JP3663759B2 - Method for manufacturing liquid crystal display device and liquid crystal display device - Google Patents

Description

ここで一般式（１）のｎは１〜２である。Ｒ1 は少なくとも２個の炭素原子を有する３価または４価の有機基である。Ｒ1 は環状炭化水素、芳香族環または芳香族複素環を含有することが好ましく、かつ炭素数６から３０の３価または４価の基が好ましい。Ｒ1 の例として、フェニル残基、ビフェニル残基、ターフェニル残基、ナフタレン残基、ペリレン残基、ジフェニルエーテル残基、ジフェニルスルフォン残基、ジフェニルプロパン残基、ベンゾフェノン残基、ビフェニルトリフルオロプロパン残基、シクロブチル残基、シクロペンチル残基などが挙げられるがこれらに限定されるものではない。またＲ2 は少なくとも２個の炭素原子を有する２価の有機基である。耐熱性の面から、Ｒ2 は環状炭化水素、芳香族環または芳香族複素環を含有し、かつ炭素数６から３０の２価の基が好ましい。Ｒ2 の例として、フェニル残基、ビフェニル残基、ターフェニル残基、ナフタレン残基、ペリレン残基、ジフェニルエーテル残基、ジフェニルスルフォン残基、ジフェニルプロパン残基、ベンゾフェノン残基、ビフェニルトリフルオロプロパン残基、ジフェニルメタン残基、シクロヘキシルメタン残基などが挙げられるがこれらに限定されるものではない。一般式（１）で表わされる構造単位を主成分とするポリマはＲ1 、Ｒ2 がこれらの内各々１個から構成されていても良いし、各々２種以上から構成される共重合体であっても良い。接着力を向上させるため耐熱性を低下させない範囲でジアミン成分として、シロキサン構造を有するビス（３−アミノプロピル）テトラメチルジシロキサンなどを共重合させても良い。またアミン末端の封止剤として無水マレイン酸などの無水物をポリアミック酸の重合終了後に末端濃度に応じて加え、反応させても良い。ポリアミック酸を閉環して得られるポリイミド膜の力学的特性は、分子量が大きいほど良好である。このため、ポリアミック酸の分子量も大きい事が望まれる。これらのポリアミック酸において、特に酸無水物成分の少なくとも１部として３，３´，４，４´−ベンゾフェノンテトラカルボン酸とジアミン成分を反応せしめて得られるポリアミック酸が好ましく使用される。また本発明においてはあらかじめ閉環されたポリイミド樹脂溶液組成物が使用されても良く、このような樹脂溶液組成物成分としては例えば２，３，５−トリカルボキシシクロペンチル酢酸無水物のような脂環族テトラカルボン酸無水物とジアミン成分を反応せしめて得られる溶媒可溶型のポリイミド成分が好ましく使用できる。
【００１５】
その他、本発明のポリイミドおよび／あるいはその前駆体成分として Jpn.J. Appl.Phys.Lett.,50,18(1987) 、Mol.Cryst.Liq.Cryst.,163,157(1988)、Japan Display,1992 Digest,819(1992) 、電子材料、３０（１１），３８（１９９１）に記載されるようなポリマ成分を好ましく使用できる。
【００１６】
本発明において好ましく使用される塗液の溶剤成分としてはポリアミック酸、ポリイミドあるいはポリイミドシロキサン前駆体溶液調製に使用されるＮ−メチルピロリドン、Ｎ，Ｎ´−ジメチルアセトアミド、γ−ブチロラクトン、１，３−ジメチル−２−イミダゾリジノン等の極性溶剤が使用できるが、特に本発明で使用される塗液組成物においてポリイミドシロキサン前駆体を使用された場合、多量のアルコール成分を使用することができる特徴を有している。従来、実用されているポリイミド系液晶配向膜形成用樹脂溶液組成物において、アルコール溶剤を使用した例は無く、またポリマー成分の析出を避けるために溶剤成分として２０重量％以上のアルコール成分を使用することができなかったものであるが、本発明の液晶配向性付与の透明層形成の樹脂溶液組成物においては溶剤成分の３０重量％以上、さらには５０重量％以上のアルコール成分を使用することもでき、このような溶剤組成は例えば塗布ラインの耐溶剤性レベルを緩和することができ、インキジェット塗布を可能ならしめるものである。アルコール成分は通常Ｎ−メチルピロリドン、Ｎ，Ｎ´−ジメチルアセトアミド、γ−ブチロラクトンあるいは１，３−ジメチル−２−イミダゾリジノン等の極性溶剤とともにポリイミドシロキサン前駆体溶液調製に使用され、好ましくは、別途調製されたポリイミドおよび／あるいはその前駆体溶液と混合され、本発明のインキジェット塗布の塗液用樹脂溶液組成物の溶剤成分を構成するものであるが、混合調製後に添加することも可能である。本発明において使用される塗液中のアルコール成分としては特に限定されるものでは無いが、プロピレングリコールモノアルキルエーテル、エチレングリコールモノアルキルエーテル、ジエチレングリコールモノアルキルエーテル、３−メトキシ−３−メチルブタノールのごときエーテル結合を有するアルコール類が好ましく使用され、特に３−メトキシ−３−メチルブタノールが適している。本発明のインキジェット塗布に使用される塗液用樹脂溶液組成物の固形部濃度は２〜１５重量％、好ましくは３〜１０重量％である。
【００１７】
本発明のインキジェット塗布に使用される塗液用樹脂溶液組成物はＴＦＴ基板上の所望のパターン状にインキジェット塗布されるものであり、画面構成部の有効領域上に透明層があり、該透明層の境界がカラーフィルター画素を囲む額縁上に相当する位置にある構成とすることが好ましい。
【００１８】
また本発明のインキジェット塗布は、特にカラーフィルターの画素上に透明導電層を持たないところの透明基板に対して平行な向きの電界（横電界）により駆動されるカラー液晶表示装置のＴＦＴ基板に好ましく適用され、このＴＦＴ基板では本発明の透明層は保護膜と配向膜の機能を兼ね備える。
【００１９】
以下、実施例でより詳細に説明する。
【００２０】
【実施例】
参考例１
メチルトリメトキシシラン１３６ｇ（１．０モル）、フェニルトリメトキシシラン１９８ｇ（１．０モル）、３，３´，４，４´−ベンゾフェノンテトラカルボン酸二無水物３２．２ｇ（０．１モル）をγ−ブチロラクトン１４０ｇ、３−メチル−３−メトキシブタノ−ル４２１ｇに溶解し、３０℃で撹拌しながら、１１８ｇの蒸留水を加え、１時間撹拌し、加水分解・縮合を行なった。
【００２１】
この溶液を、バス温１０５℃で３時間加熱・攪拌し生成したアルコ−ルと水１４０ｇを留去させた後、γ−アミノプロピルメチルジエトキシシラン３８．３ｇ（０．２モル）をγ−ブチロラクトン１３３ｇ、３−メチル−３−メトキシブタノ−ル３５５．０ｇに溶解した混合液を添加して、同温で１時間加熱、攪拌した後、徐々に加熱、攪拌下に昇温して１時間後にバス温１３５℃として２時間、加熱攪拌し、反応温度を１２５℃まで上げて生成したアルコ−ルと水７５ｇを留去させた。
【００２２】
この様にして得られた溶液を冷却して室温とした後、シリコーン系界面活性剤ＢＹＫ３０２（ビック・ケミー社）０．５ｇの３−メチル−３−メトキシブタノ−ル６０．０ｇ溶液で稀釈して、ポリイミドシロキサン前駆体溶液を得た。
【００２３】
このようにして得られた溶液の固形分濃度を３００℃、３０分加熱の溶剤除去法で測定すると１８．３重量％であり、粘度は１７．５センチポイズ（２５℃）であった。
【００２４】
参考例２
３，３´，４，４´−ベンゾフェノンテトラカルボン酸二無水物１６１．１１ｇ（０．５０モル）およびピロメリット酸二無水物９７．２０ｇ（０．４９モル）をγブチロラクトン２６７７．７ｇとともに仕込み、これを攪拌しながら４，４´−ジアミノジフェニルエーテル１５０．２０ｇ（０．７５モル）、３，３´−ジアミノジフェニルスルフォン４９．６４ｇ（０．２モル）およびビス（３−アミノプロピル）テトラメチルジシロキサン１２．４２ｇ（０．０２０モル）を添加し、６０℃で２時間反応させた後、無水マレイン酸１．９７ｇ（０．０２０モル）を加えてさらに６０℃で２時間反応させ、粘度９．２ポイズのポリアミック酸溶液を得た。
【００２５】
参考例３
メチルトリメトキシシラン１３．６ｇ（０．１モル）とフェニルトリメトキシシラン１９．８ｇ（０．１モル）およびγアミノプロピルメチルジエトキシシラン９６．０ｇ（０．５モル）を３−メチル−３−メトキシブタノ−ル４２８．０ｇおよびγブチロラクトン３３３．３ｇの混合液に加えて、３０℃攪拌下に蒸留水２８．８ｇ（１．８モル）を添加した。この溶液を６０℃で２時間攪拌した後、３，３´，４，４´−ベンゾフェノンテトラカルボン酸二無水物８０．６ｇ（０．２５モル）を加えて、そのまま２時間攪拌を続けアミック酸含有のシロキサン溶液を得た。本溶液の粘度をＥ型粘度計で測定すると２２．５センチポイズ（２５℃）であった。
【００２６】
参考例４
３，３´，４，４´−ベンゾフェノンテトラカルボン酸二無水物３２．２３ｇ（０．１０モル）を３−メチル−３−メトキシブタノ−ル１００．０ｇおよびγブチロラクトン１００．０ｇの混合液に加え、溶解させた後、γアミノプロピルメチルジエトキシシラン３８．４０ｇ（０．２モル）を３−メチル−３−メトキシブタノ−ル６８．１ｇに溶解した液を約１０分間で滴下して、４０℃で１時間反応させた。本溶液の粘度をＥ型粘度計で測定すると１７．５センチポイズ（２５℃）であった。
【００２７】
参考例５
メチルトリメトキシシラン１３６ｇ（１．０モル）、フェニルトリメトキシシラン１９８ｇ（１．０モル）、無水ナジック酸１６４．０ｇ（１．０モル）をγ−ブチロラクトン２００ｇ、３−メチル−３−メトキシブタノ−ル６００ｇに溶解し、３０℃で撹拌しながら、１４４ｇの蒸留水を加え、１時間撹拌し、加水分解・縮合を行なった。
【００２８】
この溶液を、バス温７０℃で２時間加熱・攪拌した後、γ−アミノプロピルメチルジエトキシシラン１９１．５ｇ（１．０モル）をγ−ブチロラクトン１４１ｇ、３−メチル−３−メトキシブタノ−ル１９５．６ｇに溶解した混合液を添加して、同温で１時間加熱、攪拌した後、徐々に加熱、攪拌下に昇温して２時間後にバス温１２５℃として２時間、加熱攪拌し、反応温度を１１５℃まで上げて生成したアルコ−ルと水１９２ｇを留去させた。
【００２９】
この様にして得られた溶液を冷却、γ−ブチロラクトン１９２ｇで稀釈して、ポリナジックイミドシロキサン前駆体溶液を得た。
【００３０】
このようにして得られた溶液の固形分濃度を３００℃、３０分加熱の溶剤除去法で測定すると２０．３重量％であり、粘度は１２．５センチポイズ（２５℃）であった。
【００３１】
参考例６
メチルトリメトキシシラン２７２．０ｇ（２．０モル）、フェニルトリメトキシシラン３９６．０ｇ（２．０モル）、酢酸０．３４ｇを３−メチル−３−メトキシブタノ−ル７８５．６ｇに溶解し、３０℃で撹拌しながら、２１６ｇの蒸留水を加え、１時間加熱撹拌し、加水分解・縮合を行なった。
【００３２】
この溶液を、徐々に加熱、攪拌下に昇温して２時間後にバス温１３０℃として２時間、加熱攪拌し、生成したアルコ−ルと水４４９．１ｇを留去させた後、この溶液を８０℃まで冷却して、３−メチル−３−メトキシブタノ−ル８５．７ｇを添加して、オルガノシルセスキオキサンオリゴマー溶液を得た。このように得られた溶液の固形分濃度を３００℃、３０分加熱の溶剤除去法で測定すると３１．５重量％であり、粘度は５１センチポイズ（２５℃）であった
参考例７
参考例３で得られた溶液１００ｇ，参考例６で得られた溶液２００ｇおよび参考例２で得られた溶液１００ｇを混合して本発明のインキジェット用塗液原液を得た。
【００３３】
参考例８
参考例５で得られた溶液１００ｇ，参考例６で得られた溶液２００ｇおよび参考例２で得られた溶液１００ｇを混合して本発明のインキジェット用塗液原液を得た。
【００３４】
参考例９
参考例４で得られた溶液１００ｇに参考例１で得られた溶液２０ｇを添加混合して本発明のインキジェット用塗液原液を得た。
【００３５】
参考例１０
参考例５で得られた溶液１００ｇに参考例２で得られた溶液２０ｇを添加混合して本発明のインキジェット用塗液原液を得た。
【００３６】
実施例１
ポリアミック酸中に黒色顔料を分散してなる黒色ペーストを無アルカリガラス上にスピンコートし、５０℃で１０分間、９０℃で１０分間、１１０℃で２０分間オーブンを用いて空気中で加熱乾燥して、膜厚１．６μｍのポリイミド前駆体着色膜を得た。この膜上にポジ型フォトレジスト（東京応化社製ＯＦＰＲ−８００）を塗布し８０℃で２０分加熱乾燥して膜厚１μｍのレジスト膜を得た。キャノン社製紫外線露光機ＰＬＡ−５０１Ｆを用い、クロム製のフォトマスクを介して、波長３６５ｎｍでの強度が５０ｍＪ／ｃｍ² の紫外線を照射した。露光後、テトラメチルアンモニウムハイドロオキサイドの２．３８ｗｔ％の水溶液からなる現像液に浸漬し、フォトレジストおよびポリイミド前駆体の現像を同時に行った。エッチング後、不要となったフォトレジスト層をメチルセロソルブアセテートで剥離した。さらにこのようにして得られたポリイミド前駆体着色被膜を窒素雰囲気中で３００℃で３０分間熱処理し、膜厚１．２μｍのポリイミド着色被膜によりブラックマトリクスパターンを得た。
【００３７】
さらにポリアミック酸中に顔料分散してなる青、赤、緑の各色のカラーペーストについて、順次同様のプロセスによりパターン化されたポリイミド着色被膜を作製した。該着色被膜上に、参考例１で得られたポリイミドシロキサン前駆体溶液をプロピレングリコールモノエチルエーテルで６重量％に稀釈して参考したインキジェット用塗液をプログラム制御されたオンデマンド型インキジェット塗布装置でカラーフィルターの有効領域上に塗布した。
【００３８】
これを１００℃熱風オーブン中で１０分間予備乾燥した後、２８０℃で０．５時間熱処理し１．１μｍ厚みの塗膜を形成しカラーフィルターを得た。
【００３９】
こうして得られたカラーフィルターの塗膜を直接ラビング処理機にてラビング処理した。
【００４０】
ついで薄膜トランジスタ素子を備えた対向基板を次の手順で作製した。
【００４１】
まず、無アルカリガラス上にクロムを用いてフォトエッチングの手法によりゲート電極とコモン電極をパターニングした後、これらの電極を覆うように窒化シリコン（ＳｉＮ）膜からなる絶縁膜を形成した。ゲート絶縁膜上に非晶質シリコン（ａ―Ｓｉ）膜を形成し、この膜上にアルミニウムを用いて、ソース電極とドレイン電極を形成した。その際、コモン電極とドレイン電極の間に基板に平行な向きに電界がかかるよう電極をパターニングした。これらの電極上に、参考例１で得られたポリイミドシロキサン前駆体溶液をプロピレングリコールモノエチルエーテルで６重量％に稀釈して調製したインキジェット用塗液をプログラム制御されたオンデマンド型インキジェット塗布装置でＴＦＴ基板の有効領域上に塗布した。これを１００℃熱風オーブン中で１０分間予備乾燥した後、２８０℃で０．５時間熱処理し１．１μｍ厚みの塗膜を形成しＴＦＴ基板を得た。
【００４２】
こうして得られたＴＦＴ基板の塗膜を直接ラビング処理機にてラビング処理して、薄膜トランジスタを備えた電極付き対向基板を得た。
【００４３】
電極付き対向基板とカラーフィルターとを貼り合わせ、液晶表示装置を作製し問題なく動作することを確認した。
【００４４】
実施例２
参考例７で得られた溶液１０ｇをプロピレングリコールモノメチルエーテル２０ｇおよびγブチロラクトン２０ｇの混合液で稀釈した後、ＩＴＯからなる透明導電層を有するガラス基板上に、オンデマンド型インキジェット塗布装置で噴霧塗布し２９０℃で１時間熱処理し、０．１５μｍ厚みの塗膜を形成した。この膜をナイロン製フェルトを巻き付けたロールを有するラビング装置により、ロール回転数８００ｒｐｍ、ステージ移動速度５０ｍｍ／秒で５回ラビング処理を行なった。ラビングによる塗膜の損傷はまったく認められ無かった。このようにして得られた配向膜を有する基板一対をラビング方向が逆平行になるように対向させて配置し、１ｍｍのスペーサー膜を使用して、基板側面にエポキシシール剤（三井東圧化学（株）製“ストラクトボンド”ＥＳ−４５００）を塗布し、１２０℃で３０分間硬化させて封止した。この素子の内部に液晶（メルク製ＺＬＩ−２２９３）を真空下で注入し、注入口をエポキシシール剤でふさぎ、１２０℃で３０分間加熱して封止樹脂の硬化および液晶のアイソトロピック処理を行なった。このようにして作製された試験用液晶セルを偏光顕微鏡のクロスニコル間で回転し観察したところ、明瞭な明暗が見られ、液晶はラビング方向に配向していることが認められた。またこの液晶セルについて磁場容量法によりプレチルト角を測定したところ３°であった。
【００４５】
実施例３
無アルカリガラス基板上に形成された着色被膜上に、実施例２と同様の塗液・装置を使用して高密度噴霧塗布し、２８０℃で２時間熱処理し、１．５μｍの塗膜を形成した。別途無アルカリガラス基板上に、１０００オングストロームの配向膜（日本合成ゴム製 オプトマーＡＬ１０５１）をスピンコートにて形成した。 上記１．５μｍの塗膜並びに配向膜をラビングマシンにてラビング処理した。ラビング処理された配向膜上に，スクリーン印刷機を用いて熱硬化性エポキシ樹脂をガラス基板の縁に沿って、液晶注入口部分を除いて線状に印刷し、ラビング処理された１μｍ塗膜を形成したガラス基板と、配向膜とが向かい合い、かつラビング処理方向が互いに直交するようにように張り合わせ、１２０℃で１５分間、１５０℃で１時間加熱処理してエポキシ樹脂を硬化させた。貼り合わせたガラスセル中に、液晶注入口を通じてツイストネマチック型の液晶（メルク社製 ＺＬＩ４７９２）を注入した後、注入口に紫外線硬化性樹脂を塗布し、紫外線を照射、硬化させて注入口を封じた。
【００４６】
このようにして得られたガラスセルを偏光顕微鏡にて観察したところ、液晶部分がパラレルニコル下で消光し、クロスニコル下で光を透過した。これによりラビング処理した１．５μｍ塗膜が配向膜として働く事を確認した。
【００４７】
実施例４〜７
実施例３において参考例７で得られた硬化性組成物の溶液の代わりに参考例８〜１０で得られた硬化性組成物を使用して、同様の結果を得ることができた。
【００４８】
【発明の効果】
ガラス基板上にＴＦＴが形成されてなる基板において、該基板上にインキジェット法により保護膜を形成せしめる手法により、ＴＦＴ基板の有効領域のみに，平坦化膜と配向膜の機能を併せ持つ保護膜が形成されたＴＦＴ基板を容易に得ることができる。
【図面の簡単な説明】
【図１】本発明の応用例１における液晶表示装置の断面図である。
【符号の説明】
１ 透明基板
２ 遮光層
３ 着色膜
４ 保護膜
５ 配向膜
６ 保護膜
７ 絶縁膜
８ ゲート電極
９ ドレイン電極
１０ ソース電極（画素電極）
１１ コモン電極
１２ 薄膜電極
１３ 液晶層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a liquid crystal display device and a liquid crystal display device.
[0002]
[Prior art]
The structure of a liquid crystal cell of a thin film transistor (TFT) type color liquid crystal display device is composed of a substrate having a color filter and a counter substrate (TFT substrate) having electrodes formed on a transparent substrate.
[0003]
As a manufacturing method of this TFT substrate, after patterning the gate electrode and the common electrode by a photo-etching method using chromium on an alkali-free substrate, an insulating film covering these electrodes is formed, and the gate insulating film is formed on the gate insulating film. Then, an amorphous silicon film is formed, and a source electrode and a drain electrode are formed on the film using aluminum. A protective film is formed with a silicon nitride film on these electrodes, and a polyimide-based alignment film is provided as the uppermost layer. This protective film is a protective film for the TFT substrate and at the same time functions to flatten the steps of the substrate and smooth the surface. However, the cell gap is shortened due to the high-speed response of the liquid crystal display device, and further, In a color liquid crystal display device driven by an electric field (lateral electric field) in a direction parallel to the transparent substrate as shown in FIG. 1, formation of a protective film as a planarizing film is expected, and further, alignment is performed on this protective film. It is expected to provide a function as a film. Alternatively, it is desirable to provide the alignment film with a function as a planarizing film. As a method for forming such a flattened film, a method of applying and heat-curing a resin overcoat agent having the function of an alignment film by spin coating can be considered, but the formation of the protective film covers the entire surface of the TFT substrate. Therefore, there are problems that cause a decrease in the reliability of the liquid crystal display device, such as poor adhesion to the glass part, poor adhesion to the cell liquid crystal sealant, and poor adhesion to the cell external electrode. As a means for avoiding these problems, patterning of a protective film is conceivable, and it is desirable to form a protective film that covers only the effective part that forms the cell part of the TFT substrate. The present condition is that the coating method which forms is not found.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a coating means effective for forming a patterned protective film on a TFT substrate, and to propose a novel method for manufacturing a liquid crystal display device.
[0005]
[Means for Solving the Problems]
The above object is achieved by a method for manufacturing a liquid crystal display device comprising a step of forming a transparent layer (hereinafter abbreviated as a pattern transparent layer) patterned by an ink jet method. That is, the present inventors examined various coating methods including various printing methods for forming a patterned protective film on a TFT substrate in the production of a liquid crystal display device. It has been found that the conventional problems can be avoided by carrying out the above using an ink jet, and the present invention has been achieved.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
As the ink jet coating method carried out in the present invention, a continuous jet method (RG Sweet, Rev. Sci. Instur., 36 (1965), RG Sweet et al., US Pat. 3,373,437 (1968), Takehiro Yamada et al., IEICE Technical Report, IE, 83, 62 (1982), CH Herz et al., US Pat. 3,416, 153 (1968). , Intermittent injection system (S. Sugihara et al., SID Japan Display (1983), and on-demand type (EL Kyser, JP-B 53-12138 (1978), SI Zoltan et al., U.S. Pat. Any of S. Pat., 3,683, 212 (1972), etc. may be applied, for example, the relationship with the composition of the coating solution The on-demand type is preferably used, and can be applied to the formation of a patterned transparent layer on a TFT substrate, for example, a liquid crystal display device in which an electrode having a configuration in which an electric field is applied in a direction parallel to the substrate is driven by a thin film transistor As a coating liquid used in the ink jet coating method carried out in the present invention, a polyimide siloxane is used for forming a protective film or a flattened film on a colored film. A resin solution composition containing a precursor component and a solvent component is preferably used, but a resin solution composition containing an acrylic resin and a solvent component can also be used. Pattern transmission in the manufacture of TFT substrates for liquid crystal display devices in which electrodes having a structure to be applied are driven by thin film transistors. For the layer formation, from the viewpoint of imparting liquid crystal orientation to the transparent layer, a resin solution composition containing a polyimide siloxane precursor component and a solvent component is most preferably used, and polyimide and / or a polyimide precursor component and a solvent component are used. Resin solution composition comprising, polyimide siloxane precursor component, polyimide and / or polyimide precursor component and solvent component resin composition, acrylic resin, polyimide and / or polyimide precursor component and solvent Resin solution composition comprising components, resin solution composition comprising acrylic resin, polyimidesiloxane precursor component and solvent component are preferably used, and resin solution composition comprising acrylic resin and solvent component Can also be used.
[0007]
The polyimide siloxane precursor component, which is a resin component of the coating liquid preferably used in the ink jet coating method of the present invention, is not particularly limited, but those prepared as described below are preferably used.
[0008]
(A) A hydrolyzate of aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane, or a reaction product of these condensate and polyvalent carboxylic acid anhydride.
[0009]
(B) A hydrolyzate of aminoalkyl polyvalent alkoxysilane or a hydrolyzate of aminoaryl polyvalent alkoxysilane or a condensate thereof and a reactant of polyvalent carboxylic acid.
[0010]
(C) A reactant of an aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane and a polyvalent carboxylic anhydride.
[0011]
(D) A reaction product of a hydrolyzate of aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane or a condensate thereof and a polyvalent carboxylic acid.
[0012]
(E) Mixture of alkyl or arylsilsesquioxane oligomer obtained by hydrolysis or hydrolysis / condensation of alkyltrialkoxysilane or aryltrialkoxysilane and the reactants obtained in (A) to (B) above . These polyimidesiloxane precursor components form a polyimidesiloxane film by heat treatment.
[0013]
Similarly, as the polyimide and / or precursor component of the coating resin component used in the ink jet coating method, known polyimide and / or polyamic acid that is a precursor thereof can be widely used. Polyamic acid mainly composed of the structural unit represented by the formula (1) and / or polyimide obtained by ring-closing this amic acid with imide can be used.
[0014]
[Chemical 1]

Here, n in the general formula (1) is 1-2. R1 is a trivalent or tetravalent organic group having at least 2 carbon atoms. R1 preferably contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle, and is preferably a trivalent or tetravalent group having 6 to 30 carbon atoms. Examples of R1 include phenyl residue, biphenyl residue, terphenyl residue, naphthalene residue, perylene residue, diphenyl ether residue, diphenyl sulfone residue, diphenylpropane residue, benzophenone residue, biphenyl trifluoropropane residue , Cyclobutyl residue, cyclopentyl residue and the like, but are not limited thereto. R2 is a divalent organic group having at least 2 carbon atoms. From the viewpoint of heat resistance, R2 preferably contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and is a divalent group having 6 to 30 carbon atoms. Examples of R2 include phenyl residue, biphenyl residue, terphenyl residue, naphthalene residue, perylene residue, diphenyl ether residue, diphenyl sulfone residue, diphenylpropane residue, benzophenone residue, biphenyl trifluoropropane residue , Diphenylmethane residue, cyclohexylmethane residue and the like, but are not limited thereto. In the polymer having the structural unit represented by the general formula (1) as a main component, R1 and R2 may be composed of one of each, or a copolymer composed of two or more of each. Also good. Bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure or the like may be copolymerized as a diamine component within a range where the heat resistance is not lowered in order to improve the adhesive force. Further, an anhydride such as maleic anhydride may be added as an amine-terminal blocking agent after the polymerization of the polyamic acid is completed in accordance with the terminal concentration, and reacted. The mechanical properties of the polyimide film obtained by ring closure of polyamic acid are better as the molecular weight is larger. For this reason, it is desired that the molecular weight of the polyamic acid is also large. Of these polyamic acids, polyamic acid obtained by reacting 3,3 ′, 4,4′-benzophenonetetracarboxylic acid with a diamine component is preferably used as at least a part of the acid anhydride component. In the present invention, a preliminarily closed polyimide resin solution composition may be used. Examples of such resin solution composition components include alicyclic groups such as 2,3,5-tricarboxycyclopentylacetic anhydride. A solvent-soluble polyimide component obtained by reacting a tetracarboxylic anhydride and a diamine component can be preferably used.
[0015]
In addition, as the polyimide of the present invention and / or its precursor component, Jpn. J. Appl. Phys. Lett., 50, 18 (1987), Mol. Cryst. Liq. Cryst., 163, 157 (1988), Japan Display, 1992 Polymer components as described in Digest, 819 (1992), Electronic Materials, 30 (11), 38 (1991) can be preferably used.
[0016]
Solvent components of the coating solution preferably used in the present invention include polyamic acid, polyimide or N-methylpyrrolidone, N, N'-dimethylacetamide, γ-butyrolactone used for preparing the polyimidesiloxane precursor solution, 1,3- Although polar solvents such as dimethyl-2-imidazolidinone can be used, particularly when a polyimide siloxane precursor is used in the coating liquid composition used in the present invention, a feature that a large amount of alcohol component can be used. Have. Conventionally, there are no examples of using an alcohol solvent in a resin solution composition for forming a polyimide-based liquid crystal alignment film, and an alcohol component of 20% by weight or more is used as a solvent component in order to avoid precipitation of a polymer component. In the resin solution composition for forming a transparent layer imparting liquid crystal orientation according to the present invention, an alcohol component of 30% by weight or more, further 50% by weight or more of the solvent component may be used. Such a solvent composition can, for example, reduce the solvent resistance level of the coating line and enable ink jet coating. The alcohol component is usually used for preparing a polyimidesiloxane precursor solution together with a polar solvent such as N-methylpyrrolidone, N, N′-dimethylacetamide, γ-butyrolactone or 1,3-dimethyl-2-imidazolidinone, It is mixed with separately prepared polyimide and / or its precursor solution and constitutes the solvent component of the resin solution composition for coating liquid of ink jet coating of the present invention, but it can also be added after mixing preparation. is there. Although it does not specifically limit as an alcohol component in the coating liquid used in this invention, Propylene glycol monoalkyl ether, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, 3-methoxy-3-methylbutanol, etc. Alcohols having an ether bond are preferably used, and 3-methoxy-3-methylbutanol is particularly suitable. The solid part concentration of the resin solution composition for coating liquid used in the ink jet coating of the present invention is 2 to 15% by weight, preferably 3 to 10% by weight.
[0017]
The resin solution composition for coating liquid used in the ink jet coating of the present invention is one that is ink jet coated in a desired pattern on the TFT substrate, and has a transparent layer on the effective area of the screen component, It is preferable that the transparent layer has a boundary at a position corresponding to the frame surrounding the color filter pixels.
[0018]
In addition, the ink jet coating of the present invention is particularly applied to a TFT substrate of a color liquid crystal display device driven by an electric field (transverse electric field) in a direction parallel to a transparent substrate that does not have a transparent conductive layer on a color filter pixel. In this TFT substrate, the transparent layer of the present invention has both functions of a protective film and an alignment film.
[0019]
Hereinafter, the embodiment will be described in more detail.
[0020]
【Example】
Reference example 1
136 g (1.0 mol) of methyltrimethoxysilane, 198 g (1.0 mol) of phenyltrimethoxysilane, 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Was dissolved in 140 g of γ-butyrolactone and 421 g of 3-methyl-3-methoxybutanol, 118 g of distilled water was added with stirring at 30 ° C., and the mixture was stirred for 1 hour for hydrolysis and condensation.
[0021]
This solution was heated and stirred at a bath temperature of 105 ° C. for 3 hours to distill off the generated alcohol and 140 g of water, and then 38.3 g (0.2 mol) of γ-aminopropylmethyldiethoxysilane was added to γ- After adding a mixed solution dissolved in 133 g of butyrolactone and 355.0 g of 3-methyl-3-methoxybutanol, heating and stirring at the same temperature for 1 hour, gradually heating, raising the temperature under stirring, and 1 hour later The mixture was heated and stirred at a bath temperature of 135 ° C. for 2 hours to raise the reaction temperature to 125 ° C., and 75 g of the generated alcohol and water were distilled off.
[0022]
The solution thus obtained was cooled to room temperature, and then diluted with a solution of silicone surfactant BYK302 (Bic Chemie) 0.5 g of 3-methyl-3-methoxybutanol 60.0 g. A polyimide siloxane precursor solution was obtained.
[0023]
The solid content concentration of the solution thus obtained was 18.3% by weight as measured by a solvent removal method heated at 300 ° C. for 30 minutes, and the viscosity was 17.5 centipoise (25 ° C.).
[0024]
Reference example 2
Charged 161.11 g (0.50 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 97.20 g (0.49 mol) of pyromellitic dianhydride together with 2677.7 g of γ-butyrolactone. While stirring this, 150.20 g (0.75 mol) of 4,4′-diaminodiphenyl ether, 49.64 g (0.2 mol) of 3,3′-diaminodiphenylsulfone and bis (3-aminopropyl) tetramethyl After adding 12.42 g (0.020 mol) of disiloxane and reacting at 60 ° C. for 2 hours, 1.97 g (0.020 mol) of maleic anhydride was added and further reacted at 60 ° C. for 2 hours. A 9.2 poise polyamic acid solution was obtained.
[0025]
Reference example 3
13.6 g (0.1 mol) of methyltrimethoxysilane, 19.8 g (0.1 mol) of phenyltrimethoxysilane and 96.0 g (0.5 mol) of γ-aminopropylmethyldiethoxysilane were added to 3-methyl-3 In addition to 428.0 g of -methoxybutanol and 333.3 g of γ-butyrolactone, 28.8 g (1.8 mol) of distilled water was added with stirring at 30 ° C. After stirring this solution at 60 ° C. for 2 hours, 80.6 g (0.25 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added, and the stirring was continued for 2 hours as it was. A siloxane solution was obtained. When the viscosity of this solution was measured with an E-type viscometer, it was 22.5 centipoise (25 ° C.).
[0026]
Reference example 4
Add 32.23 g (0.10 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride to a mixture of 100.0 g of 3-methyl-3-methoxybutanol and 100.0 g of γ-butyrolactone. Then, a solution prepared by dissolving 38.40 g (0.2 mol) of γ-aminopropylmethyldiethoxysilane in 68.1 g of 3-methyl-3-methoxybutanol was added dropwise over about 10 minutes, For 1 hour. When the viscosity of this solution was measured with an E-type viscometer, it was 17.5 centipoise (25 ° C.).
[0027]
Reference Example 5
136 g (1.0 mol) of methyltrimethoxysilane, 198 g (1.0 mol) of phenyltrimethoxysilane, and 164.0 g (1.0 mol) of nadic anhydride were added to 200 g of γ-butyrolactone, 3-methyl-3-methoxybutano- While stirring at 30 ° C., 144 g of distilled water was added and stirred for 1 hour for hydrolysis and condensation.
[0028]
This solution was heated and stirred at a bath temperature of 70 ° C. for 2 hours, and then 191.5 g (1.0 mol) of γ-aminopropylmethyldiethoxysilane was added to 141 g of γ-butyrolactone and 3-methyl-3-methoxybutanol 195. Add the mixed solution dissolved in .6g, heat and stir at the same temperature for 1 hour, gradually heat, heat up under stirring, and then heat and stir for 2 hours at a bath temperature of 125 ° C after 2 hours. The generated alcohol and 192 g of water were distilled off by raising the temperature to 115 ° C.
[0029]
The solution thus obtained was cooled and diluted with 192 g of γ-butyrolactone to obtain a polynadicimide siloxane precursor solution.
[0030]
The solid concentration of the solution thus obtained was 20.3% by weight as measured by a solvent removal method heated at 300 ° C. for 30 minutes, and the viscosity was 12.5 centipoise (25 ° C.).
[0031]
Reference Example 6
272.0 g (2.0 mol) of methyltrimethoxysilane, 396.0 g (2.0 mol) of phenyltrimethoxysilane and 0.34 g of acetic acid were dissolved in 785.6 g of 3-methyl-3-methoxybutanol, and 30 While stirring at ° C., 216 g of distilled water was added, and the mixture was heated and stirred for 1 hour for hydrolysis and condensation.
[0032]
The solution was gradually heated and heated with stirring, and after 2 hours, the bath temperature was 130 ° C. and heated and stirred for 2 hours to distill off the formed alcohol and 449.1 g of water. After cooling to 80 ° C., 85.7 g of 3-methyl-3-methoxybutanol was added to obtain an organosilsesquioxane oligomer solution. The solid content concentration of the solution thus obtained was 31.5% by weight measured by a solvent removal method heated at 300 ° C. for 30 minutes, and the viscosity was 51 centipoise (25 ° C.) Reference Example 7
100 g of the solution obtained in Reference Example 3, 200 g of the solution obtained in Reference Example 6 and 100 g of the solution obtained in Reference Example 2 were mixed to obtain a coating liquid stock solution for ink jet according to the present invention.
[0033]
Reference Example 8
100 g of the solution obtained in Reference Example 5, 200 g of the solution obtained in Reference Example 6 and 100 g of the solution obtained in Reference Example 2 were mixed to obtain a coating liquid stock solution for ink jet according to the present invention.
[0034]
Reference Example 9
20 g of the solution obtained in Reference Example 1 was added to and mixed with 100 g of the solution obtained in Reference Example 4 to obtain a coating liquid stock solution for ink jet according to the present invention.
[0035]
Reference Example 10
20 g of the solution obtained in Reference Example 2 was added to and mixed with 100 g of the solution obtained in Reference Example 5 to obtain an ink jet coating liquid stock solution of the present invention.
[0036]
Example 1
A black paste in which a black pigment is dispersed in polyamic acid is spin-coated on an alkali-free glass and dried in air using an oven at 50 ° C. for 10 minutes, 90 ° C. for 10 minutes, and 110 ° C. for 20 minutes. Thus, a colored polyimide precursor film having a thickness of 1.6 μm was obtained. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on this film and dried by heating at 80 ° C. for 20 minutes to obtain a resist film having a thickness of 1 μm. Using a UV exposure machine PLA-501F manufactured by Canon Inc., UV light having an intensity at a wavelength of 365 nm of 50 mJ / cm ² was irradiated through a chromium photomask. After the exposure, the photoresist and the polyimide precursor were simultaneously developed by immersing in a developer composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. Further, the polyimide precursor colored film thus obtained was heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere, and a black matrix pattern was obtained from the polyimide colored film having a thickness of 1.2 μm.
[0037]
Furthermore, a polyimide colored coating was prepared by sequentially patterning the blue, red, and green color pastes obtained by dispersing the pigment in polyamic acid by the same process. On-demand type ink jet coating by which the ink jet coating liquid obtained by diluting the polyimide siloxane precursor solution obtained in Reference Example 1 to 6% by weight with propylene glycol monoethyl ether was controlled on the colored coating. It was applied on the effective area of the color filter with an apparatus.
[0038]
This was pre-dried in a 100 ° C. hot air oven for 10 minutes and then heat treated at 280 ° C. for 0.5 hours to form a 1.1 μm thick coating film to obtain a color filter.
[0039]
The color filter coating film thus obtained was directly rubbed with a rubbing machine.
[0040]
Next, a counter substrate provided with a thin film transistor element was produced by the following procedure.
[0041]
First, after patterning a gate electrode and a common electrode by a photo-etching technique using chromium on an alkali-free glass, an insulating film made of a silicon nitride (SiN) film was formed so as to cover these electrodes. An amorphous silicon (a-Si) film was formed on the gate insulating film, and a source electrode and a drain electrode were formed on the film using aluminum. At that time, the electrode was patterned so that an electric field was applied between the common electrode and the drain electrode in a direction parallel to the substrate. On-demand ink-jet application under program control of an ink-jet coating solution prepared by diluting the polyimidesiloxane precursor solution obtained in Reference Example 1 with propylene glycol monoethyl ether to 6% by weight on these electrodes. It was applied on the effective area of the TFT substrate with the apparatus. This was pre-dried in a 100 ° C. hot air oven for 10 minutes and then heat-treated at 280 ° C. for 0.5 hours to form a 1.1 μm thick coating film to obtain a TFT substrate.
[0042]
The coating film of the TFT substrate thus obtained was directly rubbed with a rubbing machine to obtain a counter substrate with electrodes provided with a thin film transistor.
[0043]
A counter substrate with electrodes and a color filter were bonded together to produce a liquid crystal display device, which was confirmed to operate without problems.
[0044]
Example 2
After diluting 10 g of the solution obtained in Reference Example 7 with a mixed solution of 20 g of propylene glycol monomethyl ether and 20 g of γ-butyrolactone, spray coating is performed on a glass substrate having a transparent conductive layer made of ITO with an on-demand ink jet coating apparatus. And heat-treated at 290 ° C. for 1 hour to form a coating film having a thickness of 0.15 μm. This film was rubbed five times with a rubbing apparatus having a roll around which nylon felt was wound at a roll rotation speed of 800 rpm and a stage moving speed of 50 mm / sec. The coating film was not damaged by rubbing. A pair of substrates having the alignment film obtained in this way are placed facing each other so that the rubbing direction is antiparallel, and an epoxy sealant (Mitsui Toatsu Chemical ( “Struct Bond” ES-4500) was applied and cured at 120 ° C. for 30 minutes for sealing. Liquid crystal (Merck ZLI-2293) was injected into the device under vacuum, the injection port was closed with an epoxy sealant, and heated at 120 ° C. for 30 minutes to cure the sealing resin and perform isotropic treatment of the liquid crystal. It was. When the test liquid crystal cell thus produced was rotated and observed between crossed Nicols of a polarizing microscope, clear brightness and darkness were observed, and it was confirmed that the liquid crystal was aligned in the rubbing direction. Further, when the pretilt angle of this liquid crystal cell was measured by the magnetic field capacity method, it was 3 °.
[0045]
Example 3
On the colored coating formed on the alkali-free glass substrate, high-density spray coating is performed using the same coating solution and apparatus as in Example 2, and heat treatment is performed at 280 ° C. for 2 hours to form a 1.5 μm coating film. did. Separately, a 1000 angstrom alignment film (Nippon Synthetic Rubber Optomer AL1051) was formed on a non-alkali glass substrate by spin coating. The 1.5 μm coating film and the alignment film were rubbed with a rubbing machine. On the alignment film subjected to rubbing treatment, a thermosetting epoxy resin is printed in a line shape along the edge of the glass substrate using a screen printing machine except for the liquid crystal injection port portion, and a 1 μm coating film subjected to rubbing treatment is formed. The formed glass substrate and the alignment film face each other so that the rubbing treatment directions were orthogonal to each other, and the epoxy resin was cured by heat treatment at 120 ° C. for 15 minutes and 150 ° C. for 1 hour. A twisted nematic type liquid crystal (ZLI4792 manufactured by Merck) is injected into the bonded glass cell through a liquid crystal injection port, and then an ultraviolet curable resin is applied to the injection port and irradiated and cured to seal the injection port. It was.
[0046]
When the glass cell thus obtained was observed with a polarizing microscope, the liquid crystal portion was quenched under parallel Nicol and light was transmitted under crossed Nicol. Thus, it was confirmed that the rubbed 1.5 μm coating film works as an alignment film.
[0047]
Examples 4-7
Similar results could be obtained by using the curable compositions obtained in Reference Examples 8 to 10 instead of the curable composition solution obtained in Reference Example 7 in Example 3.
[0048]
【The invention's effect】
In a substrate in which a TFT is formed on a glass substrate, a protective film having both functions of a planarizing film and an alignment film is formed only in an effective region of the TFT substrate by a method of forming a protective film on the substrate by an ink jet method. The formed TFT substrate can be easily obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a liquid crystal display device according to an application example 1 of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light shielding layer 3 Colored film 4 Protective film 5 Alignment film 6 Protective film 7 Insulating film 8 Gate electrode 9 Drain electrode 10 Source electrode (pixel electrode)
11 Common electrode 12 Thin film electrode 13 Liquid crystal layer

Claims (3)

A liquid crystal display comprising a step of forming a transparent layer patterned by using an ink jet on a counter substrate in a liquid crystal display device comprising a substrate having a color filter and a counter substrate having electrodes formed on the transparent substrate A method for producing an apparatus, wherein a coating solution for forming a patterned transparent layer comprises any one of the following polyimide siloxane precursor components and solvent components (A) to (E): A method of manufacturing a liquid crystal display device, wherein
(A) A hydrolyzate of aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane, or a reaction product of these condensate and polyvalent carboxylic acid anhydride.
(B) A hydrolyzate of aminoalkyl polyvalent alkoxysilane or a hydrolyzate of aminoaryl polyvalent alkoxysilane or a condensate thereof and a reactant of polyvalent carboxylic acid.
(C) A reactant of an aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane and a polyvalent carboxylic anhydride.
(D) A reaction product of a hydrolyzate of aminoalkyl polyvalent alkoxysilane or aminoaryl polyvalent alkoxysilane or a condensate thereof and a polyvalent carboxylic acid.
(E) Mixture of alkyl or arylsilsesquioxane oligomer obtained by hydrolysis or hydrolysis / condensation of alkyltrialkoxysilane or aryltrialkoxysilane and the reactants obtained in (A) to (B) above . 2. The method of manufacturing a liquid crystal display device according to claim 1, wherein the patterned transparent layer is a transparent layer having both functions of an alignment film and a planarizing film. 2. The method for producing a liquid crystal display device according to claim 1, wherein 30% by weight or more of the solvent component of the coating liquid for forming the patterned transparent layer comprises an alcohol component .

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