JP4378783B2 - Substrate for liquid crystal display device, liquid crystal display device, and method of manufacturing liquid crystal display device - Google Patents

Description

また、ポリイミド系樹脂には、イミド結合の他に、アミド結合、スルホン結合、エーテル結合、カルボニル結合などのイミド結合以外の結合が含まれていても差支えない。
【００４１】
上記一般式（１）中、Ｒ１ は少なくとも２個以上の炭素原子を有する３価または４価の有機基である。耐熱性の面から、Ｒ１ は環状炭化水素、芳香族環又は芳香族複素環を含有し、かつ、炭素数６〜３０の３価または４価の基が好ましい。 Ｒ１ の例として、フェニル基、ビフェニル基、ターフェニル基、ナフタレン基、ペリレン基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルプロパン基、ベンゾフェノン基、ビフェニルトリフルオロプロパン基、シクロブチル基、シクロペンチル基などが挙げられるが、これらに限定されない。
【００４２】
Ｒ２ は少なくとも２個以上の炭素原子を有する２価の有機基であるが、耐熱性の面から、Ｒ２ は環状炭化水素、芳香族環又は芳香族複素環を含有し、かつ炭素数６〜３０の２価の基が好ましい。Ｒ２ の例として、フェニル基、ビフェニル基、ターフェニル基、ナフタレン基、ペリレン基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルプロパン基、ベンゾフェノン基、ビフェニルトリフルオロプロパン基、ジフェニルメタン基、ジシクロヘキシルメタン基などが挙げられるが、これらに限定されない。構造単位（１）を主成分とするポリマは、Ｒ１ 、Ｒ２ がこれらのうち各々１種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つてもよい。さらに、基板との接着性を向上させるために、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するのが好ましい。
【００４３】
構造単位（１）を主成分とするポリマーの具体的な例として、ピロメリット酸二無水物、３、３´，４、４´−ベンゾフェノンテトラカルボン酸二無水物、３、３´，４、４´−ビフェニルトリフルオロプロパンテトラカルボン酸二無水物、３、３´，４、４´−ビフェニルスルホンテトラカルボン酸二無水物、２，３，５，−トリカルボキシシクロペンチル酢酸二無水物などからなる群から選ばれた１種以上のカルボン酸二無水物と、パラフェニレンジアミン、３、３´−ジアミノジフェニルエーテル、４、４´−ジアミノジフェニルエーテル、３、４´ジアミノジフェニルエーテル、３、３´−ジアミノジフェニルスルホン、４、４´−ジアミノジフェニルスルホン、４、４´−ジアミノジシクロヘキシルメタン、４、４´−ジアミノジフェニメタンなどの群から選ばれた１種以上のジアミンから合成されたポリイミド前駆体が挙げられるが、これらに限定されない。これらのポリイミド前駆体は公知の方法すなわち、テトラカルボン酸二無水物とジアミンを選択的に組み合わせ、溶媒中で反応させることにより合成される。
【００４４】
ブラックマトリクス用の遮光剤としては、カーボンブラック、酸化チタン、酸化窒化チタン、四酸化鉄などの金属酸化物粉、金属硫化物粉、金属粉、顔料やこれらの混合物などを用いることができる。この中でも、特にカーボンブラックや酸化窒化チタンは遮光性が優れており、特に好ましい。分散のよい粒径の小さいカーボンブラックは主として茶系統の色調を呈するので、カーボンブラックに対する補色の顔料を混合させて無彩色にするのが好ましい。
【００４５】
ブラックマトリクス用の樹脂がポリイミドの場合、黒色ペースト溶媒としては、通常、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド系極性溶媒、γ−ブチロラクトンなどのラクトン系極性溶媒などが好適に使用される。
【００４６】
カーボンブラックやカーボンブラックに対して補色の顔料等の遮光剤を分散させる方法としては、例えば、ポリイミド前駆体溶液中に遮光剤や分散剤等を混合させた後、三本ロール、サンドグラインダー、ボールミル等の分散機中で分散させる方法などがあるが、この方法に特に限定されない。また、カーボンブラックの分散性向上、あるいは塗布性やレベリング性向上のために種々の添加剤が加えられていてもよい。
【００４７】
樹脂ブラックマトリクスの製法としては、例えば黒色ペーストを基板上に塗布・乾燥した後に、パターニングを行う方法などがある。黒色ペーストを塗布する方法としては、ディップ法、ロールコータ法、スピナー法、ダイコーティング法、ワイヤーバーによる方法などが好適に用いられ、この後、オーブンやホットプレートを用いて加熱乾燥（セミキュア）を行う。セミキュア条件は、使用する樹脂、溶媒、ペースト塗布量により異なるが、通常６０〜２００℃で１〜６０分加熱することが好ましい。
【００４８】
このようにして得られた黒色ペースト被膜は、樹脂が非感光性の樹脂である場合は、その上にフォトレジストの被膜を形成した後に、また、樹脂が感光性の樹脂である場合は、そのままかあるいは酸素遮断膜を形成した後に、露光・現像を行う。必要に応じて、フォトレジストまたは酸素遮断膜を除去し、また、加熱乾燥（本キュア）する。本キュア条件は、前駆体からポリイミド系樹脂を得る場合には、塗布量により若干異なるが、通常２００〜３００℃で１〜６０分加熱するのが一般的である。以上のプロセスにより、基板上にブラックマトリクスが形成される。
【００４９】
本発明で用いられる樹脂ブラックマトリクスの膜厚は、好ましくは０．５〜２０μｍ、より好ましくは０．８μｍ〜１．５μｍである。樹脂ブラックマトリクスの膜厚は、膜厚が０．５μｍよりも薄い場合は遮光性が不十分になることからも好ましくない。また、膜厚が２．０μｍよりも厚い場合は、遮光性は確保できるものの、カラーフィルタの平坦性が犠牲になり、段差が生じ易い。表面段差が生じた場合、カラーフィルタ上部に透明導電膜や液晶配向膜を形成させても段差は殆ど軽減されず、液晶配向膜のラビングによる配向処理が不均一になったり、セルギャップにバラツキが生じたりして、液晶表示装置の表示品位が低下する。表面段差を小さくするためには、着色層上にオーバーコート膜を設けることが有効であるが、カラーフィルタの構造が複雑になり、製造コストが高くなる点では不利である。
【００５０】
また、ブラックマトリクスの遮光性は、ＯＤ値（透過率の逆数の常用対数）で表されるが、液晶表示装置の表示品位を向上させるためには、ＯＤ値は好ましくは２．０以上であり、より好ましくは２．５以上さらに好ましくは３．０以上である。また、樹脂ブラックマトリクスの膜厚の好適な範囲を前述したが、ＯＤ値の上限は、これとの関係で定められるべきである。
【００５１】
表示画面内のブラックマトリクス間には、通常（２０〜２００）μｍ×（２０〜３００）μｍの開口部が設けられるが、この開口部を少なくとも被覆するように３原色からなる着色層が複数配列される。
【００５２】
カラーフィルタを構成する画素を形成する着色層は、少なくとも３原色の色彩を含む。すなわち、加色法によりカラー表示を行う場合は、赤（Ｒ）、緑（Ｇ）、青（Ｂ）の３原色が選ばれ、減色法によりカラー表示を行う場合は、シアン（Ｃ）、マゼンタ（Ｍ）、イエロー（Ｙ）の３原色が選ばれる。一般には、これらの３原色を含んだ要素を１単位としてカラー表示の絵素とすることができる。着色層には、着色剤により着色された樹脂が用いられる。
【００５３】
着色層に用いられる着色剤としては、有機顔料、無機顔料、染料などを好適に用いることができ、さらには、紫外線吸収剤、分散剤、レベリング剤などの種々の添加剤を添加しても良い。有機顔料としては、フタロシアニン系、アジレーキ系、縮合アゾ系、キナクリドン系、アントラキノン系、ペリレン系、ペリノン系が好適に用いられる。
【００５４】
着色層に用いられる樹脂としては、エポキシ系樹脂、アクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、ゼラチンなどの感光性または非感光性の材料が好ましく用いられ、着色剤をこれらの樹脂中に分散あるいは溶解させて着色することが好ましい。感光性の樹脂としては、光分解型樹脂、光架橋型樹脂光重合型樹脂などのタイプがあり、特に、エチレン不飽和結合を有するモノマ、オリゴマまたはポリマと紫外線によりラジカルを発生する開始剤とを含む感光性組成物、感光性ポリアミック酸組成物などが好適に用いられる。非感光性の樹脂としては、上記の各種ポリマなどで現像処理が可能なものが好ましく用いられるが、透明導電膜の成膜工程や液晶表示装置の製造工程でかかる熱に耐えられるような耐熱性を有する樹脂が好ましく、また、液晶表示装置の製造工程で使用される有機溶剤への耐性を持つ樹脂が好ましいことから、ポリイミド系樹脂が特に好ましく用いられる。
【００５５】
着色層を形成する方法としては、例えば、着色ペーストを基板上に塗布・乾燥した後に、パターニングを行う方法などがある。着色剤を分散または溶解させ着色ペーストを得る方法としては、溶媒中に樹脂と着色剤を混合させた後、三本ロール、サンドグラインダー、ボールミル等の分散機中で分散させる方法などがあるが、この方法に特に限定されない。
【００５６】
着色ペーストを塗布する方法としては、黒色ペーストの場合と同様、ディップ法、ロールコータ法、スピナー法、ダイコーティング法、ワイヤーバーによる方法などが好適に用いられ、この後、オーブンやホットプレートを用いて加熱乾燥（セミキュア）を行う。セミキュア条件は、使用する樹脂、溶媒、ペースト塗布量によりことなるが通常６０〜２００℃で１〜６０分加熱することが好ましい。このようにして得られた着色ペースト被膜は、樹脂が非感光性の樹脂である場合は、その上にフォトレジストの被膜を形成した後に、また、樹脂が感光性の樹脂である場合は、そのままかあるいはポリビニルアルコールなどの酸素遮断膜を形成した後に、露光・現像を行う。必要に応じて、フォトレジストまたは酸素遮断膜を除去し、また、加熱乾燥（本キュア）する。本キュア条件は、樹脂により異なるが、前駆体からポリイミド系樹脂を得る場合には、通常２００〜３００℃で１〜６０分加熱するのが一般的である。以上のプロセスにより、基板上にパターニングされた着色層が形成される。
【００５７】
スペーサの形成は画素の着色層の積層を用いても良いし、画素形成後別途スペーサを形成しても良い。画素の着色層の積層は、着色ペースト被膜をパターニングする際に、スペーサ部に残留するようにパターニングすることにより形成できる。
【００５８】
カラーフィルタにはオーバーコートが形成されていても良い。オーバーコートの形成を行う場合には、スペーサの形成の前後どちらでも構わない。スペーサーの形成後にオーバーコートを形成することで、スペーサの強度向上、スペーサからの不純物の溶出防止ができる。オーバーコートを形成後、別途樹脂層を形成しスペーサを形成することで、スペーサとカラーフィルタ間でオーバーコートが接着改良の役割をして密着力が向上し、スペーサの剥がれが防止できる。
【００５９】
カラーフィルタには必要に応じて、導電膜を形成しても良い。本発明における導電膜は、ディッピング法、化学気相成長、真空蒸着法、スパッタリング法、イオンプレーティング法等を経て作成され、主として液晶を駆動させるために用いられるのである。導電膜の形成はスペーサの形成の前後どちらでも構わない。本発明に使用される導電膜としては、抵抗値が低く、透明性が高く、カラー表示特性を損なわれないものが好ましい。代表的な導電膜の具体例を示すと、酸化インジウムスズ（ＩＴＯ）、酸化亜鉛、酸化スズ等及びその合金を用いることができる。このような導電膜の厚みは、０．０１〜１μｍ、好ましくは０．０３〜０．５μｍである。
【００６０】
次に本発明のカラーフィルタを用いて作製したカラー液晶表示装置について説明する。本発明のカラー液晶表示装置の一例を図１６に示す。上記カラーフィルタと対向基板とを貼り合わせて作製する。対向基板上には、画素電極以外に、薄膜トランジスタ（ＴＦＴ）素子や薄膜ダイオード（ＴＦＤ）素子、および走査線、信号線などを設け、ＴＦＴ液晶表示装置やＴＦＤ液晶表示装置を作製することができる。
【００６１】
パネル組立工程は公知の方法を用いて行った。カラーフィルタおよび対向基板上には液晶配向膜を設ける。次にラビングもしくは光照射により配向処理を行う。一方の基板上にシール材を基板周囲にスクリーン印刷やディスペンサ等を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧を行う。シールの圧着・硬化を充分に行うために、数分〜数時間加熱および加圧をすることが好ましい。ただし、この時の温度および圧力は、本発明を満たす製造方法で行った。すなわち圧力が一定で温度を±５℃変えた場合の変形量差αが０．５μｍ以下となり、かつ温度が一定で圧力を基板平面当たり±０．０５ｋｇｆ／ｃｍ²変えた場合の変形量差βが０．５μｍ以下となるＡ点で加熱圧縮される行程を含み、さらにＡ点が１００〜１７０℃および基板平面当たり０．２〜１ｋｇｆ／ｃｍ²に存在することを特徴とする液晶表示装置の製造方法で行った。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【００６２】
また、使用する液晶としては特に限定されないが、より好ましくはネマチック液晶やスメクチック液晶が良好な表示を得るために用いられる。スメクチック液晶には強誘電性液晶や反強誘電性液晶や無しきい値反強誘電性液晶等が含まれる。
【００６３】
液晶表示方式にも特に限定されず、例えばネマチック液晶を用いた場合には、ツイストネマチック方式、スーパーツイストネマチック方式、インプレーンスイッチング方式、バーチカリーアライメント方式（日経マイクロデバイス、Ｐ１３６、１９９８年１月号）等に好適に用いられる。
【００６４】
本発明のカラーフィルタおよびそれを用いたカラー液晶表示装置は、パソコン、ワードプロセッサー、エンジニアリング・ワークステーション、ナビゲーションシステム、液晶テレビ、ビデオなどの表示画面に用いられ、また、液晶プロジェクションなどにも好適に用いられる。また、光通信や光情報処理の分野において、液晶を用いた空間変調素子としても好適に用いられる。空間変調素子は、素子への入力信号に応じて、素子に入射する光の強度や位相、偏向方向等を変調させるもので、実時間ホログラフィーや空間フィルタ、インコヒーレント／コヒーレント変換等に用いられるものである。
【００６５】
【実施例】
以下、特に液晶表示装置用基板がカラーフィルタである場合について、本発明を実施例に基づき、さらに具体的に説明する。もっとも、本発明は下記実施例に限定されるものではない。
【００６６】
実施例１
(1) 樹脂ブラックマトリックス及びシール部パターンの作製
3,3',4,4'-ビフェニルテトラカルボン酸二無水物、4,4'- ジアミノジフェニルエーテル、及び、ビス（３−アミノプロピル）テトラメチルジシロキサンをＮ−メチル−２−ピロリドン溶媒中で反応させ、ポリマー濃度２０重量％のポリイミド前駆体（ポリアミック酸）溶液を得た。
【００６７】
下記の組成を有するカーボンブラックミルベースをホモジナイザーを用いて7500 rpｍで２０分間分散し、ガラスビーズをろ過してブラックペーストを調製した。
【００６８】
カーボンブラックミルベース
カーボンブラック（MA100 、三菱化学（株）製） ４．６部
ポリイミド前駆体溶液 ２４．０部
Ｎ−メチルピロリドン ６１．４部
ガラスビーズ ９０．０部
300 x 350 ｍｍのサイズの無アルカリガラス（日本電気ガラス（株）製、ＯＡ−２）基板上にスピナーを用いて、ブラックペーストを塗布し、オーブン中１３０℃で２０分間セミキュアした。続いて、ポジ型レジスト（Shipley "Microposit" RC100 30cp)をスピナーで塗布し、９０℃で１０分間乾燥した。レジスト膜厚は１．５μｍとした。キヤノン（株）製露光機ＰＬＡ−５０１Ｆを用い、フォトマスクを介して露光を行った。
【００６９】
次に、テトラメチルアンモニウムヒドロキシドを２重量％含む２３℃の水溶液を現像液に用い、基板を現像液にディップさせ、同時に１０ｃｍ幅を５秒で１往復するように基板を揺動させて、ポジ型レジストの現像とポリイミド前駆体のエッチングを同時に行った。現像時間は６０秒であった。その後、メチルセルソルブアセテートでポジ型レジストを剥離し、さらに、３００℃で３０分間キュアし、ポリイミドに転換し、樹脂ブラックマトリックス基板を得た。樹脂ブラックマトリックスの膜厚は、１．０μｍであった。
【００７０】
(２) 着色層とスぺーサーの作製
次に、赤、緑、青の顔料として各々Color Index No.65300 Pigment Red 177で示されるジアントラキノン系顔料、Color Index No. 74265 Pigment Green 36で示されるフタロシアニングリーン系顔料、Color Index No.74160 Pigment Blue 15-4で示されるフタロシアニンブルー系顔料を用意した。ポリイミド前駆体溶液に上記顔料を各々（ポリイミド前駆体／顔料）重量比８：２の割合で混合分散させて、赤、緑、青の３種類の着色ペーストを得た。
【００７１】
まず、樹脂ブラックマトリックス基板上に青ペーストを塗布し、８０℃で１０分間熱風乾燥し、１２０℃２０分間セミキュアした。この後、ポジ型レジスト（Shipley "Microposit" RC100 30cp)をスピナーで塗布後、８０℃で２０分間乾燥した。マスクを用いて露光し、アルカリ現像液（Shipley "Microposit" 351) に基板をディップし、同時に基板を揺動させながら、ポジ型レジストの現像及びポリイミド前駆体のエッチングを同時に行った。その後、ポジ型レジストをメチルセルソルブアセテートで剥離し、さらに、３００℃で３０分間キュアした。着色画素部の膜厚は２．２μｍであった。このパターニングにより青色画素の形成とともに樹脂ブラックマトリックス上にスぺーサーの１段目を形成した。スぺーサーの１段目の形状は、角の丸まった長方形の形をしており、その面積は約５００μｍ²であった。
【００７２】
水洗後、同様にして、赤色画素の形成とともに樹脂ブラックマトリックス上にスぺーサーの２段目を形成した。赤色画素部の膜厚は１．８μｍであった。スぺーサーの２段目の形状も、角の丸まった長方形の形をしており、その面積は約３００μｍ²であった。
【００７３】
さらに水洗後、同様にして緑色画素の形成とともに樹脂ブラックマトリックス上にスぺーサーの３段目を形成し、カラーフィルターを作製した。緑色画素部の膜厚は１．８μｍであった。スぺーサーの３段目の形状は、トラック形をしており、その面積は約２００μｍ²であった。
【００７４】
着色層の積層により樹脂ブラックマトリックス上に設けられたスペーサーの画面内の１個当たりの平均面積は、スペーサーの３段目の面積から求まり、約２００μｍ２であった。画面内のスぺーサーは３画素に１個の割合で画面内に設け、平均個数を約１１個／ｍｍ²とした。従って、画面内のスペーサー面積の割合は、２００μｍ２×１１個／ｍｍ²で求まり、約０．２２％である。
【００７５】
２５℃でのスぺーサーの高さは４．１μｍであった。スペーサーのトータル高さは、スペーサー部の樹脂ブラックマトリックスと青着色層と赤着色層と緑着色層との和であり６．２μｍであった。
【００７６】
また、画面外に樹脂ブラックマトリックスで形成した額縁上の一部および額縁周辺部のシール部の樹脂ブラックマトリックス上には、約５個／ｍｍ²の割合でスペーサーを設けた。
【００７７】
この遮光層と赤画素、緑画素、青画素を有し、表示画面部及び額縁、額縁周辺部のシール部の樹脂ブラックマトリックス上にスぺーサーを有する無アルカリガラス基板上に、スパッタリング法にてＩＴＯ膜を形成し、液晶表示素子用基板として用いられるカラーフィルターを得た。ＩＴＯ膜の膜厚は１５０ｎｍであり、表面抵抗は２０Ω／□であった。
【００７８】
(3) スペーサーの変形量の測定
加熱装置を備えた微小圧縮試験機を用いて、形成されたスペーサー１個（高さ４．１μｍ）の変形量を測定した。
【００７９】
＜測定方法＞
測定機：株式会社島津製作所製「ダイナミック超微小硬度計ＤＵＨ−２０１Ｓ」
測定方法：負荷試験：モード１を用いて測定
測定条件：設定荷重：０．１４ｇｆ、０．１８ｇｆ、０．２２ｇｆ（０．１４ｋｇｆは、０．１５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。同様に０．１８ｋｇｆは、０．２ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値、０．２２ｋｇｆは、０．２５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。）、０．５１ｇｆ、０．５５ｇｆ、０．５９ｇｆ（０．５１ｋｇｆは、０．５５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。同様に０．５５ｋｇｆは、０．６ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値、０．５９ｋｇｆは、０．６５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。）、０．８７ｇｆ、０．９１ｇｆ、０．９５ｇｆ（０．８７ｋｇｆは、０．９５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。同様に０．９１ｋｇｆは、１．０ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値、０．９５ｋｇｆは、１．０５ｋｇｆ／ｃｍ²を１１個／ｍｍ²で割った値である。）
設定温度：９５℃、１００℃、１０５℃、１３０℃、１３５℃、１４０℃、１６５℃、１７０℃、１７５℃。
【００８０】
保持時間：６０秒
圧子種類：円柱圧子 直径５０μｍ
測定した結果を表１に記す。Ａ点が１００〜１７０℃および基板平面当たり０．２〜１ｋｇｆ／ｃｍ２に存在することがわかった。またＢ点も１００〜１７０℃および基板平面当たり０．２〜１ｋｇｆ／ｃｍ²に存在することがわかった。
【００８１】
【表１】

次にスペーサの２５℃での高さと、１時間温度一定かつ圧力一定で加圧した後のスペーサの２５℃での高さとの差が１μｍ以下であるＣ点を求めたところＣ点も１００〜１７０℃および基板平面当たり０．２〜１ｋｇｆ／ｃｍ²に存在することがわかった。測定結果を表２示す。また温度一定かつ圧力一定で２時間および１０時間保持した後の高さも測定した結果も示した。
【００８２】
【表２】

(4) カラー液晶表示装置の作製と評価
このスぺーサーが設けられたカラーフィルター上にポリイミド系の配向膜を設け、ラビング処理を施した。また、同様に対向する液晶表示素子用基板についてもポリイミド系の配向膜を設け、ラビング処理を施した。一方の基板上にシール材（ＳＴＲＵＣＴ ＢＯＮＤ ＸＮ−２１−Ｓ−Ｂ 三井東圧化学製）を基板周囲にスクリーン印刷を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧しシールの圧着・硬化を行う。シールの圧着・硬化を充分に行うために、２時間加熱および加圧をした。この時の温度および圧力は、１−a,b,c,d,e,f,g,h,iの条件でおこなった。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【００８３】
シールの圧着・硬化時の全ての温度および圧力条件で液晶表示装置は表３のようにセルギャップムラのない良好な表示特性を示した。
【００８４】
【表３】

実施例２
実施例１と同様に、ブラックマトリックスおよび画素と画素を構成する着色層の積層を行った。次にアクリル系オーバーコート用樹脂を塗布し加熱硬化し、膜厚約０．２μｍのオーバーコート膜を形成した。
【００８５】
着色層の積層により樹脂ブラックマトリックス上に設けられたスペーサーの画面内の１個当たりの平均面積は、ほぼスペーサーの３段目の着色層の面積等しく、約１９０μｍ²であった。画面内のスぺーサーは９画素に１個の割合で画面内に設け、平均個数を約４個／ｍｍ²とした。従って、画面内のスペーサー面積の割合は、１９０μｍ２×４個／ｍｍ²で求まり、約０．０８％である。
【００８６】
２５℃でのスぺーサーの高さは４．０μｍであった。スペーサーのトータル高さは、スペーサー部の樹脂ブラックマトリックスと青着色層と赤着色層と緑着色層とオーバーコート膜の和であり６．４μｍであった。
【００８７】
また、画面外に樹脂ブラックマトリックスで形成した額縁上の一部および額縁周辺部のシール部の樹脂ブラックマトリックス上には、約５個／ｍｍ²の割合でスペーサーを設けた。
【００８８】
この遮光層と赤画素、緑画素、青画素を有し、表示画面部及び額縁、額縁周辺部のシール部の樹脂ブラックマトリックス上にスぺーサーを有する無アルカリガラス基板上に、スパッタリング法にてＩＴＯ膜を形成し、液晶表示素子用基板として用いられるカラーフィルターを得た。ＩＴＯ膜の膜厚は１５０ｎｍであり、表面抵抗は１８Ω／□であった。
【００８９】
(3) スペーサーの変形量の測定
加熱装置を備えた微小圧縮試験機を用いて、形成されたスペーサー１個（高さ４．０μｍ）の変形量を実施例１と同様に測定し表４の結果を得た。Ａ点およびＢ点をもつことがわかった。
【００９０】
【表４】

試験前のスペーサーの２５℃での高さと、加熱圧縮した状態で１、２、１０時間保持し除荷除冷した後のスペーサーの２５℃での高さの差は表５のようであった。Ｃ点をもつことがわかった。
【００９１】
【表５】

(4) カラー液晶表示装置の作製と評価
このスぺーサーが設けられたカラーフィルター上にポリイミド系の配向膜を設け、ラビング処理を施した。また、同様に対向する液晶表示素子用基板についてもポリイミド系の配向膜を設け、ラビング処理を施した。一方の基板上にシール材を基板周囲にスクリーン印刷を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧しシールの圧着・硬化を行う。シールの圧着・硬化を充分に行うために、２時間加熱および加圧をした。この時の温度および圧力は、２−a,b,c,d,e,f,g,h,iの条件でおこなった。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【００９２】
シールの圧着・硬化時の全ての温度および圧力条件で液晶表示装置は表６のようにセルギャップムラのない良好な表示特性を示した。
【００９３】
【表６】

実施例３
実施例１と同様に、ブラックマトリックスおよび画素を形成した。画素を構成する着色層の積層は行わなかった。次にアクリル系オーバーコート用樹脂を塗布し加熱硬化し、膜厚約０．２μｍのオーバーコート膜を形成した。
【００９４】
この遮光層と赤画素、緑画素、青画素を有する無アルカリガラス基板上に、スパッタリング法にてＩＴＯ膜を形成し、液晶表示素子用基板として用いられるカラーフィルターを得た。ＩＴＯ膜の膜厚は１５０ｎｍであり、表面抵抗は１７Ω／□であった。
【００９５】
次にスペーサー用樹脂として感光性アクリル樹脂を塗布し、青画素ストライプ上に露光、現像し、スペーサー高さ４．０μｍのスペーサーを得た。
【００９６】
スペーサーの画面内の１個当たりの平均面積は、約２００μｍ²であった。画面内のスぺーサーは３画素に１個の割合で画面内に設け、平均個数を約１１個／ｍｍ２とした。従って、画面内のスペーサー面積の割合は、２００μｍ²×１１個／ｍｍで求まり、約０．２２％である。
【００９７】
２５℃でのスぺーサーの高さは４．０μｍであった。スペーサーのトータル高さは、スペーサー部の樹脂ブラックマトリックスと青着色層とオーバーコート膜とスペーサー用樹脂の和であり６．５μｍであった。
【００９８】
また、画面外に樹脂ブラックマトリックスで形成した額縁上の一部および額縁周辺部のシール部の樹脂ブラックマトリックス上には、約５個／ｍｍ²の割合でスペーサーを設けた。
【００９９】
(3) スペーサーの変形量の測定
加熱装置を備えた微小圧縮試験機を用いて、形成されたスペーサー１個（高さ４．０μｍ）の変形量を実施例１と同様に測定し表７の結果を得た。Ａ点およびＢ点をもつことがわかった。
【０１００】
【表７】

試験前のスペーサーの２５℃での高さと、加熱圧縮した状態で１、２、１０時間保持し除荷除冷した後のスペーサーの２５℃での高さの差は表８のようであった。Ｃ点をもつことがわかった。
【０１０１】
【表８】

(4) カラー液晶表示装置の作製と評価
このスぺーサーが設けられたカラーフィルター上にポリイミド系の配向膜を設け、ラビング処理を施した。また、同様に対向する液晶表示素子用基板についてもポリイミド系の配向膜を設け、ラビング処理を施した。一方の基板上にシール材を基板周囲にスクリーン印刷を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧しシールの圧着・硬化を行う。シールの圧着・硬化を充分に行うために、２時間加熱および加圧をした。この時の温度および圧力は、３−a,b,c,d,e,fの条件でおこなった。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【０１０２】
表９に示すようにシールの圧着・硬化時の温度および圧力条件（３−a,b,c,e,fの条件）で液晶表示装置はセルギャップムラのない良好な表示特性を示した。
【０１０３】
【表９】

実施例４
(1) ブラックマトリックス及びシール部パターンの作製
基板上にクロムおよびその酸化物からなる遮光膜を真空蒸着法により形成した。これにフォトレジストを塗布して、加熱乾燥によりフォトレジストの被膜を形成した。これを紫外線露光機を用いて、フォトマスクを介して露光した。露光後アルカリ現像液に浸漬し、フォトレジストの現像を行った。その後酸現像液により遮光膜をエッチングし、エッチング後不要となったフォトレジスト層を剥離し、ブラックマトリックスを形成した。
【０１０４】
実施例３と同様な手法を用い、赤画素、緑画素、青画素を形成した。次にアクリル系オーバーコート用樹脂を塗布し加熱硬化し、膜厚約０．２μｍのオーバーコート膜を形成した。
【０１０５】
この遮光層と赤画素、緑画素、青画素を有する無アルカリガラス基板上に、スパッタリング法にてＩＴＯ膜を形成し、液晶表示素子用基板として用いられるカラーフィルターを得た。ＩＴＯ膜の膜厚は１６０ｎｍであり、表面抵抗は１６Ω／□であった。
【０１０６】
次にスペーサー用樹脂として感光性アクリル樹脂を塗布し、青画素ストライプ上に露光、現像し、スペーサー高さ４．０μｍのスペーサーを得た。
【０１０７】
スペーサーの画面内の１個当たりの平均面積は、約２００μｍ２であった。画面内のスぺーサーは３画素に１個の割合で画面内に設け、平均個数を約１１個／ｍｍ²とした。従って、画面内のスペーサー面積の割合は、２００μｍ²×１１個／ｍｍ²で求まり、約０．２２％である。
【０１０８】
２５℃でのスぺーサーの高さは４．０μｍであった。スペーサーのトータル高さは、スペーサー部の金属ブラックマトリックスと青着色層とオーバーコート膜とスペーサー用樹脂の和であり６．０μｍであった。
【０１０９】
また、画面外に樹脂ブラックマトリックスで形成した額縁上の一部および額縁周辺部のシール部の樹脂ブラックマトリックス上には、約５個／ｍｍ²の割合でスペーサーを設けた。
【０１１０】
(3) スペーサーの変形量の測定
加熱装置を備えた微小圧縮試験機を用いて、形成されたスペーサー１個（高さ４．０μｍ）の変形量を実施例１と同様に測定し表１０の結果を得た。Ａ点およびＢ点をもつことがわかった。
【０１１１】
【表１０】

試験前のスペーサーの２５℃での高さと、加熱圧縮した状態で１、２、１０時間保持し除荷除冷した後のスペーサーの２５℃での高さの差は表１１のようであった。Ｃ点をもつことがわかった。
【０１１２】
【表１１】

(4) カラー液晶表示装置の作製と評価
このスぺーサーが設けられたカラーフィルター上にポリイミド系の配向膜を設け、ラビング処理を施した。また、同様に対向する液晶表示素子用基板についてもポリイミド系の配向膜を設け、ラビング処理を施した。一方の基板上にシール材を基板周囲にスクリーン印刷を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧しシールの圧着・硬化を行う。シールの圧着・硬化を充分に行うために、２時間加熱および加圧をした。この時の温度および圧力は、４−a,b,c,d,e,f,gの条件でおこなった。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【０１１３】
表１２に示すようにシールの圧着・硬化時の温度および圧力条件（４−a,b,c,e,f,gの条件）で液晶表示装置はセルギャップムラのない良好な表示特性を示した。
【０１１４】
【表１２】

比較例１
実施例１と同様に、ブラックマトリックスおよび画素を形成した。画素を構成する着色層の積層は行わなかった。次にアクリル系オーバーコート用樹脂を塗布し加熱硬化し、膜厚約２．０μｍのオーバーコート膜を形成した。
【０１１５】
この遮光層と赤画素、緑画素、青画素を有する無アルカリガラス基板上に、スパッタリング法にてＩＴＯ膜を形成し、液晶表示素子用基板として用いられるカラーフィルターを得た。ＩＴＯ膜の膜厚は１５０ｎｍであり、表面抵抗は１７Ω／□であった。
【０１１６】
次にスペーサー用樹脂として実施例４と異なる感光性アクリル樹脂を塗布し、青画素ストライプ上に露光、現像し、スペーサー高さ１２．０５μｍのスペーサーを得た。
【０１１７】
スペーサーの画面内の１個当たりの平均面積は、約２００μｍ²であった。画面内のスぺーサーは９画素に１個の割合で画面内に設け、平均個数を約４個／ｍｍ２とした。従って、画面内のスペーサー面積の割合は、１００μｍ²×４個／ｍｍ²で求まり、約０．０４％である。２５℃でのスぺーサーの高さは１２．０μｍであった。
【０１１８】
また、画面外に樹脂ブラックマトリックスで形成した額縁上の一部および額縁周辺部のシール部の樹脂ブラックマトリックス上には、約５個／ｍｍ²の割合でスペーサーを設けた。
【０１１９】
(3) スペーサーの変形量の測定
加熱装置を備えた微小圧縮試験機を用いて、形成されたスペーサー１個（高さ１２．０５μｍ）の変形量を実施例１と同様に測定し表１３の結果を得た。Ａ点をもたなかった。
【０１２０】
【表１３】

試験前のスペーサーの２５℃での高さと、加熱圧縮した状態で１、２、１０時間保持し除荷除冷した後のスペーサーの２５℃での高さの差は表１４のようであった。
【０１２１】
【表１４】

(4) カラー液晶表示装置の作製と評価
このスぺーサーが設けられたカラーフィルター上にポリイミド系の配向膜を設け、ラビング処理を施した。また、同様に対向する液晶表示素子用基板についてもポリイミド系の配向膜を設け、ラビング処理を施した。一方の基板上にシール材を基板周囲にスクリーン印刷を用いて塗布する。２枚の基板を張り合わせ、加熱および加圧しシールの圧着・硬化を行う。シールの圧着・硬化を充分に行うために、２時間加熱および加圧をした。この時の温度および圧力は、５−a,b,c,d,e,f,g,h,iの条件でおこなった。こののち、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。偏光板を基板の外側に貼り合わせ後にＩＣドライバー等を実装することによりモジュールが完成する。
【０１２２】
表１５に示すように全ての条件で、セルギャップムラが発生し、表示品位が低下した。
【０１２３】
【表１５】

【０１２４】
【発明の効果】
本発明の液晶表示素子用基板では、スぺーサーの変形量の変位が特定の範囲内を満たす特定圧縮応力範囲、特定温度範囲があるので、この基板を用いて特定圧縮応力範囲、特定温度範囲で液晶表示装置を作製した場合に、表示ムラが生じず、良好な表示特性が得られるという効果が奏される。
【図面の簡単な説明】
【図１】スペーサーを有する液晶表示装置用基板の断面図の１例である。
【図２】スペーサーを有する液晶表示装置用基板の断面図の１例である。
【図３】スペーサーを有する液晶表示装置用基板の断面図の１例である。
【図４】スペーサーを有する液晶表示装置用基板の断面図の１例である。
【図５】スペーサーを有する液晶表示装置用基板の断面図の１例である。
【図６】スペーサーの変形量を求める荷重試験を説明する図である。
【図７】スペーサーの変形量を求める押込荷重−押込変位線図である。
【図８】スペーサーの高さを説明する図である。
【図９】スペーサーの高さを説明する図である。
【図１０】スペーサーの高さを説明する図である。
【図１１】スペーサーの高さを説明する図である。
【図１２】スペーサーを加熱圧縮し長時間保持する試験を説明する図である。
【図１３】スペーサーのトータル高さを説明する図である。
【図１４】スペーサーのトータル高さを説明する図である。
【図１５】スペーサーのトータル高さを説明する図である。
【図１６】液晶表示装置用基板の画面内、画面外を説明する図である。
【図１７】スペーサーの横断面の形状の１例である。
【図１８】スペーサーの上面積および下面積を説明する図である。
【図１９】本発明の液晶表示装置用基板を用いて作成した液晶表示装置の一例である。
【符号の説明】
１ スペーサー用樹脂
２ 透明導電膜
３ オーバーコート膜
４ 画素（Ｒ）
５ ブラックマトリックス
６ 透明基板
７ 画素（Ｇ）と同一の着色層
８ 画素（Ｂ）と同一の着色層
９ 圧子
１０ スペーサー高さ
１１ 光学フラット
１２ スペーサーを有する液晶表示用基板
１３ スペーサー形成面
１４ トータル高さ
１５ 画面内
１６ 額縁
１７ 画面外
１８ 液晶表示装置用基板
１９ 円
２０ 楕円
２１ トラック形
２２ 角の丸い長方形
２３ 上面積
２４ 下面積
２５ 画素電極
２６ 配向膜
２７ 液晶
２８ 画素（Ｇ）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substrate for a liquid crystal display device having a spacer function with a counter substrate, a liquid crystal display device including the same, and a method for manufacturing the liquid crystal display device, and the spacer is optimal at a specific strength in a specific temperature range and a specific pressure range. It is characterized by that.
[0002]
[Prior art]
In a conventional liquid crystal display device, a spacer is provided between the two liquid crystal display device substrates facing each other so that the thickness of the liquid crystal layer is uniformly maintained in the plane. It has been known. For this spacer, spherical particles of plastic or silica are usually used as gap control powder. As the spacer, one having a diameter of 1.0 to 8.0 μm is used according to the use and the thickness of the liquid crystal. In addition, the spacer is used by spraying on one liquid crystal display device substrate and sealing the outer peripheral portion with a sealing material. However, since it is performed in the spraying process as described above, the part where the spacer is placed cannot be scheduled, and a situation occurs where the spacer is located in the display pixel portion or several pieces gather and aggregate. In addition, the spacer may move during application of voltage or during cell conveyance to damage the alignment film. For this reason, for the purpose of specifying the installation position and preventing the movement of the spacer, the substrate for the liquid crystal display device with a gap function in which the layer patterned on the substrate for the liquid crystal display device is replaced with a spacer by using photolithography or printing. Has been proposed. When the substrate for a liquid crystal display device is a color filter, a color filter with a gap function has been proposed in which a three-layer structure formed by overlapping three colored layers of the color filter is substituted for a spacer (special feature). Kaihei 5-196946). However, although the publication discloses that a three-layer structure is formed in the black matrix portion, it does not disclose that the spacer functions sufficiently.
[0003]
On the other hand, in JP-A-10-82909, a spacer is formed on a color filter which is one of substrates for a liquid crystal display device, and the plastic deformation amount of the spacer with respect to a load of 5 mN is 0.05 μm or less. However, there is a disclosure that the function of the spacer is sufficiently satisfied. However, when a liquid crystal display device is manufactured using a spacer using the disclosed technique, the function of the spacer may not be sufficiently satisfied.
[0004]
[Problems to be solved by the invention]
In other words, the gaps of the conventional spacers vary greatly, and the gap control may not be performed with high accuracy. As the gap changes, display unevenness occurs when the liquid crystal display device is driven, and the display quality may be significantly reduced.
[0005]
[Means for Solving the Problems]
In order to solve the above problems, the present invention has the following configuration.
[0006]
  Spacers that control the gap with the substrate for the opposing liquid crystal display devicePaintingIn the liquid crystal display device substrate that is out of plane,The difference between the amount of deformation under compression conditions with a constant pressure and a 5 ° C increase in temperature and the amount of deformation under compression conditions with a 5 ° C decrease in temperatureα is 0.5 μm or less, andKeep temperature constant and pressure 0.05kgf / cm ² The amount of deformation and pressure under increased compression conditions are 0.05 kgf / cm. ² The amount of deformation under reduced compression conditionsThe point A at which the difference β is 0.5 μm or less is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane.²The average area per spacer formed in the screen is 25 to 500 μm.²And the average number of spacers formed in the screen is 1 / mm²more thanAnd the ratio of the area of the spacer in the screen is 0.08 to 1%A substrate for a liquid crystal display device.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The liquid crystal display device according to the present invention has a structure in which liquid crystal is sandwiched between two liquid crystal display device substrates bonded together via a spacer. The substrate for a liquid crystal display device may have an electrode, a thin film transistor, a colored layer, and a reflection plate on the substrate as necessary depending on the liquid crystal, the display method, and the like. Specifically, it may be a color filter having a colored layer or a monochrome filter, or a substrate having a plurality of thin film transistors such as a TFT substrate. A substrate in which a color filter is formed on a thin film transistor (color filter on array substrate) may be used.
[0008]
As a result of detailed examination of the cell gap control mechanism by the spacer in the panel assembling process, the present inventors have found that the amount of deformation due to the compressive load of the spacer changes with the temperature change and the spacer with the change of the compressive load. It was estimated that the amount of deformation due to the compressive load was the main cause. In order to perform the cell gap control with high accuracy, it is considered that the temperature and pressure conditions in the panel assembly process should be optimized and the variation in temperature and pressure should be reduced. In particular, a high temperature and high pressure are applied to the spacer during the pressure bonding / curing of the seal in the panel assembly process, and it is considered that the pressure bonding / curing conditions of the seal should be optimized. However, the temperature and pressure conditions are limited in the pressure bonding / curing conditions of the seal. That is, when the temperature is lower than 80 ° C., the sealing material does not sufficiently react, and unreacted substances may elute in the liquid crystal, causing display unevenness. On the other hand, when the temperature is higher than 190 ° C., it is not preferable from the viewpoint of heat resistance of a member such as a sealing agent or an alignment film. On the other hand, the pressure is 0.2 kgf / cm per substrate plane.²If it is made smaller, a gap may be formed between a part or most of the spacers formed in the substrate surface due to the undulation or warpage of the substrate, and the cell gap may become unstable. The pressure is 2.0 kgf / cm per substrate plane.²If it is larger, the substrate may be cracked. Therefore, in order to perform panel assembly stably, 0.2 to 1.0 kgf / cm per substrate plane in a state heated at a temperature of 100 to 170 ° C.²Compression is required.
[0009]
In general, the temperature and pressure applied to the spacer often vary within one panel and between a plurality of panels in the panel assembly process. In particular, when the panel is assembled by curing the sealing material in a thermosetting batch process (liquid crystal: LCD basics and new applications, Sigma Publishing, P43, 1998), etc., variations in temperature and pressure increase. In general, variations in pressure and temperature are -0.05 to +0.05 kgf / cm per substrate plane relative to the setting.²And about -5 to + 5 ° C. The amount of deformation of the spacer changes in accordance with variations in pressure and temperature during such panel assembly, and the cell gap changes accordingly. Therefore, the smaller the degree of fluctuation of the cell gap in accordance with changes in pressure and temperature, the more uniform the cell gap within one panel and between a plurality of panels, and a stable panel can be manufactured.
[0010]
The cell gap allowed within one panel and between a plurality of panels is required to have an accuracy of 0.5 μm or less. An accuracy of 0.4 μm or less is more preferable, and 0.3 μm or less is more preferable. The accuracy of the cell gap is preferably more accurate. When the accuracy of the cell gap becomes larger than ± 0.5 μm, the cell gap unevenness is visually recognized as display unevenness. In particular, in the case of a narrow cell gap liquid crystal display device having a cell gap of 4 μm or less, the accuracy of the cell gap is preferably more accurate. In particular, if there is a large cell gap variation in one panel, it is easily recognized as display unevenness.
[0011]
Therefore, in view of these, the deformation amount difference α when the pressure is constant and the temperature is changed ± 5 ° C. is 0.5 μm or less, and the temperature is constant and the pressure is ± 0.05 kgf / cm per substrate plane.²The point A at which the deformation difference β when changing is 0.5 μm or less is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane²It is important that the substrate is a substrate for a liquid crystal display device having a spacer.
[0012]
Furthermore, the point B where the deformation of the spacer at a constant temperature and constant pressure is 1 μm or less is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane.²It is preferable to have a spacer present in When the amount of deformation of the spacer is greater than 1 μm, the amount of plastic deformation of the spacer increases, and a sufficient height cannot be obtained when the load applied to the spacer is unloaded. In addition, due to cracks on the surface of the spacer caused by plastic deformation, impurities may elute from the inside of the spacer into the liquid crystal and cause display defects.
[0013]
Temperature T ° C. and pressure per substrate plane Pkgf / cm²The amount of deformation when heated and compressed with can be measured as follows.
[0014]
That is, the spacers are individually compressed using a micro compression tester equipped with a heating device. First, the substrate for a liquid crystal display device having a spacer is heated to a temperature T ° C. and the temperature is maintained. Next, while increasing the indentation load at a constant speed, a load is applied up to the indentation load F on one spacer at a temperature T ° C. The indentation load F at this time is the pressure Pkgf / cm per substrate plane.²Is the value divided by the average number of spacers per substrate plane. That is, the pressure per substrate plane is 1 kgf / cm.²The average number of spacers 0.5 / cm²1kgf / cm for each spacer when loading on the substrate²/0.5 piece / cm²A push load of = 2 kgf may be used. The indenter that compresses the spacer is a tip that is larger than the spacer and flat. For example, a cylindrical indenter or the like may be used. An example of the measurement method is shown in FIG. Measure the amount of deformation with indentation load F and determine the amount of deformation. An example in which the indentation load is plotted on the horizontal axis and the indentation displacement is plotted on the vertical axis is shown in FIG. By changing the temperature and the indentation load, the deformation amount difference of the spacer can be obtained.
[0015]
Also, the point C where the difference between the height at 25 ° C. of the spacer and the height at 25 ° C. of the spacer after pressurizing at constant temperature and constant pressure for 1 hour is 1 μm or less is 100 to 170 ° C. per substrate plane 0.2-1kgf / cm²It is preferable to have a spacer present in The time for maintaining the temperature and pressure is more preferably 2 hours, still more preferably 10 hours. Most of the difference between the height of the spacer at 25 ° C. and the height of the spacer at 25 ° C. after pressing at a constant temperature and pressure for 1 hour is due to the amount of plastic deformation of the spacer. Plastic deformation may occur due to collapse of some or most of the spacer. At this time, cracks are generated in and / or on the surface of the spacer, and fragments of the spacer are scattered around. In addition, the elution of impurities into the liquid crystal through the cracks generated on the spacer surface and the disorder of the alignment starting from the fragments of the spacer may cause display defects.
[0016]
Here, the height of the spacer at 25 ° C. and the height of the spacer at 25 ° C. after being unloaded and cooled for 1 hour while being heated and compressed at a constant temperature and constant pressure are as follows. Can be done.
[0017]
First, the height of the spacer before heating and compression is measured under temperature control. The height of the spacer may be measured using a commercially available contact level meter or a non-contact type surface shape measuring instrument. Here, the height of the spacer refers to a single spacer as shown in FIGS. 8, 9, 10, and 11, and the flat portion of the display portion (in the case of a color filter, the colored portion of the opening, the TFT substrate). In this case, it means the distance between the pixel electrode) and the uppermost surface of the spacer. In addition, when the height of the display part flat part on a board | substrate is uneven, it means the largest thing among the distances between the uppermost surface of a spacer and each display part flat part.
[0018]
Next, as shown in FIG. 12, the spacer is placed on the substrate on which the spacer is formed so as to support the optical flat. By changing the weight of the optical flat and the area of the substrate for the liquid crystal display device having the spacer, the load applied to the spacer can be changed and set to a desired load per substrate plane. In this state, the temperature is raised and maintained at a desired temperature of 0 ° C. for a desired time. After holding, the sample is cooled to 25 ° C., and the height of the spacer is measured in the same manner as before the heat compression test. The difference in the height of the spacer before and after the heat compression test is 1 μm or less as the C point. C point is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane²It is preferable that it exists in.
[0019]
The height of the spacer at 25 ° C. is preferably 1 to 8 μm, and more preferably 2 to 7 μm. If the height of the spacer is lower than 1 μm, it is difficult to ensure a sufficient cell gap. On the other hand, if the thickness exceeds 8 μm, the cell gap of the liquid crystal display element becomes too large, which increases the voltage required for driving, which is not preferable.
[0020]
The total spacer height at 25 ° C. is preferably 1 to 10 μm. If the total height of the spacer is lower than 1 μm, it is difficult to ensure a sufficient cell gap. In particular, when the substrate for a liquid crystal display device is a color filter and a three-layer structure formed by superimposing three colored layers of the color filter is used as a spacer substitute, a sufficiently high height and a desired color can be obtained. It is difficult to form a colored layer of a color filter having characteristics. On the other hand, if it exceeds 10 μm, the amount of deformation at the time of heat compression becomes large and cell gap control becomes difficult. The total height of the spacer means the distance between the substrate plane and the uppermost surface of the spacer, focusing on one spacer as shown in FIGS. For example, when a spacer is formed by forming a black matrix, pixels, and a layer thereon on a flat substrate, the distance between the substrate surface and the uppermost surface of the spacer is defined.
[0021]
The spacers may be formed inside and / or outside the screen of the liquid crystal display substrate. As shown in FIG. 16, “outside the screen” means a frame portion around the liquid crystal display device, a seal portion, and the periphery and outside thereof. Spacers may be formed in portions that are separated when a liquid crystal display device is manufactured.
[0022]
The spacers in the screen are preferably formed in the black matrix region on the substrate or so as to abut against the black matrix of the opposing substrate. Around the spacer in the screen, the orientation of the liquid crystal is likely to be disturbed, so that it tends to cause display defects. Therefore, it is preferable to provide a black matrix so as to hide display defects around the spacer.
[0023]
Both the two liquid crystal display device substrates constituting the liquid crystal display device may have spacers, or one of the liquid crystal display device substrates may have a spacer. However, from the viewpoint of ease of assembly of the liquid crystal display device, it is preferable to have a spacer on one of the substrates for the liquid crystal display device.
[0024]
The average area per spacer formed in the screen is 10 to 1000 μm.² Is preferred, more preferably 25-500 μm² It is. This area is 10μm² If it is less than 1000 μm, it is difficult to form and stack precise patterns.²If it exceeds, the spacer appears on the display area in the screen although it depends on the shape of the spacer, and an alignment defect occurring around the spacer may deteriorate the display quality. Note that the average area per spacer refers to the average of the areas in which the spacer contacts the opposing substrate when two liquid crystal display element substrates are bonded together to form a liquid crystal display device.
[0025]
The average number of spacers formed in the screen is 1 piece / mm.²The above is preferable. Average number is 1 / mm²If it is smaller, the distance between the adjacent spacers becomes longer, and it becomes difficult to maintain the cell gap between the adjacent spacers. The upper limit of the number of spacers in the screen is determined by the ratio (opening ratio) of the display area in the screen and the area of the spacers per piece.
[0026]
Since the area per spacer formed outside the screen is not limited by the aperture ratio compared to the case inside the screen, it can be increased. In general, the larger the spacer area, the easier it is to form the spacer. Therefore, the spacer area outside the screen is preferably larger than the spacer area inside the screen. On the other hand, it is preferable that the ratio of the spacer area in the substrate for a liquid crystal display device does not change greatly between the inside and the outside of the screen. Therefore, it is preferable that the average number of spacers is small because the average area per spacer is large outside the screen. The ratio of the spacer area in the screen of the liquid crystal display substrate is preferably 0.1 to 1%.
[0027]
As a method for forming the spacer, the spacer is preferably formed by a photolithography method, a printing method, an ink jet method, a film transfer method, or the like. In particular, it is preferable to use a photolithography method from the viewpoint of accuracy of spacer formation. For example, in the case where a resin is used as the spacer material, there is a method of performing patterning using photolithography after applying and drying an uncured resin material on a substrate.
[0028]
As a method for applying the spacer material, a dip method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, etc. are suitably used, and then heat drying using a oven or a hot plate (semi-cure) I do. Semi-cure conditions vary depending on the amount of resin, solvent, and spacer material used, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes. In the case of spacer formation by a photolithography method, the spacer material film obtained in this way is, after the spacer material film is a non-photosensitive resin, after forming a positive type or photoresist film thereon, When the spacer material film is a photosensitive resin, exposure or development is performed as it is or after an oxygen blocking film is formed. If necessary, the photoresist or the oxygen blocking film is removed and heat-dried (main cure). Although this cure condition changes with resin, when obtaining a polyimide-type resin from a precursor, it is common to heat at 200-300 degreeC normally for 1 to 60 minutes. By repeating the above process as necessary, a patterned spacer composed of one layer or a plurality of layers is formed on the substrate.
[0029]
The shape of the spacer, that is, the shape of the cross section when the spacer is cut in a plane parallel to the substrate is not particularly limited, but as shown in FIG. 17, a circle, an ellipse, a polygon with rounded corners, a track Shape, cross, T-shape or L-shape are preferred. By rounding the corners, the load resistance at the time of panel assembly increases, and the occurrence of spacer cracks can be prevented. In addition, in a substrate for a liquid crystal display device that is subjected to alignment treatment by rubbing, it is possible to prevent the rubbing cloth from being caught and to prevent alignment defects caused by that.
[0030]
The upper area of the spacer layer is preferably equal to or smaller than the lower area in order to obtain the strength of the spacer. When the lower area of the layer is smaller than the upper area, cracks may occur around the upper area when a liquid crystal display device is manufactured. Here, the upper area and the lower area will be described with an example of the shape of the layer as shown in FIG.
[0031]
In the case where the spacer is formed by stacking a plurality of layers, it is preferable that the areas of the facing surfaces of the layer and the adjacent layer are different from each other. If the areas of the opposing surfaces are different from each other, it is possible to prevent variations in the thickness of the spacer due to a positional shift at the time of layer formation. When variations in spacer thickness occur, the mechanical properties of the spacer vary.
[0032]
As the spacer material, a resin is preferable, and a photosensitive or non-photosensitive material such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or gelatin is preferably used. Among these resins, acrylic resins and polyimide resins are particularly preferably used because they are easy to form and easy to obtain the strength of the present invention. There are two types of photosensitive resins, a negative type and a positive type, but either type may be used in the present invention. However, when the area per layer constituting the spacer is small (100 μm²In the following), the positive type is preferable because of the ease of pattern formation. Thus, when the spacer material is photosensitive, the spacer and the overcoat film can be formed simultaneously. In this case, for example, the double exposure is performed by combining the flash exposure of the entire surface and the pattern exposure of the resin layer portion separately formed. In the case of the negative type, the exposed area remains in the exposed area, so that the integrated exposure amount of the spacer portion only needs to be larger than that of the overcoat film portion. In the case of the positive type, since a pattern after development is left in a region that has not been exposed, the integrated exposure amount of the separately formed spacer portion may be smaller than that of the overcoat film portion. As the non-photosensitive resin, those which can be developed with the above-mentioned various polymers are preferably used.
[0033]
In these resins, various additives such as a colorant, an ultraviolet absorber, a dispersant, and a leveling agent used for a resin black matrix and a colored layer of a color filter may be added as necessary. The same material as the colored layer constituting the color filter may be used. As a method of dispersing or dissolving the colorant or the like in the resin material, after mixing the resin and the colorant in a solvent, there is a method of dispersing in a disperser such as a triple roll, sand grinder, ball mill, etc. The method is not particularly limited.
[0034]
As a substrate for a liquid crystal display device on which such a spacer is formed, a substrate in which a color filter having a colored layer or a color filter is formed on a thin film transistor is preferable because of the ease of forming the spacer.
[0035]
Hereinafter, the case where a spacer is provided on the color filter will be described in detail.
[0036]
The color filter of the present invention is obtained by arranging a plurality of pixels composed of colored layers on a substrate. A black matrix may be provided as necessary. The black matrix referred to here generally indicates a light shielding region arranged between pixels, and is provided to improve the display contrast of the liquid crystal display device.
[0037]
The substrate used in the color filter of the present invention is not particularly limited, but includes inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, plastic film or A transparent substrate such as a sheet is preferably used.
[0038]
A black matrix is formed on the substrate as necessary. The black matrix may be formed of a metal such as chromium or nickel or an oxide thereof, but it is preferable to form a resin black matrix made of a resin and a light shielding agent from the viewpoint of manufacturing cost and waste disposal cost. Moreover, when forming a spacer on a black matrix, it is preferable to use a resin black matrix from the viewpoint of securing the height of the spacer. The resin used for the resin black matrix is not particularly limited, but is a photosensitive or non-photosensitive material such as epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, and gelatin. Is preferably used. The resin for the black matrix is preferably a resin having higher heat resistance than the resin used for the pixel or the protective film, and is also preferably a polyimide resin because it is preferably a resin resistant to the organic solvent used in the process after the black matrix is formed. Resins are particularly preferably used.
[0039]
Although it does not specifically limit as polyimide-type resin, The thing which imidized the polyimide precursor (n = 1-2) which has a structural unit represented by general formula (1) as a main component by heating or a suitable catalyst normally Are preferably used.
[0040]
[Chemical 1]

The polyimide resin may contain bonds other than imide bonds such as amide bonds, sulfone bonds, ether bonds and carbonyl bonds in addition to imide bonds.
[0041]
In the general formula (1), R1 is a trivalent or tetravalent organic group having at least 2 carbon atoms. From the viewpoint of heat resistance, R1 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 group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group and the like. However, it is not limited to these.
[0042]
R2 is a divalent organic group having at least 2 carbon atoms. From the viewpoint of heat resistance, R2 contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle, and has 6 to 30 carbon atoms. These divalent groups are preferred. Examples of R2 include phenyl, biphenyl, terphenyl, naphthalene, perylene, diphenyl ether, diphenylsulfone, diphenylpropane, benzophenone, biphenyltrifluoropropane, diphenylmethane, and dicyclohexylmethane. However, it is not limited to these. In the polymer having the structural unit (1) as a main component, R1 and R2 may be composed of one of each of these, or may be a copolymer composed of two or more of each. Furthermore, in order to improve the adhesion to the substrate, it is preferable to copolymerize bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure as a diamine component within a range that does not lower the heat resistance.
[0043]
Specific examples of the polymer having the structural unit (1) as a main component include pyromellitic dianhydride, 3, 3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride, 3, 3 ′, 4, 4'-biphenyltrifluoropropanetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 2,3,5, -tricarboxycyclopentylacetic acid dianhydride, etc. One or more carboxylic dianhydrides selected from the group and paraphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′diaminodiphenyl ether, 3,3′-diaminodiphenyl Sulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenime Polyimide precursors synthesized from one or more diamines selected from the group of such emissions include, but are not limited to. These polyimide precursors are synthesized by a known method, that is, by selectively combining tetracarboxylic dianhydride and diamine and reacting them in a solvent.
[0044]
As the light shielding agent for the black matrix, metal oxide powder such as carbon black, titanium oxide, titanium oxynitride, and iron tetroxide, metal sulfide powder, metal powder, pigment, and a mixture thereof can be used. Among these, carbon black and titanium oxynitride are particularly preferable because of their excellent light shielding properties. Since carbon black having a good dispersion and small particle size mainly exhibits a color tone of tea, it is preferable to mix a pigment complementary to carbon black to make it achromatic.
[0045]
When the black matrix resin is polyimide, the black paste solvent is usually an amide polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, etc. The lactone polar solvent is preferably used.
[0046]
Examples of a method for dispersing a light-blocking agent such as a complementary color pigment in carbon black or carbon black include, for example, mixing a light-blocking agent or a dispersing agent in a polyimide precursor solution, and then a three-roll, sand grinder, or ball mill. There is a method of dispersing in a dispersing machine such as, but not limited to this method. Various additives may be added to improve the dispersibility of carbon black or to improve the coating property and leveling property.
[0047]
As a method for producing the resin black matrix, for example, there is a method of performing patterning after applying and drying a black paste on a substrate. As a method of applying the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, etc. are preferably used, and thereafter, heat drying (semi-cure) using an oven or a hot plate is performed. Do. Semi-cure conditions vary depending on the resin, solvent, and paste application amount to be used, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.
[0048]
When the resin is a non-photosensitive resin, the black paste film obtained in this way is formed after a photoresist film is formed thereon, and when the resin is a photosensitive resin, Alternatively, after the oxygen blocking film is formed, exposure and development are performed. If necessary, the photoresist or the oxygen blocking film is removed and heat-dried (main cure). In the case of obtaining a polyimide resin from a precursor, the present curing conditions are generally slightly increased depending on the coating amount, but are generally heated at 200 to 300 ° C. for 1 to 60 minutes. Through the above process, a black matrix is formed on the substrate.
[0049]
The film thickness of the resin black matrix used in the present invention is preferably 0.5 to 20 μm, more preferably 0.8 μm to 1.5 μm. When the film thickness of the resin black matrix is thinner than 0.5 μm, it is not preferable because the light shielding property is insufficient. Further, when the film thickness is thicker than 2.0 μm, the light shielding property can be secured, but the flatness of the color filter is sacrificed and a step is likely to occur. If a surface step occurs, even if a transparent conductive film or liquid crystal alignment film is formed on the color filter, the step is hardly reduced, the alignment treatment by rubbing the liquid crystal alignment film becomes uneven, and the cell gap varies. Or the display quality of the liquid crystal display device deteriorates. In order to reduce the surface level difference, it is effective to provide an overcoat film on the colored layer, but it is disadvantageous in that the structure of the color filter becomes complicated and the manufacturing cost increases.
[0050]
Further, the light blocking property of the black matrix is represented by an OD value (common logarithm of the reciprocal of the transmittance). In order to improve the display quality of the liquid crystal display device, the OD value is preferably 2.0 or more. More preferably, it is 2.5 or more, more preferably 3.0 or more. Moreover, although the suitable range of the film thickness of the resin black matrix was mentioned above, the upper limit of OD value should be defined in relation to this.
[0051]
An opening of (20 to 200) μm × (20 to 300) μm is usually provided between the black matrices in the display screen, and a plurality of colored layers of three primary colors are arranged so as to cover at least the opening. Is done.
[0052]
The colored layer forming the pixels constituting the color filter includes at least three primary colors. That is, when performing color display by the additive color method, three primary colors of red (R), green (G), and blue (B) are selected, and when performing color display by the subtractive color method, cyan (C), magenta Three primary colors (M) and yellow (Y) are selected. In general, an element including these three primary colors can be used as a unit as a color display picture element. For the colored layer, a resin colored with a colorant is used.
[0053]
As the colorant used in the colored layer, organic pigments, inorganic pigments, dyes, and the like can be suitably used, and various additives such as ultraviolet absorbers, dispersants, and leveling agents may be added. . As the organic pigment, phthalocyanine, azirake, condensed azo, quinacridone, anthraquinone, perylene, and perinone are preferably used.
[0054]
As the resin used for the colored layer, a photosensitive or non-photosensitive material such as epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, gelatin is preferably used. It is preferable to color by dispersing or dissolving the agent in these resins. Photosensitive resins include photodegradable resins, photocrosslinkable resins, and photopolymerizable resins. Particularly, monomers, oligomers or polymers having an ethylenically unsaturated bond and an initiator that generates radicals by ultraviolet rays are used. A photosensitive composition, a photosensitive polyamic acid composition, and the like are preferably used. As the non-photosensitive resin, those that can be developed with the above-mentioned various polymers are preferably used, but they are heat resistant to withstand the heat applied in the transparent conductive film forming process and the liquid crystal display manufacturing process. Since a resin having a resistance to organic solvents used in the manufacturing process of a liquid crystal display device is preferable, a polyimide resin is particularly preferably used.
[0055]
As a method of forming the colored layer, for example, there is a method of performing patterning after applying and drying a colored paste on a substrate. Examples of a method for obtaining a colored paste by dispersing or dissolving a colorant include a method in which a resin and a colorant are mixed in a solvent and then dispersed in a dispersing machine such as a three roll, sand grinder, or ball mill. The method is not particularly limited.
[0056]
As a method of applying the colored paste, as in the case of the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, etc. are preferably used, and then an oven or a hot plate is used. Heat drying (semi-cure). Semi-cure conditions vary depending on the resin, solvent, and paste coating amount used, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes. When the resin is a non-photosensitive resin, the colored paste film obtained in this way is formed after forming a photoresist film thereon, and when the resin is a photosensitive resin, Alternatively, after forming an oxygen barrier film such as polyvinyl alcohol, exposure and development are performed. If necessary, the photoresist or the oxygen blocking film is removed and heat-dried (main cure). Although this cure condition changes with resin, when obtaining a polyimide-type resin from a precursor, it is common to heat at 200-300 degreeC normally for 1 to 60 minutes. Through the above process, a patterned colored layer is formed on the substrate.
[0057]
The spacer may be formed by stacking colored layers of pixels, or a separate spacer may be formed after the pixels are formed. The lamination of the colored layers of the pixels can be formed by patterning so as to remain in the spacer portion when patterning the colored paste film.
[0058]
An overcoat may be formed on the color filter. When the overcoat is formed, it may be before or after the formation of the spacer. By forming the overcoat after the formation of the spacer, the strength of the spacer can be improved and the elution of impurities from the spacer can be prevented. After the overcoat is formed, a resin layer is separately formed to form a spacer, so that the overcoat plays a role in improving adhesion between the spacer and the color filter, thereby improving the adhesion and preventing the spacer from peeling off.
[0059]
A conductive film may be formed on the color filter as necessary. The conductive film in the present invention is produced through dipping, chemical vapor deposition, vacuum deposition, sputtering, ion plating, and the like, and is mainly used for driving liquid crystals. The conductive film may be formed either before or after the formation of the spacer. As the conductive film used in the present invention, one having a low resistance value, high transparency and not impairing color display characteristics is preferable. As a specific example of a typical conductive film, indium tin oxide (ITO), zinc oxide, tin oxide, or an alloy thereof can be used. The thickness of such a conductive film is 0.01 to 1 μm, preferably 0.03 to 0.5 μm.
[0060]
Next, a color liquid crystal display device manufactured using the color filter of the present invention will be described. An example of the color liquid crystal display device of the present invention is shown in FIG. The color filter and the counter substrate are attached to each other. In addition to the pixel electrode, a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, and the like can be provided over the counter substrate to manufacture a TFT liquid crystal display device or a TFD liquid crystal display device.
[0061]
The panel assembly process was performed using a known method. A liquid crystal alignment film is provided on the color filter and the counter substrate. Next, alignment treatment is performed by rubbing or light irradiation. A sealant is applied on one substrate around the substrate using screen printing or a dispenser. Two substrates are bonded together and heated and pressurized. In order to sufficiently perform pressure bonding and curing of the seal, it is preferable to heat and press for several minutes to several hours. However, the temperature and pressure at this time were performed by the manufacturing method satisfying the present invention. That is, when the pressure is constant and the temperature is changed by ± 5 ° C., the deformation amount difference α is 0.5 μm or less, and the temperature is constant and the pressure is ± 0.05 kgf / cm per substrate plane.²Including the process of heating and compressing at point A where the deformation amount difference β when changing is 0.5 μm or less, further, point A is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane²The liquid crystal display device was manufactured by a method of manufacturing a liquid crystal display device. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0062]
The liquid crystal to be used is not particularly limited, but more preferably a nematic liquid crystal or a smectic liquid crystal is used for obtaining a good display. Smectic liquid crystals include ferroelectric liquid crystals, antiferroelectric liquid crystals, thresholdless antiferroelectric liquid crystals, and the like.
[0063]
The liquid crystal display method is not particularly limited. For example, when nematic liquid crystal is used, a twisted nematic method, a super twisted nematic method, an in-plane switching method, a vertical alignment method (Nikkei Microdevices, P136, January 1998 issue) ) And the like.
[0064]
The color filter of the present invention and the color liquid crystal display device using the color filter are used for display screens of personal computers, word processors, engineering workstations, navigation systems, liquid crystal televisions, videos, etc., and also suitably used for liquid crystal projections, etc. It is done. Further, in the field of optical communication and optical information processing, it is also suitably used as a spatial modulation element using liquid crystal. A spatial modulation element modulates the intensity, phase, deflection direction, etc. of light incident on an element according to an input signal to the element, and is used for real-time holography, spatial filter, incoherent / coherent conversion, etc. It is.
[0065]
【Example】
Hereinafter, the present invention will be described more specifically based on examples, particularly when the substrate for a liquid crystal display device is a color filter. However, the present invention is not limited to the following examples.
[0066]
Example 1
(1) Preparation of resin black matrix and seal pattern
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and bis (3-aminopropyl) tetramethyldisiloxane in N-methyl-2-pyrrolidone solvent The reaction was performed to obtain a polyimide precursor (polyamic acid) solution having a polymer concentration of 20% by weight.
[0067]
A carbon black mill base having the following composition was dispersed at 7500 rpm for 20 minutes using a homogenizer, and glass beads were filtered to prepare a black paste.
[0068]
Carbon black mill base
Carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 4.6 parts
Polyimide precursor solution 24.0 parts
N-methylpyrrolidone 61.4 parts
Glass beads 90.0 parts
A black paste was applied onto a non-alkali glass (OA-2, manufactured by Nippon Electric Glass Co., Ltd.) substrate having a size of 300 × 350 mm using a spinner, and semi-cured in an oven at 130 ° C. for 20 minutes. Subsequently, a positive resist (Shipley “Microposit” RC100 30cp) was applied with a spinner and dried at 90 ° C. for 10 minutes. The resist film thickness was 1.5 μm. Exposure was performed via a photomask using an exposure machine PLA-501F manufactured by Canon Inc.
[0069]
Next, an aqueous solution of 23 ° C. containing 2% by weight of tetramethylammonium hydroxide is used as a developer, the substrate is dipped in the developer, and simultaneously the substrate is swung to reciprocate once in 10 cm width in 5 seconds, Development of the positive resist and etching of the polyimide precursor were performed simultaneously. The development time was 60 seconds. Thereafter, the positive resist was peeled off with methyl cellosolve acetate, and further cured at 300 ° C. for 30 minutes to convert to polyimide, thereby obtaining a resin black matrix substrate. The film thickness of the resin black matrix was 1.0 μm.
[0070]
(2) Production of colored layers and spacers
Next, as red, green and blue pigments, respectively, dianthraquinone pigments represented by Color Index No. 65300 Pigment Red 177, phthalocyanine green pigments represented by Color Index No. 74265 Pigment Green 36, Color Index No. 74160 Pigment A phthalocyanine blue pigment represented by Blue 15-4 was prepared. The above pigments were mixed and dispersed in the polyimide precursor solution at a ratio of (polyimide precursor / pigment) weight ratio of 8: 2, respectively, to obtain three kinds of colored pastes of red, green, and blue.
[0071]
First, a blue paste was applied on a resin black matrix substrate, dried with hot air at 80 ° C. for 10 minutes, and semi-cured at 120 ° C. for 20 minutes. Thereafter, a positive resist (Shipley “Microposit” RC100 30 cp) was applied with a spinner and then dried at 80 ° C. for 20 minutes. Exposure was performed using a mask, the substrate was dipped in an alkali developer (Shipley “Microposit” 351), and simultaneously the substrate was rocked while simultaneously developing the positive resist and etching the polyimide precursor. Thereafter, the positive resist was peeled off with methyl cellosolve acetate and further cured at 300 ° C. for 30 minutes. The film thickness of the colored pixel portion was 2.2 μm. By this patterning, blue pixels were formed and the first stage of the spacer was formed on the resin black matrix. The first stage of the spacer has a rectangular shape with rounded corners, and its area is about 500μm.²Met.
[0072]
After washing with water, the second stage of the spacer was formed on the resin black matrix together with the formation of red pixels. The film thickness of the red pixel portion was 1.8 μm. The shape of the second stage of the spacer is also a rectangular shape with rounded corners, and its area is about 300μm.²Met.
[0073]
Further, after washing with water, a green pixel was formed and a third stage of spacers was formed on the resin black matrix to produce a color filter. The film thickness of the green pixel portion was 1.8 μm. The shape of the third stage of the spacer is a track shape, and its area is about 200μm.²Met.
[0074]
The average area per spacer in the screen of the spacer provided on the resin black matrix by the lamination of the colored layers was found from the area of the third step of the spacer, and was about 200 μm 2. Spacers in the screen are provided in the screen at a rate of one for every three pixels, and the average number is about 11 / mm.²It was. Therefore, the ratio of the spacer area in the screen is 200 μm 2 × 11 pieces / mm.²Is about 0.22%.
[0075]
The height of the spacer at 25 ° C. was 4.1 μm. The total height of the spacer was the sum of the resin black matrix, the blue colored layer, the red colored layer, and the green colored layer in the spacer portion, and was 6.2 μm.
[0076]
In addition, about 5 pieces / mm are formed on the resin black matrix on the part of the frame formed with the resin black matrix outside the screen and on the seal part around the frame.²Spacers were provided at a ratio of
[0077]
This non-alkali glass substrate having a light-shielding layer and a red pixel, a green pixel, a blue pixel, a spacer on the resin black matrix of the display screen part and the frame, and the seal part around the frame is formed by sputtering. An ITO film was formed to obtain a color filter used as a substrate for a liquid crystal display element. The thickness of the ITO film was 150 nm, and the surface resistance was 20Ω / □.
[0078]
(3) Measurement of spacer deformation
Using a micro compression tester equipped with a heating device, the amount of deformation of one formed spacer (height 4.1 μm) was measured.
[0079]
<Measurement method>
Measuring machine: “Dynamic ultra-small hardness meter DUH-201S” manufactured by Shimadzu Corporation
Measurement method: Load test: Measured using mode 1
Measurement conditions: set load: 0.14 gf, 0.18 gf, 0.22 gf (0.14 kgf is 0.15 kgf / cm²11 pieces / mm²The value divided by. Similarly, 0.18kgf is 0.2kgf / cm²11 pieces / mm²The value divided by 0.22kgf is 0.25kgf / cm²11 pieces / mm²The value divided by. ), 0.51 gf, 0.55 gf, 0.59 gf (0.51 kgf is 0.55 kgf / cm²11 pieces / mm²The value divided by. Similarly, 0.55 kgf is 0.6 kgf / cm²11 pieces / mm²The value divided by 0.59kgf is 0.65kgf / cm²11 pieces / mm²The value divided by. ), 0.87 gf, 0.91 gf, 0.95 gf (0.87 kgf is 0.95 kgf / cm)²11 pieces / mm²The value divided by. Similarly, 0.91 kgf is 1.0 kgf / cm²11 pieces / mm²The value divided by 0.95kgf is 1.05kgf / cm²11 pieces / mm²The value divided by. )
Setting temperature: 95 ° C, 100 ° C, 105 ° C, 130 ° C, 135 ° C, 140 ° C, 165 ° C, 170 ° C, 175 ° C.
[0080]
Holding time: 60 seconds
Indenter type: Cylindrical indenter Diameter 50μm
The measured results are shown in Table 1. It was found that point A exists at 100 to 170 ° C. and 0.2 to 1 kgf / cm 2 per substrate plane. The point B is also 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane.²It was found to exist.
[0081]
[Table 1]

Next, when the C point where the difference between the height at 25 ° C. of the spacer and the height at 25 ° C. of the spacer after pressurizing at a constant temperature and pressure for 1 hour was 1 μm or less was obtained, the C point was also 100 to 100 170 ° C. and 0.2-1 kgf / cm per substrate plane²It was found to exist. Table 2 shows the measurement results. The results of measuring the height after holding at constant temperature and constant pressure for 2 hours and 10 hours are also shown.
[0082]
[Table 2]

(4) Fabrication and evaluation of color liquid crystal display devices
A polyimide-based alignment film was provided on the color filter provided with the spacer and subjected to rubbing treatment. Similarly, a polyimide alignment film was provided on the opposing liquid crystal display element substrate, and a rubbing treatment was performed. On one substrate, a sealing material (STRUCT BOND XN-21-SB, manufactured by Mitsui Toatsu Chemicals) is applied around the substrate using screen printing. Two substrates are bonded together, heated and pressed to perform pressure bonding and curing of the seal. In order to fully press and cure the seal, it was heated and pressurized for 2 hours. The temperature and pressure at this time were the conditions of 1-a, b, c, d, e, f, g, h, i. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0083]
As shown in Table 3, the liquid crystal display device showed good display characteristics with no cell gap unevenness as shown in Table 3 under all temperature and pressure conditions during pressure bonding and curing of the seal.
[0084]
[Table 3]

Example 2
In the same manner as in Example 1, a black matrix and a pixel and a coloring layer constituting the pixel were laminated. Next, an acrylic overcoat resin was applied and heated and cured to form an overcoat film having a thickness of about 0.2 μm.
[0085]
The average area per one spacer screen provided on the resin black matrix by laminating the colored layers is approximately equal to the area of the third colored layer of the spacer, approximately 190 μm.²Met. Spacers in the screen are provided in the screen at a rate of 1 in 9 pixels, and the average number is about 4 / mm.²It was. Therefore, the ratio of the spacer area in the screen is 190 μm 2 × 4 / mm²Is about 0.08%.
[0086]
The height of the spacer at 25 ° C. was 4.0 μm. The total height of the spacer was the sum of the resin black matrix, the blue colored layer, the red colored layer, the green colored layer, and the overcoat film in the spacer portion, and was 6.4 μm.
[0087]
In addition, about 5 pieces / mm are formed on the resin black matrix on the part of the frame formed with the resin black matrix outside the screen and on the seal part around the frame.²Spacers were provided at a ratio of
[0088]
This non-alkali glass substrate having a light-shielding layer and a red pixel, a green pixel, a blue pixel, a spacer on the resin black matrix of the display screen part and the frame, and the seal part around the frame is formed by sputtering. An ITO film was formed to obtain a color filter used as a substrate for a liquid crystal display element. The thickness of the ITO film was 150 nm, and the surface resistance was 18Ω / □.
[0089]
(3) Measurement of spacer deformation
Using a micro compression tester equipped with a heating device, the amount of deformation of one formed spacer (height: 4.0 μm) was measured in the same manner as in Example 1, and the results shown in Table 4 were obtained. It was found to have A point and B point.
[0090]
[Table 4]

Table 5 shows the difference between the height of the spacer before the test at 25 ° C. and the height of the spacer at 25 ° C. after unloading and cooling for 1, 2, and 10 hours in the heat-compressed state. . It was found to have C point.
[0091]
[Table 5]

(4) Fabrication and evaluation of color liquid crystal display devices
A polyimide-based alignment film was provided on the color filter provided with the spacer and subjected to rubbing treatment. Similarly, a polyimide alignment film was provided on the opposing liquid crystal display element substrate, and a rubbing treatment was performed. A sealant is applied on one substrate using screen printing around the substrate. Two substrates are bonded together, heated and pressed to perform pressure bonding and curing of the seal. In order to fully press and cure the seal, it was heated and pressurized for 2 hours. The temperature and pressure at this time were the conditions of 2-a, b, c, d, e, f, g, h, i. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0092]
As shown in Table 6, the liquid crystal display device showed good display characteristics with no cell gap unevenness under all temperature and pressure conditions during the pressure bonding and curing of the seal.
[0093]
[Table 6]

Example 3
As in Example 1, a black matrix and pixels were formed. The coloring layers constituting the pixels were not stacked. Next, an acrylic overcoat resin was applied and heated and cured to form an overcoat film having a thickness of about 0.2 μm.
[0094]
An ITO film was formed by sputtering on the non-alkali glass substrate having the light shielding layer and the red, green, and blue pixels to obtain a color filter used as a substrate for a liquid crystal display element. The thickness of the ITO film was 150 nm, and the surface resistance was 17Ω / □.
[0095]
Next, a photosensitive acrylic resin was applied as a spacer resin, exposed and developed on the blue pixel stripe, and a spacer having a spacer height of 4.0 μm was obtained.
[0096]
The average area per spacer screen is about 200μm²Met. Spacers in the screen were provided in the screen at a rate of one for every three pixels, and the average number was about 11 / mm2. Therefore, the ratio of the spacer area in the screen is 200 μm.²It is found at x11 pieces / mm and is about 0.22%.
[0097]
The height of the spacer at 25 ° C. was 4.0 μm. The total height of the spacer was the sum of the resin black matrix, the blue colored layer, the overcoat film, and the spacer resin in the spacer portion, and was 6.5 μm.
[0098]
In addition, about 5 pieces / mm are formed on the resin black matrix on the part of the frame formed with the resin black matrix outside the screen and on the seal part around the frame.²Spacers were provided at a ratio of
[0099]
(3) Measurement of spacer deformation
Using a micro compression tester equipped with a heating device, the amount of deformation of one formed spacer (height: 4.0 μm) was measured in the same manner as in Example 1, and the results shown in Table 7 were obtained. It was found to have A point and B point.
[0100]
[Table 7]

Table 8 shows the difference between the height of the spacer before the test at 25 ° C. and the height of the spacer at 25 ° C. after unloading and cooling for 1, 2, 10 hours in the heat-compressed state. . It was found to have C point.
[0101]
[Table 8]

(4) Fabrication and evaluation of color liquid crystal display devices
A polyimide-based alignment film was provided on the color filter provided with the spacer and subjected to rubbing treatment. Similarly, a polyimide alignment film was provided on the opposing liquid crystal display element substrate, and a rubbing treatment was performed. A sealant is applied on one substrate using screen printing around the substrate. Two substrates are bonded together, heated and pressed to perform pressure bonding and curing of the seal. In order to fully press and cure the seal, it was heated and pressurized for 2 hours. The temperature and pressure at this time were performed under the conditions of 3-a, b, c, d, e, and f. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0102]
As shown in Table 9, the liquid crystal display device exhibited good display characteristics without cell gap unevenness under the temperature and pressure conditions (3-a, b, c, e, and f conditions) at the time of pressure bonding / curing of the seal.
[0103]
[Table 9]

Example 4
(1) Fabrication of black matrix and seal pattern
A light shielding film made of chromium and its oxide was formed on the substrate by vacuum deposition. A photoresist was applied to this, and a photoresist film was formed by heat drying. This was exposed through a photomask using an ultraviolet exposure machine. After exposure, the photoresist was developed by dipping in an alkaline developer. Thereafter, the light shielding film was etched with an acid developer, and the photoresist layer which became unnecessary after the etching was peeled off to form a black matrix.
[0104]
Using a method similar to that in Example 3, red pixels, green pixels, and blue pixels were formed. Next, an acrylic overcoat resin was applied and heated and cured to form an overcoat film having a thickness of about 0.2 μm.
[0105]
An ITO film was formed by sputtering on the non-alkali glass substrate having the light shielding layer and the red, green, and blue pixels to obtain a color filter used as a substrate for a liquid crystal display element. The thickness of the ITO film was 160 nm, and the surface resistance was 16Ω / □.
[0106]
Next, a photosensitive acrylic resin was applied as a spacer resin, exposed and developed on the blue pixel stripe, and a spacer having a spacer height of 4.0 μm was obtained.
[0107]
The average area per one spacer in the screen was about 200 μm 2. Spacers in the screen are provided in the screen at a rate of one for every three pixels, and the average number is about 11 / mm.²It was. Therefore, the ratio of the spacer area in the screen is 200 μm.²× 11 / mm²Is about 0.22%.
[0108]
The height of the spacer at 25 ° C. was 4.0 μm. The total height of the spacer was 6.0 μm, which was the sum of the metal black matrix, the blue colored layer, the overcoat film and the spacer resin in the spacer portion.
[0109]
In addition, about 5 pieces / mm are formed on the resin black matrix on the part of the frame formed with the resin black matrix outside the screen and on the seal part around the frame.²Spacers were provided at a ratio of
[0110]
(3) Measurement of spacer deformation
Using a micro compression tester equipped with a heating device, the amount of deformation of one formed spacer (height: 4.0 μm) was measured in the same manner as in Example 1, and the results shown in Table 10 were obtained. It was found to have A point and B point.
[0111]
[Table 10]

Table 11 shows the difference between the height of the spacer before the test at 25 ° C. and the height of the spacer at 25 ° C. after unloading and cooling for 1, 2, 10 hours in the heat-compressed state. . It was found to have C point.
[0112]
[Table 11]

(4) Fabrication and evaluation of color liquid crystal display devices
A polyimide-based alignment film was provided on the color filter provided with the spacer and subjected to rubbing treatment. Similarly, a polyimide alignment film was provided on the opposing liquid crystal display element substrate, and a rubbing treatment was performed. A sealant is applied on one substrate using screen printing around the substrate. Two substrates are bonded together, heated and pressed to perform pressure bonding and curing of the seal. In order to fully press and cure the seal, it was heated and pressurized for 2 hours. The temperature and pressure at this time were performed under the conditions of 4-a, b, c, d, e, f, and g. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0113]
As shown in Table 12, the temperature and pressure conditions (4-a, b, c, e, f, g conditions) during pressure bonding / curing of the seal show good display characteristics with no cell gap unevenness. It was.
[0114]
[Table 12]

Comparative Example 1
As in Example 1, a black matrix and pixels were formed. The coloring layers constituting the pixels were not stacked. Next, an acrylic overcoat resin was applied and heat-cured to form an overcoat film having a thickness of about 2.0 μm.
[0115]
An ITO film was formed by sputtering on the non-alkali glass substrate having the light shielding layer and the red, green, and blue pixels to obtain a color filter used as a substrate for a liquid crystal display element. The thickness of the ITO film was 150 nm, and the surface resistance was 17Ω / □.
[0116]
Next, a photosensitive acrylic resin different from that of Example 4 was applied as a spacer resin, exposed and developed on the blue pixel stripe, and a spacer having a spacer height of 12.05 μm was obtained.
[0117]
The average area per spacer screen is about 200μm²Met. Spacers in the screen were provided in the screen at a rate of one for every nine pixels, and the average number was about 4 / mm2. Therefore, the ratio of the spacer area in the screen is 100 μm.²× 4 / mm²Is about 0.04%. The height of the spacer at 25 ° C. was 12.0 μm.
[0118]
In addition, about 5 pieces / mm are formed on the resin black matrix on the part of the frame formed with the resin black matrix outside the screen and on the seal part around the frame.²Spacers were provided at a ratio of
[0119]
(3) Measurement of spacer deformation
Using a micro compression tester equipped with a heating device, the amount of deformation of one formed spacer (height 12.05 μm) was measured in the same manner as in Example 1, and the results shown in Table 13 were obtained. There was no A point.
[0120]
[Table 13]

Table 14 shows the difference between the height of the spacer at 25 ° C. before the test and the height of the spacer at 25 ° C. after unloading and cooling for 1, 2, 10 hours in the heat-compressed state. .
[0121]
[Table 14]

(4) Fabrication and evaluation of color liquid crystal display devices
A polyimide-based alignment film was provided on the color filter provided with the spacer and subjected to rubbing treatment. Similarly, a polyimide alignment film was provided on the opposing liquid crystal display element substrate, and a rubbing treatment was performed. A sealant is applied on one substrate using screen printing around the substrate. Two substrates are bonded together, heated and pressed to perform pressure bonding and curing of the seal. In order to fully press and cure the seal, it was heated and pressurized for 2 hours. The temperature and pressure at this time were the conditions of 5-a, b, c, d, e, f, g, h, i. After that, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A module is completed by attaching an IC driver or the like after the polarizing plate is bonded to the outside of the substrate.
[0122]
As shown in Table 15, cell gap unevenness occurred under all conditions, and the display quality deteriorated.
[0123]
[Table 15]

[0124]
【The invention's effect】
In the substrate for a liquid crystal display element of the present invention, there is a specific compressive stress range and a specific temperature range in which the displacement of the spacer is changed within a specific range. Thus, when a liquid crystal display device is manufactured, display unevenness does not occur, and an excellent display characteristic can be obtained.
[Brief description of the drawings]
FIG. 1 is an example of a cross-sectional view of a substrate for a liquid crystal display device having a spacer.
FIG. 2 is an example of a cross-sectional view of a substrate for a liquid crystal display device having a spacer.
FIG. 3 is an example of a cross-sectional view of a substrate for a liquid crystal display device having a spacer.
FIG. 4 is an example of a cross-sectional view of a substrate for a liquid crystal display device having a spacer.
FIG. 5 is an example of a cross-sectional view of a substrate for a liquid crystal display device having a spacer.
FIG. 6 is a diagram illustrating a load test for obtaining a deformation amount of a spacer.
FIG. 7 is an indentation load-indentation displacement diagram for obtaining a deformation amount of a spacer.
FIG. 8 is a diagram illustrating the height of a spacer.
FIG. 9 is a diagram illustrating the height of a spacer.
FIG. 10 is a diagram illustrating the height of a spacer.
FIG. 11 is a diagram illustrating the height of a spacer.
FIG. 12 is a diagram illustrating a test in which a spacer is heated and compressed and held for a long time.
FIG. 13 is a diagram illustrating the total height of the spacer.
FIG. 14 is a diagram illustrating the total height of the spacer.
FIG. 15 is a diagram for explaining the total height of spacers;
FIG. 16 is a diagram for explaining the inside and outside of the screen of the substrate for a liquid crystal display device.
FIG. 17 is an example of the shape of the cross section of the spacer.
FIG. 18 is a diagram illustrating an upper area and a lower area of a spacer.
FIG. 19 illustrates an example of a liquid crystal display device manufactured using the substrate for a liquid crystal display device of the present invention.
[Explanation of symbols]
1 Resin for spacer
2 Transparent conductive film
3 Overcoat film
4 pixels (R)
5 Black matrix
6 Transparent substrate
7 The same colored layer as the pixel (G)
8 The same colored layer as the pixel (B)
9 Indenter
10 Spacer height
11 Optical flat
12 Liquid crystal display substrate having spacers
13 Spacer formation surface
14 Total height
15 screen
16 picture frames
17 Off screen
18 Substrate for liquid crystal display
19 yen
20 ellipse
21 Track type
22 rectangle with rounded corners
23 Top area
24 Lower area
25 Pixel electrode
26 Alignment film
27 LCD
28 pixels (G)

Claims (17)

In the substrate for a liquid crystal display device having a spacer for performing gap control between the substrate for a liquid crystal display device which faces the beauty screen outside Oyo the screen, the pressure constant, the amount of deformation of the compression conditions the temperature was increased 5 ° C. The difference α between the size and the amount of deformation under the compression condition with the temperature reduced by 5 ° C. is 0.5 μm or less, the temperature is constant, and the amount of deformation under the compression condition is increased by 0.05 kgf / cm ² . The point A where the difference β between the size and the amount of deformation under the compression condition with the pressure reduced by 0.05 kgf / cm ² is 0.5 μm or less is 100 to 170 ° C. and 0.2 to 1 kgf / cm per substrate plane. ² having a spacer existing in the range of ² , the average area per spacer formed in the screen is 25 to 500 μm ² , and the average number of spacers formed in the screen is 1 / mm ² or more , And in the screen A substrate for a liquid crystal display device , wherein the ratio of the spacer area is 0.08 to 1% . ^2. The substrate for a liquid crystal display device according to claim 1, wherein the spacer has a spacer in which the deformation amount of the spacer is 1 [mu] m or less in the range of 100 to 170 [deg.] C. and 0.2 to 1 kgf / cm < ² > per substrate plane. The difference between the height of the spacer at 25 ° C. and the height of the spacer at 25 ° C. after pressing at a constant temperature and pressure for 1 hour is 1 μm or less is 100 to 170 ° C. and 0 per substrate plane. 3. The substrate for a liquid crystal display device according to claim 1, further comprising a spacer existing in a range of ^{2 to 1} kgf / cm ² . 4. The substrate for a liquid crystal display device according to claim 1, wherein the height of the spacer at 25 [deg.] C. is 1 to 6 [mu] m. 5. The substrate for a liquid crystal display device according to claim 1, wherein the total height of the spacer, which is the distance between the substrate plane at 25 [deg.] C. and the uppermost surface of the spacer, is 1 to 10 [mu] m. . 6. The substrate for a liquid crystal display device according to claim 1, wherein the average number of spacers formed outside the screen is smaller than the average number of spacers formed inside the screen. The substrate for a liquid crystal display device according to any one of claims 1 to 6, wherein a ratio of an area of the spacer in the screen is 0.1 to 1%. The substrate for a liquid crystal display device according to any one of claims 1 to 7, wherein the spacer is formed on a seal portion outside the screen and / or around the seal portion. The substrate for a liquid crystal display device according to any one of claims 1 to 8, wherein the spacer is made of a material mainly composed of one of polyimide resin, acrylic resin, and epoxy resin. The substrate for a liquid crystal display device according to claim 1, wherein the substrate is a color filter having a pixel composed of a black matrix and a colored layer. 11. The substrate for a liquid crystal display device according to claim 10, wherein the spacer is formed on a colored layer constituting the pixel. 12. The substrate for a liquid crystal display device according to claim 10, wherein the spacer is formed on a black matrix. The substrate for a liquid crystal display device according to any one of claims 10 to 12, wherein a spacer is formed after disposing a pixel and an overcoat film on the substrate. The substrate for a liquid crystal display device according to claim 10, wherein the spacer is formed by stacking colored layers constituting pixels. 15. The substrate for a liquid crystal display device according to claim 14, wherein an overcoat film is disposed after forming a spacer by laminating colored layers constituting pixels. 16. A liquid crystal display device in which liquid crystal is filled between two liquid crystal display device substrates, wherein at least one liquid crystal display device substrate is the liquid crystal display device substrate according to any one of claims 1 to 15. A liquid crystal display device characterized by the above. A step of bonding the substrate for a liquid crystal display device which faces the substrate for a liquid crystal display device having a spacer for performing gap control each time screen outside Oyo screen, and a step formed by injecting a liquid crystal between the substrates at least In the manufacturing method of the liquid crystal display device having the above, the laminating step makes the pressure constant and the deformation amount under the compression condition with the temperature increased by 5 ° C. and the deformation amount under the compression condition with the temperature decreased by 5 ° C. The amount of deformation under the compression condition when the difference α is 0.5 μm or less, the temperature is constant, and the pressure is increased by 0.05 kgf / cm ² and the deformation amount under the compression condition when the pressure is reduced by 0.05 kgf / cm ² of includes the step of difference between the magnitude β is heated compressed at point a to be 0.5μm or less, further a point exist in 100 to 170 ° C. and the substrate plane per 0.2~1kgf / cm ^2, the screen Formed in The average area of 25 to 500 [mu] m ² per one spacer, and the average number of spacer formed in the screen 1 / mm ² or more, and the ratio of the area of the spacer within the screen, 0.08 to 1% A method of manufacturing a liquid crystal display device, wherein

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