lyophilic. Examples of surface treatment of the material surface to be lyophilic include lyophilic surface treatment by plasma treatment using argon, water, etc., as a lyophilic layer formed on the substrate, For example, a silica film formed by a sol-gel method of tetraethoxysilane can be used.
[0181]
The decomposition removal type wettability changing layer used in the present embodiment is the same as that in the fourth embodiment described above, and the photocatalyst processing layer side substrate is the photocatalyst processing layer side substrate described in the third embodiment described above. The description is omitted here.
[0182]
(2) Substrate
Next, the base material used for the pattern forming body of the present embodiment will be described. In this embodiment, when the wettability changing layer does not have self-supporting property, when the functional element requires strength, or when the wettability changing layer is the fifth embodiment of the above-described wettability changing layer, The wettability changing layer is formed on the material.
[0183]
The substrate used in the present embodiment may be one having flexibility, for example, a resin film or the like, or one having no flexibility, for example, a glass substrate.
[0184]
Further, in the present embodiment, it is necessary to irradiate energy when forming a pattern in which the wettability of the wettability changing layer is changed, but in this energy irradiation, when energy is irradiated from the base material side, Requires transparency of the base material.
[0185]
Note that an anchor layer may be formed on the substrate in order to improve the adhesion between the surface of the substrate and the wettability changing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0186]
(3) Other
In the present embodiment, a light-shielding portion may be formed in the pattern forming body depending on the type of the functional element. When the light-shielding portion is provided in this manner, it is not necessary to use a photomask or perform drawing irradiation by laser light when forming a pattern by energy irradiation. Therefore, the process can be simplified, and an expensive apparatus required for drawing irradiation is not required, which is advantageous in terms of cost.
[0187]
Such a light-shielding portion may be formed on a base material and a wettability changing layer is formed on the base material, that is, when the light-shielding portion is formed between the base material and the wettability changing layer. When the wettability changing layer or the pattern-formed body on the side opposite to the surface on which is formed has the above-mentioned substrate, it may be formed in a pattern on the surface of the substrate.
[0188]
In any case, the energy irradiation is performed from the pattern forming body side, but by irradiating the entire surface, a wettability change pattern can be formed in a pattern on the wettability change layer surface.
[0189]
The method of forming such a light-shielding portion is not particularly limited, and is appropriately selected and used depending on the characteristics of the surface on which the light-shielding portion is formed, the shielding property against required energy, and the like. Regarding the method of forming the light-shielding portion, it is possible to use the same method as that described in the section of the photocatalyst processing layer-side light-shielding portion in the photocatalyst processing layer-side substrate in the third embodiment of the wettability changing layer described above. Therefore, the description here is omitted.
[0190]
(4) Formation of pattern composed of lyophilic area and lyophobic area
Next, formation of a pattern including a lyophilic region and a lyophobic region on the wettability changing layer will be described. In this embodiment, a pattern due to the difference in wettability is formed on the surface of the wettability changing layer by irradiating the pattern with energy from a predetermined direction, and a functional portion described later is formed along the pattern. It is.
[0191]
The term “energy irradiation (exposure)” in the present embodiment is a concept including irradiation of any energy ray capable of changing the wettability of the wettability changing layer, and is limited to visible light irradiation. Not something.
[0192]
Usually, the wavelength of light used for such energy irradiation is set in a range of 400 nm or less, preferably in a range of 380 nm or less. This is because, as described above, titanium dioxide is preferably used for the photocatalyst, and light having the above-mentioned wavelength is preferable as the energy for activating the photocatalysis by the titanium dioxide.
[0193]
Examples of the light source that can be used for such energy irradiation include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and various other light sources.
[0194]
In addition to the above-described method using a light source and irradiating a pattern through a photomask, a method of drawing and irradiating a pattern using a laser such as excimer or YAG can also be used.
[0195]
Further, the energy irradiation amount at the time of the energy irradiation is an irradiation amount necessary for the wettability changing layer to change the wettability by the action of the photocatalyst.
[0196]
At this time, by irradiating energy while heating the photocatalyst-containing layer, the sensitivity can be increased, which is preferable in that the wettability can be changed efficiently. Specifically, it is preferable to heat in the range of 30 ° C to 80 ° C.
[0197]
Here, as described above, in a case where the photocatalyst-containing layer or the photocatalyst-treated layer is not provided in the wettability-change layer, the aforementioned photocatalyst-treatment-layer-side substrate is placed at a predetermined distance from the wettability-change layer. It is necessary to perform energy irradiation from a predetermined direction.
[0198]
The above-mentioned arrangement means a state in which the action of the photocatalyst substantially extends to the surface of the wettability changing layer. The photocatalyst treatment layer and the wettability changing layer are arranged to be separated from each other. This gap is preferably 200 μm or less.
[0199]
In the present embodiment, the gap is particularly good in the range of 0.2 μm to 10 μm in consideration of the fact that the pattern accuracy is extremely good, the sensitivity of the photocatalyst is high, and thus the efficiency of the wettability changing layer is good. , Preferably within a range of 1 μm to 5 μm. Such a range of the gap is particularly effective for a small-area wettability variable layer in which the gap can be controlled with high accuracy.
[0200]
On the other hand, when processing is performed on a wettability changing layer having a large area of, for example, 300 mm × 300 mm, a small gap as described above is formed between the photocatalyst processing layer side substrate and the wettability changing layer without contact. Is extremely difficult to form. Therefore, when the wettability changing layer has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly preferably in the range of 50 to 75 μm. By setting the gap within such a range, problems such as a decrease in pattern accuracy such as blurring of the pattern and a problem such as a decrease in the sensitivity of the photocatalyst and a decrease in the efficiency of change in wettability do not occur. This is because there is an effect that unevenness does not occur in the wettability change on the property change layer.
[0201]
When the relatively large-area wettability changing layer is irradiated with the energy as described above, the setting of the gap in the positioning device between the photocatalyst processing layer side substrate and the wettability changing layer in the energy irradiation device is set in the range of 10 μm to 200 μm. It is preferable to set the distance in the range of 25 μm to 75 μm. By setting the set value within such a range, the pattern accuracy is not significantly reduced, the sensitivity of the photocatalyst is not significantly deteriorated, and the photocatalyst processing layer side substrate and the wettability changing layer are arranged without contact. This is because it becomes possible.
[0202]
By arranging the photocatalyst treatment layer and the surface of the wettability changing layer at a predetermined distance in this manner, oxygen and water and active oxygen species generated by the photocatalysis can be easily desorbed. That is, when the distance between the photocatalyst treatment layer and the wettability changing layer is narrower than the above range, the desorption of the active oxygen species becomes difficult, and as a result, the wettability change speed may be reduced. Is not preferred. In addition, if they are arranged at an interval from the above range, it becomes difficult for the generated active oxygen species to reach the wettability changing layer, and in this case, it is not preferable because the speed of the wettability change may be reduced. .
[0203]
In this embodiment, such an arrangement need only be maintained at least during the energy irradiation.
[0204]
As a method of forming such an extremely narrow gap uniformly and disposing the photocatalyst treatment layer and the wettability changing layer, for example, a method using a spacer can be mentioned. By using such a spacer, a uniform gap can be formed, and at the portion where the spacer comes into contact, the action of the photocatalyst does not reach the surface of the wettability changing layer. By having the same pattern as the wettability change pattern, it becomes possible to form a predetermined wettability change pattern on the wettability change layer.
[0205]
In this embodiment, such an arrangement need only be maintained at least during the energy irradiation.
[0206]
B. Color filter
Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter formed by the above-described method for manufacturing a functional element.
[0207]
The shape of the pixel portion in the color filter is usually a matrix or a stripe, and the same applies to the present invention. In the present invention, before applying the pixel portion forming coating liquid for forming such a pixel portion, by cooling the pattern formed body on which the pattern of the lyophilic region is formed, It is possible to form a pixel portion with high precision and a desired film thickness. Thus, a color filter that can be used for various applications can be obtained.
[0208]
Here, the color filter of the present invention can be manufactured by the above-described method for manufacturing a functional element, and a material used for manufacturing a general color filter can be used.
[0209]
C. Functional device manufacturing equipment
Next, an apparatus for manufacturing a functional element of the present invention will be described.
[0210]
The apparatus for manufacturing a functional element according to the present invention includes: a discharge unit that discharges the coating liquid for forming a functional part by an inkjet method; and a substrate on which the coating liquid for forming a functional part discharged from the discharge unit lands. And cooling means for setting the surface temperature of the substrate fixed to the fixing means within a range of 0 ° C. to 25 ° C.
[0211]
In the present invention, by using such an apparatus for producing a functional element, the coating liquid for forming a functional part can be stably discharged, and the coating amount of the coating liquid for forming a functional part can be more than before. Can be secured, so that the selection range of the film thickness of the functional part formed from the functional part forming coating liquid can be widened, and a high-definition pattern can be easily formed. be able to.
[0212]
An apparatus for manufacturing a functional element according to the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of a functional device manufacturing apparatus of the present invention.
[0213]
First, the apparatus for manufacturing a functional element of the present invention has a head 10 for applying a coating liquid for forming a functional part on the surface of a substrate 11 by an ink jet method. Further, there is provided a fixing means 12 for fixing the substrate 11 on which the functional part forming coating liquid is applied by such a head 10. The fixing means 12 is not particularly limited as long as it can stably hold the substrate 11 in a horizontal state. For example, means for fixing the substrate 11 by suction on a stage can be used. Further, there is provided a cooling means 13 for cooling the surface temperature of the substrate 11 fixed by such fixing means 12 within the above-mentioned range. The cooling means 13 in the present invention is not particularly limited as long as the temperature of the surface of the substrate 11 can be kept within the above-mentioned range. Specifically, as described above, a method of circulating a coolant in a member that comes into contact with the substrate 11, a method of exposing the substrate 11 to a low temperature state, and the like can be given. Among them, a method of circulating a coolant in a member that contacts the substrate 11 is preferable. For example, there is a method of arranging the substrate 11 on a stage where a coolant is circulated and cooled. In this case, liquid nitrogen or the like can be used as the refrigerant.
[0214]
Note that the present invention is not limited to the above embodiment. The above 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 has the same effect. Within the technical scope of
[0215]
【Example】
Hereinafter, the present invention will be further described with reference to Examples.
[0216]
[Example]
(1) Preparation of coating liquid for photocatalyst containing layer
The following components were mixed and stirred at 100 ° C. for 20 minutes to prepare a coating solution for a photocatalyst-containing layer.
Composition of coating liquid for photocatalyst containing layer
・ Isopropyl alcohol: 3g
Fluoroalkylsilane (manufactured by Tochem Products, MF-160E: N- [3- (trimethoxysilyl) propyl] -N-ethyl-perfluorooctanesulfonamide in 50% by weight isopropyl ether solution): 0.07 g
・ Titanium oxide sol (STK-01, manufactured by Ishihara Sangyo): 3 g
-Silica sol (Nippon Synthetic Rubber, Glasca HPC7002): 0.6 g
・ Alkylalkoxysilane (Nippon Synthetic Rubber, HPC402C): 0.2 g
(2) Formation of photocatalyst containing layer
The above-mentioned coating solution for a photocatalyst-containing layer is applied on a transparent substrate made of soda glass having a black matrix composed of a chromium thin film pattern having an opening of 76 μm × 259 μm and a line width of 23 μm by a spin coater, and is applied at 150 ° C. for 10 minutes. After the drying treatment, the hydrolysis and polycondensation reactions were allowed to proceed to form a 0.5 μm thick transparent photocatalyst-containing layer in which the photocatalyst was firmly fixed in the organopolysiloxane.
[0217]
70 mW / cm by means of a mercury lamp (wavelength 365 nm) through a mask on this photocatalyst containing layer.²Irradiation was performed at an illuminance of 3 minutes for 3 minutes, and the contact angles of the non-irradiated portion and the irradiated portion to water were measured. The contact angle was measured 30 seconds after a water drop was dropped from a micro syringe onto a non-irradiated part or an irradiated part using a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.). As a result, the contact angle of water at the non-irradiated part was 70 °, whereas the contact angle of water at the irradiated part was 10 ° or less, and the irradiated part became highly hydrophilic and became non-irradiated with the irradiated part. It was confirmed that pattern formation was possible using the difference in wettability with the site.
[0218]
Further, the contact angle (θ) was measured 30 seconds after the droplet was brought into contact with the non-irradiated portion of the photocatalyst-containing layer using the standard solution shown in the wettability test specified in JIS K6768, and the Zisman plot ( (Horizontal axis: surface tension of standard solution, vertical axis: cos θ) was prepared and extrapolated from the graph. The surface tension indicated by the point where cos θ = 0, that is, the critical surface tension of the non-irradiated portion was 30 mN / m. . When the critical surface tension at the irradiation site was measured by the same method, it was 70 mN / m.
[0219]
(3) Exposure of photocatalyst containing layer
A mask having a pattern pitch of 76 μm × 259 μm and a light-shielding pattern having a width (10 μm) smaller than the line width (23 μm) of the black matrix is arranged on the photocatalyst-containing layer of the transparent substrate, and overlaps with the black matrix. After that, 70 mW / cm by a mercury lamp (wavelength 365 nm) through this mask.²The photocatalyst containing layer was exposed for 50 seconds at an illuminance of, to make the irradiated site highly hydrophilic. Each irradiated part is defined by a non-irradiated part having a width of 10 μm existing on the black matrix, and has a pixel part formation region of 76 μm × 259 μm surrounded by the black matrix and a region overlapping with the surrounding black matrix. Was.
[0220]
(4) Adjustment of colored ink for pixel unit
UV curable ink for color filter Colored ink composition for blue pixel
-Pigment (CI Pigment Blue 15: 6): 5 parts by weight
・ Polymer dispersant (Solsperse 24000, manufactured by AVECIA): 2 parts by weight
Binder (benzyl methacrylate-methacrylic acid copolymer): 3 parts by weight
-Monomer 1 (dipentaerythritol pentaacrylate): 2 parts by weight
-Monomer 2 (tripropylene glycol diacrylate): 5 parts by weight
-Initiator (2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropane) -1-one: 2 parts by weight
-Solvent (diethylene glycol monobutyl ether acetate, 29.9 dyn / cm): 81 parts by weight
Further, C.I. I. Pigment Blue 15: 6 instead of C.I. I. Pigment Red 254 was prepared in the same manner as in the case of the blue pixel portion coloring ink except that the same amount of Pigment Red 254 was used. Further, C.I. I. Pigment Blue 15: 6 instead of C.I. I. Pigment Green 36 was prepared in the same manner as in the case of the blue pixel portion coloring ink except that the same amount of Pigment Green 36 was used.
[0221]
(5) Production of color filters
The ink-jet head was filled with the coloring ink for each color pixel. Next, the color ink for each color pixel was dropped from the head with a drop diameter of 30 μm to the center of the blue pixel portion forming region scattered on the substrate.
[0222]
The dropped colored ink for the pixel portion of each color was repelled in the non-irradiated portion on the black matrix, and was uniformly diffused and selectively attached in the pixel portion forming region of each color.
[0223]
Thereafter, the colored ink layers of each color were dried at 80 ° C. for 3 minutes, and 70 mW / cm using a mercury lamp (wavelength 365 nm).²Irradiation was performed for 30 seconds at an illuminance of, and heat treatment was further performed at 230 ° C. for 30 minutes to form a pixel portion.
[0224]
In the case where a cooling step of cooling the substrate at 5 ° C. is adopted, the ink droplets applied from the ink jet land on the lyophilic region of the cooling substrate, and then hardly spread in diameter and spread quickly. That was suppressed. In addition, even if the application amount applied to the lyophilic region increases from the fluidity relationship, since waves generated from the influence of continuously ejected droplets are difficult to propagate into the functional part forming coating liquid, It is less susceptible to the physical effects of such waves. This has made it possible to secure a sufficient coating amount. Further, after application by ink jet, sufficient leveling was performed while slowly returning the temperature from 5 ° C. to room temperature, followed by drying at 80 ° C. for 3 minutes. As a result, a coating thickness of 3.5 μm can be formed, whereas the maximum coating thickness was 2.5 μm when the step of cooling the surface temperature of the substrate was not included.
[0225]
Here, FIG. 9 shows the relationship between the ink temperature and the viscosity, FIG. 10 shows the relationship between the ink temperature and the contact angle, and FIG. 11 shows the relationship between the ink temperature and the surface tension.
[0226]
【The invention's effect】
According to the present invention, since the surface temperature of the pattern formed body is cooled to the above range, the coating liquid for forming a functional part discharged by the ink jet device lands on the lyophilic area of the pattern formed body. In addition, the viscosity increases due to the influence of the surface temperature of the pattern forming body, and the fluidity decreases. Further, when the pattern formed body is cooled, the wettability of the surface thereof tends to change in a direction in which the contact angle with the coating liquid for forming a functional portion becomes higher as a whole. Accordingly, the diameter of the coating liquid for forming a functional part after landing on the lyophilic region is difficult to spread, and it is suppressed that the coating liquid spreads quickly. Also, even if the application amount applied to the lyophilic region increases due to the fluidity, since waves generated from the influence of continuously ejected droplets are difficult to propagate in the functional part forming coating liquid, It is less susceptible to the physical effects of such waves. This makes it possible to secure a sufficient coating amount. Therefore, the selection range of the film thickness of the functional portion formed by the ink jet method can be widened, and a fine pattern can be formed. Furthermore, since the surface temperature of the pattern forming body is returned to the above range by the temperature raising step after the application step, the viscosity of the functional part forming coating liquid returns to its original state and the fluidity is restored. Therefore, the functional part forming coating liquid has an effect such that the coating liquid satisfactorily wets and spreads in the lyophilic region, and a high-definition pattern can be formed along the pattern in the lyophilic region.
[Brief description of the drawings]
FIG. 1 is a process chart showing an example of a method for producing a functional element by an ink jet method according to the present invention.
FIG. 2 is a schematic view showing one example of a functional device manufacturing apparatus of the present invention.
FIG. 3 is a process diagram showing an example of a conventional method for manufacturing a functional element by an ink jet method.
FIG. 4 is a graph showing a change in a contact angle in a solvent-based coating liquid with a change in temperature in a pattern formed body using a photocatalyst-containing layer.
FIG. 5 is a schematic sectional view showing one example of a wettability changing layer in the present invention.
FIG. 6 is a schematic cross-sectional view illustrating an example of a photocatalyst processing layer side substrate according to the present invention.
FIG. 7 is a schematic sectional view showing another example of the photocatalyst processing layer side substrate in the present invention.
FIG. 8 is a schematic sectional view showing another example of the photocatalyst processing layer side substrate in the present invention.
FIG. 9 is a graph showing the relationship between the temperature and the viscosity of the ink in the example of the present invention.
FIG. 10 is a graph showing the relationship between ink temperature and contact angle in an example of the present invention.
FIG. 11 is a graph showing a relationship between ink temperature and surface tension in an example of the present invention.
[Explanation of symbols]
1 ... pattern forming body
2 ... lyophilic area
3 ... liquid repellent area
4. Inkjet device
5 ... Coating liquid for forming functional part

Claims (19)

A pattern forming body preparing step of preparing a pattern forming body having a pattern composed of a lyophilic region and a lyophobic region on the surface,
A cooling step of cooling the temperature of the surface of the pattern forming body within a range of 0 ° C to 25 ° C;
An application step of applying a functional part forming coating liquid for forming a functional part using an inkjet method in a lyophilic area of the pattern formed body surface cooled in the cooling step,
A temperature raising step of setting the temperature of the surface of the pattern forming body on which the functional part forming coating liquid is applied to be in a range of 10 ° C to 35 ° C;
A method for producing a functional element, comprising: The pattern forming body has a wettability changing layer in which a contact angle to a liquid is reduced by an external stimulus, and by applying an external stimulus in a pattern on the wettability changing layer, the lyophilic region and the liquid repellency The method for manufacturing a functional element according to claim 1, wherein a pattern including regions is formed. The method for manufacturing a functional element according to claim 2, wherein the pattern formed body has a base material and a wettability changing layer formed on the base material. The external stimulus is energy irradiation, and the wettability changing layer contains at least a photocatalyst and a binder, and is a photocatalyst containing layer in which the contact angle with a liquid is reduced by the action of the photocatalyst accompanying the energy irradiation. A method for producing a functional element according to claim 2 or claim 3. The method according to claim 4, wherein the binder is a layer containing an organopolysiloxane. The method according to claim 5, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The _{organopolysiloxane, Y n SiX (4-n} ) ( wherein, Y represents an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group or epoxy group, X represents an alkoxyl group or a halogen. n is an integer from 0 to 3.) An organopolysiloxane which is one or more hydrolytic condensates or co-hydrolytic condensates of a silicon compound represented by the formula: Or a method for producing a functional element formed body according to claim 6. The external stimulus is energy irradiation, and the wettability changing layer is a photocatalyst treated layer containing at least a photocatalyst, and a photocatalyst associated with the energy irradiation formed on the photocatalyst treated layer reacts with the liquid on the surface. The method for producing a functional element according to claim 2, wherein the functional element is a layer comprising a surface-change-type wettability-change layer that is a layer having a reduced contact angle. The external stimulus is energy irradiation, and the wettability change layer is a photocatalyst treatment layer side substrate having a photocatalyst treatment layer containing a photocatalyst and a substrate, and the wettability change layer and the photocatalyst treatment layer are 200 μm or less. A surface-changeable wettability changing layer in which the wettability changes so that the contact angle with the liquid on the surface is reduced by irradiating energy from a predetermined direction after being arranged with a gap so that The method for producing a functional element according to claim 2, wherein: The method according to claim 8, wherein the surface-change-type wettability-change layer is a layer containing an organopolysiloxane. The method according to claim 10, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The _{organopolysiloxane, Y n SiX (4-n} ) ( wherein, Y represents an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group or epoxy group, X represents an alkoxyl group or a halogen. n is an integer from 0 to 3.) An organopolysiloxane which is one or more hydrolytic condensates or co-hydrolytic condensates of a silicon compound represented by the formula: Alternatively, a method for manufacturing the functional element according to claim 11. The external stimulus is energy irradiation, and the wettability changing layer is decomposed and removed by the action of a photocatalyst treatment layer containing at least a photocatalyst and a photocatalyst accompanying the energy irradiation formed on the photocatalyst treatment layer. The contact angle of the liquid to the decomposition-removal type wettability changing layer, and the contact angle of the liquid to the photocatalyst treatment layer exposed when the decomposition-removal type wettability change layer is decomposed and removed. The method for producing a functional element according to claim 2, wherein the functional element is a layer composed of different layers. The external stimulus is energy irradiation, and the wettability change layer is a photocatalyst treatment layer side substrate having a photocatalyst treatment layer containing a photocatalyst and a substrate, and the wettability change layer and the photocatalyst treatment layer are 200 μm or less. After being disposed with a gap so as to form a decomposed / removable wettability changing layer which is decomposed and removed by energy irradiation from a predetermined direction, the contact angle of the liquid with the decomposed / removable wettability changing layer 4. The functional element according to claim 2, wherein the decomposition-removal type wettability changing layer is a layer having a different contact angle of a liquid with a substrate exposed after being decomposed and removed. 5. Method. The functional element according to claim 13, wherein the decomposition removal type wettability changing layer is any one of a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternate adsorption film. Manufacturing method. The photocatalyst includes 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 oxidized method for producing a functional element according to any one of claims of claims 4 to claim 15, characterized in that one or more substances selected from iron (Fe 2 _{O 3).} Method for producing a functional element according to claim 16, wherein the photocatalyst is titanium oxide (TiO _2). A color filter manufactured by the method for manufacturing a functional element according to any one of claims 1 to 17. Discharging means for discharging the functional part forming coating liquid by an ink jet method, fixing means for fixing a substrate on which the functional part forming coating liquid discharged from the discharging means lands, and fixed to the fixing means A cooling means for controlling the surface temperature of the substrate to be in the range of 0 ° C to 25 ° C.

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