[發明所欲解決之問題] [0005] 本發明，以提供一種可製得具有優良再製性的液晶配向膜之液晶配向劑為目的。 [解決問題之方法] [0006] 本發明者們，對於解決上述問題，經過深入研究結果，得知經使用含有特定的芳香族四羧酸二酐之四羧酸二酐與具有特定結構的二胺所得的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物，與含有脂肪族四羧酸二酐之四羧酸二酐與具有特定結構的二胺所得的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物時，可製得具有優良再製性的液晶配向膜，因而完成本發明。 [0007] 即，本發明為基於上述結果所提出者，其具有下述主要內容。 1. 一種液晶配向劑，其特徵為含有： (A-1)由使用含有下述式(1)所表示之四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 (A-2)由使用含有脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物， 及有機溶劑。 [0008][0009] (式(1)中，i為0或1，X為單鍵、醚鍵結、羰基、酯鍵結、伸苯基、碳原子數1至20的直鏈伸烷基、碳原子數2至20的分支伸烷基、碳原子數3至12之環狀伸烷基、磺醯基、醯胺鍵結或由該些組合而形成之基，其中，碳原子數1至20的伸烷基，可被由酯鍵結及醚鍵結所選出的鍵結所中斷，伸苯基及伸烷基的碳原子可被由鹵素原子、氰基、烷基、鹵烷基、烷氧基及鹵烷氧基所選出的1個或複數個相同或相異的取代基所取代。 式(2)中，Y1
為：具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的2價之有機基，B1
、B2
各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基)。 [0010] 2.如1記載之液晶配向劑，其中，前述(A-1)之四羧酸二酐成份中之10～100莫耳%為前述式(1)所表示之四羧酸二酐。 [0011] 3.如1或2記載之液晶配向劑，其中，前述(A-2)之四羧酸二酐成份中之10～100莫耳%為脂肪族四羧酸二酐。 [0012] 4.如1至3中任一項記載之液晶配向劑，其中，前述(A-1)及前述(A-2)之二胺成份中之10～100莫耳%，為式(2)之二胺。 [0013] 5.如1至4中任一項記載之液晶配向劑，其中，式(2)中之Y1
為由下述式(YD-1)～(YD-5)之結構所選出之至少1種。 [0014][0015] (式(YD-1)中，A1
為碳數3～15之含氮原子的雜環，Z1
為氫原子，或可具有取代基的碳數1～20的烴基；式(YD-2)中，W1
為碳數1～10的烴基，A2
為具有含氮原子的雜環之碳數3～15之1價之有機基，或被碳數1至6的脂肪族基所取代的二取代胺基；式(YD-3)中，W2
為碳數6～15，且具有1至2個苯環的2價之有機基，W3
為碳數2～5之伸烷基或伸聯苯基，Z2
為氫原子、碳數1～5之烷基、苯環，或熱解離性基，a為0～1之整數；式(YD-4)中，A3
為碳數3～15之含氮原子的雜環；式(YD-5)中，A4
為碳數3～15之含氮原子的雜環，W5
為碳數2～5之伸烷基)。 [0016] 6. 如5記載之液晶配向劑，其中，式(YD-1)、(YD-2)、(YD-4)，及(YD-5)記載之A1
、A2
、A3
，及A4
，為由吡咯啶、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌嗪、吡啶、吡、吲哚、苯併咪唑、喹啉、異喹啉所成之群所選出之至少1種。 [0017] 7. 如1至6中任一項記載之液晶配向劑，其中，式(2)中之Y1
為由具有下述式(YD-6)～(YD-21)之結構的2價之有機基所成之群所選出之至少1種。 [0018][0019] (式(YD-17)中，h為1～3之整數，式(YD-14)及(YD-21)中，j為1至3之整數)。 [0020] 8.如7記載之液晶配向劑，其中，式(2)中之Y1
為由具有上述式(YD-14)及(YD-18)之結構的2價之有機基所成之群所選出之至少1種。 [0021] 9.如1至8中任一項記載之液晶配向劑，其中，前述式(1)所表示之四羧酸二酐為3,3’,4,4’-聯苯四羧酸二酐。 [0022] 10.如1至9中任一項記載之液晶配向劑，其中，前述脂肪族四羧酸二酐為雙環[3.3.0]辛烷2,4,6,8-四羧酸2,4：6,8二酐。 [0023] 11.一種液晶配向膜，其特徵為，將1至10中任一項記載之液晶配向劑經塗佈、燒結而得者。 [0024] 12.一種液晶顯示元件，其特徵為，具備11記載之液晶配向膜。 [發明之效果] [0025] 由本發明之液晶配向劑所得之液晶配向膜具有優良再製性。 [實施發明之形態] [0026] 本發明之液晶配向劑為含有： (A-1)由使用含有下述式(1)所表示之特定四羧酸二酐之四羧酸二酐成份與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物、 (A-2)由使用含有特定之脂肪族四羧酸二酐之四羧酸二酐成份，與含有下述式(2)所表示之二胺的二胺成份而得之聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物， 及有機溶劑。 [0027][0028] 式(1)中，i為0或1，X為單鍵、醚鍵結、羰基、酯鍵結、伸苯基、碳原子數1至20的直鏈伸烷基、碳原子數2至20的分支伸烷基、碳原子數3至12之環狀伸烷基、磺醯基、醯胺鍵結或由該些組合而形成之基，其中，碳原子數1至20的伸烷基，可被由酯鍵結及醚鍵結所選出的鍵結所中斷，伸苯基及伸烷基的碳原子可被由鹵素原子、氰基、烷基、鹵烷基、烷氧基及鹵烷氧基所選出的1個或複數個相同或相異的取代基所取代。 式(2)中，Y1
為：具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的2價之有機基，B1
、B2
各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基。 [0029] 以下，將詳細敘述各構成要件。 [0030] ＜(A-1)成份及(A-2)成份＞ 本發明之液晶配向劑所使用的(A-1)成份為由含有上述式(1)所表示之四羧酸二酐之四羧酸二酐成份與含有上述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物。 [0031] 又，本發明之液晶配向劑所使用的(A-2)成份為由含有脂肪族四羧酸二酐之四羧酸二酐成份與含有上述式(2)所表示之二胺的二胺成份而得的聚醯胺酸，及該聚醯胺酸之醯亞胺化聚合物所選出之至少1種的聚合物。 [0032] ＜四羧酸二酐成份＞ 上述式(1)所表示之四羧酸二酐，例如，以下所列舉之化合物，但並不僅限定於該些內容。 [0033][0034] (式中，q表示1至20之整數)。 [0035] 該些式(1)所表示之四羧酸二酐中就具有高度提升再製性效果之觀點，以式(1)中之i為1之四羧酸二酐，即，具有2個以上苯環的四羧酸二酐為佳，上述具體例中，又以(1-2)～(1-11)為佳，就同時含有聯苯結構與具有剛直結構之觀點，又以式(1-5)所表示之3,3’,4,4’-聯苯四羧酸二酐為特佳。 [0036] 本發明所使用的特定脂肪族四羧酸二酐，例如，下述式(3)所表示之四羧酸二酐等。 [0037][0038] 式中，X1
可為下述(X-1)～(X-28)中之任一者。 [0039][0040][0041][0042] 式(X-1)中，R3
～R6
，各自獨立為氫原子、碳數1～6之烷基，或苯基，又以氫原子，或甲基為較佳。 [0043] 上述之中，(X-1)至(X-20)以不含芳香族部位之觀點而為較佳，以(X-10)特別不易進行熱醯亞胺化之觀點而為最佳。 [0044] (A-1)成份中，四羧酸二酐成份全體中的式(1)所表示之四羧酸二酐所佔之量，其量過少時，將無法得到本發明之效果。因此，式(1)所表示之四羧酸二酐之量，相對於製造(A-1)成份時所使用的全四羧酸二酐1莫耳，以10～100莫耳%為佳，更佳為50～100莫耳%，特佳為80～100莫耳%。 (A-2)成份中，四羧酸二酐成份全體中之脂肪族酸二酐所佔之量，其量過少時，將無法得到本發明之效果。因此，脂肪族四羧酸二酐之量，相對於製造(A-2)成份時所使用的全四羧酸二酐1莫耳，以10～100莫耳%為佳，更佳為50～100莫耳%，特佳為80～100莫耳%。 [0045] 式(1)所表示之四羧酸二酐及脂肪族四羧酸二酐，其可分別單獨使用，或將複數個合併使用亦可，該情形中，式(1)所表示之四羧酸二酐及脂肪族四羧酸二酐之合計量，以使用上述較佳之量者為佳。 [0046] 本發明之液晶配向劑所含有的聚醯胺酸，除式(1)所表示之四羧酸二酐與脂肪族四羧酸二酐以外，亦可使用下述式(4)所表示之四羧酸二酐。 [0047][0048] 式(4)中，X為4價之有機基，其結構並未有特別之限定。列舉具體例時，例如，下述式(X-31)～(X-36)之結構等。 [0049][0050] ＜二胺成份＞ 本發明之(A-1)成份或(A-2)成份之製造所使用的二胺成份，為含有上述式(2)之二胺。式(2)中，Y1
為：具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，或由氮原子上被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出的2價之有機基，B1
、B2
各自獨立表示氫原子，或可具有取代基的碳數1～10之烷基、烯基、炔基。 [0051] 上述烷基之具體例，例如，甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基等。烯基，例如，上述烷基中所存在的1個以上之CH-CH結構，被C＝C結構所取代者，更具體而言，例如，乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-己烯基、環丙烯基、環戊烯基、環己烯基等。炔基，例如，前述之烷基所存在的1個以上之CH2
-CH2
結構被C≡C結構所取代者，更具體而言，例如，乙炔基、1-丙炔基、2-丙炔基等。 [0052] 上述之烷基、烯基、炔基，以全體為碳數1～10者時，其可具有取代基，更可經由取代基而形成環結構。又，經由取代基而形成環結構之意，係指取代基相互間或取代基與主骨架的一部份鍵結而形成環結構之意。 [0053] 該取代基之例，例如，鹵素基、羥基、硫醇基、硝基、芳基、有機氧基、有機硫基、有機矽烷基、醯基、酯基、硫酯基、磷酸酯基、醯胺基、烷基、烯基、炔基等。 [0054] 作為取代基之鹵素基，例如，氟原子、氯原子、溴原子、碘原子等。 [0055] 作為取代基之芳基，例如，苯基等。該芳基可再被前述其他取代基所取代。 [0056] 作為取代基之有機氧基，例如，O-R所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷氧基之具體例，例如，甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基等。 [0057] 作為取代基之有機硫基，例如，-S-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷基硫基之具體例，例如，甲基硫基、乙基硫基、丙基硫基、丁基硫基、戊基硫基、己基硫基、庚基硫基、辛基硫基等。 [0058] 作為取代基之有機矽烷基，例如，-Si-(R)3
所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。烷基矽烷基之具體例，例如，三甲基矽烷基、三乙基矽烷基、三丙基矽烷基、三丁基矽烷基、三戊基矽烷基、三己基矽烷基、戊基二甲基矽烷基、己基二甲基矽烷基等。 [0059] 作為取代基之醯基，例如，-C(O)-R所表示之結構。該R，例如，前述之烷基、烯基、芳基等例示。該些之R中，可再被前述取代基所取代。醯基之具體例，例如，甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、苯甲醯基等。 [0060] 作為取代基之酯基，例如，-C(O)O-R，或 -OC(O)-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 [0061] 作為取代基之硫酯基，例如，具有 -C(S)O-R，或-OC(S)-R所表示之結構。該R，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 [0062] 作為取代基之磷酸酯基，例如，-OP(O)-(OR)2
所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 [0063] 作為取代基之醯胺基，例如，-C(O)NH2
，或 -C(O)NHR、-NHC(O)R、-C(O)N(R)2
、-NRC(O)R所表示之結構。該R可為相同或相異皆可，例如，前述之烷基、烯基、炔基、芳基等例示。該些之R中，可再被前述取代基所取代。 [0064] 作為取代基之芳基，例如，與前述之芳基為相同之內容。該芳基可再被前述其他取代基所取代。 [0065] 作為取代基之烷基，例如，與前述之烷基為相同之內容。該烷基中，可再被前述其他取代基所取代。 [0066] 作為取代基之烯基，例如，與前述之烯基為相同之內容。該烯基中，可再被前述其他取代基所取代。 [0067] 作為取代基之炔基，例如，與前述之炔基為相同之內容。該炔基中，可再被前述其他取代基所取代。 [0068] 一般而言，導入巨大結構時，可降低胺基的反應性或液晶配向性，故B1
及B2
，例如，以氫原子，或可具有取代基的碳數1～5之烷基為較佳，以氫原子、甲基或乙基為特佳。 [0069] 式(2)中之Y1
之結構，例如，可具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構，但只要為氮原子上具有被熱解離性基所取代之胺基、亞胺基及含氮雜環所選出之至少1種之結構時，其結構並未有特別之限定。因此，該具體例，可列舉如，具有由下述式(YD-1)～(YD-5)所表示之胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基等。 [0070][0071] 式(YD-1)中，A1
為碳數3～15之含氮原子的雜環，Z1
為氫原子，或可具有取代基之碳數1～20的烴基。 式(YD-2)中，W1
為碳數1～10的烴基，A2
為具有含氮原子的雜環之碳數3～15之1價之有機基，或被碳數1至6的脂肪族基所取代的二取代胺基。 式(YD-3)中，W2
為碳數6～15，且具有1至2個苯環的2價之有機基，W3
為碳數2～5之伸烷基或伸聯苯基，Z2
為氫原子、碳數1～5之烷基、苯環，或熱解離性基，a為0～1之整數。 式(YD-4)中，A3
為碳數3～15之含氮原子的雜環。 式(YD-5)中，A4
為碳數3～15之含氮原子的雜環，W5
為碳數2～5之伸烷基。 [0072] 式(YD-1)、(YD-2)、(YD-4)，及(YD-5)之A1
、A2
、A3
，及A4
之碳數3～15之含氮原子的雜環，例如，只要為公知之結構時，則未有特別之限定。其中，又可例如，吡咯啶、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌嗪、吡啶、吡、吲哚、苯併咪唑、喹啉、異喹啉、咔唑等，又以哌嗪、哌啶、吲哚、苯併咪唑、咪唑、咔唑，及吡啶為較佳。 又，熱解離性基，例如，於室溫下不會解離、於燒結配向膜之際會產生解離而可被氫原子所取代的取代基即可，具體而言，可列舉如，tert-丁氧基羰基及9-茀基甲氧基羰基等。 [0073] 此外，式(2)中之Y2
之具體例，例如，具有下述式(YD-6)～(YD-52)所表示之氮原子的2價之有機基等，就可抑制因交流驅動所造成的電荷蓄積之觀點，以式 (YD-14)～式(YD-21)為較佳，以(YD-14)及(YD-18)為特佳。 [0074][0075] 式(YD-14)及(YD-21)中，j為0至3之整數；式(YD-17)中，h為1～3之整數。 [0076][0077] 式(YD-24)、(YD-25)、(YD-28)及(YD-29)中，j為0至3之整數。 [0078][0079][0080][0081][0082] (式(YD-50)中，m、n分別為1至11之整數，m＋n為2至12之整數)。 [0083] 本發明之(A-1)成份或(A-2)成份的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中之式(2)所表示之二胺之比例，相對於製造(A-1)成份或(A-2)成份所使用的全二胺1莫耳，以10～100莫耳%為佳，更佳為30～100莫耳%，特佳為50～100莫耳%。 [0084] 本發明之(A-1)成份及(A-2)成份中，製造聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中之式(2)所表示之二胺，可單獨使用亦可，將複數個合併使用亦可，於該情形中，式(2)所表示之二胺，其合計量亦以使用上述較佳之量為佳。又，(A-1)成份與(A-2)成份中，以使用相同的二胺之情形，就更能提高本案發明效果之觀點為較佳者。 又，本發明中，(A-1)成份及(A-2)成份中，製造聚醯胺酸及聚醯胺酸之醯亞胺化聚合物之際所使用的二胺，以相同者為佳。 [0085] 本發明之液晶配向劑所含有的(A-1)成份或 (A-2)成份的聚醯胺酸，除上述式(2)所表示之二胺以外，亦可使用下述式(5)所表示之二胺。下述式(5)中之Y2
為2價之有機基，其結構並未有特別限定之內容，亦可將2種類以上混合使用。又，該具體例示，可列舉如，下述(Y-1)～(Y-49)及(Y-57)～(Y-97)等。 [0086][0087][0088][0089][0090][0091][0092][0093][0094][0095][0096] 本發明之液晶配向劑所含有的(A-1)成份或 (A-2)成份的聚醯胺酸及聚醯胺酸之醯亞胺化聚合物中，式(5)所表示之二胺之比例過多時，會有損害本發明效果之可能性，而為不佳。因此，式(5)所表示之二胺之比例，相對於全二胺1莫耳，以0～90莫耳%為佳，更佳為0～50莫耳%，特佳為0～20莫耳%。 [0097] ＜聚醯胺酸之製造方法＞ 本發明所使用的聚醯亞胺前驅體之聚醯胺酸，可依以下所示方法合成。 具體而言，將四羧酸二酐與二胺於有機溶劑之存在下，於-20～150℃，較佳為0～70℃之間，進行30分鐘～24小時，較佳為1～12小時反應而合成。 上述反應所使用的有機溶劑，就單體及聚合物的溶解性之觀點，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯等為佳，該些可使用1種或將2種以上混合使用。 聚合物之濃度，於考慮不易引起聚合物的析出，且容易得到高分子量體之觀點，以1～30質量%為佳，以5～20質量%為較佳。 將依上述方法所得之聚醯胺酸，於將反應溶液充份攪拌中，注入貧溶劑時，可使聚合物析出而回收。又，進行數次析出，使用貧溶劑洗淨後，於常溫或加熱下乾燥，即可製得純化之聚醯胺酸粉末。貧溶劑，並未有特別之限定，可列舉如，水、甲醇、乙醇、2-丙醇、己烷、丁基溶纖劑(cellosolve)、丙酮、甲苯等，又以水、甲醇、乙醇、2-丙醇等為佳。 [0098] ＜聚醯亞胺之製造方法＞ 本發明所使用的聚醯亞胺，可將前述聚醯胺酸進行醯亞胺化反應而製得。 由聚醯胺酸製造聚醯亞胺之情形，以於二胺成份與四羧酸二酐反應所得之前述聚醯胺酸的溶液中，添加觸媒的化學性醯亞胺化反應為簡便之方法。化學性醯亞胺化，可於較低溫下進行醯亞胺化反應，且於醯亞胺化過程中，不易造成聚合物的分子量降低，而為較佳。 化學性醯亞胺化為，將欲進行醯亞胺化之聚合物，於有機溶劑中及鹼性觸媒與酸酐之存在下進行攪拌之方式進行。有機溶劑可使用前述聚合反應時所使用的溶劑。鹼性觸媒，可列舉如，吡啶、三乙胺、三甲胺、三丁胺、三辛胺等。其中，又以吡啶可於反應進行中維持適當的鹼性，而為較佳。又，酸酐可列舉如，乙酸酐、偏苯三甲酸酐、苯均四酸酐等，其中，又以使用乙酸酐時，於反應結束後容易進行純化，而為較佳。 進行醯亞胺化反應時之溫度，可於-20～140℃，較佳為0～100℃下，反應時間為1～100小時內進行。鹼性觸媒之量為聚醯胺酸基的0.5～30莫耳倍，較佳為2～20莫耳倍，酸酐之量為聚醯胺酸基的1～50莫耳倍，較佳為3～30莫耳倍。所得聚合物之醯亞胺化率，可以調節觸媒量、溫度、反應時間之方式予以控制。 [0099] 聚醯胺酸之醯亞胺化反應後之溶液中因殘留有所添加的觸媒等，其又以使用以下所述手段，回收所得的醯亞胺化聚合物，使其再溶解於有機溶劑，作為本發明之液晶配向劑者為佳。 [0100] 將依上述方式所得之聚醯亞胺溶液，於充份攪拌中注入貧溶劑中，即可析出聚合物。進行數次析出，使用貧溶劑洗淨後，於常溫或加熱狀態下乾燥，即可製得純化的聚合物粉末。 前述貧溶劑，並未有特別之限定，可列舉如，甲醇、2-丙醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯等，又以甲醇、乙醇、2-丙醇、丙酮等為佳。 [0101] 依該方法所製得之(A-1)成份及(A-2)成份的含有比，為可使上述式(1)所表示之特定四羧酸二酐與特定脂肪族酸二酐之含有比例達10：90至90：10之比例，又較佳為20：80至80：20，更佳為形成40：60至60：40之比例，特佳為形成46：54至54：46之比例，實質上以當量計算者為最佳。 [0102] ＜液晶配向劑＞ 本發明所使用的液晶配向劑，為具有聚合物成份溶解於有機溶劑中所形成的溶液形態。聚合物之分子量，其重量平均分子量以2,000～500,000為佳，更佳為5,000～300,000，特佳為10,000～100,000。又，數平均分子量，較佳為1,000～250,000，更佳為2,500～150,000，特佳為5,000～50,000。 本發明所使用的液晶配向劑之聚合物的濃度，可配合欲形成之塗膜的厚度設定作適當之變更，就形成均勻且無缺陷的塗膜之觀點，以1質量%以上為佳，就溶液保存安定性觀點，以10質量%以下為佳。特佳之聚合物濃度為2～8質量%。 [0103] 本發明所使用的液晶配向劑所含有的有機溶劑，只要可使聚合物成份均勻溶解者時，並未有特別之限定。其具體例，可列舉如，N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、3-甲氧基-N,N-二甲基丙烷醯胺等。該些可使用1種或將2種以上混合使用皆可。又，即使為單獨無法使聚合物成份均勻溶解之溶劑，只要為不會析出聚合物之範圍，亦可與上述有機溶劑混合使用。 [0104] 又，液晶配向劑所含有的有機溶劑，除上述溶劑以外，一般可使用與塗佈液晶配向劑之際可提高塗佈性或提升塗膜表面平滑性的溶劑合併而得的混合溶劑，本發明之液晶配向劑中，亦適合使用該些混合溶劑。可合併使用的有機溶劑之具體例，例如下述內容，但並不僅限定於該些例示。 例如，乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、2,6-二甲基-4-庚醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己烷二醇、二異丙醚、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二***、4-羥基-4-甲基-2-戊酮、二乙二醇甲基***、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、2,6-二甲基-4-庚酮、4,6-二甲基-2-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、丙烯碳酸酯、乙烯碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁醚、乙二醇單異戊醚、乙二醇單己醚、2-(己基氧基)乙醇、糠醇、二乙二醇、丙二醇、二乙二醇單***、二乙二醇單甲醚、丙二醇單丁醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲醚乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇單***、二丙二醇二甲醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單***、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單***、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、下述式[D-1]～[D-3]所表示之溶劑等。 [0105][0106] 式[D-1]中，D1
表示碳數1～3之烷基，式[D-2]中，D2
表示碳數1～3之烷基，式[D-3]中，D3
表示碳數1～4之烷基。 其中較佳溶劑之組合，例如，N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚、N-乙基-2-吡咯啶酮與丙二醇單丁醚、N-甲基-2-吡咯啶酮與γ-丁內酯與4-羥基-4-甲基-2-戊酮與二乙二醇二***、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與2,6-二甲基-4-庚酮、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與二異丙醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁醚與2,6-二甲基-4-庚醇、N-甲基-2-吡咯啶酮與γ-丁內酯與二丙二醇二甲醚等。該些溶劑之種類及含量，可配合液晶配向劑之塗佈裝置、塗佈條件、塗佈環境等作適當之選擇。 [0107] 又，本發明之液晶配向劑中，就提高膜的機械性強度之觀點，可添加以下添加物。 [0108][0109][0110] 該些之添加劑，相對於液晶配向劑所含有的聚合物成份100質量份，以0.1～30質量份為佳。未達0.1質量份時將無法期待其效果，超過30質量份時，會降低液晶配向性，故更佳為0.5～20質量份。 [0111] 本發明之液晶配向劑中，除上述以外，於無損本發明效果之範圍，可添加聚合物以外的聚合物、以改變液晶配向膜的介電係數或導電性等之電氣特性為目的之介電體或導電物質、以提升液晶配向膜與基板之密著性為目的之矽烷耦合劑、以提高作為液晶配向膜時的膜硬度或緻密度為目的之交聯性化合物、或以提高塗膜燒結時可使聚醯胺酸有效地進行醯亞胺化反應為目的之醯亞胺化促進劑等。 [0112] ＜液晶配向膜＞ ＜液晶配向膜之製造方法＞ 本發明之液晶配向膜為，將上述液晶配向劑塗佈於基板，並經乾燥、燒結而製得之膜。塗佈本發明之液晶配向劑的基板，只要為具有高度透明性之基板時，並未有特別之限定，其可使用玻璃基板、氮化矽基板、丙烯酸基板、聚碳酸酯基板等的塑膠基板等，就製成簡易化之觀點，又以使用形成有驅動液晶的ITO電極等的基板為較佳。又，反射型液晶顯示元件，若僅為單側之基板時，亦可使用矽晶圓等的不透明物質，該情形的電極也可使用鋁等可反射光線之材料。 [0113] 本發明之液晶配向劑的塗佈方法，例如，旋轉塗佈法、印刷法、噴墨法等。塗佈本發明之液晶配向劑後的乾燥、燒結步驟，可選擇任意的溫度與時間。通常為充份去除所含有的有機溶劑時，可於50℃～120℃之間乾燥1分鐘～10分鐘，隨後於150℃～300℃之間燒結5分鐘～120分鐘。燒結後塗膜之厚度，並未有特別之限定，但過薄時會有降低液晶顯示元件信賴性之情形，故通常為5～300nm，較佳為10～200nm。 [0114] 對所得液晶配向膜進行配向處理之方法，例如，摩擦法、光配向處理法等。 [0115] 摩擦處理可使用現有的摩擦裝置進行。此時摩擦布之材質，例如，棉製品、尼龍、嫘縈等。摩擦處理之條件，一般而言，為使用迴轉速度300～2000rpm、輸送速度5～100mm/s、擠壓量0.1～1.0mm之條件。隨後，使用純水或醇等去除因超音波洗淨所產生的因摩擦所生成的殘渣。 [0116] 光配向處理法之具體例，例如，使用偏向特定方向的輻射線照射前述塗膜表面，依情況差異，可再於150～250℃之溫度進行加熱處理，以賦予液晶配向能力之方法等。輻射線，例如，可使用具有100nm～800nm波長的紫外線及可見光線。其中，又以具有100nm～400nm波長之紫外線為佳，以具有200nm～400nm波長者為特佳。又，為改善液晶配向性之目的，可將塗膜基板於50～250℃加熱中照射輻射線。前述輻射線之照射量以1～10,000mJ/cm2
為佳，以100～5,000mJ/cm2
為特佳。依上述方式所製得之液晶配向膜，可使液晶分子於特定方向安定地配向。 [0117] 又，偏光的紫外線之消光比越高時，以其可賦予更高的異向性，而為更佳。具體而言，相對於直線為偏光之紫外線的消光比，以10：1以上為佳，以20：1以上為較佳。 [0118] 依上述方式所得之照射偏光的輻射線之膜，隨後可再使用含有由水及有機溶劑所選出之至少1種的溶劑進行接觸處理。 [0119] 接觸處理所使用的溶劑，例如，只要可溶解經由光照射而生成的分解物之溶劑時，並未有特別之限定。具體例，例如，水、甲醇、乙醇、2-丙醇、丙酮、甲基乙酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑(cellosolve)、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯，及乙酸環己酯等。該些溶劑亦可將2種以上合併使用。 [0120] 就廣用性或安全性之觀點，以使用由水、2-丙醇、1-甲氧基-2-丙醇及乳酸乙酯所成之群所選出之至少1種為較佳。水、2-丙醇，及水與2-丙醇之混合溶劑為特佳。 本發明中，照射偏光的輻射線之膜與含有有機溶劑的溶液之接觸處理，為使用浸潤處理、噴霧(Spray)處理等可使膜與液體進行較佳且充份的接觸之處理方式進行。其中，又以對含有有機溶劑的溶液中之膜，實施較佳為10秒～1小時，更佳為1～30分鐘浸潤處理之方法為佳。接觸處理可於常溫或加溫下進行，較佳為於10～80℃，更佳為於20～50℃之間實施。又，必要時，可施以超音波等提高接觸之手段。 上述接觸處理後，就去除使用後溶液中的有機溶劑之目的，可以水、甲醇、乙醇、2-丙醇、丙酮、甲基乙酮等之低沸點溶劑進行洗滌(Rinse)或乾燥，或兩者同時進行皆可。 [0121] 此外，上述使用溶劑進行接觸處理之膜，就乾燥溶劑及使膜中分子鏈進行再配向之目的時，亦可將其加熱至150℃以上。 [0122] 加熱之溫度，例如，150～300℃為佳。溫度越高時，雖可促進分子鏈的再配向，但溫度過高時會有伴隨分子鏈分解之疑慮。因此，加熱溫度，例如，180～250℃為較佳，以200～230℃為特佳。 [0123] 加熱之時間，過短時會有無法得到分子鏈再配向之效果的可能性，過長時，會有造成分子鏈分解之可能性，故以10秒～30分鐘為佳，以1分鐘～10分鐘為較佳。 [0124] 又，所得的液晶配向膜，可容易溶解於再製材料中，為具有優良再製性之膜。 [0125] 再製時所使用的溶劑，可列舉如以下之溶劑：乙二醇單甲醚、乙二醇單***、二乙二醇單甲醚、二乙二醇單***、丙二醇單甲醚等的二醇醚類；甲基溶纖劑(cellosolve)乙酸酯、乙基溶纖劑(cellosolve)乙酸酯、丙二醇單甲醚乙酸酯、丙二醇丙醚乙酸酯等的二醇酯類；二乙二醇、丙二醇、丁二醇、己二醇等的二醇類；甲醇、乙醇、2-丙醇、丁醇等的醇類；丙酮、甲基乙酮、環戊酮、環己酮、2-庚酮、γ-丁內酯等的酮類；2-羥基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁基等的酯類、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基-2-吡咯啶酮等之醯胺類。 再製材料，例如，於上述溶劑中含有乙醇胺等的鹼性成份的同時，又含有不會使該鹼性損害電極等的其他構件之抗鏽劑者為佳。可提供該些再製材料之廠商，例如，韓國的會明產業股份有限公司、KPX化學等。 [0126] 再製，為將上述所列舉的再製材料於室溫下，或30℃～100℃之間加熱後，將附有液晶配向膜之基板浸漬於其中，維持1秒～1000秒，較佳為30秒～500秒，或將再製材料使用噴灑式噴射之後，使用醇系溶劑或純水洗該液體之方式進行。又，再製時的再製液之溫度，就作業效率等觀點，以低溫者為佳，通常為室溫至60℃，更佳為室溫至40℃。 [0127] ＜液晶顯示元件＞ 本發明之液晶顯示元件，為使用本發明之液晶配向劑並依前述液晶配向膜之製造方法製得附有液晶配向膜之基板後，使用公知之方法製作液晶單元(cell)，並使用其作為液晶顯示元件者。 液晶單元製作方法之例，將舉被動元件矩陣結構的液晶顯示元件為例進行說明。又，其亦可為具有構成圖像顯示的各畫素部份設有TFT(Thin Film Transistor)等開閉元件的主動矩陣結構之液晶顯示元件。 首先，準備透明的玻璃製之基板，並於一側之基板上設置共用電極，另一側之基板上設置節段電極。該些之電極，例如可作為ITO電極，或可形成所期待的圖像顯示之圖型。其次，於各基板上，可設置被覆共用電極與節段電極之絕緣膜。絕緣膜，例如，由溶膠-凝膠法所得之由SiO2
-TiO2
所形成的膜。 [0128] 其次，於各基板上，依上述方法形成本發明之液晶配向膜。 其次，將一側之基板與另一側之基板，以配向膜面互相對向之方式重疊，其周邊使用密封劑接著。密封劑中，為控制基板之間隙等目的，通常為混入間隔器。又，於未設置密封劑之面內部份，亦以散佈控制基板間隙的間隔器為佳。密封劑中之一部份，設置可由外部填充液晶之開口部。 [0129] 其次，經由設置於密封劑中之開口部，將液晶材料注入由2片之基板與密封劑所包圍的空間內。隨後，使用接著劑密封該開口部。注入法，可使用真空注入法，或於大氣中利用毛細管現象之方法等皆可。隨後，進行偏光板之設置。具體而言，為將一對的偏光板貼附於與2片基板的液晶層為相反側之面。經以上之步驟，而製得本發明之液晶顯示元件。 [0130] 本發明中，密封劑，例如，可使用具有環氧基、丙烯醯基、甲基丙烯醯基、羥基、烯丙基、乙醯基等反應性基的經由紫外線照射或加熱而硬化的樹脂。特別是以使用具有環氧基與(甲基)丙烯醯基二者的反應性基之硬化樹脂系者為佳。 [0131] 本發明之密封劑中，就提升接著性、耐濕性等目的時，可添加無機填充劑。所可使用的無機填充劑，並未有特別之限定，具體而言，可列舉如，球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、硝子纖維、碳纖維、二硫化鉬、石棉等，較佳為球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁。前述無機填充劑可將2種以上混合使用。 [0132] 該液晶顯示元件中，因液晶配向膜為使用本發明的液晶配向膜之製造方法所得之液晶配向膜，故具有優良再製性者，而適合使用於大畫面且高精細的液晶電視等。[Problem to be Solved by the Invention] The present invention has an object of providing a liquid crystal alignment agent capable of producing a liquid crystal alignment film having excellent remanufacturability. [Means for Solving the Problems] [0006] The inventors of the present invention have made intensive studies to solve the above problems, and have found that a tetracarboxylic dianhydride containing a specific aromatic tetracarboxylic dianhydride and a specific structure are used. A polyamiled acid obtained from an amine and a ruthenium imidized polymer of polyaminic acid, and a polyamic acid obtained from a tetracarboxylic dianhydride containing an aliphatic tetracarboxylic dianhydride and a diamine having a specific structure and poly When a ruthenium imidized polymer of valine is used, a liquid crystal alignment film having excellent remanufacturability can be obtained, and thus the present invention has been completed. That is, the present invention has been proposed based on the above results, and has the following main contents. A liquid crystal alignment agent comprising: (A-1) a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (1), and containing the following formula (2) Polylysine obtained from the diamine component of the diamine, and at least one polymer selected from the ruthenium imidized polymer of the polyaminic acid, (A-2) containing aliphatic a tetracarboxylic dianhydride component of a tetracarboxylic dianhydride, a polyamine acid obtained from a diamine component containing a diamine represented by the following formula (2), and a ruthenium imidization polymerization of the polyglycine At least one polymer selected from the materials, and an organic solvent. [0008] (In the formula (1), i is 0 or 1, and X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenyl group, a linear alkyl group having 1 to 20 carbon atoms, or a carbon atom. a branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a sulfonyl group, a guanamine bond, or a group formed by the combination, wherein the carbon number is 1 to 20 The alkyl group can be interrupted by the bond selected by the ester bond and the ether bond. The carbon atom of the phenyl and alkyl groups can be derived from a halogen atom, a cyano group, an alkyl group, a haloalkyl group or an alkoxy group. And one or a plurality of the same or different substituents selected by the haloalkoxy group. In the formula (2), Y 1 is: having an amine group, an imido group, and a nitrogen-containing heterocyclic ring a divalent organic group having at least one structure selected from the group, or a divalent organic group selected from an amine group, an imido group and a nitrogen-containing hetero ring substituted with a pyrolytic group on the nitrogen atom, B 1 and B 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent. [0010] 2. The liquid crystal alignment agent according to 1, wherein 10 to 100 mol% of the tetracarboxylic dianhydride component of the above (A-1) is a tetracarboxylic dianhydride represented by the above formula (1). . 3. The liquid crystal alignment agent according to 1 or 2, wherein 10 to 100 mol% of the tetracarboxylic dianhydride component of the above (A-2) is an aliphatic tetracarboxylic dianhydride. [0012] The liquid crystal alignment agent according to any one of the above-mentioned (A-1) and (A-2), wherein the amount of the diamine component is from 10 to 100 mol%, which is a formula ( 2) Diamine. 5. The liquid crystal alignment agent according to any one of the above formulas, wherein Y 1 in the formula (2) is selected from the structures of the following formulas (YD-1) to (YD-5). At least one. [0014] In the formula (YD-1), A 1 is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, Z 1 is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; In YD-2), W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and A 2 is a monovalent organic group having a carbon number of 3 to 15 having a nitrogen atom-containing heterocyclic ring, or an aliphatic group having 1 to 6 carbon atoms. a disubstituted amine group substituted by a group; in the formula (YD-3), W 2 is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W 3 is a carbon number of 2 to 5 An alkyl group or a biphenyl group, Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally dissociable group, and a is an integer of 0 to 1; in the formula (YD-4), A 3 is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms; in the formula (YD-5), A 4 is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W 5 is a carbon number 2 to 5 alkylene oxide. base). [0016] 6. The liquid crystal alignment agent according to 5, wherein A 1 , A 2 , and A 3 described in the formulas (YD-1), (YD-2), (YD-4), and (YD-5) And A 4 , which are pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridyl At least one selected from the group consisting of hydrazine, benzimidazole, quinoline, and isoquinoline. [0017] The liquid crystal alignment agent of any one of the formula (2), wherein Y 1 in the formula (2) is a structure having a structure of the following formula (YD-6) to (YD-21) At least one selected from the group of organic groups of the price. [0018] (In the formula (YD-17), h is an integer of 1 to 3, and in the formulas (YD-14) and (YD-21), j is an integer of 1 to 3). [0020] 8. The liquid crystal alignment agent according to 7, wherein Y 1 in the formula (2) is a divalent organic group having a structure of the above formula (YD-14) and (YD-18). At least one selected from the group. The liquid crystal alignment agent according to any one of the above-mentioned formula (1), wherein the tetracarboxylic dianhydride represented by the above formula (1) is 3,3',4,4'-biphenyltetracarboxylic acid. Diacid anhydride. The liquid crystal alignment agent according to any one of 1 to 9, wherein the aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2 , 4:6, 8 dianhydride. [0023] A liquid crystal alignment film obtained by coating and sintering the liquid crystal alignment agent according to any one of 1 to 10. 12. A liquid crystal display device comprising the liquid crystal alignment film described in 11. [Effects of the Invention] The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has excellent remanufacturability. [Form of the Invention] The liquid crystal alignment agent of the present invention contains: (A-1) a tetracarboxylic dianhydride component and a component containing a specific tetracarboxylic dianhydride represented by the following formula (1) At least one polymer selected from the diamine component of the diamine represented by the following formula (2), and at least one polymer selected from the ruthenium imidized polymer of the polyaminic acid, (A-2 a polyamic acid obtained by using a tetracarboxylic dianhydride component containing a specific aliphatic tetracarboxylic dianhydride and a diamine component containing a diamine represented by the following formula (2), and the polyfluorene At least one polymer selected from the group consisting of amino acid imidized polymers, and an organic solvent. [0027] In the formula (1), i is 0 or 1, and X is a single bond, an ether bond, a carbonyl group, an ester bond, a phenyl group, a linear alkyl group having 1 to 20 carbon atoms, and a carbon number. a branched alkyl group of 2 to 20, a cyclic alkyl group having 3 to 12 carbon atoms, a sulfonyl group, a guanamine bond or a group formed by the combination, wherein the carbon atoms are 1 to 20 The alkyl group may be interrupted by a bond selected by an ester bond and an ether bond, and the carbon atom of the phenyl and alkyl groups may be derived from a halogen atom, a cyano group, an alkyl group, a haloalkyl group or an alkoxy group. And one or a plurality of the same or different substituents selected by the haloalkoxy group are substituted. In the formula (2), Y 1 is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, or is heated by a nitrogen atom. a divalent organic group selected from the amine group, the imine group and the nitrogen-containing heterocyclic ring substituted by the dissociable group, and B 1 and B 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent Base, alkenyl, alkynyl. [0029] Hereinafter, each constituent element will be described in detail. <Component (A-1) and (A-2)> The component (A-1) used in the liquid crystal alignment agent of the present invention is a tetracarboxylic dianhydride represented by the above formula (1). At least one selected from the group consisting of a polycarboxylic acid having a tetracarboxylic dianhydride component and a diamine component of the diamine represented by the above formula (2), and a ruthenium imidized polymer of the polyaminic acid polymer. Further, the component (A-2) used in the liquid crystal alignment agent of the present invention is a tetracarboxylic dianhydride component containing an aliphatic tetracarboxylic dianhydride and a diamine represented by the above formula (2). The polyamine acid obtained from the diamine component and the at least one polymer selected from the ruthenium imidized polymer of the polyaminic acid. <Tetracarboxylic acid dianhydride component> The tetracarboxylic dianhydride represented by the above formula (1), for example, the compounds listed below, is not limited to these contents. [0033] (wherein q represents an integer from 1 to 20). [0035] The tetracarboxylic dianhydride represented by the formula (1) has a highly enhanced remanufacturability effect, and i in the formula (1) is a tetracarboxylic dianhydride of 1, that is, has two The above benzene ring tetracarboxylic dianhydride is preferred, and in the above specific examples, (1-2) to (1-11) are preferred, and both the biphenyl structure and the rigid structure are included, and The 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by 1-5) is particularly preferred. [0036] The specific aliphatic tetracarboxylic dianhydride used in the present invention is, for example, a tetracarboxylic dianhydride represented by the following formula (3). [0037] In the formula, X 1 may be any one of the following (X-1) to (X-28). [0039] [0040] [0041] In the formula (X-1), R 3 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a hydrogen atom or a methyl group is preferred. Among the above, (X-1) to (X-20) are preferred from the viewpoint of not containing an aromatic moiety, and (X-10) is particularly difficult to be thermally imidized. good. In the component (A-1), the amount of the tetracarboxylic dianhydride represented by the formula (1) in the entire tetracarboxylic dianhydride component is too small, and the effect of the present invention cannot be obtained. Therefore, the amount of the tetracarboxylic dianhydride represented by the formula (1) is preferably from 10 to 100 mol% based on 1 mol of the total tetracarboxylic dianhydride used in the production of the component (A-1). More preferably, it is 50 to 100 mol%, and particularly preferably 80 to 100 mol%. In the component (A-2), the amount of the aliphatic acid dianhydride in the entire tetracarboxylic dianhydride component is too small, and the effect of the present invention cannot be obtained. Therefore, the amount of the aliphatic tetracarboxylic dianhydride is preferably from 10 to 100 mol%, more preferably from 50 to 100 mol% based on the total tetracarboxylic dianhydride used in the production of the component (A-2). 100% by mole, especially preferably 80 to 100% by mole. [0045] The tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride represented by the formula (1) may be used singly or in combination of plural kinds, in which case, the formula (1) is represented. The total amount of the tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride is preferably the same as the above preferred amount. The polyphthalic acid contained in the liquid crystal alignment agent of the present invention may be, in addition to the tetracarboxylic dianhydride represented by the formula (1) and the aliphatic tetracarboxylic dianhydride, the following formula (4). Represented by tetracarboxylic dianhydride. [0047] In the formula (4), X is a tetravalent organic group, and the structure thereof is not particularly limited. In the case of a specific example, for example, the structures of the following formulae (X-31) to (X-36) and the like. [0049] <Diamine component> The diamine component used for the production of the component (A-1) or the component (A-2) of the present invention is a diamine containing the above formula (2). In the formula (2), Y 1 is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, or is heated by a nitrogen atom. a divalent organic group selected from the amine group, the imine group and the nitrogen-containing heterocyclic ring substituted by the dissociable group, and B 1 and B 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent Base, alkenyl, alkynyl. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and the like. The alkenyl group, for example, one or more CH-CH structures present in the above alkyl group are substituted by a C=C structure, more specifically, for example, a vinyl group, an allyl group, a 1-propenyl group, or an iso- Propylene group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like. An alkynyl group, for example, one or more CH 2 -CH 2 structures present in the aforementioned alkyl group are substituted by a C≡C structure, more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propene group Alkynyl and the like. When the alkyl group, the alkenyl group or the alkynyl group is a carbon number of 1 to 10 as a whole, it may have a substituent and may form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the main skeleton is bonded to form a ring structure. Examples of the substituent, for example, a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate ester Alkyl, amidino, alkyl, alkenyl, alkynyl and the like. The halogen group as a substituent is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The aryl group as a substituent is, for example, a phenyl group or the like. The aryl group may be further substituted with the other substituents described above. The organooxy group as a substituent is, for example, a structure represented by OR. The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like. The organothio group as a substituent is, for example, a structure represented by -SR. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkylthio group are, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like. The organoalkylene group as a substituent is, for example, a structure represented by -Si-(R) 3 . The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the alkylalkyl group are, for example, trimethyldecyl, triethyldecyl, tripropyldecyl, tributyldecyl, tripentyldecyl, trihexyldecyl, pentyldimethyl a decyl group, a hexyl dimethyl decyl group, and the like. The thiol group as a substituent is, for example, a structure represented by -C(O)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. Specific examples of the mercapto group include, for example, a mercapto group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group and the like. The ester group as a substituent is, for example, a structure represented by -C(O)OR or -OC(O)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. The thioester group as a substituent has, for example, a structure represented by -C(S)OR or -OC(S)-R. The R is, for example, exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. Among these R, it may be further substituted by the aforementioned substituent. The phosphate group as a substituent is, for example, a structure represented by -OP(O)-(OR) 2 . The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. a mercaptoamine group as a substituent, for example, -C(O)NH 2 , or -C(O)NHR, -NHC(O)R, -C(O)N(R) 2 , -NRC( O) The structure represented by R. The R may be the same or different, and for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like are exemplified. Among these R, it may be further substituted by the aforementioned substituent. The aryl group as a substituent is, for example, the same as the above-mentioned aryl group. The aryl group may be further substituted with the other substituents described above. The alkyl group as a substituent is, for example, the same as the alkyl group described above. The alkyl group may be further substituted with the other substituents described above. The alkenyl group as a substituent is, for example, the same as the above-described alkenyl group. The alkenyl group may be further substituted with the other substituents described above. The alkynyl group as a substituent is, for example, the same as the alkynyl group described above. The alkynyl group may be further substituted with the aforementioned other substituents. [0068] In general, when a large structure is introduced, the reactivity of the amine group or the liquid crystal alignment property can be lowered, so B 1 and B 2 , for example, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent The base is preferably a hydrogen atom, a methyl group or an ethyl group. The structure of Y 1 in the formula (2), for example, may have at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, but only a nitrogen atom When at least one structure selected from the group consisting of an amine group, an imine group and a nitrogen-containing hetero ring substituted by a pyrolytic group is used, the structure thereof is not particularly limited. Therefore, the specific example includes at least one selected from the group consisting of an amine group represented by the following formulas (YD-1) to (YD-5), an imine group, and a nitrogen-containing heterocyclic ring. A divalent organic group of the structure of the species. [0070] In the formula (YD-1), A 1 is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms, Z 1 is a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In the formula (YD-2), W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and A 2 is an organic group having a monovalent number of carbon atoms of 3 to 15 having a nitrogen atom-containing heterocyclic ring, or a carbon number of 1 to 6. A disubstituted amine group substituted with an aliphatic group. In the formula (YD-3), W 2 is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W 3 is an alkylene group having 2 to 5 carbon atoms or a stretched biphenyl group. Z 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring or a thermally dissociable group, and a is an integer of 0 to 1. In the formula (YD-4), A 3 is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms. In the formula (YD-5), A 4 is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W 5 is an alkylene group having 2 to 5 carbon atoms. The nitrogen of the formula (YD-1), (YD-2), (YD-4), and (YD-5), A 1 , A 2 , A 3 , and A 4 having a carbon number of 3 to 15 The hetero ring of the atom is not particularly limited as long as it is a known structure. Among them, for example, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyridyl And hydrazine, benzimidazole, quinoline, isoquinoline, oxazole, etc., and piperazine, piperidine, hydrazine, benzimidazole, imidazole, oxazole, and pyridine are preferred. Further, the thermally dissociable group may be, for example, a substituent which is not dissociated at room temperature and which is dissociated upon sintering of the alignment film and which may be substituted by a hydrogen atom. Specifically, for example, tert-butoxy Alkylcarbonyl and 9-fluorenylmethoxycarbonyl and the like. In addition, a specific example of Y 2 in the formula (2), for example, a divalent organic group having a nitrogen atom represented by the following formulas (YD-6) to (YD-52) can be suppressed. From the viewpoint of charge accumulation by AC driving, the formula (YD-14) to the formula (YD-21) are preferable, and (YD-14) and (YD-18) are particularly preferable. [0074] In the formulae (YD-14) and (YD-21), j is an integer of 0 to 3; in the formula (YD-17), h is an integer of 1 to 3. [0076] In the formulas (YD-24), (YD-25), (YD-28), and (YD-29), j is an integer of 0 to 3. [0078] [0079] [0079] [0080] [0081] (In the formula (YD-50), m and n are each an integer of 1 to 11, and m+n is an integer of 2 to 12). The ratio of the diamine represented by the formula (2) in the (A-1) component or the (A-2) component polyamine and the polyaminic acid quinone imidized polymer, The total diamine 1 mole used for the production of the (A-1) component or the (A-2) component is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and particularly preferably 50. ~100% by mole. In the component (A-1) and the component (A-2) of the present invention, a diamine represented by the formula (2) in the ruthenium imidized polymer of polyglycolic acid and polyglycine is produced, These may be used singly or in combination of two or more. In this case, the total amount of the diamine represented by the formula (2) is preferably in the above preferred amount. Further, in the case of the component (A-1) and the component (A-2), the same diamine is used, and the effect of the invention of the present invention is further improved. Further, in the present invention, among the components (A-1) and (A-2), the diamine used in the production of the polyaminic acid and the ruthenium imidized polymer of polyglycolic acid is the same. good. The polyamino acid of the component (A-1) or the component (A-2) contained in the liquid crystal alignment agent of the present invention may be, in addition to the diamine represented by the above formula (2), the following formula: (5) The diamine represented. Y 2 in the following formula (5) is a divalent organic group, and the structure thereof is not particularly limited, and two or more types may be used in combination. Moreover, the specific examples thereof include the following (Y-1) to (Y-49) and (Y-57) to (Y-97). [0086] [0087] [0088] [0089] [0090] [0091] [0092] [0093] [0094] [0095] [0096] The (A-1) component of the liquid crystal alignment agent of the present invention or the polyaminic acid of the component (A-2) and the ruthenium imidized polymer of polyglycolic acid are represented by the formula (5) When the ratio of the diamine is too large, there is a possibility that the effect of the present invention is impaired, which is not preferable. Therefore, the ratio of the diamine represented by the formula (5) is preferably 0 to 90 mol%, more preferably 0 to 50 mol%, and particularly preferably 0 to 20 mol% based on the total diamine 1 mol. ear%. <Method for Producing Polylysine> The polylysine of the polyimide precursor used in the present invention can be synthesized by the following method. Specifically, the tetracarboxylic dianhydride and the diamine are carried out in the presence of an organic solvent at -20 to 150 ° C, preferably 0 to 70 ° C, for 30 minutes to 24 hours, preferably 1 to 12 Synthesized in hours of reaction. The organic solvent used in the above reaction is N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. from the viewpoint of solubility of the monomer and the polymer. It is preferable to use one type or a mixture of two or more types. The concentration of the polymer is preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body. The polylysine obtained by the above method can be precipitated and recovered by injecting the reaction solution while stirring the mixture in a lean solvent. Further, the precipitated product is precipitated several times, washed with a poor solvent, and dried at room temperature or under heating to obtain a purified polyamidonic acid powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, toluene, etc., and water, methanol, ethanol, and 2- Propanol and the like are preferred. <Method for Producing Polyimine] The polyimine used in the present invention can be obtained by subjecting the polyamic acid to a ruthenium reaction. In the case of producing a polyimine from polylysine, the chemical ruthenium reaction of the catalyst is added to the solution of the polyamic acid obtained by reacting the diamine component with the tetracarboxylic dianhydride. method. The chemical hydrazine imidization can carry out the oxime imidization reaction at a relatively low temperature, and it is preferable that the molecular weight of the polymer is not lowered in the hydrazine imidization process. The chemical hydrazine imidization is carried out by stirring a polymer to be imidized in an organic solvent in the presence of an alkaline catalyst and an acid anhydride. As the organic solvent, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it maintains an appropriate basicity during the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction. The temperature at which the hydrazine imidization reaction is carried out can be carried out at a temperature of from -20 to 140 ° C, preferably from 0 to 100 ° C, for a reaction time of from 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the polyamido acid group, and the amount of the acid anhydride is 1 to 50 moles of the polyamido acid group, preferably 3 to 30 moles. The ruthenium imidation ratio of the obtained polymer can be controlled in such a manner that the amount of the catalyst, the temperature, and the reaction time can be adjusted. [0099] In the solution after the imidization reaction of the poly-proline, the added catalyst or the like is left in the solution, and the obtained ruthenium-imided polymer is recovered and redissolved by the means described below. In the organic solvent, it is preferred as the liquid crystal alignment agent of the present invention. [0100] The polyimine solution obtained in the above manner is poured into a poor solvent with sufficient stirring to precipitate a polymer. The precipitated product is precipitated several times, washed with a poor solvent, and dried at normal temperature or under heating to obtain a purified polymer powder. The poor solvent is not particularly limited, and examples thereof include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. Etc., methanol, ethanol, 2-propanol, acetone, etc. are preferred. The content ratio of the component (A-1) and the component (A-2) obtained by the method is such that the specific tetracarboxylic dianhydride represented by the above formula (1) and the specific aliphatic acid are The ratio of the anhydride is from 10:90 to 90:10, more preferably from 20:80 to 80:20, more preferably from 40:60 to 60:40, and particularly preferably from 46:54 to 54. The ratio of 46 is essentially the best in terms of equivalents. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent used in the present invention is in the form of a solution having a polymer component dissolved in an organic solvent. The molecular weight of the polymer preferably has a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, particularly preferably from 5,000 to 50,000. The concentration of the polymer of the liquid crystal alignment agent used in the present invention can be appropriately changed in accordance with the thickness setting of the coating film to be formed, and a uniform and defect-free coating film is formed, preferably 1% by mass or more. The solution preservation stability viewpoint is preferably 10% by mass or less. A particularly preferred polymer concentration is from 2 to 8% by mass. The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as the polymer component can be uniformly dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidine. Ketone, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, Γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even a solvent which cannot uniformly dissolve the polymer component alone may be used in combination with the above organic solvent as long as it does not precipitate a polymer. In addition to the above-mentioned solvent, the organic solvent contained in the liquid crystal alignment agent may generally be a mixed solvent obtained by combining a solvent which can improve coating properties or improve surface smoothness of a coating film when a liquid crystal alignment agent is applied. In the liquid crystal alignment agent of the present invention, these mixed solvents are also suitably used. Specific examples of the organic solvent which can be used in combination are, for example, the following, but are not limited to the examples. For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propane Glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, dipropyl ether, dibutyl ether, dihexyl ether , dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6- Dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, B Glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, Ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(butoxy Ethyl ethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Alcohol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid , n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, a solvent represented by the following formulas [D-1] to [D-3], and the like. [0105] In the formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3] D 3 represents an alkyl group having 1 to 4 carbon atoms. Among them, a combination of preferred solvents, for example, N-methyl-2-pyrrolidone and γ-butyrolactone with ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone Propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentyl Ketone with diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl-2 -pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and 2,6-dimethyl -4-heptanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether. The type and content of the solvent can be appropriately selected in accordance with a coating device for a liquid crystal alignment agent, a coating condition, a coating environment, and the like. Further, in the liquid crystal alignment agent of the present invention, the following additives may be added from the viewpoint of improving the mechanical strength of the film. [0108] [0109] The additive is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the effect cannot be expected. When the amount is more than 30 parts by mass, the liquid crystal alignment property is lowered, and it is more preferably 0.5 to 20 parts by mass. In addition to the above, the liquid crystal alignment agent of the present invention may be added to a polymer other than the polymer to change the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, without impairing the effects of the present invention. a dielectric material or a conductive material, a decane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinking compound for the purpose of improving the film hardness or density when the liquid crystal alignment film is used, or an improvement When the coating film is sintered, the polyaminic acid can be efficiently subjected to a ruthenium imidization reaction or the like. <Liquid Crystal Alignment Film><Method for Producing Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and sintering the film. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used. For the sake of simplicity, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, when the reflective liquid crystal display element is only a single-sided substrate, an opaque substance such as a germanium wafer may be used. In this case, a material such as aluminum which can reflect light may be used. The method of applying the liquid crystal alignment agent of the present invention is, for example, a spin coating method, a printing method, an inkjet method, or the like. The drying and sintering steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, when the organic solvent contained is sufficiently removed, it may be dried between 50 ° C and 120 ° C for 1 minute to 10 minutes, and then sintered between 150 ° C and 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after sintering is not particularly limited. However, when it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is usually 5 to 300 nm, preferably 10 to 200 nm. A method of performing alignment treatment on the obtained liquid crystal alignment film, for example, a rubbing method, a photoalignment treatment method, or the like. [0115] The rubbing treatment can be performed using an existing friction device. At this time, the material of the rubbing cloth, for example, cotton products, nylon, enamel, and the like. The conditions of the rubbing treatment are generally in the range of 300 to 2000 rpm, a conveying speed of 5 to 100 mm/s, and a pressing amount of 0.1 to 1.0 mm. Subsequently, the residue generated by the friction cleaning by ultrasonic cleaning is removed using pure water or alcohol. [0116] A specific example of the photo-alignment processing method, for example, a method of irradiating the surface of the coating film with radiation that is directed in a specific direction, and depending on the case, heat treatment at a temperature of 150 to 250 ° C to impart a liquid crystal alignment ability Wait. For the radiation, for example, ultraviolet rays having a wavelength of 100 nm to 800 nm and visible rays can be used. Among them, ultraviolet rays having a wavelength of from 100 nm to 400 nm are preferred, and those having a wavelength of from 200 nm to 400 nm are particularly preferred. Further, for the purpose of improving the alignment of the liquid crystal, the coated substrate may be irradiated with radiation at a temperature of 50 to 250 °C. The exposure to radiation of 1 ~ 10,000mJ / cm 2 preferably, to 100 ~ 5,000mJ / cm 2 is particularly preferred. The liquid crystal alignment film obtained in the above manner can stably align liquid crystal molecules in a specific direction. Further, when the extinction ratio of the polarized ultraviolet rays is higher, it is more preferable because it can impart higher anisotropy. Specifically, the extinction ratio of the ultraviolet light which is polarized with respect to a straight line is preferably 10:1 or more, and more preferably 20:1 or more. The film irradiated with the polarized radiation obtained in the above manner may be further subjected to a contact treatment using a solvent containing at least one selected from water and an organic solvent. The solvent used for the contact treatment is not particularly limited as long as it can dissolve the solvent of the decomposition product generated by light irradiation. Specific examples are, for example, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve (cellosolve), ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate Wait. These solvents may be used in combination of two or more kinds. From the viewpoint of versatility or safety, it is preferred to use at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate. . Water, 2-propanol, and a mixed solvent of water and 2-propanol are particularly preferred. In the present invention, the contact treatment of the film irradiated with the polarized radiation and the solution containing the organic solvent is carried out by a treatment method in which the film and the liquid are preferably and sufficiently contacted by using a wetting treatment, a spray treatment or the like. Further, it is preferred to carry out the method of impregnating the film in the solution containing the organic solvent for preferably from 10 seconds to 1 hour, more preferably from 1 to 30 minutes. The contact treatment can be carried out at normal temperature or under heating, preferably at 10 to 80 ° C, more preferably between 20 and 50 ° C. In addition, if necessary, ultrasonic waves or the like can be applied to enhance contact. After the above contact treatment, the purpose of removing the organic solvent in the solution after use may be to wash (Rinse) or dry, or two, with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone. Both can be done at the same time. Further, when the film subjected to the contact treatment with a solvent described above is used for drying the solvent and realigning the molecular chains in the film, it may be heated to 150 ° C or higher. The temperature of the heating is preferably, for example, 150 to 300 ° C. When the temperature is higher, the molecular chain re-alignment can be promoted, but when the temperature is too high, there is a concern that the molecular chain is decomposed. Therefore, the heating temperature is preferably, for example, 180 to 250 ° C, and particularly preferably 200 to 230 ° C. [0123] When the heating time is too short, the effect of reorientation of the molecular chain may not be obtained. When the temperature is too long, the molecular chain may be decomposed. Therefore, it is preferably 10 seconds to 30 minutes. Minutes to 10 minutes are preferred. Further, the obtained liquid crystal alignment film can be easily dissolved in a reconstituted material, and is a film having excellent remanufacturability. The solvent used in the reconstitution may, for example, be a solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or propylene glycol monomethyl ether. Glycol ethers; glycolosolve acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc. Diethylene glycol, propylene glycol, butanediol, hexanediol, etc.; alcohols such as methanol, ethanol, 2-propanol, butanol; acetone, methyl ethyl ketone, cyclopentanone, cyclohexane Ketones such as ketone, 2-heptanone, γ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropane An ester of methyl ester, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-di Amidoxime such as methyl acetamide and N-methyl-2-pyrrolidone. The reconstituted material is preferably one which contains an alkaline component such as ethanolamine in the above solvent, and a rust inhibitor which does not cause the alkaline damage electrode or the like. Manufacturers of such remanufactured materials are available, for example, Korea's Huiming Industry Co., Ltd., KPX Chemical, and the like. [0126] In order to heat the above-mentioned reconstituted material at room temperature or between 30 ° C and 100 ° C, the substrate with the liquid crystal alignment film is immersed therein for 1 second to 1000 seconds, preferably. After 30 seconds to 500 seconds, or after the spray material is spray-sprayed, the liquid is washed with an alcohol solvent or pure water. Further, the temperature of the reconstituted liquid at the time of remanufacturing is preferably a low temperature from the viewpoint of work efficiency, etc., and is usually room temperature to 60 ° C, more preferably room temperature to 40 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is obtained by using the liquid crystal alignment agent of the present invention and preparing a substrate having a liquid crystal alignment film according to the method for producing a liquid crystal alignment film, and then forming a liquid crystal cell by a known method. (cell) and use it as a liquid crystal display element. An example of a method of fabricating a liquid crystal cell will be described by taking a liquid crystal display device having a passive element matrix structure as an example. Further, it may be a liquid crystal display element having an active matrix structure in which opening and closing elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display. First, a transparent glass substrate is prepared, and a common electrode is provided on one of the substrates, and a segment electrode is provided on the other substrate. The electrodes can be used, for example, as ITO electrodes or can form a pattern of desired image display. Next, an insulating film covering the common electrode and the segment electrode may be provided on each of the substrates. The insulating film is, for example, a film formed of SiO 2 -TiO 2 obtained by a sol-gel method. Next, a liquid crystal alignment film of the present invention is formed on each substrate by the above method. Next, the substrate on one side and the substrate on the other side are overlapped so that the alignment film faces are opposed to each other, and a sealant is used in the periphery. In the sealant, for the purpose of controlling the gap between the substrates, etc., a spacer is usually mixed. Further, it is preferable to disperse the spacer which controls the gap of the substrate in the inner portion where the sealant is not provided. One of the sealants is provided with an opening that can be filled with liquid crystal externally. [0129] Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant via the opening provided in the sealant. Subsequently, the opening portion is sealed with an adhesive. The injection method may be a vacuum injection method or a capillary phenomenon in the atmosphere. Subsequently, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates are attached to the surface opposite to the liquid crystal layer of the two substrates. Through the above steps, the liquid crystal display element of the present invention is obtained. In the present invention, the sealant may be cured by ultraviolet irradiation or heating, for example, using a reactive group having an epoxy group, an acryloyl group, a methacryl group, a hydroxyl group, an allyl group or an ethyl fluorenyl group. Resin. In particular, it is preferred to use a hardening resin having a reactive group having both an epoxy group and a (meth)acryl fluorenyl group. In the sealing agent of the present invention, an inorganic filler may be added for the purpose of improving adhesion, moisture resistance, and the like. The inorganic filler to be used is not particularly limited, and specific examples thereof include spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium carbide, and nitriding. Bismuth, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, calcium citrate, aluminum silicate, lithium aluminum silicate, Zirconium silicate, barium titanate, nitrocellulose, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium nitride, nitrogen Boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate. The inorganic filler may be used in combination of two or more kinds. In the liquid crystal display device, since the liquid crystal alignment film is a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film of the present invention, it has excellent remanufacturability, and is suitable for use in a large-screen, high-definition liquid crystal television or the like. .