JP4429631B2 - Curing shrinkable pattern forming material, pattern forming method, and color filter - Google Patents

Description

【００６０】
（上記式において、ｎ≦４である）。
【００６１】
更に、ケイ素アルコキシド以外の金属アルコキシドを少なくとも１種以上用いることが好ましい。また、ケイ素アルコキシド以外の金属アルコキシドは、ケイ素アルコキシドに対して好ましくは１０重量％程度含むことが好ましい。このようなケイ素アルコキシド以外の金属アルコキシドとしては、例えば、トリメトキシアルミニウム、トリエトキシアルミニウム、トリイソプロポキシアルミニウム、トリｎ−プロポキシアルミニウム、トリｎ−ブトキシアルミニウム、トリｓｅｃ−ブトキシアルミニウム、トリｔｅｒｔ−ブトキシアルミニウム、テトラメトキシチタン、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−ブトキシチタン、テトラｓｅｃ−ブトキシチタン、テトラｔｅｒｔ−ブトキシチタン、テトラメトキシジルコニウム、テトラエトキシジルコニウム、テトライソプロポキシジルコニウム、テトラｎ−ブトキシジルコニウム、テトラｓｅｃ−ブトキシジルコニウム、テトラｔｅｒｔ−ブトキシジルコニウム等を例示できる。
【００６２】
ゾルゲル反応性化合物は、色調に悪影響を与えないように、透明性の高い超微粒子、例えば、平均一次粒子径が５〜５００ｎｍであることが好ましい。
【００６３】
ゾルゲル反応においては、水分量、ｐＨ、一般式１におけるＲ’の種類、温度等が反応に影響するパラメータであり、これらはゲル化時間、ゲルのかさ密度、細孔径分布等に影響を与え、パターンの外観や硬化収縮率に反映するため、適切に選択する必要がある。
【００６４】
ゾルゲル反応性化合物が加水分解重縮合によりゾルからゲルに変化する場合には、ゾルゲル反応性化合物１モル当たり、水を１／３モル〜１モルの範囲で添加するのが好ましい。
【００６５】
加水分解重縮合反応においては触媒を用いることができ、触媒としては酸やアルカリを用いることができ、酸としては、塩酸、硫酸、硝酸等の強酸や、酢酸、または過酢酸、酸無水物、アセチル化剤等の酢酸誘導体等であることが好ましい。また、アルカリとしては、アンモニアおよびそのアンモニアの水酸化物、四級アンモニウム塩等が好ましい。触媒水溶液の水分も加水分解に利用されるため、条件によっては、それ以上の水分を添加する必要がない場合もある。
【００６６】
加水分解、重縮合反応に必要な水、及び酸やアルカリなどの触媒は、溶剤中に各材料と同時に配合しても良いし、後から添加しても良い。例えば、塗工後に加水分解、重縮合を行う場合には、塗工直前に塗工液中に添加しても良い。
【００６７】
着色剤としては、顔料又は染料を用いることができるが、着色性の観点から顔料が好ましい。用いられる顔料としては特に限定されず、種々の有機又は無機顔料を用いることができる。有機顔料の具体例としては、カラーインデックス（C.I.；The Society of Dyers and Colourists 社発行） においてピグメント（Pigment）に分類されている化合物、すなわち、下記のようなカラーインデックス（C.I.）番号が付されているものを挙げることができる。C.I.ピグメントイエロー１、C.I.ピグメントイエロー３、C.I.ピグメントイエロー１２、C.I.ピグメントイエロー１３、C.I.ピグメントイエロー８３、C.I.ピグメントイエロー１３８、C.I.ピグメントイエロー１３９、C.I.ピグメントイエロー１５０、C.I.ピグメントイエロー１８０、C.I.ピグメントイエロー１８５等のイエロー系ピグメント；C.I.ピグメントレッド１、C.I.ピグメントレッド２、C.I.ピグメントレッド３、C.I.ピグメントレッド１７７、C.I.ピグメントレッド２５４等のレッド系ピグメント；及び、C.I.ピグメントブルー１５、C.I.ピグメントブルー１５：３、C.I.ピグメントブルー１５：４、C.I.ピグメントブルー１５：６等のブルー系ピグメント；C.I.ピグメントグリーン７、C.I.ピグメントグリーン３６等のグリーン系ピグメント；C.I.ピグメントバイオレット２３、C.I.ピグメントバイオレット２３：１９など。
【００６８】
また、前記無機顔料の具体例としては、酸化チタン、硫酸バリウム、炭酸カルシウム、亜鉛華、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄(III)）、カドミウム赤、群青、紺青、酸化クロム緑、コバルト緑、アンバー、チタンブラック、合成鉄黒、カーボンブラック等を挙げることができる。本発明において顔料は、単独でまたは２種以上を混合して使用することができる。
【００６９】
本発明においては、硬化収縮性パターン形成材料の表面張力が低いと単位面積当たりの塗布量（盛りつけ量）を十分に多くすることができず、硬化収縮させた後、図１（ａ）のように塗膜がやせ細り、幅が不均一となってパターンを高精細に形成することができなくなる点から、表面張力は高い方が好ましい。本発明においては、硬化収縮性パターン形成材料はガラス基板上の接触角が８０度以上となるように調節されていることが好ましい。
【００７０】
ここで接触角は、アルカリ、熱硫酸、及び水で洗浄したガラス基板上で測定された値をいい、次のような方法で測定できる。まず、７０５９ガラス基板を、硫酸等の酸に１分間浸漬後、超音波洗浄により中和し、表面を清浄なものとする。この際、界面活性剤等を用いて表面の付着物を除去してもよい。次に、接触角測定装置により、試料を上記基板上に１滴滴下後、室温にて一分間放置した後、基板と試料とのなす角度を測定する。
【００７１】
接触角を８０度以上に調節する点からは、前記硬化収縮性化合物が、超微粒子シリカとアルキルアルコキシシランとの反応性生成物、及びＳｉＡｌＯｎ（ｎは３０以下）から選択される少なくとも１つのゾルゲル反応性化合物を使用することが好ましい。ここで、超微粒子シリカとは、平均粒子径が１００ｎｍ以下のシリカをいい、比表面積は５０〜３０００ｍ²／ｇであることが好ましい。超微粒子シリカとしては、例えばアエロジル２００（日本アエロジル（株））を用いることができる。また、アルキルアルコキシシランとしては、例えば、モノメチルトリメトキシシラン、トリメチルメトキシシラン、ノルマルプロピルメトキシシラン、イソブチルトリメトキシシラン、オクタデシルトリメトキシシラン、ヘキサデシルトリメトキシシランを用いることができる。更に、これらにフッ素化アルキルシランを添加することもできる。
【００７２】
また、ＳｉＡｌＯｎ（ｎは３０以下）を使用することが好ましい。ｎを３０以下とすることにより、溶解性が良好でインキ化が容易である上、表面積の和が大きくなり、撥水能力が良好となるため、パターン形成用材料の収縮能力が良好となる。
【００７３】
また、接触角を８０度以上に調節する点から、表面張力改善剤として、アクリレート基を有する化合物のアクリレート基とアルコキシ基を有するアルコキシシラン化合物の２つの官能基を反応させた有機−無機複合体から選ばれる少なくとも一つの化合物を更に含有することが好ましい。上記多官能アクリレートモノマーとしては、例えば、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレートを使用することができ、上記アルコキシシラン化合物としては、例えば、テトラエトキシシラン、メチルシリケートを使用することができる。また、両方の官能基を有する３−アクリロキシプロピルトリメトキシシランを用いて得られた上記有機−無機複合体を使用しても良い。表面張力改善剤は、本発明において、単独でまたは２種以上を混合して使用することができる。
【００７４】
本発明に係る硬化収縮性パターン形成用材料は、必須成分として、上記反応硬化性バインダー系、硬化収縮性化合物及び着色剤を含有するが、さらに必要に応じて、塗工液に調製するための溶剤、増感剤、紫外線遮断剤、紫外線吸収剤、表面調整剤（レベリング剤）、或いは、その他の成分を配合しても良い。
【００７５】
硬化収縮性パターン形成用材料の反応硬化性バインダー系として液状のモノマー及び／又はオリゴマーを比較的多量に用いる場合には、当該モノマー及び／又はオリゴマーが液状媒体としても機能し得るので、溶剤を用いなくても固形成分を溶解、分散、又は希釈して塗工液の状態に調製できる場合がある。従って、本発明において溶剤は必ずしも必要ではないが、固形成分を溶解分散し、濃度を調整して、塗工適性に優れた塗工液を調製するために溶剤（希釈溶剤）を使用する場合が多い。
【００７６】
そのような希釈溶剤としては、例えば、メチルアルコール、エチルアルコール、Ｎ−プロピルアルコール、ｉ−プロピルアルコールなどのアルコール系溶剤；メトキシアルコール、エトキシアルコールなどのセロソルブ系溶剤；メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤；酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、乳酸エチルなどのエステル系溶剤；アセトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤；メトキシエチルアセテート、エトキシエチルアセテート、エチルセロソルブアセテートなどのセロソルブアセテート系溶剤；メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテートなどのカルビトールアセテート系溶剤；ジエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフランなどのエーテル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンなどの非プロトン性アミド溶剤；を例示することができる。これらの溶剤の中ではカルビトール系溶剤、ケトン系溶剤、セロソルブアセテート系溶剤が特に好適に用いられる。溶剤は、単独でまたは２種類以上を混合して使用することができる。
【００７７】
塗工液を調製するための溶剤（希釈溶剤）は、反応硬化性バインダー系や硬化収縮性化合物や着色剤の溶解性、塗工の均一性、塗工後の易乾燥性や乾燥後の収縮率の制御等を考慮して選択する必要がある。
【００７８】
さらに、本発明においては、接触角が上述した範囲以上になるように、希釈溶剤を適切に選択し、固形分濃度を調節することが好ましい。したがって接触角を８０度以上に調節する点から、本発明においては、上述したような溶剤を用いて、前記反応硬化性バインダー系を構成する１又は２以上の成分、硬化収縮性化合物、着色剤、及び必要に応じて配合される他の成分を溶解又は分散させることが好ましく、中でもイソホロン、エチルソルブアセテート、及びメトキシエトキシエタノールから選ばれる少なくとも一つの溶剤を用いて溶解又は分散させることがさらに好ましい。
【００７９】
適切に選択された希釈溶剤を用いて、固形分濃度を１０〜７５重量％、より好ましくは１５〜５５重量％に調節することによって、接触角が成就した範囲内に調節され、塗工適性に優れ、適切に硬化収縮する硬化収縮性パターン形成用材料が得られる。なお、本発明において固形分とは、希釈溶剤を除く全ての配合成分のことであり、液状のモノマーやオリゴマーも希釈溶剤で溶解すべき固形分に含まれる。
【００８０】
本発明に係る硬化収縮性パターン形成用材料は、反応硬化性バインダー系の各成分、硬化収縮性化合物、着色剤等を希釈溶剤に混合し、溶解分散させるか、液状のモノマー及び／又はオリゴマーを除く反応硬化性バインダー系の成分、硬化収縮性化合物、着色剤等の成分を、液状媒体としても機能する反応硬化性バインダー系である液状モノマー及び／又はオリゴマーに混合し、溶解分散させることによって調製できる。
【００８１】
各成分の配合割合は適宜調節可能であるが、好ましくは、前記溶剤を除く配合成分（固形分）の総重量に対して、必須成分として、前記反応硬化性バインダー系を５〜７０重量％、前記硬化収縮性化合物を０．１〜３５重量％、前記着色剤を５〜５０重量％含有し、表面張力改善剤を含有する場合には、０．０１〜５重量％含有し、必要に応じてその他の成分を含有しているのが好ましい。前記反応硬化性バインダー系が光硬化性バインダー系である場合には、そのうちの光ラジカル重合開始剤の使用量は、光ラジカル重合性ポリマー及び／又はモノマー及び／又はオリゴマー１００重量部に対して、通常は３〜５０重量部の割合で配合する。また、前記反応硬化性バインダー系が熱硬化性バインダー系である場合には、そのうちの硬化剤の配合量は、エポキシ樹脂１００重量部当たり、通常は１〜７５重量部の割合で配合する。
【００８２】
このようにして得られた本発明に係る硬化収縮性パターン形成用材料は、硬化収縮性や塗工適性に優れており、特に、接触角が上述した範囲に調節されているために単位面積当たりの塗布量（盛りつけ量）を十分に多くすることができ、塗膜がやせ細らずに硬化収縮させることが可能になる。したがって、これを何らかの支持体上に硬化時の収縮率を見込んで必要とされるパターン形状に塗布して塗膜を形成し、乾燥させ、反応硬化性バインダー系を光や熱等により反応硬化させ、硬化収縮性化合物が例えばゾルゲル反応性化合物である場合にはゾルゲル反応させることによって硬化収縮させて、透明性の高い均一な細線（fine line）のパターンを高精細（fine pitch）に形成することができる。
【００８３】
上記本発明に係る硬化収縮性パターン形成用材料は、カラーフィルターの着色層のような細部や細線（fine line）のパターンを、高精細（fine pitch）に形成することが要求される種々の着色塗膜を形成するのに利用できるが、特に、カラーフィルターの着色層（画素）やブラックマトリックスを形成するのに適している。
【００８４】
本発明に係るパターン形成方法は、硬化収縮性を有するパターン形成用材料を支持体上に所定のパターン状に塗布して当該パターン形成用材料の塗膜を形成した後、当該塗膜を硬化収縮させることを特徴とする。
【００８５】
パターン形成用材料として、上記本発明に係るパターン形成材料を用いる場合には、支持体上に塗膜を形成した後、当該塗膜に含まれる反応硬化性バインダー系及び硬化収縮性化合物を硬化反応させることにより塗膜を硬化収縮させる。パターン形成用材料としては上記組成のパターン形成材料が非常に適しているが、これらに限定されず、細線化及び／又は高精細化を達成し得るために充分な硬化収縮率を有する材料であれば使用可能である。
【００８６】
以下において、本発明に係るパターン形成方法を、硬化収縮性化合物としてゾルゲル反応性化合物を用いる場合を例にとって説明する。
【００８７】
上記硬化収縮性パターン形成用材料が硬化収縮性化合物としてゾルゲル反応性化合物を含有している場合には、当該パターン形成用材料を支持体上に所定のパターン状に塗布して当該パターン形成用材料の塗膜を形成した後、当該塗膜に含まれる反応硬化性バインダー系及びゾルゲル反応性化合物をそれぞれ硬化反応及びゾルゲル反応させて当該塗膜を硬化収縮させることにより、所望のパターンを有する硬化皮膜が得られる。
【００８８】
本発明に係る硬化収縮性パターン形成用材料を支持体上に所定のパターン状に塗布するためには、被塗布面に所定のパターンを直接形成できる各種のパターン印刷法、例えばスクリーン印刷、グラビア印刷、オフセット印刷、インクジェット法等で行うことができる。その中でも、スクリーン印刷又はインクジェット法は、本発明に係るパターン形成用材料を用いるのに適した方法である。
【００８９】
スクリーン印刷を行う場合には、所定のパターンのスクリーンマスクを用いて、硬化収縮性パターン形成用材料の塗工液を、基板にスクリーン印刷して塗膜を形成し、その後、硬化反応及びゾルゲル反応を行う。
【００９０】
本発明に係る硬化収縮性パターン形成用材料に含まれるゾルゲル反応性化合物は、ゾルゲル反応によって硬化収縮する性質を有するため、当該ゾルゲル反応性化合物を反応硬化性バインダー系の材料に配合すると、塗布（及び必要に応じて乾燥）して形成した塗膜を硬化させる際に、塗膜中のゾルゲル反応性化合物がゲル化することにより収縮し、塗布したパターンのサイズよりも線幅が最大２０％以上収縮した硬化パターンが最終的に得られる。そのため、本発明に係るパターン形成材料を硬化時の収縮率を見込んで必要とされるパターン形状に塗布することにより、硬化後には所定の細線（fine line）のパターンを形成することが可能になる。典型例としては本発明をブラックマトリックスのパターン形成に応用した時に、非常に細かいパターンを形成できるので、開口率を大きくすることができる。
【００９１】
反応硬化性バインダー系として光硬化性バインダー系を用いる場合には、硬化反応は、塗膜を形成して乾燥させた後、当該塗膜に光線を照射することにより、塗膜中の光硬化性バインダー系を反応させて架橋結合のネットワークを形成し、塗膜を硬化させることができる。ラジカル重合により反応硬化させる場合には、ラジカル発生を促進させるため、酸素を遮断して行うのが好ましい。
【００９２】
硬化反応に用いる光線としては、紫外線や電離放射線のような不可視光又は可視光の中から、光硬化性バインダー系の重合反応を引き起こす波長を有するものを適宜選んで用いる。
【００９３】
一方、反応硬化性バインダー系として熱硬化性バインダー系を用いる場合には、硬化反応は、塗膜を形成して乾燥させた後、当該塗膜を加熱することにより、塗膜中の熱硬化性バインダー系を反応させて架橋結合のネットワークを形成し、塗膜を硬化させることができる。硬化反応に必要な温度は、通常、７０℃〜２００℃程度である。
【００９４】
ゾルゲル反応性化合物として加水分解重縮合性化合物を用い、加水分解重縮合によるゾルゲル反応を起こさせる場合には、加水分解重縮合性化合物と共に予め水や触媒をパターン形成用材料中に添加して支持体に塗布した後、任意のタイミングで、３０℃〜２５０℃、好ましくは５０℃〜２００℃に加熱して１５分〜１２時間放置する。これにより、塗膜内で加水分解重縮合が進行していき、加水分解重縮合性化合物がゾル状粒子となり、さらに反応を進めるとゾル状粒子が繋がってゲルになる。
【００９５】
当該塗膜に含まれる反応硬化性バインダー系及びゾルゲル反応性化合物をそれぞれ硬化反応及びゾルゲル反応させて当該塗膜を硬化収縮させる際には、塗膜中で２つの反応が均一に進行するように、反応硬化性バインダー系の反応硬化とゾルゲル反応性化合物のゾルゲル反応は同時に行う方が好ましい。架橋反応が不均一になると、ヒゲを生じ易いからである。
【００９６】
本発明に係る硬化収縮性パターン形成用材料を支持体上に所定のパターン状に塗布する際には、パターン形成用材料として第一及び第二のパターン形成用材料を用意し、第一のパターン形成用材料を支持体上に所定のパターン状に塗布して当該第一のパターン形成用材料の塗膜を形成した後、当該塗膜に含まれる反応硬化性バインダー系及びゾルゲル反応性化合物をそれぞれ硬化反応及びゾルゲル反応させて当該塗膜を硬化収縮させて第一の硬化パターンを形成し、同じ支持体上の第一の硬化パターンが設けられていない部分に、第二のパターン形成用材料を所定のパターン状に且つ第一のパターン形成用材料の塗膜を硬化収縮させる前に塗布するのであれば当該第一のパターン形成用材料の塗膜と接触してしまう幅に塗布して第二のパターン形成用材料の塗膜を形成した後、当該塗膜に含まれる反応硬化性バインダー系及びゾルゲル反応性化合物をそれぞれ硬化反応及びゾルゲル反応させて当該塗膜を硬化収縮させて第二の硬化パターンを形成するのが好ましい。
【００９７】
特に、支持体上の第一の硬化パターンが設けられていない部分に、前記第一のパターン形成用材料の塗膜を硬化収縮させる前に露出していた非塗工部の幅よりも広い幅に塗布して前記第二のパターン形成用材料の塗膜を形成することができる。
【００９８】
硬化収縮を全く又はほとんど生じない第一及び第二のパターン形成用材料を用いて第一の硬化パターンの間に第二の硬化パターンを形成する場合には、第一及び第二のパターン形成用材料からなる塗膜それぞれの硬化前パターンの幅は、そのまま硬化後においても第一及び第二の硬化パターンそれぞれの幅となる。この場合、第一及び第二の硬化パターンそれぞれの最小ピッチは、第一及び第二のパターン形成用材料同士の塗膜間引力も考慮した上で双方が接触しないような幅に制約される。
【００９９】
例えば、第一及び第二のパターン形成用材料が硬化収縮を全く又はほとんど生じない塗工材料であり、第一のパターン形成用材料からなる塗膜の硬化前パターンの幅がｘで、第二のパターン形成用材料からなる塗膜の硬化前パターンの幅がｙで、第一及び第二の硬化前パターンが塗膜間引力により合体しない最小幅がｚであり、第一及び第二の硬化パターンを最も近接させて形成する場合には、図３に示すように、硬化後における第一の硬化パターン１及び第二の硬化パターン２それぞれの幅は硬化前と同じくｘ及びｙであり、第一の硬化パターンのピッチはｘ＋ｙ＋２ｚとなり、第二のパターン形成用材料を塗布するために第一の硬化パターンの間に確保されるスペースの幅は、ｙ＋２ｚとなる。
【０１００】
これに対し、硬化収縮性を有する第一及び第二のパターン形成用材料を用いて第一の硬化パターンの間に第二の硬化パターンを形成する場合には、塗膜が硬化収縮するために、図２（ｂ）に示すように、通常の場合の図２（ａ）では第一の硬化パターンと第二の硬化パターンが接触してしまう幅や、第一のパターン形成用材料からなる塗膜を硬化させる前に露出していた幅よりも広い幅に第二のパターン形成用材料を塗布し、その後硬化収縮させることができるため、硬化収縮しない塗工材料を用いる場合と比べて、細線（fine line）のパターンを高精細（fine pitch）に形成することが可能となる。
【０１０１】
例えば、第一及び第二のパターン形成用材料の硬化収縮率が２０％であり、第一のパターン形成用材料からなる塗膜の硬化前パターンの幅がｘで、第二のパターン形成用材料からなる塗膜の硬化前パターンの幅がｙで、第一及び第二の硬化前パターンが塗膜間引力により合体しない最小幅がｚであり、第一及び第二の硬化パターンを最も近接させて形成する場合を考える。この場合に先ず、第一のパターン形成用材料を用いて硬化前の幅がｘの塗膜を、ピッチ幅をｘ＋ｙ＋２ｚと設定して支持体上に形成すると、第一のパターン形成用材料からなる硬化前塗膜１’、１’の間の露出面の幅は図４（ａ）に示すようにｙ＋２ｚとなるのに対して、収縮率２０％で硬化した後には第一の硬化パターン１、１の間の露出面の幅は、図４（ｂ）に示すように、０．２ｘ＋ｙ＋２ｚとなる。従って、第一のパターン形成用材料からなる塗膜を硬化させる前に露出していた幅よりも広い幅に第二のパターン形成用材料を塗布することができる。
【０１０２】
また、別の例として、第一及び第二のパターン形成用材料の硬化収縮率が２０％である場合に、先ず、第一のパターン形成用材料を用いて硬化前の幅がｘの塗膜を、硬化収縮率を見込んでピッチ幅を０．８ｘ＋ｙ＋２ｚと設定して支持体上に形成すると、第一のパターン形成用材料からなる硬化前塗膜１’、１’の間の露出面の幅は図５（ａ）に示すようにｙ＋２ｚ−０．２ｘとなるのに対して、収縮率２０％で硬化した後には第一の硬化パターン１、１の間の露出面の幅は、図５（ｂ）に示すようにｙ＋２ｚとなる。従って、第一の硬化パターン１、１の間が狭いピッチでも、幅の広い露出面を確保することができ、通常では第一の硬化パターンと第二の硬化パターンが接触してしまうピッチ幅に第二のパターン形成用材料を塗布することができる。その結果、典型例としては、カラーフィルターにおける着色層に応用でき、複数色の着色層を非常に狭いピッチで形成することが可能になる。
【０１０３】
また、被塗布面上のパターン形成用材料の硬化パターンを設けたい領域のパターン形成用材料に対する親和性を、その周囲の領域よりも相対的に高くしてから、前記パターン形成用材料の塗布を行うことによって、前述の図１（ｂ）のように単位面積当たりの塗布量（盛りつけ量）を十分に多くすることができ、塗膜がやせ細っていない優れた形状の硬化パターンを形成できるので好ましい。
【０１０４】
パターン形成用材料に対するパターン形成領域の親和性を相対的に高める方法としては、例えば、被塗布面の濡れ性を光触媒の作用により所定のパターン状に選択的に変化させる方法がある。
【０１０５】
すなわち、オルガノポリシロキサン等のケイ素化合物のように、酸化チタン等の光触媒の作用により親水性が大幅に高くなる材料（光触媒反応性材料）がある。そこで先ず、このような光触媒反応性材料を含有する濡れ性変化層をパターン形成用材料の被塗布面に形成する。濡れ性変化層は、光触媒反応性材料と光触媒を混合した層であってもよいし、光触媒反応性材料の層と光触媒の層を重ねて設けた複合層であってもよい。或いは、濡れ性変化層は、光触媒反応性材料の層のみからなるものであってもよく、この場合にはプラスチックフィルムやプラスチック板等の基材上に別個独立に設けられた光触媒含有層支持部材と組み合わせて用いられる。
【０１０６】
上記光触媒反応性材料としてはオルガノポリシロキサンを用いることが好ましく、その中でもフルオロアルキル基を有するものが特に好ましい。オルガノポリシロキサンとしては、例えば、（１）ゾルゲル反応等によりクロロまたはアルコキシシラン等を加水分解、重縮合して大きな強度を発揮するオルガノポリシロキサン、（２）撥水牲や撥油性に優れた反応性シリコーンを架橋したオルガノポリシロキサン等のオルガノポリシロキサンを挙げることができる。
【０１０７】
上記（１）の場合、下記一般式３：
Ｙ_ｎＳｉＸ_{（４−ｎ）}
（ここで、Ｙはアルキル基、フルオロアルキル基、ビニル基、アミノ基、フェニル基またはエポキシ基を示し、Ｘはアルコキシル基またはハロゲンを示す。ｎは０〜３までの整数である。）
で示されるケイ素化合物の１種または２種以上の加水分解縮合物若しくは共加水分解縮合物であるオルガノポリシロキサンであることが好ましい。なお、ここでＹで示される基の炭素数は１〜２０の範囲内であることが好ましく、また、Ｘで示されるアルコキシ基は、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基であることが好ましい。
【０１０８】
また、特にフルオロアルキル基を含有するオルガノポリシロキサンを好ましく用いることができ、具体的には、下記のフルオロアルキルシランの１種または２種以上の加水分解縮合物、共加水分解縮合物が挙げられ、一般にフッ素系シランカップリング剤として知られたものを使用することができる。
【０１０９】
ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_９ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_４ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_８ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_５（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_７（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４Ｓｉ（ＯＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_９ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_４ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６ＣＨ_２ＣＨ_２Ｓｉ ＣＨ_３（ＯＣＨ_３）_２；
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_８ＣＨ_２ＣＨ_２Ｓｉ ＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_３（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_５（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_７（Ｃ_６Ｈ_４）Ｃ_２Ｈ_４ＳｉＣＨ_３（ＯＣＨ_３）_２；
ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３；
ＣＦ_３（ＣＦ_２）_９ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３；および
ＣＦ_３（ＣＦ_２）_７ＳＯ_２Ｎ（Ｃ_２Ｈ_５）Ｃ_２Ｈ_４ＣＨ_２Ｓｉ（ＯＣＨ_３）_３。
【０１１０】
また、上記の（２）の反応性シリコーンとしては、下記一般式４で表される骨格をもつ化合物を挙げることができる。
【０１１１】
【化２】

【０１１２】
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。
【０１１３】
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。
【０１１４】
また、光触媒としては、例えば、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）等の粒子を用いることができ、その中でも酸化チタン（ＴｉＯ_２）が特に好ましい。
【０１１５】
上記光触媒反応性材料に、必要に応じてバインダー、溶剤、光触媒及び他の成分を混合して塗工材料を調製し、パターン形成用材料の被塗布面に塗布することにより濡れ性変化層を形成することができる。また、光触媒に、必要に応じてバインダー、溶剤及び他の成分を混合して塗工材料を調製し、パターン形成用材料の被塗布面又は別個独立した基材上に塗布することにより光触媒含有層を形成できる。濡れ性変化層は、パターン形成用材料と接触する位置に配置されている必要があることから、パターン形成用材料の被塗布面の最表面に配置するのが好ましいが、濡れ性変化層の機能を発揮できる限り、その上に別の層を付加的に形成しても良い。例えば、薄い光触媒含有層はパターン形成用材料が浸透して接触可能であり、濡れ性変化層の下側に限られず、上側にも配置できる。
【０１１６】
濡れ性変化層を形成した後、被塗布面のパターン形成用材料を塗布すべき領域の周囲に選択的に光を照射する。選択的照射は、マスク露光或いはレーザー描写等の方法により行うことができる。光は、光触媒を活性化させることができる限り、どの方向からを照射してもよい。すなわち、濡れ性変化層には通常、上側から光を照射するが、被塗布体が光透過性を有する場合には、下側（被塗布面側）から光を照射して光触媒を活性化させることができる。
【０１１７】
濡れ性変化層が光触媒を含有せず、濡れ性変化層に隣接して光触媒含有層も設けられていない場合には、別個独立に用意した光触媒含有層支持部材の光触媒含有層を濡れ性変化層に接触させて重ね合わせた状態で光を照射してから、当該光触媒含有層支持部材を取り除く。通常は、光触媒含有層支持部材の基材として光透過性を有するものを使用し、光触媒含有層支持部材の上から光を照射するが、被塗布体が光透過性を有する場合には、下側（被塗布面側）から光を照射して光触媒を活性化させることができるため、光触媒含有層支持部材の基材は不透明であってもよい。
【０１１８】
パターン形成用材料の被塗布面に設けた濡れ性変化層に光触媒が作用する条件下で選択的照射を行うと、当該被塗布面において、パターン形成用材料を塗布すべき領域の周囲は親水性が高くなってパターン形成用材料に対する親和性が低くなり、パターン形成用材料を塗布すべき領域内は、その結果として周囲よりも相対的にパターン形成用材料に対する親和性、すなわち濡れ性が高くなる。このようにして、パターン形成用材料の塗布領域を制限することにより、単位面積当たりの塗布量を増やすことが可能である。
【０１１９】
このようにして、本発明に係る硬化収縮性パターン形成材料を用いてパターンを形成すると、収縮率が最大２０％以上で、２０μｍの孤立線のパターン形成が可能であり、ヒゲもタックもなく、ストレート性や平滑性が良好で、透明性も良好であり、断面形状は順テーパーであり、硬度もカラーフィルターの着色層やブラックマトリックスにとっては充分である、良好なパターンが得られる。
【０１２０】
得られたパターンは、反応硬化性バインダー系の反応硬化物及び硬化収縮性化合物の反応硬化物（例えばゾルゲル反応性化合物の重縮合物）により形成された架橋結合のネットワーク中に着色剤が包み込まれたマトリックス構造を有している。着色剤が架橋結合のネットワーク中に包み込まれた構造をとることにより、形成されたパターンの耐熱性、耐光性が向上するという効果が得られる。
【０１２１】
以上のように、本発明に係るパターン形成方法は、カラーフィルターの着色層のような細部や、細線（fine line）のパターンを高精細（fine pitch）に形成することが必要とされる種々の着色塗膜を形成するのに利用できるが、特に、カラーフィルターの着色層（画素）やブラックマトリックスを形成するのに適している。
【０１２２】
次に、本発明に係るカラーフィルターについて説明する。本発明に係るカラーフィルターは、本発明に係る硬化収縮性パターン形成用材料を用いて形成した着色層又はブラックマトリックスを備えることを特徴とする。
【０１２３】
本発明に係るカラーフィルターは、反応硬化性バインダー系と硬化収縮性化合物との混合物の反応硬化物により形成された架橋結合のネットワーク中に着色剤が包み込まれたマトリックス構造を有する着色層又はブラックマトリックスを備えることが、耐熱性、耐光性の点から、より好ましい。
【０１２４】
なお、着色剤として顔料を用いる場合には、架橋結合のネットワークに包まれた顔料が周囲のゲル化した重合体と化学結合するので、耐熱性、耐光性が特に向上する。
【０１２５】
カラーフィルターは、透明基板に所定のパターンで形成されたブラックマトリックスと、当該ブラックマトリックス上に所定のパターンで形成した画素部と、必要に応じて当該画素部を覆うように形成された保護膜を備えている。保護膜上に必要に応じて液晶駆動用の透明電極が形成される場合もある。また、ブラックマトリックス層が形成された領域に合わせて、透明電極板上若しくは画素部上若しくは保護膜上に柱状スペーサーが形成される場合もある。
【０１２６】
画素部は赤色パターン、緑色パターン及び青色パターンがモザイク型、ストライプ型、トライアングル型、４画素配置型等の所望の形態で配列されてなり、ブラックマトリックスは各着色パターンの間及び画素部形成領域の外側の所定領域に設けられている。画素部は顔料分散法、印刷法、電着法、染色法等、様々な方法で形成できるが、上記本発明に係る硬化収縮性パターン形成用材料を用いて形成した着色層を備えるのが好ましい。すなわち、赤、緑、青の着色剤を含有する各々の本発明に係る硬化収縮性パターン形成用材料を、支持体上に所定のパターン状にスクリーン印刷により塗布して当該パターン形成用材料の塗膜を形成した後、反応硬化性バインダー系と硬化収縮性化合物とを硬化収縮させることで画素部を形成できる。
【０１２７】
反応硬化性バインダー系が光硬化系の場合には、紫外線等の光線を照射し、熱硬化系の場合にはクリーンオーブン等で加熱して、硬化させることができる。また、硬化収縮性化合物としてゾルゲル反応性化合物を用いている場合には、反応硬化性バインダー系を光又は熱硬化させて、同時にゾルゲル反応をさせて当該塗膜を硬化収縮させることによって、画素部を形成できる。画素部は、通常、１０μｍ程度の厚さに形成する。
【０１２８】
ブラックマトリックスは、顔料分散法、印刷法、電着法、染色法、クロム蒸着等、種々の方法により形成されるが、画素部と同様に、上記本発明に係る硬化収縮性パターン形成用材料を用いて形成した着色層を備えるのが好ましい。この場合、黒色顔料を着色剤として含有する硬化収縮性パターン形成用材料を調製し、画素部を形成するのと同様にして塗膜形成後、硬化反応及びゾルゲル反応をさせることにより塗膜が硬化収縮して、ブラックマトリックスが得られる。この方法においては、ブラックマトリックスを通常、１０μｍ程度の厚さに形成する。
【０１２９】
保護膜は、光又は熱硬化性を有する透明樹脂組成物の塗工液を、スピンコーター、ロールコーター、スプレイ、印刷等の方法により塗布し反応硬化させることによって形成できる。保護膜は、例えば、２μｍ程度の厚さに形成する。スピンコーターを使用する場合、回転数は５００〜１５００回転／分の範囲内で設定する。
【０１３０】
保護膜上の透明電極は、酸化インジウムスズ（ＩＴＯ）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ）等、およびそれらの合金等を用いて、スパッタリング法、真空蒸着法、ＣＶＤ法等の一般的な方法により形成され、必要に応じてフォトレジストを用いたエッチング又は治具の使用により所定のパターンとしたものである。この透明電極の厚みは２０〜５００ｎｍ程度、好ましくは１００〜３００ｎｍ程度とすることができる。
【０１３１】
透明電極上の柱状スペーサーは、光硬化性を有する樹脂組成物の塗工液をスピンコーター、ロールコーター、スプレイ、印刷等の方法により塗布し、フォトマスクを介する紫外線照射により露光し、アルカリ現像後、クリーンオーブン等でポストベークすることにより形成できる。柱状スペーサーは、例えば、５μｍ程度の高さに形成される。スピンコーターの回転数も保護膜を形成する場合と同様に、５００〜１５００回転／分の範囲内で設定すればよい。
【０１３２】
このようにして製造されたカラーフィルターは、反応硬化性バインダー系と硬化収縮性化合物との混合物の反応硬化物により形成された架橋結合のネットワーク中に着色剤が包み込まれたマトリックス構造を有する着色層又はブラックマトリックスを備える場合には、耐熱性、耐光性に優れるという効果を有する。また、本発明に係るカラーフィルターは、製造工程が比較的簡単な印刷法において製造されるため、カラーフィルターの製造方法として現在の主流の顔料分散法を用いたカラーフィルターに比べて、安価に製造でき、コスト競争力を有するという、コスト面の効果も有する。
【０１３３】
なお、本発明に係るカラーフィルターについて、液晶表示装置用カラーフィルターを代表例として説明したが、本発明は、他方式の表示装置用のカラーフィルター、例えばＥＬ（エレクトロルミネッセンス）デバイスのカラーフィルターにも適用可能である。ＥＬデバイスは、ＲＧＢ各色のＥＬ素子をマトリックス状に配列し、各色の発光を制御すればフルカラー表示可能であるが、ＥＬ素子の光取り出し側（鑑賞者側）にカラーフィルターを配置することにより、発色光を変調させて表示性能を向上させることができる。
【０１３４】
【実施例】
［実施例１〜５］
（１）パターン形成用材料の作製
（実施例１〜３）
＜硬化収縮性化合物の調製＞
超微粒子シリカであるＡＥＲＯＳＩＬ２００（比表面積２００ｍ^２／ｇ、平均粒子径１２ｎｍ、シラノール基密度２．５個／ｎｍ^２）（日本アエロジル（株））２０ｇを流動化させながら、表１の組成のアルキルアルコキシシランを１．０ｇ、水を５０ｇ、さらに塩化メチレンを５０ｇ、１重量％トリエチルアミン水溶液を１０ｇ、ベンジルトリエチルアンモニウムクロライドを３ｍｍｏｌ加え、８０℃にて２４時間撹拌・混合した。２４時間後、１２０℃まで温度を上昇させ、還流状態でさらに３時間撹拌させた後、有機層を抽出後、エバポレータにより溶媒の除去と、副生成物のアルコールを回収除去した。このようにして、アルキルアルコキシシラン処理によりシリカ表面へアルキル基を導入した硬化収縮性化合物を得た。
【０１３５】
【表１】

【０１３６】
＜顔料分散レジストインキ＞
表２の組成で混合し、ビーズミルを用いて２４時間分散して、顔料分散液を得た。表３の組成で均一に混合し、孔径２μｍのフィルターでろ過して各色の顔料分散レジストインキを得た。
【０１３７】
【表２】

【０１３８】
【表３】

【０１３９】
＜パターン形成用材料＞
上記得られた製造例４〜６の顔料分散レジストインキに対して、上記得られた硬化収縮性化合物を１０重量％添加して、実施例１〜３のパターン形成用材料を得た。
【０１４０】
（実施例４）
＜硬化収縮性化合物＞
超微粒子シリカであるＡＥＲＯＳＩＬ２００（比表面積２００ｍ^２／ｇ、平均粒子径１２ｎｍ、シラノール基密度２．５個／ｎｍ^２）（日本アエロジル（株））とフッ化アルキルシラン（ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＣ２Ｈ５）_３）とテトラエトシシランを重量比で２：７：１で混合して、硬化収縮性化合物を得た。
＜パターン形成用材料＞
上記実施例１〜３までと同様にして得られた顔料分散レジストインキに対して、上記得られた硬化収縮性化合物を１０重量％添加して、実施例４のパターン形成用材料を得た。
【０１４１】
（比較例１〜３）
上記製造例４〜６の顔料分散レジストインキを比較例１〜３とした。
【０１４２】
（２）パターン形成
上記で得られた実施例１〜４及び比較例１〜３のパターン形成用材料をステンレスメッシュ版（東京プロセス（株）、２５０メッシュ、５３μｍ厚）を用いて、ＰＥＴフィルム（厚さ１８５μｍ、コロナ放電処理により予め表面活性化ないし疎面化処理を施したもの）上にスクリーン印刷（スクリーン印刷機：ニューロング（株）製）をし、自然乾燥をした。乾燥膜厚７μｍのパターン形成用材料に、マスクにより所定のパターンを通して、ＵＶ波長３００〜４５０ｎｍ範囲、照射エネルギー量５０ｍＪ／ｃｍ^２となるようにＵＶ照射した。レジスト材料を積層したスクリーン紗は、ステンレスメッシュ（東京プロセスサービス（株）製ＳＴ５９０ＣＡＬＨ、５９０メッシュ、紗厚２８μｍ、線径１３μｍ、空間率４９％）を使用した。方形枠（ＳＵＳ４０４型、４４０ｍｍ×４４０ｍｍ）に対して、紗張り機を使用してスクリーン紗を固定した。紗張力は、２０００〜２３００Ｎ／ｍｍ、スクリーン紗角度３４．１度とした。スクリーン紗はアルミナ微細分研磨材により、紗部両面を研磨処理したメッシュ版とした。さらに、メッシュ版に接着層用の樹脂ＡＣＡ−２１０Ｐ（ダイセル工業（株）製、商品名サイクロマーＰ）を塗布後に自然乾燥させ、その上層に合成した感光性樹脂を紗両面にスリット塗布しＨＡＤＯＰ印刷版とした。印刷機は、日本ニューロング（株）製を用いた。スキージは機械的強度および耐溶剤性からウレタンゴムを使用した。印刷基材には、１８５μｍＰＥＴフィルムを用いた。基材はインキ密着性を良好とするため、コロナ放電処理を予め施したものを使用した。
【０１４３】
ＵＶ硬化感度およびＰＥＴフィルムとの密着性より、ＤＰＨＡとＳＲ３９９を基本材料とした。ＳＲ３９９のみの感度は６０ｍＪ／ｃｍ^２と比較的高いが、硬化膜収縮率が大きいため他の感光性樹脂との積層化は不可能であった。また、インキに使用した場合、同様にＵＶ硬化収縮率が大きいため皮膜にクラックが生じた。そこでビスフェノールＡのＥＯ変性アクリレートで比較的炭化水素鎖が長い構造のＡ−ＢＰＥ２０を少量添加することで、光硬化物に柔軟性をもたせ、かつＰＥＴとの密着力を上げることができた。ただし積層構成させた場合、現像性を含めてステンレスメッシュとの密着性からパターン解像性が悪くなった。最終的に最適化したのは、ＳＲ３９９とビスフェノールＡ型エポキシジアクリレート（１８０Ｓ７０）を混合使用することで、積層密着性も改善されＨＡＤＯＰ版用レジストとすることができた。一方、比較として、市販品アクリル樹脂ＡＣＡ−２１０ＰとＳＲ３９９を組み合わせた。感度は５０ｍＪ／ｃｍ^２と高い。ＡＣＡ−２１０Ｐはアクリル酸由来の酸価との関係より現像速度が速いためと思われるが、現像時間の制御が困難であった。ただし、ステンレスメッシュとの密着性は特に良好であるため、ステンレスメッシュと他の感光性樹脂との積層に用いる接着層用樹脂としてこれを選択した。
【０１４４】
試作した感光性樹脂に対して、テストパターンを描画したフィルムを密着して、２ｋＷ超高圧水銀灯で露光後、現像液をスプレーして未露光部を洗い流したところ、ネガ型パターン画像を得た。得られた画像に対して版に必要な物性評価を行った。その結果を表４に示す。外観を一定の評価基準（○△×の３段階）で評価した。
【０１４５】
【表４】

【０１４６】
ダイナミック硬度は、圧子を押し込んで行く過程の荷重として押し込み深さから得られる硬さで、試料の塑性変形だけでなく、弾性変形も含んだ強度特性である。試験荷重Ｐ（ｍＮ）、圧子の試料への侵入量（押し込み深さ）Ｄ（μｍ）としたとき、ダイナミック硬度ＤＨは次式で定義される。
【０１４７】
ＤＨ＝αＰ／Ｄ^２
なお、αは圧子形状による定数で事前に換算表より得られる。すなわち、本測定では１１５°三角すい圧子を用いているので、α＝３．８５８４を利用した。解像度を重視する場合にはＴｙｐｅ−Ｂが選択できるが、感度および基板−版間の弾性力を重視する場合は、ダイナミック硬度４６ｍＮ／μｍ^２を有するＴｙｐｅ−Ａが選択できた。以上より、解像度と積層機能化を考慮したＨＡＤＯＰ版用レジスト材料が得られた。
【０１４８】
ＨＡＤＯＰ版に使用する感光性樹脂は合成できたので、これをメッシュ上に構成すること検討した。ＨＡＤＯＰ機能化モデルに従って版の積層機能化を検討した。接着層樹脂として、アクリル可溶性樹脂ＡＣＡ−２１０Ｐを選択した。接着層は、ＡＣＡ−２１０Ｐを３０重量部、ＳＲ３９９＋ＤＰＨＡ（混合比１：１）２０重量部、光重合開始剤イルガキュアー９０７（チバガイギー製）１重量部、溶剤トルエン４９重量部とした。製版感度は、５０ｍＪ／ｃｍ^２であった。乾燥膜厚で５μｍとなるように塗布し、目止め処理を行った。次にインキ搭載面側には、感光性樹脂層として感光性樹脂Ｔｙｐｅ−Ｂを乾燥膜厚２０μｍになるように塗布し、露光、現像処理を行った。顕微鏡にて紗開口部を観察し、最小オープニング幅が８μｍに解像されていることを確認した。
【０１４９】
さらに、もう一方の裏面には、感光性樹脂層として感光性樹脂Ｔｙｐｅ−Ａを乾燥膜厚５μｍになるように塗布し、タックがなくなる程度に７０℃１５分程度乾燥した。さらに、感光性樹脂Ｔｙｐｅ−Ｂを乾燥膜厚５μｍとなるように塗布し、タックがなくなる程度に７０℃１５分程度乾燥した。上述同様の現像、露光により必要なパターンを追従する感光性樹脂Ｔｙｐｅ−ＡとＴｙｐｅ−Ｂよりなるバッククッション層を設けた。顕微鏡にて紗開口部を観察し、最小オープニング幅が８μｍに解像されていることを確認した。なお、感光性樹脂積層を繰り返した後、両面一括同時露光を行い、一括現像して版形成が可能であることも確認した。必要となる弾性力をダイナミック硬度で指標した場合、最適なダイナミック硬度は４０〜５０ｍＮ／μｍ^２であった。これにより、基板とＨＡＤＯＰ版との間にかかる印刷圧力が緩和されると同時に、基板密着性が向上した版が作製できた。照射部分を硬化させた後、非照射部分の未硬化の部分を０．１％ＫＯＨ水溶液により現像し、画像膜を形成した。更に形成された画像膜を１２０℃で２時間保持し、硬化反応及びゾルゲル反応を行って耐水・耐溶剤性を改善した。ステンレスメッシュ版には、パターン形成用材料との密着性改善を目的として、予めシランカップリング剤（γ−メタクリロキシプロピルトリメトキシシラン０．１％水溶液）で３０分浸析後、熱乾燥したものを使用した。
【０１５０】
（結果）
実施例１〜４については、２５μｍのストライプパターンが形成でき、収縮率は２０％であった。両端部にジャギーのない、ストレート性の高いパターンが得られた。一方、比較例１〜３については、３０μｍのストライプパターンが形成でき、収縮はしなかった。
【０１５１】
（３）接触角測定
７０５９ガラス基板を、熱硫酸で１分間浸漬後、５％ＮａＯＨ水溶液を用いて超音波洗浄にて中和し、表面を清浄なものとした。次に、実施例１〜３、比較例１〜３のパターン形成用材料を１滴滴下し、室温にて１分間放置後、接触角測定装置により、基板と上記パターン形成用材料とのなす角度を測定した。
【０１５２】
（結果）
実施例１〜３は、接触角が約８５度であった。実施例４は、接触角が約１１０度と大きかった。一方、比較例１〜３は、接触角が約６５度と小さかった。
【０１５３】
（４）カラーフィルターの形成（実施例５）
実施例１〜３で得られたパターン形成用材料を用いて、ＥＬ素子対応用カラーフィルターを作製した。フレキシブルＰＥＴ基板上に、各４０μｍの良好なストライプラインのＲＧＢ画素を形成することができた。
【０１５４】
［実施例６〜９］
（１）パターン形成用材料の作製
（実施例６）
テトラエトキシシラン１０ｇに、溶媒としてのエタノールを１００ｍｌ、ゾルゲル反応（加水分解重縮合）をさせるための水を５０ｍｌ、さらに触媒である０．３Ｎの過酢酸１ｍｌとアルミニウムアセチルアセタナート０．５Ｎを３ｍｌ加えて、高透明なゾル溶液を得た。
【０１５５】
ついで、このゾル溶液の添加量がパターン形成用材料の総重量の５重量％となるように、このゾル溶液を５ｇと、下記組成のＵＶ硬化樹脂（反応硬化性バインダー系）２００ｇと（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ３６）（着色剤）４０ｇとを（３−メトキシブチルアセテート：ＰＧＭＥＡ ５：５）（溶剤）２００ｍｌに混合し、ビーズミルにて分散を６時間行い、硬化収縮性パターン形成用材料を得た。
【０１５６】
[ＵＶ硬化樹脂の組成]
・３元共重合系アクリル樹脂（ベンジルメタクリレート（ＢｚＭＡ）：スチレン（Ｓｔ）：メタクリル酸（ＭＡＡ） ３：５：２） ５５重量部
・モノマー（ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）：トリメチロールプロパントリメタクリレート（ＴＭＰＴＡ）：エトキシ化ビスフェノールAジアクリレート ５:３：２） ３５重量部
・光重合開始剤 イルガキュアー９０７（チバガイギー社製） １０重量部
（実施例７）
実施例６におけるテトラエトキシシランの代わりにテトラメトキシシランを用いた以外は、実施例６と同様にして実施例７の硬化収縮性パターン形成用材料を得た。
【０１５７】
（実施例８）
実施例６におけるテトラエトキシシランの代わりにテトラメトキシシランを１０ｇ、及びアルミニウムブトキシドを５ｇ用いた以外は、実施例６と同様にして実施例８の硬化収縮性パターン形成用材料を得た。
【０１５８】
（実施例９）
実施例６におけるテトラエトキシシランの代わりにメチルトリメトキシシランを１０ｇ、用いた以外は、実施例６と同様にして実施例９の硬化収縮性パターン形成用材料を得た。
【０１５９】
（２）パターン形成
つぎに、実施例６〜９のパターン形成用材料を５０μｍの線幅のスクリーンマスクを用いて、ガラス基板上にスクリーン印刷をし、７０℃、湿度８０％以上の条件下で約１０時間保持し、硬化反応及びゾルゲル反応を行った。
【０１６０】
（３）評価
（３−１）収縮率
収縮率（％）＝光照射後７０℃で１時間硬化後の作製パターンサイズ／硬化前の作製パターンサイズ×１００として求めた。
【０１６１】
（３−２）針進入試験硬度
ダイナミック硬度試験機（島津製作所）を用いて測定した。
【０１６２】
（３−３）カラーフィルター透明性
可視紫外部吸収スペクトル測定装置にて、分光特性スペクトルを測定し、特に可視部域（３５０ｎｍ〜７００ｎｍ）での波長ピークの高さ（吸収量）が８０％以上であるものを○とした。
【０１６３】
（結果）
実施例６〜９の硬化収縮後の孤立線の線幅、収縮率、針進入試験硬度、カラーフィルター透明性の結果を表５に示す。
【０１６４】
【表５】

【０１６５】
得られた硬化パターンは、いずれもヒゲがなく、線のストレート性は良好で、線のタックがなく、平滑性も良好で、断面形状は順テーパーあった。実施例７は、実施例６に比べ乾燥性が速く、実施例８は、実施例６に比べ収縮率が大きく、実施例９は、実施例６に比べ粘度が高かった。
【０１６６】
【発明の効果】
以上に述べたように、本発明に係る硬化収縮性パターン形成用材料は、少なくとも、反応硬化性バインダー系を構成する１又は２以上の成分、硬化収縮性化合物及び着色剤からなり、硬化収縮性を有するものであり、本発明に係るパターン形成方法によれば、硬化収縮性パターン形成用材料を硬化して形成したパターンは塗布時よりも細く、パターン形成に用いた印刷法の技術的限界を超えた細線化を実現することも可能である。
【０１６７】
従って、非常に細かいパターンを形成できるので開口率を大きくすることができ、典型例としてはブラックマトリックスのパターン形成に応用できる。
【０１６８】
また、本発明によれば、通常では第一のパターンと第二のパターンが接触してしまう幅や、硬化収縮させる前に露出していた非塗工部の幅よりも広い幅に、第二のパターン形成用材料を塗布して、その後、硬化収縮させることができるため、硬化収縮しない材料を用いる場合と比べて、細線（fine line）のパターンを高精細（fine pitch）に形成することが可能になる。従って、パターン形成に用いた印刷法の技術的限界を超えた高精細化を実現することも可能である。典型例としては、複数色の着色層を非常に狭いピッチで形成することが可能であることから、カラーフィルターの着色層を形成する場合に応用できる。
【０１６９】
また、反応硬化性バインダー系の反応硬化物と硬化収縮性化合物との混合物により形成された架橋結合のネットワーク中に、着色剤が包み込まれたマトリックス構造を有する場合には、耐熱性、耐光性が向上したパターンを形成することができる。
【０１７０】
本発明に係るカラーフィルターは、本発明に係る硬化収縮性パターン形成用材料を用いて形成した着色層又はブラックマトリックスを備える。本発明に係るカラーフィルターは、反応硬化性バインダー系と硬化収縮性化合物との混合物の反応硬化物により形成された架橋結合のネットワーク中に着色剤が包み込まれたマトリックス構造を有する着色層又はブラックマトリックスを備える場合には、耐熱性、耐光性に優れるという効果を有する。また、本発明に係るカラーフィルターは、製造工程が比較的簡単な印刷法において製造されるため、カラーフィルターの製造方法として現在の主流の顔料分散法を用いたカラーフィルターに比べて、安価に製造でき、コスト競争力を有するという、コスト面の効果も有する。
【図面の簡単な説明】
【図１】硬化収縮性パターン形成用材料が収縮した状態を模式的に示す図である。
【図２】通常のパターン形成用材料を用いてパターンを形成した状態（ａ）と本発明に係る硬化収縮性パターン形成用材料を用いて硬化収縮させてパターンを形成した状態（ｂ）を模式的に示す図である。
【図３】通常のパターン形成用材料を用いてパターンを形成した状態の一例を模式的に示す図である。
【図４】本発明に係る硬化収縮性パターン形成用材料を硬化収縮させる前後の状態の一例を模式的に示す図である。
【図５】本発明に係る硬化収縮性パターン形成用材料を硬化収縮させる前後の状態の他の一例を模式的に示す図である。
【符号の説明】
１…第一の硬化パターン
１’…第一のパターン形成用材料からなる硬化前塗膜
２…第二の硬化パターン[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curing shrinkable pattern forming material when forming various patterns by a printing method or other methods, a pattern forming method, and a color filter produced using the curing shrinkable pattern forming material, Specifically, it realizes pattern formation that requires fine lines and fine pitches, and is useful for curing shrinkable pattern forming materials, pattern forming methods, and the like for colored layers and black matrices of color filters. The present invention relates to a color filter that realizes fine line and fine pitch pattern formation using a curing shrinkable pattern forming material and can be suitably used for a liquid crystal display device, an organic EL display element, and the like.
[0002]
[Prior art]
The development of printing technology has been remarkable in recent years, especially in screen printing, the process has been improved by the appearance of high-quality platemaking materials, high-precision printing machines, and printing inks with excellent characteristics, and the printing image accuracy has been dramatically improved. As a result, many electronic components such as high-density multilayer printed boards, thick film hybrid ICs, liquid crystal display tubes, solar cells, membrane switches, and the like are manufactured using screen printing. Screen printing allows you to freely print individual figures in individual thicknesses with individual inks, so it is essential for the production of electronic components, etc. Is suitable.
[0003]
Such screen printing has not yet been applied to color filters used in liquid crystal display devices. The performance required for the color filter is straightness of the line, no skin (smoothness of the surface), and the line width of the line. When screen printing is applied to the color filter, high-definition (fine It is necessary to draw a fine line in the pitch.
[0004]
As a method for producing a color filter, there are many conventional techniques in the ink jet method. For example, Patent Document 1 discloses a method for producing a color filter in which a colored layer (pixel portion) is formed by spraying ink on a substrate surface by an ink jet method. Are listed. The ink jet method is a kind of on-demand printing, and is essentially suitable for the production from a small number to a single number, but for fine color filter applications, it is necessary to draw fine lines with higher definition.
[0005]
Further, for example, Patent Document 2 describes an ink material used for a color filter, which is an organic color material, a binder containing at least one selected from a metal alkoxide group consisting of silicon alkoxide, and the like, and alcohols. It is disclosed that it is composed of a solvent, and is a dye fixed in a polymer network in the process of printing and coating on a glass plate and slowly hydrolyzing and condensation polymerizing at about 30 ° C. to produce a color filter. In addition, it is described that a dye or a pigment fixed in a micropore of a pigment or a polymer is chemically bonded to improve light resistance.
[0006]
However, according to these conventional techniques, a fine line pattern cannot be formed with a fine pitch.
[0007]
On the other hand, as a conventional technique for forming a desired pattern on a substrate by applying screen printing, for example, Patent Document 3 describes a method for producing a glass with a functional thin film. A method of forming a functional thin film by screen printing a solution containing a viscous agent and baking the printed film is disclosed.
[0008]
Further, for example, Patent Document 4 describes an ink for forming a functional thin film, and an organic metal oxide or at least one of metal alkoxide, metal acetylacetonate, and metal fatty acid salt as a glass component. Metal oxide sol or a mixture thereof, nitrocellulose as a thickening component, ethyl carbitol or butyl carbitol as a solvent, or a mixture thereof, and 0.01 wt% as a coloring component and a coloring component in this ink Those containing 2 wt% or less of organic pigments or organic dyes or mixtures thereof are disclosed. By setting the viscosity of the ink to 200 ps or more and 300 ps or less, a decrease in refractive index and durability can be suppressed, and screen printing can be performed. It is possible to increase the viscosity of the ink to a viscosity suitable for Is described.
[0009]
However, with these conventional technologies, fine line patterns cannot be formed with a fine pitch, and the line width that can be printed accurately and accurately with current screen printing is 200 μm, which is a further improvement. Thus, the line width is considered to be 100 μm or 50 μm, but the technology has not been established yet.
[0010]
As the color filter manufacturing method, the current mainstream is the pigment dispersion method, but the pigment dispersion method has a problem of high cost, and the technology for manufacturing a color filter in a printing method with a relatively simple manufacturing process is costly. It is also required from the point of competitiveness.
[0011]
[Patent Document 1]
JP 59-75205 A
[Patent Document 2]
JP-A 63-48372
[Patent Document 3]
Japanese Patent Laid-Open No. 3-126642
[Patent Document 4]
Japanese Patent Laid-Open No. 10-17335
[0012]
[Problems to be solved by the invention]
The present invention has been accomplished in view of the above-described actual circumstances, and a first object thereof is a material for forming a curing shrinkable pattern capable of forming a fine line pattern with a fine pitch. Is to provide.
[0013]
A second object of the present invention is to provide a pattern forming method capable of forming a fine line pattern with a fine pitch using the curing shrinkable pattern forming material according to the present invention. It is to provide.
[0014]
A third object of the present invention is to provide a color filter in which a colored layer such as a pixel portion or a black matrix is formed using the curing shrinkable pattern forming material or the pattern forming method according to the present invention.
[0015]
The present invention solves at least one of these objects.
[0016]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, a material for forming a shrinkable shrinkable pattern according to the present invention comprises at least one or two or more components constituting a reactive curable binder system, a cured shrinkable compound, and a colorant. It is characterized by having.
[0017]
By applying the curing shrinkable pattern forming material according to the present invention to the required pattern shape in anticipation of the shrinkage rate at the time of curing, it is possible to form a predetermined fine line pattern after curing. become. Therefore, it can be used to form various colored coatings that require fine details such as the colored layers of color filters and fine line patterns to be formed with a fine pitch, In particular, it is suitable for forming a colored layer (pixel) of a color filter or a black matrix.
[0018]
A sol-gel reactive compound can be used as the curing shrinkable compound. Since the sol-gel reactive compound has the property of being cured and contracted by the sol-gel reaction, when the sol-gel reactive compound is blended with a reactive curable binder material, a coating film formed by coating (and drying as necessary) is formed. When cured, the sol-gel reactive compound in the coating film shrinks due to gelation, and finally a cured pattern is obtained in which the line width is shrunk by 20% or more than the size of the applied pattern.
[0019]
In addition, since it has a matrix structure in which a colorant is encapsulated in a cross-linking network formed by a reaction cured product of a reactive curable binder system and a polycondensate of a sol-gel reactive compound, it has heat resistance and light resistance. A pattern with improved properties can be formed.
[0020]
The sol-gel reactive compound is preferably a hydrolytic polycondensable compound, more specifically preferably contains at least a metal alkoxide, and more preferably contains at least a silicon alkoxide.
[0021]
The reaction curable binder system is composed of at least a radical polymerizable compound and a photo radical initiator and is a photo curable pattern forming material, or is composed of at least an epoxy resin and is a thermo curable pattern forming material. It is preferable.
[0022]
Also, if the surface tension of the curing shrinkable pattern forming material is low, the coating amount per unit area (mounting amount) cannot be increased sufficiently, and after curing shrinkage, the coating is applied as shown in FIG. The film becomes thin and the width becomes non-uniform so that the pattern cannot be formed with high definition. With regard to the material for forming a shrinkable shrinkable pattern according to the present invention, in particular, when the contact angle is adjusted to be 80 degrees or more on the glass substrate as an index of surface tension, the coating amount per unit area (mounting amount) ) Can be increased sufficiently, as shown in Fig. 1 (b), the coating film can be cured and contracted without thinning, the width becomes uniform, and the pattern becomes finer (fine pitch). Since it can form, it is preferable.
[0023]
In terms of adjusting the contact angle to 80 degrees or more, the curing shrinkable compound is at least one sol-gel selected from a reactive product of ultrafine silica and alkylalkoxysilane, and SiAlOn (n is 30 or less). Preference is given to using reactive compounds.
[0024]
Moreover, from the point which adjusts a contact angle to 80 degree | times or more, as a surface tension improvement agent, the organic-inorganic composite with which the two functional groups of the acrylate group of the compound which has an acrylate group, and the alkoxysilane compound which has an alkoxy group were made to react It is preferable to further contain at least one compound selected from.
[0025]
Furthermore, from the point of adjusting the contact angle to 80 degrees or more, one or more components constituting the reaction curable binder system, a curing shrinkable compound, a colorant, and other components blended as necessary. It is preferable to dissolve or disperse using at least one solvent selected from isophorone, ethyl sorbacetate, and methoxyethoxyethanol.
[0026]
The pattern forming method according to the present invention for solving the above-mentioned problems is that after a pattern forming material having curing shrinkage is applied on a support in a predetermined pattern to form a coating film of the pattern forming material The coating film is cured and shrunk. When the pattern forming material according to the present invention is used as a pattern forming material, after forming the coating film on the support, a reactive curable binder system and a curing shrinkable compound contained in the coating film are used. The coating film can be cured and shrunk by a curing reaction, and a fine line pattern can be formed by this method. As a typical example, when the present invention is applied to pattern formation of a black matrix of a color filter, a very fine pattern can be formed, so that the aperture ratio can be increased.
[0027]
In order to form the coating film, the pattern forming material can be directly printed in a predetermined pattern by a pattern printing method and cured and shrunk, whereby thinning and fine pitch can be achieved.
[0028]
When forming a pattern according to the present invention, first and second pattern forming materials are prepared as the pattern forming material, and the first pattern forming material is applied in a predetermined pattern on the support. Then, after forming a coating film of the first pattern forming material, it is cured and contracted to form the first cured pattern, and the first cured pattern on the same support is not provided with the first cured pattern. If the second pattern forming material is applied in a predetermined pattern and before the coating film of the first pattern forming material is cured and shrunk, it will come into contact with the coating film of the first pattern forming material. It is preferable to form the second cured pattern by applying the width to form a coating film of the second pattern forming material and then curing and shrinking the coating film.
[0029]
In a typical embodiment, the non-coated portion exposed before the coating film of the first pattern forming material is cured and shrunk on a portion of the support where the first cured pattern is not provided. A coating film of the second pattern forming material is formed by applying a width wider than the width.
[0030]
According to the present invention, as shown in FIG. 2B, the width at which the first cured pattern and the second cured pattern come into contact with each other in FIG. The second pattern-forming material can be applied to a width wider than the width exposed before the coating film made of the material is cured, and then cured and contracted. For this reason, it is possible to form a fine line pattern with a fine pitch as compared with the case of using a coating material that does not cure and shrink. As a result, as a typical example, it can be applied to a colored layer in a color filter, and a colored layer of a plurality of colors can be formed at a very narrow pitch.
[0031]
Further, the pattern forming material is applied after the affinity for the pattern forming material in the region where the cured pattern of the pattern forming material on the support is to be provided is relatively higher than the surrounding region. This is preferable because the coating amount per unit area (mounting amount) can be sufficiently increased and a cured pattern having an excellent shape in which the coating film is not thin can be formed.
[0032]
Using a color filter substrate as the support, and forming a colored layer or black matrix cured pattern on the color filter substrate using the pattern forming material makes the manufacturing process of the color filter relatively easy. This is preferable.
[0033]
In order to solve the above problems, a color filter according to the present invention includes a colored layer or a black matrix formed using the pattern forming material according to the present invention.
[0034]
Since the color filter according to the present invention is manufactured by a printing method with a relatively simple manufacturing process, the color filter can be manufactured at a lower cost than a color filter using a current mainstream pigment dispersion method as a color filter manufacturing method. It also has the cost effect of having cost competitiveness.
[0035]
The color filter according to the present invention is a colored layer or black matrix having a matrix structure in which a colorant is encapsulated in a cross-linked network formed by a reaction cured product of a mixture of a reaction curable binder system and a curing shrinkable compound. It is more preferable from the viewpoint of heat resistance and light resistance.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. In the present specification, (meth) acrylate represents acrylate and methacrylate.
[0037]
First, the curing shrinkable pattern forming material according to the present invention will be described. The curing shrinkable pattern forming material according to the present invention comprises at least one or two or more components constituting a reactive curable binder system, a curing shrinkable compound, and a colorant, and has a curing shrinkage. Is.
[0038]
By applying this curing shrinkable pattern forming material to a required pattern shape in anticipation of the shrinkage rate at the time of curing, it becomes possible to form a pattern of a predetermined fine line after curing.
[0039]
The reaction curable binder system is a component for imparting film formability and adhesion to a surface to be coated to the material for forming a shrinkable shrinkable pattern according to the present invention. When a monomer and / or oligomer is used as a component of the reactive curable binder system, the molecular weight is small, so that the fluidity is increased, and there is an effect of improving the coating suitability of the material for forming a shrinkable shrinkable pattern. In addition, the monomer and / or oligomer functions as a diluting solvent, and it is possible to dissolve or disperse other solid components without using a solvent. The liquid curing shrinkable pattern forming material does not contain a solvent. It is also possible to prepare
[0040]
As the reaction curable binder system, a photocurable binder system or a thermosetting binder system can be used. The photocurable binder system can be composed of, for example, a radical polymerizable compound and a photo radical initiator. As the radically polymerizable compound, for example, one or two or more kinds of monomers, oligomers and polymers having one or more ethylenically unsaturated bonds can be selected and used. When a polymerizable monomer and / or oligomer is used in combination, it is preferable because the film physical properties after curing can be improved.
[0041]
Specific examples of the monomer or oligomer containing an ethylenically unsaturated bond include the following polyfunctional acrylate monomers or oligomers: ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate Glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanedioldiac Rate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol (meth) acrylate, and the like can be exemplified dipentaerythritol hexa (meth) acrylate.
[0042]
As the polymer containing an ethylenically unsaturated bond, a polyfunctional acrylate monomer or oligomer polymer as described above can be used.
[0043]
Examples of photo radical polymerization initiators include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoro An amine compound or the like is used. More specifically, benzoin tosylate, benzoin benzene sulfonate, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethyl Ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)- Examples thereof include 2-hydroxy-2-methylpropan-1-one and benzophenone.
[0044]
Any one of these can be used alone or in combination. These also exist in commercial products. For example, 1-hydroxy-cyclohexyl-phenyl-ketone can be obtained from Ciba Specialty Chemicals Co., Ltd. under the trade name Irgacure 184.
[0045]
On the other hand, examples of the thermosetting binder system include an epoxy resin, and preferably further contains a curing agent such as a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid.
[0046]
As the epoxy resin, for example, a homopolymer or copolymer obtained by polymerizing one or more monomers containing an epoxy group and an ethylenically unsaturated bond as shown below can be used: glycidyl acrylate Glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, (Meth) acrylates such as methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl; o-vinylphenylglycidyl ether, m-vinylphenylglycidyl ether, p-bi Vinyl glycidyl ethers such as ruphenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3, , 5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, and 1,3,5-trihydroxymethylstyrene triglycidyl ether .
[0047]
The epoxy resin can be selected and obtained from commercially available products. For example, bisphenol F such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 (manufactured by Yuka Shell) as a bisphenol A type epoxy resin. Epicoat 807 (manufactured by Yuka Shell) as a type epoxy resin, EPPN201, 202 (manufactured by Nippon Kayaku) as a epoxy novolac type epoxy resin, EOCN102, 103S as a cresol novolak type epoxy resin, etc. Examples thereof include 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku) and Epicoat 180S (manufactured by Yuka Shell).
[0048]
Specific examples of polycarboxylic anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbaric anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic acid Examples thereof include acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.
[0049]
Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned.
[0050]
These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more.
[0051]
The cure shrinkable compound is a component for imparting cure shrinkage to the material for forming a shrinkage shrinkable pattern according to the present invention.
[0052]
Here, the curing shrinkage rate of the pattern forming material, which is an index of curing shrinkage in the present invention, can be determined as follows.
Curing shrinkage rate (%) = preparation pattern size after complete curing / preparation pattern size before curing × 100
Here, after complete curing, in the case of photocuring, it means after curing for 1 hour at 70 ° C. after light irradiation, and in the case of thermosetting, the curing shrinkage of the pattern forming material is as follows: Can be determined.
Curing shrinkage rate (%) = preparation pattern size after complete curing / preparation pattern size before curing × 100
Here, after complete curing is different depending on the type of substrate used. For example, when a plastic substrate (PET, 180 μm) is used as the substrate, it is cured at 100 ° C. for 1 hour (using an oven). In addition, when a glass substrate (7059, 1.2 mm thickness) is used as the substrate, it means after curing at 150 ° C. for 1 hour (using an oven). In addition, the term “before curing” refers to a production pattern size before light irradiation in the case of photocuring, and refers to a production pattern size before heating in the case of thermosetting.
[0053]
The pattern size is a value obtained by measuring a portion where the height of the sample coating film thickness (average value of peak values) is uniform from the substrate using a stylus type film thickness meter (deck tack).
[0054]
Here, if the cure shrinkage rate is too large, problems such as disconnection occur, and if the cure shrinkage rate is too small, a fine line pattern cannot be formed with high definition. A range of 1 to 30% is preferable.
[0055]
A sol-gel reactive compound can be used as the curing shrinkable compound. Since the sol-gel reactive compound has the property of curing and shrinking due to the sol-gel reaction, when the sol-gel reactive compound is blended with a reactive curable binder material, the coating film formed by coating (and drying if necessary) is cured. In this case, the sol-gel reactive compound in the coating film shrinks due to gelation, and a cured pattern is finally obtained in which the line width is shrunk by 20% or more than the size of the applied pattern.
[0056]
As the sol-gel reactive compound, a hydrolytic polycondensable compound can be used, and more specifically, a metal alkoxide can be exemplified.
[0057]
In the present invention, a metal alkoxide in which one or more alkoxyl groups are bonded to a metal atom can be used. As long as one or more alkoxyl groups are bonded to the metal atom, an atom or atomic group that does not participate in polycondensation is used. It may be combined. As such a metal alkoxide, what is represented by the following general formula 1 can be used conveniently.
Formula 1: RmM (OR ') n
(In the above formula, M is a metal atom, R may be the same or different, and an alkyl group having 100 or less carbon atoms, preferably an alkyl group having 1 to 30 carbon atoms, a halogen such as a chloro atom, a hydroxyl group, an ester group, The amide group and R ′ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, and m + n is a valence of the metal M, and m ≧ 1 and n ≧ 1).
[0058]
In the general formula 1, as the metal atom M, for example, Si, Al, P, Ti, Zr, Ge, Sn, In, Zn, Ta, or the like is used. Preferably, it is a silicon alkoxide using Si as a metal. Examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, and the following general formula 2.
[0059]
[Chemical 1]

[0060]
(In the above formula, n ≦ 4).
[0061]
Furthermore, it is preferable to use at least one metal alkoxide other than silicon alkoxide. Further, the metal alkoxide other than silicon alkoxide is preferably contained in an amount of about 10% by weight based on the silicon alkoxide. Examples of such metal alkoxides other than silicon alkoxide include trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum, tri n-propoxy aluminum, tri n-butoxy aluminum, tri sec-butoxy aluminum, tri tert-butoxy aluminum. , Tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, tetra sec-butoxy titanium, tetra tert-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-butoxy zirconium , Tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium and the like.
[0062]
The sol-gel reactive compound preferably has a highly transparent ultrafine particle, for example, an average primary particle diameter of 5 to 500 nm so as not to adversely affect the color tone.
[0063]
In the sol-gel reaction, the amount of water, pH, type of R ′ in the general formula 1, temperature, and the like are parameters that affect the reaction, and these affect the gelation time, the bulk density of the gel, the pore size distribution, etc. In order to reflect the pattern appearance and cure shrinkage, it is necessary to select appropriately.
[0064]
When the sol-gel reactive compound changes from sol to gel by hydrolysis polycondensation, it is preferable to add water in the range of 1/3 mol to 1 mol per mol of the sol-gel reactive compound.
[0065]
In the hydrolysis polycondensation reaction, a catalyst can be used, and an acid or alkali can be used as the catalyst. Examples of the acid include strong acids such as hydrochloric acid, sulfuric acid, and nitric acid, acetic acid, or peracetic acid, acid anhydrides, An acetic acid derivative such as an acetylating agent is preferred. Moreover, as an alkali, ammonia, its ammonia hydroxide, a quaternary ammonium salt, etc. are preferable. Since the water of the catalyst aqueous solution is also used for hydrolysis, it may not be necessary to add more water depending on the conditions.
[0066]
Water necessary for the hydrolysis and polycondensation reaction, and a catalyst such as acid or alkali may be blended in the solvent simultaneously with each material, or may be added later. For example, when hydrolysis and polycondensation are performed after coating, they may be added to the coating solution immediately before coating.
[0067]
A pigment or a dye can be used as the colorant, but a pigment is preferable from the viewpoint of colorability. The pigment to be used is not particularly limited, and various organic or inorganic pigments can be used. Specific examples of organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), that is, the following Color Index (CI) numbers. You can list what you have. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, etc. CI pigment red 1, CI pigment red 2, CI pigment red 3, CI pigment red 177, CI pigment red 254 and other red pigments; and CI pigment blue 15, CI pigment blue 15: 3, CI CI pigments such as CI Pigment Blue 15: 4, CI Pigment Blue 15: 6; CI pigments such as CI Pigment Green 7 and CI Pigment Green 36; CI pigments Violet 23, C.I. Pigment Violet 23:19, and the like.
[0068]
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.
[0069]
In the present invention, if the surface tension of the curing shrinkable pattern forming material is low, the coating amount per unit area (mounting amount) cannot be increased sufficiently, and after curing shrinkage, as shown in FIG. It is preferable that the surface tension is high from the viewpoint that the coating film is thin and thin and the width becomes non-uniform and the pattern cannot be formed with high definition. In the present invention, the curing shrinkable pattern forming material is preferably adjusted so that the contact angle on the glass substrate is 80 degrees or more.
[0070]
Here, the contact angle refers to a value measured on a glass substrate washed with alkali, hot sulfuric acid, and water, and can be measured by the following method. First, a 7059 glass substrate is immersed in an acid such as sulfuric acid for 1 minute and then neutralized by ultrasonic cleaning to clean the surface. At this time, surface deposits may be removed using a surfactant or the like. Next, after a drop of the sample is dropped on the substrate by a contact angle measuring device, the sample is left at room temperature for 1 minute, and then the angle formed between the substrate and the sample is measured.
[0071]
In terms of adjusting the contact angle to 80 degrees or more, the curing shrinkable compound is at least one sol-gel selected from a reactive product of ultrafine silica and alkylalkoxysilane, and SiAlOn (n is 30 or less). Preference is given to using reactive compounds. Here, the ultrafine silica means silica having an average particle diameter of 100 nm or less, and the specific surface area is 50 to 3000 m.²/ G is preferable. As the ultrafine silica, for example, Aerosil 200 (Nippon Aerosil Co., Ltd.) can be used. Examples of the alkylalkoxysilane include monomethyltrimethoxysilane, trimethylmethoxysilane, normal propylmethoxysilane, isobutyltrimethoxysilane, octadecyltrimethoxysilane, and hexadecyltrimethoxysilane. Further, a fluorinated alkylsilane can be added to them.
[0072]
Moreover, it is preferable to use SiAlOn (n is 30 or less). By setting n to 30 or less, the solubility is good and the ink can be easily formed, and the sum of the surface areas is increased and the water repellency is improved, so that the pattern forming material has a good shrinkage.
[0073]
Moreover, from the point which adjusts a contact angle to 80 degree | times or more, as a surface tension improvement agent, the organic-inorganic composite with which the two functional groups of the acrylate group of the compound which has an acrylate group, and the alkoxysilane compound which has an alkoxy group were made to react It is preferable to further contain at least one compound selected from. For example, pentaerythritol triacrylate and trimethylolpropane triacrylate can be used as the polyfunctional acrylate monomer, and tetraethoxysilane and methyl silicate can be used as the alkoxysilane compound, for example. Moreover, you may use the said organic-inorganic composite obtained using 3-acryloxypropyl trimethoxysilane which has both functional groups. In the present invention, the surface tension improving agent can be used alone or in admixture of two or more.
[0074]
The curing shrinkable pattern forming material according to the present invention contains, as essential components, the above reactive curable binder system, a curing shrinkable compound, and a colorant, and, if necessary, for preparing a coating liquid. You may mix | blend a solvent, a sensitizer, a ultraviolet blocker, a ultraviolet absorber, a surface conditioner (leveling agent), or another component.
[0075]
When a relatively large amount of a liquid monomer and / or oligomer is used as a reaction-curable binder system for a material for forming a shrinkable pattern, a solvent is used because the monomer and / or oligomer can function as a liquid medium. In some cases, the solid component may be dissolved, dispersed, or diluted to prepare a coating solution. Accordingly, a solvent is not necessarily required in the present invention, but a solvent (diluting solvent) may be used to dissolve and disperse the solid components, adjust the concentration, and prepare a coating solution having excellent coating suitability. Many.
[0076]
Examples of such a diluting solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol, and the like. Carbitol solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone; methoxyethyl acetate, ethoxyethyl acetate Cellosolve acetate solvents such as ethyl cellosolve acetate; Carbitol acetate such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Examples of such solvents include ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; can do. Among these solvents, carbitol solvents, ketone solvents, and cellosolve acetate solvents are particularly preferably used. A solvent can be used individually or in mixture of 2 or more types.
[0077]
Solvents (dilution solvents) for preparing the coating liquid are reactive curable binder systems, curing shrinkable compounds and colorants, coating uniformity, easy drying after coating, and shrinkage after drying. It is necessary to select in consideration of rate control.
[0078]
Furthermore, in the present invention, it is preferable to appropriately select the diluting solvent and adjust the solid content concentration so that the contact angle is not less than the above-mentioned range. Therefore, from the point of adjusting the contact angle to 80 degrees or more, in the present invention, using the solvent as described above, one or more components constituting the reaction-curable binder system, a curing shrinkable compound, a colorant. In addition, it is preferable to dissolve or disperse other components to be blended as necessary, and it is more preferable to dissolve or disperse using at least one solvent selected from isophorone, ethylsolv acetate, and methoxyethoxyethanol. .
[0079]
By adjusting the solid content concentration to 10 to 75% by weight, more preferably 15 to 55% by weight, using an appropriately selected diluent solvent, the contact angle is adjusted within the range achieved, thereby improving the coating suitability. An excellent and shrinkable pattern-forming material that can be cured and shrunk appropriately can be obtained. In the present invention, solid content refers to all blended components excluding the dilution solvent, and liquid monomers and oligomers are also included in the solid content to be dissolved in the dilution solvent.
[0080]
The curing shrinkable pattern forming material according to the present invention is prepared by mixing each component of a reactive curable binder system, a curing shrinkable compound, a colorant and the like in a diluent solvent and dissolving or dispersing the liquid monomer and / or oligomer. Prepared by mixing components such as reactive curable binders, curing shrinkable compounds, and colorants with liquid monomers and / or oligomers that are reactive curable binders that also function as a liquid medium, and dissolving and dispersing them. it can.
[0081]
The blending ratio of each component can be adjusted as appropriate, but preferably, the reaction curable binder system is included in an amount of 5 to 70% by weight as an essential component with respect to the total weight of the blending component (solid content) excluding the solvent. 0.1 to 35% by weight of the curing shrinkable compound, 5 to 50% by weight of the colorant, and 0.01 to 5% by weight when a surface tension improver is contained, if necessary It is preferable to contain other components. When the reaction curable binder system is a photocurable binder system, the amount of the radical photopolymerization initiator used is 100 parts by weight of the radical photopolymerizable polymer and / or monomer and / or oligomer. Usually, it mix | blends in the ratio of 3-50 weight part. When the reaction-curable binder system is a thermosetting binder system, the amount of the curing agent is usually 1 to 75 parts by weight per 100 parts by weight of the epoxy resin.
[0082]
The thus obtained curing shrinkable pattern forming material according to the present invention is excellent in cure shrinkage and coating suitability, and in particular, because the contact angle is adjusted to the above-mentioned range, It is possible to sufficiently increase the coating amount (amount of application) of the coating film, and to cure and shrink the coating film without thinning. Therefore, this is applied to some support in the required pattern shape in anticipation of the shrinkage rate at the time of curing to form a coating film, dried, and the reaction curable binder system is reacted and cured by light or heat. When the curing shrinkable compound is, for example, a sol-gel reactive compound, it is cured and contracted by a sol-gel reaction to form a highly transparent uniform fine line pattern with a fine pitch. Can do.
[0083]
The curing shrinkable pattern forming material according to the present invention has various colorings required to form a fine line pattern with fine details such as a colored layer of a color filter and a fine line pattern. Although it can be used to form a coating film, it is particularly suitable for forming a colored layer (pixel) of a color filter or a black matrix.
[0084]
In the pattern forming method according to the present invention, a pattern forming material having curing shrinkage is applied on a support in a predetermined pattern to form a coating film of the pattern forming material, and then the coating film is cured and contracted. It is characterized by making it.
[0085]
When the pattern forming material according to the present invention is used as the pattern forming material, after forming the coating film on the support, the reaction-curable binder system and the curing shrinkable compound contained in the coating film are cured. To cure and shrink the coating film. A pattern forming material having the above composition is very suitable as a pattern forming material, but the material is not limited to these, and any material having a curing shrinkage rate sufficient to achieve thinning and / or high definition can be achieved. Can be used.
[0086]
In the following, the pattern forming method according to the present invention will be described by taking as an example the case where a sol-gel reactive compound is used as the curing shrinkable compound.
[0087]
When the curing shrinkable pattern forming material contains a sol-gel reactive compound as a curing shrinkable compound, the pattern forming material is applied on a support in a predetermined pattern, and the pattern forming material is applied. After forming the coating film, the reaction-curable binder system and the sol-gel reactive compound contained in the coating film are respectively subjected to a curing reaction and a sol-gel reaction to cure and shrink the coating film, thereby having a desired pattern. Is obtained.
[0088]
In order to apply the curing shrinkable pattern forming material according to the present invention on the support in a predetermined pattern, various pattern printing methods capable of directly forming the predetermined pattern on the surface to be coated, such as screen printing and gravure printing. , Offset printing, ink jet method and the like. Among them, the screen printing or the ink jet method is a method suitable for using the pattern forming material according to the present invention.
[0089]
When screen printing is performed, using a screen mask with a predetermined pattern, a coating liquid of a curing shrinkable pattern forming material is screen printed on a substrate to form a coating film, and then a curing reaction and a sol-gel reaction I do.
[0090]
Since the sol-gel reactive compound contained in the curing shrinkable pattern forming material according to the present invention has a property of being cured and shrunk by a sol-gel reaction, when the sol-gel reactive compound is blended with a reactive curable binder material, coating ( When the coating film formed by drying) is cured, the sol-gel reactive compound in the coating film shrinks by gelation, and the line width is 20% or more than the size of the applied pattern. A contracted cured pattern is finally obtained. Therefore, by applying the pattern forming material according to the present invention to the required pattern shape in anticipation of the shrinkage rate at the time of curing, it becomes possible to form a predetermined fine line pattern after curing. . As a typical example, when the present invention is applied to pattern formation of a black matrix, a very fine pattern can be formed, so that the aperture ratio can be increased.
[0091]
When a photocurable binder system is used as the reactive curable binder system, the curing reaction is performed by forming a coating film and drying it, and then irradiating the coating film with light to thereby cure the photocurable property in the coating film. The coating can be cured by reacting the binder system to form a network of crosslinks. In the case of reactive curing by radical polymerization, it is preferable to block oxygen in order to promote radical generation.
[0092]
As a light beam used for the curing reaction, a light beam having a wavelength that causes a polymerization reaction of a photocurable binder system is appropriately selected from invisible light and visible light such as ultraviolet rays and ionizing radiation.
[0093]
On the other hand, when a thermosetting binder system is used as the reactive curable binder system, the curing reaction is performed by forming the coating film and drying it. The coating can be cured by reacting the binder system to form a network of crosslinks. The temperature required for the curing reaction is usually about 70 ° C to 200 ° C.
[0094]
When using a hydrolyzed polycondensable compound as the sol-gel reactive compound and causing a sol-gel reaction by hydrolytic polycondensation, water and a catalyst are added to the pattern forming material in advance together with the hydrolyzed polycondensable compound for support. After applying to the body, it is heated at 30 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C., and allowed to stand for 15 minutes to 12 hours at an arbitrary timing. As a result, hydrolytic polycondensation proceeds in the coating film, the hydrolyzed polycondensable compound becomes sol-like particles, and when the reaction proceeds further, the sol-like particles are connected to form a gel.
[0095]
When the reactive curable binder system and the sol-gel reactive compound contained in the coating are cured and sol-gel reacted, respectively, so that the coating is cured and contracted, the two reactions proceed uniformly in the coating. The reaction curing of the reactive curable binder system and the sol-gel reaction of the sol-gel reactive compound are preferably performed simultaneously. This is because if the cross-linking reaction becomes non-uniform, beards are likely to occur.
[0096]
When the curing shrinkable pattern forming material according to the present invention is applied on the support in a predetermined pattern, first and second pattern forming materials are prepared as the pattern forming material, and the first pattern After forming the coating material of the first pattern forming material by applying the forming material on the support in a predetermined pattern, the reactive curable binder system and the sol-gel reactive compound contained in the coating film are respectively Curing reaction and sol-gel reaction to cure and shrink the coating film to form the first cured pattern, and the second pattern forming material is applied to the portion on the same support where the first cured pattern is not provided. If it is applied in a predetermined pattern and before the coating film of the first pattern-forming material is cured and shrunk, it is applied to a width that makes contact with the coating film of the first pattern-forming material. The putter After forming the coating film of the forming material, the reactive curable binder system and the sol-gel reactive compound contained in the coating film are cured and sol-gel reacted, respectively, and the coating film is cured and contracted to form a second cured pattern. Preferably formed.
[0097]
In particular, a width wider than the width of the non-coated portion exposed before curing and shrinking the coating film of the first pattern forming material on the portion of the support where the first cured pattern is not provided. It can apply | coat and form the coating film of said 2nd pattern formation material.
[0098]
When the second cured pattern is formed between the first cured patterns using the first and second pattern forming materials that cause no or little curing shrinkage, the first and second pattern forming materials are used. The width of the pattern before curing of each coating film made of the material is the width of each of the first and second cured patterns even after curing as it is. In this case, the minimum pitch of each of the first and second cured patterns is restricted to such a width that the first and second pattern forming materials do not come into contact with each other in consideration of the attractive force between the coating films.
[0099]
For example, the first and second pattern forming materials are coating materials that cause little or no curing shrinkage, and the width of the pattern before curing of the coating film made of the first pattern forming material is x, The width of the pattern before curing of the coating film made of the pattern forming material is y, the minimum width at which the first and second uncured patterns are not merged by the attractive force between the coating films is z, and the first and second curing In the case of forming the patterns closest to each other, as shown in FIG. 3, the widths of the first cured pattern 1 and the second cured pattern 2 after curing are x and y as before the curing, The pitch of one cured pattern is x + y + 2z, and the width of the space secured between the first cured patterns for applying the second pattern forming material is y + 2z.
[0100]
On the other hand, when the second cured pattern is formed between the first cured patterns using the first and second pattern forming materials having curing shrinkage, the coating film is cured and contracted. As shown in FIG. 2 (b), in FIG. 2 (a) in a normal case, the width at which the first cured pattern and the second cured pattern come into contact with each other, and the coating made of the first pattern forming material. Compared to the case of using a coating material that does not cure and shrink, the second pattern forming material can be applied to a width wider than the width exposed before the film is cured and then cured and contracted. It becomes possible to form a (fine line) pattern with high definition (fine pitch).
[0101]
For example, the first and second pattern forming materials have a curing shrinkage rate of 20%, the width of the pattern before curing of the coating film made of the first pattern forming material is x, and the second pattern forming material The width of the pre-curing pattern of the coating consisting of y is y, the minimum width at which the first and second pre-curing patterns do not coalesce due to the attractive force between the coatings is z, and the first and second curing patterns are brought closest to each other Consider the case of forming. In this case, first, when a coating film having a width x before curing is formed on the support using the first pattern forming material and the pitch width is set to x + y + 2z, the first pattern forming material is used. The width of the exposed surface between the pre-cured coatings 1 ′ and 1 ′ is y + 2z as shown in FIG. 4A, whereas the first cured pattern 1 after curing at a shrinkage rate of 20%, The width of the exposed surface between 1 and 0.2 is 0.2x + y + 2z as shown in FIG. Therefore, the second pattern forming material can be applied to a width wider than the width exposed before the coating film made of the first pattern forming material is cured.
[0102]
As another example, when the curing shrinkage of the first and second pattern forming materials is 20%, first, the first pattern forming material is used and the width before curing is x. Is formed on the support by setting the pitch width to 0.8x + y + 2z in anticipation of the curing shrinkage rate, the width of the exposed surface between the pre-cured coating films 1 ′ and 1 ′ made of the first pattern forming material 5 becomes y + 2z−0.2x as shown in FIG. 5A, whereas after curing at a shrinkage rate of 20%, the width of the exposed surface between the first cured patterns 1 and 1 is as shown in FIG. As shown in (b), y + 2z. Therefore, even when the pitch between the first cured patterns 1 and 1 is narrow, a wide exposed surface can be secured, and normally the pitch width at which the first cured pattern and the second cured pattern come into contact with each other. A second pattern forming material can be applied. As a result, as a typical example, it can be applied to a colored layer in a color filter, and a colored layer of a plurality of colors can be formed at a very narrow pitch.
[0103]
Further, the affinity for the pattern forming material in the region where the cured pattern of the pattern forming material on the coated surface is to be provided is relatively higher than that in the surrounding region, and then the pattern forming material is applied. This is preferable because the coating amount per unit area (mounting amount) can be sufficiently increased as shown in FIG. 1B, and a cured pattern having an excellent shape in which the coating film is not thin can be formed. .
[0104]
As a method for relatively increasing the affinity of the pattern formation region to the pattern forming material, for example, there is a method of selectively changing the wettability of the surface to be coated into a predetermined pattern by the action of a photocatalyst.
[0105]
That is, there is a material (photocatalytic reactive material) whose hydrophilicity is significantly increased by the action of a photocatalyst such as titanium oxide, such as a silicon compound such as organopolysiloxane. Therefore, first, a wettability changing layer containing such a photocatalytic reactive material is formed on the coated surface of the pattern forming material. The wettability changing layer may be a layer in which a photocatalytic reactive material and a photocatalyst are mixed, or may be a composite layer in which a photocatalytic reactive material layer and a photocatalytic layer are provided in an overlapping manner. Alternatively, the wettability changing layer may consist of only a layer of a photocatalytic reactive material, and in this case, a photocatalyst-containing layer support member provided independently on a substrate such as a plastic film or a plastic plate. Used in combination.
[0106]
As the photocatalytic reactive material, it is preferable to use organopolysiloxane, and among them, those having a fluoroalkyl group are particularly preferable. Examples of organopolysiloxanes include (1) organopolysiloxanes that exhibit high strength by hydrolyzing and polycondensing chloro or alkoxysilane, etc. by sol-gel reaction, etc., and (2) reactions with excellent water and oil repellency. An organopolysiloxane such as an organopolysiloxane crosslinked with a functional silicone can be exemplified.
[0107]
In the case of (1) above, the following general formula 3:
Y_nSiX_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen. 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.
[0108]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used. 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.
[0109]
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.
[0110]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula 4.
[0111]
[Chemical 2]

[0112]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0113]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0114]
Examples of the photocatalyst include titanium oxide (TiO 2).₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃) And the like, and among them, titanium oxide (TiO 2)₂Is particularly preferred.
[0115]
A binder, solvent, photocatalyst and other components are mixed with the photocatalytic reactive material as necessary to prepare a coating material, and a wettability changing layer is formed by applying it to the coated surface of the pattern forming material. can do. In addition, a photocatalyst-containing layer is prepared by mixing a photocatalyst with a binder, a solvent and other components as necessary to prepare a coating material, and applying the mixture onto a coated surface of a pattern forming material or a separate independent substrate. Can be formed. Since the wettability changing layer needs to be arranged at a position in contact with the pattern forming material, it is preferable to arrange the wettability changing layer on the outermost surface of the coated surface of the pattern forming material. As long as the above can be exhibited, another layer may be additionally formed thereon. For example, the thin photocatalyst-containing layer can be penetrated and contacted with the pattern forming material, and is not limited to the lower side of the wettability changing layer, but can be arranged on the upper side.
[0116]
After the wettability changing layer is formed, light is selectively irradiated around the area where the pattern forming material on the surface to be coated is to be applied. The selective irradiation can be performed by a method such as mask exposure or laser drawing. Light may be emitted from any direction as long as the photocatalyst can be activated. That is, the wettability changing layer is usually irradiated with light from the upper side, but when the coated body is light transmissive, the photocatalyst is activated by irradiating light from the lower side (coated surface side). be able to.
[0117]
When the wettability changing layer does not contain a photocatalyst and the photocatalyst containing layer is not provided adjacent to the wettability changing layer, the photocatalyst containing layer of the photocatalyst containing layer supporting member prepared separately is changed to the wettability changing layer. The photocatalyst-containing layer support member is removed after irradiating light in a state of being brought into contact with and overlapping. Usually, a light-transmitting material is used as the base material of the photocatalyst-containing layer support member, and light is irradiated from above the photocatalyst-containing layer support member. Since the photocatalyst can be activated by irradiating light from the side (surface to be coated), the base material of the photocatalyst-containing layer support member may be opaque.
[0118]
When selective irradiation is performed under conditions in which a photocatalyst acts on the wettability changing layer provided on the coated surface of the pattern forming material, the area around the region to which the pattern forming material is to be coated is hydrophilic on the coated surface. And the affinity for the patterning material is lowered, and as a result, the affinity for the patterning material, that is, the wettability is relatively higher in the region where the patterning material is to be applied. . In this way, it is possible to increase the application amount per unit area by limiting the application region of the pattern forming material.
[0119]
In this way, when the pattern is formed using the curing shrinkable pattern forming material according to the present invention, the shrinkage rate is 20% or more at maximum, and a pattern of an isolated line of 20 μm is possible. A good pattern having good straightness and smoothness, good transparency, a cross-sectional shape of a forward taper, and sufficient hardness for a colored layer or black matrix of a color filter can be obtained.
[0120]
In the resulting pattern, the colorant is encapsulated in a network of crosslinks formed by a reaction cured product of a reactive curable binder system and a reaction cured product of a curing shrinkable compound (for example, a polycondensate of a sol-gel reactive compound). It has a matrix structure. By adopting a structure in which the colorant is encapsulated in a cross-linking network, the effect of improving the heat resistance and light resistance of the formed pattern can be obtained.
[0121]
As described above, the pattern forming method according to the present invention requires various details such as a colored layer of a color filter and fine line patterns to be formed with a fine pitch. Although it can be used to form a colored coating film, it is particularly suitable for forming a colored layer (pixel) or a black matrix of a color filter.
[0122]
Next, the color filter according to the present invention will be described. The color filter according to the present invention is characterized by including a colored layer or a black matrix formed using the curing shrinkable pattern forming material according to the present invention.
[0123]
The color filter according to the present invention is a colored layer or black matrix having a matrix structure in which a colorant is encapsulated in a cross-linked network formed by a reaction cured product of a mixture of a reaction curable binder system and a curing shrinkable compound. It is more preferable from the viewpoint of heat resistance and light resistance.
[0124]
In the case of using a pigment as the colorant, since the pigment wrapped in the cross-linked network is chemically bonded to the surrounding gelled polymer, heat resistance and light resistance are particularly improved.
[0125]
The color filter includes a black matrix formed in a predetermined pattern on a transparent substrate, a pixel portion formed in a predetermined pattern on the black matrix, and a protective film formed to cover the pixel portion as necessary. I have. A transparent electrode for driving liquid crystal may be formed on the protective film as necessary. Further, columnar spacers may be formed on the transparent electrode plate, the pixel portion, or the protective film in accordance with the region where the black matrix layer is formed.
[0126]
The pixel portion is formed by arranging a red pattern, a green pattern, and a blue pattern in a desired form such as a mosaic type, a stripe type, a triangle type, or a four pixel arrangement type. It is provided in a predetermined area outside. The pixel portion can be formed by various methods such as a pigment dispersion method, a printing method, an electrodeposition method, and a dyeing method, but it is preferable to include a colored layer formed using the curing shrinkable pattern forming material according to the present invention. . That is, each of the curing shrinkable pattern forming materials according to the present invention containing red, green, and blue colorants is applied to a support in a predetermined pattern by screen printing, and the pattern forming material is applied. After forming the film, the pixel portion can be formed by curing and shrinking the reactive curable binder system and the curing shrinkable compound.
[0127]
When the reaction curable binder system is a photo-curing system, it can be cured by irradiation with light such as ultraviolet rays, and when it is a thermosetting system, it can be heated by a clean oven or the like. Further, when a sol-gel reactive compound is used as the curing shrinkable compound, the pixel portion is obtained by curing the reactive curable binder system with light or heat and simultaneously causing the sol-gel reaction to cure and shrink the coating film. Can be formed. The pixel portion is usually formed to a thickness of about 10 μm.
[0128]
The black matrix is formed by various methods such as a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, and a chromium vapor deposition method. The black shrinkable pattern forming material according to the present invention is formed in the same manner as the pixel portion. It is preferable to provide a colored layer formed by using. In this case, a film for curing shrinkage pattern formation containing a black pigment as a colorant is prepared, and the coating film is cured by a curing reaction and a sol-gel reaction after the coating film is formed in the same manner as the pixel portion is formed. Shrinking to obtain a black matrix. In this method, the black matrix is usually formed to a thickness of about 10 μm.
[0129]
The protective film can be formed by applying a reaction liquid of a coating solution of a transparent resin composition having light or thermosetting property by a method such as spin coater, roll coater, spray, printing or the like. The protective film is formed to a thickness of about 2 μm, for example. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute.
[0130]
The transparent electrode on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and their alloys, etc., such as sputtering, vacuum deposition, CVD, etc. This is formed by a simple method, and is formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.
[0131]
Columnar spacers on the transparent electrode are coated with a photocurable resin composition coating solution by a method such as spin coater, roll coater, spray, printing, etc., exposed by ultraviolet irradiation through a photomask, and after alkali development It can be formed by post-baking in a clean oven or the like. The columnar spacer is formed with a height of about 5 μm, for example. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film.
[0132]
The color filter thus produced has a colored layer having a matrix structure in which a colorant is encapsulated in a cross-linking network formed by a reaction cured product of a mixture of a reaction curable binder system and a curing shrinkable compound. Or when it has a black matrix, it has the effect of being excellent in heat resistance and light resistance. In addition, since the color filter according to the present invention is manufactured by a printing method with a relatively simple manufacturing process, the color filter is manufactured at a lower cost than a color filter using the current mainstream pigment dispersion method as a manufacturing method of the color filter. It has a cost effect of being cost competitive.
[0133]
Although the color filter for the liquid crystal display device has been described as a representative example of the color filter according to the present invention, the present invention also applies to a color filter for other types of display devices, for example, a color filter for an EL (electroluminescence) device. Applicable. The EL device can arrange full color display by arranging the EL elements of RGB colors in a matrix and control the light emission of each color, but by arranging a color filter on the light extraction side (viewer side) of the EL elements, The display performance can be improved by modulating the colored light.
[0134]
【Example】
[Examples 1 to 5]
(1) Preparation of pattern forming material
(Examples 1-3)
<Preparation of curing shrinkage compound>
AEROSIL200 (specific surface area 200m) which is ultrafine silica²/ G, average particle size 12 nm, silanol group density 2.5 / nm²) (Nippon Aerosil Co., Ltd.) While fluidizing 20 g, 1.0 g of alkylalkoxysilane having the composition shown in Table 1, 50 g of water, 50 g of methylene chloride, 10 g of 1 wt% triethylamine aqueous solution, benzyltriethylammonium chloride 3 mmol was added, and it stirred and mixed at 80 degreeC for 24 hours. After 24 hours, the temperature was raised to 120 ° C., and the mixture was further stirred for 3 hours in a reflux state. After the organic layer was extracted, the solvent was removed and the by-product alcohol was recovered and removed by an evaporator. In this way, a curing shrinkable compound in which an alkyl group was introduced onto the silica surface by an alkylalkoxysilane treatment was obtained.
[0135]
[Table 1]

[0136]
<Pigment-dispersed resist ink>
It mixed by the composition of Table 2, and it disperse | distributed for 24 hours using the bead mill, and obtained the pigment dispersion liquid. It mixed uniformly with the composition of Table 3, and filtered with the filter of the hole diameter of 2 micrometers, and obtained the pigment dispersion resist ink of each color.
[0137]
[Table 2]

[0138]
[Table 3]

[0139]
<Pattern forming material>
10 wt% of the obtained curing shrinkable compound was added to the obtained pigment-dispersed resist inks of Production Examples 4 to 6 to obtain pattern forming materials of Examples 1 to 3.
[0140]
Example 4
<Curing shrinkable compound>
AEROSIL200 (specific surface area 200m) which is ultrafine silica²/ G, average particle size 12 nm, silanol group density 2.5 / nm²) (Nippon Aerosil Co., Ltd.) and fluorinated alkylsilane (CF₃(CF₂)₃CH₂CH₂Si (OC2H5)₃) And tetraethisilane were mixed at a weight ratio of 2: 7: 1 to obtain a curing shrinkable compound.
<Pattern forming material>
10 wt% of the obtained curing shrinkable compound was added to the pigment-dispersed resist ink obtained in the same manner as in Examples 1 to 3 to obtain the pattern forming material of Example 4.
[0141]
(Comparative Examples 1-3)
The pigment-dispersed resist inks of Production Examples 4 to 6 were referred to as Comparative Examples 1 to 3.
[0142]
(2) Pattern formation
Using the stainless steel mesh plate (Tokyo Process Co., Ltd., 250 mesh, 53 μm thickness) for the pattern forming materials of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above, a PET film (thickness 185 μm, corona) Screen printing (screen printing machine: made by Neurong Co., Ltd.) was performed on the surface which had been subjected to surface activation or surface-roughening treatment in advance by electric discharge treatment, and air-dried. A pattern forming material having a dry film thickness of 7 μm is passed through a predetermined pattern with a mask, and the UV wavelength is in the range of 300 to 450 nm, and the irradiation energy is 50 mJ / cm.²UV irradiation was performed so that A stainless steel mesh (ST590CALH, 590 mesh, manufactured by Tokyo Process Service Co., Ltd., a thickness of 28 μm, a wire diameter of 13 μm, and a space ratio of 49%) was used as the screen cage on which the resist material was laminated. The screen wrinkle was fixed to a square frame (SUS404 type, 440 mm × 440 mm) using a tensioning machine. The heel tension was 2000 to 2300 N / mm, and the screen heel angle was 34.1 degrees. The screen wrinkle was a mesh plate in which both sides of the wrinkle were polished with an alumina fine abrasive. Furthermore, after applying the resin ACA-210P (product name: Cyclomer P, manufactured by Daicel Industrial Co., Ltd.) for the adhesive layer to the mesh plate, it is naturally dried, and the photosensitive resin synthesized on the upper layer is slit-coated on both sides of the mesh plate. A printing plate was used. A printing machine manufactured by Nippon Neurong Co., Ltd. was used. The squeegee used urethane rubber because of its mechanical strength and solvent resistance. A 185 μm PET film was used as the printing substrate. In order to improve the ink adhesion, the substrate used was subjected to corona discharge treatment in advance.
[0143]
DPHA and SR399 were used as basic materials from the viewpoints of UV curing sensitivity and adhesion to a PET film. The sensitivity of SR399 only is 60mJ / cm²However, because of the large shrinkage of the cured film, it was impossible to laminate with other photosensitive resins. Further, when used in ink, similarly, the UV curing shrinkage rate was large, so that cracks occurred in the film. Therefore, by adding a small amount of bisphenol A EO-modified acrylate having a structure with a relatively long hydrocarbon chain, the photocured product was made flexible and improved in adhesion to PET. However, when the laminated structure was used, the pattern resolution deteriorated due to the adhesion to the stainless steel mesh including the developability. The final optimization was that SR399 and bisphenol A type epoxy diacrylate (180S70) were used in a mixed manner to improve the lamination adhesion and to be a resist for HADPOP plate. On the other hand, as a comparison, commercially available acrylic resins ACA-210P and SR399 were combined. Sensitivity is 50mJ / cm²And high. Although it seems that ACA-210P has a higher development speed than the relationship with the acid value derived from acrylic acid, it was difficult to control the development time. However, since the adhesion with the stainless steel mesh was particularly good, this was selected as the resin for the adhesive layer used for laminating the stainless steel mesh with another photosensitive resin.
[0144]
A film on which a test pattern was drawn was brought into close contact with the prototyped photosensitive resin, and after exposure with a 2 kW ultra-high pressure mercury lamp, the developer was sprayed to wash away the unexposed areas, whereby a negative pattern image was obtained. The physical properties necessary for the plate were evaluated on the obtained image. The results are shown in Table 4. The appearance was evaluated according to certain evaluation criteria (three levels of ◯ Δ ×).
[0145]
[Table 4]

[0146]
The dynamic hardness is a hardness obtained from the indentation depth as a load in the process of indenting the indenter, and is a strength characteristic including not only plastic deformation of the sample but also elastic deformation. When the test load P (mN) and the amount of penetration of the indenter into the sample (indentation depth) D (μm), the dynamic hardness DH is defined by the following equation.
[0147]
DH = αP / D²
Α is a constant depending on the shape of the indenter and is obtained from the conversion table in advance. That is, in this measurement, since a 115 ° triangular cone indenter is used, α = 3.8854 is used. Type-B can be selected when emphasizing resolution, but dynamic hardness is 46 mN / μm when emphasizing sensitivity and elastic force between the substrate and the plate.²Type-A having As described above, a resist material for a HADOP plate in consideration of the resolution and the layering function was obtained.
[0148]
Since the photosensitive resin used for the HADOP plate could be synthesized, it was examined to construct it on a mesh. We examined the functionalization of the plates according to the HADOP functional model. Acrylic soluble resin ACA-210P was selected as the adhesive layer resin. The adhesive layer was 30 parts by weight of ACA-210P, 20 parts by weight of SR399 + DPHA (mixing ratio 1: 1), 1 part by weight of photopolymerization initiator Irgacure 907 (manufactured by Ciba Geigy), and 49 parts by weight of solvent toluene. Plate making sensitivity is 50mJ / cm²Met. The film was applied so as to have a dry film thickness of 5 μm, and a sealing treatment was performed. Next, on the ink mounting surface side, a photosensitive resin Type-B was applied as a photosensitive resin layer so as to have a dry film thickness of 20 μm, and exposure and development processing were performed. The eyelid opening was observed with a microscope, and it was confirmed that the minimum opening width was resolved to 8 μm.
[0149]
Further, on the other back surface, a photosensitive resin Type-A was applied as a photosensitive resin layer so as to have a dry film thickness of 5 μm, and dried at 70 ° C. for about 15 minutes so as to eliminate tack. Further, the photosensitive resin Type-B was applied so as to have a dry film thickness of 5 μm, and dried at 70 ° C. for about 15 minutes so as not to cause tack. The back cushion layer which consists of photosensitive resin Type-A and Type-B which follows a required pattern by the image development and exposure similar to the above was provided. The eyelid opening was observed with a microscope, and it was confirmed that the minimum opening width was resolved to 8 μm. In addition, after repeating the photosensitive resin lamination, it was also confirmed that a double-sided batch simultaneous exposure was performed, and a plate was formed by batch development. When the required elastic force is indicated by dynamic hardness, the optimum dynamic hardness is 40 to 50 mN / μm.²Met. Thereby, the printing pressure applied between the substrate and the HADOP plate was eased, and at the same time, a plate with improved substrate adhesion could be produced. After the irradiated part was cured, the uncured part of the non-irradiated part was developed with a 0.1% KOH aqueous solution to form an image film. Further, the formed image film was held at 120 ° C. for 2 hours, and a curing reaction and a sol-gel reaction were performed to improve water resistance and solvent resistance. The stainless steel mesh plate is pre-heated for 30 minutes after leaching with a silane coupling agent (γ-methacryloxypropyltrimethoxysilane 0.1% aqueous solution) for the purpose of improving adhesion to the pattern forming material. It was used.
[0150]
(result)
In Examples 1 to 4, a 25 μm stripe pattern could be formed, and the shrinkage rate was 20%. A highly straight pattern with no jaggy at both ends was obtained. On the other hand, in Comparative Examples 1 to 3, a 30 μm stripe pattern could be formed and no shrinkage occurred.
[0151]
(3) Contact angle measurement
A 7059 glass substrate was immersed in hot sulfuric acid for 1 minute, and then neutralized by ultrasonic cleaning using a 5% NaOH aqueous solution to clean the surface. Next, one drop of the pattern forming material of Examples 1 to 3 and Comparative Examples 1 to 3 is dropped and left at room temperature for 1 minute, and then the angle formed between the substrate and the pattern forming material by a contact angle measuring device. Was measured.
[0152]
(result)
In Examples 1 to 3, the contact angle was about 85 degrees. In Example 4, the contact angle was as large as about 110 degrees. On the other hand, Comparative Examples 1-3 had a small contact angle of about 65 degrees.
[0153]
(4) Formation of color filter (Example 5)
Using the pattern forming materials obtained in Examples 1 to 3, EL element-compatible color filters were produced. RGB pixels having good stripe lines of 40 μm each could be formed on a flexible PET substrate.
[0154]
[Examples 6 to 9]
(1) Preparation of pattern forming material
(Example 6)
To 10 g of tetraethoxysilane, 100 ml of ethanol as a solvent, 50 ml of water for sol-gel reaction (hydrolysis polycondensation), 1 ml of 0.3N peracetic acid as a catalyst and 0.5 N of aluminum acetylacetate 3 ml was added to obtain a highly transparent sol solution.
[0155]
Next, 5 g of this sol solution, 200 g of a UV curable resin (reactive curable binder system) having the following composition (C.I.) were added so that the amount of the sol solution added was 5% by weight of the total weight of the pattern forming material. I. Pigment 36) (colorant) 40 g was mixed with 200 ml of (3-methoxybutyl acetate: PGMEA 5: 5) (solvent), and dispersed for 6 hours with a bead mill to obtain a material for forming a shrinkable shrinkable pattern. .
[0156]
[Composition of UV curable resin]
-Terpolymeric acrylic resin (benzyl methacrylate (BzMA): styrene (St): methacrylic acid (MAA) 3: 5: 2) 55 parts by weight
Monomer (dipentaerythritol hexaacrylate (DPHA): trimethylolpropane trimethacrylate (TMPTA): ethoxylated bisphenol A diacrylate 5: 3: 2) 35 parts by weight
Photopolymerization initiator Irgacure 907 (Ciba Geigy) 10 parts by weight
(Example 7)
A material for forming a curing shrinkable pattern of Example 7 was obtained in the same manner as in Example 6 except that tetramethoxysilane was used instead of tetraethoxysilane in Example 6.
[0157]
(Example 8)
A curing shrinkable pattern forming material of Example 8 was obtained in the same manner as in Example 6 except that 10 g of tetramethoxysilane and 5 g of aluminum butoxide were used instead of tetraethoxysilane in Example 6.
[0158]
Example 9
A curing shrinkable pattern forming material of Example 9 was obtained in the same manner as in Example 6 except that 10 g of methyltrimethoxysilane was used instead of tetraethoxysilane in Example 6.
[0159]
(2) Pattern formation
Next, the pattern forming materials of Examples 6 to 9 were screen-printed on a glass substrate using a screen mask having a line width of 50 μm and held for about 10 hours at 70 ° C. and a humidity of 80% or more. A curing reaction and a sol-gel reaction were performed.
[0160]
(3) Evaluation
(3-1) Shrinkage rate
Shrinkage rate (%) = preparation pattern size after curing for 1 hour at 70 ° C. after light irradiation / preparation pattern size before curing × 100.
[0161]
(3-2) Needle penetration test hardness
Measurement was performed using a dynamic hardness tester (Shimadzu Corporation).
[0162]
(3-3) Color filter transparency
A spectral characteristic spectrum was measured with a visible ultraviolet absorption spectrum measuring apparatus, and in particular, a wavelength peak height (absorption) in the visible region (350 nm to 700 nm) was 80% or more.
[0163]
(result)
Table 5 shows the results of the line width, shrinkage rate, needle penetration test hardness, and color filter transparency after curing shrinkage in Examples 6 to 9.
[0164]
[Table 5]

[0165]
All of the obtained cured patterns had no whiskers, good line straightness, no line tack, good smoothness, and a cross-sectional shape with a forward taper. Example 7 had a faster drying property than Example 6, Example 8 had a higher shrinkage than Example 6, and Example 9 had a higher viscosity than Example 6.
[0166]
【The invention's effect】
As described above, the curing shrinkable pattern forming material according to the present invention comprises at least one or two or more components constituting a reactive curable binder system, a curing shrinkable compound, and a colorant, and has a cure shrinkage. According to the pattern forming method according to the present invention, the pattern formed by curing the curing shrinkable pattern forming material is thinner than that at the time of application, which limits the technical limit of the printing method used for pattern formation. It is also possible to realize a finer line than that.
[0167]
Therefore, since a very fine pattern can be formed, the aperture ratio can be increased, and as a typical example, it can be applied to pattern formation of a black matrix.
[0168]
In addition, according to the present invention, the width of the first pattern and the second pattern that are normally in contact with each other, or the width that is wider than the width of the non-coated portion that was exposed before being cured and shrunk, Since a pattern forming material can be applied and then cured and shrunk, a fine line pattern can be formed with a fine pitch compared to the case of using a material that does not cure and shrink. It becomes possible. Therefore, it is possible to realize high definition exceeding the technical limit of the printing method used for pattern formation. As a typical example, since it is possible to form a colored layer of a plurality of colors with a very narrow pitch, it can be applied when forming a colored layer of a color filter.
[0169]
In addition, in the case of having a matrix structure in which a colorant is encased in a cross-linking network formed by a mixture of a reaction curable binder-based reaction cured product and a curing shrinkable compound, heat resistance and light resistance are improved. An improved pattern can be formed.
[0170]
The color filter according to the present invention includes a colored layer or a black matrix formed using the curing shrinkable pattern forming material according to the present invention. The color filter according to the present invention is a colored layer or black matrix having a matrix structure in which a colorant is encapsulated in a crosslinked network formed by a reaction cured product of a mixture of a reaction curable binder system and a curing shrinkable compound. Is provided, it has the effect of being excellent in heat resistance and light resistance. In addition, since the color filter according to the present invention is manufactured by a printing method with a relatively simple manufacturing process, the color filter is manufactured at a lower cost than a color filter using the current mainstream pigment dispersion method as a manufacturing method of the color filter. It has a cost effect of being cost competitive.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram schematically showing a state in which a curing shrinkable pattern forming material is shrunk.
FIG. 2 schematically shows a state (a) in which a pattern is formed using a normal pattern forming material and a state (b) in which a pattern is formed by curing and shrinking using the curing shrinkable pattern forming material according to the present invention. FIG.
FIG. 3 is a diagram schematically showing an example of a state in which a pattern is formed using a normal pattern forming material.
FIG. 4 is a diagram schematically showing an example of a state before and after curing shrinkage of the material for forming a shrinkable shrinkable pattern according to the present invention.
FIG. 5 is a view schematically showing another example of the state before and after the curing shrinkable pattern forming material according to the present invention is cured and shrunk.
[Explanation of symbols]
1 ... First curing pattern
1 '... Pre-curing coating film comprising first pattern forming material
2 ... Second curing pattern

Claims (14)

At least one or two or more components constituting a reactive curable binder system, a curing shrinkable compound and a colorant, and a pattern forming material having curing shrinkage,
The reaction curable binder system is a photocurable pattern forming material composed of at least a radical polymerizable compound and a photo radical initiator, or a thermosetting pattern forming material composed of at least an epoxy resin,
The pattern forming material, wherein the curing shrinkable compound is a sol-gel reactive compound containing at least a metal alkoxide . The pattern forming material according to claim 1 , wherein the metal alkoxide contains at least silicon alkoxide.   The curing shrinkable compound is at least one sol-gel reactive compound selected from a reactive product of ultrafine silica and alkylalkoxysilane, and SiAlOn (n is 30 or less). The pattern forming material according to claim 1 or 2. 4. The pattern forming material according to claim 1 , wherein the contact angle is adjusted to be 80 degrees or more on the glass substrate. The surface tension improver further contains at least one compound selected from an organic-inorganic composite obtained by reacting two functional groups of an acrylate group of a compound having an acrylate group and an alkoxysilane compound having an alkoxy group. The material for pattern formation according to any one of claims 1 to 4 . One or more components constituting the reaction curable binder system, a curing shrinkable compound, a colorant, and other components blended as necessary are selected from isophorone, ethyl sorb acetate, and methoxyethoxyethanol. The pattern forming material according to claim 1 , wherein the pattern forming material is dissolved or dispersed using at least one solvent. The pattern forming material according to any one of claims 1 to 6 , which is used for forming a colored layer or a black matrix of a color filter. After forming the coating film on the support using the pattern forming material according to any one of claims 1 to 7, the reactive curable binder system and curing contained in the coating film A pattern forming method comprising: curing and shrinking a coating film by curing reaction of a shrinkable compound. The pattern forming method according to claim 8 , wherein the coating film is formed by applying the pattern forming material by a pattern printing method. First and second pattern forming materials are prepared as the pattern forming material,
After the first pattern forming material is applied on the support in a predetermined pattern to form a coating film of the first pattern forming material, the first cured pattern is formed by curing and shrinking,
A second pattern forming material is applied to a portion of the same support where the first cured pattern is not provided in a predetermined pattern and before the coating film of the first pattern forming material is cured and contracted. If it is, after apply | coating to the width | variety which will contact with the coating film of the said 1st pattern formation material and forming the coating film of the 2nd pattern formation material, the said coating film is hardened and shrunk and the 2nd The pattern forming method according to claim 8 , wherein a cured pattern is formed. In a portion where the first cured pattern on the support is not provided, a width wider than the width of the non-coated portion exposed before curing and shrinking the coating film of the first pattern forming material. The pattern forming method according to claim 10 , wherein a coating film of the second pattern forming material is formed by coating. After the affinity for the pattern forming material in the region where the cured pattern of the pattern forming material on the support is to be provided is relatively higher than the surrounding region, the pattern forming material is applied. The pattern forming method according to claim 8, wherein the pattern forming method is performed. The use of a substrate for a color filter as a support, and forming a cured pattern of the colored layer or a black matrix using the pattern forming material on the color filter substrate of claim 12, claim 8 the pattern forming method according to any one of up to. A color filter comprising a colored layer or a black matrix formed using the pattern forming material according to any one of claims 1 to 7 .

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