JP4009113B2 - Composition for wet dispersion of spacer particles - Google Patents

Description

【００２０】
（ここで、Ｒ^aは水素原子またはメチル基を示し；Ｒ^bは、置換基を有していても良い炭素数１〜２０の２価の有機基を示し；Ｒ^cは、水素原子と、炭素数１〜５のアルキル基と、炭素数２〜５のアシル基とからなる群から選ばれる少なくとも１つの１価基を示す。Ｒ¹は、炭素数１〜５のアルキル基とフェニル基とからなる群から選ばれた少なくとも１種の１価の基を示す。ｌは１または２であり、ｐは０または１である。）
と、下記一般式（２）：
【００２１】
【化２】

【００２２】
（ここで、Ｒ^dは水素原子またはメチル基を示し；Ｒ^eは、水素原子と、炭素数１〜５のアルキル基と、炭素数２〜５のアシル基とからなる群から選ばれる少なくとも１つの１価基を示す。Ｒ²は、炭素数１〜５のアルキル基とフェニル基とからなる群から選ばれた少なくとも１種の１価の基を示す。ｍは１または２であり、ｑは０または１である。）
と、下記一般式（３）：
【００２３】
【化３】

【００２４】
（ここで、Ｒ^fは水素原子またはメチル基を示し；Ｒ^gは、置換基を有していても良い炭素数１〜２０の２価の有機基を示し；Ｒ^hは、水素原子と、炭素数１〜５のアルキル基と、炭素数２〜５のアシル基とからなる群から選ばれる少なくとも１つの１価基を示す。Ｒ³は、炭素数１〜５のアルキル基とフェニル基とからなる群から選ばれた少なくとも１種の１価の基を示す。ｎは１または２であり、ｒは０または１である。）
とからなる群から選ばれる少なくとも１つの一般式で表される化合物またはその誘導体であることが好ましい。
【００２５】
上記重合工程は、上記縮合工程中および／または上記縮合工程後に、ラジカル重合性基をラジカル重合反応させて粒子を得る工程であることが好ましい。
上記熱処理工程は、上記重合工程で生成した重合体粒子を８００℃以下、より好ましくは１００〜６００℃の温度で乾燥および焼成する工程であり、たとえば、１０容量％以下の酸素濃度を有する雰囲気中や減圧下で行われることが好ましい。
上記の縮合工程、重合工程および熱処理工程から選ばれる少なくとも１つの工程中および／または後に、生成した上記スペーサー粒子を着色する着色工程をさらに含んでいてもよく、詳しくは、上記スペーサー粒子は染料および顔料からなる群から選ばれる少なくとも１つ等を含むことで着色されていてもよい。その色は、光が透過しにくいか、または、透過しない色が、スペーサー粒子自身の光抜けを防止でき画質のコントラストを向上できる点で好ましい。光が透過しにくいか、または、透過しない色としては、たとえば、黒、濃青、紺、紫、青、濃緑、緑、茶、赤等の色を好ましく挙げることができるが、特に好ましくは、黒、濃青、紺色である。なお、染料および／または顔料は、単にスペーサー粒子に含まれるものでもよく、あるいは、染料および／または顔料とスペーサー粒子を構成するマトリックスとが化学結合によって結び付けられた構造を有するものでもよいが、特にこれらに限定されない。
【００２６】
上記染料は、着色しようとする色に応じて適宜選択して使用され、たとえば、染色方法によって分類された、分散染料、酸性染料、塩基性染料、反応染料、硫化染料等が挙げられる。これらの染料の具体例は、「化学便覧応用化学編 日本化学会編」（１９８６年丸善株式会社発行）の１３９９頁〜１４２７頁、「日本化薬染料便覧」（１９７３年日本化薬株式会社発行）に記載されている。
スペーサー粒子を染色する方法としては、従来公知の方法がとられる。たとえば、上記の「化学便覧応用化学編 日本化学会編」や「日本化薬染料便覧」に記載されている方法等で行うことができる。
【００２７】
上記顔料としては、特に限定はされないが、たとえば、カーボンブラック、鉄黒、クロムバーミリオン、モリブデン赤、べんがら、黄鉛、クロム緑、コバルト緑、群青、紺青などの無機顔料；フタロシアニン系、アゾ系、キナクリドン系などの有機顔料が挙げられる。なお、上記顔料は、その平均粒子径が０．４μｍ以下でないと、スペーサー粒子中に導入されない場合があるので、この場合は染料を使用する方が好ましい。上記スペーサー粒子が着色されている場合、液晶表示装置用スペーサー粒子として用いると、バックライトの光抜けを防止でき、液晶表示装置の画質向上を達成することができる。
【００２８】
上記の縮合工程、重合工程および熱処理工程から選ばれた少なくとも１種の工程中および／または後に、生成した上記スペーサー粒子を表面処理する表面処理工程をさらに含んでいても良い。
上記表面処理に用いる表面処理剤としては、特に限定されないが、下記一般式（４）〜（６）から選ばれる少なくとも１種のシラン化合物が好ましい。
ＳｉＸ₄ （４）
Ｒ⁴ＳｉＸ₃ （５）
Ｒ⁵Ｒ⁶ＳｉＸ₂ （６）
（ここで、Ｘは塩素原子、水素原子、炭素数１〜５のアルコキシ基および炭素数２〜５のアシロキシ基から選ばれた少なくとも１種；Ｒ⁴およびＲ⁵は、いずれも、炭素数１〜２２のアルキル基および炭素数６〜２２のアリール基から選ばれる少なくとも１種であり、その基の中の１つ以上の水素原子が、アミノ基、メルカプト基、アルキレンオキシド基、エポキシ基、シアノ基、塩素原子およびフッ素原子から選ばれる少なくとも１種で置換されていても良い；Ｒ⁶は、炭素数１〜５のアルキル基とフェニル基とからなる群から選ばれる少なくとも１種の１価の基である。）
本発明のスペーサー粒子湿式散布用組成物においては、該組成物全体中、スペーサー粒子の含有割合は０．００５〜３０重量％であることが好ましく、より好ましくは０．０１〜２０重量％、さらにより好ましくは０．０５〜１０重量％である。上記スペーサー粒子の含有割合が０．００５重量％未満であると、所望の散布個数密度とするにあたり散布時間がかかりすぎるおそれがあり、３０重量％を超える場合は、スペーサー粒子湿式散布用組成物がスラリー状になり流動性が低下し、また、スペーサー粒子の凝集が発生するおそれがある。
【００２９】
本発明のスペーサー粒子湿式散布用組成物は、スペーサー粒子と溶媒とを含むものであるが、これら以外にも適宜必要に応じて他の成分を含んでいてもよい。〔液晶表示装置の製造方法〕
本発明にかかる液晶表示装置の製造方法（以下、本発明の液晶表示装置の製造方法、本発明の製造方法と称することがある。）は、上記本発明のスペーサー粒子湿式散布用組成物を用いてスペーサー粒子を基板上等に湿式散布する工程を含む、液晶表示装置の製造方法である。
本発明の液晶表示装置の製造方法においては、電極基板、シール材、液晶材料などについては従来と同様のものを従来と同様に材料として使用することができる。また、スペーサー粒子は、使用する上記本発明のスペーサー粒子湿式散布用組成物に含まれる。よって、本発明の製造方法に用いるスペーサー粒子としては、上記本発明のスペーサー粒子湿式散布用組成物に含むスペーサー粒子として記載したものと同様のものが好ましい。
【００３０】
電極基板としては、特に限定はされないが、具体的には、例えば、ガラス基板、フィルム基板などの基板と、基板の表面に形成された電極とを有しており、必要に応じて、電極基板の表面に電極を覆うように形成された配向膜をさらに有する。また、カラー対応の液晶表示装置の場合、カラーフィルタを有する。
シール材としては、特に限定はされないが、具体的には、例えば、エポキシ樹脂接着シール材などが使用される。
液晶（液晶材料）としては、特に限定はされず、従来より用いられているものでよく、具体的には、例えば、ビフェニル系、フェニルシクロヘキサン系、シッフ塩基系、アゾ系、アゾキシ系、安息香酸エステル系、ターフェニル系、シクロヘキシルカルボン酸エステル系、ビフェニルシクロヘキサン系、ピリミジン系、ジオキサン系、シクロヘキシルシクロヘキサンエステル系、シクロヘキシルエタン系、シクロヘキセン系、フッ素系などの液晶が使用できる。
【００３１】
本発明の液晶表示装置を製造する方法としては、具体的には、例えば、２枚の電極基板のうちの一方の電極基板に上記スペーサー粒子湿式散布用組成物を散布してスペーサー粒子（面内スペーサー粒子）を所定の位置に分散配置したものの上に、エポキシ樹脂等の接着シール材にシール部スペーサー粒子を分散させたものをもう一方の電極基板の接着シール部分にスクリーン印刷などの手段により塗布したものを載せ、適度の圧力を加え、１００〜１８０℃の温度で１〜６０分間の加熱、または、照射量４０〜３００ｍＪ／ｃｍ²の紫外線照射により、接着シール材を加熱硬化させた後、液晶を注入し、注入部を封止する方法を挙げることができるが、特にこのような製法に限定されるわけではない。
【００３２】
ここで、本発明の製造方法により得られる液晶表示装置の構成について、図１を参照しながら説明するが、液晶表示装置の構成は特にこれに限定されるわけではない。すなわち、得られた液晶表示装置は、液晶材料を介在して対向配置された一対の電極基板（第１電極基板１１０と第２電極基板１２０）と、スペーサー粒子とを備える。第１電極基板１１０は、第１基板１１と、第１基板１１の表面に形成された電極５とを有する。第２電極基板１２０は、第２基板１２と、第２基板１２の表面に形成された電極５とを有する。第１電極基板１１０と第２電極基板１２０とはその周辺部でシール材２によって接着されている。スペーサー粒子は、前記基板間に選択的に分散配置されて、前記基板の間隔を保持するものであり、シール材２中に分散するシール部スペーサー粒子３と、面内に分散する面内スペーサー粒子８とが存在する。液晶材料７は、第１電極基板１１０と第２電極基板１２０との間に封入されており、第１電極基板１１０と第２電極基板１２０とシール材２とで囲まれた空間に充填されている。
【００３３】
本発明の液晶表示装置の製造方法においては、上記スペーサー粒子湿式散布用組成物を散布することによりスペーサー粒子を湿式散布するが、スペーサー粒子湿式散布用組成物の散布方法としては、特に限定はされないが、具体的には、例えば、スプレー方式やインクジェット方式などを採用した機器等を用いて散布することが好ましい。なかでも、インクジェット方式が、基板上の所望の位置にスペーサー粒子を分散配置しやすいためより好ましい。
インクジェット方式は、インクとして用いるスペーサー粒子湿式散布用組成物の液滴生成原理により、連続ジェット方式とドロップ・オン・デマンド方式の２方式に分類される。本発明の製造方法では、いずれの方式も好ましく採用できる。（なお、以下、「スペーサー粒子湿式散布用組成物の液滴」を、単に「液滴」と称する。）
連続ジェット方式は、液滴を連続して生成させ、記録信号に応じて液滴を選択して記録を行う方式である。連続ジェット方式では液滴の発生を定常状態で行わせるため、液滴の発生周期を短くすることができ高速記録が可能である。また、噴出した液滴の飛翔速度も速いため、ノズルと記録媒体までの間隔を離すことができるので、曲面などへの記録も可能である。連続ジェット方式には、Ｓｗｅｅｔ型、マイクロドット型、Ｈｅｒｚ型、ＩＲＩＳ型などがある。
【００３４】
Ｓｗｅｅｔ型では、外部からノズルに機械的振動を与え、その周波数を液滴の自然発生的な分裂速度と一致させ、分裂した液滴の質量が同一の質量になるように発生した液滴を利用する。具体的には、ノズル部にピエゾ圧電素子を取り付け、スペーサー粒子湿式散布用組成物の分裂周期で加振し、均一な液滴を発生させる。スペーサー粒子湿式散布用組成物が分裂する部分に荷電電極を設け、液滴を帯電させる。この帯電した液滴は偏向電極の間を通過する。液滴は電界により垂直方向の静電力を受けて、その軌道が変化する。このときの偏向電圧の加え方により、２値偏向型と多値偏向型がある。
【００３５】
マイクロドット型は、液滴が分裂する際に液滴の間にサテライトと呼ばれる小滴を取り出して記録を行う方式である。この方法では一対の電極の各々に異なる電圧を印加することにより、帯電と偏向の両方の動作を行わせる。
Ｈｅｒｚ型では、細いノズルから加圧したスペーサー粒子湿式散布用組成物を噴出させ、液滴をリング状の電極中を通過させる。電極に電圧を印加すると液滴に帯電した電荷の反発力によって、スプレー状の細かい霧へ分裂する。分裂してスプレーとなったときは記録せず、分裂しないときの液滴を記録に用いる。
ＩＲＩＳ型は、Ｈｅｒｚ型の改良形で、ピエゾ振動子をノズルに設置することにより液滴の大きさを一定に保つようにしているのが特徴である。
【００３６】
ドロップ・オン・デマンド方式は、記録信号に応じてスペーサー粒子湿式散布用組成物を噴出させる方式である。記録速度は連続ジェット方式に比べ遅いが、全体の機構としては簡単になる。ドロップ・オン・デマンド方式には、圧力パルス方式、サーマルジェット方式、ＥＲＦ方式などがある。
圧力パルス方式は、ピエゾ圧電素子などを用い、インクチャンバ内で圧力波を発生させ、スペーサー粒子湿式散布用組成物を噴出させる方式であり、プリントヘッドの構造により、Ｓｔｅｍｍｅ方式、Ｇｏｕｌｄ方式、Ｋｙｓｅｒ方式などがある。
【００３７】
サーマルジェット方式は、ノズル内に発熱素子を設け、スペーサー粒子湿式散布用組成物を気化させて気泡とし、この気泡によりスペーサー粒子湿式散布用組成物が押し出されてノズルにより噴出される。
ＥＲＦ方式は、プリントヘッドがスペーサー粒子湿式散布用組成物の流路とそれを挟むように設けられた一対の電極からなり、スペーサー粒子湿式散布用組成物はポンプなどにより加圧されている。電極間に電圧が印加されるとスペーサー粒子湿式散布用組成物に加わる見かけの圧力が０となり、スペーサー粒子湿式散布用組成物はノズルから噴出されず、電極の電圧を０にするとスペーサー粒子湿式散布用組成物は加圧されているのでノズルより噴出する。
【００３８】
本発明の製造方法においては、スペーサー粒子湿式散布用組成物を散布してスペーサー粒子を湿式散布し分散配置する場合に、通常は、まず液晶表示装置の電極基板上あるいはカラーフィルタ上の、どの位置にスペーサー粒子を配置するのか決めておく。得られる液晶表示装置のコントラスト向上や高表示品位を達成するためには、画素領域すなわち表示領域にスペーサー粒子を分散配置するのは好ましくなく、非画素領域すなわち非表示領域にスペーサー粒子を分散配置することが好ましい。画素領域に分散配置されるとスペーサー粒子の存在部分が表示されず、スペーサー粒子自身や、液晶の配向乱れによりスペーサー粒子周囲は光抜けが発生するからである。したがって、例えば、ＴＮモードの場合には、文字や図案の周辺や間隙等、表示に直接かかわらない領域のみにスペーサー粒子を分散配置させることが好ましい。また、例えば、ＳＴＮモードの場合には、電極基板の透明電極がストライプ状に配列されているので、それらの透明電極の間隙にスペーサー粒子を分散配置させることが好ましい。また、例えば、ＴＦＴやＳＴＮのカラー表示の場合、カラーフィルタの画素のＲ、Ｇ、Ｂ以外の部分、すなわち、ブラックマトリクス上に分散配置させることが好ましい。また、カラーフィルタのある基板と対向させる電極基板上に分散配置する場合は、ブラックマトリクスの位置に対応する部分に分散配置させることが好ましい。
【００３９】
また、分散配置させるスペーサー粒子の位置の数は、液晶表示装置のセルギャップが均一に保持できれば特に限定はなく、適宜設定すればよいが、少なすぎるとギャップの均一性が悪くなり、多すぎると低温発泡等が発生し易くなる。また、分散配置の数は表示領域の一つの画素の大きさによっても左右される。ここで、分散配置されるスペーサー粒子は、非画素領域に配置されていれば、単粒子であっても複数個であってもよく適宜設定すればよいが、多すぎるとギャップ均一性が悪くなり、また、表示画素に配置されるスペーサー粒子の割合が多くなり表示品位が低下する。
【００４０】
本発明の製造方法により得られる液晶表示装置は、従来の液晶表示装置と同じ用途、例えば、テレビ、モニター、パーソナルコンピューター、ワードプロセッサー、カーナビゲーションシステム、ＤＶＤ、デジタルビデオカメラ、ＰＨＳ（携帯情報端末）などの画像表示装置として使用され得る。
【００４１】
【実施例】
以下に、実施例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下では、便宜上、「重量部」を単に「部」と、または、「重量％」を単に「ｗｔ％」と記すことがある。
まず、本発明の実施例において記載する測定値の定義、測定方法、評価基準について以下に示す。
〔スペーサー粒子の平均粒子径、粒子径の変動係数〕
スペーサー粒子の平均粒子径および粒子径の変動係数は、下記測定方法により測定した。すなわち、平均粒子径は、コールターマルチサイザー（ベックマンコールター社製）により、３００００個の粒子の粒子径を測定し、その平均の粒子径として求めた。また、粒子径の変動係数は、下記式に従って求めた。
【００４２】
【数１】

【００４３】
〔スペーサー粒子の破壊強度〕
スペーサー粒子の破壊強度は、島津微小圧縮試験機（島津製作所社製、ＭＣＴＭ−２００）により、室温（２５℃）において、試料台（材質：ＳＫＳ平板）上に散布した試料粒子１個について、直径５０μｍの円形平板圧子（材質：ダイヤモンド）を用いて、粒子の中心方向へ一定の負荷速度で荷重をかけ、試料粒子が破壊したときの圧縮荷重（Ｎ）の値とする。
〔スペーサー粒子の１０％圧縮弾性率〕
スペーサー粒子の１０％圧縮弾性率とは、上記破壊強度の測定と同様の装置により、試料台の上に散布した試料粒子１個について、円形平板圧子を用いて、粒子の中心方向へ一定の負荷速度で荷重をかけ、圧縮変位が粒子径の１０％となる時の荷重と圧縮変位のミリメートル数を測定する。測定した圧縮荷重、粒子の圧縮変位、粒子の半径を、下記式：
【００４４】
【数２】

【００４５】
（ここで、Ｅ：圧縮弾性率（ＧＰａ）、Ｆ：圧縮荷重（Ｎ）、Ｓ：圧縮変位（ｍｍ）、Ｒ：粒子の半径（ｍｍ）である。）
に代入し、値を算出する。この操作を、異なる３個の粒子について行い、その平均値を粒子の１０％圧縮弾性率とする。
−製造例１−
〔スペーサー粒子の製造例〕
冷却管、温度計、滴下口のついた四つ口フラスコ中に２５％アンモニア水溶液２．９ｇ、メタノール１０．１、水１４１．１ｇを混合した溶液（Ａ液）を入れ、２５±２℃に保持し、攪拌しながら該溶液中に、γ−メタクリロキシプロピルトリメトキシシラン２７ｇ、メタノール５４ｇ、ラジカル重合開始剤として２，２’−アゾビス−（２，４−ジメチルバレロニトリル）０．１４ｇ、テトラエトキシシランの２〜５量体（多摩化学株式会社製、製品名：「シリケート４０」（ＳｉＯ₂として４０ｗｔ％））５ｇを混合した溶液（Ｂ液）を滴下口から添加して、γ−メタクリロキシプロピルトリメトキシシランの加水分解・重縮合を行った。攪拌を継続しながら２０分後、窒素雰囲気中で７０±５℃に加熱し、ラジカル重合を行った。
【００４６】
２時間加熱を続けた後、室温まで冷却し、重合体粒子の懸濁体を得た。この懸濁体を濾過により固液分離し、得られたケーキをメタノールによるデカンテーションで３回洗浄し、真空乾燥機中で２００℃で２時間真空乾燥して有機質無機質複合体粒子であるスペーサー粒子（Ａ）を得た。得られた複合体粒子は平均粒子径４．２４μｍ、変動係数３．８％、ポリシロキサン骨格を構成するＳｉＯ₂の量３４．７ｗｔ％、１０％圧縮弾性率４８０ｋｇ／ｍｍ²、１０％変形後の残留変位２．２％、破壊強度２．４ｇであった。
−製造例２−
〔接着性スペーサー粒子の製造例〕
バインダー樹脂（１）として、ブチルアクリレート／スチレン（重量比２０／８０）のモノマー組成からなる樹脂をソープフリー乳化重合で合成した。ガラス転移温度は６７℃、軟化温度は１１７℃、平均粒子径は０．３μｍであった。
【００４７】
上記製造例１で得られたスペーサー粒子（Ａ）３０ｇと、バインダー樹脂（１）１０ｇとを混合した後、奈良機械製作所（株）製ハイブリダイゼーションシステムＮＨＳ−０型を使用して高速気流中衝撃法により、スペーサー粒子（Ａ）の表面を、バインダー樹脂（１）で被覆処理し、接着性スペーサー粒子（Ｂ）を得た。
−実施例１−
ジエチレングリコール（沸点２４５℃）を３０ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（１）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（１）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。
【００４８】
その後、実際に電極基板上に散布されたスペーサー粒子（Ａ）の散布個数と単粒子率を、以下に示す方法により測定したところ、散布個数密度は２０５個／ｍｍ²、単粒子率は９８％であった。
さらに、電極基板上に散布されたスペーサー粒子（Ａ）の基板に対する付着力を、以下に示すエアブロー法によって評価したところ、スペーサー粒子（Ａ）の残存率は９８％であった。
上記散布個数、単粒子率、スペーサー粒子残存率の結果を表１に示す。
〔散布個数密度〕
電極基板上の任意の１ｍｍ²の観察区域を９か所選び、各区域内のスペーサー粒子の個数を光学顕微鏡により計数し、計９区域の個数の平均値をもって、散布個数密度（個／ｍｍ²）とした。
〔単粒子率〕
上記散布個数の測定における、全粒子個数に対する単粒子の個数の比率を、単粒子率（％）とした。
〔エアブロー法〕
スペーサー粒子を散布した電極基板上において、任意の一定面積の観察区域を選び、光学顕微鏡により、この観察区域のエアブロー前後の粒子個数をそれぞれ計数し、次式に従ってスペーサー粒子残存率（％）を求めた。算出したスペーサー粒子残存率により基板に対する付着力を評価する。
【００４９】
スペーサー粒子残存率（％）
＝〔（エアブロー後の残存粒子数）／（エアブロー前の粒子数）〕×１００（エアブロー法試験条件：エアー圧２ｋｇ／ｃｍ²、ブロー時間１０秒、ノズル内径２ｍｍ、基板とノズルとの距離５ｍｍ）
次に、以下の手順でＴＦＴ型液晶表示装置を作製した。ＴＦＴ素子を有する透明電極基板と、スペーサー粒子が散布され分散配置されたカラーフィルタを有する透明電極基板とを、接着シール材で貼り合わせ、その後、両電極基板の隙間を真空として更に大気圧に戻すことによりＴＦＴ用フッ素系ＴＮ液晶を注入し、注入部を封止した。そして、上下電極基板の外側に偏光フィルムを貼り、１４インチのＴＦＴ型液晶表示装置（１）を得た。
【００５０】
液晶表示装置（１）は、隙間距離が均一化されており、色ムラがないものであった。液晶表示装置（１）はスペーサー粒子の密度ムラがなく、ギャップ均一性が優れたものであることがわかる。
また、液晶表示装置（１）について、５０℃で５００時間後の電圧保持率を測定したところ９８％であり、電圧保持率の低下は見られなかった。
液晶表示装置（１）に、所定電圧を印加したところ、液晶表示板（１）は長時間優れた駆動安定性を示し、液晶の配向特性も良好レベルであった。つまり、上記スペーサー粒子湿式散布用組成物（１）を用いて作製した液晶表示装置（１）は、信頼性を有するものであることがわかる。
【００５１】
さらに、液晶表示装置（１）を、Ｘ軸、Ｙ軸およびＺ軸方向に、それぞれ１時間ずつ２Ｇの加速度をかけながら振動させた。振動後の面内ギャップ均一性は良好であり、スペーサー粒子の移動によって配向膜が傷つけられること（振動試験による配向膜損傷）に起因する光抜けの増大は認められなかった。
上記色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷の結果を表２に示す。色ムラ、液晶表示装置の信頼性、振動試験による配向膜損傷については、下記評価基準に基づいて示す。
色ムラ:
◎：色ムラおよび表示面のざらつきが無く画質良好
○：色ムラ無し
△：わずかに色ムラ有り
×：非常に色ムラが多い
振動試験による配向膜損傷：
○：損傷無し
△：やや損傷有り
×：多数損傷有り
液晶表示装置の信頼性：
○：信頼性有り
×：信頼性無し
−実施例２−
ジエチレングリコール（沸点２４５℃）を３０ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、実施例１と同様のスペーサー粒子湿式散布用組成物（１）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板のブラックマトリクス上に、従来公知のインクジェット装置を用いてスペーサー粒子湿式散布用組成物（１）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにしたところ、スペーサー粒子（Ａ）はブラックマトリクス上に７０μｍおきに分散配置されていた。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５２】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（２）を得た。液晶表示装置（２）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−実施例３−
ジエチレングリコール（沸点２４５℃）を０．２５ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（２）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（２）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５３】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（３）を得た。液晶表示装置（３）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−実施例４−
ジエチレングリコール（沸点２４５℃）を４８０ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（３）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（３）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５４】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（４）を得た。液晶表示装置（４）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−実施例５−
トリメチレングリコール（沸点２１０℃）を３０ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（４）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（４）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５５】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（５）を得た。液晶表示装置（５）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−比較例１−
ジエチレングリコール（沸点２４５℃）を０．０５ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（ｃ１）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（ｃ１）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５６】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（ｃ１）を得た。液晶表示装置（ｃ１）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−比較例２−
ジエチレングリコール（沸点２４５℃）を０．０５ｐｐｍ含む２−プロパノールに接着性スペーサー粒子（Ｂ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（ｃ２）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（ｃ２）を散布し、接着性スペーサー粒子（Ｂ）の散布個数密度が約２００個／ｍｍ²となるようにした。散布後、電極基板を１５０℃で６０分間加熱して、接着性スペーサー粒子（Ｂ）をカラーフィルタ上に固定した。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５７】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（ｃ２）を得た。液晶表示装置（ｃ２）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−比較例３−
ジエチレングリコール（沸点２４５℃）を６００ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（ｃ３）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（ｃ３）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５８】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（ｃ３）を得た。液晶表示装置（ｃ３）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
−比較例４−
エチレングリコールジアセテート（沸点１９０℃）を３０ｐｐｍ含む２−プロパノールにスペーサー粒子（Ａ）が０．５重量％となるように混合し、超音波分散させ、スペーサー粒子湿式散布用組成物（ｃ５）を得た。次に、１４インチＴＦＴ型液晶表示装置用の、カラーフィルタが設置された電極基板上に、従来公知のスプレー方式の湿式散布装置を用いてスペーサー粒子湿式散布用組成物（ｃ５）を散布し、スペーサー粒子（Ａ）の散布個数密度が約２００個／ｍｍ²となるようにした。電極基板上の散布個数密度、単粒子率、スペーサー粒子残存率について、実施例１と同様の方法により測定した。その結果を表１に示す。
【００５９】
次に、実施例１と同様の方法により１４インチのＴＦＴ液晶表示装置（ｃ５）を得た。液晶表示装置（ｃ５）における色ムラ、電圧保持率、液晶表示装置の信頼性、振動試験による配向膜損傷について、実施例１と同様の方法により測定、評価を行った。その結果を表２に示す。
【００６０】
【表１】

【００６１】
【表２】

【００６２】
【発明の効果】
本発明によれば、スペーサー粒子を湿式散布した場合に、基板にスペーサー粒子を確実に付着させることができ、かつ、優れたスペーサー粒子散布性を達成することのでき、例えば液晶の信頼性等も確保し得る、スペーサー粒子湿式散布用組成物を提供することができる。
また、本発明によれば、上記本発明のスペーサー粒子湿式散布用組成物を用いることにより、優れたスペーサー粒子散布性と、基板への確実なスペーサー粒子付着性とを備えるとともに、液晶の信頼性も十分確保した、液晶表示装置を提供することができる。
【図面の簡単な説明】
【図１】本発明の製造方法により得られる液晶表示装置の一例を示す部分断面図である。
【符号の説明】
７ 液晶
８ 面内スペーサー粒子
１１０ 電極基板
１１３ シール部スペーサー粒子
１２０ 電極基板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a spacer particle wet spraying composition comprising spacer particles and a solvent, and a method for producing a liquid crystal display device using the spacer particle wet spraying composition.
[0002]
[Prior art]
For example, spacer particles used in a liquid crystal display device or the like are dispersed on a panel serving as a substrate, and a spacer particle wet spraying composition comprising spacer particles and a solvent containing an organic solvent (and water if necessary) ( For example, it is well known that the spacer particles are wet sprayed by spraying spacer particles in a solvent containing an organic solvent (and water if necessary) in which the spacer particles are dispersed. Yes.
In the above-mentioned wet spraying, usually, spacer particles only remain on the substrate by evaporation of the solvent component in the composition when the spacer particle wet spraying composition is sprayed or when the substrate is heated after spraying. In this case, since the adhesion of the spacer particles to the substrate is not sufficient, for example, the spacer particles easily move in the substrate transport process after the dispersion, and the cell gap becomes non-uniform. In other words, color unevenness occurs, and spacer particles move in the obtained liquid crystal display device to damage the alignment film.
[0003]
In addition, in order to solve such problems, instead of ordinary spacer particles, spacer particles whose surface is coated with a thermoplastic resin or grafted with a polymer are adhered (attached to the substrate by heating after spraying). The composition for dispersing spacer particles including so-called adhesive spacer particles, which can be used, is often used, but in the first place, it is necessary to increase the number of complicated manufacturing procedures and manufacturing processes. In addition, spacer particle dispersibility has a problem that spacer particles are more likely to aggregate than when ordinary spacer particles are used, and the display quality of the obtained liquid crystal display device is degraded.
[0004]
[Problems to be solved by the invention]
Accordingly, the problem to be solved by the present invention is that when the spacer particles are wet-sprayed, the spacer particles can be reliably attached to the substrate, and excellent spacer particle sprayability can be achieved. It is in providing the composition for spacer particle | grain wet spraying which can also ensure the reliability of this.
Another object of the present invention is to provide a liquid crystal display device obtained using the spacer particle wet dispersion composition.
[0005]
[Means for Solving the Problems]
The present inventor has intensively studied to solve the above problems.
As a result, when the spacer particles are wet-sprayed on the substrate, the spacer particle wet-spraying composition comprising spacer particles and a solvent is used as before, and attention is paid to the solvent component in the composition. It was decided to. As described above, conventionally, as a means for solving the problems in the case of using a normal spacer particle wet dispersion composition, improvements focused only on the spacer particles in the composition were repeated, This is because when the adhesion to the spacer particles is imparted so as to improve the adhesion to the substrate, another problem arises that the dispersibility of the spacer particles decreases. In other words, if the adhesion of the spacer particles to the substrate can be sufficiently improved by the composition and physical properties of the solvent component, the conventional idea that wet spraying can be performed without reducing sprayability. From this point of view, it was thought that a new composition for spacer particle wet spraying should be studied.
[0006]
Based on such knowledge, experiments and examinations were repeated by trial and error, and it was considered to include a hardly volatile organic solvent in the solvent component in the composition for wet dispersion of spacer particles. Usually, as the organic solvent in the solvent component, an organic solvent rich in volatility is used in order to prevent the remaining of the organic solvent from adversely affecting the reliability of the liquid crystal, for example. It was speculated that the inclusion of a moderately non-volatile organic solvent within the range in which the reliability of the liquid crystal can be secured would be a clue to solving the above problems. Specifically, if the above-mentioned solvent component contains a hardly volatile organic solvent having a boiling point higher than a specific temperature in a concentration within a specific range, moderately remaining hardly volatile organic solvent will cause spacer particles. I thought that it could be sufficiently attached to the substrate. Then, when the spacer particle wet spraying was performed using the spacer particle wet spraying composition as described above, it was confirmed that the above problems could be solved at once, and the present invention was completed.
[0007]
Moreover, if it was the manufacturing method of the liquid crystal display device using the composition for spacer particle | grain wet spraying concerning the said invention, it confirmed that the said subject could be solved and came to complete this invention.
That is, the spacer particle wet spraying composition according to the present invention is a spacer particle wet spraying composition comprising spacer particles and a solvent, wherein the solvent is an organic solvent having a boiling point of 200 ° C. or higher. As glycols Is contained in an amount of 0.1 to 500 ppm.
Moreover, the manufacturing method of the liquid crystal display device concerning this invention includes the process of carrying out the wet dispersion | spreading of the spacer particle | grains using the composition for spacer particle | grain wet dispersion | distribution concerning the said invention.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the spacer particle wet spraying composition according to the present invention and a method for manufacturing a liquid crystal display device using the spacer particle wet spraying composition will be described in detail. However, the scope of the present invention is restricted by these descriptions. However, other than the following examples, the present invention can be implemented as appropriate without departing from the spirit of the present invention.
[Composition for spacer particle wet dispersion]
The spacer particle wet spraying composition according to the present invention (hereinafter sometimes referred to as the spacer particle wet spraying composition of the present invention) is a spacer particle wet spraying technique comprising spacer particles and a solvent. In the composition for use, the solvent contains 0.1 to 500 ppm of an organic solvent having a boiling point of 200 ° C. or higher.
[0009]
The spacer particle wet spraying composition of the present invention is preferably one in which spacer particles are dispersed or can be dispersed in the solvent (hereinafter sometimes referred to as a solvent component).
In the spacer particle wet dispersion composition of the present invention, the solvent is an organic solvent having a boiling point of 200 ° C. or higher (hereinafter sometimes referred to as a specific solvent), and is generally used for wet dispersion of spacer particles. Spraying solvent (hereinafter referred to as other solvent).
In the spacer particle wet dispersion composition of the present invention, the specific solvent is an organic solvent having a boiling point of 200 ° C. or higher as described above, preferably 205 to 300 ° C., more preferably 210 to 280 ° C. It is. When the boiling point of the specific solvent is less than 200 ° C., the other solvent is volatilized and the desired adhesion cannot be obtained, so that the spacer particles move. For example, in the liquid crystal display device, gap uniformity is impaired. This may cause uneven color.
[0010]
Although it does not specifically limit as a specific solvent, For example, alcohols, glycols, cellosolves, glycerol etc. can be mentioned preferably, for example, n-decanol, trimethylnonyl alcohol, diethylene glycol, Triethylene glycol, trimethylene glycol, dipropylene glycol, ethylene glycol monophenyl ether, ethylene glycol benzyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, 1,4-butanediol, 1,5-pentanediol, glycerin, etc. More preferred. These may be used alone or in combination of two or more.
[0011]
The other solvent is not particularly limited as long as it can disperse the spacer particles satisfactorily, and may be an organic solvent that is generally known for use in wet spraying. For example, alcohols, glycols, ethers, acetals, ketones, esters and the like can be preferably mentioned. Of these, alcohols and glycols are more preferable, and methanol, ethanol, n are more preferable. -Propyl alcohol, 2-propanol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2- Butanol, isopentyl alcohol, tert-pentyl alcohol Ethylene glycol and the like. These may be used alone or in combination of two or more. The other solvent may be only the above-mentioned various organic solvents, but may further contain water.
[0012]
In the spacer particle wet dispersion composition of the present invention, the concentration of the specific solvent is 0.1 to 500 ppm, preferably 1 to 300 ppm, more preferably 5 to 200 ppm in the whole solvent. When the concentration of the specific solvent is less than 0.1 ppm, desired adhesion cannot be obtained, and spacer particles move. For example, in liquid crystal display devices, gap uniformity may be impaired and color unevenness may occur. When the voltage exceeds 500 ppm, for example, when a voltage is applied for a long time in the liquid crystal display device, the voltage holding ratio is lowered, the orientation characteristics are deteriorated, and the reliability of the liquid crystal display device may be lowered.
In the composition for wet dispersion of spacer particles of the present invention, the spacer particles determine the gap distance between the two electrode substrates sandwiching the liquid crystal layer when used in, for example, a liquid crystal display device. These particles are necessary for maintaining a uniform and constant shape. The average particle diameter of the spacer particles is preferably 1 to 30 μm, more preferably 1 to 20 μm, and still more preferably 1 to 15 μm. When the average particle diameter of the spacer particles is out of the above range, it is a region not usually used as spacer particles for liquid crystal display devices.
[0013]
The coefficient of variation (CV) of the spacer particle size is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less. When the coefficient of variation of the particle diameter exceeds 10%, for example, when used as spacer particles for a liquid crystal display device, it becomes difficult to keep the thickness of the liquid crystal layer uniform and constant, which may cause image unevenness. This is not preferable.
In addition, the definition and measurement method of the average particle diameter and the coefficient of variation of the particle diameter are described in the following examples.
Regarding the spacer particles, the ratio between the theoretical surface area and the actually measured surface area (theoretical surface area / actually measured surface area) is not particularly limited, but specifically, it is preferably 500 or less, more preferably 100 or less, and even more preferably 50. It is as follows. When the above ratio exceeds 500, the solvent on the surface of the spacer particles is hardly volatilized, the spacer particles are often aggregated, and the reliability of the liquid crystal display device may be lowered.
[0014]
Although it does not necessarily limit as spacer particle | grains, Specifically, an organic crosslinked polymer particle, an inorganic type particle | grain, an organic inorganic composite particle | grain etc. can be mentioned preferably, for example. Among these, organic crosslinked polymer particles and / or organic inorganic composite particles can easily prevent damage to the electrode substrate, the alignment film, or the color filter and obtain uniformity in the gap distance ((cell) gap) between the two electrode substrates. The organic-inorganic composite particles are most preferable.
The shape of the spacer particles may be any particle shape such as a spherical shape, needle shape, plate shape, scale shape, pulverized shape, bowl shape, eyebrows shape, scallop shape, etc., and is not particularly limited, but between the electrode substrates. In order to make the gap distance uniform, the spherical shape is preferable. This is because a spherical shape has a constant or substantially constant grain shape in all or almost all directions.
[0015]
The spacer particles may be preferably colored by containing a dye and / or a pigment.
The organic crosslinked polymer particles are not particularly limited. For example, an amino acid obtained by a condensation reaction from at least one amino compound selected from the group consisting of benzoguanamine, melamine and urea and formaldehyde. Cured resin particles (see JP-A-62-268811); divinylbenzene crosslinked resin particles obtained by polymerizing divinylbenzene alone or copolymerizing with other vinyl monomers (see JP-A-1-144429) ) Etc. can be mentioned preferably.
[0016]
Although it does not necessarily limit as said inorganic type particle, For example, spherical fine particles, such as glass, a silica, an alumina, etc. can be mentioned preferably.
The organic / inorganic composite particles are preferably composite particles including an organic part and an inorganic part. In this organic-inorganic composite particle, the proportion of the inorganic part is not particularly limited. For example, it is 10 to 90% by weight in terms of inorganic oxide with respect to the weight of the organic-inorganic composite particle. It is preferable that it is a range, More preferably, it is 25 to 85 weight%, More preferably, it is 30 to 80 weight%. The above-mentioned inorganic oxide conversion is preferably expressed as a percentage by weight obtained by measuring the weight before and after firing organic-inorganic composite particles at a high temperature (for example, 1000 ° C.) in an oxidizing atmosphere such as air. If the proportion of the inorganic portion of the organic-inorganic composite particle is less than 10% by weight in terms of inorganic oxide, the organic-inorganic composite particle is preferably soft, and the number of sprayed particles on the electrode substrate is increased. Further, if it exceeds 90% by weight, it is not preferable because it is too hard and damage of the alignment film or disconnection of the TFT is likely to occur.
[0017]
The organic-inorganic composite particles as described above are not particularly limited. For example, organic silicon having an organic polymer skeleton and silicon atoms directly bonded to at least one carbon atom in the organic polymer skeleton. SiO containing the polysiloxane skeleton in the molecule and constituting the polysiloxane skeleton ₂ Preferred examples include organic-inorganic composite particles A and the like in which the amount is 10% by weight or more. As the organic polymer skeleton, a vinyl-based polymer is preferable because it provides high resilience capable of controlling the gap control. Here, the organic-inorganic composite particle A has G ≧ 14 · Y ^1.75 (Here, G represents the breaking strength [kg]; Y represents the particle diameter [mm]) and preferably 10% compression modulus is 300 to 2000 kg / mm. ² More preferably, the residual displacement after 10% deformation is 0 to 5%.
[0018]
Although it does not necessarily limit about the manufacturing method of the said organic inorganic composite particle A, For example, the manufacturing method containing the condensation process shown below and a superposition | polymerization process and a heat treatment process can be mentioned preferably.
The condensation step is preferably a step of hydrolysis / condensation using the radical polymerizable group-containing first silicon compound. In this condensation step, a basic catalyst such as ammonia may be preferably used.
The radical polymerizable group-containing first silicon compound has the following general formula (1):
[0019]
[Chemical 1]

[0020]
(Where R ^a Represents a hydrogen atom or a methyl group; R ^b Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; R ^c Represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. R ¹ Represents at least one monovalent group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a phenyl group. l is 1 or 2, and p is 0 or 1. )
And the following general formula (2):
[0021]
[Chemical 2]

[0022]
(Where R ^d Represents a hydrogen atom or a methyl group; R ^e Represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. R ² Represents at least one monovalent group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a phenyl group. m is 1 or 2, and q is 0 or 1. )
And the following general formula (3):
[0023]
[Chemical 3]

[0024]
(Where R ^f Represents a hydrogen atom or a methyl group; R ^g Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; R ^h Represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. R ^Three Represents at least one monovalent group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a phenyl group. n is 1 or 2, and r is 0 or 1. )
It is preferably a compound represented by at least one general formula selected from the group consisting of or a derivative thereof.
[0025]
The polymerization step is preferably a step in which particles are obtained by radical polymerization reaction of a radical polymerizable group during and / or after the condensation step.
The heat treatment step is a step of drying and firing the polymer particles produced in the polymerization step at a temperature of 800 ° C. or less, more preferably 100 to 600 ° C., for example, in an atmosphere having an oxygen concentration of 10% by volume or less. Or under reduced pressure.
In and / or after at least one step selected from the condensation step, the polymerization step and the heat treatment step, a coloring step for coloring the generated spacer particles may be further included. It may be colored by containing at least one selected from the group consisting of pigments. The color is preferably a light that does not easily transmit light, or a color that does not transmit light, from the viewpoint of preventing light leakage of the spacer particles themselves and improving the image quality contrast. Examples of colors that are difficult to transmit or do not transmit light include black, dark blue, amber, purple, blue, dark green, green, brown, red, and the like, but particularly preferably, Black, dark blue, and scarlet. The dye and / or pigment may be simply contained in the spacer particles, or may have a structure in which the dye and / or pigment and the matrix constituting the spacer particles are combined by a chemical bond. It is not limited to these.
[0026]
The above dyes are appropriately selected and used according to the color to be colored, and examples thereof include disperse dyes, acid dyes, basic dyes, reactive dyes, sulfur dyes and the like classified according to the dyeing method. Specific examples of these dyes are “Chemical Handbook Applied Chemistry, Japan Chemical Society” (published by Maruzen Co., Ltd., 1986), pages 1399-1427, “Nippon Kayaku Dye Handbook” (1973, published by Nippon Kayaku Co., Ltd.). )It is described in.
As a method for staining the spacer particles, a conventionally known method is used. For example, it can be carried out by the methods described in the above-mentioned “Chemical Handbook Applied Chemistry, Japanese Chemical Society” or “Nippon Kayaku Dye Handbook”.
[0027]
The pigment is not particularly limited. For example, inorganic pigments such as carbon black, iron black, chrome vermilion, molybdenum red, red pepper, chrome yellow, chrome green, cobalt green, ultramarine blue, and bitumen; phthalocyanine series, azo series And organic pigments such as quinacridone. In addition, since the said pigment may not be introduce | transduced in a spacer particle unless the average particle diameter is 0.4 micrometer or less, it is more preferable to use dye in this case. When the spacer particles are colored, when used as spacer particles for a liquid crystal display device, light leakage from the backlight can be prevented, and an improvement in image quality of the liquid crystal display device can be achieved.
[0028]
A surface treatment step for surface-treating the generated spacer particles may be further included during and / or after at least one step selected from the above condensation step, polymerization step and heat treatment step.
Although it does not specifically limit as a surface treating agent used for the said surface treatment, The at least 1 sort (s) of silane compound chosen from following General formula (4)-(6) is preferable.
SiX _Four (4)
R ^Four SiX _Three (5)
R ^Five R ⁶ SiX ₂ (6)
(Wherein X is at least one selected from a chlorine atom, a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyloxy group having 2 to 5 carbon atoms; R ^Four And R ^Five Is at least one selected from an alkyl group having 1 to 22 carbon atoms and an aryl group having 6 to 22 carbon atoms, and one or more hydrogen atoms in the group are an amino group, a mercapto group, May be substituted with at least one selected from an alkylene oxide group, an epoxy group, a cyano group, a chlorine atom and a fluorine atom; R ⁶ Is at least one monovalent group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a phenyl group. )
In the spacer particle wet dispersion composition of the present invention, the content ratio of the spacer particles in the entire composition is preferably 0.005 to 30% by weight, more preferably 0.01 to 20% by weight, More preferably, it is 0.05 to 10% by weight. When the content ratio of the spacer particles is less than 0.005% by weight, it may take too much spray time to obtain a desired spray number density, and when it exceeds 30% by weight, the spacer particle wet spraying composition is There is a risk that the slurry will be in the form of a slurry and the fluidity will be reduced, and the spacer particles may aggregate.
[0029]
The spacer particle wet dispersion composition of the present invention contains spacer particles and a solvent, but may contain other components as needed in addition to these. [Manufacturing method of liquid crystal display device]
The method for producing a liquid crystal display device according to the present invention (hereinafter sometimes referred to as the method for producing a liquid crystal display device of the present invention or the production method of the present invention) uses the spacer particle wet spraying composition of the present invention. And a method of manufacturing a liquid crystal display device including a step of wet-spreading spacer particles onto a substrate or the like.
In the manufacturing method of the liquid crystal display device of the present invention, the electrode substrate, the sealing material, the liquid crystal material, and the like can be the same as the conventional materials. In addition, the spacer particles are included in the composition for wet dispersion of the spacer particles of the present invention to be used. Accordingly, the spacer particles used in the production method of the present invention are preferably the same as those described as the spacer particles contained in the spacer particle wet dispersion composition of the present invention.
[0030]
Although it does not specifically limit as an electrode substrate, Specifically, it has substrates, such as a glass substrate and a film substrate, and the electrode formed in the surface of a substrate, and an electrode substrate is needed as needed. An alignment film is further formed on the surface of the substrate so as to cover the electrodes. A color-compatible liquid crystal display device has a color filter.
Although it does not specifically limit as a sealing material, Specifically, an epoxy resin adhesive sealing material etc. are used, for example.
The liquid crystal (liquid crystal material) is not particularly limited and may be those conventionally used. Specifically, for example, biphenyl, phenylcyclohexane, Schiff base, azo, azoxy, benzoic acid Ester-based, terphenyl-based, cyclohexylcarboxylic acid ester-based, biphenylcyclohexane-based, pyrimidine-based, dioxane-based, cyclohexylcyclohexane-ester-based, cyclohexylethane-based, cyclohexene-based, and fluorine-based liquid crystals can be used.
[0031]
As a method for producing the liquid crystal display device of the present invention, specifically, for example, the spacer particle wet dispersion composition is spread on one of the two electrode substrates to form spacer particles (in-plane). Apply spacer particles dispersed in a predetermined position on the adhesive seal part of the other electrode substrate by means such as screen printing. Put the material, apply moderate pressure, heat for 1 to 60 minutes at a temperature of 100 to 180 ° C., or irradiation dose 40 to 300 mJ / cm ² Although the adhesive sealing material is heated and cured by UV irradiation, a method of injecting liquid crystal and sealing the injection portion can be mentioned. However, the manufacturing method is not particularly limited.
[0032]
Here, the configuration of the liquid crystal display device obtained by the manufacturing method of the present invention will be described with reference to FIG. 1, but the configuration of the liquid crystal display device is not particularly limited thereto. That is, the obtained liquid crystal display device includes a pair of electrode substrates (a first electrode substrate 110 and a second electrode substrate 120) arranged to face each other with a liquid crystal material interposed therebetween, and spacer particles. The first electrode substrate 110 includes a first substrate 11 and an electrode 5 formed on the surface of the first substrate 11. The second electrode substrate 120 includes the second substrate 12 and the electrode 5 formed on the surface of the second substrate 12. The first electrode substrate 110 and the second electrode substrate 120 are bonded together by the sealing material 2 at the periphery thereof. The spacer particles are selectively distributed between the substrates to maintain the distance between the substrates, and the seal portion spacer particles 3 dispersed in the sealing material 2 and the in-plane spacer particles dispersed in the surface. There are eight. The liquid crystal material 7 is sealed between the first electrode substrate 110 and the second electrode substrate 120, and is filled in a space surrounded by the first electrode substrate 110, the second electrode substrate 120, and the sealing material 2. Yes.
[0033]
In the method for producing a liquid crystal display device of the present invention, the spacer particles are wet-sprayed by spraying the spacer particle wet-spraying composition, but the method for spraying the spacer particle wet-spraying composition is not particularly limited. However, specifically, for example, it is preferable to spray using a device that employs a spray method, an inkjet method, or the like. Among these, the ink jet method is more preferable because it is easy to disperse and arrange the spacer particles at desired positions on the substrate.
The ink jet method is classified into two methods, a continuous jet method and a drop-on-demand method, according to the droplet generation principle of the spacer particle wet dispersion composition used as the ink. Any method can be preferably employed in the production method of the present invention. (Hereinafter, the “droplet of the composition for spacer particle wet dispersion” is simply referred to as “droplet”.)
The continuous jet method is a method in which droplets are continuously generated and recording is performed by selecting the droplets according to a recording signal. In the continuous jet method, since droplets are generated in a steady state, the droplet generation cycle can be shortened and high-speed recording is possible. In addition, since the ejection speed of the ejected liquid droplets is fast, the distance between the nozzle and the recording medium can be increased, so that recording on a curved surface or the like is possible. The continuous jet system includes a Sweet type, a micro dot type, a Herz type, an IRIS type and the like.
[0034]
In the Sweet type, a mechanical vibration is applied to the nozzle from the outside, the frequency is made to coincide with the spontaneous breakup speed of the drop, and the droplet generated so that the mass of the split droplet becomes the same mass is used. To do. Specifically, a piezoelectric element is attached to the nozzle portion, and the liquid is vibrated with a splitting cycle of the composition for dispersing the spacer particles to generate uniform droplets. A charged electrode is provided at a portion where the spacer particle wet spraying composition is split to charge the droplets. This charged droplet passes between the deflection electrodes. The droplet receives an electrostatic force in the vertical direction by an electric field, and its trajectory changes. Depending on how the deflection voltage is applied, there are a binary deflection type and a multi-value deflection type.
[0035]
The micro dot type is a system in which recording is performed by taking out small droplets called satellites between droplets when the droplets are split. In this method, by applying different voltages to each of the pair of electrodes, both charging and deflection operations are performed.
In the Herz type, a pressurized composition for spraying spacer particles is ejected from a thin nozzle, and droplets are passed through a ring-shaped electrode. When a voltage is applied to the electrodes, the droplets are split into fine spray-like mists by the repulsive force of the charges charged in the droplets. When it breaks and becomes a spray, it is not recorded, and the droplet when it does not break is used for recording.
The IRIS type is an improved version of the Herz type and is characterized in that the size of the droplet is kept constant by installing a piezo vibrator on the nozzle.
[0036]
The drop-on-demand method is a method in which a composition for wet dispersion of spacer particles is ejected according to a recording signal. The recording speed is slower than the continuous jet method, but the overall mechanism is simple. Examples of the drop-on-demand method include a pressure pulse method, a thermal jet method, and an ERF method.
The pressure pulse method is a method in which a piezoelectric wave is used to generate a pressure wave in an ink chamber, and a spacer particle wet spray composition is ejected. Depending on the structure of the print head, the Stemme method, the Gould method, the Kyser method and so on.
[0037]
In the thermal jet method, a heating element is provided in a nozzle, the spacer particle wet spraying composition is vaporized to form bubbles, and the spacer particle wet spraying composition is extruded by the bubbles and ejected from the nozzle.
The ERF system comprises a flow path of a spacer particle wet spray composition and a pair of electrodes provided so as to sandwich the print head, and the spacer particle wet spray composition is pressurized by a pump or the like. When a voltage is applied between the electrodes, the apparent pressure applied to the spacer particle wet spraying composition becomes zero, the spacer particle wet spraying composition is not ejected from the nozzle, and when the electrode voltage is zero, the spacer particle wet spraying is performed. Since the composition for use is pressurized, it is ejected from the nozzle.
[0038]
In the production method of the present invention, when the spacer particle wet spraying composition is sprayed and the spacer particles are wet sprayed and dispersedly arranged, usually, first, on the electrode substrate of the liquid crystal display device or on the color filter, Decide whether to place spacer particles in In order to achieve an improvement in contrast and high display quality of the obtained liquid crystal display device, it is not preferable to disperse and arrange the spacer particles in the pixel region, that is, the display region, and the spacer particles are dispersed in the non-pixel region, that is, the non-display region. It is preferable. This is because when the pixel particles are dispersedly arranged, the existence part of the spacer particles is not displayed, and light leakage occurs around the spacer particles due to the alignment of the spacer particles or the liquid crystal. Therefore, for example, in the case of the TN mode, it is preferable to disperse and arrange the spacer particles only in a region that is not directly related to display, such as the periphery of a character or a design or a gap. Further, for example, in the STN mode, since the transparent electrodes of the electrode substrate are arranged in stripes, it is preferable to disperse and arrange spacer particles in the gaps between these transparent electrodes. Further, for example, in the case of color display of TFT or STN, it is preferable to disperse and arrange on the portion other than R, G, B of the pixel of the color filter, that is, on the black matrix. Further, in the case of dispersively disposing on the electrode substrate facing the substrate having the color filter, it is preferable to disperse and dispose on the portion corresponding to the position of the black matrix.
[0039]
Further, the number of spacer particles to be dispersed and arranged is not particularly limited as long as the cell gap of the liquid crystal display device can be maintained uniformly, and may be set as appropriate. Low temperature foaming is likely to occur. The number of dispersed arrangements also depends on the size of one pixel in the display area. Here, the spacer particles dispersedly arranged may be single particles or a plurality of spacer particles as long as they are arranged in the non-pixel region, and may be set as appropriate. In addition, the ratio of the spacer particles arranged in the display pixel is increased and the display quality is lowered.
[0040]
The liquid crystal display device obtained by the manufacturing method of the present invention has the same application as the conventional liquid crystal display device, such as a television, a monitor, a personal computer, a word processor, a car navigation system, a DVD, a digital video camera, and a PHS (personal digital assistant). It can be used as an image display device.
[0041]
【Example】
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. Hereinafter, for convenience, “parts by weight” may be simply referred to as “parts”, or “wt%” may be simply referred to as “wt%”.
First, definitions of measurement values, measurement methods, and evaluation criteria described in the examples of the present invention are shown below.
[Average particle diameter of spacer particles, coefficient of variation of particle diameter]
The average particle diameter of the spacer particles and the coefficient of variation of the particle diameter were measured by the following measuring method. That is, the average particle size was determined as the average particle size by measuring the particle size of 30000 particles with a Coulter Multisizer (manufactured by Beckman Coulter). Further, the coefficient of variation of the particle diameter was determined according to the following formula.
[0042]
[Expression 1]

[0043]
[Fracture strength of spacer particles]
The fracture strength of the spacer particles is the diameter of one sample particle dispersed on a sample table (material: SKS flat plate) at room temperature (25 ° C.) using a Shimadzu micro compression tester (manufactured by Shimadzu Corporation, MCTM-200). Using a 50 μm circular flat plate indenter (material: diamond), a load is applied in the direction of the center of the particle at a constant load speed to obtain a value of the compressive load (N) when the sample particle breaks.
[10% compression modulus of spacer particles]
The 10% compressive modulus of the spacer particles is a constant load in the center direction of the particles using a circular flat plate indenter for each sample particle spread on the sample table by the same apparatus as the measurement of the fracture strength. A load is applied at a speed, and the load when the compressive displacement becomes 10% of the particle diameter and the number of millimeters of the compressive displacement are measured. The measured compression load, particle compression displacement, and particle radius are expressed as follows:
[0044]
[Expression 2]

[0045]
(Here, E: compression modulus (GPa), F: compression load (N), S: compression displacement (mm), R: radius of particle (mm))
Substituting for and calculating the value. This operation is performed for three different particles, and the average value is taken as the 10% compression modulus of the particles.
-Production Example 1-
[Production example of spacer particles]
In a four-necked flask equipped with a condenser, a thermometer, and a dripping port, a solution (solution A) in which 2.9 g of 25% aqueous ammonia solution, methanol 10.1 and water 141.1 g were mixed was placed, and the temperature was adjusted to 25 ± 2 ° C. While maintaining and stirring, 27 g of γ-methacryloxypropyltrimethoxysilane, 54 g of methanol, 0.14 g of 2,2′-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator, 2- to 5-mer of ethoxysilane (manufactured by Tama Chemical Co., Ltd., product name: “silicate 40” (SiO 2 ₂ (40 wt%))) 5 g mixed solution (Liquid B) was added from the dropping port, and γ-methacryloxypropyltrimethoxysilane was hydrolyzed and polycondensed. After 20 minutes while continuing stirring, the mixture was heated to 70 ± 5 ° C. in a nitrogen atmosphere to perform radical polymerization.
[0046]
After heating for 2 hours, the mixture was cooled to room temperature to obtain a suspension of polymer particles. This suspension is subjected to solid-liquid separation by filtration, and the resulting cake is washed three times by decantation with methanol and vacuum dried at 200 ° C. for 2 hours in a vacuum drier to form spacer particles that are organic-inorganic composite particles. (A) was obtained. The obtained composite particles had an average particle size of 4.24 μm, a coefficient of variation of 3.8%, and SiO constituting the polysiloxane skeleton. ₂ 34.7 wt%, 10% compressive modulus 480kg / mm ² The residual displacement after deformation by 10% was 2.2% and the fracture strength was 2.4 g.
-Production Example 2-
[Production example of adhesive spacer particles]
As the binder resin (1), a resin having a monomer composition of butyl acrylate / styrene (weight ratio 20/80) was synthesized by soap-free emulsion polymerization. The glass transition temperature was 67 ° C., the softening temperature was 117 ° C., and the average particle size was 0.3 μm.
[0047]
After mixing 30 g of the spacer particles (A) obtained in Production Example 1 above and 10 g of the binder resin (1), impact in a high-speed air current using a hybridization system NHS-0 manufactured by Nara Machinery Co., Ltd. By the method, the surface of the spacer particles (A) was coated with the binder resin (1) to obtain adhesive spacer particles (B).
Example 1
Spacer particles (A) were mixed with 2-propanol containing 30 ppm of diethylene glycol (boiling point 245 ° C.) so that the spacer particles (A) would be 0.5 wt%, and ultrasonically dispersed to obtain a spacer particle wet dispersion composition (1). Next, the spacer particle wet spraying composition (1) is sprayed on the electrode substrate on which the color filter is installed for the 14-inch TFT liquid crystal display device using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become.
[0048]
Then, when the number of dispersed particles and the single particle ratio of the spacer particles (A) actually dispersed on the electrode substrate were measured by the following method, the number of dispersed particles was 205 particles / mm. ² The single particle ratio was 98%.
Furthermore, when the adhesion force of the spacer particles (A) dispersed on the electrode substrate to the substrate was evaluated by the air blow method shown below, the residual rate of the spacer particles (A) was 98%.
Table 1 shows the results of the number of sprayed particles, the single particle ratio, and the spacer particle residual ratio.
[Spreading number density]
Any 1mm on the electrode substrate ² 9 observation areas were selected, the number of spacer particles in each area was counted with an optical microscope, and the average number of the total number of 9 areas was calculated as the number distribution density (pieces / mm ² ).
[Single particle ratio]
The ratio of the number of single particles to the total number of particles in the measurement of the number of dispersed particles was defined as the single particle ratio (%).
[Air blow method]
Select an observation area of any fixed area on the electrode substrate on which spacer particles are dispersed, count the number of particles before and after air blowing in this observation area with an optical microscope, and obtain the spacer particle residual rate (%) according to the following formula. It was. The adhesion force to the substrate is evaluated based on the calculated spacer particle residual ratio.
[0049]
Spacer particle residual rate (%)
= [(Number of remaining particles after air blow) / (Number of particles before air blow)] x 100 (Air blow method test condition: air pressure 2 kg / cm ² Blow time 10 seconds, nozzle inner diameter 2mm, distance between substrate and nozzle 5mm)
Next, a TFT type liquid crystal display device was produced according to the following procedure. A transparent electrode substrate having a TFT element and a transparent electrode substrate having a color filter in which spacer particles are dispersed and arranged in a dispersed manner are bonded together with an adhesive sealant, and then the gap between both electrode substrates is reduced to a further atmospheric pressure. Thereby, the fluorine-type TN liquid crystal for TFT was inject | poured and the injection | pouring part was sealed. And a polarizing film was stuck on the outside of the upper and lower electrode substrates to obtain a 14-inch TFT liquid crystal display device (1).
[0050]
The liquid crystal display device (1) had a uniform gap distance and no color unevenness. It can be seen that the liquid crystal display device (1) has no gap density unevenness and excellent gap uniformity.
Further, with respect to the liquid crystal display device (1), the voltage holding ratio after 500 hours at 50 ° C. was measured and found to be 98%, and no decrease in the voltage holding ratio was observed.
When a predetermined voltage was applied to the liquid crystal display device (1), the liquid crystal display plate (1) showed excellent driving stability for a long time, and the alignment characteristics of the liquid crystal were also at a satisfactory level. That is, it turns out that the liquid crystal display device (1) produced using the said spacer particle | grain wet coating composition (1) has reliability.
[0051]
Furthermore, the liquid crystal display device (1) was vibrated in the X-axis, Y-axis, and Z-axis directions while applying an acceleration of 2 G for 1 hour each. The uniformity of the in-plane gap after vibration was good, and no increase in light leakage due to the alignment film being damaged by the movement of the spacer particles (alignment film damage by vibration test) was not observed.
Table 2 shows the results of the color unevenness, the voltage holding ratio, the reliability of the liquid crystal display device, and the alignment film damage by the vibration test. Color unevenness, reliability of the liquid crystal display device, and alignment film damage due to a vibration test will be described based on the following evaluation criteria.
Color unevenness:
◎: Good image quality with no color unevenness and display surface roughness
○: No color unevenness
Δ: Slightly uneven color
×: Very large color unevenness
Alignment film damage by vibration test:
○: No damage
Δ: Slightly damaged
×: Many damages
Reliability of LCD devices:
○: Reliable
×: No reliability
-Example 2-
The spacer particles (A) having 30 ppm of diethylene glycol (boiling point: 245 ° C.) mixed with 2-propanol so that the spacer particles (A) are 0.5% by weight, and ultrasonically dispersed. 1) was obtained. Next, spacer composition wet spraying composition (1) is sprayed on a black matrix of an electrode substrate for a 14-inch TFT liquid crystal display device, on which a color filter is installed, using a conventionally known ink jet device. Particle number density of particles (A) is about 200 / mm ² As a result, the spacer particles (A) were dispersed and arranged at intervals of 70 μm on the black matrix. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0052]
Next, a 14-inch TFT liquid crystal display device (2) was obtained in the same manner as in Example 1. In the liquid crystal display device (2), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Example 3-
Spacer particles (A) are mixed in 2-propanol containing 0.25 ppm of diethylene glycol (boiling point 245 ° C.) so that the spacer particles (A) are 0.5% by weight, and are ultrasonically dispersed to obtain a spacer particle wet spraying composition (2). It was. Next, a spacer particle wet spraying composition (2) is sprayed onto an electrode substrate on which a color filter is installed for a 14-inch TFT liquid crystal display device using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0053]
Next, a 14-inch TFT liquid crystal display device (3) was obtained in the same manner as in Example 1. In the liquid crystal display device (3), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
Example 4
Spacer particles (A) were mixed with 2-propanol containing 480 ppm of diethylene glycol (boiling point 245 ° C.) so that the spacer particles (A) would be 0.5 wt%, and ultrasonically dispersed to obtain a spacer particle wet spraying composition (3). Next, the spacer particle wet spraying composition (3) is sprayed onto the electrode substrate on which the color filter is installed for the 14-inch TFT liquid crystal display device using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0054]
Next, a 14-inch TFT liquid crystal display device (4) was obtained in the same manner as in Example 1. In the liquid crystal display device (4), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Example 5
Spacer particles (A) are mixed in 2-propanol containing 30 ppm of trimethylene glycol (boiling point 210 ° C.) so that the spacer particles (A) are 0.5 wt%, and are ultrasonically dispersed to obtain a spacer particle wet dispersion composition (4). It was. Next, the spacer particle wet spraying composition (4) is sprayed on an electrode substrate for a 14-inch TFT type liquid crystal display device, on which a color filter is installed, using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0055]
Next, a 14-inch TFT liquid crystal display device (5) was obtained by the same method as in Example 1. In the liquid crystal display device (5), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Comparative Example 1-
Spacer particles (A) are mixed in 2-propanol containing 0.05 ppm of diethylene glycol (boiling point 245 ° C.) so that the spacer particles (A) are 0.5% by weight, and are ultrasonically dispersed to obtain a spacer particle wet spraying composition (c1). It was. Next, the spacer particle wet spraying composition (c1) is sprayed on an electrode substrate for a 14-inch TFT type liquid crystal display device on which a color filter is installed using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0056]
Next, a 14-inch TFT liquid crystal display device (c1) was obtained in the same manner as in Example 1. In the liquid crystal display device (c1), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Comparative Example 2-
A composition for wet spraying of spacer particles (c2) is mixed with 2-propanol containing 0.05 ppm of diethylene glycol (boiling point 245 ° C.) so that the adhesive spacer particles (B) are 0.5% by weight and dispersed ultrasonically. Got. Next, a spacer particle wet spraying composition (c2) is sprayed on an electrode substrate for a 14-inch TFT liquid crystal display device on which a color filter is installed using a conventionally known spray-type wet spraying device, Scattering number density of adhesive spacer particles (B) is about 200 / mm ² It was made to become. After spraying, the electrode substrate was heated at 150 ° C. for 60 minutes to fix the adhesive spacer particles (B) on the color filter. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0057]
Next, a 14-inch TFT liquid crystal display device (c2) was obtained by the same method as in Example 1. In the liquid crystal display device (c2), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Comparative Example 3-
Spacer particles (A) were mixed in 2-propanol containing 600 ppm of diethylene glycol (boiling point 245 ° C.) so that the spacer particles (A) would be 0.5 wt%, and ultrasonically dispersed to obtain a spacer particle wet dispersion composition (c3). Next, a spacer particle wet spraying composition (c3) is sprayed on an electrode substrate on which a color filter is installed for a 14-inch TFT liquid crystal display device using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0058]
Next, a 14-inch TFT liquid crystal display device (c3) was obtained by the same method as in Example 1. In the liquid crystal display device (c3), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
-Comparative Example 4-
Spacer particles (A) are mixed in 2-propanol containing 30 ppm of ethylene glycol diacetate (boiling point 190 ° C.) so that the spacer particles (A) are 0.5% by weight, and ultrasonically dispersed to prepare a spacer particle wet dispersion composition (c5). Obtained. Next, the spacer particle wet spraying composition (c5) is sprayed on the electrode substrate on which the color filter is installed for the 14-inch TFT liquid crystal display device using a conventionally known spray-type wet spraying device, Dispersion number density of spacer particles (A) is about 200 / mm ² It was made to become. The scattered number density, single particle ratio, and spacer particle residual ratio on the electrode substrate were measured by the same method as in Example 1. The results are shown in Table 1.
[0059]
Next, a 14-inch TFT liquid crystal display device (c5) was obtained by the same method as in Example 1. In the liquid crystal display device (c5), color unevenness, voltage holding ratio, reliability of the liquid crystal display device, and alignment film damage by a vibration test were measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0060]
[Table 1]

[0061]
[Table 2]

[0062]
【The invention's effect】
According to the present invention, when spacer particles are wet-sprayed, the spacer particles can be reliably attached to the substrate, and excellent spacer particle dispersibility can be achieved. The composition for spacer particle | grain wet spraying which can be ensured can be provided.
In addition, according to the present invention, by using the spacer particle wet dispersion composition of the present invention, it has excellent spacer particle dispersibility and reliable spacer particle adhesion to a substrate, and also has a liquid crystal reliability. In addition, a sufficiently secured liquid crystal display device can be provided.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view showing an example of a liquid crystal display device obtained by a manufacturing method of the present invention.
[Explanation of symbols]
7 Liquid crystal
8 In-plane spacer particles
110 Electrode substrate
113 Sealer spacer particles
120 electrode substrate

Claims (4)

Spacer particle wet spraying composition comprising spacer particles and a solvent, wherein the solvent contains 0.1 to 500 ppm of glycol as an organic solvent having a boiling point of 200 ° C. or higher. Composition.   The composition for wet dispersion of spacer particles according to claim 1, wherein the spacer particles are organic-inorganic composite particles.   The manufacturing method of a liquid crystal display device including the process of carrying out wet spraying of the spacer particle | grains using the composition for spacer particle | grain wet spraying of Claim 1 or 2.   The method for manufacturing a liquid crystal display device according to claim 3, wherein the wet spraying step is a step of spraying the spacer particle wet spraying composition by an inkjet method to wet spray the spacer particles.

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