JP3764250B2 - Polyamide and liquid crystal alignment treatment agent - Google Patents

Description

【００１５】
（式中、Ｘ ¹ およびＡ ¹ はともに単結合であるか、Ｘ ¹ が酸素原子、Ａ ¹ が炭素数２〜１２の直鎖状あるいは分岐状のアルキレン基、または下記一般式（ＩＩ）
【００１６】
【化１６】

【００１９】
で表される基であり、Ｘ ² は酸素原子であり、Ａ ² は下記一般式（ＩＶ）
【００２０】
【化１８】

【００２１】
で表される基であり、上記式中、Ｒ ¹ 、Ｒ ² 、Ｒ ⁵ はそれぞれ独立にハロゲン原子または炭素数１〜６の直鎖状あるいは分岐状の低級アルキル基もしくはアルコキシ基、ｎ ¹ 、ｎ ² 、ｎ ⁵ はそれぞれ独立に０〜２の整数である。）および下記一般式（Ｖ）
【００２２】
【化１９】

【００２３】
（式中、Ｒ⁶ はハロゲン原子または炭素数１〜６の直鎖状あるいは分岐状の低級アルキル基もしくはアルコキシ基、ｎ⁶ は０〜２の整数である。）で表わされ、前記一般式（Ｉ）と前記一般式（Ｖ）で表される繰り返し単位のモル比が９０／１０から１０／９０の範囲にあり、重量平均分子量が１，０００以上であるポリアミドからなる液晶配向処理剤に関するものである。
【００２４】
【発明の実施の形態】
前記一般式（Ｉ）中、Ａ¹およびＡ²で表される炭素数２〜１２の直鎖状あるいは分岐状のアルキレン基としては、炭素数２〜１２のポリメチレン基、あるいはメチル基、エチル基、プロピル基、iso−プロピル基、ブチル基、sec−ブチル基、t−ブチル基等を側鎖に有する炭素数２〜１２の置換ポリメチレン基が挙げられる。また、前記一般式（Ｉ）〜（Ｖ）中Ｒ¹〜Ｒ⁶で表わされる炭素数１〜６の直鎖状あるいは分岐状の低級アルキル基もしくはアルコキシ基としては、メチル基、エチル基、プロピル基、iso−プロピル基、ブチル基、sec−ブチル基、t-ブチル基、ペンチル基、ヘキシル基、メトキシ基、エトキシ基、プロポキシ基、iso−プロポキシ基、ブトキシ基、sec−ブトキシ基、t-ブトキシ基、ペントキシ基、ヘキシロキシ基等を例示することができる。
【００２５】
前記一般式（Ｉ）で表される繰り返し単位において、一般式（Ｉ）が、下記一般式（ＶＩ）
【００２６】
【化２０】

【００２７】
（式中、Ａ¹、Ａ²、Ｘ¹、Ｘ²、Ｒ¹及びｎ¹は一般式（Ｉ）の定義と同じ）
であることが、製造および液晶配向特性の観点からより好ましい。
また、前記一般式（Ｉ）中の、一般式（ＩＶ）は、同様に下記一般式（ＶＩＩ）
【００２８】
【化２１】

【００２９】
（式中、Ｒ⁵、ｎ ⁵ は一般式（Ｉ）の定義と同じ）であることが好ましい。繰り返し単位が前記一般式（Ｉ）および（Ｖ）で表わされる本発明のポリアミドは、例えば、以下に示す合成方法により製造することができる。すなわち、下記一般式（ＶＩＩＩ）
【００３０】
【化２２】

【００３１】
（式中、Ａ¹、Ａ²、Ｒ¹、Ｘ¹、Ｘ²およびｎ¹は前記定義と同様である。）
で表されるアミノカルボン酸化合物、および下記一般式（ＩＸ）
【００３２】
【化２３】

【００３３】
（式中、Ｒ⁶およびｎ⁶は前記定義と同様である。）
で表わされるアミノ安息香酸化合物とを、９０／１０から１０／９０の範囲のモル比となるように混合し、通常の方法により重縮合反応を行なうことにより合成することができる。
上記のモノマーを用いる場合、重縮合反応は縮合剤の存在下行うことが望ましく、亜リン酸トリフェニル、亜リン酸トリトルイル、亜リン酸トリ（クロロフェニル）、ジクロロ亜リン酸フェニル、ジクロロリン酸ジフェニル、トリフェニルホスフィン/ヘキサクロロエタン、ジフェニル(2,3-ヒドロ-2-チオキソ-3-ベンゾチアゾリル)ホスホナート、(C₃H₇)₃P(O)O、POCl₃、SOCl₂、SiCl₄、(CH₃)₂SiCl₂等の縮合剤に必要に応じてピリジン、4-（ジメチルアミノ）ピリジン、トリエチルアミン、Ｎ，Ｎ−ジメチルアニリン、イミダゾールなどの有機塩基を添加して用いることにより反応が好適に進行する。また、この反応は有機溶媒中で行うことが好ましく、ヘキサン、テトラヒドロフラン、ジオキサン、ジメトキシエタン、ベンゼン、トルエン、ピリジン、クロロホルム、ジクロロエタン、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルスルホキシド、Ｎ-メチルピロリドン、ヘキサメチルホスホアミド等が好適に用いられる。さらに、この縮合反応で得られるポリアミドの溶解性が低い場合には、塩化カルシウム、塩化リチウム、臭化リチウム等の無機塩基を添加して行うことにより好適に反応が進行する。この縮合反応における反応温度は、通常室温から２００℃程度の温度範囲が好ましい。
【００３４】
前記一般式（ＶＩＩＩ）中のＡ¹、Ａ²、Ｘ¹およびＸ²がいずれも単結合であるアミノカルボン酸化合物、および前記一般式（ＩＸ）で表されるアミノ安息香酸化合物の具体例としては、4-アミノ安息香酸、3-アミノ安息香酸、2-アミノ安息香酸、およびこれらのアミノ安息香酸類のベンゼン環上の任意の位置の１個ないしは２個の水素原子がフッ素原子、塩素原子、臭素原子、沃素原子、メチル基、エチル基、プロピル基、iso-プロピル基、ブチル基、sec-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、メトキシ基、エトキシ基、プロポキシ基、iso-プロポキシ基、ブトキシ基、sec-ブトキシ基、t-ブトキシ基、ペントキシ基またはヘキシロキシ基に置換された化合物等を挙げることができる。
【００３５】
前記一般式（ＶＩＩＩ）中のＡ²が前記一般式（ＩＩ）または（ＩＩＩ）で表される基であるか、あるいはが前記一般式（ＩＶ）であるアミノカルボン酸化合物は、例えば後の参考例に示した合成方法などの既存の合成手段により製造することができる。
また、前記一般式（ＶＩＩＩ）および（ＩＸ）で表される化合物から誘導される以下のモノマー類、すなわち、下記一般式（Ｘ）
【００３６】
【化２４】

【００３７】
（式中、Ｙ¹はトリオルガノシリル基、アセチル基または置換アセチル基、Ａ¹、Ａ²、Ｒ¹、Ｘ¹、Ｘ²およびｎ¹は前記定義と同様である。）で表される化合物と、下記一般式（ＸＩ）
【００３８】
【化２５】

【００３９】
（式中、Ｙ¹、Ｒ⁶およびｎ⁶は前記定義と同様である。）
で表される化合物とを、９０／１０から１０／９０の範囲のモル比となるように混合し重縮合反応を行なうか、あるいは、下記一般式（ＸＩＩ）
【００４０】
【化２６】

【００４１】
（式；中、Ｙ²は低級アルキル基、フェニル基または置換フェニル基、Ａ¹、Ａ²、Ｒ¹、Ｘ¹、Ｘ²およびｎ¹は前記定義と同様である。）
で表される化合物と、下記一般式（ＸＩＩＩ）
【００４２】
【化２７】

【００４３】
（式中、Ｙ²、Ｒ⁶およびｎ⁶は前記定義と同様である。）
で表される化合物とを、９０／１０から１０／９０の範囲のモル比となるように混合し重縮合反応を行なうことによっても、目的とする本発明のポリアミドを製造することができる。
ここで、前記一般式（Ｘ）および（ＸＩ）中Ｙ¹で表される置換基のうち、トリオルガノシリル基としては、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、t-ブチルジメチルシリル基等を、また置換アセチル基としては、トリフルオロアセチル基、ブロモアセチル基、ジブロモアセチル基、フェニルアセチル基等をそれぞれ例示できる。一方、前記一般式（Ｘ）および（ＸＩ）中Ｙ²で表される置換基のうち、低級アルキル基としては、メチル基、エチル基、プロピル基、iso−プロピル基、ブチル基、sec−ブチル基、t-ブチル基、ペンチル基、ヘキシル基等を、また置換フェニル基としては、クロロフェニル基、ニトロフェニル基等をそれぞれ例示できる。
【００４４】
前記一般式（Ｘ）と（ＸＩ）で表されるモノマー化合物、または前記一般式（ＸＩＩ）と（ＸＩＩＩ）で表されるモノマー化合物をそれぞれ用いて重縮合反応を行う場合には、前記一般式（ＶＩＩＩ）および（ＩＸ）で表されるモノマー化合物を用いて重縮合反応を行う場合と同様に、有機溶媒中で必要に応じて前述の縮合剤存在下反応させることで目的とするポリアミドが得られるが、その他にも、それぞれのモノマーを所定量混合した後必要に応じて触媒を添加し、常圧下もしくは減圧下においてモノマーが溶融する温度まで昇温する事により目的とする本発明のポリアミドを製造することができる。ここで用いられる触媒としては、硫酸、硝酸、トシル酸、水酸化リチウム、水酸化カリウム、水酸化ナトリウム、水酸化カルシウム、塩化アルミニウム、トリブチルアルミニウム、塩化チタン、トリブチルチタン、酢酸鉛等を例示できる。
【００４５】
以上述べたような製造方法により得られる、繰り返し単位が前記一般式（Ｉ）および（Ｖ）で表わされる本発明のポリアミドにおいて、前記一般式（Ｉ）と前記一般式（Ｖ）で表される繰り返し単位のモル比が９０／１０から１０／９０の範囲、より好ましくは７０／３０から３０／７０の範囲にあることが、溶解性および成形加工性等の点で好ましい。また、本発明のポリアミドの重量平均分子量は１，０００以上、より好ましくは３，０００以上であることが、安定性等の点で好ましい。分子量は、ゲルパーミエーションクロマトグラフィー、浸透圧法、光散乱法、粘度法等の公知の方法により測定される。
【００４６】
該ポリアミドを液晶配向処理剤として使用するに際しては、上記縮合反応で得られたポリアミド樹脂溶液をそのまま使用する事もできる。また得られたポリアミド溶液から一旦ポリアミドを単離したのち、適当な溶媒に再溶解させて使用することもできる。再溶解させる溶媒は、得られたポリアミドを溶解させるものであれば特に限定されないが、その例としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、ヘキサメチルホスホアミド、γ−ブチロラクトン、テトラヒドロフラン、ピリジン、クロロホルム、ジクロロメタン、クロロベンゼン、ジクロロベンゼン、フェノール、p-クロロフェノール、アニソール、クレゾール等が挙げられる。
【００４７】
また、基板への塗布性を改善する目的から、単独ではこのポリアミドを溶解させない溶媒であっても溶解性を損なわない範囲であれば上記溶媒に加えてもよい。その例としてはブチルセロソルブ、エチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、トルエン、キシレン等が挙げられる。また更に、基板への密着性を上げる目的から、シランカップリング剤等の添加剤を適宜使用する事もできる。
【００４８】
上記のようにして得られた本発明のポリアミド溶液を、スピンコート、転写印刷法などの方法を用いてガラス、ウェハーまたはプラスチック等の基板上に塗布し、これを加熱処理してポリアミド膜を形成するのが一般的である。この加熱処理温度としては、５０℃〜４５０℃、好ましくは８０℃〜３５０℃の任意の温度を選択することができるが、本発明の効果を得るための液晶配向膜の形成に際しては、一般には８０℃〜２００℃の比較的低い加熱温度を採用することが出来る。この際のポリアミド膜の厚みとしては、特に限定されるものではないが、通常の液晶配向膜として使用される上で、１００Å〜３０００Åが適当である。次いで該樹脂膜をラビング処理等の配向処理を施し、液晶配向処理剤として使用することができる。
【００４９】
ラビング処理は、一般的には綿、ナイロン、ポリエステルなどの布を巻いたローラーを回転させ、そのローラーを一定の押し込み圧で基板に接触させて基板またはローラーを一定速度で移動させることにより行うことができる。また、ローラが回転していない状態でローラーもしくは基板を移動させて行うこともできる。回転ラビングでのラビングの強さは、次の式で定義されるラビング度（ｍｍ）で表すことが報告されている。
【００５０】
【数式１】
Ｌ＝Ｎ・Ｍ｛（２πｒｎ／６０Ｖ）−１｝ （１）
（１）式に於いて、Ｎはラビング回数、Ｍは押し込み量（ｍｍ）、ｒはラビングローラーの半径（ｍｍ）、ｎはローラーの回転数（ｒｐｍ）、Ｖはステージの移動速度（ｍｍ／秒）である。本発明に用いることができるラビング度は特に限定されるものではないが、ポリアミド膜の密着性の観点から、５００ｍｍ以下が好ましい。
【００５１】
このようなラビング処理によって高分子鎖がラビング方向に配向されることが知られており、この高分子膜の配向の効果は、一般的に、ラビング処理後に誘起されるポリアミド膜の複屈折位相差およびラビング方向と遅相軸のずれ角を測定することによって評価できる。この測定の原理は、次の文献に記載されている。
Ａｎ Ｉｍｐｒｏｖｅｄ Ｍｅｔｈｏｄ ｆｏｒ Ｈｉｇｈ Ｒｅｆｌｅｃ−ｔｉｖｉｔｙ Ｅｌｌｉｐｓｏｍｅｔｒｙ Ｂａｓｅｄ ｏｎ ａ Ｎｅｗ Ｐｏｒａｒｉｚａｔｉｏｎ Ｍｏｄｕｌａｔｉｏｎ Ｔｅｃｈｎｉｑｕｅ（Ｓ．Ｎ．Ｊａｓｐｅｒｓｏｎ ＆ Ｅ．Ｓｃｈｎａｔｔｅｒｌｙ）Ｒｅｖ．Ｓｃｉ．Ｉｎｓｔ．，ｖｏｌ．４０， ｐａｇｅ７６１，１９６９
Ｈｉｇｈ Ｆｒｅｑｕｅｎｃｙ Ｐｏｌａｒｉｚａｔｉｏｎ Ｍｏｄｕｌａ−ｔｉｏｎ Ｍｅｔｈｏｄ ｆｏｒ Ｍｅｓｕｒｉｎｇ Ｂｉｒｅｆｒｉｎ−ｇｅｎｅｃｅ（Ｆ．Ａ．Ｍｏｄｏｉｎｅ， Ｒ．Ｗ．Ｍａｊｏｒ ＆ Ｅ．Ｓｏｎｄｅｒ）Ａｐｐｌ．Ｏｐｔ．，ｖｏｌ１４，Ｎｏ．３，１９７５
【００５２】
本発明に於けるポリアミド樹脂は液晶配向処理剤として特に優れた特性を有するものであるが、本発明の効果を得るためには、ポリアミド分子鎖がラビングにより延伸され、ラビング方向に均一に配向することが重要である。ラビングによって誘起される複屈折の大きさは、高分子の構造単位が有する屈折率の異方性、ラビング度、延伸される膜厚等に依存するが、複屈折位相差が大きいほど高分子鎖が配向していることを示すと考えられ、さらに、ラビング方向と遅相軸とのズレ角は、その大きさが小さいほど高分子鎖がラビング方向に配向していることを示していると考えられる。本発明の効果を得るためには、複屈折位相差の大きさがラビング度が１０〜１００ｍｍのとき０．５ｎｍ以上、ラビング度が１００ｍｍ以上で１．０ｎｍ以上であることが好ましく、また、ラビング方向と遅相軸のズレ角が、１．０°以下、さらに好ましくは０．５°以下であることが好適である。
【００５３】
このようにラビングによって均一にかつ一方向に高分子鎖が配向した液晶配向処理剤を用いることによって、液晶分子を均一に配向させることができる。以下、参考例、実施例および比較例により本発明をさらに詳しく説明する。ただし、本発明がこれらに限定されるものではないことはもちろんである。
【００５４】
【実施例】
参考例１
【００５５】
【化２８】

【００５６】
4-フルオロニトロベンゼン2.82 g（20.0 mmol）およびベンジル 4-ヒドロキシベンゾエート4.57 g（20.0 mmol）をジメチルスルホキシド(以下ＤＭＳＯと略す) 10 mLに溶解した。ここへ炭酸カリウム2.76 g（20.0 mmol）を加えて、８０℃で１６時間撹拌した。反応溶液を水1.5 Lに投入したところ容器底面に油状物が沈澱した。上澄みを捨て氷水1.0 L加えて再び上澄みを捨てるという操作を２回行い、最後に沈殿物をエーテルに溶解し硫酸ナトリウムで乾燥した。濃縮後、カラムクロマトグラフィー（充填剤；シリカゲル、 展開溶媒；エーテル／ヘキサン=1／5 Vol.)で精製したところ、上記構造式（１）で表されるエステル化合物6.91 gを薄黄色液体として得た。収率：99.0％
IR (neat, cm^-1): 3111 (w), 3079, 3034 (w), 2953 (w), 1717 (s), 1607, 1588 (s), 1518 (s), 1489, 1456, 1414 (w), 1375, 1345 (s), 1308, 1273 (s), 1246 (s), 1163 (s), 1111 (s), 1014, 880, 851, 750, 698, 513.
¹H-NMR (CDCl₃, ppm): δ= 5.38 (s, 2H), 7.09 (d, 2H, J=9.2Hz), 7.11 (d, 2H, J=8.9Hz), 7.34〜7.47 (m, 5H), 8.14 (d, 2H, J=8.9Hz), 8.25 (d, 2H, J=9.2Hz).
EI-MS: m/z = 349 (M)⁺, 319 (M - NO)⁺, 304, 242 (M - OCH₂Ph)⁺, 212 (M - OCH₂Ph - NO)⁺, 196, 168, 139 (O₂NC₆H₄OH)⁺, 107 (OCH₂Ph)⁺, 91 (CH₂Ph)⁺.
【００５７】
上記方法により得られたエステル化合物（１）8.7 g（25 mmol）および５％Ｐｄ−カーボン粉末1.0 gをテトラヒドロフラン（以下ＴＨＦと略す）30 mLおよびエタノール 30 mLに混合した。常圧下、水素ガス雰囲気内で約６時間攪拌した後、反応溶液をセライト濾過した。濾液を濃縮したところ、上記構造式（２）で表されるアミノカルボン酸化合物5.47 gを薄茶色粉末として得た。収率：96％
IR (KBr disk, cm^-1): 3360 (m, NH₂ st as), 3293 (m, NH₂ st sy), 2600 (vb, COO-H st), 1672 (s, C=O st), 1601 (s, arC-C st), 1503 (s, arC-C), 1422, 1269 (s, arC-N st), 1236 (s, arC-O-arC st), 1161, 880, 503.
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ= 5.1 (-NH₂), 6.62 (d, 2H, J=8.7Hz), 6.81 (d, 2H, J=8.7Hz), 6.90 (d, 2H, J=8.8Hz), 7.88 (d, 2H, J=8.8Hz), 12.6 (-COOH).
EI-MS: m/z = 229 (M)⁺, 156, 108 (H₂NC₆H₄O)⁺.
元素分析結果 (C1₃H₁₁NO₃, 分子量: 229.23)
計算値 C: 68.11%, H: 4.84%, N: 6.11%
実測値 C: 68.34%, H: 4.96%, N: 5.96%
参考例２
【００５８】
【化２９】

【００５９】
4-フルオロニトベンゼン2.82 g（20.0 mmol）および4-メトキシフェノール2.48 g（20.0 mmol）をＤＭＳＯ10 mLに溶解した。ここへ炭酸カリウム2.76 g（20.0 mmol）を加えて、８０℃で１４時間撹拌した後、反応溶液を水1.0 Lに投入した。生じた沈澱を濾取し、乾燥したところ上記構造式（３）で表されるメトキシ体化合物4.90 gを白色粉末として得た。収率：100％
【００６０】
IR (KBr disk, cm^-1): 3107 (w), 3007 (w), 2845 (w), 1611, 1588, 1507 (s), 1487, 1447, 1343 (s), 1298 (w), 1238 (s), 1194, 1163, 1109, 1030, 1009 (w), 878, 843, 802, 748, 714 (w), 567 (w), 532 (w), 523 (w), 492 (w).
¹H-NMR (CDCl₃, ppm): δ= 3.83 (s, 3H), 6.96 (d, 2H, J=9.2Hz), 7.0 (m, 4H), 8.18 (d, 2H, J=9.2Hz).
【００６１】
上記方法により得られたメトキシ体化合物（３）4.90 g（20.0 mmol）を酢酸50 mLおよび47％臭酸水10 mLに溶解した。オイルバスを１３０℃に設定して１４時間撹拌した。ここへ水200 mLを加えて室温まで冷却したところ析出を生じ、この黄色粉末を濾取した。６０℃で３時間減圧乾燥した後、クロロホルムから再結晶精製したところ上記構造式（４）で表されるフェノール誘導体3.63 gを褐色の板状晶として得た。収率：78.6％
IR (KBr disk, cm^-1): 3439 (s), 1609, 1588, 1507 (s), 1485, 1427, 1345 (s), 1271, 1242 (s), 1192, 1161, 1111, 1011 (w), 878, 855, 841, 814, 748, 569, 503.
¹H-NMR (CDCl₃, ppm): δ= 6.9〜7.0 (m, 6H), 8.16 (d, 2H, J=9.2Hz), 8.56 (bs, 1H).
【００６２】
上記方法により得られたフェノール誘導体（４）3.60 g（15.6 mmol）および4-フルオロベンズアルデヒド1.93 g（15.6 mmol）をＤＭＳＯ10 mLに溶解した。ここへ炭酸カリウム2.15 g（15.6 mmol）を加えて、８０℃で１６時間撹拌した。反応溶液を水1.5 Lに投入し生じた沈澱を濾取し、更に少量のメタノールで洗浄した。残査をクロロホルムから再結晶精製したところ上記構造式（５）で表されるアルデヒド化合物3.14 gを黄色結晶として得た。収率：60.1％
IR (neat, cm^-1): 1690, 1595, 1508, 1497, 1485 (s), 1340, 1235 (vs), 1188, 1155 (m), 1109 (m), 880, 847 (w), 866 (w), 748 (w), 540 (w).
¹H-NMR (CDCl₃, ppm): δ= 7.06 (d, 2H, J=9.2Hz), 7.0〜7.2 (m, 6H), 7.89 (d, 2H, J=8.8Hz), 8.23 (d, 2H, J=9.2Hz), 9.95 (s, 1H).
元素分析結果 (C₁₉H₁₃NO₅, 分子量: 335.32)
計算値 C: 68.06%, H: 3.91%, N: 4.18%
実測値 C: 67.98%, H: 3.64%, N: 4.23%
上記方法により得られたアルデヒド化合物（５）2.74 g（8.17 mmol）をアセトン200 mLに溶解した。ここへ過マンガン酸カリウム3.00 gを溶解した水溶液50 mLを加えて、還流温度で３時間撹拌した。メタノール20 mLを加えて更に３０分撹拌した後、熱いうちにガラスフィルターで濾過した。濾物を熱(水／エタノール／アセトン) 200 mLで２回洗浄した。濾液を10 N塩酸で酸性化したところ沈殿を生じ、これを乾燥したところ上記構造式（６）で表される安息香酸誘導体2.40 gを白色粉末として得た。収率：83.6％
【００６３】
IR (KBr disk, cm^-1): 2849 (b), 2560 (b), 1674, 1597, 1508, 1487, 1429 (m), 1341, 1294 (w), 1235 (vs), 1188, 1165, 1111 (m), 1015 (w), 876 (m), 847 (m), 774 (w), 750 (w), 534 (w).
¹H-NMR (CDCl₃+DMSO-d₆, ppm): δ= 7.00 (d, 2H, J=8.8Hz), 7.0〜7.1 (m, 6H), 8.05 (d, 2H, J=8.8Hz), 8.22 (d, 2H, J=9.2Hz).
元素分析結果 (C₁₉H₁₃NO₆, 分子量: 351.31)
計算値 C: 64.96%, H: 3.73%, N: 3.99%
実測値 C: 65.01%, H: 3.68%, N: 3.97%
上記方法により得られた安息香酸誘導体（６）2.17 g（6.18 mmol）および５％Ｐｄ−カーボン粉末0.26 gをＴＨＦ50 mLおよびエタノール30 mLに混合した。常圧下、水素ガス雰囲気内で約６時間攪拌した後、反応溶液をセライト濾過した。濾液を濃縮した後、ＴＨＦ／エタノール混合溶媒から再結晶精製したところ上記構造式（７）で表されるアミノカルボン酸化合物0.93gを薄茶色粉末として得た。収率：47％
【００６４】
IR (KBr disk, cm^-1): 3366 (w, NH₂ st as), 3293 (w, NH₂ st sy), 2600 (vb, COO-H st), 1684 (b, C=O st), 1601 (m, arC-C st), 1495 (s, arC-C), 1283 (m, arC-N st), 1229 (bm, arC-O-arC st), 1192 (m), 1165 (m), 872 (w), 835 (w), 507 (w).
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ= 6.60 (d, 2H, J=8.7Hz), 6.80 (d, 2H, J=8.7Hz), 6.93 (d, 2H, J=9.0Hz), 6.98 (d, 2H, J=8.8Hz), 7.09 (d, 2H, J=9.0Hz), 7.92 (d, 2H, J=8.8Hz).
EI-MS: m/z = 321 (M)⁺, 108 (H₂NC₆H₄O)⁺.
元素分析結果 (C₁₃H₁₁NO₃+1/4C₂H₅OH, 分子量: 321.33+1/4C₂H₅OH=332.85)
計算値 C: 70.37%, H: 5.00%, N: 4.21%
実測値 C: 70.36%, H: 4.92%, N: 4.19%
参考例３
【００６５】
【化３０】

【００６６】
ベンジル 4-ヒドロキシベンゾエート10.0 g（43.8 mmol）と1,4-ジブロモブタン100 g（463 mmol）をアセトン50 mLに溶解した。ここへ炭酸カリウム6.1 g（44 mmol）およびヨウ化カリウム0.5 gを加え、還流温度１５時間撹拌した。室温まで冷却後、エーテル150 mLを加えて不溶物を濾別した。減圧下、溶媒と未反応のジブロモブタンを留去した後、カラムクロマトグラフィー（充填剤；シリカゲル、展開溶媒；エーテル／ヘキサン=1／16 Vol.)で精製したところ、上記構造式（８）で表されるエステル化合物15.1 gを無色透明液体として得た。収率：94.6％
IR (neat, cm^-1): 3065 (w), 3034 (w), 2951, 2876 (w), 1713 (s), 1607, 1582 (w), 1510, 1456 (w), 1422 (w), 1377, 1314, 1256 (s), 1169, 1101, 1030, 1009 (w), 953 (w), 914 (w), 849, 770, 750 (w), 698, 648 (w), 600 (w), 561 (w), 511 (w).
¹H-NMR (CDCl₃, ppm): δ= 2.0〜2.1 (m, 4H), 3.48 (t, 2H, J=6.2Hz), 4.04 (t, 2H, J=5.7Hz), 5.33 (s, 2H), 6.89 d, 2H, J=9.0Hz), 7.3〜7.4 (m, 5H), 8.02 (d, 2H, J=9.0Hz).
【００６７】
上記方法により得られたエステル化合物（８）5.63 g（15.5 mmol）および4-ニトロフェノール2.16 g（15.5 mmol）をアセトン60 mLに溶解した。ここへ炭酸カリウム2.14 g（15.5 mmol）およびヨウ化カリウム0.1 gを加え、還流温度で１２時間撹拌した。室温まで冷却後、アセトン300 mLを加えて不溶物を濾別、洗浄した。濾液を濃縮しクロロホルム300 mLおよび水 200 mLを加えて有機相を抽出した。硫酸ナトリウムで乾燥後濃縮し、ベンゼンから再結晶精製したところ上記構造式（９）で表されるエステル化合物3.37 gを白色粉末として得た。収率：51.6％
IR (KBr disk, cm^-1): 3086 (vw), 2961 (w), 2938 (w), 2882 (w), 1709 (s), 1607, 1595, 1512 (s), 1501, 1474 (m), 1456 (w), 1424 (w), 1400 (vw), 1379 (w), 1345 (s), 1304, 1254 (s), 1173, 1113, 1057 (m), 1003, 843, 766 (m), 750 (m), 739 (m), 691 (w), 664 (m), 496 (w).
¹H-NMR (CDCl₃, ppm): δ= 2.0〜2.1 (m, 4H), 4.10 (t, 2H, J=2.0Hz), 4.14 (t, 2H, J=2.0Hz), 5.34 (s, 2H), 6.90 (d, 2H, J=9.0Hz), 6.94 (d, 2H, J=9.2Hz), 7.3〜7.4 (m, 5H), 8.03 (d, 2H, J=8.8Hz), 8.20 (d, 2H, J=9.2Hz).
上記方法により得られたエステル化合物（９）3.28 g（7.78 mmol）をＴＨＦ140 mLおよびエタノール60 mLの混合溶媒に溶解した。ここへ５％Ｐｄ−カーボン粉末0.55 gを加えた。常圧下、水素ガス雰囲気内で一晩攪拌した後、Ｎ，Ｎ−ジメチルホルムアミド（以下ＤＭＦと略す）を40 mL加えてから反応溶液をセライト濾過した。濾液を濃縮したところ、上記構造式（１０）で表されるアミノカルボン酸化合物2.32 gを薄赤茶色粉末として得た。収率：85.1％
IR (KBr disk, cm^-1): 3356 (w, NH₂ st as), 3281 (w, NH₂ st sy), 3067 (vw shoulder, arC-H st), 2949 (m, alC-H st as), 2878 (m, alC-H st sy), 2550 (b, COO-H st; hydrogen bonded), 1682 (bw, al-C=O st; hydrogen bonded), 1607 (m, arC-C), 1516 (s, -NH₂ δ), 1476 (m, -CH₂ δ), 1387 (m), 1252 (s, arC-N st), 1173 (m), 1011 (m), 828 (w, -NH₂ δ), 650, 517.
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ= 1.81 (m, 2H), 1.84 (m, 2H), 3.88 (t, 2H), 4.10 (t, 2H), 5.3 (-NH₂), 6.49 (d, 2H, J=8.8Hz), 6.65 (d, 2H, J=8.8Hz), 7.01 (d, 2H), 7.88 (d, 2H).
EI-MS: m/z = 301 (M)⁺, 193 (M - OC₆H₄NH₂)⁺, 151 (CH₂OC₆H₄COOH)⁺, 121 (C₆H₄COOH)⁺, 109 (H₂NC₆H₄OH)⁺, 92 (H₂NC₆H₄)⁺.
元素分析結果 (C₁₇H₁₉NO₄, 分子量: 301.34)
計算値 C: 67.76%, H: 6.35%, N: 4.65%
実測値 C: 67.63%, H: 6.50%, N: 4.67%
【００６８】
実施例１〜３
【００６９】
【化３１】

【００７０】
参考例１〜３で得られたアミノカルボン酸化合物（２）、（７）または（１０）に対し、それぞれ所定モル比率になるように3-アミノ安息香酸（以下ＭＡＢＡと略す）を混合し、Ｎ−メチルピロリドン（以下ＮＭＰと略す）および総モノマーのモル量に対し1.2当量のピリジン（以下Ｐｙと略す）、更に同じく1.2当量の亜リン酸トリフェニル（以下ＴＰＰと略す）を加えて、１００℃で１８時間攪拌した。実際に用いた上記のモノマー、試薬および溶媒の量を以下の表１にまとめて示す。次に、反応溶液をＮＭＰで２倍に希釈した後、約１００倍量のメタノールに攪拌しながら投入した。生じた沈殿を濾取し、減圧下６０℃で一晩乾燥させ、上記構造式ＰＡ−１、ＰＡ−２およびＰＡ−３で表されるポリアミドをそれぞれ得た。得られたポリアミドの収量、¹Ｈ−ＮＭＲスペクトルから求めた共重合組成（上記構造式のｘ／ｙ）およびゲルパーミエーションクロマトグラフィーで求めた数平均分子量および重量平均分子量を次の表２に示す。また、得られたＰＡ−１、ＰＡ−２およびＰＡ−３のＩＲスペクトルを図１、２および３に、¹Ｈ−ＮＭＲスペクトルを図４、５および６にそれぞれ示す。
【００７１】
【表１】

【００７２】
【表２】

【００７３】
実施例４
実施例１で得られたポリアミドＰＡ−１をＮＭＰおよびブチルセルソルブ（以下ＢＳと略す）の混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％の溶液を調製した。この溶液をガラス基板上に回転数２５００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００７４】
このポリアミド樹脂膜をレーヨン布を用い、表３の条件でラビング処理を施した。このようにラビング処理された各々の基板を５０μｍのスペーサーを挟んで、ラビング方向が反平行にして組み立て、ついで液晶（メルク社製ＺＬＩ−２２９３）を注入して、基板に対して平行配向したセルを作製した。このセルの配向状態を偏光顕微鏡により観察したところ、いずれのラビング条件でも欠陥は全く観測されず、液晶が均一に配向していることが確認された。また、結晶回転法により傾斜配向角を測定したところ、条件１では１．７°、条件２では１．４°、条件３では１．３°と低い傾斜配向角が安定に得られていることが確認された。
【００７５】
さらに、熱処理に対する傾斜配向角と配向状態の変化を評価するため、液晶セルを９５℃で１０分間、１２０℃で１時間、１２０℃で６時間、順次加熱処理を行なったが、熱処理による配向の乱れや欠陥の発生は一切みられず、均一な配向を保持しており、傾斜配向角の変化も全くないことが確認された。
【００７６】
【表３】

【００７７】
実施例５
実施例４に記載したポリアミド樹脂膜のラビング処理による分子鎖の配向性を評価するため、ポリアミド樹脂膜を種々の強さでラビング処理し、オーク製作所製の高感度自動複屈折測定装置により複屈折位相差（以下△ｎｄと略す）、および遅相軸とラビング方位とのずれ角を測定した。ラビングの強さを定量化するために、以下の数式（１）で算出されるラビング度Ｌ（ｍｍ）を導入した。
【００７８】
【数２】
Ｌ＝Ｎ・Ｍ｛（２πｒｎ／６０Ｖ）−１｝ （１）
（１）式に於いて、Ｎはラビング回数、Ｍは押し込み量（ｍｍ）、ｒはラビングローラーの半径（ｍｍ）、ｎはローラーの回転数（ｒｐｍ）、Ｖはステージの移動速度（ｍｍ／秒）である。表４にラビング強度に対する複屈折位相差と遅相軸のずれ角のラビング度依存性を示す。比較的小さいラビング度に於いても、大きな△ｎｄ値が観測され、また遅相軸のずれ角も極めて小さいことから、ポリアミド分子鎖がラビング処理によって、ラビング方向へ均一に配向していることが確認された。
【００７９】
【表４】

【００８０】
実施例６
実施例２で得られたポリアミドＰＡ−２をＮＭＰとＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％溶液を調製した。この溶液をガラス基板上に回転数２８００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００８１】
実施例４と同様に、異なるラビング条件でラビング処理を行って液晶セルを作製し、配向の均一性および傾斜配向角を評価したところ、いずれのラビング条件でも均一で良好な配向状態が得られ、ラビング条件１では１．４°、条件２では１．２°、条件３では１．０°の低い傾斜配向角が安定して得られていることが確認された。
【００８２】
さらに、実施例４と同様の条件で、熱処理に対する傾斜配向性と配向状態の変化を評価したところ、熱処理による配向の乱れや欠陥の発生はみられず、また傾斜配向角の変化もみられなかった。
【００８３】
実施例７
実施例６に記載したポリアミド樹脂膜のラビング処理による分子鎖の配向性を評価するため、実施例５と同様にラビング処理に対する△ｎｄ、および遅相軸とラビング方向とのずれ角を測定したところ、ラビング度の増加に伴い△ｎｄが増加し、また遅相軸のずれ角は小さいことから、ラビング処理によってポリアミド分子鎖がラビング方向へ均一に配向することが確認された。
【００８４】
実施例８
実施例３で得られたポリアミドＰＡ−３をＮＭＰとＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％溶液を調製した。この溶液をガラス基板上に回転数３０００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００８５】
実施例４と同様に、異なるラビング条件でラビング処理を行って液晶セルを作製し、配向の均一性および傾斜配向角を評価したところ、いずれのラビング条件でも均一で良好な配向状態が得られ、ラビング条件１では２．０°、条件２では１．７°、条件３では１．３°の低い傾斜配向角が安定して得られていることが確認された。
【００８６】
さらに、実施例４と同様の条件で、熱処理に対する傾斜配向性と配向状態の変化を評価したところ、熱処理による配向の乱れや欠陥の発生はみられず、また傾斜配向角の変化もみられなかった。
【００８７】
実施例９
実施例８に記載したポリアミド樹脂膜のラビング処理による分子鎖の配向性を評価するため、実施例５と同様にラビング処理に対する△ｎｄ、および遅相軸とラビング方向とのずれ角を測定したところ、ラビング度の増加に伴い△ｎｄが増加し、また遅相軸のずれ角は小さいことからラビング処理によってポリアミド分子鎖がラビング方向へ均一に配向することが確認された。
【００８８】
実施例１０
実施例１で得られたポリアミドＰＡ−１をＮＭＰおよびＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％の溶液を調製した。この溶液をガラス基板上に回転数２５００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００８９】
このポリアミド樹脂膜をナイロン布を用い、表３に記載の条件１でラビング処理を施した。このようにラビング処理された各々の基板を２μｍのスペーサーを挟んで、ラビング方向が平行にして組み立て、ついで強誘電性液晶（メルク社製ＺＬＩ−３４８９）を注入して、表面安定化型液晶セルを作製した。このセルの配向状態を偏光顕微鏡により観察したところ、液晶セルの全領域にわたり欠陥は観測されず、強誘電性液晶が均一に配向していることが確認された。
【００９０】
実施例１１
実施例２で得られたポリアミドＰＡ−２をＮＭＰおよびＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％の溶液を調製した。この溶液をガラス基板上に回転数２８００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００９１】
このポリアミド樹脂膜をナイロン布を用い、表３に記載の条件１でラビング処理を施した。このようにラビング処理された各々の基板を１．５μｍのスペーサーを挟んで、ラビング方向が平行にして組み立て、ついで強誘電性液晶（メルク社製ＺＬＩ−３４８９）を注入して、表面安定化型液晶セルを作製した。このセルの配向状態を偏光顕微鏡により観察したところ、液晶セルの全領域にわたり欠陥は観測されず、強誘電性液晶が均一に配向していることが確認された。
【００９２】
実施例１２
実施例３で得られたポリアミドＰＡ−３をＮＭＰおよびＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％の溶液を調製した。この溶液をガラス基板上に回転数３０００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリアミド樹脂膜を形成した。
【００９３】
このポリアミド樹脂膜をナイロン布を用い、表３に記載の条件１でラビング処理を施した。このようにラビング処理された各々の基板を１．５μｍのスペーサーを挟んで、ラビング方向が平行にして組み立て、ついで強誘電性液晶（メルク社製ＺＬＩ−３４８９）を注入して、表面安定化型液晶セルを作製した。このセルの配向状態を偏光顕微鏡により観察したところ、液晶セルの全領域にわたり欠陥は観測されず、強誘電性液晶が均一に配向していることが確認された。
【００９４】
比較例１
ピロメリット酸二無水物とジアミノジフェニルエーテルをＮＭＰ中で反応させ、ポリイミド前駆体を重合した。この溶液をＮＭＰとＢＳの混合溶媒（重量比８０：２０）で希釈し、総固形分濃度５ｗｔ％溶液を調製した。このポリイミド前駆体溶液をガラス基板上に回転数３２００ｒｐｍでスピンコートし、ついで２５０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリイミド樹脂膜を形成した。
【００９５】
ローラー回転数３００ｒｐｍ、ステージ移動速度２０ｍｍ／秒、押し込み量０．５ｍｍのラビング条件でラビング処理を行い、実施例４と同様に、液晶セルを作製し配向の均一性および傾斜配向角の熱処理による変化を評価した。初期配向では、配向傾斜角２．０°で均一な配向状態が得られるものの、熱処理により配向傾斜角が２．６°に変化し、熱処理に対して安定な配向傾斜角を得ることができなかった。
【００９６】
比較例２
比較例１に記載したポリイミド樹脂膜のラビング処理による分子鎖の配向性を評価するため、実施例５と同様にラビング処理に対する△ｎｄ、および遅相軸とラビング方向とのずれ角を測定したところ、表５のように、いずれのラビング度でも△ｎｄが小さく、また遅相軸のずれ角は大きいことから、ラビング処理によるポリイミド分子鎖のラビング方向への配向の均一性が低いことが確認された。
【００９７】
【表５】

【００９８】
比較例３
等モル量のイソフタル酸クロリドとジアミノジフェニルエーテルを窒素気流中−７８℃のＮＭＰ中（濃度：1 mol/L）で反応させた後、室温で撹拌した。この溶液をメタノール中にあけ、析出した高分子を濾別して乾燥させた。この高分子を再度ＮＭＰに溶解させて、メタノールにあけ、析出した高分子を濾別して乾燥させた。この操作を繰り返して高分子を精製し、対応するポリアミド粉末を得た。得られたポリアミドをゲルパーミエーションクロマトグラフィーにより分子量測定したところ、ポリスチレン換算で数平均分子量：１．４×１０⁴、重量平均分子量：２．９×１０⁴であった。
【００９９】
このポリアミド粉末を、ＮＭＰとＢＳの混合溶媒（重量比８０：２０）に溶解させ、総固形分濃度５ｗｔ％溶液を調製した。この溶液をガラス基板上に回転数約３０００ｒｐｍでスピンコートし、ついで１８０℃で１時間加熱処理を行い、膜厚１０００Åのポリアミド樹脂膜を形成した。
このポリアミド樹脂膜のラビング処理による分子鎖の配向性を評価するため、実施例５と同様にラビング処理に対する△ｎｄ、および遅相軸とラビング方向とのズレ角を測定したところ、表６のように、いずれのラビング度でも△ｎｄが小さく、また遅相軸のズレ角は大きいことから、ラビング処理によるポリアミド分子鎖のラビング方向への配向の均一性が低いことが確認された。
【０１００】
【表６】

【０１０１】
比較例４
比較例１に記載のポリイミド前駆体溶液をＮＭＰとＢＳの混合溶媒（重量比８０：２０）で希釈し、総固形分濃度５ｗｔ％溶液を調製した。このポリイミド前駆体溶液をガラス基板上に回転数３２００ｒｐｍでスピンコートし、ついで２５０℃で１時間加熱処理を行うことによって膜厚１０００Åのポリイミド樹脂膜を形成した。
【０１０２】
このポリアミド樹脂膜をレーヨン布を用い、表３に記載の条件１でラビング処理を施した。このようにラビング処理された各々の基板を１．５μｍのスペーサーを挟んで、ラビング方向が平行にして組み立て、ついで強誘電性液晶（メルク社製ＺＬＩ−３４８９）を注入して、表面安定化型液晶セルを作製した。このセルの配向状態を偏光顕微鏡により観察したところ、多数のジグザグ欠陥、線状欠陥が観測され、強誘電性液晶の配向が不均一であった。
【図面の簡単な説明】
【図１】 実施例１で得られたポリアミドＰＡ−１のＩＲスペクトル。
【図２】 実施例２で得られたポリアミドＰＡ−２のＩＲスペクトル。
【図３】 実施例３で得られたポリアミドＰＡ−３のＩＲスペクトル。
【図４】 実施例１で得られたポリアミドＰＡ−１の¹Ｈ−ＮＭＲスペクトル。
【図５】 実施例２で得られたポリアミドＰＡ−２の¹Ｈ−ＮＭＲスペクトル。
【図６】 実施例３で得られたポリアミドＰＡ−３の¹Ｈ−ＮＭＲスペクトル。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polyamide compound and a liquid crystal aligning agent comprising the polyamide and having excellent processability and good liquid crystal alignment characteristics, and more specifically, nematic liquid crystal molecules at a relatively low film formation temperature. Has a low tilt alignment angle with respect to the substrate and exhibits good alignment stability in which the tilt alignment angle does not change during heat treatment after liquid crystal injection, and a ferroelectric liquid crystal and an antiferroelectric liquid crystal Relates to an alignment treatment agent for liquid crystal cells exhibiting excellent alignment uniformity with respect to the substrate.
[0002]
[Prior art]
A liquid crystal display element is a display element that utilizes electro-optical changes of liquid crystal, and has been noticed with characteristics such as small size and light weight and low power consumption. In recent years, it has made remarkable progress as a display device for various displays. It is accomplished. In particular, nematic liquid crystal having positive dielectric anisotropy is used, liquid crystal molecules are arranged parallel to the substrate at the respective interfaces of a pair of opposing electrode substrates, and the alignment directions of the liquid crystal molecules are orthogonal to each other. A typical example is a twisted nematic (TN) field-effect liquid crystal display element in which both substrates are combined.
[0003]
In such a TN type liquid crystal display element, it is important to align the major axis direction of the liquid crystal molecules uniformly in parallel with the substrate surface, and to align the liquid crystal molecules with a certain tilt alignment angle with respect to the substrate. is there. As a typical method for aligning liquid crystal molecules in this manner, two methods have been conventionally known.
The first method is a method in which an inorganic film such as silicon oxide is vapor-deposited obliquely with respect to the substrate to form an inorganic film on the substrate and align liquid crystal molecules in the vapor deposition direction. Although this method can provide a stable orientation having a constant tilt orientation angle, there are problems such as poor productivity and difficulty in increasing the area for industrial production.
[0004]
The second method is a method in which an organic film is provided on the surface of the substrate, the surface is rubbed in a certain direction with a cloth such as cotton, nylon, polyester, etc., and liquid crystal molecules are aligned in the rubbing direction. Since this method can obtain stable orientation relatively easily, this method is exclusively employed industrially. Examples of the organic film include polyvinyl alcohol, polyoxyethylene, polyamide, polyimide and the like, and polyimide is most commonly used from the viewpoint of chemical stability, thermal stability and the like. A typical example of polyimide used for such a liquid crystal alignment film is disclosed in Japanese Patent Application Laid-Open No. 61-47932.
[0005]
On the other hand, a ferroelectric liquid crystal or antiferroelectric liquid crystal having a chiral smectic phase is used, and liquid crystal molecules are aligned so that the layer direction is unidirectional with respect to the substrate at each interface of a pair of opposing electrode substrates. Ferroelectric liquid crystal display elements and anti-ferroelectric liquid crystal display elements have high-speed response and high viewing angle characteristics superior to those of nematic liquid crystal display elements due to the direct interaction between the spontaneous polarization of liquid crystal molecules and the electric field. It is known to have. Further, the surface stable ferroelectric liquid crystal element and the surface stable antiferroelectric liquid crystal element having a cell gap thinner than the helical pitch of the ferroelectric liquid crystal and the antiferroelectric liquid crystal are not in the nematic liquid crystal display element. It is known that it exhibits bistability and tristability, and can produce a high-definition display element even with a simple matrix electrode structure.
[0006]
In such ferroelectric liquid crystal elements and antiferroelectric liquid crystal elements, it is extremely important to align liquid crystal molecules uniformly and in a certain direction. As typical methods for aligning liquid crystals in this manner, as in the case of nematic liquid crystal display elements, an inorganic film such as silicon oxide is vapor-deposited from an oblique direction to form an inorganic film on the substrate, and an organic film is formed on the substrate surface. A method of rubbing the surface in a certain direction with a cloth is known. As the organic film to be rubbed, polyimide is generally used from the viewpoint of chemical stability, thermal stability and the like, as in the case of the nematic liquid crystal display element.
[0007]
[Problems to be solved by the invention]
Using nematic liquid crystal having positive dielectric anisotropy, both liquid crystal molecules are aligned parallel to the substrate at the respective interfaces of a pair of opposing electrode substrates, and the alignment directions of the liquid crystal molecules are orthogonal to each other. In a TN type field effect liquid crystal display element combined with a substrate, the major axis direction of the liquid crystal molecules is aligned uniformly and parallel to the substrate surface, and the liquid crystal molecules are aligned with a certain tilt alignment angle with respect to the substrate. It is important to let In particular, in recent years, in a TN type field effect liquid crystal display element, in order to improve contrast, it is required to stably obtain a tilted orientation angle as low as 3 ° or less, preferably about 1-2 °. Furthermore, development of a liquid crystal display element using a plastic film or the like as a base material has been actively promoted due to the necessity of reducing the weight of the element.
[0008]
However, in the conventional liquid crystal aligning agent using polyimide, it is common to apply a polyimide precursor solution onto a substrate and then form a polyimide film by dehydration and ring closure by heating and baking. For this reason, in general, high temperature baking at 200 ° C. or higher, preferably 250 ° C. to 300 ° C. or higher is required. In particular, baking at a higher temperature is important for obtaining more stable liquid crystal alignment.
[0009]
Depending on the type of polyimide, some polyimide itself is soluble in a solvent, and a liquid crystal aligning agent using the polyimide is heated and dried at a relatively low temperature of about 100 ° C. to 200 ° C., for example, on the substrate. A polyimide film can be formed. However, since the polyimide used in this case is soluble in a solvent, in general, the polyimide structure is often flexible, which is not always satisfactory in obtaining a more stable liquid crystal alignment.
[0010]
Furthermore, as described in, for example, Japanese Patent Application Laid-Open No. 59-200197, a polyamide resin has been used as a liquid crystal alignment film although a part of the polyamide resin has been used in the past. However, it is not always sufficient in terms of thermal stability of liquid crystal alignment or uniformity of alignment.
That is, conventionally, for a liquid crystal display element using a substrate having low heat resistance such as a plastic film, an alignment film material having a lower baking temperature has been required, and more stable and uniform liquid crystal alignment characteristics even at a low baking temperature. There has been a demand for a liquid crystal aligning agent capable of providing In particular, although there is an alignment film material that exhibits a low tilt alignment angle after liquid crystal injection, the tilt alignment angle is increased when heated above the isotropic temperature of liquid crystal (hereinafter referred to as isotropic treatment). In addition, there is a problem that the tilt alignment angle is lowered by the isotropic treatment and the alignment of the liquid crystal molecules is disturbed. Furthermore, generally, a resin film formed on a substrate is rubbed and used as a liquid crystal alignment film. At this time, liquid crystal molecules are aligned more uniformly than the conventional polyimide film in the rubbing direction. This is also an important issue in further improving the characteristics of future liquid crystal display elements. These problems are extremely important issues for further improving the performance of future liquid crystal display elements, that is, achieving a high-contrast and uniform liquid crystal display. There has been a strong demand for an alignment film material that can stably provide a low tilt orientation angle of 3 ° or less and can exhibit a uniform orientation in the rubbing direction.
[0011]
On the other hand, in ferroelectric liquid crystal elements and antiferroelectric liquid crystal elements, it is extremely important to obtain uniform initial alignment of the liquid crystal, and it is known that this alignment state greatly affects the performance of the liquid crystal element. . However, it is difficult to uniformly control the alignment state of the ferroelectric liquid crystal and the anti-ferroelectric liquid crystal. Generally, alignment defects such as zigzag defects are observed on the rubbed polyimide film, and this is a liquid crystal element such as a decrease in contrast. There has been a problem of significantly reducing the performance.
[0012]
When the liquid crystal alignment film is formed on the color filter, the alignment film is preferable because it can be fired at a lower temperature from the viewpoint of heat resistance. That is, there has been a strong demand for an alignment treatment agent that can be fired at a lower temperature and can uniformly align ferroelectric liquid crystals and antiferroelectric liquid crystals without defects.
[0013]
[Means for Solving the Problems]
The present invention relates to a polyamide and a liquid crystal aligning agent, and as a result of intensive studies on the expression of a low tilt alignment angle that is stable against heat treatment and the uniformity of liquid crystal alignment, the present inventors have found a novel polyamide resin and completed the present invention. It came to do. That is, in the present invention, the repeating unit is represented by the following general formula (I):
[0014]
Embedded image

[0015]
(WhereX ¹ And A ¹ Are both single bonds or X ¹ Is an oxygen atom, A ¹ Is a linear or branched alkylene group having 2 to 12 carbon atoms, or the following general formula (II)
[0016]
Embedded image

[0019]
Group represented byAnd X ² Is an oxygen atom and A ² Is the following general formula (IV)
[0020]
Embedded image

[0021]
A group represented by the formula:, R ¹ , R ² , R ^Five Are each independently a halogen atom or a linear or branched lower alkyl group or alkoxy group having 1 to 6 carbon atoms., N ¹ , N ² , N ^Five Are each independently an integer of 0-2The )And the following general formula (V)
[0022]
Embedded image

[0023]
(Wherein R⁶Is a halogen atom or a linear or branched lower alkyl group or alkoxy group having 1 to 6 carbon atoms, n⁶Is an integer from 0 to 2TheThe molar ratio of the repeating units represented by the general formula (I) and the general formula (V) is in the range of 90/10 to 10/90, and the weight average molecular weight is 1,000 or more. A polyamiDoIt is related with the liquid-crystal aligning agent which consists of these.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I), A¹And A²As the linear or branched alkylene group having 2 to 12 carbon atoms represented by the formula, a polymethylene group having 2 to 12 carbon atoms, or a methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec Examples thereof include a substituted polymethylene group having 2 to 12 carbon atoms having a butyl group, t-butyl group or the like in the side chain. In the general formulas (I) to (V), R¹~ R⁶Examples of the linear or branched lower alkyl group or alkoxy group having 1 to 6 carbon atoms represented by: methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, t-butyl Group, pentyl group, hexyl group, methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexyloxy group and the like.
[0025]
In the repeating unit represented by the general formula (I), the general formula (I) is represented by the following general formula (VI):
[0026]
Embedded image

[0027]
(Where A¹, A², X¹, X², R¹And n¹Is the same as defined in formula (I))
It is more preferable from the viewpoint of production and liquid crystal alignment characteristics.
In the general formula (I), the general formula (IV) is similarly represented by the following general formula (VII).
[0028]
Embedded image

[0029]
(Wherein R^Five,n ^Five Is preferably the same as defined in formula (I). The polyamide of the present invention in which the repeating unit is represented by the general formulas (I) and (V) can be produced, for example, by the synthesis method shown below. That is, the following general formula (VIII)
[0030]
Embedded image

[0031]
(Where A¹, A², R¹, X¹, X²And n¹Is as defined above. )
And an aminocarboxylic acid compound represented by the following general formula (IX)
[0032]
Embedded image

[0033]
(Wherein R⁶And n⁶Is as defined above. )
Can be synthesized by mixing with an aminobenzoic acid compound represented by the formula (1) to a molar ratio in the range of 90/10 to 10/90 and performing a polycondensation reaction by an ordinary method.
When the above monomer is used, the polycondensation reaction is preferably performed in the presence of a condensing agent, such as triphenyl phosphite, tritoluyl phosphite, tri (chlorophenyl) phosphite, phenyl dichlorophosphite, diphenyl dichlorophosphate. , Triphenylphosphine / hexachloroethane, diphenyl (2,3-hydro-2-thioxo-3-benzothiazolyl) phosphonate, (C_ThreeH₇)_ThreeP (O) O, POCl_Three, SOCl₂, SiCl_Four, (CH_Three)₂SiCl₂The reaction proceeds favorably by adding an organic base such as pyridine, 4- (dimethylamino) pyridine, triethylamine, N, N-dimethylaniline, imidazole or the like to a condensing agent such as, for example. This reaction is preferably carried out in an organic solvent, hexane, tetrahydrofuran, dioxane, dimethoxyethane, benzene, toluene, pyridine, chloroform, dichloroethane, dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoamide and the like are preferably used. Furthermore, when the solubility of the polyamide obtained by this condensation reaction is low, the reaction proceeds suitably by adding an inorganic base such as calcium chloride, lithium chloride or lithium bromide. The reaction temperature in this condensation reaction is usually preferably in the temperature range from room temperature to about 200 ° C.
[0034]
A in the general formula (VIII)¹, A², X¹And X²Specific examples of the aminocarboxylic acid compound in which each is a single bond and the aminobenzoic acid compound represented by the general formula (IX) include 4-aminobenzoic acid, 3-aminobenzoic acid, and 2-aminobenzoic acid. , And one or two hydrogen atoms at any position on the benzene ring of these aminobenzoic acids are a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a propyl group, or an iso-propyl group Butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, sec-butoxy group, t-butoxy group, pentoxy group or Examples include compounds substituted with a hexyloxy group.
[0035]
A in the general formula (VIII)²Is a group represented by the above general formula (II) or (III), or is an aminocarboxylic acid compound of the above general formula (IV), for example, an existing method such as a synthesis method shown in a later Reference Example It can be produced by synthetic means.
The following monomers derived from the compounds represented by the general formulas (VIII) and (IX), that is, the following general formula (X)
[0036]
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[0037]
(Where Y¹Is a triorganosilyl group, an acetyl group or a substituted acetyl group, A¹, A², R¹, X¹, X²And n¹Is as defined above. And a compound represented by the following general formula (XI)
[0038]
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[0039]
(Where Y¹, R⁶And n⁶Is as defined above. )
Or a polycondensation reaction is carried out in such a manner that the molar ratio is in the range of 90/10 to 10/90, or the following general formula (XII)
[0040]
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[0041]
(Formula; middle, Y²Is a lower alkyl group, a phenyl group or a substituted phenyl group, A¹, A², R¹, X¹, X²And n¹Is as defined above. )
And a compound represented by the following general formula (XIII)
[0042]
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[0043]
(Where Y², R⁶And n⁶Is as defined above. )
The target polyamide of the present invention can also be produced by mixing the compound represented by formula (I) with a molar ratio in the range of 90/10 to 10/90 and performing a polycondensation reaction.
Here, Y in the general formulas (X) and (XI)¹Among the substituents represented by the following formulas, the triorganosilyl group includes trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, t-butyldimethylsilyl group and the like, and the substituted acetyl group includes trifluoroacetyl group, bromo Examples thereof include an acetyl group, a dibromoacetyl group, and a phenylacetyl group. On the other hand, Y in the general formulas (X) and (XI)²Among the substituents represented by the following, as the lower alkyl group, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, etc. Examples of the substituted phenyl group include a chlorophenyl group and a nitrophenyl group.
[0044]
When the polycondensation reaction is performed using the monomer compounds represented by the general formulas (X) and (XI) or the monomer compounds represented by the general formulas (XII) and (XIII), respectively, Similar to the case of performing the polycondensation reaction using the monomer compounds represented by (VIII) and (IX), the desired polyamide is obtained by reacting in the presence of the above-mentioned condensing agent in an organic solvent as necessary. In addition, after adding a predetermined amount of each monomer, a catalyst is added if necessary, and the target polyamide of the present invention is obtained by raising the temperature to a temperature at which the monomer melts under normal pressure or reduced pressure. Can be manufactured. Examples of the catalyst used here include sulfuric acid, nitric acid, tosylic acid, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, aluminum chloride, tributylaluminum, titanium chloride, tributyltitanium, lead acetate and the like.
[0045]
In the polyamide of the present invention in which the repeating unit obtained by the production method as described above is represented by the general formulas (I) and (V), it is represented by the general formula (I) and the general formula (V). The molar ratio of the repeating units is preferably in the range of 90/10 to 10/90, more preferably in the range of 70/30 to 30/70, from the viewpoints of solubility and moldability. The weight average molecular weight of the polyamide of the present invention is preferably 1,000 or more, more preferably 3,000 or more from the viewpoint of stability and the like. The molecular weight is measured by a known method such as gel permeation chromatography, osmotic pressure method, light scattering method, viscosity method and the like.
[0046]
When using the polyamide as a liquid crystal aligning agent, the polyamide resin solution obtained by the condensation reaction can be used as it is. Further, after once isolating the polyamide from the obtained polyamide solution, it can be redissolved in an appropriate solvent and used. The solvent to be re-dissolved is not particularly limited as long as it can dissolve the obtained polyamide. Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, hexa Examples include methylphosphoamide, γ-butyrolactone, tetrahydrofuran, pyridine, chloroform, dichloromethane, chlorobenzene, dichlorobenzene, phenol, p-chlorophenol, anisole, cresol and the like.
[0047]
Further, for the purpose of improving the coating property to the substrate, even if the solvent alone does not dissolve the polyamide, it may be added to the above solvent as long as the solubility is not impaired. Examples thereof include butyl cellosolve, ethyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, toluene, xylene and the like. Furthermore, additives such as a silane coupling agent can be appropriately used for the purpose of improving the adhesion to the substrate.
[0048]
The polyamide solution of the present invention obtained as described above is applied onto a substrate such as glass, wafer or plastic using a method such as spin coating or transfer printing, and this is heated to form a polyamide film. It is common to do. As this heat treatment temperature, an arbitrary temperature of 50 ° C. to 450 ° C., preferably 80 ° C. to 350 ° C. can be selected. However, in forming a liquid crystal alignment film for obtaining the effects of the present invention, generally, A relatively low heating temperature of 80 ° C. to 200 ° C. can be employed. The thickness of the polyamide film at this time is not particularly limited, but is suitably 100 to 3000 mm when used as a normal liquid crystal alignment film. Next, the resin film can be subjected to alignment treatment such as rubbing treatment and used as a liquid crystal alignment treatment agent.
[0049]
The rubbing treatment is generally performed by rotating a roller wrapped with a cloth such as cotton, nylon, polyester, etc., bringing the roller into contact with the substrate with a constant pressing pressure, and moving the substrate or roller at a constant speed. Can do. Moreover, it can also be performed by moving the roller or the substrate while the roller is not rotating. It has been reported that the strength of rubbing in rotational rubbing is expressed by a rubbing degree (mm) defined by the following equation.
[0050]
[Formula 1]
L = N · M {(2πrn / 60V) -1} (1)
In equation (1), N is the number of rubbing, M is the amount of pushing (mm), r is the radius of the rubbing roller (mm), n is the number of rotations of the roller (rpm), and V is the moving speed of the stage (mm / Second). The degree of rubbing that can be used in the present invention is not particularly limited, but is preferably 500 mm or less from the viewpoint of the adhesion of the polyamide film.
[0051]
It is known that the polymer chain is oriented in the rubbing direction by such rubbing treatment, and the effect of orientation of this polymer film is generally due to the birefringence phase difference of the polyamide film induced after the rubbing treatment. It can also be evaluated by measuring the deviation angle between the rubbing direction and the slow axis. The principle of this measurement is described in the following document.
An Improved Method for High Reflectivity-Elipsometry Based on a New Polarization Modulation Technique (S. N. Jasperson & E. Schnatter.) Sci. Inst. , Vol. 40, page 761, 1969
High Frequency Polarization Modulation Method for Measuring Birefrin-gene (FA Modoine, RW Major & E. Sonder) Appl. Opt. , Vol14, no. 3,1975
[0052]
The polyamide resin in the present invention has particularly excellent characteristics as a liquid crystal aligning agent, but in order to obtain the effects of the present invention, the polyamide molecular chain is stretched by rubbing and uniformly aligned in the rubbing direction. This is very important. The magnitude of birefringence induced by rubbing depends on the refractive index anisotropy of the polymer structural unit, the degree of rubbing, the stretched film thickness, etc., but the higher the birefringence phase difference, the higher the polymer chain. It is considered that the angle of deviation between the rubbing direction and the slow axis indicates that the smaller the size, the more the polymer chain is oriented in the rubbing direction. It is done. In order to obtain the effect of the present invention, the birefringence retardation is preferably 0.5 nm or more when the rubbing degree is 10 to 100 mm, and the rubbing degree is preferably 100 nm or more and 1.0 nm or more. The deviation angle between the direction and the slow axis is preferably 1.0 ° or less, more preferably 0.5 ° or less.
[0053]
Thus, by using the liquid crystal aligning agent in which the polymer chains are uniformly aligned in one direction by rubbing, the liquid crystal molecules can be uniformly aligned. Hereinafter, the present invention will be described in more detail with reference examples, examples and comparative examples. However, it is needless to say that the present invention is not limited to these.
[0054]
【Example】
Reference example 1
[0055]
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[0056]
4-Fluoronitrobenzene 2.82 g (20.0 mmol) and benzyl 4-hydroxybenzoate 4.57 g (20.0 mmol) were dissolved in 10 mL of dimethyl sulfoxide (hereinafter abbreviated as DMSO). To this, 2.76 g (20.0 mmol) of potassium carbonate was added and stirred at 80 ° C. for 16 hours. When the reaction solution was poured into 1.5 L of water, an oily substance precipitated on the bottom of the container. The operation of discarding the supernatant and adding 1.0 L of ice water and discarding the supernatant was performed twice. Finally, the precipitate was dissolved in ether and dried over sodium sulfate. After concentration, purification by column chromatography (filler; silica gel, developing solvent; ether / hexane = 1/5 Vol.) Gave 6.91 g of the ester compound represented by the structural formula (1) as a pale yellow liquid. It was. Yield: 99.0%
IR (neat, cm^-1): 3111 (w), 3079, 3034 (w), 2953 (w), 1717 (s), 1607, 1588 (s), 1518 (s), 1489, 1456, 1414 (w), 1375, 1345 (s ), 1308, 1273 (s), 1246 (s), 1163 (s), 1111 (s), 1014, 880, 851, 750, 698, 513.
¹H-NMR (CDCl_Three, ppm): δ = 5.38 (s, 2H), 7.09 (d, 2H, J = 9.2Hz), 7.11 (d, 2H, J = 8.9Hz), 7.34-7.47 (m, 5H), 8.14 (d, 2H, J = 8.9Hz), 8.25 (d, 2H, J = 9.2Hz).
EI-MS: m / z = 349 (M)⁺, 319 (M-NO)⁺, 304, 242 (M-OCH₂Ph)⁺, 212 (M-OCH₂Ph-NO)⁺, 196, 168, 139 (O₂NC₆H_FourOH)⁺, 107 (OCH₂Ph)⁺, 91 (CH₂Ph)⁺.
[0057]
8.7 g (25 mmol) of the ester compound (1) obtained by the above method and 1.0 g of 5% Pd-carbon powder were mixed with 30 mL of tetrahydrofuran (hereinafter abbreviated as THF) and 30 mL of ethanol. After stirring in a hydrogen gas atmosphere for about 6 hours under normal pressure, the reaction solution was filtered through Celite. When the filtrate was concentrated, 5.47 g of the aminocarboxylic acid compound represented by the structural formula (2) was obtained as a light brown powder. Yield: 96%
IR (KBr disk, cm^-1): 3360 (m, NH₂ st as), 3293 (m, NH₂ st sy), 2600 (vb, COO-H st), 1672 (s, C = O st), 1601 (s, arC-C st), 1503 (s, arC-C), 1422, 1269 (s, arC -N st), 1236 (s, arC-O-arC st), 1161, 880, 503.
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ = 5.1 (-NH₂), 6.62 (d, 2H, J = 8.7Hz), 6.81 (d, 2H, J = 8.7Hz), 6.90 (d, 2H, J = 8.8Hz), 7.88 (d, 2H, J = 8.8Hz), 12.6 (-COOH).
EI-MS: m / z = 229 (M)⁺, 156, 108 (H₂NC₆H_FourO)⁺.
Elemental analysis results (C1_ThreeH₁₁NO_Three, Molecular weight: 229.23)
Calculated C: 68.11%, H: 4.84%, N: 6.11%
Found C: 68.34%, H: 4.96%, N: 5.96%
Reference example 2
[0058]
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[0059]
4-Fluoronitrobenzene 2.82 g (20.0 mmol) and 4-methoxyphenol 2.48 g (20.0 mmol) were dissolved in DMSO 10 mL. To this, 2.76 g (20.0 mmol) of potassium carbonate was added and stirred at 80 ° C. for 14 hours, and then the reaction solution was poured into 1.0 L of water. The resulting precipitate was collected by filtration and dried to obtain 4.90 g of a methoxy compound represented by the above structural formula (3) as a white powder. Yield: 100%
[0060]
IR (KBr disk, cm^-1): 3107 (w), 3007 (w), 2845 (w), 1611, 1588, 1507 (s), 1487, 1447, 1343 (s), 1298 (w), 1238 (s), 1194, 1163, 1109 , 1030, 1009 (w), 878, 843, 802, 748, 714 (w), 567 (w), 532 (w), 523 (w), 492 (w).
¹H-NMR (CDCl_Three, ppm): δ = 3.83 (s, 3H), 6.96 (d, 2H, J = 9.2Hz), 7.0 (m, 4H), 8.18 (d, 2H, J = 9.2Hz).
[0061]
4.90 g (20.0 mmol) of the methoxy compound (3) obtained by the above method was dissolved in 50 mL of acetic acid and 10 mL of 47% odorous acid water. The oil bath was set at 130 ° C. and stirred for 14 hours. When 200 mL of water was added and cooled to room temperature, precipitation occurred, and this yellow powder was collected by filtration. After drying under reduced pressure at 60 ° C. for 3 hours and recrystallization purification from chloroform, 3.63 g of the phenol derivative represented by the above structural formula (4) was obtained as brown plate crystals. Yield: 78.6%
IR (KBr disk, cm^-1): 3439 (s), 1609, 1588, 1507 (s), 1485, 1427, 1345 (s), 1271, 1242 (s), 1192, 1161, 1111, 1011 (w), 878, 855, 841, 814 , 748, 569, 503.
¹H-NMR (CDCl_Three, ppm): δ = 6.9-7.0 (m, 6H), 8.16 (d, 2H, J = 9.2Hz), 8.56 (bs, 1H).
[0062]
3.60 g (15.6 mmol) of the phenol derivative (4) obtained by the above method and 1.93 g (15.6 mmol) of 4-fluorobenzaldehyde were dissolved in 10 mL of DMSO. Potassium carbonate 2.15 g (15.6 mmol) was added here, and it stirred at 80 degreeC for 16 hours. The reaction solution was poured into 1.5 L of water, and the resulting precipitate was collected by filtration and further washed with a small amount of methanol. The residue was recrystallized and purified from chloroform to obtain 3.14 g of an aldehyde compound represented by the structural formula (5) as yellow crystals. Yield: 60.1%
IR (neat, cm^-1): 1690, 1595, 1508, 1497, 1485 (s), 1340, 1235 (vs), 1188, 1155 (m), 1109 (m), 880, 847 (w), 866 (w), 748 (w) , 540 (w).
¹H-NMR (CDCl_Three, ppm): δ = 7.06 (d, 2H, J = 9.2Hz), 7.0-7.2 (m, 6H), 7.89 (d, 2H, J = 8.8Hz), 8.23 (d, 2H, J = 9.2Hz) , 9.95 (s, 1H).
Elemental analysis results (C₁₉H₁₃NO_Five, Molecular weight: 335.32)
Calculated C: 68.06%, H: 3.91%, N: 4.18%
Measured value C: 67.98%, H: 3.64%, N: 4.23%
2.74 g (8.17 mmol) of the aldehyde compound (5) obtained by the above method was dissolved in 200 mL of acetone. To this was added 50 mL of an aqueous solution in which 3.00 g of potassium permanganate was dissolved, and the mixture was stirred at reflux temperature for 3 hours. 20 mL of methanol was added and the mixture was further stirred for 30 minutes, and then filtered through a glass filter while hot. The filtrate was washed twice with 200 mL of heat (water / ethanol / acetone). The filtrate was acidified with 10 N hydrochloric acid to produce a precipitate, which was dried to obtain 2.40 g of a benzoic acid derivative represented by the above structural formula (6) as a white powder. Yield: 83.6%
[0063]
IR (KBr disk, cm^-1): 2849 (b), 2560 (b), 1674, 1597, 1508, 1487, 1429 (m), 1341, 1294 (w), 1235 (vs), 1188, 1165, 1111 (m), 1015 (w) , 876 (m), 847 (m), 774 (w), 750 (w), 534 (w).
¹H-NMR (CDCl_Three+ DMSO-d₆, ppm): δ = 7.00 (d, 2H, J = 8.8Hz), 7.0-7.1 (m, 6H), 8.05 (d, 2H, J = 8.8Hz), 8.22 (d, 2H, J = 9.2Hz) .
Elemental analysis results (C₁₉H₁₃NO₆, Molecular weight: 351.31)
Calculated C: 64.96%, H: 3.73%, N: 3.99%
Measured value C: 65.01%, H: 3.68%, N: 3.97%
2.17 g (6.18 mmol) of the benzoic acid derivative (6) obtained by the above method and 0.26 g of 5% Pd-carbon powder were mixed with 50 mL of THF and 30 mL of ethanol. After stirring in a hydrogen gas atmosphere for about 6 hours under normal pressure, the reaction solution was filtered through Celite. The filtrate was concentrated and recrystallized and purified from a THF / ethanol mixed solvent to obtain 0.93 g of an aminocarboxylic acid compound represented by the structural formula (7) as a light brown powder. Yield: 47%
[0064]
IR (KBr disk, cm^-1): 3366 (w, NH₂ st as), 3293 (w, NH₂ st sy), 2600 (vb, COO-H st), 1684 (b, C = O st), 1601 (m, arC-C st), 1495 (s, arC-C), 1283 (m, arC-N st), 1229 (bm, arC-O-arC st), 1192 (m), 1165 (m), 872 (w), 835 (w), 507 (w).
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ = 6.60 (d, 2H, J = 8.7Hz), 6.80 (d, 2H, J = 8.7Hz), 6.93 (d, 2H, J = 9.0Hz), 6.98 (d, 2H, J = 8.8Hz), 7.09 (d, 2H, J = 9.0Hz), 7.92 (d, 2H, J = 8.8Hz).
EI-MS: m / z = 321 (M)⁺, 108 (H₂NC₆H_FourO)⁺.
Elemental analysis results (C₁₃H₁₁NO_Three+ 1 / 4C₂H_FiveOH, molecular weight: 321.33 + 1 / 4C₂H_Five(OH = 332.85)
Calculated C: 70.37%, H: 5.00%, N: 4.21%
Measured value C: 70.36%, H: 4.92%, N: 4.19%
Reference example 3
[0065]
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[0066]
10.0 g (43.8 mmol) of benzyl 4-hydroxybenzoate and 100 g (463 mmol) of 1,4-dibromobutane were dissolved in 50 mL of acetone. To this were added potassium carbonate 6.1 g (44 mmol) and potassium iodide 0.5 g, and the mixture was stirred at reflux temperature for 15 hours. After cooling to room temperature, 150 mL of ether was added and the insoluble material was filtered off. After distilling off the solvent and unreacted dibromobutane under reduced pressure, the residue was purified by column chromatography (filler; silica gel, developing solvent; ether / hexane = 1/16 Vol.). 15.1 g of the ester compound represented was obtained as a colorless transparent liquid. Yield: 94.6%
IR (neat, cm^-1): 3065 (w), 3034 (w), 2951, 2876 (w), 1713 (s), 1607, 1582 (w), 1510, 1456 (w), 1422 (w), 1377, 1314, 1256 (s ), 1169, 1101, 1030, 1009 (w), 953 (w), 914 (w), 849, 770, 750 (w), 698, 648 (w), 600 (w), 561 (w), 511 (w).
¹H-NMR (CDCl_Three, ppm): δ = 2.0 ~ 2.1 (m, 4H), 3.48 (t, 2H, J = 6.2Hz), 4.04 (t, 2H, J = 5.7Hz), 5.33 (s, 2H), 6.89 d, 2H , J = 9.0Hz), 7.3 to 7.4 (m, 5H), 8.02 (d, 2H, J = 9.0Hz).
[0067]
The ester compound (8) obtained by the above method (8) (5.63 g, 15.5 mmol) and 4-nitrophenol (2.16 g, 15.5 mmol) were dissolved in acetone (60 mL). To this were added 2.14 g (15.5 mmol) of potassium carbonate and 0.1 g of potassium iodide, and the mixture was stirred at reflux temperature for 12 hours. After cooling to room temperature, 300 mL of acetone was added and the insoluble material was filtered off and washed. The filtrate was concentrated and 300 mL of chloroform and 200 mL of water were added to extract the organic phase. The extract was dried over sodium sulfate, concentrated, and recrystallized from benzene to obtain 3.37 g of the ester compound represented by the structural formula (9) as a white powder. Yield: 51.6%
IR (KBr disk, cm^-1): 3086 (vw), 2961 (w), 2938 (w), 2882 (w), 1709 (s), 1607, 1595, 1512 (s), 1501, 1474 (m), 1456 (w), 1424 ( w), 1400 (vw), 1379 (w), 1345 (s), 1304, 1254 (s), 1173, 1113, 1057 (m), 1003, 843, 766 (m), 750 (m), 739 ( m), 691 (w), 664 (m), 496 (w).
¹H-NMR (CDCl_Three, ppm): δ = 2.0 to 2.1 (m, 4H), 4.10 (t, 2H, J = 2.0Hz), 4.14 (t, 2H, J = 2.0Hz), 5.34 (s, 2H), 6.90 (d, 2H, J = 9.0Hz), 6.94 (d, 2H, J = 9.2Hz), 7.3 to 7.4 (m, 5H), 8.03 (d, 2H, J = 8.8Hz), 8.20 (d, 2H, J = 9.2 Hz).
3.28 g (7.78 mmol) of the ester compound (9) obtained by the above method was dissolved in a mixed solvent of 140 mL of THF and 60 mL of ethanol. To this, 0.55 g of 5% Pd-carbon powder was added. After stirring overnight in a hydrogen gas atmosphere under normal pressure, 40 mL of N, N-dimethylformamide (hereinafter abbreviated as DMF) was added, and the reaction solution was filtered through Celite. When the filtrate was concentrated, 2.32 g of the aminocarboxylic acid compound represented by the structural formula (10) was obtained as a light reddish brown powder. Yield: 85.1%
IR (KBr disk, cm^-1): 3356 (w, NH₂ st as), 3281 (w, NH₂ st sy), 3067 (vw shoulder, arC-H st), 2949 (m, alC-H st as), 2878 (m, alC-H st sy), 2550 (b, COO-H st; hydrogen bonded), 1682 (bw, al-C = O st; hydrogen bonded), 1607 (m, arC-C), 1516 (s, -NH₂ δ), 1476 (m, -CH₂ δ), 1387 (m), 1252 (s, arC-N st), 1173 (m), 1011 (m), 828 (w, -NH₂ δ), 650, 517.
¹H-NMR (DMSO-d₆, 400MHz, ppm): δ = 1.81 (m, 2H), 1.84 (m, 2H), 3.88 (t, 2H), 4.10 (t, 2H), 5.3 (-NH₂), 6.49 (d, 2H, J = 8.8Hz), 6.65 (d, 2H, J = 8.8Hz), 7.01 (d, 2H), 7.88 (d, 2H).
EI-MS: m / z = 301 (M)⁺, 193 (M-OC₆H_FourNH₂)⁺, 151 (CH₂OC₆H_FourCOOH)⁺, 121 (C₆H_FourCOOH)⁺, 109 (H₂NC₆H_FourOH)⁺, 92 (H₂NC₆H_Four)⁺.
Elemental analysis results (C₁₇H₁₉NO_Four, Molecular weight: 301.34)
Calculated C: 67.76%, H: 6.35%, N: 4.65%
Actual value C: 67.63%, H: 6.50%, N: 4.67%
[0068]
Examples 1-3
[0069]
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[0070]
To the aminocarboxylic acid compound (2), (7) or (10) obtained in Reference Examples 1 to 3, 3-aminobenzoic acid (hereinafter abbreviated as MABA) is mixed so as to have a predetermined molar ratio, N-methylpyrrolidone (hereinafter abbreviated as NMP) and 1.2 equivalents of pyridine (hereinafter abbreviated as Py) and 1.2 equivalents of triphenyl phosphite (hereinafter abbreviated as TPP) with respect to the molar amount of the total monomers, Stir at 18 ° C. for 18 hours. The amounts of the above-mentioned monomers, reagents and solvents actually used are summarized in Table 1 below. Next, the reaction solution was diluted 2 times with NMP and then poured into about 100 times amount of methanol with stirring. The resulting precipitate was collected by filtration and dried overnight at 60 ° C. under reduced pressure to obtain polyamides represented by the structural formulas PA-1, PA-2 and PA-3, respectively. The yield of the polyamide obtained,¹The copolymer composition (x / y in the above structural formula) determined from the 1 H-NMR spectrum and the number average molecular weight and weight average molecular weight determined by gel permeation chromatography are shown in Table 2 below. In addition, IR spectra of the obtained PA-1, PA-2 and PA-3 are shown in FIGS.¹H-NMR spectra are shown in FIGS. 4, 5 and 6, respectively.
[0071]
[Table 1]

[0072]
[Table 2]

[0073]
Example 4
The polyamide PA-1 obtained in Example 1 was dissolved in a mixed solvent (weight ratio 80:20) of NMP and butyl cellosolve (hereinafter abbreviated as BS) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotational speed of 2500 rpm, followed by heat treatment at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0074]
The polyamide resin film was rubbed using rayon cloth under the conditions shown in Table 3. Each of the substrates thus rubbed is assembled with a 50 μm spacer in between and the rubbing direction is anti-parallel, and then liquid crystal (ZLI-2293 manufactured by Merck) is injected to align the cells in parallel with the substrate. Was made. When the alignment state of the cell was observed with a polarizing microscope, no defects were observed under any rubbing condition, and it was confirmed that the liquid crystal was uniformly aligned. In addition, when the tilt angle was measured by the crystal rotation method, the tilt angle as low as 1.7 ° under condition 1, 1.4 ° under condition 2, and 1.3 ° under condition 3 was stably obtained. Was confirmed.
[0075]
Further, in order to evaluate the change in the tilted orientation angle and the orientation state with respect to the heat treatment, the liquid crystal cell was sequentially heated at 95 ° C. for 10 minutes, 120 ° C. for 1 hour, and 120 ° C. for 6 hours. It was confirmed that no disorder or defect was observed, uniform orientation was maintained, and there was no change in tilt orientation angle.
[0076]
[Table 3]

[0077]
Example 5
In order to evaluate the orientation of the molecular chain by the rubbing treatment of the polyamide resin film described in Example 4, the polyamide resin film was rubbed at various strengths, and the birefringence was measured by a high-sensitivity automatic birefringence measuring apparatus manufactured by Oak Manufacturing Co., Ltd. A phase difference (hereinafter abbreviated as Δnd) and a deviation angle between the slow axis and the rubbing direction were measured. In order to quantify the strength of rubbing, a rubbing degree L (mm) calculated by the following formula (1) was introduced.
[0078]
[Expression 2]
L = N · M {(2πrn / 60V) -1} (1)
In equation (1), N is the number of rubbing, M is the amount of pushing (mm), r is the radius of the rubbing roller (mm), n is the number of rotations of the roller (rpm), and V is the moving speed of the stage (mm / Second). Table 4 shows the rubbing degree dependency of the birefringence phase difference and the slow axis deviation angle with respect to the rubbing intensity. Even when the degree of rubbing is relatively small, a large Δnd value is observed, and the deviation angle of the slow axis is extremely small, so that the polyamide molecular chains are uniformly oriented in the rubbing direction by rubbing treatment. confirmed.
[0079]
[Table 4]

[0080]
Example 6
The polyamide PA-2 obtained in Example 2 was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotation speed of 2800 rpm, and then heat-treated at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0081]
As in Example 4, a rubbing treatment was performed under different rubbing conditions to prepare a liquid crystal cell, and the uniformity of alignment and the tilted orientation angle were evaluated. A uniform and good alignment state was obtained under any rubbing condition, It was confirmed that a low tilt orientation angle of 1.4 ° under rubbing condition 1, 1.2 ° under condition 2 and 1.0 ° under condition 3 was stably obtained.
[0082]
Furthermore, when the change in the tilt orientation and orientation state with respect to the heat treatment was evaluated under the same conditions as in Example 4, no orientation disorder or defect was observed due to the heat treatment, and no change in the tilt orientation angle was seen. .
[0083]
Example 7
In order to evaluate the orientation of the molecular chain by the rubbing treatment of the polyamide resin film described in Example 6, Δnd with respect to the rubbing treatment and the deviation angle between the slow axis and the rubbing direction were measured in the same manner as in Example 5. As the rubbing degree increased, Δnd increased and the slow axis deviation angle was small, so it was confirmed that the polyamide molecular chains were uniformly oriented in the rubbing direction by rubbing treatment.
[0084]
Example 8
The polyamide PA-3 obtained in Example 3 was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution with a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotational speed of 3000 rpm, followed by heat treatment at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0085]
As in Example 4, a rubbing treatment was performed under different rubbing conditions to prepare a liquid crystal cell, and the uniformity of alignment and the tilted orientation angle were evaluated. A uniform and good alignment state was obtained under any rubbing condition, It was confirmed that a low tilt orientation angle of 2.0 ° under rubbing condition 1, 1.7 ° under condition 2 and 1.3 ° under condition 3 was stably obtained.
[0086]
Furthermore, when the change in the tilt orientation and orientation state with respect to the heat treatment was evaluated under the same conditions as in Example 4, no orientation disorder or defect was observed due to the heat treatment, and no change in the tilt orientation angle was seen. .
[0087]
Example 9
In order to evaluate the orientation of the molecular chain by the rubbing treatment of the polyamide resin film described in Example 8, Δnd with respect to the rubbing treatment and the deviation angle between the slow axis and the rubbing direction were measured in the same manner as in Example 5. As the rubbing degree increased, Δnd increased and the slow axis deviation angle was small, and it was confirmed that the polyamide molecular chains were uniformly oriented in the rubbing direction by rubbing treatment.
[0088]
Example 10
The polyamide PA-1 obtained in Example 1 was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotational speed of 2500 rpm, followed by heat treatment at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0089]
This polyamide resin film was subjected to rubbing treatment under the condition 1 shown in Table 3 using a nylon cloth. Each of the substrates thus rubbed is assembled with a 2 μm spacer in between and the rubbing directions are parallel, and then a ferroelectric liquid crystal (ZLI-3489 manufactured by Merck) is injected to form a surface-stabilized liquid crystal cell. Was made. When the alignment state of the cell was observed with a polarizing microscope, no defects were observed over the entire area of the liquid crystal cell, and it was confirmed that the ferroelectric liquid crystal was uniformly aligned.
[0090]
Example 11
The polyamide PA-2 obtained in Example 2 was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotation speed of 2800 rpm, and then heat-treated at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0091]
This polyamide resin film was subjected to rubbing treatment under the condition 1 shown in Table 3 using a nylon cloth. Each of the substrates thus rubbed is assembled with a 1.5 μm spacer in between and the rubbing directions are parallel, and then a ferroelectric liquid crystal (ZLI-3389 manufactured by Merck) is injected to stabilize the surface. A liquid crystal cell was produced. When the alignment state of the cell was observed with a polarizing microscope, no defects were observed over the entire area of the liquid crystal cell, and it was confirmed that the ferroelectric liquid crystal was uniformly aligned.
[0092]
Example 12
The polyamide PA-3 obtained in Example 3 was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotational speed of 3000 rpm, followed by heat treatment at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
[0093]
This polyamide resin film was subjected to rubbing treatment under the condition 1 shown in Table 3 using a nylon cloth. Each of the substrates thus rubbed is assembled with a 1.5 μm spacer in between and the rubbing directions are parallel, and then a ferroelectric liquid crystal (ZLI-3389 manufactured by Merck) is injected to stabilize the surface. A liquid crystal cell was produced. When the alignment state of the cell was observed with a polarizing microscope, no defects were observed over the entire area of the liquid crystal cell, and it was confirmed that the ferroelectric liquid crystal was uniformly aligned.
[0094]
Comparative Example 1
Pyromellitic dianhydride and diaminodiphenyl ether were reacted in NMP to polymerize the polyimide precursor. This solution was diluted with a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This polyimide precursor solution was spin-coated on a glass substrate at a rotational speed of 3200 rpm, and then a heat treatment was performed at 250 ° C. for 1 hour to form a polyimide resin film having a thickness of 1000 mm.
[0095]
A rubbing process was performed under a rubbing condition of a roller rotation speed of 300 rpm, a stage moving speed of 20 mm / sec, and an indentation amount of 0.5 mm, and a liquid crystal cell was prepared in the same manner as in Example 4 to change the alignment uniformity and the tilt alignment angle by heat treatment. Evaluated. In the initial orientation, a uniform orientation state can be obtained at an orientation tilt angle of 2.0 °, but the orientation tilt angle is changed to 2.6 ° by heat treatment, and a stable orientation tilt angle cannot be obtained with respect to the heat treatment. It was.
[0096]
Comparative Example 2
In order to evaluate the orientation of the molecular chain by the rubbing treatment of the polyimide resin film described in Comparative Example 1, Δnd with respect to the rubbing treatment and the deviation angle between the slow axis and the rubbing direction were measured in the same manner as in Example 5. As shown in Table 5, since Δnd is small and the slow axis deviation angle is large at any rubbing degree, it was confirmed that the uniformity of orientation in the rubbing direction of the polyimide molecular chain by rubbing treatment was low. It was.
[0097]
[Table 5]

[0098]
Comparative Example 3
An equimolar amount of isophthalic acid chloride and diaminodiphenyl ether were reacted in NMP (concentration: 1 mol / L) in a nitrogen stream at −78 ° C. and then stirred at room temperature. This solution was poured into methanol, and the precipitated polymer was separated by filtration and dried. This polymer was dissolved again in NMP, poured into methanol, and the precipitated polymer was filtered and dried. This operation was repeated to purify the polymer and obtain the corresponding polyamide powder. When the molecular weight of the obtained polyamide was measured by gel permeation chromatography, the number average molecular weight in terms of polystyrene was 1.4 × 10.^Four, Weight average molecular weight: 2.9 × 10^FourMet.
[0099]
This polyamide powder was dissolved in a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This solution was spin-coated on a glass substrate at a rotational speed of about 3000 rpm, followed by heat treatment at 180 ° C. for 1 hour to form a polyamide resin film having a thickness of 1000 mm.
In order to evaluate the orientation of the molecular chain by rubbing treatment of this polyamide resin film, Δnd with respect to the rubbing treatment as well as the deviation angle between the slow axis and the rubbing direction were measured in the same manner as in Example 5. In addition, since Δnd was small for each rubbing degree and the shift angle of the slow axis was large, it was confirmed that the alignment uniformity of the polyamide molecular chain in the rubbing direction by rubbing treatment was low.
[0100]
[Table 6]

[0101]
Comparative Example 4
The polyimide precursor solution described in Comparative Example 1 was diluted with a mixed solvent of NMP and BS (weight ratio 80:20) to prepare a solution having a total solid content concentration of 5 wt%. This polyimide precursor solution was spin-coated on a glass substrate at a rotational speed of 3200 rpm, and then a heat treatment was performed at 250 ° C. for 1 hour to form a polyimide resin film having a thickness of 1000 mm.
[0102]
The polyamide resin film was subjected to rubbing treatment under the condition 1 shown in Table 3 using a rayon cloth. Each of the substrates thus rubbed is assembled with a 1.5 μm spacer in between and the rubbing directions are parallel, and then a ferroelectric liquid crystal (ZLI-3389 manufactured by Merck) is injected to stabilize the surface. A liquid crystal cell was produced. When the alignment state of this cell was observed with a polarizing microscope, many zigzag defects and linear defects were observed, and the alignment of the ferroelectric liquid crystal was non-uniform.
[Brief description of the drawings]
1 is an IR spectrum of polyamide PA-1 obtained in Example 1. FIG.
2 is an IR spectrum of polyamide PA-2 obtained in Example 2. FIG.
3 is an IR spectrum of polyamide PA-3 obtained in Example 3. FIG.
FIG. 4 shows the polyamide PA-1 obtained in Example 1.¹H-NMR spectrum.
FIG. 5 shows the polyamide PA-2 obtained in Example 2.¹H-NMR spectrum.
FIG. 6 shows the polyamide PA-3 obtained in Example 3.¹H-NMR spectrum.

Claims (3)

The repeating unit is represented by the following general formula (I)

Wherein X ¹ and A ¹ are both a single bond, X ¹ is an oxygen atom, A ¹ is a linear or branched alkylene group having 2 to 12 carbon atoms, or the following general formula (II)

A group represented by
X ² is an oxygen atom,
A ² is a group represented by the following general formula (IV),

In the above formula , R ¹ , R ² and R ⁵ are each independently a halogen atom or a linear or branched lower alkyl group or alkoxy group having 1 to 6 carbon atoms , and n ¹ , n ² and n ⁵ are each independently to Ru integer der of 0-2. )
And the following general formula (V)

(Wherein, R ⁶ is a halogen atom or a linear or branched lower alkyl group or an alkoxy group having 1 to 6 carbon atoms, n ⁶ is an integer of 0 to 2.)
The molar ratio of the repeating units represented by the general formula (I) and the general formula (V) is in the range of 90/10 to 10/90, and the weight average molecular weight is 1,000 or more. Liquid crystal aligning agent made of polyamide. The general formula (I) of the repeating unit is represented by the following general formula (VI)

^{(Wherein, A 1, A 2, X} 1, X 2, R 1 and n ¹ are defined as the same in general formula (I)) liquid crystal alignment treating agent of claim 1 which is represented by. The general formula (IV) described in the general formula (I) of the repeating unit is represented by the following general formula (VII).

(Wherein, R ^5, n ⁵ is defined as the same in general formula (I)) liquid crystal alignment treating agent according to claim 1 or claim 2 represented by.

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