JP3572787B2 - Liquid crystal cell manufacturing method - Google Patents

Description

【００１９】
からなるものがあるが、本発明はこれに限定されるものでない。
本発明全体において、基板を、その主面をカップラー層で被覆した平板からなるのが、均一で薄いメソーゲン層を得るのに、効果的であった。また、このための基板として、その主面を有極性有機樹脂層で被覆した平板からなるのが効果的であった。例えば、重合性液晶性モノマーとしては、少なくとも
【００２０】
【化７】

【００２１】
【化８】

【００２２】
【化９】

【００２３】
【化１０】

【００２４】
のいずれか、一つを含むようなものがあるが、本発明はこれに限定されるものでない。
【００２５】
【発明の実施の形態】
非接触法での液晶分子用配向膜形成法は、発塵の可能性が極めて小さいこと、薄膜トランジスターに悪影響を及ぼす静電気の発生の極端な抑圧等、長所がある。しかしながら、約１０゜近辺までのプレチルトの発現には成功していなかった。ここでは、まず、このあたりの事情について、若干、説明する。
【００２６】
まず、可視光ないし、紫外線光では、波長が短くても約２０００オングストローム程度であり、これは、液晶配向膜の望ましい厚みと同程度である。プレチルト発現のため、これらの偏光を使用し、かつまた斜め光を使い、なんらかの樹脂膜との相互作用、例えば重合等を行っても、多分、プレチルトは発現しない。ここでは、プレチルト発現のためには、液晶配向膜を構成する樹脂主鎖が基板に平行になっているのでなく、発現すべきプレチルトに対応して、基板に斜めに積まれるか、液晶配向膜となるべき樹脂膜の微細凹凸の分子レベルでの傾斜角度の鋭さが必要と考えている。もちろん、樹脂の側鎖がこのような状態でも、同等にプレチルトが発現すると考えられるが。このような議論から、偏光ないし、斜め光を使って、プレチルト角を発現するためには、波長が、多分１００オングストローム程度以下である必要があると考える。これは、Ｘ線領域であり、実施にはおのずから、ある困難性がある。
【００２７】
磁場により、液晶分子の環部分の電子雲の反磁性の故に、低分子液晶が配向することは分かっている。もちろん、誘起分極のため、電場に対して配向するのもよく知られた事実である。一方向の磁場または、一方向の電場で低分子液晶をプレチルトを持って配向させて、次に基板壁に吸着した液晶分子のみを残留させ、大部の低分子液晶を洗い流し、配向膜となすことが考えられる。学会の今までの結果からも推測されるが、この種の配向膜から液晶セルを作製すると、充填された液晶分子はプレチルトを持たず、基板壁近傍では基板壁に平行に並ぶ。すなわち、基板壁に吸着した液晶分子はプレチルト角を記憶しない。すなわち、プレチルトを記憶するためには、基板壁に所望のプレチルトに対応した、より剛直な構造が必要である。本発明の端緒の一つはここにある。
【００２８】
液晶分子を過剰の溶剤に希釈、液晶状態を喪失させた液体に、電場もしくは磁場を印加した場合、どうなるか。妥当な電場もしくは磁場の強度では、熱運動のため、液晶分子は配向しなかった。これは、液晶状態における分子間の相互作用が、この配向効果のためには、本質的役割を果しているという考えから理解される。
【００２９】
前述のより剛直な構造のため、液晶モノマーの重合により、より配向の記憶を安定にすることに、本発明の本質の一つはある。ただし、この重合の際、分子の再配列により、前記配向の記憶は一部、失われるという犠牲は常に存在はするが。
【００３０】
紫外線照射による重合ののち、有機溶剤で処理して、前記重合物の表層を溶出することは、これから液晶セルを作製した場合に、配向ムラを極少にするのに効果的であった。
【００３１】
基板を通して、紫外線を照射するのは、どうも、基板壁近傍においてのみ重合度が高くなる傾向にあるようで、これも、液晶セルの配向ムラの削減に資する。このとき、有機溶剤での処理は、結果としての配向膜の厚みをかなり薄く、均一に出来るようであり、望ましい。このような効果は、紫外線吸収染料を混入させることにより、一段と高まった。なお、この紫外線吸収染料の紫外線の吸光係数が、光重合開始剤のそれの二桁以上大きい方が、有効紫外線が基板壁近傍に限られるようであり、このあとの有機溶剤出の処理とあいまって、出来上がった液晶用配向膜の厚みをかなり薄く出来た。
【００３２】
また、磁場に加えて電圧を印加しつつ、紫外線を照射、重合させる方法は、メソーゲン層の有機分子の配向を促進し、紫外線によりこれを固化させるものである。すなわち、電圧により、有機分子が動く直前の状態に対応するポテンシアルを与え、実際の有機分子の配向方向の厳密な制御は、もちろん、磁場が行うものである。これにより、必要とされる磁場強度は節約され得る。
【００３３】
ガラス基板等、カップラー処理をなすことにより、メソーゲン層するのに、スピナー塗布を行うと、均一な薄膜が形成出来る。また、ガラス基板等、極性有機樹脂、例えば、ポリイミド樹脂、ポリパラバン酸樹脂、ポリアクリロニトリル樹脂、ポリアミド樹脂等で被覆し、この上にメソーゲン層を形成するのが均一な薄膜形成に容易であった。
【００３４】
（実施例１）
本実施例での、基板の状況を、構成断面図の形式で図１に示す。図１において、１は基板、２は基板主面、３はカップラー層、４は形成されたメソーゲン層である。
【００３５】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、ビニルトリメトキシシラン、品番ＫＢＭ１００３を、スピナーで塗布し、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【００３６】
つぎに、大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）と４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）の、それぞれ５０重量％の混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【００３７】
この希釈液を、スピナーで、最初、１分、４００ＲＰＭの回転数で、さらに、約２分、１０００ＲＰＭの回転数で、さらに、約１分、１５００ＲＰＭの回転数でカップラー層４の上に塗布した。そのまま、しばらく風乾して、溶媒のアセトンを揮発させ、約３１０ｎｍの厚みのメソーゲン層を得た。偏光顕微鏡観察によれば、このメソーゲン層は、液晶相を示していた。
【００３８】
次に、図２の構成断面図に示す装置で、重合性液晶性モノマーを配向させながら光重合させた。同図において、５、６は電磁石のポールであり、７は対応する磁力線であり、８は紫外線ランプ、９は前述のメソーゲン層、１０は基板である。便宜上、図１の基板１とカップラー層３を、図２では、基板１０とした。
【００３９】
紫外線ランプ８は、フィリップス社製、ＰＬ１０を用いた。これは、３６５ｎｍの紫外線を放射し、基板１０との距離は約２０ｃｍとした。電磁石は、ハーベイ・ウェルズ・コーポレーション社製のものである。
【００４０】
まず、結果する液晶セルでの液晶分子の所望プレチルトや所望配向方向に対応して、メソーゲン層を有する基板１０を、磁力線７に対して、傾けて、電磁石のポール５、６間に設置する。この実施例の場合、基板１０の法線と磁力線のなす角を、約６５゜にした。つぎに、磁束密度が約３０Ｋガウスとなるように、磁場を印加する。その状態で、紫外線ランプ８を点灯、約２分間、紫外線を照射する。紫外線は、メソゲン層に直接照射した。かくして、少なくとも一部、重合した高分子層が得られる。
【００４１】
次に、アセトンに数分、浸漬をのみすることにより、有機溶剤洗浄を行った。結果として、基板上に高分子層が残留する。
【００４２】
この基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００４３】
公知の方法で、このような、一対の基板で、前記残留した高分子層を対向させて、間隙を約１０ミクロンにした空セルを製作した。この時、上、下基板の貼り合わせ方向は、図１の処理の際、各基板に加えられた磁力線の方向が、反平行となるようにした。この空セルに、メルク社製、ネマチック液晶、ＺＬＩ−２２９３を公知の方法で充填して液晶セルを得た。
【００４４】
このようにして、１０個の液晶セルを得た。
偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００４５】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、２３．２゜から２３．５゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。と言うよりも、このような高チルトは、従来のラビング法では不能と考えられている。
【００４６】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約６００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【００４７】
この液晶セル製作の全工程において、ゴミの発生は無い。これは、従来のラビング法と両極端をなすものである。また、全工程において、静電メーターで、基板表面の帯電を評価したところ、従来の工程のそれと比較して、発生する静電気の最大電圧値は、百分の一以下であった。
【００４８】
（実施例２）
実施例１とほぼ同様にして、液晶セルを製作した。ただし、図２において、基板１０の法線と磁力線のなす角を、約８０゜にした。かつ、有機溶剤洗浄を省略した。
【００４９】
図２に対応する処理をされたすべての基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００５０】
偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００５１】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、９．４゜から９．７゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【００５２】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約７００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【００５３】
（実施例３）
以下の点を除いて、実施例１とほぼ同様にして、液晶セルを製作した。
【００５４】
ただし、図１の基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、γ−グリシドキシプロピルトリエトキシシラン、品番ＫＢＥ４０３を、スピナーで塗布し、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【００５５】
つぎは、メソーゲン層の構成材料に係る。関東化学（株）から入手した低分子液晶、４−ｎ−プロピル−４’−シアノフェニルシクロヘキサン
【００５６】
【化１１】

【００５７】
を入手した。また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）、３３．３重量％と、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、３３．３重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【００５８】
（化１１）の低分子液晶を約７５重量％、前記混合物を約２５重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【００５９】
また、図２において、基板１０の法線と磁力線のなす角を、約８０゜にして処理した。かくて、基板上、少なくとも、一部重合した高分子層が得られた。図２に対応する処理のあと、ロータリーポンプを用いた減圧雰囲気内に、約１時間置いた。そのあとかつ、実施例１と同様の方法で、浸漬時間、約１分のエタノールを用いた有機溶剤洗浄を行った。この時、基板上に、残留した高分子層が得られた。
【００６０】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００６１】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００６２】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、９．５゜から９．７゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【００６３】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約７５０：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【００６４】
（実施例４）
以下の点を除いて、実施例１とほぼ同様にして、液晶セルを製作した。
【００６５】
ただし、図１の基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、γ−グリシドキシプロピルトリエトキシシラン、品番ＫＢＥ４０３を、スピナーで塗布し、約１００℃の熱処理を行い、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【００６６】
つぎは、メソーゲン層の構成材料に係る。メルク社から入手した２種の低分子液晶成分、４−ｎ−ペンタニル−４’−シアノビフェニル
【００６７】
【化１２】

【００６８】
、５９モル％と、４−ｎ−ペンタニル−４’−シアノビフェニル
【００６９】
【化１３】

【００７０】
、４１モル％の混合による低分子液晶を調合した。また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、５０重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【００７１】
（化１１）の低分子液晶を約７５重量％、前記混合物を約２５重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【００７２】
また、図２において、基板１０の法線と磁力線のなす角を、約８０゜にした。図２に対応する処理のあと、実施例１と同様の方法で、浸漬時間、約２分のアセトンを用いた有機溶剤洗浄を行った。
【００７３】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００７４】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００７５】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、９．３゜から９．５゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【００７６】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約７００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【００７７】
（実施例５）
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【００７８】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％のアルドリッチ・ケミカル・カンパニー製、ポリアクリロニトリル（ＰＡＮ）を溶解させたノーマルメチルピロリドン（ＮＭＰ）を約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約１００℃、３時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、１０ｎｍ程度である。
【００７９】
つぎに、大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−プロピル−シクロヘキシルベンゼン（化８）、４０重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）、４０重量％と、４−アクリルオイルオイル−４’−シアノビフェニール（化１０）、２０重量％の、混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【００８０】
この希釈液を、スピナーで、最初、１分、４００ＲＰＭの回転数で、さらに、約２分、１０００ＲＰＭの回転数で、さらに、約１分、１５００ＲＰＭの回転数でカップラー層４の上に塗布した。そのまま、しばらく風乾して、溶媒のアセトンを揮発させ、約２００ｎｍの厚みのメソーゲン層を得た。偏光顕微鏡観察によれば、このメソーゲン層は、液晶相を示していた。
【００８１】
次に、図３の構成断面図に示す装置で、重合性液晶性モノマーを配向させながら光重合させた。図３において、１１、１２は電磁石のポールであり、１３は対応する磁力線であり、１４は紫外線ランプ、１５は前述のメソーゲン層、１６は基板である。便宜上、図１の基板１と有極性有機樹脂層３を、図３では、基板１６とした。使用した、電磁石や、紫外線ランプは、実施例１と同様である。
【００８２】
まず、結果する液晶セルでの液晶分子の所望プレチルトや所望配向方向に対応して、メソーゲン層を有する基板１６を、磁力線１３に対して、傾けて、電磁石のポール１１、１２間に設置する。この実施例の場合、基板１６の法線と磁力線のなす角を、約８３゜にした。つぎに、磁束密度が約３５Ｋガウスとなるように、磁場を印加する。その状態で、紫外線ランプ１４を点灯、約３分間、紫外線を照射する。紫外線は、基板１６の裏から、基板を通して、メソーゲン層１５に照射される。かくして、少なくとも一部、重合した高分子層が得られた。
【００８３】
次に、アセトンに数分、浸漬をのみすることにより、有機溶剤洗浄を行った。結果、基板上、高分子層が一様に存在した。
【００８４】
この基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００８５】
公知の方法で、このような、一対の基板で、前記高分子層が対向するように、間隙を約１０ミクロンにした空セルを製作した。この時、上、下基板の貼り合わせ方向は、図１の処理の際、各基板に加えられた磁力線の方向が、反平行となるようにした。この空セルに、メルク社製、ネマチック液晶、ＺＬＩ−２２９３を公知の方法で充填して液晶セルを得た。
【００８６】
このようにして、１０個の液晶セルを得た。
偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００８７】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、６．５゜から６．８゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【００８８】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約６００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【００８９】
この液晶セル製作の全工程において、ゴミの発生は無い。これは、従来のラビング法と両極端をなすものである。また、全工程において、静電メーターで、基板表面の帯電を評価したところ、従来の工程のそれと比較して、発生する静電気の最大電圧値は、百分の一以下であった。
【００９０】
（実施例６）
以下の点以外は実施例５とほぼ同様にして、液晶セルを製作した。
【００９１】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【００９２】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％のアルドリッチ・ケミカル・カンパニー製、ナイロン６／６を溶解させたｍ−クレゾールを約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約１００℃、３時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、１０ｎｍ程度である。
【００９３】
つぎは、メソーゲン層の構成材料に係る。メルク社から入手した２種の低分子液晶成分、４−ｎ−ペンタニル−４’−シアノビフェニル（化１２）、５９モル％と、４−ｎ−ペンタニル−４’−シアノビフェニル（化１３）、４１モル％の混合による低分子液晶を調合した。また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、５０重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【００９４】
（化１１）の低分子液晶を約７５重量％、前記混合物を約２５重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【００９５】
また、図３において、基板１６の法線と磁力線のなす角を、約８５゜にした。図３に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約２分のアセトンを用いた有機溶剤洗浄を行った。
【００９６】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【００９７】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【００９８】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、５゜±０．１゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【００９９】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約７００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１００】
（実施例７）
以下の点以外は実施例５とほぼ同様にして、液晶セルを製作した。
【０１０１】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【０１０２】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％の窒素石油化学（株）製、ポリアミック酸を溶解させたノーマルメチルピロリドンを約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約２００℃、１時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５０ｎｍ程度である。
【０１０３】
つぎは、メソーゲン層の構成材料に係る。大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）と４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）の、それぞれ５０重量％の混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％と、アルドリッチ・ケミカル・カンパニー社から入手した紫外線吸収剤、４−（１−スルホニル−２−ヘキシル）−４’−（１−オキサ−６−ヘキサノル）−トランススチルベン（化６）を約１．５重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１０４】
また、図３において、基板１６の法線と磁力線のなす角を、約８５゜にした。図３に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約５分のアセトンを用いた有機溶剤洗浄を行った。
【０１０５】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１０６】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１０７】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、５゜±０．１゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１０８】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約７００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１０９】
（実施例８）
以下の点以外は実施例５とほぼ同様にして、液晶セルを製作した。
【０１１０】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３はカップラー層である。
【０１１１】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の ただし、図１の基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、γ−グリシドキシプロピルトリエトキシシラン、品番ＫＢＥ４０３を、スピナーで塗布し、約１００℃の熱処理を行い、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【０１１２】
つぎは、メソーゲン層の構成材料に係る。関東化学（株）から入手した低分子液晶、４−ｎ−プロピル−４’−シアノフェニルシクロヘキサン（化１１）を入手した。
【０１１３】
また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）、３３．３重量％と、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、３３．３重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【０１１４】
（化１１）の低分子液晶を約７０重量％、前記混合物を約３０重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％、アルドリッチ・ケミカル・カンパニー社から入手した紫外線吸収剤、４−（１−スルホニル−２−ヘキシル）−４’−（１−オキサ−６−ヘキサノル）−トランススチルベン（化６）を約１．５重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１１５】
また、図３において、基板１６の法線と磁力線のなす角を、約７５゜にした。図３に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約５分のアセトンを用いた有機溶剤洗浄を行った。
【０１１６】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１１７】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１１８】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、１３．６゜〜１３．８゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１１９】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約６４０：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１２０】
（実施例９）
以下の点以外は実施例８とほぼ同様にして、液晶セルを製作した。
【０１２１】
本実施例での、基板の状況を説明する。図１における、カップラー層または有極性有機樹脂層３を省略した。すなわち、図１において、コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめた基材の上に、メソーゲン層が直接、積層される。
【０１２２】
メソーゲン層の形成の前には、基材は、よく洗浄し、約１２０℃の乾燥後、時間をおかず、メソーゲン層の形成がなされる。
【０１２３】
実施例８と同様の評価を、図３に対応する処理後の基板や、液晶セルについて行ったが、良好な結果を得た。
【０１２４】
（実施例１０）
本実施例での、基板の状況を、構成断面図の形式で図１に示す。同図において、１は基板、２は基板主面、３はカップラー層、４は形成されたメソーゲン層である。
【０１２５】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、ビニルトリメトキシシラン、品番ＫＢＭ１００３を、スピナーで塗布し、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【０１２６】
つぎに、大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）と４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）の、それぞれ５０重量％の混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１２７】
この希釈液を、スピナーで、最初、１分、４００ＲＰＭの回転数で、さらに、約２分、１０００ＲＰＭの回転数で、さらに、約１分、１５００ＲＰＭの回転数でカップラー層４の上に塗布した。そのまま、しばらく風乾して、溶媒のアセトンを揮発させ、約３１０ｎｍの厚みのメソーゲン層を得た。偏光顕微鏡観察によれば、このメソーゲン層は、液晶相を示していた。
【０１２８】
次に、図４の構成断面図に示す装置で、重合性液晶性モノマーを配向させながら光重合させた。同図において、１７、１８は電磁石のポールであり、１９は対応する磁力線であり、２０は紫外線ランプ、２１は石英ガラス基板、２２はＩＴＯ電極層、２３はメソーゲン層、２４はＩＴＯ電極層、２５は基板、２６は、ＩＴＯ電極層２２と２４に電圧を印加するための電圧印加端子である。また、同図では明瞭には示さなかったが、ＩＴＯ電極層２２とメソーゲン層２３の間には、数１０ミクロン程度の、空気、ガス、または真空の間隙を設ける。これは、液晶用ガラス・スペーサーをスペーサーとして分散させることにより、なされた。便宜上、（図１）の基板１とカップラー層３を、図４では、基板２５とした。使用した、電磁石や、紫外線ランプは、実施例１と同様である。
【０１２９】
本実施例では、スペーサーとして、約３０ミクロン径のガラス・ファイバーを分散させた。
【０１３０】
まず、結果する液晶セルでの液晶分子の所望プレチルトや所望配向方向に対応して、メソーゲン層を有する基板２５を、磁力線１９に対して、傾けて、電磁石のポール１７、１８間に設置する。この実施例の場合、基板２５の法線と磁力線１９のなす角を、約６５゜にした。つぎに、電圧印加端子２６に、２ボルトの直流電圧を印加しつつ、磁束密度が約２５Ｋガウスとなるように、磁場を印加する。磁場強度はやや低めでよい。その状態で、紫外線ランプ２０を点灯、約４分間、紫外線を照射する。紫外線は、石英ガラス基板２１側から、これを通してメソゲン層に照射した。この処理の後、ＩＴＯ電極層２２付きの石英ガラス基板２１は分離された。得られたものは、ＩＴＯ電極層２４付きの基板２５の上に、処理され、少なくとも一部重合した高分子層を有するものである。
【０１３１】
次に、アセトンにこれを、数分、浸漬をのみすることにより、有機溶剤洗浄を行った。もちろん、基板３５上に付着したガラス・ファイバーはこの段階で洗い流された。結果、基板上、一様な高分子層が残留していた。
【０１３２】
この基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１３３】
公知の方法で、このような、一対の基板で、前記高分子層を対向させ、間隙を約１０ミクロンにした空セルを製作した。この時、上、下基板の貼り合わせ方向は、図１の処理の際、各基板に加えられた磁力線の方向が、反平行となるようにした。この空セルに、メルク社製、ネマチック液晶、ＺＬＩ−２２９３を公知の方法で充填して液晶セルを得た。
【０１３４】
このようにして、１０個の液晶セルを得た。
偏光顕微鏡で観察したところ、すべての液晶セルは期待通り、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１３５】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、２３．７゜から２３．８゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。と言うよりも、このような高チルトは、従来のラビング法では不能と考えられている。
【０１３６】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約４４０：１以上で極めて良好であった。前述のガラス・スペーサーに起因する高分子層の傷による光漏れにより、若干、レベルが下がるが、このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１３７】
（実施例１１）
実施例１０とほぼ同様にして、液晶セルを製作した。ただし、図４において、基板２５の法線と磁力線のなす角を、約８０゜にした。かつ、有機溶剤洗浄を省略した。
【０１３８】
図４に対応する処理をされたすべての基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１３９】
偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１４０】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、９．２゜から９．５゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１４１】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約４１０：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１４２】
（実施例１２）
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【０１４３】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％のアルドリッチ・ケミカル・カンパニー製、ポリアクリロニトリル（ＰＡＮ）を溶解させたノーマルメチルピロリドン（ＮＭＰ）を約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約１００℃、３時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、１０ｎｍ程度である。
【０１４４】
つぎに、大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−プロピル−シクロヘキシルベンゼン（化８）、４０重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）、４０重量％と、４−アクリルオイルオイル−４’−シアノビフェニール（化１０）、２０重量％の、混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１４５】
この希釈液を、スピナーで、最初、１分、４００ＲＰＭの回転数で、さらに、約２分、１０００ＲＰＭの回転数で、さらに、約１分、１５００ＲＰＭの回転数でカップラー層４の上に塗布した。そのまま、しばらく風乾して、溶媒のアセトンを揮発させ、約２００ｎｍの厚みのメソーゲン層を得た。偏光顕微鏡観察によれば、このメソーゲン層は、液晶相を示していた。
【０１４６】
次に、図５に示す構成断面図に示す装置で、重合性液晶性モノマーを配向させながら光重合させた。同図において、２７、２８は電磁石のポールであり、２９は対応する磁力線であり、３０は紫外線ランプ、３１は石英ガラス基板、３２はＩＴＯ電極層、３３はメソーゲン層、３４はＩＴＯ電極層、３５は基板、３６は、ＩＴＯ電極層３２と３４に電圧を印加するための電圧印加端子である。また、同図では明瞭には示さなかったが、ＩＴＯ電極層３２とメソーゲン層３３の間には、数１０ミクロン程度の、空気、ガス、または真空の間隙を設ける。これは、液晶用ガラス・スペーサーをスペーサーとして分散させることにより、なされた。便宜上、図１の基板１とカップラー層３を、図５では、基板３５とした。使用した、電磁石や、紫外線ランプは、実施例１と同様である。
【０１４７】
本実施例では、スペーサーとして、約３０ミクロン径のガラス・ファイバーを分散させた。
【０１４８】
まず、結果する液晶セルでの液晶分子の所望プレチルトや所望配向方向に対応して、メソーゲン層を有する基板３５を、磁力線２９に対して、傾けて、電磁石のポール２７、２８間に設置する。この実施例の場合、基板３５の法線と磁力線２９のなす角を、約８３゜にした。つぎに、電圧印加端子３６に、２ボルトの直流電圧を印加しつつ、磁束密度が約２５Ｋガウスとなるように、磁場を印加する。磁場強度はやや低めでよい。その状態で、紫外線ランプ３０を点灯、約４分間、紫外線を照射する。紫外線は、基板３５の裏面から、これを通してメソゲン層３３に照射した。この処理の後、ＩＴＯ電極層３２付きの石英ガラス基板３１は分離された。得られたものは、ＩＴＯ電極層３４付きの基板３５の上に、処理され、少なくとも一部重合した高分子層を有するものである。
【０１４９】
次に、アセトンにこれを、数分、浸漬をのみすることにより、有機溶剤洗浄を行った。もちろん、基板３５上に付着したガラス・ファイバーはこの段階で洗い流された。結果、基板上、一様な高分子層が残留していた。
【０１５０】
この基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１５１】
公知の方法で、このような、一対の基板で、前記高分子層を対向させ、間隙を約１０ミクロンにした空セルを製作した。この時、上、下基板の貼り合わせ方向は、図５の処理の際、各基板に加えられた磁力線の方向が、反平行となるようにした。この空セルに、メルク社製、ネマチック液晶、ＺＬＩ−２２９３を公知の方法で充填して液晶セルを得た。
【０１５２】
このようにして、１０個の液晶セルを得た。
偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１５３】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、６．７゜から６．８゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。と言うよりも、このような高チルトは、従来のラビング法では不能と考えられている。
【０１５４】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約４８０：１以上で極めて良好であった。前述のガラス・スペーサーに起因する高分子層の傷による光漏れにより、若干、レベルが下がるが、このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１５５】
（実施例１３）
以下の点以外は実施例１２とほぼ同様にして、液晶セルを製作した。
【０１５６】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【０１５７】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％のアルドリッチ・ケミカル・カンパニー製、ナイロン６／６を溶解させたｍ−クレゾールを約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約１００℃、３時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、１０ｎｍ程度である。
【０１５８】
つぎは、メソーゲン層の構成材料に係る。メルク社から入手した２種の低分子液晶成分、４−ｎ−ペンタニル−４’−シアノビフェニル（化１２）、５９モル％と、４−ｎ−ペンタニル−４’−シアノビフェニル（化１３）、４１モル％の混合による低分子液晶を調合した。また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、５０重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【０１５９】
（化１１）の低分子液晶を約７５重量％、前記混合物を約２５重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１６０】
また、図５において、基板３５の法線と磁力線のなす角を、約８５゜にした。図５に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約２分のアセトンを用いた有機溶剤洗浄を行った。
【０１６１】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１６２】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１６３】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、５゜±０．１゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１６４】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約５００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１６５】
（実施例１４）
以下の点以外は実施例１２とほぼ同様にして、液晶セルを製作した。
【０１６６】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３は有極性有機樹脂層である。
【０１６７】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の主面２に、約２重量％の窒素石油化学（株）製、ポリアミック酸を溶解させたノーマルメチルピロリドンを約３０００ＲＰＭ、３分の条件で、スピナーで塗布し、有極性有機樹脂層３を形成した。このあと、約２００℃、１時間、熱処理した。もちろん、この有機樹脂層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５０ｎｍ程度である。
【０１６８】
つぎは、メソーゲン層の構成材料に係る。大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）と４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）の、それぞれ５０重量％の混合物を入手した。この混合物は、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％と、アルドリッチ・ケミカル・カンパニー社から入手した紫外線吸収剤、４−（１−スルホニル−２−ヘキシル）−４’−（１−オキサ−６−ヘキサノル）−トランススチルベン（化６）を約１．５重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１６９】
また、図５において、基板３５の法線と磁力線のなす角を、約８５゜にした。図５に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約５分のアセトンを用いた有機溶剤洗浄を行った。
【０１７０】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１７１】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１７２】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、５゜±０．１゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１７３】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約５００：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１７４】
（実施例１５）
以下の点以外は実施例１２とほぼ同様にして、液晶セルを製作した。
【０１７５】
本実施例での、基板の状況を、構成断面図の形式で図１のようなものであり、この場合、３はカップラー層である。
【０１７６】
コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめたものを、基板１となした。基板１の ただし、（図１）基板１の主面２に、約４０００ＲＰＭ、３分の条件で、信越シリコーン（株）製、シランカップラー、γ−グリシドキシプロピルトリエトキシシラン、品番ＫＢＥ４０３を、スピナーで塗布し、約１００℃の熱処理を行い、カップラー層３を形成した。もちろん、このカップラー層３の厚みは、スローン（株）製、デクタック段差計でも、正確な測定が不能なほど、薄い。多分、５ｎｍ以下である。
【０１７７】
つぎは、メソーゲン層の構成材料に係る。関東化学（株）から入手した低分子液晶、４−ｎ−プロピル−４’−シアノフェニルシクロヘキサン（化１１）を入手した。
【０１７８】
また大日本インク（株）製、重合性液晶性モノマーである、４−アクリルオイルオイル−４’−ブチル−シクロヘキシルシクロヘキサン（化７）、３３．３重量％と、４−アクリルオイルオイル−４’−プロピルシクロヘキシルベンゼン（化８）、３３．３重量％と、４−アクリルオイルオイル−４’−ヘプチルジベンジリジン（化９）が残部であるところの混合物を入手した。
【０１７９】
（化１１）の低分子液晶を約７０重量％、前記混合物を約３０重量％になるような新たな混合物を調合した。これは、常温でネマチック液晶相を示す。これに、チバ・ガイギー（株）製、ベンゾフェノン系光重合開始剤、品番イルガキュア−６５１を、約１重量％、アルドリッチ・ケミカル・カンパニー社から入手した紫外線吸収剤、４−（１−スルホニル−２−ヘキシル）−４’−（１−オキサ−６−ヘキサノル）−トランススチルベン（化６）を約１．５重量％加え、メソーゲン物質とした。このメソーゲン物質を、アセトンで約２０倍に希釈して、希釈液を得た。
【０１８０】
また、図５において、基板３５の法線と磁力線のなす角を、約７５゜にした。図５に対応する処理のあと、実施例５と同様の方法で、浸漬時間、約５分のアセトンを用いた有機溶剤洗浄を行った。
【０１８１】
前記有機溶剤洗浄後の基板について、オーク製作所（株）製の微小複屈折計で面内の光学的リターデーション測定を行ったところ、リターデーションが存在することを確認した。
【０１８２】
完了した液晶セルについて、偏光顕微鏡で観察したところ、すべての液晶セルは期待どうり、各基板に加えられた磁力線の方向に、充填された液晶分子は配向していた。いわゆる、ユニフォーム配向をなしていた。
【０１８３】
プレチルト角は、磁場−容量法によった。測定されたプレチルト値は、１３．９゜〜１４．０゜の範囲に入っており、従来のラビング法に対応する、プレチルトのばらつきよりはるかに小さい。
【０１８４】
液晶分子の配向程度を光学的に精査するために、直交ニコル下でしかも入射側偏光板の偏光軸を充填された液晶分子の長軸に一致させて、透過光を観察したところ、黒の沈み込みは、すべての液晶セルで約５３０：１以上で極めて良好であった。このレベルは、従来のラビング法に対応する液晶セルの到達し得る最高レベルである。
【０１８５】
（実施例１６）
以下の点以外は実施例１２とほぼ同様にして、液晶セルを製作した。
【０１８６】
本実施例での、基板の状況を説明する。図１における、カップラー層または有極性有機樹脂層３を省略した。すなわち、図１において、コーニング製、品番７０５９、低アルカリガラスに錫を含む酸化インジウム透明電極（以後、ＩＴＯと称する）を沈積せしめた基材の上に、メソーゲン層が直接、積層される。
【０１８７】
メソーゲン層の形成の前には、基材は、よく洗浄し、約１２０℃の乾燥後、時間をおかず、メソーゲン層の形成がなされる。
【０１８８】
実施例１２と同様の評価を、図５に対応する処理後の基板や、液晶セルについて行ったが、良好な結果を得た。
【０１８９】
【発明の効果】
以上のように、主に液晶分子の配向法に係わるが、この技術は大きくは、高配向フィルムの生産にも係わり、これは新機能フィルムに結びつくように考えられ、産業上の価値は大である。
【図面の簡単な説明】
【図１】本発明の実施例を説明するための構成断面図
【図２】本発明の実施例を説明するための構成断面図
【図３】本発明の実施例を説明するための構成断面図
【図４】本発明の実施例を説明するための構成断面図
【図５】本発明の実施例を説明するための構成断面図
【符号の説明】
１ 基板
２ 基板主面
３ カップラー層
４ メソーゲン層
５，６ 電磁石のポール
７ 磁力線
８ 紫外線ランプ
９ メソーゲン層
１０ 基板
１１，１２ 電磁石のポール
１３ 磁力線
１４ 紫外線ランプ
１５ メソーゲン層
１６ 基板
１７，１８ 電磁石のポール
１９ 磁力線
２０ 紫外線ランプ
２１ 石英ガラス基板
２２ ＩＴＯ電極層
２３ メソーゲン層
２４ ＩＴＯ電極層
２５ 基板
２６ 電圧印加端子
２７，２８ 電磁石のポール
２９ 磁力線
３０ 紫外線ランプ
３１ 石英ガラス基板
３２ ＩＴＯ電極層
３３ メソーゲン層
３４ ＩＴＯ電極層
３５ 基板
３６ 電圧印加端子[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a liquid crystal cell relating to alignment of liquid crystal molecules.
[0002]
[Prior art]
Conventionally, an organic film, especially a polyimide film, having a thickness of several hundred nm is formed on a substrate by coating, and then rubbed with a high-speed fiber bundle. This is a so-called rubbing process. Thus, for example, the main chain of the polyimide film is stretched in the movement direction of the fiber bundle. This is a so-called orientation phenomenon of the polyimide film. When the polyimide main chain and the liquid crystal molecules come into contact with each other, the liquid crystal molecules are aligned by mutual interaction. For this reason, the oriented polyimide film is referred to as an oriented film. This area is detailed in Baifukan, “Liquid Crystal-Basics”, edited by Okano and Kobayashi.
[0003]
[Problems to be solved by the invention]
In the production of liquid crystal elements, only the rubbing method is applied. This rubbing method rubs the polyimide film at high speed, and inevitably involves more or less generation of dust. This is, for example, a display defect in the case of a liquid crystal display device, and is an event that should be avoided at all.
[0004]
In addition, in order to sufficiently perform the rubbing treatment on the polyimide film, it is necessary to considerably strongly rub. This may cause local destructive flaws in the polyimide film, possibly impairing the uniformity of the alignment of the liquid crystal molecules. In order to avoid this, strict control of the frictional state is required.
[0005]
Further, at the time of this rubbing, static electricity is possibly generated between the rubbing and the polyimide film. As a result, for example, in the case of an active matrix type liquid crystal display device, the thin film transistor may be broken.
[0006]
To overcome these weaknesses, some non-contact methods have been tried to cause the orientation phenomenon of the organic film on the substrate. A typical approach is an anisotropic polymerization of a polyvinyl cinnamate film with polarized ultraviolet light. This has succeeded in aligning the liquid crystal molecules. However, such a non-contact method is in a research and development stage, and has not been applied to production sites at all. One of the reasons is that the non-contact method has not succeeded in reproducibly expressing a pretilt of about 2 °.
[0007]
On the other hand, in the conventional rubbing method, as the alignment film material, we succeeded in expressing reproducible pretilt by devising the structure of the polyimide main chain or attaching an alkyl group or fluoroalkyl group to the side chain. I have.
[0008]
The expression of reproducible pretilt is an essential technique for stable alignment of liquid crystal molecules. In the current liquid crystal element, it is considered necessary to exhibit a pretilt at a predetermined angle of about 10 °.
[0009]
The present invention contemplates the successful expression of stable pretilt at any angle up to about 10 ° in a non-contact process.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention provides a method in which a mesogen layer composed of a photopolymerization initiator and a polymerizable liquid crystal monomer formed on a pair of substrate main surfaces is maintained at a predetermined temperature such that a mesogen layer is maintained in a liquid crystal state. Then, while applying a magnetic field in a desired direction independently or applying a magnetic field in a desired direction and applying an electric field in another desired direction, simultaneously applying ultraviolet rays to the substrate. A liquid crystal cell that irradiates and polymerizes the monomer to form a polymer layer, maintains a desired gap, faces the polymer layer, attaches the pair of substrates, and fills the gap with liquid crystal. Is a manufacturing method.
[0011]
Irradiation of the ultraviolet light may be performed by directly irradiating the mesogen layer. Alternatively, the substrate may be a substrate through which ultraviolet light can pass, and the ultraviolet light may be irradiated through the substrate. Further, in this manufacturing method, after the formation of the polymer layer, the main surface of the substrate is washed with an organic solvent, a desired gap is maintained, the polymer layer is opposed, and the pair of substrates are bonded to each other. A more desirable result was obtained when the liquid crystal was filled to complete the liquid crystal cell.
[0012]
The present invention further comprises maintaining the substrate at a predetermined temperature such that a mesogen layer formed of a low-molecular liquid crystal, a photopolymerization initiator, and a polymerizable liquid crystal monomer formed on a pair of substrate main surfaces is maintained in a liquid crystal state. Next, while applying a magnetic field in a desired direction independently, or while applying a magnetic field in a desired direction and applying an electric field in another desired direction, the substrate is irradiated with ultraviolet rays at the same time. Forming a polymer layer by polymerizing the monomers, washing the main surface of the substrate with an organic solvent, keeping a desired gap, facing the polymer layer, and bonding the pair of substrates together; A method of manufacturing a liquid crystal cell in which the gap is filled with liquid crystal will be clarified.
[0013]
Irradiation of the ultraviolet light may be performed by directly irradiating the mesogen layer. Alternatively, the substrate may be a substrate through which ultraviolet light can pass, and the ultraviolet light may be irradiated through the substrate. Further, using a volatile one as the low-molecular liquid crystal, after forming the polymer layer, performing a volatilization treatment of the low-molecular liquid crystal, lightly cleaning the substrate main surface with an organic solvent, maintaining a desired gap, Desirable results were obtained by laminating the pair of substrates with the polymer layers facing each other and filling the gap with liquid crystal to complete the liquid crystal cell. The volatilization refers to a heat treatment or a reduced pressure treatment.
[0014]
In order to solve the above-mentioned problems, the present invention maintains a mesogen layer composed of an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystal monomer formed on a pair of main surfaces of a substrate capable of transmitting ultraviolet light in a liquid crystal state. The substrate is kept at a predetermined temperature such that it can be dripped, and then a magnetic field in a desired direction is applied alone, or a magnetic field in a desired direction is applied and an electric field in another desired direction is applied in two. While irradiating the main surface of the substrate with ultraviolet light through the substrate at the same time, polymerizing the monomer to form a polymer layer, washing the main surface of the substrate with an organic solvent, maintaining a desired gap, A method of manufacturing a liquid crystal cell in which the pair of substrates are bonded together with the polymer layers facing each other and the gap is filled with liquid crystal will be clarified.
[0015]
Further, according to the present invention, a mesogen layer formed of a pair of low-molecular liquid crystal, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystalline monomer formed on a main surface of a substrate capable of transmitting a pair of ultraviolet light is maintained in a liquid crystal state. Keeping the substrate at such a predetermined temperature, and then applying a magnetic field in a desired direction alone, or applying a magnetic field in a desired direction and applying an electric field in another desired direction while two At the same time, the main surface of the substrate is irradiated with ultraviolet rays through the substrate to polymerize the monomer to form a polymer layer, and the main surface of the substrate is washed with an organic solvent, and a desired gap is maintained. A method for manufacturing a liquid crystal cell in which the pair of substrates are attached to each other with the layers facing each other and a liquid crystal is filled in the gap is provided.
[0016]
In the whole of the present invention, ultraviolet light has a wavelength that is effective for polymerization in a system comprising a photopolymerization initiator and a polymerizable liquid crystalline monomer in a mesogen layer. Usually, the ultraviolet light is preferably a discharge lamp for generating ultraviolet light. In order to further enhance the effect of the present invention, it is desirable that the light be pseudo-parallel ultraviolet light linearly polarized in a desired direction.
[0017]
It is very desirable that the extinction coefficient of the ultraviolet ray of the ultraviolet absorber be at least two orders of magnitude greater than that of the photopolymerization initiator. For example, as an ultraviolet absorber,
[0018]
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[0019]
However, the present invention is not limited to this.
In the whole of the present invention, it was effective to obtain a uniform and thin mesogen layer by forming the substrate as a flat plate whose main surface was covered with a coupler layer. In addition, it was effective to use a flat plate whose main surface was covered with a polar organic resin layer as a substrate for this purpose. For example, at least as a polymerizable liquid crystalline monomer,
[0020]
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[0021]
Embedded image

[0022]
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[0023]
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[0024]
However, the present invention is not limited to this.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for forming an alignment film for liquid crystal molecules by a non-contact method has advantages such as extremely low possibility of dust generation and extreme suppression of generation of static electricity which adversely affects a thin film transistor. However, expression of pretilt up to about 10 ° has not been successful. First, a brief description of the circumstances will be given here.
[0026]
First, in the case of visible light or ultraviolet light, even if the wavelength is short, it is about 2000 angstroms, which is about the same as the desired thickness of the liquid crystal alignment film. Even if these polarized light is used for the expression of the pretilt and oblique light is used to perform any interaction with the resin film, for example, polymerization, etc., the pretilt probably does not occur. Here, in order to exhibit the pretilt, the resin main chain constituting the liquid crystal alignment film is not parallel to the substrate, but is obliquely stacked on the substrate or corresponds to the pretilt to be developed. It is considered necessary to have a sharp inclination angle at the molecular level of the fine unevenness of the resin film to be formed. Of course, it is considered that even in such a state of the side chain of the resin, the pretilt is equally expressed. From such a discussion, it is considered that the wavelength needs to be about 100 Å or less in order to express the pretilt angle using polarized light or oblique light. This is the X-ray region and there are certain difficulties in implementing it.
[0027]
It has been found that low-molecular liquid crystals are oriented by a magnetic field due to the diamagnetism of the electron cloud in the ring portion of the liquid crystal molecules. Of course, it is a well-known fact that orientation is caused by an electric field due to induced polarization. Align the low-molecular liquid crystal with a pretilt in a unidirectional magnetic field or unidirectional electric field, then leave only the liquid crystal molecules adsorbed on the substrate wall, wash out most of the low-molecular liquid crystal, and form an alignment film. It is possible. As can be inferred from the results of the academic conference, when a liquid crystal cell is fabricated from this type of alignment film, the filled liquid crystal molecules do not have a pretilt, and are arranged parallel to the substrate wall near the substrate wall. That is, the liquid crystal molecules adsorbed on the substrate wall do not store the pretilt angle. That is, in order to store the pretilt, a more rigid structure corresponding to the desired pretilt is required on the substrate wall. Here is one of the starting points of the present invention.
[0028]
What happens when an electric or magnetic field is applied to a liquid in which liquid crystal molecules are diluted in an excessive solvent and the liquid crystal state is lost? At reasonable electric or magnetic field strength, the liquid crystal molecules did not align due to thermal motion. This is understood from the idea that the interaction between molecules in the liquid crystal state plays an essential role for this alignment effect.
[0029]
One of the essences of the present invention lies in stabilizing the memory of the orientation by polymerizing the liquid crystal monomer due to the above-mentioned more rigid structure. However, during the polymerization, there is always a sacrifice that part of the memory of the orientation is lost due to the rearrangement of the molecules.
[0030]
After polymerization by ultraviolet irradiation, treatment with an organic solvent to elute the surface layer of the polymer was effective in minimizing alignment unevenness in the case where a liquid crystal cell was prepared from this.
[0031]
Irradiation with ultraviolet light through the substrate seems to tend to increase the degree of polymerization only in the vicinity of the substrate wall, which also contributes to the reduction of the alignment unevenness of the liquid crystal cell. At this time, the treatment with an organic solvent is preferable because the resulting alignment film can be made to be considerably thin and uniform. Such an effect was further enhanced by mixing an ultraviolet absorbing dye. It should be noted that, when the absorption coefficient of ultraviolet light of the ultraviolet absorbing dye is larger than that of the photopolymerization initiator by two orders of magnitude or more, effective ultraviolet light seems to be limited to the vicinity of the substrate wall. As a result, the thickness of the completed alignment film for liquid crystal was considerably reduced.
[0032]
The method of irradiating and polymerizing ultraviolet rays while applying a voltage in addition to a magnetic field promotes the orientation of the organic molecules in the mesogen layer and solidifies the organic molecules with the ultraviolet rays. That is, the voltage gives a potential corresponding to the state immediately before the organic molecules move, and the strict control of the actual orientation direction of the organic molecules is, of course, performed by the magnetic field. This may save the required magnetic field strength.
[0033]
By applying a spinner coating to a mesogen layer by performing a coupler process on a glass substrate or the like, a uniform thin film can be formed. Further, it was easy to form a uniform thin film by coating a glass substrate or the like with a polar organic resin, for example, a polyimide resin, a polyparabanic acid resin, a polyacrylonitrile resin, or a polyamide resin, and forming a mesogen layer thereon.
[0034]
(Example 1)
The condition of the substrate in this embodiment is shown in FIG. 1 in the form of a configuration sectional view. In FIG. 1, 1 is a substrate, 2 is a substrate main surface, 3 is a coupler layer, and 4 is a formed mesogen layer.
[0035]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. A silane coupler, vinyltrimethoxysilane, product number KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd. was applied to the main surface 2 of the substrate 1 at a condition of about 4000 RPM for 3 minutes with a spinner to form a coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0036]
Next, 4-acrylic oil-4′-butyl-cyclohexylcyclohexane (Chem. 7) and 4-acrylic oil-4′-propylcyclohexylbenzene (polymerizable liquid crystal monomers, manufactured by Dainippon Ink and Chemicals, Inc.) A mixture of 50% by weight of each of the chemical formulas 8) was obtained. This mixture shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0037]
The diluent was first applied on the coupler layer 4 with a spinner at a rotation speed of 400 RPM for 1 minute, further at a rotation speed of 1000 RPM for about 2 minutes, and further at a rotation speed of 1500 RPM for about 1 minute. . As it was, it was air-dried for a while to evaporate the acetone as a solvent to obtain a mesogen layer having a thickness of about 310 nm. According to observation with a polarizing microscope, this mesogen layer showed a liquid crystal phase.
[0038]
Next, photopolymerization was performed while aligning the polymerizable liquid crystalline monomer using the apparatus shown in the sectional view of FIG. In the figure, reference numerals 5 and 6 denote poles of an electromagnet, reference numeral 7 denotes a corresponding line of magnetic force, reference numeral 8 denotes an ultraviolet lamp, reference numeral 9 denotes the mesogen layer described above, and reference numeral 10 denotes a substrate. For convenience, the substrate 1 and the coupler layer 3 in FIG. 1 are referred to as a substrate 10 in FIG.
[0039]
As the ultraviolet lamp 8, PL10 manufactured by Philips was used. This emitted ultraviolet light of 365 nm, and the distance from the substrate 10 was about 20 cm. The electromagnet is manufactured by Harvey Wells Corporation.
[0040]
First, the substrate 10 having the mesogen layer is placed between the poles 5 and 6 of the electromagnet so as to be inclined with respect to the magnetic force lines 7 in accordance with the desired pretilt and desired orientation direction of the liquid crystal molecules in the resultant liquid crystal cell. In the case of this embodiment, the angle between the normal line of the substrate 10 and the line of magnetic force was set to about 65 °. Next, a magnetic field is applied so that the magnetic flux density becomes about 30K Gauss. In this state, the ultraviolet lamp 8 is turned on, and ultraviolet light is irradiated for about 2 minutes. Ultraviolet light was directly applied to the mesogen layer. Thus, a polymerized polymer layer is obtained at least partially.
[0041]
Next, the organic solvent was washed by immersing only in acetone for several minutes. As a result, the polymer layer remains on the substrate.
[0042]
The substrate was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0043]
By a known method, an empty cell having a gap of about 10 microns was manufactured by facing the residual polymer layer with such a pair of substrates. At this time, the bonding directions of the upper and lower substrates were set so that the directions of the lines of magnetic force applied to the respective substrates in the process of FIG. 1 were antiparallel. The empty cell was filled with a nematic liquid crystal (manufactured by Merck) and ZLI-2293 by a known method to obtain a liquid crystal cell.
[0044]
Thus, ten liquid crystal cells were obtained.
Observation with a polarizing microscope revealed that all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0045]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values fall in the range of 23.2 ° to 23.5 °, much smaller than the pretilt variation corresponding to the conventional rubbing method. Rather, such a high tilt is considered impossible with the conventional rubbing method.
[0046]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 600: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0047]
No dust is generated in all the steps of manufacturing the liquid crystal cell. This is the extreme of the conventional rubbing method. In addition, when the charge on the substrate surface was evaluated by an electrostatic meter in all the processes, the maximum voltage value of the generated static electricity was 1/100 or less as compared with that in the conventional process.
[0048]
(Example 2)
A liquid crystal cell was manufactured in substantially the same manner as in Example 1. However, in FIG. 2, the angle between the normal line of the substrate 10 and the line of magnetic force was set to about 80 °. In addition, the organic solvent cleaning was omitted.
[0049]
The in-plane optical retardation measurement was performed on all the substrates treated in accordance with FIG. 2 with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0050]
Observation with a polarizing microscope revealed that all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0051]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values fall in the range of 9.4 ° to 9.7 °, much less than the pretilt variation corresponding to the conventional rubbing method.
[0052]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 700: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0053]
(Example 3)
A liquid crystal cell was manufactured in substantially the same manner as in Example 1 except for the following points.
[0054]
However, the main surface 2 of the substrate 1 of FIG. 1 was coated with a silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403, manufactured by Shin-Etsu Silicone Co., Ltd., at about 4000 RPM for 3 minutes using a spinner. Then, a coupler layer 3 was formed. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0055]
The following relates to the constituent material of the mesogen layer. Low molecular liquid crystal obtained from Kanto Chemical Co., Ltd., 4-n-propyl-4'-cyanophenylcyclohexane
[0056]
Embedded image

[0057]
Was obtained. Also, 43.3% by weight of 4-acryloyl oil-4′-butyl-cyclohexylcyclohexane (Chem. 7), a polymerizable liquid crystalline monomer, manufactured by Dainippon Ink and Co., Ltd., and 4-acrylic oil-4 ′ A mixture of -propylcyclohexylbenzene (Chemical formula 8), 33.3% by weight, and 4-acryloyl oil-4'-heptyldibenzylidine (Chemical formula 9) as a balance was obtained.
[0058]
A new mixture was prepared so that the low-molecular liquid crystal of formula (11) was about 75% by weight and the above mixture was about 25% by weight. It shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0059]
In FIG. 2, the angle between the normal line of the substrate 10 and the line of magnetic force was about 80 °. Thus, at least a partially polymerized polymer layer was obtained on the substrate. After the treatment corresponding to FIG. 2, the substrate was placed in a reduced pressure atmosphere using a rotary pump for about one hour. After that, in the same manner as in Example 1, the organic solvent was washed using ethanol for about 1 minute for the immersion time. At this time, a residual polymer layer was obtained on the substrate.
[0060]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0061]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0062]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values are in the range of 9.5 ° to 9.7 °, much less than the pretilt variation corresponding to the conventional rubbing method.
[0063]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 750: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0064]
(Example 4)
A liquid crystal cell was manufactured in substantially the same manner as in Example 1 except for the following points.
[0065]
However, the main surface 2 of the substrate 1 of FIG. 1 is coated with a silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403, manufactured by Shin-Etsu Silicone Co., Ltd. with a spinner at about 4000 RPM for 3 minutes. A heat treatment at about 100 ° C. was performed to form the coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0066]
The following relates to the constituent material of the mesogen layer. Two low molecular liquid crystal components obtained from Merck, 4-n-pentanyl-4'-cyanobiphenyl
[0067]
Embedded image

[0068]
, 59 mol%, and 4-n-pentanyl-4′-cyanobiphenyl
[0069]
Embedded image

[0070]
, 41 mol% was mixed to prepare a low molecular liquid crystal. Also, 50% by weight of 4-acryloyl oil-4′-propylcyclohexylbenzene (Chem. 8), a polymerizable liquid crystal monomer, manufactured by Dainippon Ink Co., Ltd., and 4-acrylic oil-4′-heptyldiene A mixture was obtained in which benzylidine (Chem. 9) was the balance.
[0071]
A new mixture was prepared so that the low-molecular liquid crystal of formula (11) was about 75% by weight and the above mixture was about 25% by weight. It shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0072]
In FIG. 2, the angle between the normal line of the substrate 10 and the line of magnetic force was set to about 80 °. After the treatment corresponding to FIG. 2, in the same manner as in Example 1, the organic solvent was washed with acetone for about 2 minutes in an immersion time.
[0073]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0074]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0075]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values are in the range of 9.3 ° to 9.5 °, much less than the pretilt variation corresponding to the conventional rubbing method.
[0076]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 700: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0077]
(Example 5)
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0078]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. On the main surface 2 of the substrate 1, about 2% by weight of normal methylpyrrolidone (NMP) in which polyacrylonitrile (PAN) dissolved by Aldrich Chemical Company is applied at about 3000 RPM for 3 minutes with a spinner, The polar organic resin layer 3 was formed. Thereafter, heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 10 nm.
[0079]
Next, 40% by weight of 4-acrylic oil-4'-propyl-cyclohexylbenzene (Chem. 8), a polymerizable liquid crystalline monomer, manufactured by Dainippon Ink and Co., Ltd., and 4-acrylic oil-4 ' A mixture of heptyl dibenzylidine (Chem. 9), 40% by weight, and 4-acrylic oil-4'-cyanobiphenyl (Chem. 10), 20% by weight was obtained. This mixture shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0080]
The diluent was first applied on the coupler layer 4 with a spinner at a rotation speed of 400 RPM for 1 minute, further at a rotation speed of 1000 RPM for about 2 minutes, and further at a rotation speed of 1500 RPM for about 1 minute. . As it was, it was air-dried for a while to evaporate the acetone as a solvent to obtain a mesogen layer having a thickness of about 200 nm. According to observation with a polarizing microscope, this mesogen layer showed a liquid crystal phase.
[0081]
Next, photopolymerization was performed while aligning the polymerizable liquid crystalline monomer using the apparatus shown in the sectional view of FIG. In FIG. 3, reference numerals 11 and 12 denote electromagnet poles, reference numeral 13 denotes corresponding lines of magnetic force, reference numeral 14 denotes an ultraviolet lamp, reference numeral 15 denotes a mesogen layer described above, and reference numeral 16 denotes a substrate. For convenience, the substrate 1 and the polar organic resin layer 3 in FIG. 1 are referred to as a substrate 16 in FIG. The used electromagnets and ultraviolet lamps are the same as in the first embodiment.
[0082]
First, a substrate 16 having a mesogen layer is disposed between the poles 11 and 12 of the electromagnet at an angle with respect to the lines of magnetic force 13 in accordance with the desired pretilt and desired orientation direction of the liquid crystal molecules in the resulting liquid crystal cell. In the case of this embodiment, the angle between the normal line of the substrate 16 and the line of magnetic force was set to about 83 °. Next, a magnetic field is applied so that the magnetic flux density becomes about 35K Gauss. In this state, the ultraviolet lamp 14 is turned on, and ultraviolet light is irradiated for about 3 minutes. Ultraviolet rays are applied to the mesogen layer 15 from behind the substrate 16 through the substrate. Thus, at least a part of the polymerized polymer layer was obtained.
[0083]
Next, the organic solvent was washed by immersing only in acetone for several minutes. As a result, the polymer layer was uniformly present on the substrate.
[0084]
The substrate was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0085]
By a known method, an empty cell having a gap of about 10 microns was manufactured using such a pair of substrates so that the polymer layers face each other. At this time, the bonding directions of the upper and lower substrates were set so that the directions of the lines of magnetic force applied to the respective substrates in the process of FIG. 1 were antiparallel. The empty cell was filled with a nematic liquid crystal (manufactured by Merck) and ZLI-2293 by a known method to obtain a liquid crystal cell.
[0086]
Thus, ten liquid crystal cells were obtained.
Observation with a polarizing microscope revealed that all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0087]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values fall in the range 6.5 ° to 6.8 °, much less than the pretilt variation corresponding to the conventional rubbing method.
[0088]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 600: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0089]
No dust is generated in all the steps of manufacturing the liquid crystal cell. This is the extreme of the conventional rubbing method. In addition, when the charge on the substrate surface was evaluated by an electrostatic meter in all the processes, the maximum voltage value of the generated static electricity was 1/100 or less as compared with that in the conventional process.
[0090]
(Example 6)
A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.
[0091]
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0092]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. On the main surface 2 of the substrate 1, about 2% by weight of m-cresol made of Aldrich Chemical Company and nylon 6/6 dissolved is applied by a spinner at about 3000 RPM for 3 minutes using a polar organic resin. Layer 3 was formed. Thereafter, heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 10 nm.
[0093]
The following relates to the constituent material of the mesogen layer. Two low molecular liquid crystal components obtained from Merck, 4-n-pentanyl-4′-cyanobiphenyl (Chem. 12), 59 mol%, and 4-n-pentanyl-4′-cyanobiphenyl (Chem. 13); A low-molecular liquid crystal was prepared by mixing 41 mol%. Also, 50% by weight of 4-acryloyl oil-4′-propylcyclohexylbenzene (Chem. 8), a polymerizable liquid crystal monomer, manufactured by Dainippon Ink Co., Ltd., and 4-acrylic oil-4′-heptyldiene A mixture was obtained in which benzylidine (Chem. 9) was the balance.
[0094]
A new mixture was prepared so that the low-molecular liquid crystal of formula (11) was about 75% by weight and the above mixture was about 25% by weight. It shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0095]
In FIG. 3, the angle between the normal line of the substrate 16 and the line of magnetic force was set to about 85 °. After the treatment corresponding to FIG. 3, in the same manner as in Example 5, the organic solvent was washed with acetone for about 2 minutes in an immersion time.
[0096]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0097]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0098]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 5 ± 0.1 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0099]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 700: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0100]
(Example 7)
A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.
[0101]
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0102]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. The main surface 2 of the substrate 1 is coated with a normal methylpyrrolidone in which about 2% by weight of Nitrogen Petrochemical Co., Ltd., dissolved in polyamic acid, at about 3000 RPM for 3 minutes using a spinner to form a polar organic resin layer. 3 was formed. Thereafter, heat treatment was performed at about 200 ° C. for 1 hour. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 50 nm.
[0103]
The following relates to the constituent material of the mesogen layer. 4-acrylic oil-4'-butyl-cyclohexylcyclohexane (Chem. 7) and 4-acrylic oil-4'-propylcyclohexylbenzene (Chem. 8), which are polymerizable liquid crystalline monomers manufactured by Dainippon Ink and Chemicals, Inc. In each case 50% by weight of a mixture were obtained. This mixture shows a nematic liquid crystal phase at room temperature. About 1% by weight of a benzophenone-based photopolymerization initiator (product number: Irgacure-651, manufactured by Ciba Geigy KK) and an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl- About 1.5% by weight of 2-hexyl) -4 ′-(1-oxa-6-hexanol) -transstilbene (Formula 6) was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0104]
In FIG. 3, the angle between the normal line of the substrate 16 and the line of magnetic force was set to about 85 °. After the treatment corresponding to FIG. 3, in the same manner as in Example 5, the organic solvent was washed with acetone using an immersion time of about 5 minutes.
[0105]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0106]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0107]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 5 ± 0.1 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0108]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 700: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0109]
(Example 8)
A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.
[0110]
In this embodiment, the situation of the substrate is as shown in FIG. 1 in the form of a structural sectional view. In this case, reference numeral 3 denotes a coupler layer.
[0111]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. On the main surface 2 of the substrate 1 shown in FIG. 1, a silane coupler, γ-glycidoxypropyltriethoxysilane, and a product number KBE403 manufactured by Shin-Etsu Silicone Co., Ltd. And a heat treatment at about 100 ° C. was performed to form the coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0112]
The following relates to the constituent material of the mesogen layer. A low molecular liquid crystal, 4-n-propyl-4'-cyanophenylcyclohexane (Chemical Formula 11), obtained from Kanto Chemical Co., Ltd. was obtained.
[0113]
Also, 43.3% by weight of 4-acryloyl oil-4′-butyl-cyclohexylcyclohexane (Chem. 7), a polymerizable liquid crystalline monomer, manufactured by Dainippon Ink and Co., Ltd., and 4-acrylic oil-4 ′ A mixture of -propylcyclohexylbenzene (Chemical formula 8), 33.3% by weight, and 4-acryloyl oil-4'-heptyldibenzylidine (Chemical formula 9) as a balance was obtained.
[0114]
A new mixture was prepared so that the low-molecular liquid crystal of the formula (11) was about 70% by weight and the above mixture was about 30% by weight. It shows a nematic liquid crystal phase at room temperature. About 1% by weight of a benzophenone-based photopolymerization initiator manufactured by Ciba Geigy Co., Ltd., Irgacure-651, an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl-2) -Hexyl) -4 '-(1-oxa-6-hexanol) -transstilbene (Formula 6) was added at about 1.5% by weight to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0115]
In FIG. 3, the angle between the normal line of the substrate 16 and the line of magnetic force was set to about 75 °. After the treatment corresponding to FIG. 3, in the same manner as in Example 5, the organic solvent was washed with acetone using an immersion time of about 5 minutes.
[0116]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0117]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0118]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 13.6 ° to 13.8 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0119]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 640: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0120]
(Example 9)
A liquid crystal cell was manufactured in substantially the same manner as in Example 8, except for the following points.
[0121]
The situation of the substrate in this embodiment will be described. In FIG. 1, the coupler layer or the polar organic resin layer 3 is omitted. That is, in FIG. 1, a mesogen layer is directly laminated on a substrate made of Corning, product number 7059, on which a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) is deposited on low alkali glass.
[0122]
Prior to the formation of the mesogen layer, the substrate is thoroughly washed, and after drying at about 120 ° C., the formation of the mesogen layer is performed in a short time.
[0123]
The same evaluation as in Example 8 was performed on the processed substrate and the liquid crystal cell corresponding to FIG. 3, and good results were obtained.
[0124]
(Example 10)
The condition of the substrate in this embodiment is shown in FIG. 1 in the form of a configuration sectional view. In the figure, 1 is a substrate, 2 is a main surface of the substrate, 3 is a coupler layer, and 4 is a formed mesogen layer.
[0125]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. A silane coupler, vinyltrimethoxysilane, product number KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd. was applied to the main surface 2 of the substrate 1 at a condition of about 4000 RPM for 3 minutes with a spinner to form a coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0126]
Next, 4-acrylic oil-4′-butyl-cyclohexylcyclohexane (Chem. 7) and 4-acrylic oil-4′-propylcyclohexylbenzene (polymerizable liquid crystal monomers, manufactured by Dainippon Ink and Chemicals, Inc.) A mixture of 50% by weight of each of the chemical formulas 8) was obtained. This mixture shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0127]
The diluent was first applied on the coupler layer 4 with a spinner at a rotation speed of 400 RPM for 1 minute, further at a rotation speed of 1000 RPM for about 2 minutes, and further at a rotation speed of 1500 RPM for about 1 minute. . As it was, it was air-dried for a while to evaporate the acetone as a solvent to obtain a mesogen layer having a thickness of about 310 nm. According to observation with a polarizing microscope, this mesogen layer showed a liquid crystal phase.
[0128]
Next, photopolymerization was performed while aligning the polymerizable liquid crystalline monomer using the apparatus shown in the sectional view of FIG. In the figure, 17 and 18 are poles of an electromagnet, 19 is a corresponding magnetic field line, 20 is an ultraviolet lamp, 21 is a quartz glass substrate, 22 is an ITO electrode layer, 23 is a mesogen layer, 24 is an ITO electrode layer, Reference numeral 25 denotes a substrate; and 26, a voltage application terminal for applying a voltage to the ITO electrode layers 22 and 24. Although not clearly shown in the figure, an air, gas, or vacuum gap of about several tens of microns is provided between the ITO electrode layer 22 and the mesogen layer 23. This was achieved by dispersing the glass spacers for the liquid crystal as spacers. For convenience, the substrate 1 and the coupler layer 3 (FIG. 1) were used as the substrate 25 in FIG. The used electromagnets and ultraviolet lamps are the same as in the first embodiment.
[0129]
In this example, glass fibers having a diameter of about 30 microns were dispersed as spacers.
[0130]
First, a substrate 25 having a mesogen layer is disposed between the poles 17 and 18 of the electromagnet at an angle with respect to the lines of magnetic force 19 in accordance with the desired pretilt and desired orientation direction of the liquid crystal molecules in the resultant liquid crystal cell. In the case of this embodiment, the angle between the normal line of the substrate 25 and the line of magnetic force 19 was set to about 65 °. Next, while applying a DC voltage of 2 volts to the voltage application terminal 26, a magnetic field is applied so that the magnetic flux density becomes about 25K gauss. The magnetic field strength may be slightly lower. In this state, the ultraviolet lamp 20 is turned on, and ultraviolet light is irradiated for about 4 minutes. Ultraviolet rays were applied to the mesogen layer from the quartz glass substrate 21 side. After this treatment, the quartz glass substrate 21 with the ITO electrode layer 22 was separated. The obtained one has a polymer layer which has been treated and at least partially polymerized on a substrate 25 having an ITO electrode layer 24.
[0131]
Next, this was immersed in acetone for a few minutes to wash the organic solvent. Of course, the glass fibers deposited on the substrate 35 were washed away at this stage. As a result, a uniform polymer layer remained on the substrate.
[0132]
The substrate was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0133]
By a known method, an empty cell in which the gap was reduced to about 10 microns was manufactured by facing the polymer layer between a pair of substrates. At this time, the bonding directions of the upper and lower substrates were set so that the directions of the lines of magnetic force applied to the respective substrates in the process of FIG. 1 were antiparallel. The empty cell was filled with a nematic liquid crystal (manufactured by Merck) and ZLI-2293 by a known method to obtain a liquid crystal cell.
[0134]
Thus, ten liquid crystal cells were obtained.
Observation with a polarizing microscope revealed that all the liquid crystal cells had the filled liquid crystal molecules oriented in the direction of the lines of magnetic force applied to each substrate, as expected. What was called a uniform orientation.
[0135]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values are in the range of 23.7 ° to 23.8 °, much less than the pretilt variation corresponding to the conventional rubbing method. Rather, such a high tilt is considered impossible with the conventional rubbing method.
[0136]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 440: 1 or more in all the liquid crystal cells. Although the level slightly decreases due to the light leakage due to the damage of the polymer layer caused by the glass spacer described above, this level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.
[0137]
(Example 11)
A liquid crystal cell was manufactured in substantially the same manner as in Example 10. However, in FIG. 4, the angle between the normal line of the substrate 25 and the line of magnetic force was set to about 80 °. In addition, the organic solvent cleaning was omitted.
[0138]
The in-plane optical retardation measurement was performed on all the substrates treated in accordance with FIG. 4 with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0139]
Observation with a polarizing microscope revealed that all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0140]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values fall in the range of 9.2 ° to 9.5 °, much less than the pretilt variation corresponding to the conventional rubbing method.
[0141]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was very good at about 410: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0142]
(Example 12)
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0143]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. On the main surface 2 of the substrate 1, about 2% by weight of normal methylpyrrolidone (NMP) in which polyacrylonitrile (PAN) dissolved by Aldrich Chemical Company is applied at about 3000 RPM for 3 minutes with a spinner, The polar organic resin layer 3 was formed. Thereafter, heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 10 nm.
[0144]
Next, 40% by weight of 4-acrylic oil-4'-propyl-cyclohexylbenzene (Chem. 8), a polymerizable liquid crystalline monomer, manufactured by Dainippon Ink and Co., Ltd., and 4-acrylic oil-4 ' A mixture of heptyl dibenzylidine (Chem. 9), 40% by weight, and 4-acrylic oil-4'-cyanobiphenyl (Chem. 10), 20% by weight was obtained. This mixture shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0145]
The diluent was first applied on the coupler layer 4 with a spinner at a rotation speed of 400 RPM for 1 minute, further at a rotation speed of 1000 RPM for about 2 minutes, and further at a rotation speed of 1500 RPM for about 1 minute. . As it was, it was air-dried for a while to evaporate the acetone as a solvent to obtain a mesogen layer having a thickness of about 200 nm. According to observation with a polarizing microscope, this mesogen layer showed a liquid crystal phase.
[0146]
Next, photopolymerization was performed while aligning the polymerizable liquid crystalline monomer with the apparatus shown in the sectional view of the configuration shown in FIG. In the same figure, 27 and 28 are poles of an electromagnet, 29 is a corresponding line of magnetic force, 30 is an ultraviolet lamp, 31 is a quartz glass substrate, 32 is an ITO electrode layer, 33 is a mesogen layer, 34 is an ITO electrode layer, Reference numeral 35 denotes a substrate, and 36 denotes a voltage application terminal for applying a voltage to the ITO electrode layers 32 and 34. Although not clearly shown in the figure, an air, gas, or vacuum gap of about several tens of microns is provided between the ITO electrode layer 32 and the mesogen layer 33. This was achieved by dispersing the glass spacers for the liquid crystal as spacers. For convenience, the substrate 1 and the coupler layer 3 in FIG. 1 are used as the substrate 35 in FIG. The used electromagnets and ultraviolet lamps are the same as in the first embodiment.
[0147]
In this example, glass fibers having a diameter of about 30 microns were dispersed as spacers.
[0148]
First, a substrate 35 having a mesogen layer is disposed between the poles 27 and 28 of the electromagnet so as to be inclined with respect to the lines of magnetic force 29 in accordance with the desired pretilt and desired orientation direction of the liquid crystal molecules in the resultant liquid crystal cell. In the case of this embodiment, the angle between the normal line of the substrate 35 and the magnetic force lines 29 was set to about 83 °. Next, while applying a DC voltage of 2 volts to the voltage application terminal 36, a magnetic field is applied so that the magnetic flux density becomes about 25K Gauss. The magnetic field strength may be slightly lower. In this state, the ultraviolet lamp 30 is turned on, and ultraviolet light is irradiated for about 4 minutes. Ultraviolet light was applied to the mesogen layer 33 from the back surface of the substrate 35 through it. After this treatment, the quartz glass substrate 31 with the ITO electrode layer 32 was separated. The obtained one has a polymer layer that has been treated and at least partially polymerized on a substrate 35 with an ITO electrode layer 34.
[0149]
Next, this was immersed in acetone for a few minutes to wash the organic solvent. Of course, the glass fibers deposited on the substrate 35 were washed away at this stage. As a result, a uniform polymer layer remained on the substrate.
[0150]
The substrate was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0151]
By a known method, an empty cell in which the gap was reduced to about 10 microns was manufactured by facing the polymer layer between a pair of substrates. At this time, the bonding directions of the upper and lower substrates were set so that the directions of the lines of magnetic force applied to the respective substrates in the processing of FIG. 5 were antiparallel. The empty cell was filled with a nematic liquid crystal (manufactured by Merck) and ZLI-2293 by a known method to obtain a liquid crystal cell.
[0152]
Thus, ten liquid crystal cells were obtained.
Observation with a polarizing microscope revealed that all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0153]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt values are in the range of 6.7 ° to 6.8 °, much less than the pretilt variation corresponding to the conventional rubbing method. Rather, such a high tilt is considered impossible with the conventional rubbing method.
[0154]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 480: 1 or more in all the liquid crystal cells. Although the level slightly decreases due to the light leakage due to the damage of the polymer layer caused by the glass spacer described above, this level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.
[0155]
(Example 13)
A liquid crystal cell was manufactured in substantially the same manner as in Example 12 except for the following points.
[0156]
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0157]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. On the main surface 2 of the substrate 1, about 2% by weight of m-cresol made of Aldrich Chemical Company and nylon 6/6 dissolved is applied by a spinner at about 3000 RPM for 3 minutes using a polar organic resin. Layer 3 was formed. Thereafter, heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 10 nm.
[0158]
The following relates to the constituent material of the mesogen layer. Two low molecular liquid crystal components obtained from Merck, 4-n-pentanyl-4′-cyanobiphenyl (Chem. 12), 59 mol%, and 4-n-pentanyl-4′-cyanobiphenyl (Chem. 13); A low-molecular liquid crystal was prepared by mixing 41 mol%. Also, 50% by weight of 4-acryloyl oil-4′-propylcyclohexylbenzene (Chem. 8), a polymerizable liquid crystal monomer, manufactured by Dainippon Ink Co., Ltd., and 4-acrylic oil-4′-heptyldiene A mixture was obtained in which benzylidine (Chem. 9) was the balance.
[0159]
A new mixture was prepared so that the low-molecular liquid crystal of formula (11) was about 75% by weight and the above mixture was about 25% by weight. It shows a nematic liquid crystal phase at room temperature. To this, about 1% by weight of a benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba-Geigy Corporation was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0160]
In FIG. 5, the angle between the normal line of the substrate 35 and the line of magnetic force was set to about 85 °. After the treatment corresponding to FIG. 5, in the same manner as in Example 5, the organic solvent was washed with acetone for about 2 minutes in an immersion time.
[0161]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0162]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0163]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 5 ± 0.1 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0164]
In order to optically inspect the degree of alignment of the liquid crystal molecules, the transmitted light was observed under orthogonal Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 500: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0165]
(Example 14)
A liquid crystal cell was manufactured in substantially the same manner as in Example 12 except for the following points.
[0166]
The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural sectional view, and in this case, 3 is a polar organic resin layer.
[0167]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. The main surface 2 of the substrate 1 is coated with a normal methylpyrrolidone in which about 2% by weight of Nitrogen Petrochemical Co., Ltd., dissolved in polyamic acid, at about 3000 RPM for 3 minutes using a spinner to form a polar organic resin layer. 3 was formed. Thereafter, heat treatment was performed at about 200 ° C. for 1 hour. Of course, the thickness of the organic resin layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Probably about 50 nm.
[0168]
The following relates to the constituent material of the mesogen layer. 4-acrylic oil-4'-butyl-cyclohexylcyclohexane (Chem. 7) and 4-acrylic oil-4'-propylcyclohexylbenzene (Chem. 8), which are polymerizable liquid crystalline monomers manufactured by Dainippon Ink and Chemicals, Inc. In each case 50% by weight of a mixture were obtained. This mixture shows a nematic liquid crystal phase at room temperature. About 1% by weight of a benzophenone-based photopolymerization initiator (product number: Irgacure-651, manufactured by Ciba Geigy KK) and an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl- About 1.5% by weight of 2-hexyl) -4 ′-(1-oxa-6-hexanol) -transstilbene (Formula 6) was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0169]
In FIG. 5, the angle between the normal line of the substrate 35 and the line of magnetic force was set to about 85 °. After the treatment corresponding to FIG. 5, in the same manner as in Example 5, the organic solvent was washed using acetone for about 5 minutes with immersion time.
[0170]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0171]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0172]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 5 ± 0.1 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0173]
In order to optically inspect the degree of alignment of the liquid crystal molecules, the transmitted light was observed under orthogonal Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was extremely good at about 500: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0174]
(Example 15)
A liquid crystal cell was manufactured in substantially the same manner as in Example 12 except for the following points.
[0175]
In this embodiment, the situation of the substrate is as shown in FIG. 1 in the form of a structural sectional view. In this case, reference numeral 3 denotes a coupler layer.
[0176]
A substrate 1 was prepared by depositing a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) on a low alkali glass manufactured by Corning, product number 7059. However, on the main surface 2 of the substrate 1 (FIG. 1), a silane coupler, γ-glycidoxypropyltriethoxysilane, and a product number KBE403 manufactured by Shin-Etsu Silicone Co., Ltd. Coating was performed with a spinner and heat treatment was performed at about 100 ° C. to form a coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that accurate measurement is not possible even with a DECTAC step gauge manufactured by Sloan Co., Ltd. Maybe less than 5 nm.
[0177]
The following relates to the constituent material of the mesogen layer. A low molecular liquid crystal, 4-n-propyl-4'-cyanophenylcyclohexane (Chemical Formula 11), obtained from Kanto Chemical Co., Ltd. was obtained.
[0178]
Also, 43.3% by weight of 4-acryloyl oil-4′-butyl-cyclohexylcyclohexane (Chem. 7), a polymerizable liquid crystalline monomer, manufactured by Dainippon Ink and Co., Ltd., and 4-acrylic oil-4 ′ A mixture of -propylcyclohexylbenzene (Chemical formula 8), 33.3% by weight, and 4-acryloyl oil-4'-heptyldibenzylidine (Chemical formula 9) as a balance was obtained.
[0179]
A new mixture was prepared so that the low-molecular liquid crystal of the formula (11) was about 70% by weight and the above mixture was about 30% by weight. It shows a nematic liquid crystal phase at room temperature. About 1% by weight of a benzophenone-based photopolymerization initiator manufactured by Ciba Geigy Co., Ltd., Irgacure-651, an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl-2) -Hexyl) -4 '-(1-oxa-6-hexanol) -transstilbene (Formula 6) was added at about 1.5% by weight to obtain a mesogenic substance. This mesogenic substance was diluted about 20-fold with acetone to obtain a diluted solution.
[0180]
In FIG. 5, the angle between the normal line of the substrate 35 and the line of magnetic force was set to about 75 °. After the treatment corresponding to FIG. 5, in the same manner as in Example 5, the organic solvent was washed using acetone for about 5 minutes with immersion time.
[0181]
The substrate after the washing with the organic solvent was subjected to in-plane optical retardation measurement using a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.
[0182]
When the completed liquid crystal cells were observed with a polarizing microscope, all the liquid crystal cells were as expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. What was called a uniform orientation.
[0183]
The pretilt angle was determined by a magnetic field-capacity method. The measured pretilt value is in the range of 13.9 ° to 14.0 °, which is much smaller than the pretilt variation corresponding to the conventional rubbing method.
[0184]
In order to optically examine the degree of orientation of the liquid crystal molecules, the transmitted light was observed under crossed Nicols and the polarization axis of the incident side polarizing plate was aligned with the long axis of the filled liquid crystal molecules. The penetration was very good at about 530: 1 or more in all the liquid crystal cells. This level is the highest attainable level of the liquid crystal cell corresponding to the conventional rubbing method.
[0185]
(Example 16)
A liquid crystal cell was manufactured in substantially the same manner as in Example 12 except for the following points.
[0186]
The situation of the substrate in this embodiment will be described. In FIG. 1, the coupler layer or the polar organic resin layer 3 is omitted. That is, in FIG. 1, a mesogen layer is directly laminated on a substrate made of Corning, product number 7059, on which a transparent electrode of indium oxide containing tin (hereinafter referred to as ITO) is deposited on low alkali glass.
[0187]
Prior to the formation of the mesogen layer, the substrate is thoroughly washed, and after drying at about 120 ° C., the formation of the mesogen layer is performed in a short time.
[0188]
The same evaluation as in Example 12 was performed on the processed substrate and the liquid crystal cell corresponding to FIG. 5, and good results were obtained.
[0189]
【The invention's effect】
As described above, this technology is mainly concerned with the method of aligning liquid crystal molecules, but this technology is largely related to the production of highly oriented films, which is thought to be linked to new functional films, and has great industrial value. is there.
[Brief description of the drawings]
FIG. 1 is a sectional view of a configuration for explaining an embodiment of the present invention.
FIG. 2 is a sectional view of a configuration for explaining an embodiment of the present invention.
FIG. 3 is a sectional view illustrating a configuration for explaining an embodiment of the present invention;
FIG. 4 is a sectional view of a configuration for explaining an embodiment of the present invention.
FIG. 5 is a sectional view of a configuration for explaining an embodiment of the present invention.
[Explanation of symbols]
1 substrate
2 PCB main surface
3 Coupler layer
4 Mesogen layer
5,6 Electromagnetic pole
7 lines of magnetic force
8 UV lamp
9 Mesogen layer
10 Substrate
11,12 Electromagnet pole
13 lines of magnetic force
14 UV lamp
15 Mesogen layer
16 Substrate
17,18 Electromagnetic pole
19 Magnetic field lines
20 UV lamp
21 Quartz glass substrate
22 ITO electrode layer
23 Mesogen layer
24 ITO electrode layer
25 substrate
26 Voltage application terminal
27,28 Electromagnet pole
29 Magnetic field lines
30 UV lamp
31 quartz glass substrate
32 ITO electrode layer
33 Mesogen layer
34 ITO electrode layer
35 substrate
36 Voltage application terminal

Claims (10)

Maintaining the substrate at a predetermined temperature such that a mesogen layer composed of a UV absorber, a photopolymerization initiator, and a polymerizable liquid crystal monomer formed on a main surface of the substrate capable of transmitting a pair of ultraviolet rays is maintained in a liquid crystal state, While applying a magnetic field in a desired direction, simultaneously irradiating ultraviolet rays to the main surface of the substrate through the substrate to polymerize the monomer to form a polymer layer, and washing the main surface of the substrate with an organic solvent, A method for manufacturing a liquid crystal cell, comprising: bonding the pair of substrates with the polymer layer facing each other while maintaining the gap, and filling the gap with liquid crystal. Maintaining the substrate at a predetermined temperature such that a mesogen layer composed of a UV absorber, a photopolymerization initiator, and a polymerizable liquid crystal monomer formed on a main surface of the substrate capable of transmitting a pair of ultraviolet rays is maintained in a liquid crystal state, Applying a magnetic field in a desired direction and applying an electric field in another desired direction, simultaneously irradiating ultraviolet rays to the main surface of the substrate through the substrate to polymerize the monomers and form a polymer layer A liquid crystal cell characterized by washing the main surface of the substrate with an organic solvent, keeping a desired gap, facing the polymer layer, laminating the pair of substrates, and filling the gap with liquid crystal. Manufacturing method. The mesogen layer composed of a low-molecular liquid crystal, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet-permeable main surfaces of the substrate is maintained at a predetermined temperature such that the liquid crystal state is maintained. While maintaining the substrate, while applying a magnetic field in a desired direction, simultaneously irradiating ultraviolet rays to the main surface of the substrate through the substrate to polymerize the monomer to form a polymer layer, the main surface of the substrate with an organic solvent A method for manufacturing a liquid crystal cell, comprising washing, maintaining a desired gap, facing the polymer layer, bonding the pair of substrates, and filling the gap with liquid crystal. The mesogen layer composed of a low-molecular liquid crystal, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet-permeable main surfaces of the substrate is maintained at a predetermined temperature such that the liquid crystal state is maintained. While holding the substrate, applying a magnetic field in a desired direction and applying an electric field in another desired direction, simultaneously irradiating ultraviolet rays to the main surface of the substrate through the substrate to polymerize the monomer and polymer layer Is formed, the main surface of the substrate is washed with an organic solvent, a desired gap is maintained, the polymer layers are opposed to each other, the pair of substrates are bonded, and the gap is filled with liquid crystal. Liquid crystal cell manufacturing method. Method of manufacturing a liquid crystal cell according to claim 1, 2, 3 or 4 UV is characterized in that substantially parallel ultraviolet desired direction of linearly polarized light. Extinction coefficient of a predetermined ultraviolet UV absorber, than the absorption coefficient of a predetermined ultraviolet photoinitiators, the production method of the liquid crystal cell according to claim 1, 2, 3 or 4, characterized in that two orders of magnitude or more larger. UV absorber,

5. The method for manufacturing a liquid crystal cell according to claim 1, comprising: The substrate manufacturing method of a liquid crystal cell according to claim 1, 2, 3 or 4, characterized in that it consists of a flat plate that covers the main surface with the coupler layer. 5. The method for manufacturing a liquid crystal cell according to claim 1, wherein the substrate is formed of a flat plate whose main surface is covered with a polar organic resin layer. The polymerizable liquid crystalline monomer is at least

5. The method for manufacturing a liquid crystal cell according to claim 1, wherein the method includes one of the following.

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