JP4515699B2 - Manufacturing method of color filter - Google Patents

Description

【００５７】
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。
【００５８】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコーン化合物を混合してもよい。
【００５９】
本発明においては、このようにオルガノポリシロキサン等の種々の材料を濡れ性変化層に用いることができるのであるが、上述したように、濡れ性変化層にフッ素を含有させることが、濡れ性のパターン形成に効果的である。したがって、光触媒の作用により劣化・分解しにくい材料にフッ素を含有させる、具体的にはオルガノポリシロキサン材料にフッ素を含有させて濡れ性変化層とすることが好ましいといえる。
【００６０】
本発明における濡れ性変化層には、さらに界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００６１】
また、濡れ性変化層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００６２】
このような濡れ性変化層は、上述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を透明基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディップコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層を形成することができる。
【００６３】
また、本発明に用いられる濡れ性変化層は、表面の濡れ性が光触媒の作用により変化し得る材料で形成されたものであれば、自己支持性を有する材料であってもよく、また自己支持性を有さない材料であってもよい。なお、本発明でいう自己支持性を有するとは、他の支持材無しで有形な状態で存在し得ることをいうこととする。
【００６４】
濡れ性変化層が自己支持性を有する材料である場合には、例えば濡れ性変化層となり得る材料からなる市販の樹脂製フィルムを用いることが可能であり、コスト面で有利であるといえる。このような材料としては、上述した材料を製膜したものが自己支持性を有するのであれば、これを用いることも可能であるが、例えば、ポリエチレン、ポリカーボネート、ポリプロピレン、ポリスチレン、ポリエステル、ポリビニルフロライド、アセタール樹脂、ナイロン、ABS、PTFE、メタクリル樹脂、フェノール樹脂、ポリ弗化ビニリデン、ポリオキシメチレン、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレンテレフタレート、シリコーン等を挙げることができる。
【００６５】
本発明における濡れ性変化層は、自己支持性のない濡れ性変化層であることが好ましい。上述した濡れ性が大幅に変化する材料で形成される濡れ性変化層は、通常自己支持性のある材料が少ないからである。
【００６６】
本発明において上述した成分の濡れ性変化層を用いることにより、光触媒含有層中の光触媒の作用により、上記成分の一部である有機基の酸化、分解等の作用を用いて、エネルギー照射部の濡れ性を変化させて親水性とし、エネルギー未照射部との濡れ性に大きな差を生じさせることができる。よって、親水性領域にのみ湿し水を塗布することが容易に可能であり、また着色部を容易に撥水性領域のみに形成することが可能となることから、高精細な着色部が形成されたカラーフィルタを容易な工程で製造することが可能となるのである。
【００６７】
なお、本発明に用いられる濡れ性変化層は、上述したように光触媒の作用により濡れ性の変化する層であれば特に限定されるものではないが、特に、光触媒を含まない層であることが好ましい。例えば、濡れ性変化層中に光触媒が含有されている場合には、後述する湿し水塗布工程または着色部形成工程において、明所での作業を行った場合、湿し水により高感度化された光触媒の作用により、濡れ性変化層の濡れ性が変化し、高精細に着色部を形成することが困難となる可能性がある。本発明において、濡れ性変化層内に光触媒が含まれなければ、上記のような問題を心配する必要がないことから、簡便な装置によりカラーフィルタを製造することが可能であり、またその後カラーフィルタとして用いた場合に、経時的に影響を受ける心配をする必要がなく、長期間に渡り問題なく使用することが可能だからである。
【００６８】
（２）透明基材
次に、本発明のカラーフィルタ形成用基板に用いられる透明基材について説明する。本発明においては、上述した濡れ性変化層が自己支持性がない場合や、カラーフィルタ形成用基板に強度が必要な場合には、例として図１（ａ）に示すように、透明基材１上に濡れ性変化層２が形成されていてもよい。
【００６９】
このような透明基材としては、最終的に得られるカラーフィルタに応じて適宜選択されるものであり、この透明基材としては、従来よりカラーフィルタに用いられているものであれば特に限定されるものではないが、例えば石英ガラス、パイレックス（登録商標）、合成石英板等の可撓性のない透明なリジット材、あるいは透明樹脂フィルム、光学用樹脂板等の可撓性を有する透明なフレキシブル材を用いることができる。この中で特にコーニング社製７０５９ガラスは、熱膨脹率の小さい素材であり寸法安定性および高温加熱処理における作業性に優れ、また、ガラス中にアルカリ成分を含まない無アルカリガラスであるため、アクティブマトリックス方式によるカラー液晶表示装置用のカラーフィルタに適している。本発明において、透明基材は通常透明なものを用いるが、反射性の透明基材や白色に着色した透明基材でも用いることは可能である。また、透明基材は、必要に応じてアルカリ溶出防止用やガスバリア性付与その他の目的の表面処理を施したものを用いてもよい。
【００７０】
（光触媒含有層側基板）
次に、本発明に用いられる光触媒含有層側基板について説明する。本発明に用いられる光触媒含有層側基板は、少なくとも光触媒含有層と基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含有層が形成されてなるものである。また、この光触媒含有層側基板には、パターン状に形成された光触媒含有層側遮光部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。以下、この光触媒含有層側基板の各構成について説明する。
【００７１】
（１）光触媒含有層
本発明に用いられる光触媒含有層は、光触媒含有層中の光触媒が、上述した濡れ性変化層の濡れ性を変化させるような構成であれば、特に限定されるものではなく、光触媒とバインダとから構成されているものであってもよく、光触媒単体で製膜されたものであってもよい。また、その表面の濡れ性は、特に親水性であっても撥水性であってもよい。
【００７２】
本発明において用いられる光触媒含有層は、例えば上記図１（ａ）等に示すように、基体１上に全面に形成されたものであってもよいが、例えば図２に示すように、基体１上に光触媒含有層２がパターン状に形成されたものであってもよい。
【００７３】
このように光触媒含有層をパターン状に形成することにより、後述するパターンの形成の項において説明するように、濡れ性変化層にエネルギーを照射する際に、フォトマスク等を用いるパターン照射をする必要がなく、全面に照射することにより、濡れ性変化層上に親水性領域と撥水性領域とからなるパターンを形成することができる。
【００７４】
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。
【００７５】
また、光触媒含有層と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、実際に光触媒含有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含有層と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。
【００７６】
このような光触媒含有層における、後述するような二酸化チタンに代表される光触媒の作用機構は、必ずしも明確なものではないが、光の照射によって生成したキャリアが、近傍の化合物との直接反応、あるいは、酸素、水の存在下で生じた活性酸素種によって、有機物の化学構造に変化を及ぼすものと考えられている。本発明においては、このキャリアが光触媒含有層上で濡れ性変化層中の化合物に作用を及ぼすものであると思われる。
【００７７】
本発明で使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【００７８】
本発明においては、特に二酸化チタンが、バンドギャップエネルギーが高く、化学的に安定で毒性もなく、入手も容易であることから好適に使用される。二酸化チタンには、アナターゼ型とルチル型があり本発明ではいずれも使用することができるが、アナターゼ型の二酸化チタンが好ましい。アナターゼ型二酸化チタンは励起波長が３８０ｎｍ以下にある。
【００７９】
このようなアナターゼ型二酸化チタンとしては、例えば、塩酸解膠型のアナターゼ型チタニアゾル（石原産業（株）製ＳＴＳ−０２（平均粒径７ｎｍ）、石原産業（株）製ＳＴ−Ｋ０１）、硝酸解膠型のアナターゼ型チタニアゾル（日産化学（株）製ＴＡ−１５（平均粒径１２ｎｍ））等を挙げることができる。
【００８０】
光触媒の粒径は小さいほど光触媒反応が効果的に起こるので好ましく、平均粒径が５０ｎｍ以下が好ましく、２０ｎｍ以下の光触媒を使用するのが特に好ましい。
【００８１】
本発明における光触媒含有層は、上述したように光触媒単独で形成されたものであってもよく、またバインダと混合して形成されたものであってもよい。光触媒のみからなる光触媒含有層の場合は、濡れ性変化層上の濡れ性の変化に対する効率が向上し、処理時間の短縮化等のコスト面で有利である。一方、光触媒とバインダとからなる光触媒含有層の場合は、光触媒含有層の形成が容易であるという利点を有する。
【００８２】
光触媒のみからなる光触媒含有層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒含有層を形成することにより、均一な膜でかつ光触媒のみを含有する光触媒含有層とすることが可能であり、これにより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。
【００８３】
また、光触媒のみからなる光触媒含有層の他の形成方法としては、例えば光触媒が二酸化チタンの場合は、基体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。
【００８４】
また、バインダを用いる場合は、バインダの主骨格が上記の光触媒の光励起により分解されないような高い結合エネルギーを有するものが好ましく、例えば上述した濡れ性変化層の欄で説明したオルガノポリシロキサン等を挙げることができる。
【００８５】
このようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒含有層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基体上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。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。
【００８６】
また、バインダとして無定形シリカ前駆体を用いることができる。この無定形シリカ前駆体は、一般式ＳｉＸ_４で表され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【００８７】
具体的には、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−プロポキシシラン、テトラブトキシシラン、テトラメトキシシラン等が挙げられる。また、この場合には、無定形シリカの前駆体と光触媒の粒子とを非水性溶媒中に均一に分散させ、基体上に空気中の水分により加水分解させてシラノールを形成させた後、常温で脱水縮重合することにより光触媒含有層を形成できる。シラノールの脱水縮重合を１００℃以上で行えば、シラノールの重合度が増し、膜表面の強度を向上できる。また、これらの結着剤は、単独あるいは２種以上を混合して用いることができる。
【００８８】
バインダを用いた場合の光触媒含有層中の光触媒の含有量は、５〜６０重量％、好ましくは２０〜４０重量％の範囲で設定することができる。また、光触媒含有層の厚みは、０．０５〜１０μｍの範囲内が好ましい。
【００８９】
また、光触媒含有層には上記の光触媒、バインダの他に、界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００９０】
さらに、光触媒含有層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００９１】
ｂ．基体
本発明においては、例えば図１（ａ）に示すように、光触媒含有層側基板３は、少なくとも基体１とこの基体１上に形成された光触媒含有層２とを有するものである。
【００９２】
この際、用いられる基体を構成する材料は、後述するパターンの形成の項におけるエネルギーの照射方向や、得られるカラーフィルタの構造等により適宜選択される。
【００９３】
例えば、後述するように光触媒含有層側基板に光触媒含有層側遮光部を予め所定のパターンで形成しておき、この光触媒含有層側遮光部を用いてパターンを形成する場合においては、光触媒含有層側基板側からエネルギーを照射する必要がある。このような場合、基体は透明性を有するものであることが必要となる。
【００９４】
一方、カラーフィルタの構造によっては、カラーフィルタ形成用基板側にフォトマスクを配置してエネルギーを照射することも可能である。また、後述する着色部形成工程により形成される着色部が画素部である場合、上述したように、カラーフィルタ形成用基板内に遮光部が形成されていてもよく、この場合は、カラーフィルタ形成用基板側からエネルギーが照射される必要がある。このような場合においては、基体の透明性は特に必要とされない。
【００９５】
また本発明に用いられる基体は、可撓性を有するもの、例えば樹脂製フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、後述するパターンの形成の項におけるエネルギー照射方法により適宜選択されるものである。
【００９６】
このように、本発明における光触媒含有層側基板に用いられる基体は特にその材料を限定されるものではないが、本発明においては、この光触媒含有層側基板は、繰り返し用いられるものであることから、所定の強度を有し、かつその表面が光触媒含有層との密着性が良好である材料が好適に用いられる。
【００９７】
具体的には、ガラス、セラミック、金属、プラスチック等を挙げることができる。
【００９８】
なお、基体表面と光触媒含有層との密着性を向上させるために、基体上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【００９９】
ｃ．光触媒含有層側遮光部
本発明に用いられる光触媒含有層側基板には、パターン状に形成された光触媒含有層側遮光部が形成されたものを用いても良い。このように光触媒含有層側遮光部を有する光触媒含有層側基板を用いることにより、エネルギー照射に際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒含有層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１００】
このような光触媒含有層側遮光部を有する光触媒含有層側基板は、光触媒含有層側遮光部の形成位置により、下記の二つの態様とすることができる。
【０１０１】
一つが、例えば図３に示すように、基体１上に光触媒含有層側遮光部１５を形成し、この光触媒含有層側遮光部１５上に光触媒含有層２を形成して、光触媒含有層側基板とする態様である。もう一つは、例えば図４に示すように、基体１上に光触媒含有層２を形成し、その上に光触媒含有層側遮光部１５を形成して光触媒含有層側基板とする態様である。
【０１０２】
いずれの態様においても、フォトマスクを用いる場合と比較すると、光触媒含有層側遮光部が、上記光触媒含有層と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。
【０１０３】
さらに、上記光触媒含有層上に光触媒含有層側遮光部を形成する発明においては、光触媒含有層と濡れ性変化層とを所定の位置に配置する際に、この光触媒含有層側遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記光触媒含有層側遮光部を上記間隙を一定のものとするためのスペーサとしても用いることができるという利点を有する。
【０１０４】
すなわち、所定の間隙をおいて上記光触媒含有層と濡れ性変化層とを対向させた状態で配置する際に、上記光触媒含有層側遮光部と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含有層側基板からエネルギーを照射することにより、濡れ性変化層上に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。
【０１０５】
このような光触媒含有層側遮光部の形成方法は、特に限定されるものではなく、光触媒含有層側遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１０６】
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。
【０１０７】
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。
【０１０８】
なお、上記説明においては、光触媒含有層側遮光部の形成位置として、基体と光触媒含有層との間、および光触媒含有層表面の二つの場合について説明したが、その他、基体の光触媒含有層が形成されていない側の表面に光触媒含有層側遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、形成する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。
【０１０９】
ｄ．プライマー層
次に、本発明の光触媒含有層側基板に用いられるプライマー層について説明する。本発明において、上述したように基体上に光触媒含有層側遮光部をパターン状に形成して、その上に光触媒含有層を形成して光触媒含有層側基板とする場合においては、上記光触媒含有層側遮光部と光触媒含有層との間にプライマー層を形成してもよい。
【０１１０】
このプライマー層の作用・機能は必ずしも明確なものではないが、光触媒含有層側遮光部と光触媒含有層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による濡れ性変化層の濡れ性の変化を阻害する要因となる光触媒含有層側遮光部および光触媒含有層側遮光部間に存在する開口部からの不純物、特に、光触媒含有層側遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で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。
【０１１１】
なお、本発明においてプライマー層は、光触媒含有層側遮光部のみならず光触媒含有層側遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた光触媒含有層側遮光部全面にわたって形成されていることが好ましい。
【０１１２】
図５はこのようなプライマー層を形成した光触媒含有層側基板の一例を示すものである。光触媒含有層側基板の光触媒含有層側遮光部１５が形成された基体１の光触媒含有層側遮光部１５が形成されている側の表面にプライマー層１６が形成されており、このプライマー層１６の表面に光触媒含有層２が形成されている。
【０１１３】
本発明におけるプライマー層は、光触媒含有層側基板の光触媒含有層側遮光部と光触媒含有層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１１４】
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。
【０１１５】
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。
【０１１６】
（パターンの形成）
次に、カラーフィルタ形成用基板上への、親水性領域および撥水性領域からなるパターンの形成について説明する。本発明のパターン形成工程においては、上記光触媒含有層および上記濡れ性変化層を所定の位置に配置した後、所定の方向からエネルギーを照射することにより、上記濡れ性変化層表面に親水性領域および撥水性領域からなるパターンを形成する工程が行われる。以下、このパターンの形成について説明する。
【０１１７】
ａ．光触媒含有層および濡れ性変化層の配置
本発明のパターン形成工程においては、まずエネルギー照射時に光触媒含有層と濡れ性変化層とを光触媒の作用が及ぶように所定の間隔をおいて配置する必要があり、本発明においては、上述した光触媒含有層および濡れ性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向からエネルギーを照射する。この際、光触媒含有層および濡れ性変化層を密着させてもよい。
【０１１８】
本発明において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって濡れ性変化層の濡れ性の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。
【０１１９】
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含有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。
【０１２０】
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含有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、かつ光触媒含有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。
【０１２１】
このように光触媒含有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含有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、結果的に濡れ性が変化する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、この場合も濡れ性が変化する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。
【０１２２】
本発明においては、このような配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０１２３】
このような極めて狭い間隙を均一に形成して光触媒含有層と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撥水性領域の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パターンを形成することが可能となる。
【０１２４】
本発明においては、このようなスペーサを一つの部材として形成してもよいが、工程の簡略化等のため、上記光触媒含有層側基板の欄で説明したように、光触媒含有層側基板の光触媒含有層表面に形成することが好ましい。なお、上記光触媒含有層側基板における説明においては、光触媒含有層側遮光部として説明したが、本発明においては、このようなスペーサは濡れ性変化層表面に光触媒の作用が及ばないように表面を保護する作用を有すればよいものであることから、特に照射されるエネルギーを遮蔽する機能を有さない材料で形成されたものであってもよい。
【０１２５】
ｂ．エネルギー照射
次に、上述したような配置を維持した状態で、対向する部分へのエネルギー照射が行われる。なお、本発明でいうエネルギー照射（露光）とは、光触媒含有層による濡れ性変化層表面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。
【０１２６】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１２７】
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。
【０１２８】
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。
【０１２９】
また、エネルギー照射に際してのエネルギーの照射量は、光触媒含有層中の光触媒の作用により濡れ性変化層表面の濡れ性の変化が行われるのに必要な照射量とする。
【０１３０】
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、感度を上昇させることが可能となり、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。
【０１３１】
本発明におけるエネルギー照射方向は、光触媒含有層側遮光部もしくはカラーフィルタ形成用基板側に遮光部が形成されているか否か等のパターンの形成方法等により決定される。
【０１３２】
すなわち、光触媒含有層側遮光部が形成されている場合は、光触媒含有層側基板側からエネルギー照射が行なわれる必要があり、かつこの場合は光触媒含有層側基板が照射されるエネルギーに対して透明である必要がある。なお、この場合、光触媒含有層上に光触媒含有層側遮光部が形成され、かつこの光触媒含有層側遮光部を上述したようなスペーサとしての機能を有するように用いた場合においては、エネルギー照射方向は光触媒含有層側基板側からでもカラーフィルタ形成用基板側からであってもよい。
【０１３３】
一方、カラーフィルタ形成用基板側に遮光部が形成されている場合は、カラーフィルタ形成用基板側からエネルギー照射が行われる必要があり、かつこの場合は、カラーフィルタ形成用基板が照射されるエネルギーに対して透明である必要がある。なお、この場合も、濡れ性変化層上に遮光部が形成され、この遮光部が上述したようなスペーサとしての機能を有するように用いられた場合、エネルギー照射方向は光触媒含有層側基板側からでもカラーフィルタ形成用基板側からであってもよい。
【０１３４】
また、光触媒含有層がパターン状に形成されている場合におけるエネルギー照射方向は、上述したように、光触媒含有層と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のであればいかなる方向から照射されてもよい。
【０１３５】
同様に、上述したスペーサを用いる場合も、対向する部分にエネルギーが照射されるのであればいかなる方向から照射されてもよい。
【０１３６】
フォトマスクを用いる場合は、フォトマスクが配置された側からエネルギーが照射される。この場合は、フォトマスクが配置された側の基板、すなわち光触媒含有層側基板もしくはカラーフィルタ形成用基板のいずれかが透明である必要がある。
【０１３７】
ｃ．光触媒含有層側基板の取り外し
上述したようなエネルギー照射が終了すると、光触媒含有層側基板が濡れ性変化層との配置位置から離され、これにより図１（ｃ）に示すように濡れ性変化層５の濡れ性が変化した親水性領域９および撥水性領域１０からなるパターンが形成される。
【０１３８】
２．湿し水塗布工程
次に、本発明の湿し水塗布工程について説明する。本発明における湿し水塗布工程とは、上述したパターン形成工程により形成された親水性領域および撥水性領域からなるパターン上の、親水性領域のみに湿し水を塗布する工程である。
【０１３９】
上記湿し水が親水性領域に塗布されていることにより、後述する着色部形成工程により着色部を形成する際に、目的とするパターン以外の部分に着色部を形成する着色部形成用塗工液等が付着することを防ぐことが可能となり、高精細な着色部を形成することが可能となるのである。
【０１４０】
本発明に用いられる湿し水は、一般的にオフセット印刷等に用いられている湿し水等を用いることが可能である。湿し水は、具体的には水にイソプロピルアルコール等を添加したものである。
【０１４１】
また、湿し水の塗布方法は、上記カラーフィルタ用基板上の親水性領域上に塗布することが可能であれば、特に限定されるものではなく、上記撥水性領域には、湿し水が付着しないことから、ロールコート、ビードコート等によるカラーフィルタ用基板上の全面に塗布する方法であってもよく、またインクジェット法等のノズル吐出法のような目的とするパターン状に塗布する方法であってもよい。
【０１４２】
３．着色部形成工程
次に、本発明の着色部形成工程について説明する。本発明における着色部形成工程は、上述したカラーフィルタ形成用基板上の撥水性かつ親インキ性である撥水性領域に、例えば着色部形成用塗工液等を用いて着色部を形成する工程である。本発明においては、上述したパターン形成工程により、着色部を形成するパターン状に形成された撥水性かつ親インキ性を有する撥水性領域が形成されており、この撥水性かつ親インキ性を有する撥水性領域に沿って、着色部形成用塗工液を塗布し、硬化させること等により着色部を形成することが可能となるのである。また、上記カラーフィルタ形成用基板上の着色部を形成しない部分には、上述した湿し水塗布工程により、湿し水が塗布されており、この湿し水により保護されていることから、着色部形成用塗工液等が付着することがなく、高精細に着色部を形成することが可能となるのである。
【０１４３】
本工程により形成される着色部は、ブラックマトリックス（以下、第一実施態様とする）、また画素部（以下、第二実施態様とする）であり、以下、それぞれの実施態様についてわけて説明する。
【０１４４】
（第一実施態様）
まず、着色部がブラックマトリックスである場合の第一実施態様について説明する。本実施態様の場合、上述したパターン形成工程において、形成される親水性領域および撥水性領域からなるパターンは、ブラックマトリックスが形成される部位が撥水性かつ親インキ性を有する撥水性領域、例えば画素部等が形成される部分が親水性領域であり、その親水性領域は上述した湿し水塗布工程によって、湿し水により保護されている。これにより、画素部を形成する部位等に、ブラックマトリックスを形成するブラックマトリックス形成用塗工液等が付着することなく、高精細にブラックマトリックスを形成することが可能となるのである。
【０１４５】
本実施態様においては、上記ブラックマトリックス形成用塗工液としては、上記湿し水への溶解性がなく、上記濡れ性変化層上に塗布可能な材料であれば、特に限定されるものではなく、一般的なカラーフィルタにおけるブラックマトリックスを形成する材料等を用いることが可能である。
【０１４６】
ここで、本発明に用いられるブラックマトリックス形成用塗工液は、上述した中でも水への溶解度が、２０℃において０．５重量％〜１０重量％の範囲内であることが好ましい。上記ブラックマトリックス形成用塗工液の水への溶解度が上記範囲内であることにより、ブラックマトリックス形成用塗工液が湿し水へ溶解せず、撥水性領域のみに高精細にブラックマトリックスを形成することが可能となるからである。
【０１４７】
ブラックマトリックス形成用塗工液として具体的には、樹脂バインダ中と、カーボン微粒子、チタン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子とを、水に非溶解性を示す溶媒に溶解させた塗工液を用いる方法等が挙げられる。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。
【０１４８】
ここで、ブラックマトリックスの形成方法としては、上記親水性領域は、湿し水により保護されており、ブラックマトリックス形成用塗工液は付着しないことから、ロールコート等によるカラーフィルタ用基板上の全面に塗布する方法であってもよく、またインクジェット法等のノズル吐出法のような目的とするパターン状に塗布する方法であってもよい。
【０１４９】
（第二実施態様）
次に、着色部が画素部である場合の第二実施態様について説明する。本実施態様の場合、上述したパターン形成工程において、形成される親水性領域および撥水性領域からなるパターンは、画素部が形成される部位が撥水性かつ親インキ性の撥水性領域であり、かつ例えばブラックマトリックス等が形成される画素部と画素部の境界部分が親水性領域であり、その親水性領域は上述した湿し水塗布工程によって、湿し水により保護されている。
【０１５０】
一般的に、カラーフィルタの画素部は赤（Ｒ）、緑（Ｇ）、青（Ｂ）の三色により形成されており、本実施態様においても同様である。本実施態様においては、画素部形成時に、画素部間に湿し水が塗布されていることから、隣接する異なる色の画素部が混色することなく、高精細な画素部を形成することが可能となるのである。
【０１５１】
本実施態様の場合、上記画素部を形成する画素部形成用塗工液としては、上記湿し水への溶解性がなく、上記撥水性かつ親インキ性を有する濡れ性変化層上に塗布可能な材料であれば、特に限定されるものではなく、一般的に画素部を形成する油性の材料等を用いることが可能である。
【０１５２】
ここで、本発明に用いられる上記画素部形成用塗工液は、中でも水への溶解度が、２０℃において０．５重量％〜１０重量％の範囲内であることが好ましい。
【０１５３】
上記画素部形成用塗工液の水への溶解度が上記範囲内であることにより、画素部形成用塗工液が湿し水へ溶解せず、撥水性領域のみに高精細に画素部を形成することが可能となるからである。
【０１５４】
また、本実施態様の場合、上記の異なる画素部の混色を防止するために、画素部はインクジェット法等のノズル吐出法により、目的とするパターンのみに形成されることが好ましい。
【０１５５】
なお、本実施態様の場合、最終的に製造されるカラーフィルタは、ブラックマトリックスが形成されていてもよく、そのブラックマトリックスは、画素部間にブラックマトリックスが形成されたものであってもよく、また透明基材と濡れ性変化層の間にブラックマトリックスが形成されたもの等であってもよい。
【０１５６】
上記ブラックマトリックスの形成方法としては、特に限定されるものではなく、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する方法等であってもよく、また、上述した第一実施態様に用いられる樹脂性のブラックマトリックスをフォトリソ法、印刷法等により形成したものであってもよい。
【０１５７】
４．湿し水乾燥工程
次に、本発明における湿し水乾燥工程について説明する。本発明における湿し水乾燥工程は、上述した着色部を形成した後に、湿し水を乾燥させる工程である。本発明においては、湿し水を乾燥させることが可能であれば、その方法については、特に限定されるものではなく、例えば上述した着色部を加熱することにより硬化させる工程にて、湿し水を同時に揮発させ、その後純水にてスプレー洗浄し、さらに熱乾燥する工程等が挙げられる。
【０１５８】
５．その他
また、本発明においては、上述した着色部形成工程により形成される着色部が、ブラックマトリックスである場合には、上記湿し水乾燥工程後、画素部を形成する工程等を有していてもよい。
【０１５９】
また、本発明において、最終的に製造されるカラーフィルタは、上述した画素部やブラックマトリックス上に保護層を形成する保護層形成工程や、必要な他の機能層の形成工程が行われてもよい。
【０１６０】
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。
【０１６１】
例えば、上記説明においては、ブラックマトリックスを有することを前提として記載したが、ブラックマトリックスのないカラーフィルタに適用することも可能である。
【０１６２】
【実施例】
以下に実施例を示して、本発明をさらに具体的に説明する。
【０１６３】
（光触媒含有層側基板の形成）
フォトマスク表面に、テイカ（株）製の光触媒用酸化チタンコーティング剤ＴＫＣ３０１をコーティングし、３５０℃で３時間乾燥させ、光触媒含有層側基板を調整した。フォトマスクは、カーボンブラックと樹脂の分散体にて形成された膜厚１μｍのブラックマトリックスが、９０μｍの幅のラインにて１００μｍピッチに配置されたものを使用した。
【０１６４】
（濡れ性変化層の形成）
次にフルオロアルキルシランが主成分であるＭＦ−１６０Ｅ（商品名、トーケムプロダクツ（株）製）０．２ｇに０．１Ｎ塩酸水３ｇを添加し、１時間室温にて攪拌した溶液を、膜厚０．７ｍｍの石英ガラス基板上にスピンコーティングし、１５０℃で１０分間乾燥させた。これにより、基板上に臨界表面張力が４０ｍＮ／ｍである膜厚０．１μｍの親インキ性かつ撥水性である濡れ性変化層が形成された。
【０１６５】
（濡れ性変化パターン形成）
上記濡れ性変化層表面に、上記光触媒含有層側基板を介して、超高圧水銀ランプにて露光した。露光量は３６５ｎｍにて２０００ｍＪであった。これにより、濡れ性変化層表面の露光された部分のみ親水性領域となった。
【０１６６】
（湿し水の付与）
上記濡れ性変化層上にビードコーティング法にて湿し水を全面に塗布したところ、親水性領域のみに湿し水が付着し、撥水性領域に付着することはなかった。このとき使用した湿し水は、日研化学研究所製クリーンエッチ液１０ｇと蒸留水（純正化学製）１９０ｇとを混合して得たものである。上記濡れ性変化層上の未露光部である撥水性領域に対する接触角は７０°、露光部である親水性領域に対する接触角は、１０°であった。
【０１６７】
（着色部形成用塗工液の付与）
上記湿し水がパターン状に形成された濡れ性変化層上に、ロールコーティング法にて、着色層（ブラックマトリックス）形成用塗工液を塗布した。着色層形成用塗工液は上記濡れ性変化層の湿し水が塗布されていない撥水性かつ親インキ性である撥水性領域のみに濡れ広がり、湿し水と混合することはなかった。着色層形成用塗工液の組成は、プロピレングリコールモノメチルエーテルアセテートを溶媒として、エポキシ基を含有したアクリル系熱硬化型樹脂中に平均粒径０．１μｍのカーボンブラック微粒子を分散させた系を用いた。
【０１６８】
（湿し水の乾燥およびクリーニング）
上記着色部形成用塗工液および湿し水が付与された濡れ性変化層を、クリーンオーブンで１５０℃にて３０分間乾燥させ、着色部（ブラックマトリックス）形成用塗工液の硬化および湿し水の乾燥を行った。さらに、純水にてスプレー洗浄し、水切りをした後、クリーンオーブンで１２０℃にて５分間乾燥させることにより、幅１０μｍ、膜厚０．５μｍのカラーフィルタ用ブラックマトリックスを形成した。
【０１６９】
（カラーフィルタの作製）
上記の手法によりブラックマトリクスが形成されたカラーフィルタ用基板の開口部に、インクジェット法にて赤、青、緑の通常用いられる着色層形成用インキを吐出し、乾燥硬化させることにより、ＬＣＤ液晶ディスプレイ用カラーフィルタを作製した。
【０１７０】
【発明の効果】
本発明によれば、上記光触媒含有層を用いて上記濡れ性変化層上にエネルギーを照射することにより、エネルギー照射された部分を親水性領域、エネルギー照射されていない部分を撥水性領域とすることができる。この際、着色部を形成する領域を撥水性領域、着色部を形成しない領域を親水性領域とすることにより、撥水性領域上に着色部を形成する際に、着色部を形成しない親水性領域を湿し水により保護することができ、例えば着色層を形成する着色層形成用塗工液として油性のインキ等によって、ブラックマトリックスや画素部等の着色部を撥水性領域上に、容易にかつ高精細に形成することが可能となる。
【０１７１】
また、本発明においては、上記光触媒含有層側基板を用いることから、上記濡れ性変化層中に光触媒が含有される必要がなく、明所で湿し水を用いて着色部を形成した際にも、目的とするパターン以外の部分が露光されることがなく、簡便な製造装置によりカラーフィルタを製造することが可能となる。
【図面の簡単な説明】
【図１】本発明の半透過型液晶用カラーフィルタの製造方法の一例を示す工程図である。
【図２】本発明に用いられる光触媒含有層側基板の一例を示す概略断面図である。
【図３】本発明に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【図４】本発明に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【図５】本発明に用いられる光触媒含有層側基板の他の例を示す概略断面図である。
【符号の説明】
１ … 基体
２ … 光触媒含有層
３ … 光触媒含有層側基板
４ … 透明基材
５ … 濡れ性変化層
６ … カラーフィルタ形成用基板
９ … 親水性領域
１０… 撥水性領域
１１… 湿し水
１２… ブラックマトリックス
１４… 画素部
１５… 光触媒含有層側遮光部
１６… プライマー層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a color filter used in a liquid crystal display device or the like.
[0002]
[Prior art]
In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having a high specific gravity.
[0003]
In such a color filter, it is usually provided with coloring patterns of three primary colors of red (R), green (G), and blue (B), and electrodes corresponding to the respective pixels of R, G, and B are turned on, By turning it off, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed. In addition, high contrast can be reproduced by forming a black matrix between the pixel portions.
[0004]
In the formation of a pixel portion or a black matrix, a pigment dispersion method or the like has been conventionally used. For example, in a black matrix manufacturing method, a resin layer in which a black pigment is dispersed is formed on a glass substrate, and this is patterned through a photolithography process. However, this method has a large number of steps and has a problem in terms of cost.
[0005]
Conventionally, in offset printing, etc., a layer containing a photocatalyst that becomes hydrophilic by exposure is provided on the support to expose it in a pattern, and the unexposed area is oleophilic and the exposed area is dampened to receive water. A method of making it amphiphilic is known (for example, see Patent Document 1). By applying this offset printing method, a method of forming a colored portion such as a black matrix or a pixel portion of a color filter can be considered. However, in this method, since the layer containing the photocatalyst is provided on the support, the photocatalyst that has been made highly sensitive by the fountain solution is exposed in a bright place other than the target pattern. Therefore, there is a problem that it is difficult to form a high-definition pattern.
[0006]
[Patent Document 1]
JP-A-11-305422
[0007]
[Problems to be solved by the invention]
From the above, it is desired to provide a method for manufacturing a color filter that can form a colored portion such as a high-definition black matrix in an easy process.
[0008]
[Means for solving the problems]
  The present inventionIs repellentA substrate for forming a color filter, which is water-based and ink-philic, and further has a wettability changing layer that changes so that the contact angle with water is lowered by the action of the photocatalyst accompanying energy irradiation, a photocatalyst-containing layer containing a photocatalyst, and The photocatalyst-containing layer side substrate having a substrate is disposed with a gap so that the wettability changing layer and the photocatalyst-containing layer are 200 μm or less, and then irradiated with energy, and the color filterFor formationA pattern forming step for forming a pattern composed of a hydrophilic region and a water repellent region on the substrate, a dampening water applying step for applying dampening water on the hydrophilic region, and forming a colored portion on the water repellent region And a dampening water drying step of drying the dampening water. A method for producing a color filter is provided.
[0009]
According to the present invention, by irradiating the wettability changing layer with energy using the photocatalyst-containing layer, the energy-irradiated portion is made a hydrophilic region and the non-energy-irradiated portion is made a water-repellent region. Can do. At this time, the region where the colored portion is formed is a water-repellent region, and the region where the colored portion is not formed is a hydrophilic region, so that when the colored portion is formed on the water-repellent region, the hydrophilic region where the colored portion is not formed. For example, an oily ink or the like as a colored layer forming coating liquid for forming a colored layer can be used to easily form a colored portion such as a black matrix or a pixel portion on a water-repellent region. High definition can be formed.
[0010]
Further, in the present invention, since the photocatalyst-containing layer side substrate is used, it is not necessary to contain a photocatalyst in the wettability changing layer, and when a colored portion is formed using dampening water in a bright place. However, portions other than the target pattern are not exposed, and a color filter can be manufactured with a simple manufacturing apparatus.
[0011]
  In the above invention,The color filter forming substrate may have a transparent base material and a wettability changing layer formed on the transparent base material. When the wettability changing layer has self-supporting property, the wettability changing layer may not be formed on the transparent substrate, but the wettability changing layer has no self-supporting property or color This is because when the filter needs strength, it may be formed on a transparent substrate.
[0012]
  In the above invention,The wettability changing layer has a critical surface tension within a range of 20 mN / m or more and less than 50 mN / m in a portion not irradiated with energy, and a critical surface tension of 50 mN / m or more and less than 75 mN / m in a portion irradiated with energy. It is preferable to be within the range.
[0013]
This is because, when the critical surface tension of the portion of the wettability changing layer that is not irradiated with energy is within the above range, the water repellency and the ink affinity can be achieved. Accordingly, the dampening water does not adhere to the water-repellent region that is not irradiated with energy, and the colored portion can be formed, for example, with oil-based ink as a colored portion forming coating liquid. Further, when the critical surface tension of the portion irradiated with energy of the wettability changing layer is within the above range, it becomes possible to make it hydrophilic. This is because it becomes possible to apply the water.
[0014]
  Also,In the above invention,The wettability changing layer has a contact angle with a liquid having a surface tension of 70 mN / m within a range of 50 ° or more and less than 120 ° in a portion not irradiated with energy, and 0 ° or more and 50 ° in a portion irradiated with energy. It is preferable to be within the range of less than. The part of the wettability changing layer that is not irradiated with energy is a part that requires water repellency.If the contact angle is lower than the above range, the water repellency is not sufficient. This is because the fountain solution may adhere when applied.
[0015]
In addition, the portion of the wettability changing layer that has been irradiated with energy is a portion that requires hydrophilicity. When the contact angle is higher than the above range, the dampening solution is applied when the dampening solution is applied. This is because it becomes difficult to uniformly attach the dampening water due to the repelling.
[0016]
  In the above invention,The wettability changing layer is preferably a layer containing an organopolysiloxane. By forming a wettability changing layer using such an organopolysiloxane as a material, it is possible to make a water-repellent and ink-philic layer before energy irradiation, and the action of the photocatalyst accompanying energy irradiation makes it hydrophilic. It is because it becomes possible to make it sex.
[0017]
  In the above invention,The organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. This is because by using a polysiloxane containing a fluoroalkyl group, the difference between water repellency before energy irradiation and hydrophilicity after energy irradiation can be further increased.
[0018]
  In the above invention,The organopolysiloxane is Y_nSiX_(4-n)Wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n is an integer from 0 to 3. It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolyzed condensate or cohydrolyzed condensate of the silicon compound. This is because the difference between the water repellency before energy irradiation and the hydrophilicity after energy irradiation can be further increased by forming a wettability changing layer using such an organopolysiloxane as a material.
[0019]
  In the above invention,The wettability changing layer is preferably a layer containing no photocatalyst. When the wettability changing layer is a layer that does not contain a photocatalyst, for example, in the fountain solution application step or the colored portion forming step, portions other than the target pattern are exposed by work in a bright place. This is because the color filter can be manufactured with a simple apparatus.
[0020]
  In the above invention,The photocatalyst-containing layer can be a layer made of a photocatalyst. This is because, when the photocatalyst-containing layer is a layer composed only of a photocatalyst, it is possible to efficiently form a pattern on the wettability changing layer.
[0021]
  In the above invention,The photocatalyst-containing layer is preferably a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. It is possible to form a uniform photocatalyst-containing layer having a uniform surface thickness with little surface irregularities, and uniform and highly efficient formation of a pattern composed of a hydrophilic region and a water-repellent region on the color filter substrate. Because it can be done.
[0022]
  In the above invention,The photocatalyst-containing layer may be a layer having a photocatalyst and a binder. By using the binder in this way, it is possible to form the photocatalyst-containing layer relatively easily, and as a result, it is possible to manufacture a color filter at a low cost.
[0023]
  In the above invention,The photocatalyst is titanium oxide (TiO₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃It is preferable that it is 1 type, or 2 or more types of substances selected from the above, and as described in claim 13, the photocatalyst is titanium oxide (TiO 2).₂) Is preferable. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, non-toxic and easily available.
[0024]
  In the above invention,The colored portion is preferably a black matrix. This is because when the colored portion is a black matrix, a color filter having a high-definition black matrix and capable of reproducing high contrast can be obtained.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for manufacturing a color filter capable of forming a high-definition colored portion. This will be described in detail below.
[0026]
The method for producing the color filter of the present invention includes:
A substrate for forming a color filter having a water-repellent and ink-philic property and having a wettability changing layer that changes so that the contact angle with water is lowered by the action of the photocatalyst associated with energy irradiation, and a photocatalyst-containing layer containing a photocatalyst And a photocatalyst-containing layer side substrate having a substrate are arranged with a gap so that the wettability changing layer and the photocatalyst-containing layer are 200 μm or less, and then irradiated with energy to make hydrophilic on the color filter substrate. A pattern forming step of forming a pattern composed of a conductive region and a water repellent region;
A fountain solution application step of applying a fountain solution onto the hydrophilic region;
A colored portion forming step of forming a colored portion on the water repellent region;
A dampening water drying step of drying the dampening water;
It is the method characterized by having.
[0027]
Here, the colored portion in the present invention refers to a pixel portion or a black matrix in a color filter. Hereinafter, the manufacturing method of the color filter of the present invention will be described with reference to the drawings, taking as an example the case where the colored portion is a black matrix.
[0028]
First, it has a photocatalyst containing layer side substrate 3 having a base 1 and a photocatalyst containing layer 2 formed on the base 1, and a transparent base 4 and a wettability changing layer 5 formed on the transparent base 4. A color filter forming substrate 6 is prepared (FIG. 1A). Next, the photocatalyst-containing layer 2 and the wettability changing layer 5 are arranged so as to have a predetermined gap, and the pattern 8 forming the black matrix is irradiated with energy 8 from a predetermined direction using, for example, a photomask 7 or the like. A pattern forming step is performed (FIG. 1B). As a result, a pattern is formed which includes the hydrophilic region 9 where the wettability on the wettability changing layer 5 of the portion irradiated with the energy 8 is changed and the water repellent region 10 of the portion where the energy 8 is not irradiated. (FIG. 1 (c)).
[0029]
Next, a fountain solution application step of applying the fountain solution 11 onto the hydrophilic region 9 is performed (FIG. 1D). Since the portion other than the hydrophilic region 9 is the water-repellent region 10, the fountain solution does not adhere, and the fountain solution can be applied only to the hydrophilic region 9. Next, a colored portion forming step for forming the black matrix 12 in the water repellent region 10 is performed (FIG. 1 (e)). At this time, since the portion other than the water repellent region 10 forming the black matrix 12 is protected by the fountain solution 11, for example, the black matrix forming coating solution for forming the black matrix is not attached, and the This makes it possible to easily form the black matrix 12 only in the aqueous region 10 with high definition.
[0030]
Next, a dampening water drying process for drying the dampening water 11 is performed (FIG. 1 (f)). Thereafter, a pixel portion forming coating solution or the like for forming the pixel portion is applied between the black matrix 12 by, for example, the ink jet device 13 (FIG. 1F) to form the pixel portion 13 and color The filter is used (FIG. 1 (g)).
[0031]
According to the present invention, by using the above-described method, it is possible to form a colored layer such as a black matrix or a pixel portion with high definition. Each of the above steps will be described separately.
[0032]
1. Pattern formation process
First, the pattern formation process in this invention is demonstrated. The pattern forming step in the present invention is a color filter forming substrate having a water-repellent and ink-philic property, and further having a wettability changing layer that changes so that a contact angle with water is lowered by the action of a photocatalyst accompanying energy irradiation. The photocatalyst containing layer containing the photocatalyst and the photocatalyst containing layer side substrate having the substrate are arranged with a gap so that the wettability changing layer and the photocatalyst containing layer are 200 μm or less, and then irradiated with energy, In this step, a pattern comprising a hydrophilic region and a water-repellent region is formed on the color filter substrate.
[0033]
In this step, by forming a water-repellent region and a hydrophilic region whose wettability has been changed by the action of the photocatalyst associated with energy irradiation on the color filter forming substrate, no colored portion is formed in the step described later. The hydrophilic region can be protected with fountain solution, which makes it possible to form high-definition colored portions. Hereinafter, each structure of the pattern formation process of this invention is demonstrated.
[0034]
(Color filter forming substrate)
First, the color filter forming substrate used in the present invention will be described. The substrate for forming a color filter used in the present invention has water repellency and ink affinity, and further has a wettability changing layer that changes so that the contact angle with water is lowered by the action of a photocatalyst accompanying energy irradiation. If it exists, it will not specifically limit, The said wettability change layer may be formed on the transparent base material. Moreover, when the colored part formed in the colored part formation process mentioned later is a pixel part, you may have a light-shielding part etc. on the substrate for color filter formation. Hereinafter, each configuration of the color filter forming substrate of the present invention will be described.
[0035]
(1) Wetting change layer
First, the wettability changing layer used for the color filter forming substrate of the present invention will be described. The wettability changing layer used in the present invention is a layer that is water-repellent and ink-philic, and further changes so that the contact angle with water decreases due to the action of a photocatalyst accompanying energy irradiation. In the present invention, by having the wettability changing layer, in the pattern formation described later, it is possible to make a portion irradiated with energy a hydrophilic region and a portion not irradiated with energy a water repellent region. Become. At this time, the region where the colored portion is formed is a water-repellent region, and the region where the colored portion is not formed is a hydrophilic region, so that the hydrophilic region where the colored portion is not formed is protected with dampening water, and the parent of the water-repellent region. Taking advantage of the ink properties, it is possible to form colored portions only in the water-repellent region using, for example, oil-based ink as a colored portion forming coating liquid.
[0036]
In the present invention, the critical surface tension before energy irradiation of the wettability changing layer is in the range of 20 mN / m or more and less than 50 mN / m, and particularly in the range of 35 mN / m or more and less than 50 mN / m. preferable.
[0037]
When the critical surface tension is within the above range, the wettability changing layer before energy irradiation can be made a water-repellent region having water repellency and ink affinity. Here, by setting the wettability changing layer before the energy irradiation to be ink-philic, it becomes possible to uniformly apply a colored portion forming coating liquid or the like for forming the colored portion.
[0038]
In addition, the contact angle between the wettability changing layer and the 70 mN / m liquid before energy irradiation is preferably in the range of 50 ° to less than 120 °, and more preferably in the range of 70 ° to less than 120 °. When the contact angle with the liquid is lower than the above range, for example, in the dampening water application process described later, dampening water may adhere to the water-repellent region. This is because it becomes difficult to form the colored portion with high definition.
[0039]
In addition, the critical surface tension of the wettability changing layer whose wettability has been changed by the action of the photocatalyst upon energy irradiation may be in the range of 50 mN / m or more and less than 75 mN / m, particularly 60 mN / m or more and less than 75 mN / m. preferable. This is because when the critical surface tension is within the above range, the wettability changing layer whose wettability has been changed by the action of the photocatalyst can be made hydrophilic.
[0040]
Further, the contact angle between the wettability changing layer having changed wettability and the liquid of 70 mN / m is preferably in the range of 0 ° to less than 50 °, and more preferably in the range of 0 ° to less than 40 °.
[0041]
When the contact angle with the liquid is higher than the above range, the hydrophilicity is not sufficient, for example, when dampening water is applied, there is a possibility of repelling, and a region other than forming the colored portion This is because the fountain solution makes it difficult to protect and it is difficult to form a high-definition colored portion.
[0042]
In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.
[0043]
Here, the wettability changing layer in the present invention contains fluorine in the wettability changing layer, and when the fluorine content on the surface of the wettability changing layer is irradiated with energy to the wettability changing layer, The wettability changing layer may be formed so as to be lower than that before energy irradiation due to the action of the photocatalyst.
[0044]
In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a hydrophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a hydrophilic region pattern in the water repellent region.
[0045]
Therefore, when such a wettability changing layer is used, the pattern of the hydrophilic region can be easily formed in the water repellent region by irradiating the pattern with energy. When applying the coating liquid for forming, etc., the hydrophilic region that does not form the colored portion is protected with dampening water, and the colored portion is formed with high definition only in the water-repellent and water-repellent water-repellent region. It becomes possible.
[0046]
As described above, the fluorine content contained in the wettability changing layer containing fluorine is not irradiated with energy in the hydrophilic region with low fluorine content formed by energy irradiation. When the fluorine content in the water repellent region is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0047]
By setting it within such a range, it is possible to make a great difference in wettability between the hydrophilic region irradiated with energy and the water repellent region not irradiated with energy. Therefore, it becomes possible to easily apply dampening water only to the hydrophilic region, and to apply the colored portion forming composition only to the water repellent region, so that the colored portion can be formed with high definition. It becomes. This rate of decrease is based on weight.
[0048]
The fluorine content in such a wettability changing layer can be measured by various commonly used methods such as X-ray Photoelectron Spectroscopy, ESCA (Electron Spectroscopy for Chemical Analysis)), and any method that can quantitatively measure the amount of fluorine on the surface, such as X-ray fluorescence analysis, mass spectrometry, etc., is not particularly limited.
[0049]
As a material used for such a wettability changing layer, the wettability of the above-described wettability changing layer, that is, a material whose wettability is changed by the photocatalyst in the photocatalyst containing layer opposed by energy irradiation, and by the action of the photocatalyst. The main chain is not particularly limited as long as it has a main chain that is difficult to degrade and decompose, and specific examples include organopolysiloxane. In the present invention, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group.
[0050]
Examples of such an organopolysiloxane include (1) an organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) water repellency and oil repellency. Mention may be made of organopolysiloxanes such as organopolysiloxanes crosslinked with excellent reactive silicones.
[0051]
In the case of (1) above, the general formula:
Y_nSiX_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolytic condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0052]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those known as fluorine-based silane coupling agents can be used.
[0053]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;and
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0054]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the water repellency of the non-irradiated part of the wettability changing layer is greatly improved. It becomes possible to prevent adhesion. In addition, since the substance is ink-philic, it is possible to apply oil-based ink or the like as a colored portion forming coating liquid for forming a colored portion. Moreover, it becomes possible to attach dampening water to the hydrophilic area | region which is an energy irradiation part.
[0055]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0056]
[Chemical 1]

[0057]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total by mole ratio is vinyl, phenyl or phenyl halide. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0058]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0059]
In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
[0060]
The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0061]
In addition to the above surfactants, the wettability changing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate. , Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. Can be contained.
[0062]
Such a wettability changing layer is formed by preparing a coating liquid by dispersing the above-described components in a solvent together with other additives as necessary, and coating the coating liquid on a transparent substrate. Can do. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0063]
Further, the wettability changing layer used in the present invention may be a self-supporting material as long as it is formed of a material whose surface wettability can be changed by the action of a photocatalyst. The material which does not have property may be sufficient. In addition, having self-supporting property as used in the field of this invention means that it can exist in a tangible state without another support material.
[0064]
When the wettability changing layer is a material having a self-supporting property, for example, a commercially available resin film made of a material that can become the wettability changing layer can be used, which can be said to be advantageous in terms of cost. As such a material, if the above-mentioned material formed into a film has a self-supporting property, it can be used. For example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride Acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone and the like.
[0065]
The wettability changing layer in the present invention is preferably a wettability changing layer having no self-supporting property. This is because the above-described wettability changing layer formed of a material that greatly changes the wettability usually has few self-supporting materials.
[0066]
By using the wettability changing layer of the above-described component in the present invention, the action of the photocatalyst in the photocatalyst containing layer is used to oxidize, decompose, etc. the organic group that is a part of the above component, and It is possible to change the wettability to make it hydrophilic and to make a great difference in wettability with the non-energy-irradiated part. Therefore, it is possible to easily apply the fountain solution only to the hydrophilic region, and it is possible to easily form the colored portion only in the water-repellent region, so that a high-definition colored portion is formed. In addition, the color filter can be manufactured by an easy process.
[0067]
In addition, the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. For example, in the case where a photocatalyst is contained in the wettability changing layer, when the work is performed in a bright place in a dampening water application step or a colored portion forming step described later, the sensitivity is increased by dampening water. Due to the action of the photocatalyst, the wettability of the wettability changing layer changes, and it may be difficult to form a colored portion with high definition. In the present invention, if the photocatalyst is not included in the wettability changing layer, there is no need to worry about the above-mentioned problems. Therefore, it is possible to manufacture a color filter with a simple device, and then the color filter. This is because there is no need to worry about being affected by the passage of time, and it can be used without problems for a long time.
[0068]
(2) Transparent substrate
Next, the transparent base material used for the color filter forming substrate of the present invention will be described. In the present invention, when the above-described wettability changing layer is not self-supporting or when the color filter forming substrate requires strength, as shown in FIG. The wettability changing layer 2 may be formed thereon.
[0069]
Such a transparent substrate is appropriately selected according to the finally obtained color filter, and the transparent substrate is not particularly limited as long as it is conventionally used for a color filter. Although not intended, for example, a transparent flexible material such as quartz glass, Pyrex (registered trademark), synthetic quartz plate or the like, or a flexible flexible material such as a transparent resin film or an optical resin plate. Materials can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices. In the present invention, the transparent substrate is usually transparent, but it is also possible to use a reflective transparent substrate or a white transparent colored substrate. In addition, the transparent substrate may be subjected to surface treatment for preventing alkali elution, imparting gas barrier properties or other purposes as required.
[0070]
(Photocatalyst containing layer side substrate)
Next, the photocatalyst containing layer side substrate used in the present invention will be described. The photocatalyst-containing layer side substrate used in the present invention has at least a photocatalyst-containing layer and a substrate, and is usually formed by forming a thin-film photocatalyst-containing layer formed by a predetermined method on the substrate. is there. In addition, as the photocatalyst-containing layer side substrate, a substrate in which a photocatalyst-containing layer side light-shielding portion or primer layer formed in a pattern is formed can be used. Hereinafter, each structure of this photocatalyst containing layer side board | substrate is demonstrated.
[0071]
(1) Photocatalyst containing layer
The photocatalyst-containing layer used in the present invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the wettability of the wettability changing layer described above. From the photocatalyst and the binder, It may be configured, or may be formed with a photocatalyst alone. Further, the wettability of the surface may be particularly hydrophilic or water repellent.
[0072]
The photocatalyst-containing layer used in the present invention may be formed on the entire surface of the substrate 1 as shown in FIG. 1 (a), for example, but for example, as shown in FIG. The photocatalyst containing layer 2 may be formed in a pattern on the top.
[0073]
By forming the photocatalyst-containing layer in a pattern like this, it is necessary to irradiate a pattern using a photomask or the like when irradiating energy to the wettability changing layer as described in the section of pattern formation described later. By irradiating the entire surface, a pattern composed of a hydrophilic region and a water repellent region can be formed on the wettability changing layer.
[0074]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0075]
In addition, when the photocatalyst-containing layer and the wettability changing layer are subjected to energy irradiation, for example, the wettability of only the portion where the photocatalyst-containing layer is actually formed changes, so the energy irradiation direction May be irradiated from any direction as long as the photocatalyst-containing layer and the wettability changing layer are opposed to each other. Further, the irradiated energy may be a parallel light such as parallel light. It has the advantage that it is not limited to a thing.
[0076]
The action mechanism of a photocatalyst represented by titanium dioxide as described later in such a photocatalyst-containing layer is not necessarily clear, but a carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In the present invention, it is considered that this carrier acts on the compound in the wettability changing layer on the photocatalyst-containing layer.
[0077]
As the photocatalyst used in the present invention, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these.
[0078]
In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0079]
Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0080]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst having a particle size of 20 nm or less.
[0081]
The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder. In the case of a photocatalyst-containing layer comprising only a photocatalyst, the efficiency with respect to the change in wettability on the wettability changing layer is improved, which is advantageous in terms of cost such as shortening of the processing time. On the other hand, in the case of a photocatalyst containing layer comprising a photocatalyst and a binder, there is an advantage that the photocatalyst containing layer can be easily formed.
[0082]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, thereby uniformly changing the wettability on the wettability changing layer. In addition, since it consists of only a photocatalyst, it is possible to efficiently change the wettability on the wettability changing layer as compared with the case where a binder is used.
[0083]
In addition, as another method for forming a photocatalyst-containing layer composed only of a photocatalyst, for example, when the photocatalyst is titanium dioxide, an amorphous titania is formed on the substrate, and then a phase change is made to crystalline titania by firing. It is done. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0084]
In the case of using a binder, those having a high binding energy such that the main skeleton of the binder is not decomposed by photoexcitation of the above-mentioned photocatalyst are preferable. Examples include the organopolysiloxane described in the column of the wettability changing layer described above. be able to.
[0085]
When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. The coating solution can be formed by coating on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0086]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, silanol as a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less.
[0087]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.
[0088]
When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0089]
In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0090]
Furthermore, in addition to the above surfactants, the photocatalyst containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.
[0091]
b. Substrate
In the present invention, for example, as shown in FIG. 1A, the photocatalyst containing layer side substrate 3 has at least a base 1 and a photocatalyst containing layer 2 formed on the base 1.
[0092]
At this time, the material constituting the substrate to be used is appropriately selected depending on the energy irradiation direction in the pattern formation section described later, the structure of the obtained color filter, and the like.
[0093]
For example, in the case where a photocatalyst containing layer side light-shielding part is formed in a predetermined pattern in advance on the photocatalyst containing layer side light shield as will be described later, and a pattern is formed using this photocatalyst containing layer side light shielding part, It is necessary to irradiate energy from the side substrate side. In such a case, the substrate needs to be transparent.
[0094]
On the other hand, depending on the structure of the color filter, it is possible to irradiate energy by arranging a photomask on the color filter forming substrate side. Further, when the colored portion formed by the colored portion forming step described later is a pixel portion, as described above, the light shielding portion may be formed in the color filter forming substrate. In this case, the color filter formation is performed. It is necessary to irradiate energy from the substrate side. In such a case, the transparency of the substrate is not particularly required.
[0095]
The substrate used in the present invention may be a flexible substrate such as a resin film, or may be a non-flexible substrate such as a glass substrate. This is appropriately selected according to the energy irradiation method in the section of pattern formation described later.
[0096]
Thus, the substrate used for the photocatalyst-containing layer side substrate in the present invention is not particularly limited in material, but in the present invention, the photocatalyst-containing layer side substrate is used repeatedly. A material having a predetermined strength and having a surface having good adhesion to the photocatalyst containing layer is preferably used.
[0097]
Specific examples include glass, ceramic, metal, and plastic.
[0098]
In order to improve the adhesion between the substrate surface and the photocatalyst containing layer, an anchor layer may be formed on the substrate. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0099]
c. Photocatalyst containing layer side shading part
As the photocatalyst containing layer side substrate used in the present invention, a substrate on which a photocatalyst containing layer side light shielding portion formed in a pattern is formed may be used. Thus, by using the photocatalyst containing layer side substrate having the photocatalyst containing layer side light-shielding portion, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0100]
The photocatalyst-containing layer side substrate having such a photocatalyst-containing layer side light-shielding part can have the following two modes depending on the formation position of the photocatalyst-containing layer side light-shielding part.
[0101]
For example, as shown in FIG. 3, a photocatalyst-containing layer side light-shielding portion 15 is formed on a substrate 1, and a photocatalyst-containing layer 2 is formed on the photocatalyst-containing layer side light-shielding portion 15 to form a photocatalyst-containing layer-side substrate. It is an aspect to make. For example, as shown in FIG. 4, the photocatalyst containing layer 2 is formed on the substrate 1, and the photocatalyst containing layer side light-shielding portion 15 is formed thereon to form a photocatalyst containing layer side substrate.
[0102]
In any aspect, as compared with the case where a photomask is used, the photocatalyst containing layer side light shielding portion is arranged in the vicinity of the arrangement portion of the photocatalyst containing layer and the wettability changing layer. Since it is possible to reduce the influence of energy scattering, the energy pattern irradiation can be performed very accurately.
[0103]
Furthermore, in the invention for forming the photocatalyst containing layer side light shielding portion on the photocatalyst containing layer, when the photocatalyst containing layer and the wettability changing layer are arranged at predetermined positions, the film thickness of the photocatalyst containing layer side light shielding portion is determined. By keeping the width equal to the width of the gap, there is an advantage that the photocatalyst containing layer side light-shielding portion can be used as a spacer for making the gap constant.
[0104]
That is, when the photocatalyst-containing layer and the wettability changing layer are arranged facing each other with a predetermined gap, the photocatalyst-containing layer side light-shielding portion and the wettability changing layer are arranged in close contact with each other. Thus, the predetermined gap can be made accurate, and in this state, the pattern can be accurately formed on the wettability changing layer by irradiating energy from the photocatalyst containing layer side substrate. It is.
[0105]
The method for forming such a photocatalyst-containing layer side light-shielding part is not particularly limited, and is appropriately selected according to the characteristics of the formation surface of the photocatalyst-containing layer side light-shielding part, the shielding property against the required energy, and the like. Used.
[0106]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0107]
Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0108]
In the above description, the two positions of the photocatalyst containing layer side light shielding portion between the substrate and the photocatalyst containing layer and the surface of the photocatalyst containing layer have been described as the formation position of the photocatalyst containing layer side. It is also possible to adopt a mode in which the photocatalyst-containing layer side light shielding portion is formed on the surface that is not provided. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be suitably used when the pattern to be formed is changed in a small lot.
[0109]
d. Primer layer
Next, the primer layer used for the photocatalyst containing layer side substrate of the present invention will be described. In the present invention, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate as described above, and the photocatalyst-containing layer is formed on the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side substrate is used. A primer layer may be formed between the side light shielding part and the photocatalyst containing layer.
[0110]
Although the action and function of this primer layer are not necessarily clear, by forming a primer layer between the photocatalyst-containing layer side light-shielding portion and the photocatalyst-containing layer, the primer layer is a wettability changing layer by the action of the photocatalyst. Impurities from the opening present between the photocatalyst containing layer side light shielding part and the photocatalyst containing layer side light shielding part, which are factors that inhibit the change in wettability, in particular, residues generated when patterning the photocatalyst containing layer side light shielding part, It is considered to exhibit a function of preventing diffusion of impurities such as metals and metal ions. Therefore, by forming the primer layer, the wettability change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0111]
In the present invention, the primer layer prevents impurities existing in not only the photocatalyst containing layer side light shielding part but also the opening formed between the photocatalyst containing layer side light shielding parts from affecting the action of the photocatalyst. The primer layer is preferably formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.
[0112]
FIG. 5 shows an example of the photocatalyst containing layer side substrate on which such a primer layer is formed. A primer layer 16 is formed on the surface of the substrate 1 on which the photocatalyst containing layer side light shielding portion 15 of the substrate on which the photocatalyst containing layer side light shielding portion 15 is formed. The photocatalyst containing layer 2 is formed on the surface.
[0113]
The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the photocatalyst containing layer side light-shielding portion of the photocatalyst containing layer side substrate is not in contact with the photocatalyst containing layer.
[0114]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX.₄X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0115]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0116]
(Pattern formation)
Next, formation of a pattern composed of a hydrophilic region and a water-repellent region on the color filter forming substrate will be described. In the pattern formation step of the present invention, after the photocatalyst-containing layer and the wettability changing layer are disposed at predetermined positions, energy is irradiated from a predetermined direction, whereby hydrophilic regions and A step of forming a pattern composed of a water repellent region is performed. Hereinafter, formation of this pattern will be described.
[0117]
a. Arrangement of photocatalyst containing layer and wettability changing layer
In the pattern formation process of the present invention, it is necessary to dispose the photocatalyst-containing layer and the wettability changing layer at a predetermined interval so that the action of the photocatalyst can be applied at the time of energy irradiation. After disposing the containing layer and the wettability changing layer with a gap of 200 μm or less, energy is irradiated from a predetermined direction. At this time, the photocatalyst-containing layer and the wettability changing layer may be adhered to each other.
[0118]
In the present invention, the gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good wettability change efficiency of the wettability changing layer, particularly in the range of 0.2 μm to 10 μm. The thickness is preferably in the range of 1 μm to 5 μm. Such a gap range is particularly effective for a small-area wettability changing layer capable of controlling the gap with high accuracy.
[0119]
On the other hand, when the treatment is performed on a wettability changing layer having a large area of, for example, 300 mm × 300 mm, there is no contact between the photocatalyst containing layer side substrate and the wettability changing layer. It 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 in the range of 50 to 75 μm. By setting the gap within such a range, there is no problem of pattern accuracy deterioration such as blurring of the pattern, or problems such as deterioration of the photocatalyst sensitivity and deterioration of wettability change efficiency. This is because there is an effect that unevenness does not occur in the wettability change on the property change layer.
[0120]
In this way, when the wettability changing layer having a relatively large area is irradiated with energy, the gap setting in the positioning device between the photocatalyst containing layer side substrate and the wettability changing layer in the energy irradiation device is set in the range of 10 μm to 200 μm. Especially, it is preferable to set in the range of 25 micrometers-75 micrometers. By setting the set value within such a range, the pattern accuracy is not significantly lowered and the sensitivity of the photocatalyst is not greatly deteriorated, and the photocatalyst-containing layer side substrate and the wettability changing layer are not in contact with each other. Because it becomes possible to do.
[0121]
Thus, by disposing the photocatalyst-containing layer and the wettability changing layer surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the interval between the photocatalyst-containing layer and the wettability changing layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the rate at which the wettability changes may be reduced. This is not preferable. In addition, it is preferable that the active oxygen species generated are difficult to reach the wettability changing layer, and in this case as well, there is a possibility that the rate at which the wettability changes may be slowed when arranged at a distance from the above range. Absent.
[0122]
In the present invention, such an arrangement state only needs to be maintained at least during energy irradiation.
[0123]
As a method of forming such a very narrow gap uniformly and arranging the photocatalyst containing layer and the wettability changing layer, for example, a method using a spacer can be mentioned. Further, by using the spacer in this way, a uniform gap can be formed, and at the portion where the spacer contacts, the photocatalytic action does not reach the wettability changing layer surface. By having a pattern similar to the pattern of the water-repellent region, a predetermined pattern can be formed on the wettability changing layer.
[0124]
In the present invention, such a spacer may be formed as one member. However, for simplification of the process, as described in the column of the photocatalyst containing layer side substrate, the photocatalyst of the photocatalyst containing layer side substrate is used. It is preferable to form on the surface of the containing layer. In the description of the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side light-shielding portion has been described. However, in the present invention, such a spacer has a surface so that the photocatalyst does not act on the wettability changing layer surface. Since what is necessary is just to have the effect | action which protects, it may be formed with the material which does not have a function which shields especially the energy irradiated.
[0125]
b. Energy irradiation
Next, energy irradiation is performed on the opposing portions while maintaining the above-described arrangement. The energy irradiation (exposure) in the present invention is a concept including irradiation of any energy ray capable of changing the wettability of the wettability changing layer surface by the photocatalyst-containing layer. It is not limited.
[0126]
Usually, the wavelength of light used for such energy irradiation is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0127]
Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0128]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0129]
Further, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for changing the wettability of the wettability changing layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0130]
At this time, it is preferable in that the sensitivity can be increased by irradiating the photocatalyst-containing layer with energy while heating, and the wettability can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0131]
The energy irradiation direction in the present invention is determined by a pattern forming method or the like, such as whether or not the light shielding part is formed on the photocatalyst containing layer side light shielding part or the color filter forming substrate side.
[0132]
That is, when the photocatalyst containing layer side light shielding portion is formed, it is necessary to irradiate energy from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate is transparent to the energy irradiated. Need to be. In this case, when the photocatalyst-containing layer side light-shielding part is formed on the photocatalyst-containing layer and this photocatalyst-containing layer side light-shielding part is used so as to function as a spacer as described above, the energy irradiation direction May be from the photocatalyst containing layer side substrate side or from the color filter forming substrate side.
[0133]
On the other hand, when the light shielding portion is formed on the color filter forming substrate side, it is necessary to irradiate energy from the color filter forming substrate side, and in this case, the energy irradiated to the color filter forming substrate side. Must be transparent to In this case as well, when a light shielding portion is formed on the wettability changing layer and this light shielding portion is used so as to function as a spacer as described above, the energy irradiation direction is from the photocatalyst containing layer side substrate side. However, it may be from the color filter forming substrate side.
[0134]
In addition, the energy irradiation direction in the case where the photocatalyst-containing layer is formed in a pattern is, as described above, from any direction as long as energy is irradiated to the portion where the photocatalyst-containing layer and the wettability changing layer face each other. It may be irradiated.
[0135]
Similarly, in the case of using the above-described spacer, irradiation may be performed from any direction as long as energy is irradiated to the facing portion.
[0136]
In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the color filter forming substrate needs to be transparent.
[0137]
c. Removing the photocatalyst-containing layer side substrate
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is separated from the arrangement position with the wettability changing layer, thereby changing the wettability of the wettability changing layer 5 as shown in FIG. A pattern composed of the hydrophilic region 9 and the water repellent region 10 is formed.
[0138]
2. Dampening water application process
Next, the dampening water application | coating process of this invention is demonstrated. The fountain solution application step in the present invention is a step of applying fountain solution only to the hydrophilic region on the pattern composed of the hydrophilic region and the water-repellent region formed by the pattern forming step described above.
[0139]
By applying the fountain solution to the hydrophilic region, a colored part forming coating is used to form a colored part in a part other than the target pattern when the colored part is formed by a colored part forming step described later. This makes it possible to prevent the liquid or the like from adhering and to form a high-definition colored portion.
[0140]
As the fountain solution used in the present invention, a fountain solution generally used for offset printing or the like can be used. Specifically, the fountain solution is obtained by adding isopropyl alcohol or the like to water.
[0141]
Further, the application method of the fountain solution is not particularly limited as long as the fountain solution can be applied onto the hydrophilic region on the color filter substrate. Since it does not adhere, it may be a method of applying to the entire surface of the color filter substrate by roll coating, bead coating or the like, or a method of applying in a desired pattern like a nozzle discharge method such as an ink jet method. There may be.
[0142]
3. Colored part formation process
Next, the colored part forming step of the present invention will be described. The colored portion forming step in the present invention is a step of forming a colored portion in the above-described water-repellent and water-repellent region on the color filter forming substrate using, for example, a colored portion forming coating solution. is there. In the present invention, the water-repellent region having water repellency and ink repellency formed in the pattern forming the colored portion is formed by the pattern forming process described above, and this water repellency and ink repellency having water repellency is formed. A colored portion can be formed by applying and curing a colored portion forming coating solution along the aqueous region. Further, the portion that does not form the colored portion on the color filter forming substrate is coated with dampening water by the dampening water application step described above, and is protected by this dampening water. The part forming coating liquid or the like is not attached, and the colored part can be formed with high definition.
[0143]
The colored portion formed by this step is a black matrix (hereinafter referred to as a first embodiment) and a pixel portion (hereinafter referred to as a second embodiment). Hereinafter, each embodiment will be described separately. .
[0144]
(First embodiment)
First, the first embodiment when the colored portion is a black matrix will be described. In the case of this embodiment, in the pattern forming step described above, the pattern formed of the hydrophilic region and the water-repellent region is a water-repellent region in which the portion where the black matrix is formed has water repellency and ink affinity, such as pixels. A portion where a portion is formed is a hydrophilic region, and the hydrophilic region is protected by dampening water by the dampening water application step described above. As a result, it is possible to form the black matrix with high definition without the black matrix forming coating solution or the like forming the black matrix adhering to the part or the like that forms the pixel portion.
[0145]
In the present embodiment, the black matrix forming coating solution is not particularly limited as long as it is a material that is not soluble in the fountain solution and can be applied onto the wettability changing layer. It is possible to use a material for forming a black matrix in a general color filter.
[0146]
Here, the black matrix-forming coating solution used in the present invention preferably has a solubility in water in the range of 0.5 wt% to 10 wt% at 20 ° C., as described above. When the solubility of the black matrix forming coating solution in water is within the above range, the black matrix forming coating solution does not dissolve in the fountain solution and forms a black matrix with high definition only in the water-repellent region. Because it becomes possible to do.
[0147]
Specifically, as a black matrix forming coating solution, a resin binder and light-shielding particles such as carbon fine particles, titanium fine particles, metal oxides, inorganic pigments, and organic pigments are used as solvents that are insoluble in water. Examples include a method using a dissolved coating solution. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used.
[0148]
Here, as a method for forming the black matrix, the hydrophilic region is protected by a dampening solution, and the black matrix forming coating solution does not adhere to the entire surface on the color filter substrate by roll coating or the like. The method of apply | coating to the surface may be sufficient, and the method of apply | coating to the target pattern shape like nozzle discharge methods, such as an inkjet method, may be sufficient.
[0149]
(Second embodiment)
Next, a second embodiment in the case where the coloring portion is a pixel portion will be described. In the case of this embodiment, in the pattern forming step described above, the pattern formed of the hydrophilic region and the water repellent region is a water repellent and ink-philic water repellent region where the pixel portion is formed, and For example, a boundary portion between a pixel portion where a black matrix or the like is formed is a hydrophilic region, and the hydrophilic region is protected by dampening water by the dampening water application process described above.
[0150]
In general, the pixel portion of the color filter is formed of three colors of red (R), green (G), and blue (B), and the same applies to this embodiment. In this embodiment, since dampening water is applied between the pixel portions when the pixel portions are formed, it is possible to form a high-definition pixel portion without mixing adjacent pixel portions of different colors. It becomes.
[0151]
In the case of this embodiment, the pixel part forming coating liquid for forming the pixel part is not soluble in the fountain solution and can be applied on the wettability changing layer having water repellency and ink affinity. The material is not particularly limited as long as it is a material, and it is generally possible to use an oily material or the like for forming the pixel portion.
[0152]
Here, the above-mentioned pixel portion forming coating solution used in the present invention preferably has a solubility in water in the range of 0.5% by weight to 10% by weight at 20 ° C.
[0153]
The solubility of the pixel portion forming coating solution in water is within the above range, so that the pixel portion forming coating solution does not dissolve in the fountain solution, and the pixel portion is formed with high definition only in the water-repellent region. Because it becomes possible to do.
[0154]
In the case of this embodiment, in order to prevent color mixing of the different pixel portions, it is preferable that the pixel portions are formed only in a target pattern by a nozzle discharge method such as an ink jet method.
[0155]
In the case of this embodiment, the finally produced color filter may be formed with a black matrix, and the black matrix may be one in which a black matrix is formed between pixel portions. Moreover, what formed the black matrix between the transparent base material and the wettability change layer may be used.
[0156]
The method for forming the black matrix is not particularly limited. For example, a metal thin film such as chromium having a thickness of about 1000 to 2000 mm is formed by sputtering, vacuum deposition, or the like, and the thin film is patterned. Alternatively, the resin black matrix used in the first embodiment described above may be formed by a photolithography method, a printing method, or the like.
[0157]
4). Dampening water drying process
Next, the dampening water drying process in this invention is demonstrated. The fountain solution drying step in the present invention is a step of drying the fountain solution after forming the colored portion described above. In the present invention, the method is not particularly limited as long as the fountain solution can be dried. For example, the fountain solution is used in the step of curing the colored portion by heating. Can be volatilized at the same time, followed by spray cleaning with pure water and further heat drying.
[0158]
5. Other
In the present invention, when the colored portion formed by the above-described colored portion forming step is a black matrix, it may have a step of forming a pixel portion after the dampening water drying step. Good.
[0159]
In the present invention, the finally produced color filter may be subjected to a protective layer forming step for forming a protective layer on the pixel portion or the black matrix described above or a step for forming other necessary functional layers. Good.
[0160]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
[0161]
For example, in the above description, it has been described on the assumption that it has a black matrix, but it can also be applied to a color filter without a black matrix.
[0162]
【Example】
The present invention will be described more specifically with reference to the following examples.
[0163]
(Formation of photocatalyst-containing layer side substrate)
The photomask surface was coated with a photocatalyst titanium oxide coating agent TKC301 manufactured by Teika Co., Ltd. and dried at 350 ° C. for 3 hours to prepare a photocatalyst-containing layer side substrate. The photomask used was a black matrix having a thickness of 1 μm formed of a dispersion of carbon black and resin arranged at a pitch of 100 μm with a line having a width of 90 μm.
[0164]
(Formation of wettability change layer)
Next, a solution obtained by adding 3 g of 0.1N hydrochloric acid water to 0.2 g of MF-160E (trade name, manufactured by Tochem Products Co., Ltd.) containing fluoroalkylsilane as a main component and stirring for 1 hour at room temperature, It spin-coated on the quartz glass substrate of thickness 0.7mm, and was dried for 10 minutes at 150 degreeC. As a result, a wettability changing layer having an ink affinity and water repellency with a film thickness of 0.1 μm and a critical surface tension of 40 mN / m was formed on the substrate.
[0165]
(Wetting change pattern formation)
The wettability changing layer surface was exposed with an ultra-high pressure mercury lamp through the photocatalyst-containing layer side substrate. The exposure amount was 2000 mJ at 365 nm. Thereby, only the exposed part of the wettability change layer surface became a hydrophilic region.
[0166]
(Applying dampening water)
When dampening water was applied to the entire surface of the wettability changing layer by a bead coating method, dampening water adhered only to the hydrophilic region and did not adhere to the water repellent region. The fountain solution used at this time was obtained by mixing 10 g of a clean etchant manufactured by Nikken Chemical Laboratory and 190 g of distilled water (manufactured by Junsei Kagaku). The contact angle with respect to the water-repellent region which is an unexposed portion on the wettability changing layer was 70 °, and the contact angle with respect to the hydrophilic region which was an exposed portion was 10 °.
[0167]
(Applying the coating solution for forming the colored portion)
On the wettability changing layer in which the fountain solution was formed in a pattern, a colored layer (black matrix) forming coating solution was applied by a roll coating method. The coloring layer forming coating solution spreads only in the water-repellent and ink-repellent water-repellent region where the fountain solution of the wettability changing layer is not applied, and was not mixed with the fountain solution. The composition of the colored layer forming coating solution is a system in which carbon black fine particles with an average particle size of 0.1 μm are dispersed in an acrylic thermosetting resin containing an epoxy group using propylene glycol monomethyl ether acetate as a solvent. It was.
[0168]
(Dampening water drying and cleaning)
The above-described wettability changing layer to which the colored portion forming coating solution and the fountain solution are applied is dried in a clean oven at 150 ° C. for 30 minutes to cure and wet the colored portion (black matrix) forming coating solution. Water was dried. Further, after spray washing with pure water, draining, and drying at 120 ° C. for 5 minutes in a clean oven, a black matrix for a color filter having a width of 10 μm and a film thickness of 0.5 μm was formed.
[0169]
(Production of color filter)
An LCD liquid crystal display is formed by discharging ink for forming colored layers of red, blue, and green, which are usually used, by an ink jet method to the openings of the color filter substrate on which the black matrix is formed by the above method, and drying and curing the ink. A color filter was prepared.
[0170]
【The invention's effect】
According to the present invention, by irradiating the wettability changing layer with energy using the photocatalyst-containing layer, the energy-irradiated portion is made a hydrophilic region and the non-energy-irradiated portion is made a water-repellent region. Can do. At this time, the region where the colored portion is formed is a water-repellent region, and the region where the colored portion is not formed is a hydrophilic region, so that when the colored portion is formed on the water-repellent region, the hydrophilic region where the colored portion is not formed. For example, an oily ink or the like as a colored layer forming coating liquid for forming a colored layer can be used to easily form a colored portion such as a black matrix or a pixel portion on a water-repellent region. High definition can be formed.
[0171]
Further, in the present invention, since the photocatalyst-containing layer side substrate is used, it is not necessary to contain a photocatalyst in the wettability changing layer, and when a colored portion is formed using dampening water in a bright place. However, portions other than the target pattern are not exposed, and a color filter can be manufactured with a simple manufacturing apparatus.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an example of a method for producing a color filter for transflective liquid crystal according to the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of a photocatalyst-containing layer side substrate used in the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present invention.
FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate used in the present invention.
FIG. 5 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present invention.
[Explanation of symbols]
1 ... Base
2 ... Photocatalyst containing layer
3 ... Photocatalyst containing layer side substrate
4 ... Transparent substrate
5… wettability change layer
6 ... Color filter forming substrate
9 ... hydrophilic region
10 ... Water repellent area
11 ... Dampening water
12 ... Black Matrix
14 ... Pixel part
15 ... Photocatalyst containing layer side light shielding part
16 ... Primer layer

Claims (12)

A substrate for forming a color filter having a wettability changing layer that is water-repellent and ink-philic, changes so that the contact angle with water is lowered by the action of the photocatalyst accompanying energy irradiation, and does not contain a photocatalyst, and a photocatalyst. The color filter containing the photocatalyst-containing layer and the photocatalyst-containing layer-side substrate having the substrate are arranged with a gap so that the wettability changing layer and the photocatalyst-containing layer are 200 μm or less, and then irradiated with energy, and the color filter A pattern forming step of forming a pattern consisting of a hydrophilic region and a water-repellent region on a forming substrate;
A fountain solution application step of applying a fountain solution onto the hydrophilic region;
A colored portion forming step of forming a colored portion on the water repellent region;
A dampening water drying step of drying the dampening water,
The wettability variable layer, the critical surface tension in the portion which is not energy irradiation is in the range of less than 20 mN / m or more 50 mN / m, Contact Keru critical surface tension energy irradiated portion is 50 mN / m or more 75 mN / A method for producing a color filter, which is within a range of less than m.   The method for producing a color filter according to claim 1, wherein the color filter forming substrate has a transparent base material and a wettability changing layer formed on the transparent base material.   The wettability changing layer has a contact angle with a liquid having a surface tension of 70 mN / m within a range of 50 ° or more and less than 120 ° in a portion not irradiated with energy, and 0 ° or more and 50 ° in a portion irradiated with energy. The method for producing a color filter according to claim 1 or 2, wherein the color filter is within a range of less than.   The method for producing a color filter according to any one of claims 1 to 3, wherein the wettability changing layer is a layer containing an organopolysiloxane.   The method for producing a color filter according to claim 4, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. 5. n is an integer from 0 to 3. This is an organopolysiloxane which is one or more of the hydrolytic condensates or co-hydrolytic condensates of the silicon compound represented by (4). Or the manufacturing method of the color filter of Claim 5.   The method for producing a color filter according to claim 1, wherein the photocatalyst-containing layer is a layer made of a photocatalyst.   The method for producing a color filter according to claim 7, wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method.   The method for producing a color filter according to any one of claims 1 to 6, wherein the photocatalyst-containing layer is a layer having a photocatalyst and a binder. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. The method for producing a color filter according to any one of claims 1 to 9, wherein the material is one or more substances selected from iron (Fe ₂ O ₃ ). The method for producing a color filter according to claim 10, wherein the photocatalyst is titanium oxide (TiO ₂ ).   The method for producing a color filter according to any one of claims 1 to 11, wherein the colored portion is a black matrix.

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