JP4132622B2 - Color filter for liquid crystal display device and liquid crystal display device using the same - Google Patents

Description

【００１８】
本発明は、カラーフィルタの赤（Ｒ）、緑（Ｇ）、青（Ｂ）三原色のＣ光源によるＣＩＥ色度図上での色度点が、赤（Ｒ）はｘ＝０．６２〜０．６９、ｙ＝０．３１０〜０．３５、緑（Ｇ）はｘ＝０．２０〜０．３２、ｙ＝０．５７〜０．７３、青（Ｂ）はｘ＝０．１３〜０．１７、ｙ＝０．０４〜０．１１の色度座標内にあり、また、色再現域が、ＮＴＳＣ方式の規格値の色再現域１００％に対し６６％〜１２０％の色再現域を有することを特徴とするものであるが、あるカラーフィルタ（ｉ）の、ＮＴＳＣ方式の規格値の色再現域１００％に対する色再現域の％（ＮＴＳＣ比）は、下記の式により求められる。
【００１９】
（Ｓｉ ／Ｓ）×１００
ここで、 Ｓｉ ：あるカラーフィルタ（ｉ）のＣＩＥ色度図上での三角形の 面積
Ｓ ：０．１５８２
また、Ｓｉ は、下記の式により求められる。

ここで、Ｒｘｉ 、Ｒｙｉ 、Ｇｘｉ 、Ｇｙｉ 、Ｂｘｉ 、Ｂｙｉ は、あるカラーフィルタ（ｉ）の色度座標
【００２０】
本発明による上記色再現域を有するカラーフィルタは、以下に述べる感光性着色組成物を用いて各色のパターンを膜厚１．８μｍ〜３．５μｍの範囲に形成することにより得られるものである。本発明における感光性着色組成物の調製は、先ず、アクリル系樹脂と顔料とを良く混合するために２本ロールを用いて練り合わせてチップ化し、その後、分散剤と溶剤を用いてチップを溶解して着色樹脂（ペースト）を作製する。次に、この着色樹脂（ペースト）に光重合性モノマーと光重合性開始剤を添加して感光性着色組成物を調製するものである。
【００２１】
この時用いられるアクリル系樹脂は、アクリル酸、メタクリル酸、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレートなどのアルキルアクリレートまたはアルキルメタクリレート、環状のシクロヘキシルアクリレートまたはメタクリレート、ヒドロキシエチルアクリレート、またはメタクリレートなどの内から３〜５種類程度のモノマーを用いて、分子量５０００〜１０００００程度に合成した樹脂を用いる。
また、アクリル系樹脂の一部に不飽和二重結合を付加させた樹脂、上記のアクリル樹脂、イソシアネート基と少なくとも１個以上のビニル基を有するイソシアネートエチルアクリレート、メタクリロイルイソシアネートなどの化合物を反応させて得られる酸価５０〜１５０の感光性共重合体が使用できる。
【００２２】
顔料としては、赤（Ｒ）としてＣ．Ｉ．Ｎｏ．９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２５４，２６４など、緑（Ｇ）としてはＣ．Ｉ．Ｎｏ．７、３６、青（Ｂ）としてはＣ．Ｉ．Ｎｏ．１５、２２、６０、６４が一般的に用いられる。
黄としては、ピグメントＮｏ．１３，８３，１３８，１３９，１５０などがあるが中でもイソインドリン系、モノアゾＮｉ錯体系、アゾ系がよい。緑としては、銅フタロシアニンのハロゲン化物、青としては、銅フタロシアニン系であり結晶構造がα、β、ε型がよい。紫としては、Ｃ．Ｉ．Ｎｏ．２３が用いられる。
また、特に赤顔料に於いては、アントラキノン系（チバガイギ製、Ａ２Ｂ，Ａ３Ｂなど）、ジケトピロロピロール系（チバガイギ製、Ｂ−ＣＦ、オレンジＴＲ、ルビンＴＲなど）、ペリレン系を用いる事が望ましいが、特にこれだけに限定される物ではない。
【００２３】
分散剤としては、界面活性剤、顔料の中間体、染料の中間体、ソルスパースなどの広範囲のものが使用される。好ましくは、有機色素の誘導体であり、母体となる有機色素としてはアゾ系、フタロシアニン系、キナクリドン系、アントラキノン系、ペリレン系、チオインジコ系、ギオキサン系、ピロール系金属錯塩系である。これらの有機色素に置換基を有し、色素の分散に有効な誘導体が用いられる。
置換基としては、水酸基、カルボキシル基、スルホン基、カルボンアミド基、スルホンアミド基、あるいは下記の一般式で示されるいずれかの置換基である。これらの置換基から選ばれる少なくとも１種置換基を有する誘導体が用いられる。
【００２４】
【化１】

【００２５】
【化２】

【００２６】
なお、本発明に使用する色素と分散剤の母体有機色素とは、通常相の関係から同一のものが組み合わせられるが、必ずしも一致している必要はない。分散の際の組成の割合は、特に限定されるものではないが、分散用アクリル樹脂に対する顔料の添加量は５０〜１５０重量部程度であり、分散剤は顔料の１〜１０重量部程度である。
また、カラーフィルタの分光調整の為には任意の顔料を２〜３点混ぜ合わせて調整する。
【００２７】
光重合性モノマーとしては、２官能、３官能、多官能モノマーがあり、２官能モノマーとして、１，６−ヘキサンジオールジアクリレート、エチレングリコールジアクリレート、ネオペンチルグリコールシアクリレート、トリエチレングリコールジアクリレートなどがあり、３官能モノマーとして、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、トリス（２−ヒドロキシエチル）イソシアネートなどがあり、多官能モノマーとして、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールペンタおよびヘキサアクリレートなどがある。
これらのモノマーとして、昭和高分子（株）、東亞合成（株）、日本化薬（株）などの市販品がある。光重合性モノマーの添加量は、特に限定されるものではないが、分散用アクリル樹脂の２０〜１５０重量部程度である。
【００２８】
溶剤としては、メタノール、エタノール、トルエン、キシレン、エチルセロソルブ、エチルセロソルブアセテート、ジグライム、シクロヘキサノン、エチルベンゼン、酢酸イソミル、酢酸ｍアミル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、液体ポリエチレングリコール、１−メトキシー２−プロパノール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、乳酸エチルなどが用いられるが、樹脂のモノマー組成、光重合性モノマー、光重合開始剤などによって溶解性が異なるので単一または複数の溶剤組成の溶剤を適宜選択する。
【００２９】
また、光重合開始剤としては、従来のトリアジン系化合物、２，４，６−トリス（トリクロロメチル）−Ｓ一トリアジン、２−（ｐ−メトキシスチリル）−４，６−ピス（トリクロロメチル）−Ｓ−トリアジン、２−フエニルー４，６−ビス（トリクロロメチル）−Ｓ−トリアジン、２−（ｐ−メトキシフェニル）−４，６−ビス（トリクロロメチル）−Ｓ−トリアジン、２−（ｐ−クロロフェニル）−４，６一ビス（トリクロロメチル）−Ｓ−トリアジン、２−（４’−メトキシー１’−ナフチル）−４，６−ヒス（トリクロロメチル）−Ｓ一トリアジンなど混合系で用いても良い。
【００３０】
さらに、アセトフェノン系化合物としては、２−メチルー２−モルホリノ（４−チオメチルフェニル）プロパンー１−オン、ジエトキシアセトフエノン、２−ヒドロキシー２−メチルー１−エニル（４−ドデシル）プロパンー１−オンなどがある。
ベンゾフェノン系化合物としては、ベンゾフェノン、４、４−ジエチルアミノベンゾフェノン、３、３−ジメチルー４−メトキシベンゾフェノン、０−ベンゾフェノン安息香酸メチルなどがある。
チオキサンソン系化合物としては、２、４−ジエチルチオキサンソン、２、４−ジイソプロピルチオキサンソン、２、４−ジメチルチオキサンソンなどがある。
【００３１】
また、イミダゾール系化合物としては、２−（２，３−ジクロロフェニル）−４，５−ジフェニルーイミダゾールニ量体、２−（２，３−ジクロロフエニル）−４，５一ビス（３−メトキシフェニル）−イミダゾールニ量体、２−（２，３−ジクロロフェニル）−４，５−ビス（４−メトキシフェニル）−イミダゾールニ量体、２−（２，３−ジクロロフェニル）−４，５−ビス（４−クロロフェニル）−イミダゾールニ量体、２−（２，３−ジクロロフエニル）−４，５−ジ（２−フリル）−イミダゾール、２，２’−ビス（２−クロロフェニル）−４，５，４’，５’−テトラフエニルー１−２’−ビイミダゾール、ＨＢ２２（保土ヶ谷化学製）などがある。
【００３２】
なお、光重合開始剤の添加量は特に限定されるものではないが、トリアジン系化合物を１種または２種を用いる場合の添加量は、光重合性モノマーの５〜５０重量部、好ましくは１０〜３０重量部を１種または２種添加して用いる。
また、トリアジン系化合物と他の光重合開始剤との混合で用いる場合の添加量はトリアジン系化合物が、光重合性モノマーの１〜５０重量部、好ましくは５〜３０重量部、ベンゾフェノン系化合物、チオキサンソン系化合物、イミダゾール系化合物については、光重合性モノマーの１〜４０重量部、好ましくは５〜２０重量部の割合で添加する。
【００３３】
【実施例】
＜実施例１＞
（感光性着色組成物の調製）
アクリル樹脂（メタクリル酸２０部、ブチルアクリレート３０部、ブチルメタクリレート５０部をエチルセロソルブ３００部に溶解し、窒素雰囲気下でアゾビスイソブチルニトリル０．７５部を加えて７０℃、５時間反応により得られたアクリル樹脂）を樹脂濃度２０％になる様にエチルセロソルブで希釈した。
この希釈樹脂５０ｇに対して顔料１２．３ｇ、分散剤１．３ｇ、溶剤としてシクロヘキサノン３６．４ｇを添加して３本ロールで十分混練して赤の着色樹脂（ペースト）を作製した。同様に希釈樹脂４５ｇに対して顔料１５ｇ、分散剤１．１ｇ、溶剤としてシクロヘキサノン３８．９ｇを添加して３本ロールで十分混練して緑の着色樹脂（ペースト）を作製した。そして、さらに希釈樹脂５０ｇに対して顔料９．５ｇ、分散剤１．０ｇ、溶剤としてシクロヘキサノン３９．５ｇを添加して３本ロールで十分混練して青の着色樹脂（ペースト）を作製した。
【００３４】
以下に顔料及び分散剤を示す。
・［赤用］
（１）顔料
Ｂ−ＣＦ（チバガイギ製ＤＰＰ顔料Ｃ．Ｉ．ピグメントレッド２５４）１２ｇとＡ２Ｂ（チバガイギ製Ｃ．Ｉ．ピグメントレッド１７７）０．３ｇとの混合物。
（２）分散剤
下記構造の化合物
【００３５】
【化３】

【００３６】
・［緑用］
（１）顔料
リオノールグリーン６ＹＫ（東洋インキ製Ｃ．Ｉ．ピグメントグリーン３６）１０．４ｇと５ＧＮ（バイエル製Ｃ．Ｉ．ピグメントイエロー１５０）４．６ｇの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
ＣｕＰＣ［ＳＯ２ Ｎ（Ｃ１８Ｈ３７）２ ］２
【００３７】
・［青用］
（１）顔料
リオノールブルーＥＳ（東洋インキ製Ｃ．Ｉ．ピグメントブルー１５：６）９．０ｇとリオノーゲンバイオレットＨＲ（東洋インキ製Ｃ．Ｉ．ピグメントバイオレット２３）５ｇとの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
【００３８】
【化４】

【００３９】
各着色樹脂（ペースト）５０ｇに対してジペンタエリスリトールアクリレート５ｇ、２−メチルー１−（４−（メチルチオ）フエニル）−２−モルホリノープロパンー１−オン０．８ｇ、メトキシスチリルトリアジン０．２ｇ、さらに先に合成した希釈樹脂３ｇ、さらにプロピレングリコールジメチルアセテート４１ｇを加えて良く攪拌し各色の感光性着色組成物とした。
【００４０】
（カラーフィルタの作製）
まず、ブラックマトリクスが形成された基板上に赤色の感光性着色組成物をスピンコートし乾燥させた。７０℃２０分プレベーク後、液晶表示素子の１画素と同じ画素サイズのマスクを用いて４００ｍＪ／ｃｍ２ 露光した。
２．５％炭酸ナトリウムの水溶液で現像し水洗し、さらに水洗、乾燥後２３０℃３０分で乾燥してパターンを固めた。ベーク後の膜厚は１．８μｍであった。
次に、緑色の感光性着色組成物をスピンコートし乾燥させた。以下赤色と同様のプロセスにて膜厚１．８μｍの緑色のパターンを得た。さらに、青色の感光性着色組成物をスピンコートし乾燥させた。以下前色と同じプロセスにて膜厚１．８μｍの青色のパターンを得た。得られたカラーフィルタの分光を測定した。
Ｃ光源を用いた各色の色度座標は、赤はｘ＝０．６５０２、ｙ＝０．３２９１、緑はｘ＝０．２７８４、ｙ＝０．５８５４、青はｘ＝０．１３５８、ｙ＝０．０９７、またＮＴＳＣ方式の規格値の色再現域１００％に対する色再現域の％（ＮＴＳＣ比）は、６８．９４％であった。
【００４１】
このカラーフィルタを用いて、カラーフィルタ上に１４０ｎｍのＩＴＯを形成し２２０℃で１時間乾燥、次に配向膜を５０ｎｍ塗り乾燥させた。あらかじめ作製しておいたＴＦＴ素子とを一部張り合わせ、残りの部分から液晶を注入、最後に注入打ちを張り合わせて表示素子を完成させた。
【００４２】
＜実施例２＞
実施例１と同じ感光性着色樹脂を用いて以下の条件にてカラーフィルタを作製した。
まず、ブラックマトリクスが形成されたの基板上に赤色の感光性着色組成物をスピンコートし乾燥させた。７０℃２０分プレベーク後、液晶表示素子の１画素と同じ画素サイズのマスクを用いて４００ｍＪ／ｃｍ２ 露光した。
２．５％炭酸ナトリウムの水溶液で現像し水洗し、さらに水洗、乾燥後２３０℃３０分で乾燥してパターンを固めた。ベーク後の膜厚は２．５μｍであった。
次に、緑色の感光性着色組成物をスピンコートし乾燥させた。以下赤色と同様のプロセスにて膜厚２．５μｍの緑色のパターンを得た。さらに、青色の感光性着色組成物をスピンコートし乾燥させた。以下前色と同じプロセスにて膜厚２．５μｍの青色のパターンを得た。得られたカラーフィルタの分光を測定した。
Ｃ光源を用いた各色の色度座標は、赤はｘ＝０．６６５３、ｙ＝０．３２８７、緑はｘ＝０．２６６１、ｙ＝０．６０９９、青はｘ＝０．１３６４、ｙ＝０．０８２、またＮＴＳＣ比は、７８．１３％であった。
【００４３】
このカラーフィルタを用いて、カラーフィルタ上に１４０ｎｍのＩＴＯを形成し２２０℃で１時間乾燥、次に配向膜を５０ｎｍ塗り乾燥させた．あらかじめ作製しておいたＴＦＴ素子とを一部張り合わせ、残りの部分から液晶を注入、最後に注入打ちを張り合わせて表示素子を完成させた。
【００４４】
＜実施例３＞
（感光性着色組成物の調製）
アクリル樹脂（メタクリル酸２０部、ブチルアクリレート３０部、ブチルメタクリレート５０部をエチルセロソルブ３００部に溶解し、窒素雰囲気下でアゾビスイソブチルニトリル０．７５部を加えて７０℃、５時間反応により得られたアクリル樹脂）を樹脂濃度２０％になる様にエチルセロソルブで帝釈した。
この希釈樹脂５０ｇに対して顔料１３ｇ、分散剤０．６ｇ、溶剤としてシクロヘキサノン３６．４ｇを添加して３本ロールで十分混練して赤の着色樹脂（ペースト）を作製した。
同様に希釈樹脂５０ｇに対して顔料１１ｇ、分散剤１．０ｇ、溶剤としてシクロヘキサノン３８．０ｇを添加して３本ロールで十分混練して緑の着色樹脂（ペースト）を作製した。そして、さらに希釈樹脂５０ｇに対して顔料９．５ｇ、分散剤１．０ｇ、溶剤としてシクロヘキサノン３９．５ｇを添加して３本ロールで十分混練して青の着色樹脂（ペースト）を作製した。
【００４５】
以下に顔料及び分散剤を示す。
・［赤用］
（１）顔料
ルビンＴＲ（チバガイギ製Ｃ．Ｉ．ピグメントレッド２６４）１３ｇ。
（２）分散剤
下記構造の化合物
【００４６】
【化５】

【００４７】
・［緑用］
（１）顔料
（東洋インキ製Ｃ．Ｉ．ピグメントグリーン７）６．５ｇとＬＹ２３１１（東洋インキ製Ｃ．Ｉ．ピグメントイエロー１３）３．５ｇの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
ＣｕＰＣ［ＳＯ２ Ｎ（Ｃ１８Ｈ３７）２ ］２
【００４８】
・［青用］
（１）顔料
リオノールブルーＥＳ（東洋インキ製Ｃ．Ｉ．ピグメントブルー１５：６）１０．０ｇとリオノーゲンバイオレットＨＲ（東洋インキ製Ｃ．Ｉ．ピグメントバイオレット２３）０．５ｇとの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
【００４９】
【化６】

【００５０】
各着色樹脂５０ｇに対してジペンタエリスリトールアクリレート４ｇ、２−メチルー１−（４−（メチルチオ）フエニル）−２−モルホリノープロパンー１−オン０．８ｇ、メトキシスチリルトリアジン０．２ｇ、さらに先に合成した希釈樹脂３ｇ、さらにプロピレングリコールジメチルアセテート４１ｇを加えて良く攪拌し各色の感光性着色組成物とした。
【００５１】
（カラーフィルタの作製）
まず、ブラックマトリクスが形成された基板上に赤色の感光性着色組成物をスピンコートし乾燥させた。７０℃２０分プレベーク後、液晶表示素子の１画素と同じ画素サイズのマスクを用いて４００ｍＪ／ｃｍ２ 露光した。
２．５％炭酸ナトリウムの水溶液で現像し水洗し、さらに水洗、乾燥後２３０℃３０分で乾燥してパターンを固めた。ベーク後の膜厚は２．４μｍであった。
次に、緑色の感光性着色組成物をスピンコートし乾燥させた。以下赤と同様のプロセスにて膜厚２．４μｍの緑色パターンを得た。さらに、青色の感光性着色組成物をスピンコートし乾燥させた。以下前色と同じプロセスにて膜厚２．４μｍの青色パターンを得た。得られたカラーフィルタの分光を測定した。
Ｃ光源を用いた各色の色度座標は、赤はｘ＝０．６８４４、ｙ＝０．３１４８、緑はｘ＝０．２５４６、ｙ＝０．６８３０、青はｘ＝０．１３８８、ｙ＝０．０７３５、またＮＴＳＣ比は、９６．２７％であった。
【００５２】
このカラーフィルタを用いて、カラーフィルタ上に１４０ｎｍのＩＴＯを形成し２２０℃で１時間乾燥、次に配向膜を５０ｎｍ塗り乾燥させた．あらかじめ作製しておいたＴＦＴ素子とを一部張り合わせ、残りの部分から液晶を注入、最後に注入打ちを張り合わせて表示素子を完成させた。
【００５３】
＜実施例４＞
（感光性着色組成物の調製）
アクリル樹脂（メタクリル酸２０部、ブチルアクリレート３０部、ブチルメタクリレート５０部をエリルセロソルブ３００部に溶解し、窒素雰囲気下でアゾビスイソプチルニトリル０．７５部を加えて７０℃、５時間反応により得られたアクリル樹脂）を樹脂濃度２０％になる様にエチルセロソルブで希釈した。
この希釈樹脂５０ｇに対して顔料１３ｇ、分散剤０．６ｇ、溶剤としてシクロヘキサノン３６．４ｇを添加して３本ロールで十分混練して赤の着色樹脂（ペースト）を作製した。
同様に希釈樹脂５０ｇに対して顔料１１ｇ、分散剤１．０ｇ、溶剤としてシクロヘキサノン３８．０ｇを添加して３本ロールで十分混練して緑の着色樹脂（ペースト）を作製した。そして、さらに希釈樹脂５０ｇに対して顔料９．５ｇ、分散剤１．０ｇ、溶剤としてシクロヘキサノン３９．５ｇを添加して３本ロールで十分混練して青の着色樹脂（ペースト）を作製した。
【００５４】
以下に顔料及び分散剤を示す。
・［赤用］
（１）顔料
ルビンＴＲ（チバガイギ製Ｃ．Ｉ．ピグメントレッド２６４）１３ｇ。
（２）分散剤
下記構造の化合物
【００５５】
【化７】

【００５６】
・［緑用］
（１）顔料
（東洋インキ製Ｃ．Ｉ．ピグメントグリーン７）６．５ｇとＬＹ２３１１（東洋インキ製Ｃ．Ｉ．ピグメントイエロー１３）３．５ｇの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
ＣｕＰＣ［ＳＯ２ Ｎ（Ｃ１８Ｈ３７）２ ］２
【００５７】
・［青用］
（１）顔料
リオノールブルーＥＳ（東洋インキ製Ｃ．Ｉ．ピグメントブルー１５：６）１０．０ｇとリオノーゲンバイオレットＨＲ（東洋インキ製Ｃ．Ｉ．ピグメントバイオレット２３）０．５ｇとの混合物。
（２）分散剤
下記の銅フタロシアニン誘導体
【００５８】
【化８】

【００５９】
各着色樹脂５０ｇに対してジペンタエリスリトールアクリレート４ｇ、２−メチルー１−（４−（メチルチオ）フェニル）−２−モルホリノープロパンー１−オン０．８ｇ、メトキシスチリルトリアジン０．２ｇ、さらに先に合成した希釈樹脂３ｇ、さらにプロピレングリコールジメチルアセテート４１ｇを加えて良く攪拌し各色の感光性着色組成物とした。
【００６０】
（カラーフィルタの作製）
まず、ブラックマトリクスが形成された基板上に赤色の感光性着色組成物をスピンコートし乾燥させた。７０℃２０分プレベーク後、液晶表示素子の１画素と同じ画素サイズのマスクを用いて４００ｍＪ／ｃｍ２ 露光した。
２．５％炭酸ナトリウムの水溶液で現像し水洗し、さらに水洗、乾燥後２３０℃３０分で乾燥してパターンを固めた。ベーク後の膜厚は３．０μｍであった。
次に、緑色の感光性着色組成物をスピンコートし乾燥させた。以下赤と同様のプロセスにて膜厚３．０μｍの緑色パターンを得た。さらに、青色の感光性着色組成物をスピンコートし乾燥させた。以下前色と同じプロセスにて膜厚３．０μｍの青色パターンを得た。得られたカラーフィルタの分光を測定した。
Ｃ光源を用いた各色の色度座標は、赤はｘ＝０．６８７８、ｙ＝０．３１１９、緑はｘ＝０．２４４６、ｙ＝０．６９８８、青はｘ＝０．１３９９、ｙ＝０．０６３６、またＮＴＳＣ比は、１０１．７８％であった。
【００６１】
このカラーフィルタを用いて、カラーフィルタ上に１４０ｎｍのＩＴＯを形成し２２０℃で１時間乾燥、次に配向膜を５０ｎｍ塗り乾燥させた．あらかじめ作製しておいたＴＦＴ素子とを一部張り合わせ、残りの部分から液晶を注入、最後に注入打ちを張り合わせて表示素子を完成させた。
【００６２】
【発明の効果】
本発明は、液晶表示装置用カラーフィルタであって、カラーフィルタの赤（Ｒ）、緑（Ｇ）、青（Ｂ）三原色のＣ光源によるＣＩＥ色度図上での色度点が、赤（Ｒ）はｘ＝０．６２〜０．６９、ｙ＝０．３１０〜０．３５、緑（Ｇ）はｘ＝０．２０〜０．３２、ｙ＝０．５７〜０．７３、青（Ｂ）はｘ＝０．１３〜０．１７、ｙ＝０．０４〜０．１１の色度座標内にあり、色再現域が、ＮＴＳＣ方式の規格値の色再現域１００％に対し６６％〜１２０％の色再現域を有し、カラーフィルタはアクリル系樹脂に、赤（Ｒ）としてＣ．Ｉ．Ｎｏ．９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２５４，２６４、アントラキノン系、ジケトピロロピロール系、ペリレン系、緑（Ｇ）としてＣ．Ｉ．Ｎｏ．７、３６、青（Ｂ）としてＣ．Ｉ．Ｎｏ．１５、２２、６０、６４、銅フタロシアニンのハロゲン化物、銅フタロシアニン系で結晶構造がα、β、ε型、黄としてピグメントＮｏ．１３，８３，１３８，１３９，１５０、イソインドリン系、モノアゾＮｉ錯体系、アゾ系、紫としてＣ．Ｉ．Ｎｏ．２３の各顔料を三原色毎に２〜３点、アクリル系樹脂に対する顔料の添加量を５０〜１５０重量部として混ぜ合わせた感光性着色組成物を用いて形成され、膜厚が、１．８μｍ〜３．５μｍの範囲にあることを特徴とする液晶表示装置用カラーフィルタであるので、カラーＣＲＴのＮＴＳＣ方式の規格値の色再現域と同等の色再現域を有する液晶表示装置を可能とする液晶表示装置用カラーフィルタとなる。
【００６３】
また、上記液晶表示装置用カラーフィルタを用いることにより、カラーＣＲＴのＮＴＳＣ方式の規格値の色再現域と同等の色再現域を有する液晶表示装置が得られる。また、白表示のレベルを示す色温度で見たとき特に７５００Ｋ〜１５０００Ｋの高いところで良好な色特性を示す液晶表示装置となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a color filter for a liquid crystal display device, and more particularly to a color filter for a liquid crystal display device having a color gamut equivalent to that of a color CRT and a liquid crystal display device using the same.
[0002]
[Prior art]
Color liquid crystal display devices are expected to generate great demand for personal computers, particularly notebook personal computers, and to be further developed into desktop personal computers, monitors, and televisions.
The demand for display colors of color liquid crystal display devices used in notebook personal computers, portable terminals, etc. is that, from the point of power consumption, saturation (that is, lightness (transmittance)) is high even if the color reproduction range is somewhat inferior. As a color filter, a color filter having high brightness (transmittance) corresponding to this demand has been demanded.
[0003]
In order to meet these demands, color filters have been improved by developing pigments, dispersants, and dispersion technologies used in color filters, but color reproduction is inferior and color reproduction is not sufficient. For example, if you try to express dark red, you will feel orange, and if you try to express dark blue, it will remain light blue and color reproduction will not be good.
On the other hand, as a demand for display colors of color liquid crystal display devices used for televisions, monitors, etc., even if the lightness (transmittance) is somewhat inferior, a color reproduction range with improved saturation, for example, a chromaticity diagram The upper color reproduction range is set to be the same color reproduction range as the color CRT.
[0004]
[Problems to be solved by the invention]
The present invention has been made to meet the demand for display colors of color liquid crystal display devices used in such televisions and monitors. The color reproduction range is NTSC (color CRT) on the CIE chromaticity diagram. It is an object of the present invention to provide a color filter for a liquid crystal display device that enables a liquid crystal display device having a color gamut equivalent to the standard color gamut of the National Television System Committee (National Television System Committee).
It is another object of the present invention to provide a liquid crystal display device having the color gamut using the color filter for the liquid crystal display device.
[0005]
[Means for Solving the Problems]
The present invention is a color filter for a liquid crystal display device, wherein the chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors red (R), green (G), and blue (B) is red ( R) is x = 0.62 to 0.69, y = 0.310 to 0.35, green (G) is x = 0.20 to 0.32, y = 0.57 to 0.73, blue ( B) is in the chromaticity coordinates of x = 0.13 to 0.17 and y = 0.04 to 0.11, and the color gamut is 66% with respect to the color gamut 100% of the NTSC standard value. It has a color gamut of ~ 120% and the color filter is made of acrylic resin. Red pigment for red pixel C.I. I. No. 177 and red pigment C.I. I. No. 254 mixed pigment, green pigment for green pixel C.I. I. No. 36 and yellow pigment C.I. I. No. 150 mixed pigments, blue pigments for blue pixels C.I. I. No. 15: 6 and purple pigment C.I. I. No. 23 mixed pigments A liquid crystal formed using a photosensitive coloring composition in which the amount of pigment added to the acrylic resin is mixed at 50 to 150 parts by weight, and having a thickness in the range of 1.8 μm to 3.5 μm It is a color filter for display devices.
[0006]
The present invention also provides a liquid crystal display device using the color filter for a liquid crystal display device according to the above invention.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
In many cases, each color pattern constituting the color filter for a liquid crystal display device is formed by a photolithography method using a photosensitive coloring composition.
In the preparation of the photosensitive coloring composition, the basic concept for each color pattern is to first select a pigment having an appropriate spectral distribution, and then determine the content of the pigment contained in each color pattern. When the pigment content is small, for example, the red (R) chromaticity coordinate x is smaller than 0.62, the green (G) chromaticity coordinate y is smaller than 0.57, and the blue (B) The chromaticity coordinate y is larger than 0.11, and a sufficient color reproduction range cannot be obtained.
[0008]
Therefore, in order to widen the color gamut, the pigment content in each color pattern is increased to improve the saturation of each color pattern, but the brightness (transmittance) of each color pattern decreases. In order not to overdo it, it shall have a content that maintains a balance between saturation and lightness (transmittance).
Then, by increasing the content of the pigment contained in each color pattern, the film thickness of each color pattern can be simultaneously reduced, and thereby the shape of each color pattern formed by the photolithography method is good. To be something.
[0009]
That is, according to the above concept, each color pattern having good saturation, lightness (transmittance), and shape is obtained. However, in a filter used for a TV, a monitor, etc., the brightness (transmittance) of each color pattern is obtained. ) Is inferior, it will be prepared with a wide color reproduction range with improved saturation.
[0010]
On the other hand, with respect to the coating property when the photosensitive coloring composition is applied on the substrate, the photosensitive coloring composition is composed of, for example, main components such as resin, pigment, dispersant, photopolymerizable monomer, and solvent. The ratio of the solid content other than the solvent to the photosensitive coloring composition (solid content ratio) is kept at a certain value or less to improve the coating property.
This is to avoid problems such as uneven coating and non-uniform film thickness in the coating film on the substrate when the solid content ratio exceeds a certain value.
[0011]
Furthermore, with respect to the dispersibility and temporal stability of the photosensitive coloring composition, the ratio of the pigment in the solid content of the photosensitive coloring composition is kept below a certain value to improve the dispersibility and temporal stability. .
This is because when the proportion of the pigment increases, for example, the red (R) chromaticity coordinate x is 0.69 or more, the green (G) chromaticity coordinate y is 0.73 or more, and the blue (B) color. Although y of the degree coordinate is 0.04 or less and the color reproduction range is surely wide, the dispersibility of the photosensitive coloring composition is lowered, and the equilibrium as the dispersion system is easily broken with time, and the photosensitive coloring composition. This is in order to avoid problems such as a problem that the gelation of an object proceeds.
[0012]
As described above, the photosensitive coloring composition is prepared in consideration of the saturation, brightness (transmittance), and shape of each color pattern to be obtained, and in consideration of coating properties, dispersibility, and stability over time. Is.
[0013]
As a method corresponding to the demand for widening the color gamut, a method of increasing the saturation by increasing the film thickness of each color pattern and increasing the content of the pigment contained in each color pattern can be considered.
This method sacrifices lightness (transmittance), but is a practical method for widening the color reproduction range.
However, as the film thickness of each color pattern is increased, problems such as coating unevenness and film thickness unevenness are likely to occur in the coating film. In particular, the size of the glass substrate for manufacturing the liquid crystal display device is large. From about 400 × 500 mm to about 550 × 650 mm, about 650 × 750 mm, and further to larger sizes, uneven coating and non-uniform film thickness are more likely to occur as the glass substrate becomes larger.
[0014]
Further, in this method, as the thickness of each color pattern is increased, the shape of each color pattern is deteriorated. That is, as the thickness of each color pattern increases, the cross-sectional shape of each color pattern becomes an overhang. This is because when the coating film becomes thicker, UV light at the time of exposure is attenuated in the lower layer portion and the lower layer portion is not sufficiently cured, and therefore, the lower layer portion is easily dissolved from the lateral direction by development. If the cross-sectional shape is an overhang shape, problems such as disconnection occur in the electrode layer formed on the pattern of each color, which is not preferable. The film thickness of each color pattern is preferably about 3.6 μm or less, 1.8μ Below m, the color reproduction range becomes narrow, which is not preferable.
[0015]
The range of colors that can be reproduced by the color CRT of a color television receiver is surrounded by three chromaticity points on the chromaticity diagram of the three primary colors emitted by the phosphors of red (R), green (G), and blue (B). The inside of the triangle.
For example, the area of a triangle on the chromaticity diagram surrounded by three chromaticity points according to the standard value of the NTSC (National Television System Committee) system is the color gamut in the NTSC system.
[0016]
The standard values of the three primary colors of the NTSC system red (R), green (G), and blue (B) in the chromaticity diagram of the CIE 1931 standard display system are shown below.
Rx = 0.67, Ry = 0.33
Gx = 0.21, Gy = 0.71
Bx = 0.14, By = 0.08
[0017]
In addition, the following shows a mathematical formula for obtaining a color reproduction range (a triangular area (S) formed by three chromaticity points) in the standard value of the NTSC system on the chromaticity diagram of the CIE 1931 standard display system.

[0018]
In the present invention, the chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors red (R), green (G), and blue (B) of the color filter is x = 0.62-0. .69, y = 0.310 to 0.35, green (G) x = 0.20 to 0.32, y = 0.57 to 0.73, blue (B) x = 0.13 to 0 .17, y = 0.04 to 0.11 in the chromaticity coordinates, and the color reproduction range is 66% to 120% with respect to the NTSC standard value color reproduction range of 100%. The color reproduction area% (NTSC ratio) with respect to the color reproduction area 100% of the standard value of the NTSC system of a certain color filter (i) can be obtained by the following equation.
[0019]
(Si / S) × 100
Where Si: area of a triangle on the CIE chromaticity diagram of a color filter (i)
S: 0.1582
Si is obtained by the following equation.

Here, Rxi, Ryi, Gxi, Gyi, Bxi, Byi are the chromaticity coordinates of a certain color filter (i).
[0020]
The color filter having the above color gamut according to the present invention has a film thickness of each color pattern using the photosensitive coloring composition described below. 1.8 It is obtained by forming in the range of μm to 3.5 μm. In the preparation of the photosensitive coloring composition in the present invention, first, in order to mix the acrylic resin and the pigment well, they are kneaded using two rolls to form chips, and then the chips are dissolved using a dispersant and a solvent. To prepare a colored resin (paste). Next, a photosensitive polymerizable composition is prepared by adding a photopolymerizable monomer and a photopolymerizable initiator to the colored resin (paste).
[0021]
The acrylic resin used at this time is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or other alkyl acrylate or alkyl methacrylate, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate Alternatively, a resin synthesized to have a molecular weight of about 5000 to 100,000 using about 3 to 5 types of monomers from among methacrylate and the like is used.
In addition, a resin obtained by adding an unsaturated double bond to a part of an acrylic resin, the above acrylic resin, an isocyanate group having an isocyanate group and at least one vinyl group, a compound such as methacryloyl isocyanate is reacted. The resulting photosensitive copolymer having an acid value of 50 to 150 can be used.
[0022]
As the pigment, red (R) as C.I. I. No. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, 264, etc., green (G) is C.I. I. No. 7, 36, blue (B) as C.I. I. No. 15, 22, 60, 64 are generally used.
As yellow, Pigment No. 13, 83, 138, 139, 150, etc., among which isoindoline, monoazo Ni complex, and azo are preferred. Green is a halide of copper phthalocyanine, and blue is a copper phthalocyanine type, and the crystal structure is preferably α, β, or ε type. As purple, C.I. I. No. 23 is used.
Particularly for red pigments, it is desirable to use anthraquinone (Ciba-Gigi, A2B, A3B, etc.), diketopyrrolopyrrole (Ciba-Gigi, B-CF, Orange TR, Rubin TR, etc.) and perylene. However, it is not particularly limited to this.
[0023]
A wide range of dispersants such as surfactants, pigment intermediates, dye intermediates, and Solsperse are used as the dispersant. Preferably, it is a derivative of an organic dye, and the organic dye as a base is an azo, phthalocyanine, quinacridone, anthraquinone, perylene, thioindico, dioxane, or pyrrole metal complex. These organic dyes have a substituent and are effective in dispersing the dye.
Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfone group, a carbonamide group, a sulfonamide group, or any substituent represented by the following general formula. A derivative having at least one substituent selected from these substituents is used.
[0024]
[Chemical 1]

[0025]
[Chemical 2]

[0026]
In addition, although the same thing is combined with the pigment | dye used for this invention, and the base organic pigment | dye of a dispersing agent from the relationship of a normal phase, it does not necessarily need to correspond. The ratio of the composition at the time of dispersion is not particularly limited, but the addition amount of the pigment to the acrylic resin for dispersion is about 50 to 150 parts by weight, and the dispersant is about 1 to 10 parts by weight of the pigment. .
For spectral adjustment of the color filter, two or three arbitrary pigments are mixed and adjusted.
[0027]
Photopolymerizable monomers include bifunctional, trifunctional, and polyfunctional monomers. Examples of bifunctional monomers include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol acrylate, and triethylene glycol diacrylate. There are trifunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, and polyfunctional monomers such as ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. There is.
As these monomers, there are commercially available products such as Showa Polymer Co., Ltd., Toagosei Co., Ltd., Nippon Kayaku Co., Ltd. and the like. The addition amount of the photopolymerizable monomer is not particularly limited, but is about 20 to 150 parts by weight of the acrylic resin for dispersion.
[0028]
Solvents include methanol, ethanol, toluene, xylene, ethyl cellosolve, ethyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, isoamyl acetate, mamyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, lactic acid Ethyl etc. are used, Monomer composition of fat, photopolymerizable monomer, solubility and the like photopolymerization initiator appropriately selecting the solvent for single or multiple solvent composition is different.
[0029]
Examples of the photopolymerization initiator include conventional triazine compounds, 2,4,6-tris (trichloromethyl) -S monotriazine, 2- (p-methoxystyryl) -4,6-pis (trichloromethyl)- S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) ) -4,6 monobis (trichloromethyl) -S-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-hist (trichloromethyl) -S monotriazine, etc. .
[0030]
Further, as acetophenone compounds, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-enyl (4-dodecyl) propan-1-one and so on.
Examples of benzophenone compounds include benzophenone, 4,4-diethylaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, and methyl 0-benzophenone benzoate.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone.
[0031]
Examples of imidazole compounds include 2- (2,3-dichlorophenyl) -4,5-diphenyl-imidazole dimer, 2- (2,3-dichlorophenyl) -4,5 monobis (3-methoxy). Phenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-chlorophenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-di (2-furyl) -imidazole, 2,2′-bis (2-chlorophenyl) -4, 5,4 ′, 5′-tetraphenyl1-2′-biimidazole, HB22 (manufactured by Hodogaya Chemical) and the like.
[0032]
The addition amount of the photopolymerization initiator is not particularly limited, but the addition amount when using one or two triazine compounds is 5 to 50 parts by weight of the photopolymerizable monomer, preferably 10 ˜30 parts by weight are added and used.
In addition, when used in a mixture of a triazine compound and another photopolymerization initiator, the addition amount of the triazine compound is 1 to 50 parts by weight of the photopolymerizable monomer, preferably 5 to 30 parts by weight, a benzophenone compound, About a thioxanthone type compound and an imidazole type compound, it adds in the ratio of 1-40 weight part of a photopolymerizable monomer, Preferably it is 5-20 weight part.
[0033]
【Example】
<Example 1>
(Preparation of photosensitive coloring composition)
Acrylic resin (20 parts of methacrylic acid, 30 parts of butyl acrylate, 50 parts of butyl methacrylate are dissolved in 300 parts of ethyl cellosolve, 0.75 part of azobisisobutylnitrile is added under a nitrogen atmosphere, and the reaction is obtained at 70 ° C. for 5 hours. Acrylic resin) was diluted with ethyl cellosolve to a resin concentration of 20%.
To this diluted resin 50g, 12.3g of pigment, 1.3g of dispersant and 36.4g of cyclohexanone as a solvent were added and sufficiently kneaded with three rolls to prepare a red colored resin (paste). Similarly, 15 g of pigment, 1.1 g of dispersant and 38.9 g of cyclohexanone as a solvent were added to 45 g of diluted resin, and kneaded sufficiently with three rolls to prepare a green colored resin (paste). Further, 9.5 g of a pigment, 1.0 g of a dispersant and 39.5 g of cyclohexanone as a solvent were added to 50 g of the diluted resin, and sufficiently kneaded with three rolls to prepare a blue colored resin (paste).
[0034]
The pigments and dispersants are shown below.
・ [For red]
(1) Pigment
A mixture of 12 g of B-CF (DPP pigment CI Pigment Red 254 from Ciba-Gaigi) and 0.3 g of A2B (CI Pigment Red 177 from Ciba-Gaigi).
(2) Dispersant
Compounds with the following structure
[0035]
[Chemical 3]

[0036]
・ [For green]
(1) Pigment
A mixture of 10.4 g of Lionol Green 6YK (CI Pigment Green 36 manufactured by Toyo Ink) and 4.6 g of 5GN (CI Pigment Yellow 150 manufactured by Bayer).
(2) Dispersant
The following copper phthalocyanine derivatives
CuPC [SO2N (C18H37) 2] 2
[0037]
・ [For blue]
(1) Pigment
A mixture of 9.0 g of Lionol Blue ES (CI Pigment Blue 15: 6 from Toyo Ink) and 5 g of Lionogen Violet HR (CI Pigment Violet 23 from Toyo Ink).
(2) Dispersant
The following copper phthalocyanine derivatives
[0038]
[Formula 4]

[0039]
50 g of each colored resin (paste), 5 g of dipentaerythritol acrylate, 0.8 g of 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 0.2 g of methoxystyryltriazine, Further, 3 g of the diluted resin synthesized earlier and 41 g of propylene glycol dimethyl acetate were added and stirred well to obtain a photosensitive coloring composition of each color.
[0040]
(Production of color filter)
First, a red photosensitive coloring composition was spin-coated on a substrate on which a black matrix was formed and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed at 400 mJ / cm 2 using a mask having the same pixel size as one pixel of the liquid crystal display element.
The pattern was solidified by developing with an aqueous solution of 2.5% sodium carbonate, washing with water, further washing with water, drying and drying at 230 ° C. for 30 minutes. The film thickness after baking was 1.8 μm.
Next, the green photosensitive coloring composition was spin-coated and dried. Thereafter, a green pattern having a film thickness of 1.8 μm was obtained by the same process as that for red. Further, a blue photosensitive coloring composition was spin-coated and dried. Thereafter, a blue pattern having a film thickness of 1.8 μm was obtained by the same process as the previous color. The spectrum of the obtained color filter was measured.
The chromaticity coordinates of each color using the C light source are as follows: red x = 0.6502, y = 0.3291, green x = 0.2784, y = 0.5854, blue x = 0.1358, y = The% of the color gamut (NTSC ratio) with respect to the color reproduction gamut of 100% of the standard value of the NTSC system was 68.94%.
[0041]
Using this color filter, ITO having a thickness of 140 nm was formed on the color filter and dried at 220 ° C. for 1 hour, and then an alignment film was applied and dried by 50 nm. A part of the TFT element prepared in advance was bonded together, liquid crystal was injected from the remaining part, and finally injection bonding was performed to complete the display element.
[0042]
<Example 2>
A color filter was prepared using the same photosensitive colored resin as in Example 1 under the following conditions.
First, a red photosensitive coloring composition was spin-coated on a substrate on which a black matrix was formed and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed at 400 mJ / cm 2 using a mask having the same pixel size as one pixel of the liquid crystal display element.
The pattern was solidified by developing with an aqueous solution of 2.5% sodium carbonate, washing with water, further washing with water, drying and drying at 230 ° C. for 30 minutes. The film thickness after baking was 2.5 μm.
Next, the green photosensitive coloring composition was spin-coated and dried. Thereafter, a green pattern having a thickness of 2.5 μm was obtained by the same process as that for red. Further, a blue photosensitive coloring composition was spin-coated and dried. Thereafter, a blue pattern having a film thickness of 2.5 μm was obtained by the same process as the previous color. The spectrum of the obtained color filter was measured.
The chromaticity coordinates of each color using the C light source are as follows: red x = 0.6653, y = 0.3287, green x = 0.2661, y = 0.6099, blue x = 0.1364, y = 0.082 and the NTSC ratio was 78.13%.
[0043]
Using this color filter, ITO having a thickness of 140 nm was formed on the color filter and dried at 220 ° C. for 1 hour, and then an alignment film was applied and dried by 50 nm. A part of the TFT element prepared in advance was bonded together, liquid crystal was injected from the remaining part, and finally injection bonding was performed to complete the display element.
[0044]
<Example 3>
(Preparation of photosensitive coloring composition)
Acrylic resin (20 parts of methacrylic acid, 30 parts of butyl acrylate, 50 parts of butyl methacrylate are dissolved in 300 parts of ethyl cellosolve, 0.75 part of azobisisobutylnitrile is added under a nitrogen atmosphere, and the reaction is obtained at 70 ° C. for 5 hours. (Acrylic resin) was impregnated with ethyl cellosolve to a resin concentration of 20%.
13 g of pigment, 0.6 g of dispersant and 36.4 g of cyclohexanone as a solvent were added to 50 g of this diluted resin, and kneaded sufficiently with three rolls to prepare a red colored resin (paste).
Similarly, 11 g of pigment, 1.0 g of dispersant and 38.0 g of cyclohexanone as a solvent were added to 50 g of diluted resin, and kneaded sufficiently with three rolls to prepare a green colored resin (paste). Further, 9.5 g of a pigment, 1.0 g of a dispersant and 39.5 g of cyclohexanone as a solvent were added to 50 g of the diluted resin, and sufficiently kneaded with three rolls to prepare a blue colored resin (paste).
[0045]
The pigments and dispersants are shown below.
・ [For red]
(1) Pigment
13 g of Rubin TR (Ciba Pigeon CI Pigment Red 264).
(2) Dispersant
Compounds with the following structure
[0046]
[Chemical formula 5]

[0047]
・ [For green]
(1) Pigment
(Toyo Ink CI Pigment Green 7) 6.5g and LY2311 (Toyo Ink CI Pigment Yellow 13) 3.5g mixture.
(2) Dispersant
The following copper phthalocyanine derivatives
CuPC [SO2N (C18H37) 2] 2
[0048]
・ [For blue]
(1) Pigment
A mixture of 10.0 g Lionol Blue ES (Toyo Ink CI Pigment Blue 15: 6) and 0.5 g Lionogen Violet HR (Toyo Ink CI Pigment Violet 23).
(2) Dispersant
The following copper phthalocyanine derivatives
[0049]
[Chemical 6]

[0050]
For each colored resin 50 g, 4 g of dipentaerythritol acrylate, 0.8 g of 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 0.2 g of methoxystyryltriazine, and further 3 g of the synthesized diluted resin and 41 g of propylene glycol dimethyl acetate were added and stirred well to obtain a photosensitive coloring composition of each color.
[0051]
(Production of color filter)
First, a red photosensitive coloring composition was spin-coated on a substrate on which a black matrix was formed and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed at 400 mJ / cm 2 using a mask having the same pixel size as one pixel of the liquid crystal display element.
The pattern was solidified by developing with an aqueous solution of 2.5% sodium carbonate, washing with water, further washing with water, drying and drying at 230 ° C. for 30 minutes. The film thickness after baking was 2.4 μm.
Next, the green photosensitive coloring composition was spin-coated and dried. Thereafter, a green pattern having a film thickness of 2.4 μm was obtained by the same process as that for red. Further, a blue photosensitive coloring composition was spin-coated and dried. Thereafter, a blue pattern having a film thickness of 2.4 μm was obtained by the same process as the previous color. The spectrum of the obtained color filter was measured.
The chromaticity coordinates of each color using a C light source are as follows: red is x = 0.6844, y = 0.3148, green is x = 0.2546, y = 0.6830, blue is x = 0.1388, y = 0.0735 and the NTSC ratio was 96.27%.
[0052]
Using this color filter, ITO having a thickness of 140 nm was formed on the color filter and dried at 220 ° C. for 1 hour, and then an alignment film was applied and dried by 50 nm. A part of the TFT element prepared in advance was bonded together, liquid crystal was injected from the remaining part, and finally injection bonding was performed to complete the display element.
[0053]
<Example 4>
(Preparation of photosensitive coloring composition)
Acrylic resin (20 parts of methacrylic acid, 30 parts of butyl acrylate, 50 parts of butyl methacrylate are dissolved in 300 parts of erythr cellosolve, and 0.75 parts of azobisisoptylnitrile is added in a nitrogen atmosphere, and obtained by reaction at 70 ° C. for 5 hours. The obtained acrylic resin) was diluted with ethyl cellosolve so that the resin concentration became 20%.
13 g of pigment, 0.6 g of dispersant and 36.4 g of cyclohexanone as a solvent were added to 50 g of this diluted resin, and kneaded sufficiently with three rolls to prepare a red colored resin (paste).
Similarly, 11 g of pigment, 1.0 g of dispersant and 38.0 g of cyclohexanone as a solvent were added to 50 g of diluted resin, and kneaded sufficiently with three rolls to prepare a green colored resin (paste). Further, 9.5 g of a pigment, 1.0 g of a dispersant and 39.5 g of cyclohexanone as a solvent were added to 50 g of the diluted resin, and sufficiently kneaded with three rolls to prepare a blue colored resin (paste).
[0054]
The pigments and dispersants are shown below.
・ [For red]
(1) Pigment
13 g of Rubin TR (Ciba Pigeon CI Pigment Red 264).
(2) Dispersant
Compounds with the following structure
[0055]
[Chemical 7]

[0056]
・ [For green]
(1) Pigment
(Toyo Ink CI Pigment Green 7) 6.5g and LY2311 (Toyo Ink CI Pigment Yellow 13) 3.5g mixture.
(2) Dispersant
The following copper phthalocyanine derivatives
CuPC [SO2N (C18H37) 2] 2
[0057]
・ [For blue]
(1) Pigment
A mixture of 10.0 g Lionol Blue ES (Toyo Ink CI Pigment Blue 15: 6) and 0.5 g Lionogen Violet HR (Toyo Ink CI Pigment Violet 23).
(2) Dispersant
The following copper phthalocyanine derivatives
[0058]
[Chemical 8]

[0059]
For each colored resin 50 g, 4 g of dipentaerythritol acrylate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one 0.8 g, methoxystyryltriazine 0.2 g, 3 g of the diluted resin synthesized and 41 g of propylene glycol dimethyl acetate were added and stirred well to obtain a photosensitive coloring composition of each color.
[0060]
(Production of color filter)
First, a red photosensitive coloring composition was spin-coated on a substrate on which a black matrix was formed and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed at 400 mJ / cm 2 using a mask having the same pixel size as one pixel of the liquid crystal display element.
The pattern was solidified by developing with an aqueous solution of 2.5% sodium carbonate, washing with water, further washing with water, drying and drying at 230 ° C. for 30 minutes. The film thickness after baking was 3.0 μm.
Next, the green photosensitive coloring composition was spin-coated and dried. Thereafter, a green pattern having a thickness of 3.0 μm was obtained by the same process as that for red. Further, a blue photosensitive coloring composition was spin-coated and dried. Thereafter, a blue pattern having a thickness of 3.0 μm was obtained by the same process as the previous color. The spectrum of the obtained color filter was measured.
The chromaticity coordinates of each color using the C light source are as follows: red is x = 0.6878, y = 0.3119, green is x = 0.2446, y = 0.69888, blue is x = 0.1399, y = 0.0636 and the NTSC ratio was 101.78%.
[0061]
Using this color filter, ITO having a thickness of 140 nm was formed on the color filter and dried at 220 ° C. for 1 hour, and then an alignment film was applied and dried by 50 nm. A part of the TFT element prepared in advance was bonded together, liquid crystal was injected from the remaining part, and finally injection bonding was performed to complete the display element.
[0062]
【The invention's effect】
The present invention is a color filter for a liquid crystal display device, wherein the chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors red (R), green (G), and blue (B) of the color filter is red ( R) is x = 0.62 to 0.69, y = 0.310 to 0.35, green (G) is x = 0.20 to 0.32, y = 0.57 to 0.73, blue ( B) is in the chromaticity coordinates of x = 0.13 to 0.17 and y = 0.04 to 0.11, and the color gamut is 66% with respect to the color gamut 100% of the NTSC standard value. Has a color gamut of ~ 120%, The color filter is made of acrylic resin with C.I. I. No. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, 264, anthraquinone, diketopyrrolopyrrole, perylene, green (G) as C.I. I. No. 7, 36, blue (B) as C.I. I. No. 15, 22, 60, 64, copper phthalocyanine halide, copper phthalocyanine series, crystal structure of α, β, ε type, yellow as pigment No. 13, 83, 138, 139, 150, isoindoline, monoazo Ni complex, azo, purple, C.I. I. No. Each of the 23 pigments is formed by using a photosensitive coloring composition in which 2 to 3 points for each of the three primary colors and 50 to 150 parts by weight of the pigment added to the acrylic resin are mixed, and the film thickness is 1.8 μm. Since the color filter for a liquid crystal display device is characterized by being in the range of ˜3.5 μm, a liquid crystal display device having a color gamut equivalent to the standard color gamut of the NTSC system of the color CRT is enabled. It becomes a color filter for liquid crystal display devices.
[0063]
Further, by using the color filter for a liquid crystal display device, a liquid crystal display device having a color gamut equivalent to the color gamut of the standard value of the NTSC system of color CRT can be obtained. In addition, when viewed at a color temperature indicating the level of white display, a liquid crystal display device that exhibits good color characteristics particularly at a high temperature of 7500K to 15000K.

Claims (2)

A color filter for a liquid crystal display device, wherein the chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors red (R), green (G), and blue (B) is red (R) = 0.62 to 0.69, y = 0.310 to 0.35, green (G) is x = 0.20 to 0.32, y = 0.57 to 0.73, blue (B) is x = 0.13 to 0.17, y = 0.04 to 0.11, and the color reproduction range is 66% to 120% with respect to 100% of the color reproduction range of the NTSC standard value. It has a color gamut, the color filter is made of acrylic resin, red pigment C.I. I. No. 177 and red pigment C.I. I. No. 254 mixed pigment, green pigment for green pixel C.I. I. No. 36 and yellow pigment C.I. I. No. 150 mixed pigments, blue pigments for blue pixels C.I. I. No. 15: 6 and purple pigment C.I. I. No. 23 mixed pigments were formed using a photosensitive coloring composition obtained by mixing 50 to 150 parts by weight of the pigment added to the acrylic resin, and the film thickness was in the range of 1.8 μm to 3.5 μm. A color filter for a liquid crystal display device.   A liquid crystal display device using the color filter for a liquid crystal display device according to claim 1.