JP2004013116A - Composition for wet-spreading spacer particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for wet-spreading spacer particles which causes neither reduction in the number of spacer particles spread on a substrate (spreading number density) even after long-time spreading nor agglomeration of spacer particles and to provide a method for manufacturing a liquid crystal display using the composition. <P>SOLUTION: In the composition for wet-spreading spacer particles comprising the spacer particles and a solvent, the following conditions (1) or (2) are satisfied. (1) The viscosity of the solvent at 20°C is 1-30 mPa s and the specific gravity ratio of the spacer particles to the solvent at 20°C is 1.00-1.70. (2) The surface tension of the solvent at 20°C is 0.02-0.06 N/m and the specific gravity ratio of the spacer particles to the solvent at 20°C is 1.00-1.70. <P>COPYRIGHT: (C)2004,JPO

Description

【００２１】
（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。Ｒ^１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）：
【００２２】
【化２】

【００２３】
（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。Ｒ^２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）：
【００２４】
【化３】

【００２５】
（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。Ｒ^３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。
【００２６】
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。
【００２７】
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。
【００２８】
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。
【００２９】
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。
ＳｉＸ_４　　　　　　　　　（４）
Ｒ^４ＳｉＸ_３　　　　　　（５）
Ｒ^５Ｒ^６ＳｉＸ_２　　　（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；Ｒ^４およびＲ^５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；Ｒ^６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。
【００３０】
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。
【００３１】
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。
【００３２】
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本発明の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／ｃｍ^２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。
【００３３】
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。
【００３４】
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、該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。
【００３５】
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。
【００３６】
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。
【００３７】
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。
【００３８】
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、この気泡により該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、該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、該組成物はノズルから噴出されず、電極の電圧を０にすると該組成物は加圧されているのでノズルより噴出する。
【００３９】
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。
【００４０】
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、単粒子であることが好ましいが、非画素領域であれば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、表示領域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こととなるおそれがある。
【００４１】
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。
【００４２】
【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溶媒およびスペーサー粒子に関する値の定義、測定方法、出典などについて以下に示す。
〔溶媒の表面張力、粘度、比重〕
溶剤ポケットブック（１９６７年、オーム社書店発行）を参照する。
〔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。
【００４３】
【数１】

【００４４】
〔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：
【００４５】
【数２】

【００４６】
（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。
〔スペーサー粒子の比重〕
マイクロウルトラピクノメーター１０００（カンタクローム社製の比重測定装置）を用いて測定した。
−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４つ口フラスコ中に、２５％アンモニア水溶液２．９ｇ、メタノール１０．１ｇ、水１４１．１ｇを混合した溶液（Ａ液）を入れ、２５±２℃に保持し、撹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２９ｇ、メタノール５５ｇ、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（ＳｉＯ_２換算で４０ｗｔ％））５．０ｇ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。撹拌を継続しながら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。
【００４７】
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。この懸濁体をろ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複合粒子（１）を得た。得られた複合体粒子（１）は、平均粒子径４．２７μｍ、粒子径の変動係数３．１％、ポリシロキサン骨格を構成するＳｉＯ_２の量３３．５ｗｔ％、１０％圧縮弾性率４７８ｋｇ／ｍｍ^２、１０％変形後の残留変位３．０％、破壊強度２．５ｇであった。
−実施例１−
溶媒としてのイソプロピルアルコール（２０℃での表面張力：０．０２１（Ｎ／ｍ）、粘度：２．４（ｍＰａ・ｓ））に、スペーサー粒子として複合粒子（１）を０．５ｗｔ％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を得た。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．６５であった。
【００４８】
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ックス上に、従来公知のインクジェット装置を用いて、上記スペーサー粒子湿式散布用組成物を散布した後、１５０℃で乾燥し、スペーサー粒子である複合粒子（１）の散布個数密度が約２００個／ｍｍ^２となるようにした。
電極基板１０００枚に連続的に散布を行い、２０枚おきに電極基板上のスペーサー粒子の分散配置状態を観察し、散布個数密度、平均凝集箇所率（１０個以上のスペーサー粒子の凝集箇所の割合）を測定した。その結果を表１に示す。
【００４９】
また、スペーサー粒子湿式散布用組成物を６ヶ月間放置した後、再び超音波照射により分散させ、再分散性を観察した。その結果を表１に示す。
スペーサー粒子である複合粒子（１）は、所定位置であるブラックマトリクス上に分散配置されていた。また、再分散性についても良好であった。
なお、それぞれの測定方法、評価基準を以下に示す。
〔散布個数密度〕
電極基板上の任意の１ｍｍ^２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／ｍｍ^２）とした。散布個数の目安となる値である。
【００５０】
測定した電極基板５０枚について散布個数密度を算出し、その上限下限をもって表１に示した。
〔平均凝集箇所率（１０個以上のスペーサー粒子の凝集箇所の割合）〕
上記散布個数の測定と同時に、スペーサー粒子が複数凝集している箇所を計数し、その全計数箇所に対する「１０個以上のスペーサー粒子が凝集している箇所」の割合を、平均凝集箇所率（％）として求めた。
測定した電極基板５０枚についての平均値をもって表１に示した。
〔再分散性〕
一旦スペーサー粒子の分散処理を行ったスペーサー粒子湿式散布用組成物を、６ヶ月間放置し、スペーサー粒子を沈降させた後、超音波照射（強度：１５０Ｗ、２８ｋＨｚ、１５分間）により分散させたときのスペーサー粒子の再分散性を、以下の基準で評価した。
【００５１】
○：すぐに均一に分散した。
△：分散したがやや凝集が見られた。
×：ほとんど分散しなかった。
−実施例２−
実施例１において、溶媒をエチレングリコール（２０℃での表面張力：０．０４６（Ｎ／ｍ）、粘度：２０（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．０５であった。
【００５２】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子である複合粒子（１）は、所定位置であるブラックマトリクス上に分散配置されていた。また、再分散性についても良好であった。
−実施例３−
実施例１において、スペーサー粒子をジビニルベンゼンの架橋球状微粒子（平均粒子径：４．３１μｍ、変動係数：３．８％）に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．５７であった。
【００５３】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるジビニルベンゼンの架橋球状微粒子は、所定位置であるブラックマトリクス上に分散配置されていた。また、再分散性についても良好であった。
−実施例４−
実施例１において、スペーサー粒子をジビニルベンゼンの架橋球状微粒子（平均粒子径：４．３１μｍ、変動係数：３．８％）とし、溶媒をエチレングリコール（２０℃での表面張力：０．０４６（Ｎ／ｍ）、粘度：２０（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．１０であった。
【００５４】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるジビニルベンゼンの架橋球状微粒子は、所定位置であるブラックマトリクス上に分散配置されていた。また、再分散性についても良好であった。
−実施例５−
実施例１において、スペーサー粒子をベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子（平均粒子径：４．３５μｍ、変動係数：５．０％）とし、溶媒をエチレングリコール（２０℃での表面張力：０．０４６（Ｎ／ｍ）、粘度：２０（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．２５であった。
【００５５】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子は、所定位置であるブラックマトリクス上に分散配置されていた。また、再分散性についても良好であった。
−比較例１−
実施例１において、溶媒をヘキサン（２０℃での表面張力：０．０１８（Ｎ／ｍ）、粘度：２．４（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．９８であった。
【００５６】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子である複合粒子（１）は、散布個数密度が散布時間の経過とともにおよそ上限値から下限値へと大きく減少し、所定位置であるブラックマトリクス上に分散配置されていない箇所が多く１０個以上の凝集が多く存在していた。また、再分散は可能であった。
−比較例２−
実施例１において、溶媒をジエチレングリコール（２０℃での表面張力：０．０４８５（Ｎ／ｍ）、粘度：３８（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．０５であった。
【００５７】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子である複合粒子（１）は、所定位置であるブラックマトクス上に分散配置されていた。また、再分散することができなかった。
−比較例３−
実施例１において、溶媒をグリセリン（２０℃での表面張力：０．０６４（Ｎ／ｍ）、粘度：１４９９（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．０４であった。
【００５８】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子である複合粒子（１）は、基板によって散布個数密度のばらつきが非常に大きく（最大で、上下値と下限値との幅でのばらつき）、１０個以上の凝集が多く、表示領域にもスペーサー粒子が存在していた。また、再分散することができなかった。
−比較例４−
実施例１において、スペーサー粒子をジビニルベンゼンの架橋球状微粒子（平均粒子径：４．３１μｍ、変動係数：３．８％）とし、溶媒をヘキサン（２０℃での表面張力：０．０１８（Ｎ／ｍ）、粘度：２．４（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．８７であった。
【００５９】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるジビニルベンゼンの架橋球状微粒子は、散布個数密度が散布時間の経過とともにおよそ上限値から下限値へと大きく減少し、所定位置であるブラックマトリクス上に分散配置されていない箇所が多く１０個以上の凝集が多く存在していた。また、再分散は可能であった。
−比較例５−
実施例１において、スペーサー粒子をベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子（平均粒子径：４．３５μｍ、変動係数：５．０％）とし、溶媒をヘキサン（２０℃での表面張力：０．０１８（Ｎ／ｍ）、粘度：２．４（ｍＰａ・ｓ））に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、２．１２であった。
【００６０】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子は、散布個数密度が散布時間の経過とともにおよそ上限値から下限値へと大きく減少し、所定位置であるブラックマトリクス上に分散配置されていない箇所が多く１０個以上の凝集が多く存在していた。また、再分散は可能であった。
−比較例６−
実施例１において、スペーサー粒子をベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子（平均粒子径：４．３５μｍ、変動係数：５．０％）に代えたこと以外は同様にして電極基板上に散布を行った。ここで、スペーサー粒子の前記溶媒に対する比重比は、１．７７であった。
【００６１】
実施例１と同様の方法により散布個数密度、平均凝集箇所率、再分散性の測定および評価を行った。その結果を表１に示す。スペーサー粒子であるベンゾグアナミン−メラミン−ホルマリンの縮合架橋硬化球状微粒子は、散布個数密度が散布時間の経過とともにおよそ上限値から下限値へと大きく減少し、所定位置であるブラックマトリクス上に分散配置されていない箇所が多く存在していた。また、再分散性については可能であった。
【００６２】
【表１】

【００６３】
【発明の効果】
本発明によれば、スペーサー粒子の基板あたりの散布個数（散布個数密度）が長時間散布後でも減少することがなく、スペーサー粒子のボタ凝集が発生しない、スペーサー粒子湿式散布用組成物、および、それを用いた液晶表示装置の製造方法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]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a composition for wet-spraying spacer particles, comprising a spacer particle and a solvent, and a method for producing a liquid crystal display device having a liquid crystal display substrate having excellent dispersibility of spacer particles using the composition. Specifically, for example, when viewing each liquid crystal display substrate, the number of scattered spacer particles in the substrate surface is uniform in the surface, and the spacer particles are monodispersed and are not aggregated, and When sprayed continuously for a long time and compared between production lots, a composition for wet spraying of spacer particles that can obtain a liquid crystal display device in which the number of sprayed spacer particles between liquid crystal display substrates is stable without fluctuations And a method for easily obtaining such a liquid crystal display device.
[0002]
[Prior art]
For example, when dispersing spacer particles used in a liquid crystal display device or the like on a panel serving as a substrate, a composition for wet dispersion of spacer particles comprising a spacer particle and a solvent containing an organic solvent (and water as necessary) ( For example, it is well known that the spacer particles are wet-sprayed by spraying the spacer particles in a solvent containing an organic solvent (and water as needed). I have.
In addition, it is important that the spacer particles are scattered uniformly in the liquid crystal display device. Therefore, in the step of scattering the spacer particles, the number of scattered spacer particles is uniform within the substrate surface, and the spacer particles are singly dispersed. Many devices have been devised so that they are monodispersed and do not agglomerate.
[0003]
However, the present inventor has observed in detail that when spraying is performed for a long time, the number of sprays per substrate (spray number density) decreases because spacer particles settle in the dispersion, When the droplets adhere around the nozzle, the spacers flocculate (spray droplets containing 10 or more aggregated spacer particles), and the droplets fall on the substrate as they are, causing the aggregation of the spacer particles on the substrate. I noticed that there was a problem.
Further, usually, when spraying, the spacer particles are ultrasonically dispersed and sprayed in advance, but when the composition for spacer particle wet spraying is prepared in advance and left for a long time, the spacer once settled. It was also found that it was difficult to re-disperse the particles even if they were to be dispersed again. In particular, when the viscosity of the solvent in the composition is high, once the spacer particles have settled out for a long time, the spacer particles aggregate more firmly, and a very strong ultrasonic force or It turned out that stirring power was required. As a matter of fact, when the dispersion treatment is performed under such a heavy load, the spacer particles are damaged or destroyed, so that at present, the spacer particles cannot be redispersed.
[0004]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to provide a composition for wet-spraying spacer particles, in which the number of scattered spacer particles per substrate (sprayed number density) does not decrease even after long-time spraying, and no flocculation of the spacer particles occurs. Another object of the present invention is to provide a method for manufacturing a liquid crystal display device using the same.
[0005]
[Means for Solving the Problems]
The present inventor, in order to solve the above problems, various studies, as a result of repeated experiments, as a solvent, the viscosity is more than a certain value, or as a solvent using a solvent whose surface tension is more than a certain value. At the same time, it was found that it was necessary to use spacer particles having a specific gravity and a specific gravity of the solvent that did not greatly differ from each other.
That is, the first spacer particle wet spray composition according to the present invention comprises:
In a composition for wet dispersion of spacer particles comprising spacer particles and a solvent, the solvent has a viscosity at 20 ° C of 1 mPa · s or more and 30 mPa · s or less, and the solvent of the spacer particles at 20 ° C with respect to the solvent. The specific gravity ratio is not more than 1.70 and not less than 1.00.
[0006]
Further, the second spacer particle wet spraying composition according to the present invention,
In a composition for wet-spraying spacer particles, comprising a spacer particle and a solvent, the solvent has a surface tension at 20 ° C. of 0.02 N / m or more and 0.06 N / m or less, and the spacer at 20 ° C. The specific gravity ratio of the particles to the solvent is 1.70 or less and 1.00 or more.
Further, the method for manufacturing a liquid crystal display device according to the present invention,
The method further comprises a step of spraying the first or second spacer particle wet-spraying composition according to the present invention toward a substrate from a nozzle and spraying the composition on a substrate.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the composition for wet-spraying spacer particles according to the present invention, and a method for manufacturing a liquid crystal display device using the composition for wet-spraying spacer particles will be described in detail, but the scope of the present invention is limited by these descriptions. However, other than the following examples, the present invention can be appropriately implemented within a range that does not impair the gist of the present invention.
(Composition for wet spraying of spacer particles)
The first composition for wet dispersion of spacer particles according to the present invention (hereinafter, sometimes referred to as the first composition for wet dispersion of spacer particles of the present invention) is a spacer particle comprising spacer particles and a solvent. In the composition for wet spraying, the solvent has a viscosity at 20 ° C. of 1 mPa · s or more and 30 mPa · s or less, and a specific gravity ratio of the spacer particles to the solvent at 20 ° C. of 1.70 or less, 1.00 or less. It is characterized by the above. When the viscosity of the solvent and the specific gravity ratio of the spacer particles to the solvent satisfy the above ranges, the above-described problem can be easily solved.
[0008]
The second composition for wet-spraying spacer particles according to the present invention (hereinafter sometimes referred to as the second composition for wet-spraying spacer particles of the present invention) is a wet-spraying method comprising spacer particles and a solvent. The solvent has a surface tension at 20 ° C. of 0.02 N / m or more and 0.06 N / m or less, and a specific gravity ratio of the spacer particles to the solvent at 20 ° C. is 1. 70 or less and 1.00 or more. When the surface tension of the solvent and the specific gravity ratio of the spacer particles to the solvent satisfy the above ranges, the above-described problem can be easily solved.
[0009]
The first and second compositions for wet-spraying spacer particles of the present invention (hereinafter, may be simply referred to as the composition for wet-spraying spacer particles of the present invention) are obtained by dispersing spacer particles in the solvent. It is preferable that the material is dispersed or can be dispersed.
In the first spacer particle wet-spraying composition of the present invention, the solvent has a viscosity at 20 ° C. of 1 mPa · s or more and 30 mPa · s or less, as described above. Is 5 mPa · s or more, more preferably 10 mPa · s or more. If the viscosity of the solvent is less than 1 mPa · s, there is a possibility that the scattered droplets adhere around the nozzle to cause flocculation of spacer particles. When the viscosity of the solvent exceeds 30 mPa · s, the spacer particles are once dispersed by ultrasonic waves and then left or stored for a long time, and when the spacer particles are settled, the spacer particles are again dispersed as before. This may make it difficult, and even if a redispersible load is applied again, the spacer particles may be seriously damaged or broken. When the viscosity of the solvent is 30 mPa · s or less, such a risk can be avoided, and the handleability can be improved. In measuring the viscosity of the solvent at 20 ° C., a solvent pocket book (issued by Ohm Publishing in 1967) is referred to.
[0010]
In the second spacer particle wet-spraying composition of the present invention, as described above, the solvent has a surface tension at 20 ° C. of 0.02 N / m or more and 0.06 N / m or less. And the lower limit is preferably at least 0.025 N / m, more preferably at least 0.03 N / m. If the surface tension of the solvent is less than 0.02 N / m, the scattered droplets may adhere around the nozzle to cause flocculation of spacer particles. When the surface tension of the solvent is more than 0.06 N / m, the spacer particles are likely to aggregate after spraying, and the sprayed spacer particles may be unevenly present in the substrate surface. In measuring the surface tension of the solvent at 20 ° C., a solvent pocket book (issued by Ohm Publishing in 1967) is referred to.
[0011]
In the composition for wet-spraying spacer particles of the present invention, any solvent may be used as long as it can well disperse the spacer particles, and an organic solvent generally known as one generally used for wet-spraying spacer particles is used. Specific examples thereof include, but are not particularly limited to, alcohols, glycols, ethers, acetals, ketones, and esters.Preferred examples include methyl alcohol, Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, 2-pentyl alcohol, 3-pentyl alcohol, 2-methyl-1-butyl alcohol, 3- Methyl-2-butyl alcohol, i Alcohols such as pentyl alcohol; glycols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol and diethylene glycol; glycerin; polyhydric alcohols such as ethylene glycol methyl (or ethyl) ether and diethylene glycol methyl (or ethyl) ether And lower alkyl ethers. These may be used alone or in combination of two or more. Further, the other solvent may be only the above-mentioned various organic solvents, or may further contain water.
[0012]
In the composition for wet-spraying spacer particles of the present invention, as described above, the specific gravity ratio of the spacer particles to the solvent at 20 ° C. is 1.70 or less and 1.00 or more, as described above. However, the upper limit is preferably 1.6 or less, more preferably 1.5 or less. When the specific gravity ratio exceeds 1.70, in the case of spraying for a long time, the spacer particles are liable to settle with the lapse of time. In addition, the number of spacer particles sprayed on the substrate may be reduced. When the specific gravity ratio is less than 1.00, the spacer particles may be difficult to be uniformly dispersed in the solvent. In order to obtain the above specific gravity ratio, the specific gravity of the solvent at 20 ° C. is referred to a solvent pocket book (issued by Ohm Publishing Co., Ltd. in 1967), and when measuring the specific gravity of the spacer particles at 20 ° C. The method described in Examples described later is used.
[0013]
The spacer particles, for example, when used in a liquid crystal display device, determine the gap distance between the two electrode substrates sandwiching the liquid crystal layer, and are particles necessary to keep the thickness of the liquid crystal layer uniform and constant. is there.
The average particle size of the spacer particles is preferably 1 to 30 μm, more preferably 1 to 20 μm, and even more preferably 1 to 15 μm. When the average particle size of the spacer particles is out of the above range, it is a region not usually used as spacer particles for a liquid crystal display device.
The coefficient of variation (CV) of the particle size of the spacer particles is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less. When the variation coefficient of the particle diameter exceeds 10%, for example, when used as spacer particles for a liquid crystal display device, it is difficult to keep the thickness of the liquid crystal layer uniform and constant, and image unevenness may easily occur. Is not preferred.
[0014]
The definition and measurement method of the average particle diameter and the coefficient of variation of the particle diameter will be described in Examples below.
Regarding the spacer particles, the ratio of the theoretical surface area to the measured surface area (theoretical surface area / measured surface area) is not particularly limited, but specifically, is preferably 500 or less, more preferably 100 or less, and even more preferably 50 or less. It is as follows. If the above ratio is more than 500, the solvent on the surface of the spacer particles is less likely to evaporate, the spacer particles are likely to aggregate, and the reliability of the liquid crystal display device may be reduced.
[0015]
The spacer particles are not particularly limited, but specific examples thereof include preferably organic cross-linked polymer particles, inorganic particles, and organic-inorganic composite particles. Among these, the organic cross-linked polymer particles and / or the organic-inorganic composite particles can easily prevent damage to the electrode substrate, the alignment film or the color filter, and easily obtain uniformity of the gap distance ((cell) gap) between the two electrode substrates. Thus, organic-inorganic composite particles are most preferable.
The shape of the spacer particles may be any particle shape such as a sphere, a needle, a plate, a scale, a pulverized shape, a bale shape, a cocoon shape, a spine shape, and the like. The spherical shape is preferred in order to make the gap distance of the above uniform. This is because a spherical shape has a constant or almost constant grain shape in all or almost all directions.
[0016]
The spacer particles may be preferably colored by including a dye and / or a pigment.
The organic cross-linked polymer particles are not particularly limited, but include, for example, amino obtained by a condensation reaction from at least one amino compound selected from the group consisting of benzoguanamine, melamine and urea with formaldehyde. Cured resin particles (see JP-A-62-068811); divinylbenzene-crosslinked resin particles obtained by polymerizing divinylbenzene alone or copolymerizing with other vinyl monomers (see JP-A-1-144429) ) And the like.
[0017]
The inorganic particles are not particularly limited, but preferably include, for example, spherical fine particles such as glass, silica, and alumina.
The organic-inorganic composite particles are preferably composite particles containing an organic portion and an inorganic portion. In the organic-inorganic composite particles, the ratio of the inorganic portion is not particularly limited. For example, 10 to 90% by weight in terms of an inorganic oxide with respect to the weight of the organic-inorganic composite particles. It is preferably in the range, more preferably 25 to 85% by weight, even more preferably 30 to 80% by weight. The term “inorganic oxide conversion” is preferably represented by a weight percentage obtained by measuring the weight before and after firing the organic-inorganic composite particles at a high temperature (for example, 1000 ° C.) in an oxidizing atmosphere such as air. When the ratio of the inorganic portion of the organic-inorganic composite particles is less than 10% by weight in terms of inorganic oxide, the organic-inorganic composite particles are softened, and the number density of the particles dispersed on the electrode substrate is preferably increased. If the content is more than 90% by weight, the orientation film is too hard, which may cause damage to the alignment film or disconnection of the TFT, which is not preferable.
[0018]
The organic-inorganic composite particles as described above are not particularly limited. For example, an organic polymer skeleton and an organic silicon compound in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. And a polysiloxane skeleton having in the molecule thereof, SiO constituting the polysiloxane skeleton. ₂ The organic-inorganic composite particles A having an amount of 10% by weight or more can be preferably exemplified. As the organic polymer skeleton, a vinyl-based polymer is preferable because it provides high restoring property that can control gap control. Here, the organic-inorganic composite particles A are G ≧ 14 · Y ^1.75 (Here, G indicates breaking strength [kg]; Y indicates particle diameter [mm]), and preferably a breaking strength satisfying 10% compression elastic modulus of 300 to 2000 kg / mm. ² More preferably, the residual displacement after 10% deformation is 0 to 5%.
[0019]
The method for producing the organic-inorganic composite particles A is not particularly limited, but preferably includes, for example, a production method including a condensation step, a polymerization step, and a heat treatment step described below.
The condensation step is preferably a step of performing hydrolysis and condensation using a first silicon compound having a radical polymerizable group. In this condensation step, a basic catalyst such as ammonia may be preferably used as a catalyst.
The radical polymerizable group-containing first silicon compound has the following general formula (1):
[0020]
Embedded image

[0021]
(Where R ^a Represents a hydrogen atom or a methyl group; ^b Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; ^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):
[0022]
Embedded image

[0023]
(Where R ^d Represents a hydrogen atom or a methyl group; ^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):
[0024]
Embedded image

[0025]
(Where R ^f Represents a hydrogen atom or a methyl group; ^g Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; ^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 ³ 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. )
Preferably, the compound is a compound represented by at least one general formula selected from the group consisting of or a derivative thereof.
[0026]
The polymerization step is preferably a step of obtaining particles by performing a radical polymerization reaction of a radically 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. And under reduced pressure.
During and / or after at least one step selected from the condensation step, the polymerization step, and the heat treatment step, the method may further include a coloring step of coloring the generated spacer particles. It may be colored by including at least one selected from the group consisting of pigments. The color is preferably such that light hardly transmits or does not transmit light, since light leakage of the spacer particles themselves can be prevented and image quality contrast can be improved. Light is hardly transmitted, or, as a color that does not transmit, for example, black, dark blue, dark blue, purple, blue, dark green, green, brown, red, and the like can be preferably mentioned, particularly preferably, Black, dark blue and dark blue. 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 bonded by a chemical bond. It is not limited to these.
[0027]
The dye is 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 described in “Chemical Handbook, Applied Chemistry, edited by The Chemical Society of Japan” (1986, published by Maruzen Co., Ltd.), pp. 1399-1427, “Nippon Kayaku Dye Handbook” (1973, published by Nippon Kayaku Co., Ltd.). )It is described in.
As a method of dyeing the spacer particles, a conventionally known method is used. For example, it can be carried out by the method described in the above-mentioned “Chemical Handbook, Applied Chemistry, edited by The Chemical Society of Japan” or “Nippon Kayaku Dye Handbook”.
[0028]
Examples of the pigment include, but are not particularly limited to, inorganic pigments such as carbon black, iron black, chromium vermillion, molybdenum red, red iron oxide, graphite, chrome green, cobalt green, ultramarine, and navy blue; phthalocyanine-based, azo-based pigments And quinacridone-based organic pigments. If the pigment has an average particle diameter of not more than 0.4 μm, the pigment may not be introduced into the spacer particles. In this case, it is preferable to use a dye. When the spacer particles are colored, when they are used as spacer particles for a liquid crystal display device, light from a backlight can be prevented, and the image quality of the liquid crystal display device can be improved.
[0029]
During and / or after at least one of the steps selected from the condensation step, the polymerization step, and the heat treatment step, the method may further include a surface treatment step of subjecting the generated spacer particles to a surface treatment.
The surface treatment agent used for the surface treatment is not particularly limited, but is preferably at least one silane compound selected from the following general formulas (4) to (6).
Six ₄ (4)
R ⁴ Six ₃ (5)
R ⁵ R ⁶ Six ₂ (6)
(Where 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 ⁴ And R ⁵ Are all at least one kind 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, R 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; 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 composition for wet-spraying spacer particles of the present invention, the content of the spacer particles in the whole composition is preferably 0.005 to 30% by weight, more preferably 0.01 to 20% by weight, furthermore 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 time to obtain a desired number density of the application, and when it exceeds 30% by weight, the composition for spacer particle wet application may be used. There is a possibility that the slurry will be in a slurry state, the fluidity will be reduced, and aggregation of the spacer particles will occur.
[0030]
The composition for wet-spraying spacer particles of the present invention contains spacer particles and a solvent, but may further contain other components as necessary, if necessary.
(Manufacturing method of liquid crystal display device)
The method for manufacturing a liquid crystal display device according to the present invention (hereinafter, may be referred to as the method for manufacturing a liquid crystal display device of the present invention, and the manufacturing method of the present invention) uses the above-described composition for wet-spraying spacer particles of the present invention. And a step of wet-spraying spacer particles on a substrate or the like.
In the method of manufacturing a liquid crystal display device of the present invention, the same materials as those of the related art can be used for the electrode substrate, the sealant, the liquid crystal material, and the like. The spacer particles are included in the composition for wet-spraying spacer particles of the present invention to be used. Therefore, 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 composition for wet dispersion of the present invention.
[0031]
The electrode substrate is not particularly limited, but specifically includes, for example, a substrate such as a glass substrate and a film substrate, and an electrode formed on the surface of the substrate. Further has an alignment film formed on the surface of the substrate so as to cover the electrode. In the case of a color-compatible liquid crystal display device, it has a color filter.
The sealing material is not particularly limited, but specifically, for example, an epoxy resin adhesive sealing material is used.
The liquid crystal (liquid crystal material) is not particularly limited, and may be a conventionally used liquid crystal. Specifically, for example, biphenyl, phenylcyclohexane, Schiff base, azo, azoxy, benzoic acid Liquid crystals of ester type, terphenyl type, cyclohexyl carboxylate type, biphenylcyclohexane type, pyrimidine type, dioxane type, cyclohexylcyclohexane ester type, cyclohexylethane type, cyclohexene type, fluorine type and the like can be used.
[0032]
As a method for manufacturing the liquid crystal display device of the present invention, specifically, for example, the spacer particles are dispersed by spraying the above-mentioned composition for wet dispersion of the present invention on one of two electrode substrates. (In-plane spacer particles) are dispersed and arranged at predetermined positions, and an adhesive sealing material such as epoxy resin is used to disperse sealing spacer particles into an adhesive sealing portion of another electrode substrate by screen printing or the like. Put the thing applied by the means, apply an appropriate pressure, and heat at a temperature of 100 to 180 ° C. for 1 to 60 minutes, or an irradiation amount of 40 to 300 mJ / cm. ² After the adhesive sealant is heated and cured by the ultraviolet irradiation described above, a method of injecting liquid crystal and sealing the injection portion can be cited, but it is not particularly limited to such a manufacturing method.
[0033]
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 to this. That is, the obtained liquid crystal display device includes a pair of electrode substrates (the first electrode substrate 110 and the second electrode substrate 120) that are opposed to each other with a liquid crystal material interposed therebetween, and the spacer particles. The first electrode substrate 110 has a first substrate 11 and the electrodes 5 formed on the surface of the first substrate 11. The second electrode substrate 120 has the second substrate 12 and the electrodes 5 formed on the surface of the second substrate 12. The first electrode substrate 110 and the second electrode substrate 120 are adhered to each other at their peripheral portions by the sealing material 2. The spacer particles are selectively disposed between the substrates to maintain the distance between the substrates. The spacer spacer particles 3 dispersed in the sealing material 2 and the in-plane spacer particles dispersed in the plane. 8 exists. 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. I have.
[0034]
In the manufacturing method of the liquid crystal display device of the present invention, the spacer particles are wet-sprayed by spraying the above-mentioned composition for spacer particle wet-spraying, but the method of spraying the composition is not particularly limited, but is not particularly limited. For example, it is preferable to spray using a device employing a spray method, an ink jet method, or the like. Among them, the ink jet method is more preferable because the spacer particles are easily dispersed and arranged at desired positions on the substrate.
Ink jet systems are classified into two systems, a continuous jet system and a drop-on-demand system, based on the principle of generating droplets of a composition for wet spraying of spacer particles used as ink. In the production method of the present invention, any method can be preferably adopted. (Hereinafter, the “droplets of the composition for spacer particle wet spraying” are simply referred to as “droplets”.)
The continuous jet method is a method in which droplets are continuously generated, and droplets are selected and recorded according to a recording signal. In the continuous jet method, droplet generation is performed in a steady state, so that the generation cycle of droplets can be shortened and high-speed recording can be performed. Further, since the flying speed of the ejected droplets is high, the distance between the nozzle and the recording medium can be increased, so that recording on a curved surface or the like is also possible. The continuous jet method includes a Sweet type, a microdot type, a Herz type and an IRIS type.
[0035]
In the Sweet type, mechanical vibration is applied to the nozzle from the outside, the frequency is matched with the spontaneous division speed of the droplet, and the droplet generated so that the mass of the divided droplet becomes the same mass is used. I do. Specifically, a piezo piezoelectric element is attached to the nozzle part, and the liquid crystal composition is vibrated at a division cycle of the composition for wet dispersion of spacer particles to generate uniform droplets. A charged electrode is provided at a portion where the composition for spacer particle wet dispersion is divided, and the droplet is charged. The charged droplet passes between the deflection electrodes. The droplet receives a vertical electrostatic force by an electric field, and its trajectory changes. At this time, there are a binary deflection type and a multi-level deflection type depending on how the deflection voltage is applied.
[0036]
The microdot type is a system in which when a droplet is divided, small droplets called satellites are taken out between droplets and recording is performed. In this method, both charging and deflecting operations are performed by applying different voltages to each of the pair of electrodes.
In the Herz type, a pressurized composition for spacer particles is sprayed from a fine nozzle and droplets are passed through a ring-shaped electrode. When a voltage is applied to the electrodes, the droplets break up into fine spray-like mist due to the repulsive force of the charges charged on the droplets. The droplet is not recorded when it is divided into a spray, and the droplet when it is not divided is used for recording.
The IRIS type is an improved version of the Herz type and is characterized in that the size of a droplet is kept constant by installing a piezo vibrator in a nozzle.
[0037]
The drop-on-demand method is a method in which a composition for wet-spraying spacer particles is ejected according to a recording signal. Although the recording speed is slower than that of the continuous jet system, the whole mechanism is simplified. The drop-on-demand method includes a pressure pulse method, a thermal jet method, an ERF method, and the like.
The pressure pulse method is a method in which a pressure wave is generated in an ink chamber using a piezoelectric element or the like, and a composition for spacer particle wet spraying is ejected. Depending on the structure of a print head, a Stemme method, a Gould method, and a Kyser method are used. and so on.
[0038]
In the thermal jet method, a heating element is provided in a nozzle, and the composition for spacer particle wet spraying is vaporized into bubbles, and the composition is extruded by the bubbles and ejected by the nozzle.
In the ERF method, a print head is composed of a flow path of a composition for wet dispersion of spacer particles and a pair of electrodes provided so as to sandwich the flow path, and the 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 0, the composition is not ejected from the nozzle, and when the voltage of the electrode is set to 0, the composition is pressurized. Erupts from the nozzle.
[0039]
In the production method of the present invention, when the composition for spacer particles is wet-sprayed and the spacer particles are wet-sprayed and dispersed, usually, first, any position on the electrode substrate or the color filter of the liquid crystal display device is used. It is determined whether spacer particles are to be placed in the space. In order to improve the contrast and achieve high display quality of the obtained liquid crystal display device, it is not preferable to disperse the spacer particles in the pixel region, that is, the display region, and disperse the spacer particles in the non-pixel region, that is, the non-display region. Is preferred. This is because, if the spacer particles are dispersed and arranged in the pixel region, the existing portions of the spacer particles are not displayed, and light escape occurs around the spacer particles due to the disturbance of the alignment of the spacer particles and 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 the display, such as around a character or a design or a gap. Further, for example, in the case of the STN mode, since the transparent electrodes of the electrode substrate are arranged in a stripe shape, it is preferable to disperse and arrange the spacer particles in the gap between the transparent electrodes. Further, for example, in the case of color display of TFT or STN, it is preferable to disperse and arrange the pixels of the color filter other than R, G and B, that is, on a black matrix. In the case of dispersing and disposing them on an electrode substrate facing a substrate having a color filter, it is preferable to disperse and dispose them on a portion corresponding to the position of a black matrix.
[0040]
In addition, the number of the positions of the spacer particles to be dispersed 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.However, if too small, the uniformity of the gap becomes poor, and if too large, the gap becomes too large. Low-temperature foaming and the like easily occur. Further, the number of dispersed arrangements also depends on the size of one pixel in the display area.
Here, the spacer particles dispersed and arranged are preferably single particles, but may be plural as long as they are non-pixel regions, and may be set as appropriate. In addition, there is a possibility that the ratio of the spacer particles arranged in the display area increases, and the display quality is degraded.
[0041]
The liquid crystal display device obtained by the manufacturing method of the present invention has the same applications as conventional liquid crystal display devices, for example, televisions, monitors, personal computers, word processors, car navigation systems, DVDs, digital video cameras, PHSs (Personal Digital Assistants), etc. Can be used as an image display device.
[0042]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following, “parts by weight” may be simply referred to as “parts” or “% by weight” may be simply referred to as “wt%” for convenience.
First, the definitions, measurement methods, sources, and the like of the values of the solvent and the spacer particles described in the examples of the present invention will be described below.
(Surface tension, viscosity, specific gravity of solvent)
See Solvent Pocket Book (1967, Ohm Publishing).
(Average particle diameter of spacer particles, variation coefficient 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 measurement methods. That is, the average particle diameter was determined as the average particle diameter by measuring the particle diameter of 30,000 particles using a Coulter Multisizer (manufactured by Beckman Coulter, Inc.). The coefficient of variation of the particle diameter was determined according to the following equation.
[0043]
(Equation 1)

[0044]
[Destruction strength of spacer particles]
The breaking strength of the spacer particles was determined using a Shimadzu Micro Compression Tester (MCTM-200, manufactured by Shimadzu Corporation) at room temperature (25 ° C.) at room temperature (25 ° C.). Using a 50 μm circular flat plate indenter (material: diamond), a load is applied in the direction of the center of the particles at a constant load speed, and the value is defined as the compressive load (N) when the sample particles break.
[10% compression modulus of spacer particles]
The 10% compressive elastic modulus of the spacer particles is defined as a constant load in the direction of the center of the particles using a circular flat indenter with respect to one sample particle scattered on the sample stage by the same device as that for measuring the breaking strength. A load is applied at a speed, and the load when the compression displacement becomes 10% of the particle diameter and the number of millimeters of the compression displacement are measured. The measured compression load, particle compression displacement, and particle radius are calculated by the following formula:
[0045]
(Equation 2)

[0046]
(Here, E: compression modulus (GPa), F: compression load (N), S: compression displacement (mm), R: radius of particle (mm).)
And calculate the value. This operation is performed for three different particles, and the average value is defined as the 10% compression modulus of the particles.
(Specific gravity of spacer particles)
The measurement was performed using a micro ultra pycnometer 1000 (specific gravity measurement device manufactured by Cantachrome Co., Ltd.).
-Production Example 1-
[Production example of spacer particles]
A solution (solution A) obtained by mixing 2.9 g of a 25% aqueous ammonia solution, 10.1 g of methanol, and 141.1 g of water was placed in a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, and was placed at 25 ± 2 ° C. While stirring, 29 g of γ-methacryloxypropyltrimethoxysilane, 55 g of methanol, 0.14 g of 2,2′-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator, Tetraethoxysilane dimer to pentamer (manufactured by Tama Chemical Co., Ltd., product name: Silicate 40 (SiO ₂ A solution (solution B) mixed with 5.0 g) was added through a dropping port, and hydrolysis and polycondensation of γ-methacryloxypropyltrimethoxysilane were performed. After 20 minutes while continuing stirring, the mixture was heated to 70 ± 5 ° C. in a nitrogen atmosphere to perform radical polymerization.
[0047]
After continuing heating for 2 hours, the mixture was cooled to room temperature to obtain a suspension of polymer particles. This suspension was subjected to solid-liquid separation by filtration, and the obtained cake was washed three times by decantation with methanol, and vacuum-dried in a vacuum dryer at 200 ° C. for 2 hours to obtain composite particles as organic-inorganic composite particles. (1) was obtained. The obtained composite particles (1) had an average particle diameter of 4.27 μm, a coefficient of variation of the particle diameter of 3.1%, and a SiO constituting a polysiloxane skeleton. ₂ 33.5 wt%, 10% compression modulus 478 kg / mm ² The residual displacement after deformation by 10% was 3.0% and the breaking strength was 2.5 g.
-Example 1-
0.5 wt% of the composite particles (1) as spacer particles in isopropyl alcohol as a solvent (surface tension at 20 ° C .: 0.021 (N / m), viscosity: 2.4 (mPa · s)). And then dispersed by ultrasonic waves to obtain a composition for wet dispersion of spacer particles. Here, the specific gravity ratio of the spacer particles to the solvent was 1.65.
[0048]
Next, for a 14-inch TFT type liquid crystal display device, the above-mentioned composition for spacer particle wet spraying was sprayed on a black matrix of an electrode substrate on which a color filter was installed, using a conventionally known ink jet device. And the dispersed number density of the composite particles (1) as spacer particles is about 200 particles / mm. ² It was made to become.
Spraying is continuously performed on 1,000 electrode substrates, and the dispersed arrangement state of the spacer particles on the electrode substrate is observed every 20 sheets, and the number density of the sprayed particles, the average aggregating portion ratio (the ratio of the aggregating portions of 10 or more spacer particles) ) Was measured. Table 1 shows the results.
[0049]
After leaving the composition for spacer particle wet spraying for 6 months, it was again dispersed by ultrasonic irradiation, and redispersibility was observed. Table 1 shows the results.
The composite particles (1), which are spacer particles, were dispersed on a black matrix at a predetermined position. The redispersibility was also good.
In addition, each measuring method and evaluation criteria are shown below.
(Spray number density)
Any 1 mm on the electrode substrate ² 9 observation areas were selected, the number of spacer particles in each area was counted by an optical microscope, and the average value of the number of the 9 areas in total was used to determine the sprayed number density (number / mm). ² ). It is a value that is a guide for the number of sprays.
[0050]
The sprayed number density was calculated for the 50 electrode substrates measured, and the upper and lower limits are shown in Table 1.
[Average aggregation point ratio (ratio of aggregation points of 10 or more spacer particles)]
Simultaneously with the measurement of the number of sprayed particles, the number of locations where a plurality of spacer particles are aggregated is counted, and the ratio of “the locations where 10 or more spacer particles are aggregated” to all the counted locations is calculated as the average aggregation location ratio (% ).
Table 1 shows the average value of the measured 50 electrode substrates.
(Redispersibility)
When the spacer particle wet dispersion composition once subjected to the spacer particle dispersion treatment is left for 6 months to settle the spacer particles, and then dispersed by ultrasonic irradiation (intensity: 150 W, 28 kHz, 15 minutes). The redispersibility of the spacer particles was evaluated according to the following criteria.
[0051]
：: Immediately and uniformly dispersed.
Δ: Dispersed but slightly aggregated.
X: Almost no dispersion.
Example 2
Spraying was performed on the electrode substrate in the same manner as in Example 1, except that the solvent was changed to ethylene glycol (surface tension at 20 ° C .: 0.046 (N / m), viscosity: 20 (mPa · s)). went. Here, the specific gravity ratio of the spacer particles to the solvent was 1.05.
[0052]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The composite particles (1), which are spacer particles, were dispersed on a black matrix at a predetermined position. The redispersibility was also good.
Example 3
Spraying was performed on the electrode substrate in the same manner as in Example 1, except that the spacer particles were replaced with crosslinked spherical fine particles of divinylbenzene (average particle diameter: 4.31 μm, variation coefficient: 3.8%). Here, the specific gravity ratio of the spacer particles to the solvent was 1.57.
[0053]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The crosslinked spherical fine particles of divinylbenzene as spacer particles were dispersed and arranged on a black matrix at a predetermined position. The redispersibility was also good.
Example 4
In Example 1, the spacer particles were crosslinked spherical fine particles of divinylbenzene (average particle diameter: 4.31 μm, variation coefficient: 3.8%), and the solvent was ethylene glycol (surface tension at 20 ° C .: 0.046 (N / M) and viscosity: 20 (mPa · s)), but sprayed on the electrode substrate in the same manner. Here, the specific gravity ratio of the spacer particles to the solvent was 1.10.
[0054]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The crosslinked spherical fine particles of divinylbenzene as spacer particles were dispersed and arranged on a black matrix at a predetermined position. The redispersibility was also good.
Example 5
In Example 1, the spacer particles were benzoguanamine-melamine-formalin condensation-crosslinked cured spherical fine particles (average particle diameter: 4.35 μm, coefficient of variation: 5.0%), and the solvent was ethylene glycol (surface tension at 20 ° C .: Spraying was performed on the electrode substrate in the same manner except that 0.046 (N / m) and viscosity: 20 (mPa · s) were used. Here, the specific gravity ratio of the spacer particles to the solvent was 1.25.
[0055]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The benzoguanamine-melamine-formalin condensation-crosslinked cured spherical fine particles as spacer particles were dispersed and arranged on a black matrix at a predetermined position. The redispersibility was also good.
-Comparative Example 1-
Sprayed on the electrode substrate in the same manner as in Example 1, except that the solvent was changed to hexane (surface tension at 20 ° C .: 0.018 (N / m), viscosity: 2.4 (mPa · s)). Was done. Here, the specific gravity ratio of the spacer particles to the solvent was 1.98.
[0056]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. In the composite particles (1), which are spacer particles, the number density of the sprayed particles greatly decreases from the upper limit to the lower limit with the elapse of the spraying time, and there are many places that are not dispersed and arranged on the black matrix at predetermined positions. Many of the above aggregations were present. Also, redispersion was possible.
-Comparative Example 2-
Spraying was performed on the electrode substrate in the same manner as in Example 1, except that the solvent was changed to diethylene glycol (surface tension at 20 ° C .: 0.0485 (N / m), viscosity: 38 (mPa · s)). Was. Here, the specific gravity ratio of the spacer particles to the solvent was 1.05.
[0057]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The composite particles (1), which are spacer particles, were dispersed and arranged on the black matrix at predetermined positions. Also, it could not be redispersed.
-Comparative Example 3-
Spraying was performed on the electrode substrate in the same manner as in Example 1, except that the solvent was changed to glycerin (surface tension at 20 ° C .: 0.064 (N / m), viscosity: 1499 (mPa · s)). Was. Here, the specific gravity ratio of the spacer particles to the solvent was 1.04.
[0058]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The composite particles (1), which are spacer particles, have a very large variation in the number density of spraying depending on the substrate (the maximum is a variation in the width between the upper and lower values and the lower limit), and a large number of 10 or more agglomerations are present in the display area. Even spacer particles were present. Also, it could not be redispersed.
-Comparative Example 4-
In Example 1, the spacer particles were crosslinked spherical fine particles of divinylbenzene (average particle diameter: 4.31 μm, variation coefficient: 3.8%), and the solvent was hexane (surface tension at 20 ° C .: 0.018 (N / m) and viscosity: 2.4 (mPa · s)), but sprayed on the electrode substrate in the same manner. Here, the specific gravity ratio of the spacer particles to the solvent was 1.87.
[0059]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The crosslinked spherical fine particles of divinylbenzene, which are spacer particles, show that the number density of the spray decreases greatly from the upper limit to the lower limit with the elapse of the spray time, and many places that are not dispersed and arranged on the black matrix at predetermined positions are many. Many or more aggregates were present. Also, redispersion was possible.
-Comparative Example 5-
In Example 1, the spacer particles were benzoguanamine-melamine-formalin condensation-cured hardened spherical fine particles (average particle diameter: 4.35 μm, coefficient of variation: 5.0%), and the solvent was hexane (surface tension at 20 ° C .: 0). Was sprayed on the electrode substrate in the same manner except that the solution was changed to 0.018 (N / m) and the viscosity: 2.4 (mPa · s). Here, the specific gravity ratio of the spacer particles to the solvent was 2.12.
[0060]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The benzoguanamine-melamine-formalin condensation-cured spherical fine particles, which are spacer particles, have a dispersed number density that is greatly reduced from an upper limit to a lower limit with the passage of the spray time, and are dispersed and arranged on a black matrix that is a predetermined position. There were many absent spots and many aggregates of 10 or more. Also, redispersion was possible.
-Comparative Example 6-
In the same manner as in Example 1 except that the spacer particles were replaced with benzoguanamine-melamine-formalin condensation-crosslinked cured spherical fine particles (average particle diameter: 4.35 μm, coefficient of variation: 5.0%), the dispersion was performed on the electrode substrate in the same manner. Was done. Here, the specific gravity ratio of the spacer particles to the solvent was 1.77.
[0061]
In the same manner as in Example 1, the number density of sprayed particles, the average percentage of aggregated portions, and the redispersibility were measured and evaluated. Table 1 shows the results. The benzoguanamine-melamine-formalin condensation-crosslinked cured spherical fine particles, which are spacer particles, have a spraying number density that greatly decreases from an upper limit to a lower limit with the lapse of spraying time, and are dispersed and arranged on a black matrix as a predetermined position. There were many missing places. In addition, redispersibility was possible.
[0062]
[Table 1]

[0063]
【The invention's effect】
According to the present invention, the composition for spacer particle wet spraying, in which the number of sprayed spacer particles per substrate (sprayed number density) does not decrease even after long-time spraying, and no flocculation of the spacer particles occurs, and A method for manufacturing a liquid crystal display device using the same can be provided.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view showing one example of a liquid crystal display device obtained by a manufacturing method of the present invention.
[Explanation of symbols]
7 LCD
8 In-plane spacer particles
110 electrode substrate
113 Seal Spacer Particle
120 electrode substrate

Claims (5)

In a spacer particle wet-spraying composition comprising a spacer particle and a solvent, the solvent has a viscosity at 20 ° C of 1 mPa · s or more and 30 mPa · s or less, and the solvent of the spacer particles at 20 ° C with respect to the solvent. A composition for wet-spraying spacer particles, having a specific gravity ratio of 1.70 or less and 1.00 or more. In a composition for wet-spraying spacer particles, comprising a spacer particle and a solvent, the solvent has a surface tension at 20 ° C. of 0.02 N / m or more and 0.06 N / m or less, and the spacer at 20 ° C. A composition for wet dispersion of spacer particles, wherein the specific gravity ratio of the particles to the solvent is 1.70 or less and 1.00 or more. The composition for wet-spraying spacer particles according to claim 1 or 2, wherein the spacer particles are organic-inorganic composite particles. 4. A method for producing a liquid crystal display device, comprising a step of shot the composition for spacer particles wet spraying according to any one of claims 1 to 3 toward a substrate from a nozzle and spraying the composition on the substrate. The method according to claim 4, wherein the step of spraying 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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